KR100393323B1 - Powdered detergent composition and process for preparing the same - Google Patents

Abstract

The present invention relates to a non-polluting powder detergent composition based on high performance sodium percarbonate and bentonite as a base material and a method for producing the same.

According to the present invention, powder anhydrous ash and a small amount of synthetic surfactant and water are continuously added to a hydration reactor and heated to form a slurry product, and the slurry form product is introduced into a percarbonate reactor, In the presence, it reacts with the hydrogen peroxide solution to form a high performance percarbonate product, to which the natural surfactant bentonite is added. The granules are added to the resultant to form a powder, and the powder is encapsulated to obtain a detergent target.

The synthetic surfactant is continuously added in a ratio of 0.01 to 5% by weight, preferably 0.1 to 3% by weight relative to the anhydrous soda ash, and as the synthetic surfactant, anionic, cationic, A component or a mixture of any one of the active ingredients of a surfactant such as a nonionic, amphoteric, zwitterion and the like is employed.

As the moisture control agent, powder silica or bentonite or a mixture thereof corresponding to 1 to 6% by weight with respect to anhydrous soda ash is applied. Bentonite used as a natural surfactant is added in an amount of 5 to 35% by weight, preferably 10 to 25% by weight based on anhydrous soda ash.

In addition, the powder detergent contains an additive of an enzyme, a polish, and a flavoring agent in an amount of 0.1 to 2% based on the total weight, and one of gelatin and starch capsules is used to encapsulate the detergent powder.

Description

Pollution-free powder detergent composition and its manufacturing method {POWDERED DETERGENT COMPOSITION AND PROCESS FOR PREPARING THE SAME}

The present invention relates to a non-polluting powder detergent composition and a method for preparing the same, and more particularly, high performance sodium percarbonate (which is 200 Sodium percarbonate formed from the following fine particles (sodium percarbonate; ) And sodium carbonate hydrate, ) And a small amount of surfactants, and not a physical mixture, but a compound that exists in the state of various compounds obtained as a result of a specific chemical reaction)) and bentonite as a main component. The present invention relates to a pollution-free powder detergent composition comprising a silicate, an enzyme, a polishing agent, a gelatin, a starch, and the like, and a manufacturing method thereof.

In general, detergents provide good laundry power for laundry, but environmental pollution due to the residual water should be restrained as much as possible, and in view of such a problem, researches for developing a pollution-free detergent have been actively conducted. As a result of the development, various types of detergent compositions have been proposed and are being put into practical use or being promoted.

The detergent composition consists of seaweeds, vegetable detergents prepared by applying a liquid extracted from a specific plant as a main ingredient, or synthetic detergents obtained by synthesizing chemical substances.

The components constituting the synthetic detergent in powder form include surfactants, bleaches, builders and the like.

Among them, surfactants are mainly cationic, anionic and nonionic active agents, and are included in the detergent at about 10-45%.

Bleaches are roughly divided into chlorine-based and oxygen-based ones and are included in the detergent at about 10-25%.

In addition, the materials used as builders are various organic materials and inorganic materials. Commonly used inorganic materials include anhydrous sodium carbonate, sodium bicarbonate, phosphorus compounds, silicates, zeolites, and layered silicates. layered silicate (35-75%) is used in detergents, and the phosphorus compound, which has been used as an inorganic builder in the past, is limited in its use due to environmental pollution problems despite its superiority.

Here, the first detergent component related to the present invention is a bleach.

Chlorine-based bleach used in detergents tends to damage the dyed fibers as compared to oxygen-based bleaches, and has the disadvantage of discoloring synthetic fibers (eg yellow).

Among the oxygen-based bleaches, sodium percarbonate is widely used. So commonly used sodium percarbonate is sodium-based, boron-based, etc., and environmentally friendly sodium percarbonate meeting the object of the present invention is sodium-based. Reference is made to "percarbonate".

Percarbonate is pure and stable Although a substance having a molecular formula of, the percarbonate commonly used in detergents generically includes a substance containing 67.5 ~ 97wt% soda ash and 32.5 ~ 3wt% hydrogen peroxide.

Percarbonate is a relatively inexpensive, pollution-free bleach that provides high solubility in aqueous solutions and the active oxygen required for bleaching and carbonate ions effective for washing. However, percarbonate has a disadvantage in that its activity rapidly decreases when stored for a long time in a high temperature and high humidity environment or when washing at a low temperature.

In view of this, for example, GB 2123044A proposed the use of sodium metaborate and sodium silicate as coating materials to increase the storage stability of percarbonate. 3,677,697 proposes the addition of silicates and benzoic acid. In addition, US Patent No. 3,951,838 proposes a method of increasing the stability by adding a 3 ~ 8% silica solution 1 to 10% by weight (wt) to the percarbonate.

In addition, US Patent No. 4,260,508 proposed a method of adding sodium phosphate, and US Patent No. 5,312,557 proposed a method of increasing stability by coating boric acid and silicate on percarbonate. US Patent No. 6,017,867 proposes to add hydrophobic material silica, talc, zeolite and the like. .

In U.S. Patent No. 5,792,738, the particle size is 400 A method of coating the following percarbonate with an inorganic salt or salts of carboxylic acid has been proposed. The patent implies that the use of zeolite impairs the stability of percarbonate due to the excess of mobile water. It is disclosed that controlling the particle size of percarbonate is an important factor for improving stability. In other words, if the particle size of the percarbonate contained in the detergent is too large, it is difficult to dissolve in water during washing, on the contrary, if the particle size is too small, the stability is reduced.

In JP61069897A2, the particle size is 10 Aluminosilicates, Although it is suggested that bentonite and clay can be added to the detergent at about 0.5 to 35 wt%, the state of the detergent particle surface can be changed, but there is no mention of improving the performance of percarbonate.

Many other patents mention how to increase the stability of percarbonate.

In addition, a method of adding about 2 to 5 wt% of a bleach activator in order to increase the low temperature bleaching of percarbonate is proposed, among which US Patent No. 4,190,635 discloses tetracetyl ethylenediamine (N, N , N ', N'-tetracetyl ethylenediamine (TEAD) was proposed, and US Patent No. 5,700,771 proposed a method of adding a polyhydroxy fatty acid amide surfactant as a detergent mixture, In US Pat. No. 6,063,750, a method of preparing a bleaching agent by mixing ammonium nitrile and phyllosilicate has been proposed. The phyllosilicate uses bentonite-based materials.

In addition, US Pat. No. 6,093,343 proposes a method of using a metal compound such as copper, cobalt, iron, titanium, ruthenium, tungsten, molybdenum, and manganese as a bleach catalyst. .

All of the above patents are methods for improving the performance of the previously produced percarbonate by adding various active ingredients to the percarbonate produced once by a physical method (for example, a coating).

The above-mentioned percarbonate is widely used as a pollution-free bleaching agent due to its performance and economy despite the problems of storage and low temperature activity, and various methods for preparing the material have been proposed.

The production method of percarbonate includes roughly wet, dry and mixed methods.

Among them, examples of the wet method include an aqueous solution of hydrogen peroxide and anhydrous soda ash, as disclosed in US Pat. Nos. 2,380,620 and 2,541,733. ) Is a method of filtering the percarbonate particles produced by mixing), in which salt or other additives are used to facilitate the recovery of the target, in which the particle density is 0.9. Phosphorus percarbonate was produced. However, the method causes a decrease in the yield of percarbonate due to decomposition of hydrogen peroxide in the aqueous solution, thereby degrading hydrogen peroxide efficiency.

According to another example for the production of percarbonate, US Pat. No. 3,555,696 proposes a method of contacting anhydrous soda ash with a hydrogen peroxide solution in a spray tower, in which case a low density powder was formed.

In addition, U.S. Patent No. 3,883,640 proposes a method of increasing the particle size and stability of percarbonate by adding anhydrous soda ash, hydrogen peroxide solution, and water soluble acrylic polymer polyelectrolyte of 10 to 10,000 ppm at 15 ° C. It is.

In general, the use of excess water in the manufacturing process of percarbonate decreases the efficiency of hydrogen peroxide, while the efficiency decreases even when the amount of water is too small due to the heat of reaction generated during the reaction of soda ash and hydrogen peroxide. In particular, in the latter case, the density of the percarbonate formed is very low, which may cause a problem when mixing the detergent.

Therefore, a dry method of directly spraying hydrogen peroxide on powdered anhydrous soda ash has been proposed to dry percarbonate produced using carbon dioxide gas as in US Pat. No. 3,864,454.

However, the most problem in the production of percarbonate by the dry method is the effective regulation of the heat of reaction that occurs during the reaction of anhydrous soda ash with hydrogen peroxide. When the anhydrous soda ash and the hydrogen peroxide solution come into contact with each other, two kinds of heat of reaction occur. The first is the heat of hydration which occurs when the anhydrous soda ash reacts with water to become a hydrate, and the second anhydrous soda ash reacts with hydrogen peroxide. This is the heat of perhydration that occurs when percarbonate is produced. Both types of reaction heat increase the temperature of the reaction mixture considerably. Therefore, when effective mixing and cooling medium are not used, non-uniform percarbonate may be generated due to local temperature increase, thereby degrading performance.

In the dry method, when the raw anhydrous soda ash particles are too small, a lot of dust is produced when reacting with hydrogen peroxide, whereas when the anhydrous soda ash particles are too large, the conversion to percarbonate decreases.

U.S. Patent No. 3,860,694 proposes a method of contacting a 35-90% hydrogen peroxide solution by adjusting the raw particle size of anhydrous or hydrated soda as a representative example of a mixed formula. In this method, Mg-based stabilizers are mixed and the reactants are allowed to react for 5 minutes to 3 hours in a humid state. The hydrated soda ash raw material used in the patent is obtained by spraying water on soda ash.

U.S. Patent No. 4,970,058 is a method of reacting a mixture of anhydrous soda ash and hydrogen peroxide by mixing 0.1 to 3 wt% diphosponic acid. The addition of diphosphonic acid increases the stability of percarbonate and suppresses the production of dust. Suggested. The maximum free oxygen content of percarbonate formed at this time is 11.2%, indicating that it is 75% of pure percarbonate.

U.S. Patent No. 5,045,296 discloses a mixture of 1.5 to 13 wt% of diphosphonic acid in a solution of 50 to 75% hydrogen peroxide. By spraying an anhydrous soda ash having a particle distribution to produce percarbonate with 13 to 14.5% effective oxygen, US Pat. No. 5,328,721 uses a similar method.

In practice, a number of patents propose a method of using a mixer equipped with a stirrer and a fluidized bed in the process of producing percarbonate.

U.S. Patent No. 4,171,280 proposes a method of obtaining percarbonate containing 1 to 6% effective oxygen by reacting anhydrous soda ash and hydrogen peroxide in a fluidized bed at 35 to 70 ° C. Multistage Stirrer using a continuous mixer system of mixer type 100 The process which manufactures the following percarbonates was proposed.

In addition, recently published US Pat. No. 6,159,252 introduces a general process for preparing particles using a fluidized bed, which can be used for the production of percarbonate.

Most of the patents described above produce percarbonate using anhydrous soda ash as a raw material, but a few patents use sodium carbonate monohydrate as a raw material.

U.S. Patent No. 4,190,635 proposes a method of using hydrated soda ash obtained by carbonation as a gas containing 12% carbon dioxide in commercial anhydrous soda ash having 48% purity. According to the method, a mixture of hydrogen peroxide, a small amount of nonionic surfactant, and a hydrated soda ash mixture is reacted at a temperature of 30 ° C. in a mixer to obtain percarbonate containing 12 to 14% of active oxygen. At this time, it can be seen from the examples set forth in the patent that the addition of a small amount of the surfactant to reduce the particle size of the resulting percarbonate.

More specifically, without surfactant, it contains 12.3% free oxygen and has a density of 0.768 Particle size 600 Phosphorus percarbonate was produced, and with the addition of a nonionic surfactant, it contained 14.3% free oxygen and had a density of 0.76 Particle size 220 Phosphorus percarbonate was prepared.

Therefore, it can be expected that the surfactant plays a role to control the particle shape and size of the resulting percarbonate and to increase the amount of free radicals. The present invention focuses on this point to produce high performance percarbonate.

The second detergent component associated with the present invention is bentonite.

Bentonite has conventionally been used as a component of an effective detergent, and as a detergent component, bentonite has been mainly used as a fabric softner. That is, US Patent No. 4,472,287 proposed a fabric softener mainly composed of bentonite and water-insoluble soap components, for example, aluminum stearate, and US Patent No. 4,882,076 and Korean Patent Publication No. 93- 4512, WO 9419440A1, discloses an example in which bentonite is used as a fabric softener.

In addition, US Patent No. 4,919,847 proposes a method in which bentonite and linear alkylbenzene sulfonate (LAS) are mixed to form particles in a fluidized bed and then silicate is added to the fluidized bed.

In addition, US Pat. No. 5,080,820 proposes a powder detergent including zeolite, bentonite, and polyphosphate.

JP10183195A2 proposes a detergent composition comprising a zeolite of type A (or bentonite) and anhydrous soda ash (or sodium sulfite).

CN1071452A proposes a detergent composition in which a surfactant is mixed with bentonite, zeolite and other mineral powders. In addition, many patents propose a detergent composition in which bentonite and a surfactant are mixed.

As is well known, sodium bentonite has a molecular formula such as "Na _0.5 Al ₂ (Si _3.5 Al _0.5 ) O ₁₀ (OH) _2. (H ₂ O)" in the pure state, It can also be called a knight (sodium montmorillonite).

Sodium bentonite mined in the natural state contains metal components such as iron (Fe), magnesium (Mg), calcium (Ca), and potassium (K). Bentonite with high Ca content is called calcium bentonite, and the material is activated with sodium bentonite by reacting with soda ash. Therefore, sodium or calcium-based bentonite is generally difficult to distinguish clearly and its name is determined by the relative content of Na / Ca, so it will be simply referred to as “bentonite”.

In general, bentonite has a laminar or layered structure, and two adjacent layers each have a negative charge, and water or other polar substances are inserted in two interlayer regions to maintain electrical neutrality. (swelling) occurs. Accordingly, bentonite absorbs water equivalent to at least five times its weight in an aqueous solution, and absorbs heavy metals that are cations by ion exchange. In addition, bentonite dispersed in aqueous solution forms ultrafine particles and is known to have excellent surfactant activity.

Experimental evidence that bentonite acts as a surfactant to stabilize water and oil mixtures is also presented in the following documents.

1) G. Legaly, M. Reese, and S. Abend, "Smectites as colloidal stabilizers of emulsions I, Preparation and properties of emulsions with smectites and nonionic surfactants", Applied Clay Science 14 (1999), p 83-103.

2) G. Legaly, M. Reese, and S. Abend, "Smectites as colloidal stabilizers of emulsions II, Rheological properties of smectite-laden emulsions", Applied Clay Science 14 (1999), p 279-298.

3) S. Abend, G. Lagaly, "Sol-gel transitions of sodium montmorillonite

dispersions ", Applied Clay Science 16 (2000), p 201-227.

Based on this principle of surfactant activity, JP0302637A2 proposes an emulsion product containing 0.5-5% bentonite and not using other surfactants.

However, bentonite is likely to promote entanglement of powdered detergent particles when mixed in large amounts with detergent due to the expandability of moisture in the air. Therefore, in some cases, consideration is required to prevent this.

Forming a gel on the surface when bentonite is in contact with water prevents the infiltration of water into the inner surface of bentonite, which may prevent bentonite from dispersing into fine particles in aqueous solution.

Therefore, WO 003959A1 proposes a substance which can absorb about 2.5 times of water by activating calcium bentonite with sodium bentonite as a detergent component.

The third detergent component related to the present invention is gelatin or a substance having similar performance.

Conventionally, an anti-redeposition agent was added to the powder detergent to prevent the dirt in the laundry residue from being resorbed to the fibers.

U.S. Patent No. 3,558,499 improves performance by adding 0.5-2 wt% of polyacrylic acid, polyvinyl alcohol, methylcellulose, potato starch to the detergent by copolymerizing or physically mixing A method of becoming is disclosed. US Patent No. 5,207,941 discloses copolymerizing soy protein powder with various organic monomers to prepare a water-soluble high molecular material and use it as a detergent additive.

Korean Patent Publication No. 96-12275 proposed a method of adding 1 to 10 wt% gelatin, collagen, starch, sugar, chitosan, cellulose, and the like.

EP1045022A1 suggested that gelatin capsules can be used to prevent the fibers from turning yellow.

Other components related to the present invention are silica, silicates, enzymes, brighteners, fragrances, etc. These materials are commercially available and widely used in detergent production.

According to the method for producing percarbonate disclosed in the above-mentioned many patents, most of the methods of reacting anhydrous soda ash and hydrogen peroxide solution in a wet or dry state (in some cases in the presence of an additive) are selected, but in this case partially Hydrated soda ash is generated by the contact reaction with water and anhydrous soda ash, and percarbonate is produced by reacting with anhydrous soda ash and hydrogen peroxide. The two exothermic reactions are difficult to control independently.

In addition, as described above, there is a high possibility that non-uniform percarbonate is formed due to two types of exothermic reactions generated during the production of percarbonate.

Accordingly, the present invention has been made in view of the above-described prior art, and a new concept of a non-polluting detergent, in particular a synthetic surfactant, using a high performance percarbonate as an oxygen-based bleach and bentonite as a natural surfactant as a main component is 3% of the total amount of the detergent. It is to provide a non-polluting powder detergent composition and a method for producing the same having both excellent bleaching power and washing power at low temperature washing while maintaining below.

In order to achieve the above object, according to a preferred embodiment of the present invention, the production of high-performance percarbonate with excellent bleaching power at a low temperature of 20 ° C. or lower, and bentonite, silica, silicate, enzymes, brighteners, fragrances, etc. It has been proposed a method of increasing the safety of the detergent against water by preparing a powder by adding substances, and encapsulating the resulting powder into a water-soluble substance such as gelatin and starch.

Preferably, the method for preparing high-performance percarbonate proposed by the present invention includes a process of continuously operating a "hydration reactor" and a "perhydration reactor".

In the hydration reactor, a suspension containing 0.5 to 3, preferably 0.7 to 1.5, water by weight relative to anhydrous soda ash powder 1 is contained in an amount of 0.01 to 5% by weight relative to anhydrous soda ash, preferably 0.1 to 3%. The slurry in the form of a dough having a water content of 40% or less by being continuously added to the reactor and reacted at a temperature of 50 to 95 ° C, preferably 65 to 85 ° C for 0.3 to 4 hours, preferably 0.5 to 2 hours. slurry).

In the percarbonate reactor, the slurry produced in the hydration reactor and the 20 to 75% hydrogen peroxide solution are continuously reacted under the temperature condition of 30 to 75 ℃ to obtain a particle size of 200. The following high performance percarbonate particles are manufactured. At this time, in order to selectively control the water content of the particles in the percarbonate reactor, powdered silica or bentonite or a mixture thereof, which functions as a moisture control agent corresponding to 1 to 6 wt% with respect to anhydrous soda ash, simultaneously with hydrogen peroxide and the percarbonate reactor In succession.

It was found that the percarbonate prepared in this way has a small particle size, so that the solubility in water is enhanced and the low temperature bleaching power is excellent. In addition, since this object contains a small amount of surfactant, there is also an advantage that the washing power is also guaranteed.

Here, comparing the production of high-performance percarbonate by the method of the present invention and the percarbonate production methods known to date are as follows.

As already mentioned, conventional techniques for improving the performance of percarbonate can be roughly divided into two types. It is a method of adding various active ingredients to the percarbonate produced by the physical method and the method of adding an additive during the production of percarbonate. Since the first techniques differ from the present invention, only the techniques falling under the second category will be compared.

In the method for producing percarbonate disclosed in the above-mentioned patent, the method of partially reacting anhydrous soda ash and hydrogen peroxide solution in a wet or dry state (in some cases in the presence of an additive) is carried out. Hydrated soda ash is produced by the contact reaction of anhydrous soda ash, and at the same time, percarbonate is produced by reacting with anhydrous soda ash and hydrogen peroxide. These two exothermic reactions are difficult to control independently, and because of the two kinds of exothermic reactions generated during the production There is a high probability that non-uniform percarbonate is formed.

On the other hand, the hydration reaction system of the present invention almost all of the anhydrous soda ash raw material (sodium carbonate hydrate, ), And the hydrated soda ash obtained at this time has the characteristic of being formed into uniform fine particles irrespective of the particle distribution of the raw soda anhydrous ash. Thus, the raw material of the next percarbonate reactor is not soda ash, which is used in most of the preceding patents, but is a small, uniform hydrated soda ash.

In conclusion, the use of a hydration reactor can omit the pretreatment process for controlling the particle size of raw soda ash proposed in US Patent No. 3,860,694.

In addition, the particles produced in the hydration reactor to which the surfactant was added were found to be finer than those to which the particles were not added. Therefore, the role of the surfactant in the hydration reactor is thought to have a good effect on the post-process percarbonate reaction by changing the physical and chemical state of the product particles.

The hydrated sodium carbonate used in US Pat. No. 3,860,694 is obtained by spraying water only with anhydrous soda ash, and this method is expected to hydrate some of the anhydrous soda ash, but the technique of the patent is proposed in the present invention. It is different from a hydration reactor.

Comparing the method of preparing percarbonate of the present invention with the method of US Pat. No. 4,190,635, the latter uses sodium carbonate monohydrate obtained by carbonation as a gas containing 12% carbon dioxide in commercial anhydrous soda ash having 48% purity. Therefore, the raw materials are different. In this patent, a mixture of hydrogen peroxide, a small amount of nonionic surfactant, and a hydrated soda ash mixture is reacted at 30 ° C. in a mixer to obtain percarbonate containing 12 to 14% of active oxygen, but the surfactant employed in the present invention is It is introduced in the hydration reactor and is independent of the percarbonate reactor.

Bentonite is added in an amount of 5 to 35% by weight, preferably 10 to 25% by weight, with respect to soda anhydride.

Bentonite is a natural clay material and is therefore almost pollution-free. Therefore, in the present invention, a method for replacing synthetic surfactant with bentonite has been attempted to realize a pollution-free detergent.

As described above, bentonite contains metal materials such as Mg and Fe. Therefore, it can be expected that the low temperature bleaching of percarbonate is enhanced based on the increase of the storage stability of percarbonate by Mg and the effect of bleaching catalyst by Fe when mixed with percarbonate and bentonite. In addition, bentonite has the advantage of softening the fiber after drying the laundry because the performance of the fabric softener.

In the mixture of percarbonate and bentonite prepared as described above Sodium silicate having a molecular ratio of 1 to 4, preferably 2 to 3.5, is added in an amount of 2 to 15% by weight, preferably 3 to 10%, based on the anhydrous soda ash. In this case, in order to obtain a detergent having a uniform composition, sodium silicate is used in an aqueous solution of 10 to 50%, preferably 15 to 30%, and is 150 to 500 in a granulator. Prepared in powders of size.

Sodium silicate contained in detergents is known to act as a builder to maintain the shape of the particles and at the same time contribute to the stability of the percarbonate.

Optionally, a small amount of enzyme, brightener, flavoring agent, etc. is mixed in the powder prepared as described above with respect to the total weight of the detergent, and then encapsulated with gelatin or starch.

As described above, gelatin or starch acts as an anti-adsorption agent and at the same time encapsulates the contents of the detergent to increase the shelf life of percarbonate.

1 is a view illustrating a manufacturing process of a pollution-free powder detergent composition based on high performance sodium percarbonate and bentonite according to a preferred embodiment of the present invention.

* Description of the symbols for the main parts of the drawings *

1: hydration reactor, 5: percarbonate reactor,

8: mixer, 11: granulator,

14 mixer, 17 encapsulation device.

Hereinafter, with reference to the accompanying drawings, the present invention will be described in detail.

1 is a process chart illustrating a manufacturing process of a pollution-free detergent composition according to the present invention.

In the drawing, reference numeral 1 denotes a hydration reactor equipped with a stirrer, and the hydration reactor 1 is heated while continuously supplying powder anhydrous ash (2 in FIG. 1) and a surfactant (3 in FIG. 1) to evaporate moisture. To prepare a slurry in the form of a dough.

That is, water is added to the hydration reactor 1 at a rate of 0.5 to 3 times, preferably 0.7 to 1.5 times, by weight relative to the powder of anhydrous soda ash (2 in FIG. 1), and the surfactant (3 in FIG. 1). Is continuously added in a ratio of 0.01 to 5% by weight, preferably 0.1 to 3% by weight based on the anhydrous soda ash.

Here, the temperature of the hydration reactor (1) is maintained at a constant in the range of 50 ~ 95 ℃, preferably 65 ~ 85 ℃ to maintain the properties of the particles produced uniformly.

In addition, the residence time in the hydration reactor (1) is constantly adjusted at 0.3 to 4 hours, preferably 0.5 to 2 hours.

Accordingly, the product from the hydration reactor 1 (4 in Fig. 1) is a slurry in the form of a dough having a water content of 40% or less, and dried the product (4 in Fig. 1) and analyzed the components by XRD. All hydration soda ash ( It turned out to be).

Increasing the amount of surfactant added to the hydration reactor 1 reduces the evaporation rate of water, while the resulting slurry increases fluidity and promotes the formation of particulates.

The types of surfactant that can be added to the hydration reactor 1 are very diverse and are as follows.

The surfactant (3 in FIG. 1) applicable to the present invention is a surfactant such as anionic, cationic, nonionic, amphoteric, and zwitterion based soaps and non-soaps. Contains all of the active ingredients and mixtures thereof.

In addition, the surfactant suitable for the present invention should be stable at a maximum reaction temperature of 95 ° C. or lower of the hydration reactor, should be a low pollutant, and have excellent washing power.

Surfactant suitable for the present invention shows an excellent effect even when using about 0.5 wt% based on the total amount of detergent, if the above conditions are satisfied, even if the price is expensive, it does not burden the economics.

Materials suitable for the present invention as anionic surfactants include linear alkyl groups in alkylbenzene sulfonates. To Among the phosphorus substances, primary and secondary alkylsulfates, especially alkyl groups To Phosphorus materials, alkyl ether sulfates, alkoxy amides, olefin sulfonates, alkyl xylene sulfonates, dialkyl sulfosuccinates, fatty acids Glutamates such as fatty acid ester sulfonate, primary and secondary alcohol sulfates, especially those with 10 to 20 carbon atoms, glycerol fatty acid esters, etc. Phosphate, such as isethionate, lauryl phosphate or lauryl phosphate, taurate, alkoxyl alcohol, alkyl carboxyl (alkyl carboxylate) -based compound.

These anionic surfactants may be used in the form of sodium salts or potassium salts, and may be used in the form of acids or mixtures thereof.

In particular, when the sodium salt (or potassium salt) of the anionic surfactant is used as a raw material, the surfactant may be neutralized in whole or in part using an acid to be used as a mixture of sodium salt (or potassium salt) and acid. It's okay. In this case, a small amount of neutral salt produced by neutralization will be contained in the detergent. Acids which can be used at this time are hydrochloric acid, sulfuric acid, phosphoric acid and the like. For example, if hydrochloric acid is used, the neutral salt becomes salt.

Nonionic surfactants suitable for the present invention are polyoxyethylene (POE) alkylphenol (POE alkyl phenol), POE amine (POE amine), POE fatty acid ester (POE fatty acid ester), polyethylene glycol (PEG) PEG fatty acid esters, POE fatty acid alcohol ethers, POE and polyoxypropylene (POP) condensates, and sorbitan fatty acid ester compounds. In addition, alkylpolyglycosides, glycerol monoethers, fatty acid ethanol amides, and polyhydroxyamides are included.

Suitable cationic surfactants for the present invention are quaternary ammonium salts having the molecular formula:

here, The groups represented by are alkyl, hydroxyalkyl or ethoxylated alkyls, Is the corresponding cation.

The amphoteric surfactants suitable for the present invention are betaine-based, alkyl amphocarboxylic acid-based such as glycinate and amino propionate, and amine oxide-based. And surfactants having negative or positive charges depending on the pH of the aqueous solution.

Zwitterionic surfactants suitable for the present invention are secondary and tertiary amine compounds. Although surfactants of this series are expensive, they are excellent in cleaning at low temperatures, and thus are preferred surfactants for pollution-free detergents.

Suitable soap-based surfactants are stearic acid (lauric acid), lauric acid (lauric acid), myristic acid (myristic acid), palmitic acid (palmitic acid), oleic acid (oleic acid), linolenic acid ( linolenic acid), and other fatty acid compounds. Since the acids are hardly dissolved in water, they may be used in the form of sodium or potassium salts, or may be dissolved in a solvent such as methanol in the form of an acid and added to the hydration reactor 1.

The product (4 in FIG. 1) from the hydration reactor 1 is introduced into the percarbonate reactor (5 in FIG. 1) by a slurry pump in a slurry state of 40% or less moisture.

1, 6 is a 20 to 75% hydrogen peroxide solution, the amount of hydrogen peroxide is continuously added 20 to 110%, preferably 50 to 80% of the theory required to produce 100% percarbonate with respect to raw anhydrous ash ash. do.

When the amount of hydrogen peroxide introduced into the percarbonate reactor 5 is less than the theoretical value, the percarbonate produced (7 in FIG. 1) is a specific compound of hydrated soda ash and percarbonate containing a small amount of surfactant. If the conversion to percarbonate is above 50%, the compound was found to have better low temperature bleaching power than the currently commercially prepared 100% percarbonate. On the contrary, it was found that approaching the conversion rate to percarbonate to 100% poses a problem for shelf life.

Preferably, the operating temperature of the percarbonate reactor 5 is kept as constant as possible in the 30 ~ 75 ℃ section. The operating temperature of the percarbonate reactor 5 is set in accordance with the goal for controlling the content of water in the reactor.

The operating conditions required in the percarbonate reactor (5) is to control the particle size and the content of water. Therefore, there is no limitation on the shape of the percarbonate reactor 5, and a mixer, a spray tower, or a fluidized bed may be used, and the reactors should be equipped with a drying device for controlling moisture.

Optionally, in order to control the water content of the particles in the percarbonate reactor 5, powdered silica or bentonite or a mixture thereof as a moisture control agent of 1 to 6% by weight relative to anhydrous soda ash (2 in FIG. 1) is added. It is continuously added to the percarbonate reactor simultaneously with hydrogen peroxide.

1 7 is a percarbonate powder produced in the percarbonate reactor (5) 200 It has the following particle size. If the size of the particles of the resulting percarbonate powder is too small, the storage performance is affected.

In addition, the water content of the percarbonate powder (7 in FIG. 1) is sufficient if it is 25% or less, because the excess water is absorbed by the bentonite in the next step.

8 is a simple mixer, in which bentonite (9 in FIG. 1) is added in an amount of 5 to 35%, preferably about 10 to 25%, based on the raw anhydrous soda ash (2 in FIG. 1).

In addition, 10 of FIG. 1 is a mixture of the resulting percarbonate and bentonite.

1, 11 is a granulator, and 12 is a granulator. A solution containing sodium silicate having a molecular ratio of 1 to 4, preferably 2 to 3.5.

The sodium silicate solution (12 in FIG. 1) is used in an aqueous solution of 10 to 50%, preferably 15 to 30%, so that the resulting detergent has a uniform composition.

The sodium silicate is added in an amount of 2 to 15%, preferably 5 to 12% by weight relative to anhydrous soda ash (2 in FIG. 1).

The particle size generated in 13 of FIG. 1 is 150 to 500 to be.

Sodium silicate contained in detergents is known to act as a builder to maintain the shape of the particles and at the same time contribute to the stability of the percarbonate.

The water content of the particles produced in 13 of FIG. 1 may be 20% or less.

14 is a mixer that can be used optionally.

1, 15 means additives such as enzymes, polishes, and flavorings. They are mixed so as to contain 0.1 to 2% by weight of the total detergent.

1, 16 shows the resulting detergent powder.

Figure 17 of Figure 1 is a capsule encapsulation device of the detergent powder (16 in Figure 1) as the encapsulating agent is to use gelatin or starch capsules, these substances act as a re-adsorption inhibitor and protect the detergent contents and storage of percarbonate Can be increased.

Such encapsulation is believed to be competitive in price compared to the prior art which coats percarbonate to increase storage.

The encapsulated percarbonate produced in 7 of FIG. 1 was stored for 24 hours in an oven at 60 ° C., and the free oxygen content was measured. As a result, no change was found within the experimental error.

Embodiments that do not limit the scope of the present invention are as follows.

Example 1

50 g of anhydrous soda ash and 0.25 g of distilled water and 0.25 g of sodium dodecylbenzene sulfonate (Junesei) were reacted in a hydration reactor (1) at 80 ° C. for 1 hour to obtain a slurry having a water content of 40%. (4 in FIG. 1) was introduced into a mixer type percarbonate reactor (5).

As the temperature of the slurry approaches room temperature, the porridge forms disappear and harden within 30 minutes to form a wet powder. A 35% hydrogen peroxide solution and 2 g of powdered silica were added to the material and reacted in a percarbonate reactor (5 in FIG. 1) to form 50% percarbonate. The apparent density was 0.60. Phosphorus powder was obtained.

As a result of analyzing the produced particles by XRD, it was found that they were specific compounds of sodium hydroxide and percarbonate containing trace amounts of surfactant. And the result of observing the particle size by SEM 200 The following fine particles were observed.

In order to compare the performance of the percarbonate prepared with the reagent percarbonate (Junsei Co., Ltd.) and 1g each of the two types of percarbonate in 200cc of 18 ℃ water, and the washing power was measured for 30 minutes, Both the bleaching power and the cleaning power of carbonic acid were found to be excellent.

The percarbonate of this example was gelatin encapsulated and stored in an oven at 60 ° C. for 24 hours to determine the amount of free radicals. As a result of the measurement, no change was found within the experimental error.

In addition, the powder obtained by mixing 10 g of bentonite (manufactured by Sud-Chemie AG) having the quality of the following Table 1 in a mixer (8 in FIG. 1) to 30 g of percarbonate prepared in this example was used for home use. The low temperature washing in the washing machine determined that both the bleaching power and the washing power were excellent.

In particular, it was observed that the resultant detergent (10 in FIG. 1) of the present example obtains a laundry result in which the amount of water used for the rinse after washing is very at least satisfactory since the content of the surfactant is 0.5% or less.

Also, after washing the laundry in the air after washing, it was observed that it was relatively soft and almost no rejection.

Table 1 Bentonite Components

70.0 wt%

16.0

1.3

2.8

1.1

2.7

1.0

Loss of heating 5.0

Example 2

50 g of anhydrous soda ash was reacted with 100 cc of distilled water and 0.25 g of surfactant for 1 hour at 80 DEG C in a hydration reactor (1) to obtain a slurry having a water content of 40%, and the product (4 in FIG. 1) was subjected to a percarbonate reactor (5 35% hydrogen peroxide solution and 2 g of powdered silica were added to react to form 50% percarbonate. Thus, a detergent (10 in FIG. 1) was prepared in the same manner as in Example 1. The surfactant was a mixture of dodecylbezene sulfonic acid and salt obtained by completely neutralizing sodium dodecylbenzenesulfonate with hydrochloric acid. Detergent performance test results were similar to Example 1.

Example 3

A detergent (10 of FIG. 1) was prepared in the same manner as in Example 2. As a surfactant, sodium dodecylbenzenesulfonate was neutralized with hydrochloric acid by 50%, and a mixture of dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, and salt was used. The detergent performance test result was similar to Example 1.

Example 4

A detergent (10 of FIG. 1) was prepared in the same manner as in Example 2. However, 90% percarbonate was prepared by increasing the amount of 35% hydrogen peroxide added to the percarbonate reactor 3 (6 in FIG. 1). The resultant (7 in Fig. 1) was dried in air for 24 hours, and the particles of percarbonate were decomposed into very small particles, and the bleaching power was significantly reduced. Experiments with varying amounts of hydrogen peroxide proved to be stable with 75% percarbonate.

Example 5

A detergent was prepared in the same manner as in Example 2. However, with respect to the produced percarbonate and bentonite mixture (10 in FIG. 1) (5 wt%), (15 wt%) and water (80 wt%) were used to prepare a powder (13 in FIG. 1) in the granulator 11 using three sodium silicates (12 in FIG. 1). The weight of the sodium silicate was adjusted to 10 wt% relative to anhydrous soda ash (2 in FIG. 1).

2 g of this result was added to 1 liter of tap water and tested for goldfish. In the comparative experiments, the detergent using the chlorine bleach containing about 20-25% of the synthetic surfactant had a survival time of less than 1 hour under the same conditions.

Therefore, it can be seen that the detergent prepared according to the present invention is at least 10 times more pollution-free than conventional detergents.

Example 6

A detergent was prepared in the same manner as in Example 2. However, 0.25 g of anionic surfactants Duponol and Alkanol (from Dupont) were used in the hydration reactor as surfactants.

Detergent performance test results were similar to Example 1.

Example 7

A detergent was prepared in the same manner as in Example 2. As the surfactant, 0.25 g of non-ionic surfactants Span 20, Tween 60, Brij 30, Brij 56, Renex 30 (manufactured by ICI) and Triton X-100 (manufactured by Rhom Hass) were used in a hydration reactor. .

Detergent performance test results were similar to Example 1.

Example 8

A detergent was prepared in the same manner as in Example 2. As a surfactant, cationic dodecyltrimethylammonium chloride (manufactured by Alrich) was used in a 0.25 g hydration reactor.

Detergent performance test results were similar to Example 1. However, the prepared detergent powder was observed to have a peculiar amine smell.

Example 9

A detergent was prepared in the same manner as in Example 2. As a surfactant, zwitterionic Chaps (3- [3-Cholamidopropyl) dimethylammonio] -1-propanesulfonate hydrate, manufactured by Alrich) was used in a 0.1 g hydration reactor.

Detergent performance test results were similar to Example 1.

Example 10

A detergent was prepared in the same manner as in Example 2. However, 0.25 g of pollution-free soap prepared from commercially available waste cooking oil as a surfactant was used in a hydration reactor.

Detergent performance test results found that the performance is lower than in Example 1. And it was observed that the resulting particles of percarbonate are generally larger than the particles obtained in Examples 1-10.

Example 11

A detergent was prepared in the same manner as in Example 2. However, 0.25 g of the pollution-free soap of Example 10 as a surfactant was dissolved in water, neutralized with hydrochloric acid, and methanol was added to dissolve the produced fatty acid, and then used in a hydration reactor.

The detergent performance test results were similar to those of Example 1, and the particle size of the percarbonate produced was observed to be smaller than that of Example 10.

On the other hand, the present invention is not limited to the above examples and various changes and modifications can be made within the scope not departing from the technical gist and gist of the invention.

As described above, according to the non-polluting powder detergent composition and the manufacturing method thereof according to the present invention, it is possible to provide a detergent with good washing power while eliminating environmental pollution. In particular, it is possible to protect the water resources by saving the washing water required for rinses.

Claims (38)

Powdered anhydrous ash, synthetic surfactant and water were continuously added to a hydration reactor and heated to obtain a slurry product. Injecting the product in the form of the slurry into the percarbonate reactor, in the presence of a moisture control agent, reacted with the hydrogen peroxide solution to obtain a high performance percarbonate product, After adding bentonite, a natural surfactant, to the high-performance percarbonate product, Add granulating agents to obtain detergent powder, Pollution-free powder detergent composition obtained by encapsulating the detergent powder. According to claim 1, wherein the water is added to the hydration reactor in a ratio of 0.5 to 3 times, preferably 0.7 to 1.5 times by weight with respect to the powder of anhydrous soda ash, the surfactant is 0.01 by weight relative to the anhydrous soda ash ˜5%, preferably 0.1 to 3% of the continuously charged, the temperature of the hydration reactor is 50 to 95 ℃, preferably pollution-free powder characterized in that it is kept constant in the range of 65 ~ 85 ℃ Detergent composition. The pollution-free powder detergent composition according to claim 1, wherein the residence time in the hydration reactor is set in a range of 0.3 to 4 hours, preferably 0.5 to 2 hours. The method of claim 1, wherein the synthetic surfactant is any one of surfactant active ingredients such as anionic, cationic, nonionic, amphoteric, zwitterion, etc. Pollution-free powder detergent composition, characterized in that one component or a mixture thereof. The method according to claim 4, wherein the anionic surfactant is a linear alkyl group, particularly an alkyl group in alkylbenzene sulfonate. To Among the phosphorus substances, primary and secondary alkylsulfates, especially alkyl groups To Phosphorus materials, alkyl ether sulfates, alkoxy amides, olefin sulfonates, alkyl xylene sulfonates, dialkyl sulfosuccinates, fatty acids Glutamates such as fatty acid ester sulfonate, primary and secondary alcohol sulfates, especially those with 10 to 20 carbon atoms, glycerol fatty acid esters, etc. Phosphate, such as isethionate, lauryl phosphate or lauryl phosphate, taurate, alkoxyl alcohol, alkyl carboxyl A pollution-free powder detergent composition comprising an alkyl carboxylate-based compound. 6. The method of claim 5, wherein the ionic surfactant is in the form of sodium salts, potassium salts (potassium salts) and in the form of an acid or a mixture thereof, sodium of the anionic surfactant The salt and the potassium salt are used as a raw material, neutralized in whole or in part by an acid (acid) to be used as a mixture of sodium salt, potassium salt and acid, characterized in that the powder-free detergent composition. The pollution-free powder detergent composition according to claim 6, wherein the acid used is one of hydrochloric acid, sulfuric acid, or phosphoric acid. The nonionic surfactant of claim 4, wherein the nonionic surfactant is polyoxyethylene (POE) alkylphenol (POE alkyl phenol), POE amine (POE amine), POE fatty acid ester (POE fatty acid ester), polyethylene glycol (polyethylene) PEG (PEG) fatty acid esters, POE fatty acid alcohol ethers, POE and polyoxypropylene (POP) condensates, and sorbitan fatty acid ester compounds Included, A pollution-free powder detergent composition comprising an alkylpolyglycoside, a glycerol monoether, a fatty acid ethanol amide, and a polyhydroxyamides compound. [Claim 5] The composition of claim 4, wherein the cationic surfactant is quaternary ammonium salts having the following molecular formula. (here, The groups represented by are alkyl, hydroxyalkyl or ethoxylated alkyls, Is the corresponding cation). The method of claim 1, wherein the amphoteric surfactant is a betaine-based, alkyl amphocarboxylic acid, such as glycinate and amino propionate (amino propionate), amine oxide (amine) pollution-free powder detergent composition, characterized in that the (oxide) -based surfactant. The pollution-free powder detergent composition according to claim 4, wherein the zwitterionic surfactant is a secondary and tertiary amine compound. The method according to claim 4, wherein the soap-based surfactant is stearic acid (lauric acid), lauric acid (lauric acid), myristic acid (myristic acid), palmitic acid (palmitic acid), oleic acid (linic acid), lino Linolenic acid, other fatty acid compounds, the acids are dissolved in a solvent (methanol) in the form of sodium or potassium salts or in the form of an acid and introduced into the hydration reactor. The method according to claim 1, wherein the hydrogen peroxide is a 20 to 75% hydrogen peroxide solution, and the input amount is 20 to 110%, preferably 50 to 80%, of the theoretical value required to produce 100% percarbonate relative to the raw anhydrous ash ash. Pollution-free powder detergent composition, characterized in that it is added to. The method of claim 1, wherein the high performance percarbonate is 200 Sodium percarbonate formed of the following fine particles (sodium percarbonate; ) And sodium carbonate hydrate, And a small amount of surfactant, which is present in the form of a specific compound obtained as a result of the chemical reaction specified in paragraphs 2 to 13, rather than in the state of the physical mixture. The method of claim 1, wherein the moisture control agent is a pollution-free powder detergent composition, characterized in that 1 to 6% by weight of powdered silica or bentonite or mixtures thereof based on anhydrous soda ash. According to claim 1, wherein the bentonite comprises Na component, Ca component, Mg component and Fe component, characterized in that added to about 5 to 35%, preferably 10 to 25% with respect to the raw material anhydrous ash ash. Pollution-free powder detergent composition. The method of claim 1, wherein the granulation agent A solution containing sodium silicate having a molecular ratio of 1 to 4, preferably 2 to 3.5, wherein the sodium silicate solution is an aqueous solution of 10 to 50%, preferably 15 to 30%, and the sodium silicate is anhydrous soda ash. Pollution-free powder detergent composition, characterized in that added by 2 to 15% by weight, preferably 5 to 12% by weight. The non-polluting powder composition of claim 1, wherein the detergent powder contains an additive of an enzyme, a polishing agent, and a flavoring agent in an amount of 0.1 to 2% based on the total weight. The method of claim 1, wherein the encapsulation of the detergent powder, a powder-free detergent composition, characterized in that any one of gelatin and starch capsule is added. Powdered anhydrous ash, synthetic surfactant and water were continuously added to a hydration reactor and heated to obtain a slurry product. Injecting the product in the form of the slurry into the percarbonate reactor, in the presence of a moisture control agent, reacted with the hydrogen peroxide solution to obtain a high performance percarbonate product, After adding bentonite, a natural surfactant, to the high-performance percarbonate product, Add granulating agents to obtain detergent powder, Method for producing a pollution-free powder detergent composition, characterized in that to prepare a powder detergent by encapsulating the detergent powder. 21. The method according to claim 20, wherein water is added to the hydration reactor at a rate of 0.5 to 3 times, preferably 0.7 to 1.5 times, by weight relative to the powder of anhydrous soda ash, and the surfactant is 0.01 to weight with respect to the anhydrous soda ash. ˜5%, preferably 0.1 to 3% of the continuously charged, the temperature of the hydration reactor is 50 to 95 ℃, preferably pollution-free powder characterized in that it is kept constant in the range of 65 ~ 85 ℃ Process for preparing a detergent composition. 21. The method of claim 20, wherein the residence time in the hydration reactor is set in the range of 0.3 to 4 hours, preferably 0.5 to 2 hours. 21. The method according to claim 20, wherein the synthetic surfactant is any one of surfactant active ingredients such as anionic, cationic, nonionic, amphoteric and zwitterion based soaps and non-soaps. Method for producing a pollution-free powder detergent composition, characterized in that one component or a mixture thereof. 24. The method according to claim 23, wherein as the anionic surfactant, an alkyl group is linear in alkylbenzene sulfonate. To Among the phosphorus substances, primary and secondary alkylsulfates, especially alkyl groups To Phosphorus materials, alkyl ether sulfates, alkoxy amides, olefin sulfonates, alkyl xylene sulfonates, dialkyl sulfosuccinates, fatty acids Glutamates such as fatty acid ester sulfonate, primary and secondary alcohol sulfates, especially those with 10 to 20 carbon atoms, glycerol fatty acid esters, etc. Phosphate, such as isethionate, lauryl phosphate or lauryl phosphate, taurate, alkoxyl alcohol, alkyl carboxyl A method for producing a pollution-free powder detergent composition, characterized by containing an alkyl carboxylate compound. 25. The method of claim 24, wherein the ionic surfactants are in the form of sodium salts, in the form of potassium salts and in the form of acids or in the form of mixtures thereof, the sodium of the anionic surfactant When salts and potassium salts are used as a raw material, neutralizing all or part of them with an acid to be used as a mixture of sodium salts, potassium salts and acids, characterized in that the method for producing a pollution-free powder detergent composition. The method of claim 25, wherein the acid used is one of hydrochloric acid, sulfuric acid, or phosphoric acid. The method of claim 23, wherein the nonionic surfactant is polyoxyethylene (POE) alkylphenol (POE alkyl phenol), POE amine (POE amine), POE fatty acid ester (POE fatty acid ester), polyethylene glycol (polyethylene PEG (PEG) fatty acid esters, POE fatty acid alcohol ethers, POE and polyoxypropylene (POP) condensates, and sorbitan fatty acid ester compounds Included, A method for producing a pollution-free powder detergent composition comprising an alkylpolyglycoside, a glycerol monoether, a fatty acid ethanol amide, and a polyhydroxyamide compound. 24. The method of claim 23, wherein the cationic surfactants are quaternary ammonium salts having the following molecular formula. (here, The groups represented by are alkyl, hydroxyalkyl or ethoxylated alkyls, Is the corresponding cation). The method of claim 23, wherein the amphoteric surfactant is a betaine-based, alkyl amphocarboxylic acid, such as glycinate and amino propionate (amino propionate), amine oxide (amine) method for producing a pollution-free powder detergent composition, characterized in that it is an oxide) surfactant. 24. The method of claim 23, wherein the zwitterionic surfactant is a secondary and tertiary amine-based compound. The method of claim 23, wherein the soap-based surfactant is stearic acid (lauric acid), lauric acid (lauric acid), myristic acid (myristic acid), palmitic acid (palmitic acid), oleic acid, lino Linolenic acid, other fatty acid compounds, and the acids are dissolved in a solvent (methol) in the form of sodium or potassium salt or in the form of an acid and introduced into the hydration reactor. 21. The method according to claim 20, wherein the hydrogen peroxide is a 20 to 75% hydrogen peroxide solution, and the input amount is 20 to 110%, preferably 50 to 80%, of the theoretical value required to produce 100% percarbonate relative to the raw anhydrous ash. Method for producing a pollution-free powder detergent composition, characterized in that it is added to. 21. The method of claim 20, wherein the high performance percarbonate is 200 Sodium percarbonate formed of the following fine particles (sodium percarbonate; ) And sodium carbonate hydrate, And a small amount of surfactant, which is present in the form of a specific compound obtained as a result of the chemical reaction specified in paragraphs 2 to 13, and not in the state of the physical mixture. 21. The method of claim 20, wherein the moisture control agent is powdered silica or bentonite or a mixture thereof corresponding to 1 to 6% by weight based on anhydrous soda ash. The method of claim 20, wherein the bentonite comprises a Na component, Ca component, Mg component and Fe component, characterized in that added to about 5 to 35%, preferably 10 to 25% with respect to the raw material anhydrous ash. Process for preparing a pollution-free powder detergent composition. The method of claim 20, wherein the granulation agent A solution containing sodium silicate having a molecular ratio of 1 to 4, preferably 2 to 3.5, wherein the sodium silicate solution is an aqueous solution of 10 to 50%, preferably 15 to 30%, and the sodium silicate is anhydrous soda ash. Method for producing a pollution-free powder detergent composition, characterized in that added by 2 to 15% by weight, preferably 5 to 12% by weight. The method of claim 20, wherein the detergent powder contains an additive of an enzyme, a polishing agent, and a flavoring agent in an amount of 0.1 to 2% based on the total weight of the detergent powder. The method of claim 20, wherein in the encapsulation of the detergent powder, any one of gelatin and starch capsule is added.