KR960015154B1 - The method of sodium carbonate peroxide - Google Patents

Abstract

Sodium percarbonate is made by reacting sodium carbonate with hydrogen peroxide, wherein the composition selected from the followings(a, b) is added in the reaction: (a) esther compound of high fatted acid and sugar wherein sugar includes monosaccharide, disaccharide and polysaccharide, and fatty acid is saturated or unsaturated fatty acid having carbons between 10 and 18; (b) Na2SiO3, Na2Si2O5 or water glass having 2-3.8 ratio of SiO2/Na2O.

Description

            Process for preparing stable sodium percarbonate as a composition of bleach detergent         

The present invention relates to a method for producing stable sodium percarbonate as a composition of bleach detergent, and more particularly, sodium peroxide by reacting sodium carbonate and hydrogen peroxide solution.                 In preparing, a protective film is formed on the surface of sodium percarbonate by adding a known sodium silicate compound, an ester compound of higher fatty acids and sugars, and / or water glass.                 The present invention relates to a process for producing sodium percarbonate which is stable as a composition of bleach detergent.

Generally, sodium percarbonate is stable to moisture, but when mixed with detergent containing zeolite, sodium percarbonate can be absorbed by moisture contained in zeolite.                 Storage stability is poor because decomposition proceeds.

Therefore, to use sodium percarbonate as a composition of bleach detergent containing zeolite, the hygroscopicity must be lowered.

In the past, as a method of protecting sodium percarbonate at high humidity, there has been a study of treating the surface with an inorganic compound, an organic compound, or a high molecular material.                 I couldn't.

Recently, a patent for producing stable sodium percarbonate using a boron compound has been filed, and commercialized sodium percarbonate has appeared. However, a zeolite-containing detergent and                 As a result of checking the stability at high humidity by mixing, not only the effect of lowering the decomposition of sodium percarbonate is insufficient, but boron has the disadvantage of causing environmental pollution.                 It was difficult to use.

A conventional method for surface treatment of sodium percarbonate is described as follows.

British Patent No. 1,381,121 discloses microcrystalline waxes, polyethylene glycols, coconut monoethanol amides or carbon atoms of 14,                 A method of spraying a surface of sodium percarbonate by making a mixture of fatty acids of 16 and 18 into a slurry is proposed.                 The composition is again mentioned in British Patent No. 1,398,876 and US Patent No. 4,120,812, which extends the molecular structure of the compound to the US patent.                 No. 4,131,562 lists polyethylene oxide derivatives as stabilizing substances of sodium percarbonate.

However, polyethylene glycol itself has considerable hygroscopicity and thus does not have a long-term stabilizing effect on sodium percarbonate, and in the case of sodium percarbonate surface-treated with wax,                 It has the disadvantage of poor solubility.

In addition, the contents of British Patent No. 1,398,876 summarize the hydrophilic polyethyleneglycol or polypropyleneglycol and the hydrophobic fatty acids, in particular 8 to 8 carbon atoms.                 As a method of treating a surface with a condensation product with a saturated fatty acid between 26, stearic acid and polyethylene glycol having a molecular weight of 250 to 1,500 are typical.                 Compound was used 0.2 ~ 0.5% of the weight of sodium percarbonate, but this method also had a disadvantage that did not solve the problem of moisture absorption.

In the case of JP 47-32,200, paraffin is suspended in water containing 0.1% of a surfactant, and then the solution is sprayed onto the surface of sodium percarbonate and heated with hot air.                 Although the method of fluid drying is proposed, the sodium percarbonate thus prepared is resistant to moisture in the state of mixing with detergents, but has a low solubility in water and stability against heat.                 Falls.

In Japanese Patent Laid-Open No. 50-92,870, sodium silicate and glycine and US Pat. No. 3,951,838 used silica sol for surface treatment of sodium percarbonate.

The silica sol used herein had a size of 0.1 µm and an amount of 3 to 8% (g / 100cc).

In addition to sodium silicate, salts of alkali metals were used. Magnesium ions were used to stabilize sodium percarbonate before spraying sol on the surface of sodium percarbonate.                 It is unusual.

In addition, an example of using sodium silicate and silicon fluoride compound in a ratio of 3: 1 to 6: 1 and using 7 to 10% for surface treatment of sodium percarbonate is US patent.                 No. 3,977,988 describes a process for preparing sodium percarbonate that is stable with a composition of detergent.

Similar European Patent Publication No. 407,189 discloses salts of alkali or alkaline earth metals with carboxylic or dicarboxylic acids having 4 to 20 carbon atoms, and salts thereof,                 It also describes that silicate compounds such as sodium silicate can prevent the decomposition of sodium percarbonate by water and zeolite.

Silicate compounds, which have various functions for stabilizing sodium percarbonate, appear in the composition of surface treatment compounds that protect sodium percarbonate from moisture.                 It is effective and can be supplied in the form of powder or liquid, so that it can be adsorbed by spraying on the surface after preparation or preparation of sodium percarbonate.

However, the silicate compound alone is difficult to produce a sufficient effect and has a disadvantage of poor stability to heat.

The use of orthoboric acid or sodium perborate as a method of improving the composition of the surface treatment compound is disclosed in US Pat. Nos. 4,194,025 and 4,321,301.                 Described.

And when introducing the practical patents developed in the above patent to invent a sodium percarbonate possible as a composition of bleach detergent as follows.

According to European Patent Publication No. 459,625, the chelating agent is used as a stabilizer for sodium percarbonate, and boric acid and alkali metal silicates are respectively made into aqueous solutions and sprayed.                 Sodium percarbonate in wet state was flow dried to prepare stable sodium percarbonate.

At this time, the size of the sodium percarbonate particles is 200 ~ 1,000㎛, the amount of boric acid to form a film on the surface of sodium percarbonate is 2 to 8%, the amount of silica is 0.3 to 5%                 Sprayed.

And the weight ratio of boric acid and silica is 5: 1: 1: 1.

Sodium percarbonate as a composition of the bleach cleaner described in Japanese Patent Application Laid-Open No. 4-37,119 was surface treated with a borate and magnesium compound.                 In the case of borate, 10 to 99.5% of the total amount of the surface treatment compound and 0.5 to 50% of the magnesium compound.

In this case, the total amount of the surface treatment compound represents 0.1 to 30% of the weight of sodium percarbonate.

Examples of the surface treatment compound include sodium borate, magnesium sulfate, magnesium silicate, and the like, and other metal ion disintegrants are included.

European Patent Publication No. 567,140 relates to the preparation of sodium percarbonate with storage stability at the level of sodium perborate and introduces a new concept of dispersoids.                 The slurry is applied to the surface treatment of sodium percarbonate.

Exemplary surface treatment compounds cover almost all of the patents described above, which include carbonates and sulfates of boron compounds and alkali metal silicates in one group.                 And the like were classified into another group.

It also describes that the composition of the surface treatment compound in the form of an aqueous solution and a slurry may include a sequestering agent.

And in order to make the surface treatment more effective, the diameter of the sodium percarbonate particle was limited to 300-1,200 micrometers.

However, the layer formed on the surface of sodium percarbonate as the compound mentioned in each of the above patents did not effectively prevent the penetration of moisture.

That is, as a result of mixing with zeolite or a detergent containing zeolite and leaving it in a high humidity state, decomposition of sodium percarbonate proceeded.

This is because the role-sharing of the inorganic compound and the organic compound and the surface treatment method and amount thereof were not properly balanced.

The present invention forms a protective film that blocks the contact of zeolites or moisture and ultimately does not impede the dissolution of sodium percarbonate into water and also heats the sodium percarbonate.                 The purpose of the present invention is to provide a method for producing stable sodium percarbonate as a composition of a bleach detergent by adding a surface treatment compound capable of improving stability.                 have.

Hereinafter, the present invention will be described in detail.

In the present invention, in the preparation of sodium peroxide by reacting sodium carbonate and hydrogen peroxide solution, known stabilizers such as sodium silicate and magnesium compounds, and the following (a) or                 In the preparation of sodium percarbonate with a compound composition containing at least one or more of the compounds of group (b) or after the preparation in the form of an aqueous solution on the surface of sodium percarbonate                 Dried by hot air while spraying, and sprayed in hot water while spraying in aqueous solution on the surface of sodium percarbonate which is stable as a composition of bleach detergent.                 It relates to a method of producing sodium percarbonate.

(A) ester compounds of higher fatty acids and sugars, where sugars include all monosaccharides, disaccharides and polysaccharides, and higher fatty acids having 10 to 18 carbon atoms, saturated or unsaturated                 fatty acid).

(B) Water glass having Na ₂ SiO ₃ , Na ₂ Si ₂ O _3, or SiO ₂ / Na ₂ O of ₂ to 3.8.

Hereinafter, the present invention will be described in more detail.

In the present invention, the (A) group and the (B) group compounds may be used alone or in combination, respectively, and the addition amount is 0.1 to 10% by weight relative to sodium carbonate.                 desirable.

If the amount is less than 0.1% by weight, it is difficult to form a protective film, and when the amount exceeds 10% by weight, there is a problem of excessive energy consumption in the manufacturing process.

These surface treatment compounds are added during the preparation of sodium percarbonate, or sequentially or mixed with sodium percarbonate can be sprayed in an aqueous solution and dried with hot air.

The aqueous solution concentration of the compound to be sprayed is selected to a concentration that minimizes energy loss below the saturation concentration in consideration of the viscosity.

In addition to the above additives, sodium silicate and magnesium compounds, which are known stabilizers, may be added to further increase the effect of the present invention.

According to the present invention, a protective film is formed on the surface of sodium percarbonate without using boron inherent in environmental pollution, so that contact with the zeolite is prevented.                 By blocking, the stable sodium bicarbonate can be manufactured as a composition of a bleach detergent.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the Examples.

[Examples 1-3]

The apparatus used for the surface treatment of sodium percarbonate was built on a laboratory scale using the principle of a flow dryer.

The cylinder is 66mm inside and 56mm high (effective volume inside is 125ml), and the bottom is a plate with many fine holes through which fluid can pass.                 made.

25 g of sodium percarbonate was placed inside the cylinder, and nitrogen gas warmed at 50 to 80 ° C. was passed through a plate so that the particles of sodium percarbonate floated 5 to 10 mm above the floor.                 Flow it into the cylinder.

At the same time, a 5-20% aqueous solution of the surface treating compound is sprayed from the top of the cylinder to the bottom at a rate such that the particles of sodium percarbonate do not get entangled with each other.

Finally, continue flowing nitrogen gas or drying separately to remove any remaining moisture on the surface of sodium percarbonate.

At this time, the amount of the aqueous solution sprayed so as to be 1 to 2% of the (A) group compound forming a film on the surface based on the weight of sodium percarbonate was adjusted.

2.7 g of surface-treated sodium percarbonate was mixed with 0.3 g of zeolite, placed in a 20 ml glass bottle, and stored at a relative humidity of 70% and a temperature of 40 ° C. for 1 week.                 The residual ratio of oxygen was measured and the results are summarized in Table 1.

[Comparative Examples 1 and 2]

In order to confirm the function of the surface treatment compound shown in the existing invention, the same experiment as in Examples 1 to 3 was carried out by selecting boric acid or sodium metaborate.

The results are summarized in Table 1 together with the above examples.

[Examples 4 to 5]

The group (b) which forms a film on the surface based on the weight of sodium percarbonate was subjected to the same experiment as in Examples 1 to 3 so that the amount of the compound was 1 to 2%.

2.7 g of surface-treated sodium percarbonate was mixed with 0.3 g of zeolite, placed in a 20 ml glass bottle, and stored for 1 week at a relative humidity of 95% and a temperature of 30 ° C.                 The residual ratio of oxygen was measured and the results are summarized in Table 2.

Comparative Examples 3 to 5

In order to confirm the function of the surface treatment compound shown in the existing invention, known sodium perborate, sodium hydrogen carbonate, high-demand polymer compounds in Examples 4 to 5 and                 The same experiment was conducted.

The results are summarized in Table 2 together with the above examples.

Comparing the results of Examples 1 to 5 and Comparative Examples 1 to 5, the compounds or compositions mentioned in the existing patents have limitations in maintaining stability at high humidity.                 In order to overcome the present invention, sodium percarbonate was surface-treated with the compound composition of (A) and (B) group.

[Examples 6 to 8]

In the same manner as in Examples 1 to 3, the (A) group compound that forms a film on the surface based on the weight of sodium percarbonate is 2.5% or less.                 The amount of aqueous solution to spray was adjusted.

After the surface-treated sodium percarbonate was stored for 4 weeks at 80% RH and 30 ° C by the following (1) and (2), the residual rate of active oxygen was measured.                 The results are summarized in Tables 3 and 4, respectively.

(1) 0.3 g of zeolite and 2.7 g of sodium percarbonate are mixed evenly and placed in a 20 ml polypropylene container and covered with aluminum foil.

At this time, two or more needle holes are drilled in the aluminum foil.

(2) 20 ml of a mixture of 2.25 g of a commercial synthetic detergent (Bits manufactured by Cheil First) and 0.75 g of sodium percarbonate evenly containing 15 to 25% of zeolite                 Place in a polypropylene container and close the cap tightly.

[Comparative Examples 6-7]

Sodium percarbonate two kinds (commercially available from SOLVAY-INTEROX, USA, Tong Yang Chemical Co., Ltd.) to confirm the surface treatment effect of sodium percarbonate according to the present invention.                 Product) was selected and the same experiment as in Examples 6-8 was performed.

The results are summarized in Table 3 and Table 4 together with the above examples.

Claims (4)

In preparing sodium percarbonate by reacting sodium carbonate and hydrogen peroxide solution, a compound composition comprising one or more of the following compounds of (A) or (B)                 A method for producing stable sodium percarbonate as a composition of a bleach detergent, characterized in that it is added. (A) ester compounds of higher fatty acids and sugars, where sugars include all monosaccharides, disaccharides and polysaccharides, and higher fatty acids having 10 to 18 carbon atoms, saturated or unsaturated                 fatty acid). (B) Na ₂ SiO ₃ , Na ₂ Si ₂ O ₃ , or SiO ₂ / Na | Water glass with ₂ O of ₂ to 3.8. The method of claim 1, wherein the addition amount of the (A) or (B) group compound composition is stable as a composition of the bleach detergent, characterized in that 0.1 to 10% by weight relative to sodium percarbonate.                 Method for preparing sodium percarbonate. Bleach detergent, characterized in that the spray on the surface of the sodium pertarate compound composition consisting of one or more of the following compounds (a) or (b) in an aqueous solution state                 A method for producing stable sodium percarbonate as a composition. (A) ester compounds of higher fatty acids and sugars, where sugars include all monosaccharides, disaccharides and polysaccharides, and higher fatty acids having 10 to 18 carbon atoms, saturated or unsaturated                 fatty acid). (B) Na ₂ SiO ₃ , Na ₂ Si ₂ O ₃ , or SiO ₂ / Na | Water glass with ₂ O of ₂ to 3.8. The bleach detergent of claim 3, wherein the amount of the compound (A) or group (B) to be sprayed in the aqueous solution is 0.1 to 10% by weight relative to sodium percarbonate.                 A method for producing stable sodium percarbonate as a composition.