KR20040033166A - Preparation method of bleach activator - Google Patents

Abstract

PURPOSE: A method for preparing a bleach activator and a bleach activator prepared by the method are provided, to improve storage stability and to enhance cleaning efficiency without the damage of clothes. CONSTITUTION: The method comprises the steps of preparing low specific gravity powder; mixing the low specific gravity powder with a manganese-based activator to prepare mixture powder; adding a binder to the mixture powder to prepare a particulate bleach activator; and coating the particulate bleach activator with a high molecular weight fatty acid compound or a natural fatty acid compound. Preferably the ratio of the low specific gravity powder to the manganese-based activator is 2:98 to 98:2 by weight, and the binder is selected from the group consisting of sugar, sodium silicate, polyethylene glycol, soaps, cellulose, arabic gum and ethylene oxide-based nonionic surfactants.

Description

Production method of bleach activator {PREPARATION METHOD OF BLEACH ACTIVATOR}

[Industrial use]

The present invention relates to a method for preparing a bleach activator, and more particularly, to a method for preparing a bleach activator having excellent storage stability and excellent washing effect without damaging clothes during washing.

[Prior art]

Bleach activators are an essential ingredient included in most bleaches and bleaches, such as detergents, stain removal and dishwashing detergents.

Currently commonly used bleach is an oxygen-based bleach in powder form and includes a manganese-based material as a bleach activator. Oxygen-based powder bleach, which includes a manganese-based bleach activator, already contains about 8% of moisture at the time of product shipment, and continues to absorb moisture in the air until the consumer purchases and uses the product. In particular, during the summer rainy season, the atmospheric humidity of the air is more than 80%, so the powdered bleach continues to absorb more moisture.If the oxygen-based bleach absorbs moisture, the bleach is decomposed by the bleach activator before the actual bleach is used. Accelerates, causing the powdered bleach subscribers to become entangled with one another and to change the color of the bleach. Therefore, there is a problem in that the bleaching effect is reduced during the actual washing and leaving the brown spot-shaped marks on the garment when washing the garment.

In order to improve the problems of the manganese-based bleach activator, Korean Patent Publication Nos. 1996-017063, 1998-053424, and 2000-060373 include a method for including the bleach activator in a capsule in a bleaching agent. Is described. However, when the bleach activator is contained in the bleach in a capsule, it is difficult to add an appropriate amount of the bleach activator to the bleach. In addition, when the amount of the added bleach activator exceeds an appropriate amount, there is a problem that the bleach activator does not disperse well when the bleach activator is actually used, thereby fixing the bleach activator to the washed clothes and damaging the clothes.

An object of the present invention is to provide a method for producing a bleach activator having excellent storage stability and excellent washing effect without damaging clothes during washing.

In order to achieve the above object, the present invention comprises the steps of (a) preparing a low specific gravity powder; (b) mixing the low specific neutralization powder with a manganese activator to prepare a mixed powder; (c) preparing a granulated bleach activator by adding a binder to the mixed powder; And (d) provides a method for producing a bleach activator comprising the step of coating the granulated bleach activator with a higher fatty acid compound or a natural fatty acid compound.

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

Method for producing a bleach activator of the present invention comprises the steps of (a) preparing a low specific gravity powder; (b) mixing the low specific neutralization powder with a manganese activator to prepare a mixed powder; (c) preparing a granulated bleach activator by adding a binder to the mixed powder; And (d) coating the granulated bleach activator with a higher fatty acid compound or a natural fatty acid compound as an essential step, and may further include various other steps.

The process for the preparation of the bleach activator of the present invention first starts with (a) preparing a low specific gravity powder. At least one selected from the group consisting of layered crystalline silicate α-Na ₂ SiO ₃ , β-Na ₂ SiO ₃ , Na ₂ CO ₃ , Na ₂ SO ₄ , and NaHCO ₃ to prepare low-fat powdered powder A slurry containing 10 to 80 wt% of the above compound is mixed with water to prepare a slurry.

The content of the mixture is preferably 10 to 70% by weight based on the slurry.

The slurry is then dried to produce a low specific gravity powder. As a drying apparatus, it is preferable to use a countercurrent spray dryer generally used in manufacturing detergents.

The water content of the low specific gravity powder produced through the drying process is preferably less than 10% by weight. Bleach and detergent compositions containing bleach activators prepared by mixing low specific gravity powders with low water content with manganese-based activators have low water content to prevent degradation of the bleach and detergent compositions by the bleach activators. .

It is preferable that the apparent density of the said low specific gravity powder is 0.3-0.4 g / cm <3>.

After preparing the low specific gravity powder (b) the low specific gravity powder is mixed with a manganese-based activator to prepare a mixed powder. The low specific gravity powder and the manganese-based activator prepared in step (a) are put into a zero gravity mixer or a high speed rotary mixer having a vertical or horizontal stirring shaft (trade name: lodige mixer or schugi mixer) and then uniformly mixed to make the low specific gravity powder. To prepare a mixed powder of the manganese-based activator.

In this case, the mixed weight ratio of the low specific neutralization powder and the manganese activator is preferably 2:98 to 98: 2. When the weight ratio of the low specific gravity powder included in the mixed powder is less than 2% by weight, the effect of adding the low specific gravity powder to improve the storage stability of the bleach and the detergent composition is insignificant, and when the weight ratio of the low specific gravity powder exceeds 98% by weight. The addition amount of the manganese activator which shows the excellent performance as a bleach activator is small, so that the bleaching effect of the bleaching agent and detergent composition containing the bleach activator of this invention worsens, and it is unpreferable. The manganese-based activator used in the step (b) is preferably used the manganese-based complex compound of the formula (1) described in Republic of Korea Patent Publication No. 1999-058803.

[Formula 1]

[Mn ₂ (phen) ₂ ] or [Mn (phen) ₂ (H ₂ O) ₂ ] Y

(Wherein phen is 1,10-phenanthroline, X is Cl, Br, I or CH ₃ COO and Y is SO ₄ )

After preparing a mixed powder of a low specific gravity powder and a manganese-based activator (c) a binder is added to the mixed powder to prepare a granulated bleach activator. In other words, by adding a binder to the mixed powder and rotating at high speed, the binder causes the mixed powder to be entangled and the mixed powder is granulated. As the rotating device, the same high speed rotor as used in step (b) may be used. In addition, the binder may be a powdery binder or a liquid binder, may be used by mixing the two binders.

It is preferable to use a binder selected from the group consisting of sugar, sodium silicate, polyethylene glycol, soap, cellulose, gum arabic and ethylene oxide-based nonionic surfactant. As the nonionic surfactant, it is preferable to use a polyoxyethylene system obtained by addition polymerization of ethylene oxide in the presence of a catalyst such as aliphatic alcohol, aliphatic amine or alkylphenol having 12 to 18 carbon atoms in the presence of alkali. For example, fatty alkoxy polyoxyethylene glycol (R ₅ -CH- (O-CH ₂ -CH ₂ ) ₁ -OH, wherein R ₅ is alkyl of 11 to 18 carbon atoms, l is an integer of 5 to 25), Fatty acid polyoxyethylene glycol (R ₆ -CO- (O-CH ₂ -CH ₂ ) _m -OH, wherein R ₆ is alkyl of 11 to 18 carbon atoms, m is an integer of 5 to 25), alkylphenylpolyoxy Ethylene glycol (R ₇ -Ar-O- (CH ₂ 0CH ₂ -O) _n -H, wherein R ₇ is alkyl having 11 to 18 carbon atoms, Ar is a benzene ring, n is an integer of 5 to 25), Or polyoxyethylene glycol (H- (O-CH ₂ -CH ₂ ) _i -OH, where i is an integer having a total molecular weight of 1,000 to 30,000) and the like can be preferably used.

The mixed weight ratio of the mixed powder and the binder is preferably 50:50 to 90:10. When the content of the binder exceeds 50% by weight, the particles of the mixed powder are excessively entangled, resulting in a problem of low dispersibility in actual use, and when the content of the binder is less than 10% by weight, the content of the binder is small and the mixed powder is well There is a problem of not being granulated.

After the granulated powder is granulated, (d) further coating the granulated bleaching agent with a higher fatty acid or a natural fatty acid compound. As the coating material, hydrophobic compounds of fatty acids having 10 to 22 carbon atoms or natural acids may be preferably used. The higher fatty acid or natural fatty acid compound forms a hydrophobic coating layer on the surface of the bleach activator granulated as a poorly soluble compound insoluble in water. Therefore, the bleach or detergent composition including the bleach activator of the present invention having a hydrophobic coating layer does not react with water even when absorbing moisture, and the particles of the bleach and detergent composition do not entangle with each other, thereby improving storage stability of the bleach and detergent composition and washing. It does not damage clothing and has an excellent washing effect. As the higher fatty acids, capric acid (CH ₃ (CH ₂ ) ₈ COOH), lauric acid (CH ₃ (CH ₂ ) ₁₀ COOH ), Palmitic acid (CH ₃ (CH ₂ ) ₁₄ COOH), stearic acid (CH ₃ (CH ₂ ) ₁₆ COOH), arachic acid (CH ₃ (CH ₂ ) ₁₈ COOH) or bee Hehenic acid (CH ₃ (CH ₂ ) ₂₀ COOH) may be preferably used. In addition, the fatty acid mixture which is a natural acid may be used coconut fatty acid, resin fatty acid or salts thereof.

The particle diameter of the bleaching activator particles after the coating step (d) is preferably 0.1 to 1.5 mm, and the apparent density is preferably 0.4 to 0.5 g / cm 3.

(D) coating the granulated bleach activator with a higher fatty acid compound or a natural fatty acid compound, and then cooling the bleach activator coated with a coating material with a fluidized bed cooler and thermally controlling it by a high temperature gas used for fluidization. It is more preferable to use.

The bleach activator prepared by the method for preparing the bleach activator of the present invention may be used as a component of an oxygen-based bleach and a detergent composition. As the oxygen-based bleach and the detergent composition, all generally used may include the bleach activator of the present invention as a component.

As described above, the bleaching activator prepared by the method for preparing the bleaching activator of the present invention is mixed with a low specific gravity powder having a low water content with a manganese-based activator to prepare a mixed powder, and the mixed powder is a higher fatty acid or Since the hydrophobic coating layer is formed on the particles of the bleach activator by coating with a natural fatty acid compound, the bleach and detergent composition containing the bleach activator is prevented from being decomposed by moisture, and thus the storage stability is excellent and the decomposition of the bleach and detergent composition is prevented. The entanglement of the particles is significantly reduced and the washing effect is excellent without damaging the garment during washing. Hereinafter, preferred examples and comparative examples of the present invention will be described. The following examples are described for the purpose of more clearly expressing the present invention, but the present invention is not limited to the following examples.

(Example 1)

A slurry was prepared by mixing 5 kg of a mixture consisting of 40 wt% of a mixture comprising layered silicate α-Na ₂ SiO ₃ with 5 kg of water. The slurry was dried with a countercurrent sprayer to prepare a low specific gravity powder. Then, 10 kg of the mixture of Mn ₂ (phen) ₂ in a 50:50 weight ratio was uniformly mixed at 50 rpm for 10 minutes in a 50 L high speed mixer (lodige mixer) with the powder and manganese activator. To prepare a mixture. Then, the mixture, sugar as a powdery binder and sodium silicate solution as a liquid binder were mixed in a weight ratio of 68: 30: 2, and put into a high speed rotary mixer (trade name: schugi mixer) to prepare a granulated bleach activator. The granulated bleach activator was placed in a fluidized bed coater (trade name: POWREX) and the stearic acid melt was sprayed at 60 ° C. with a coating material to coat the granulated bleach activator. The coated particles were put back into the fluidized bed and heated slowly for 8 minutes to prepare a bleach activator.

(Example 2)

The same procedure as in Example 2 was carried out except that a mixture composed of 50 wt% of a mixture containing layered silicate α-Na ₂ SiO ₃ was used.

(Example 3)

The same procedure as in Example 2 was carried out except that a mixture consisting of 60 wt% of a mixture containing layered silicate α-Na ₂ SiO ₃ was used.

(Comparative Example 1)

The same procedure as in Example 1 was repeated except that zeolite was used instead of the layered silicate α-Na ₂ SiO ₃ .

(Comparative Example 2)

The same procedure as in Example 2 was carried out except that zeolite was used instead of the layered silicate α-Na ₂ SiO ₃ .

(Comparative Example 3)

The same procedure as in Example 3 was repeated except that zeolite was used instead of the layered silicate α-Na ₂ SiO ₃ .

Storage stability evaluation

When the bleach activator prepared by the method of Examples 1 to 3 and Comparative Examples 1 to 3 is used as a component of the detergent composition, the storage stability of the bleach included in the detergent composition is determined by an active oxygen titration method. Evaluation was made through.

0.8 g of detergent without bleaching system (30 wt% surfactant, 20 wt% soda ash, 30 wt% sodium silicate, 10 wt% forgetfulness, 9 wt% water soluble polymer and 1 wt% fluorescent dye), 0.2 g sodium percarbonate and 0.02 g of the bleach activator of Examples 1 to 3 and Comparative Examples 1 to 3 were quantified. Residual activity in each case using the bleach activator of Examples 1 to 3 and Comparative Examples 1 to 3 after storing for 6 days in a thermo-hygrostat at 40 ° C. and a relative humidity of 80% without blocking the vial. Oxygen values were titrated and compared. The active oxygen test adopted the KS method, and the reagents and test procedures used are as follows.

(reagent)

1) Bismuth sulfate manganese solution (Reinhard-Zimmermann Reagent)

2 g of Bi (NO ₃ ) ₃ and 5.5 g of MnSO ₄ .4H ₂ O were dissolved in 1 L of 2.5 M 5NH ₂ SO ₄ to prepare a non-sulphuric manganese sulfate solution as a reagent. Here, 2.5 M sulfuric acid was prepared by adding 139 ml of concentrated sulfuric acid per liter of water.

2) 0.02 M KMnO ₄ solution

(Test Procedure)

1) 1 g of the sample was weighed to 0.0001 g, and the bismuth manganese sulfate solution was added to the Erlenmeyer flask to sufficiently dissolve the sample.

2) While stirring the sample to which the bismuth sulfate manganese solution was added, 0.02 M KMnO ₄ solution was added until pinkish lasted 30 seconds. Then, the amount of active oxygen was calculated using the following equation 1 by the following equation.

[Equation 1]

(In the above formula,

C is the amount of free radicals,

A is the amount of KMnO ₄ solution added,

f is the KMnO ₄ concentration coefficient,

K is 0.8,

S is the weight of the sample in g.)

The results of the test are shown in Table 1 below.

TABLE 1

Examination Day Amount of free radicals (%) 0 2 3 4 5 6 9 Example 1 2.41 2.00 1.86 1.45 1.28 0.95 0.48 Example 2 2.46 2.06 1.88 1.46 1.21 0.99 0.56 Example 3 2.38 2.11 1.82 1.49 1.25 1.02 0.51 Comparative Example 1 2.33 1.98 1.77 1.22 0.98 0.64 0.25 Comparative Example 2 2.39 2.02 1.71 1.20 0.91 0.61 0.28 Comparative Example 3 2.42 1.99 1.76 1.26 0.95 0.58 0.27

As shown in Table 1, the detergent composition containing the bleach activator of Examples 1 to 3 of the present invention is the amount of active oxygen remaining compared to the detergent composition containing the bleach activator of Comparative Examples 1 to 3 You can see more. This indicates that the storage stability of the detergent composition including the bleach activator of Examples 1 to 3 is better. Therefore, since the storage stability is excellent, the particles of the bleach and detergent composition are not entangled, and thus the washing effect is excellent without damaging the clothes during washing.

The bleach activator of the present invention has excellent storage stability and excellent washing effect without damaging clothes during washing.

Claims (7)

(a) preparing a low specific neutralization powder; (b) mixing the low specific gravity powder with a manganese-based activator to prepare a mixed powder; (c) adding a binder to the mixed powder to prepare a granulated bleach activator; And (d) coating the granulated bleach activator with a higher fatty acid compound or a natural fatty acid compound Method for producing a bleach activator comprising a. The method of claim 1, wherein the mixing weight ratio of the low specific neutralization powder and the manganese activator in step (b) is 2:98 to 98: 2. The method of claim 1, wherein the binder in step (c) is selected from the group consisting of sugar, sodium silicate, polyethylene glycol, soap, cellulose, gum arabic and ethylene oxide based nonionic surfactant. The method of claim 1, wherein the mixing weight ratio of the mixed powder and the binder in the step (c) is 50:50 to 90:10. The method of claim 1, wherein in step (d), the higher fatty acid compound is capric acid, lauric acid, palmitic acid, stearic acid, arachnic acid or behenic acid, and the natural fatty acid compound is coconut fatty acid, resin fatty acid or salt thereof. Preparation method of the agent. The method of claim 1, wherein the low specific gravity powder in the group consisting of silicate α-Na ₂ SiO ₃ , β-Na ₂ SiO ₃ , Na ₂ CO ₃ , Na ₂ SO ₄ , and NaHCO ₃ layered crystalline Method for producing a bleach activator is prepared by mixing at least one selected compound with water to prepare a slurry, and then drying the slurry. A bleach activator prepared by the method of any one of claims 1 to 6.