KR100190821B1 - Encapsulated bleaching activator - Google Patents

Abstract

The present invention improves the storage stability of the bleach by granulating the metal (II) -substituted zeolite, which is an oxygen-based bleach activator, and then encapsulating it with an oil-in-water emulsified composition and encapsulating it with an excellent water solubility. A new type of oxygen-based bleach activator designed to exert an activating capacity for bleach, and a detergent composition containing the bleach activator together with the bleach as an active ingredient.

Description

Encapsulated Bleach Activator

The present invention relates to a new type of oxygen-based bleach activator and detergent composition containing the same, which is prepared through continuous granulation, coating and encapsulation processes in a fluidized bed. More specifically, the present invention improves the storage stability of the bleach by granulating the metal (II) -substituted zeolite, an oxygen-based bleaching chemical, and then encapsulating it with an oil-in-water emulsion composition and encapsulating it with a water-soluble material. A new type of oxygen-based bleach activator designed to improve and exert an activating capacity for bleach during washing, and a detergent composition containing such a bleach activator as an active ingredient.

Bleaches are commonly used to bleach fibers in the laundry process. The most common bleaching agents include chlorine bleaching agents such as sodium chlorite (NaClO ₂ ), sodium hypochlorite (NaClO), and bleaching powder (Ca (OCl) ₂ ). However, these chlorine-based bleaching agents are not easy to pack or store with detergent components, and have problems such as yellowing phenomenon by damaging fibers by reacting with a specific dye during washing.

Oxygen bleaches such as percarbonate, perborate, peracetic acid and perbenzoic acid are used to overcome the disadvantages of the chlorine bleach. They have a very strong bleaching power and have excellent stability to fibers compared to chlorine-based bleaches and have contributed much as bleaching agents. However, oxygen-based bleaching agent is much more expensive than chlorine-based bleaching agent, and has a problem that almost no bleaching effect is exhibited if the temperature of water during washing is not high enough to activate oxygen-based bleaching agent. For example, in the case of sodium perborate, sufficient bleaching performance can be achieved at a temperature of 70 ° C. or higher, which is much higher than a normal washing temperature, and in particular, domestic low temperature in which the water source itself is used as washing water without heating. Considering the laundry situation, the effect of bleaching by sodium perborate is very slight.

Therefore, in order for an oxygen-based bleach to exhibit sufficient bleaching ability, it is necessary to lower its activation temperature, and it is the bleach activator used for this purpose.

The bleach activator does not show its own bleaching ability, but merely serves to lower the activation temperature of the oxygen-based bleach. Examples of conventional bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium paraacylbenzenesulfonate, paraheptanoyloxybenzenesulfonsin sodium and the like. In addition to these, a series of divalent metal ions such as Mn (II), Cd (II), Cu (II), Fe (II), Zn (II), etc., are excellent for oxygen-based bleaching agents such as sodium percarbonate and sodium perborate. It is known to have excellent ability, and especially the effect of Mn (II) (see US Patent Nos. 4, 481, 129).

However, when the Mn (II) cation is used as a bleach activator, there occurs a problem of brown contamination due to oxidation at a higher valence state. U.S. Patent Nos. 4, 536, 183 attempt to prevent direct attachment or contact to fibers by replacing Mn (II) cations with a silicone support (ie zeolite). In addition, U.S. Patent Nos. 4,731 and 196 attempt to increase convenience and simplify the manufacturing process by granulating Mn (II) -substituted zeolites and applying them to powder detergent products.

However, the Mn-substituted zeolite bleach activator according to the prior art has the following serious problems in product application despite the excellent activation ability for the oxygen-based bleach. That is, the powder detergent usually contains about 10% by weight of moisture in the packaging of the product, and also absorbs a considerable amount of moisture in contact with moisture in the atmosphere while the consumer opens and uses the packaging. Especially during the rainy season, the humidity in the air is close to 90%, this phenomenon becomes more severe, so it is inevitable that the bleach activator contained in the detergent meets the moisture. However, when water is present, most of the oxygen-based bleach is decomposed by the bleach activator before washing, and as a result, the bleaching effect is hardly expected in actual washing.

Therefore, the present inventors, when the bleach activator and bleach are stored in the coexistence, in spite of the water content in the detergent, the bleach does not decompose, but only to find a way to activate the bleach to wash the excellent bleaching ability Many researches and experiments have been conducted. As a result, after granulating the bleach activator to a certain size, it is oil-coated with an oil-in-water emulsified composition and encapsulated with a water-soluble substance again to isolate the bleach activator from moisture which is in contact with storage and decompose the bleach in storage. In addition to inhibiting the present invention, the encapsulation material was completely dissolved during washing, thereby revealing that the encapsulation material can be sufficiently exerted to activate the bleach.

The present invention is formulated by blending 1000 parts by weight of a bleach activating component and 10 to 1000 parts by weight of a water-soluble binder of an oxygen-based bleach composed of divalent metal ions applied to a carrier, and granulating it in a fluidized bed to 10 to 2000 μm in size, and bleaching activating component 1000 It relates to a bleach activator prepared by coating with 20 to 1000 parts by weight of a water-based oil coating based on parts by weight, and then encapsulating with a water-soluble binder in a ratio of 20 to 2000 parts by weight.

In the present invention, it is preferable to use a metal (II) -substituted zeolite powder as the bleach activating component. This bleach activating component is prepared by replacing sodium zeolite with divalent metal ions in an aqueous solution and washing to remove excess divalent metal ions and then spray drying or drying and pulverizing. At this time, the divalent metal ion can be selected from Mn (II), Cd (II), Fe (II) or Zn (II), preferably Mn (II), the degree of substitution is 1, 2 or 3 units are used. Examples of zeolites that can be used include A, X, Y, L, omega, zelon mordenite, ZSM-5, F, W and the like, and preferably A, X, Y, ZSM-5.

The composition of the oil-in-water emulsion for oil coating the bleaching activating component prepared as described above is composed of 1 to 50% by weight of oil, 0.5 to 30% by weight of emulsifier and 50 to 90% by weight of water. Oil components include silicones 100 to 5000, silicones 10000 to 100000 dissolved in silicones 100 to 5000, silicones 100 to 5000, and 0.1 to 5 wt% wax solution, water insoluble solutions such as liquid paraffin, soybean oil, olive oil and sesame oil. Can be mentioned.

In addition, water-soluble substances which can be used to encapsulate oil coated bleach activator granules include albumin, gelatin, gum arabic, agarose, alginate, cellulose, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, One or more selected from polyvinyl alcohol, polyvinylpyrrolidone, silicone polymers, all solubles, dextrins, soaps, nonylphenylethers, polyethyleneglycols, fatty acids, fatty alcohols and chitosans may be mentioned.

The above-mentioned water-soluble encapsulating material is encapsulated by spraying it into a solution phase at a concentration of 2 to 50% by weight.

In order to prepare an oil coated and encapsulated bleach activator according to the present invention using the above-mentioned ingredients, a process as illustrated below is required, and the granulation, oil coating and encapsulation are all performed in a fluidized bed (POWREX, Continuously performed in LAB-1).

In general, the particle size of the metal (II) -substituted zeolite has a distribution of about 0.5 to 7 μm depending on the degree of aggregation, which is usually too small to encapsulate immediately using a fluidized bed, It may be necessary to grow the particles by granulating.

The granulation process adds 100 parts by weight of the metal (II) -substituted zeolite into the induction layer vessel, and 10 to 1000 parts by weight, preferably 20 to 500, through the spray nozzle at the side or bottom of the vessel while operating the device and flowing. By spraying parts by weight of binder solution. If the binder is used in less than 10 parts by weight, the granules are too small to be suitable for the encapsulation process. If the binder is used in excess of 1000 parts by weight, the granules may be too large to provide a dense encapsulation when the oil coating and encapsulation process proceeds to the desired particle size. Difficult problems can arise.

Materials usable as binders include albumin, gelatin, gum arabic, agarose, alginate, cellulose, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, silicone Polymers, soluble starches, dextrins, soaps, nonylphenylethers, polyethyleneglycols, fatty acids, fatty alcohols, chitosans or mixtures thereof which are prepared and used in water at a concentration of 5 to 30% by weight. The hot air temperature during granulation is 40 to 200 ° C., preferably 40 to 100 ° C., and the resulting final granules have a size of 10 to 2000 μm, preferably 50 to 1000 μm.

When the granulated bleach activator is encapsulated with a water-soluble substance and directly applied to the product, the encapsulated substance is partially dissolved due to the moisture contained in the product, and thus, the encapsulated substance is contacted with the oxygen-based bleach to destroy it. Therefore, to compensate for this drawback by coating a thin oil film to form a hydrophobic layer before encapsulation, the following oil coating process is carried out: 1000 parts by weight of granules are added to the fluidized bed vessel and the machine is operated to flow the granules into hot air. While spraying 20 to 1000 parts by weight, preferably 20 to 500 parts by weight of the coating material through the spray nozzle at the top or bottom of the container. If the coping material is used in an amount less than 20 parts by weight, the hydrophobicity may be insufficient, resulting in poor long-term stability in the product, and when used in excess of 1000 parts, the coating particles may be entangled with each other due to oil in the fluidized bed. On the other hand, the composition of the oil-in-water emulsion used as the coating material is as mentioned above, the hot air ondon 60 to 200 ℃, preferably 60 to 100 ℃.

The oil coated bleach activator granules in this way can be encapsulated in succession in the same fluidized bed vessel. To encapsulate, 1000 parts by weight of granules are added into the fluidized bed vessel and the machine is operated to spray 20 to 2000 parts by weight, preferably 20 to 1000 parts by weight, of the encapsulating material through a spray nozzle at the side or bottom of the container while flowing the granules with hot air. Let it be. If the encapsulation material is used in an amount less than 20 parts by weight, it is difficult to encapsulate sufficiently. If the encapsulation material is used in an amount of more than 2000 parts by weight, the particles may become too large to form a fluidized bed.

As the encapsulating material, those already mentioned can be used, which are prepared by using a solution in a concentration of 2 to 50% by weight, preferably 5 to 30% by weight in water, and the speed of the solution injection pump is slower than in the granulation process. Do it. The hot air temperature during encapsulation is 50 to 200 ° C., preferably 50 to 100 ° C., and the size of the resulting encapsulated granules is adjusted to 100 to 3000 μm, preferably 300 to 2000 μm.

Meanwhile, when the bleach activator is prepared according to the present invention, the granulation, coating, and encapsulation processes are all continuously performed in the same device, so that mass production is possible in a short time according to the capacity of the fluidized bed container used, and the existing patent ( Compared to the method proposed in Korean Patent Application No. 95-61155), the oil coating method has been improved to enable the production of better bleach activators in terms of productivity and performance.

The present invention also provides a detergent composition which normally contains the above-described bleach activator as an active ingredient together with an oxygen-based bleach.

In the detergent composition of the present invention, the bleach and the bleach activator may be used in the same amount as conventionally used, except that the amount of the various additives added during the granulation, encapsulation and coating process may be used. It is preferable to adjust so that the bleaching activating component of may be added in an appropriate amount.

Hereinafter, the present invention will be described in more detail based on the following examples.

However, these examples are only for the understanding of the present invention, but the scope of the present invention in any sense is not limited to these examples.

Example 1 Granulation of Bleach Activators

500 g of Mn (II) -substituted zeolite 4A was added to the fluid bed vessel and the binder solution was sprayed through the spray nozzle at the top of the vessel while the instrument was operated and flowed. The type, concentration and other detailed reaction conditions of the binder are as shown in Table 1 below:

Table 1. Granulation Conditions

Example 2: Oil Coating of Bleach Activator Granules

The oil coating process was carried out continuously in the fluid bed vessel used in Example 1. The fluidized bed machine was operated to place 400 g of granulated bleach activating component in the vessel and to spray the coating material through a spray nozzle at the bottom of the vessel while flowing with hot air. The composition, concentration and other detailed reaction conditions of the oil-in-water emulsion used as the coating material are as described in Table 2 below:

[Table 2. Oil Coating Conditions]

Example 3 Encapsulation of Oil Coated Bleach Activator Granules

The encapsulation process was carried out continuously in the fluid bed vessel used in Example 2. The fluidized bed machine was operated to place 400 g of oil-coated bleach activator granules into the container and spray encapsulated material through a spray nozzle at the bottom of the container while flowing with hot air. The type, concentration and other detailed reaction conditions of the encapsulated material are as described in Table 3 below:

Table 3. Encapsulation Conditions

Experimental Example 1: Evaluation of Storage Stability

When using the bleach activator of the present invention prepared according to the combination of Examples 1, 2, and 3 as a detergent composition component, an active oxygen titration method was performed as follows to test the storage stability of the bleach in the product.

0.8 parts by weight of a detergent base (30% by weight of surfactant, 20% by weight of soda ash, 20% by weight of soda silicate, 10% by weight of water-soluble polymer, 10% by weight of forget-me-not), 10% by weight of fluorescent beverage, 0.2 parts by weight of sodium perborate, 0.02 parts by weight of Mn (II) -substituted zeolite 4A was quantitatively added. With the vial lid open, it was stored for 10 days in a thermohygrostat at a temperature of 40 ° C. and a relative humidity of 90%, and then in each case using the encapsulated bleach activator and the unencapsulated conventional bleach activator. The remaining active oxygen values were measured by titration and compared. In the test of active oxygen, the KS method was adopted, and the reagents and operation methods used in this method are described in detail below.

1. Reagent

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

2 g of Bi (NO ₃ ) ₃ and 5.5 g of MnSO ₄ 4-5 H ₂ O were dissolved in 1 L of 2.5 M (5N) sulfuric acid. Here, 2.5M sulfuric acid was prepared by adding 139 ml of concentrated sulfuric acid per 1 liter of water.

2) 0.02 M KMnO ₄ solution

2. Operation

1) Accurately quantify 1 g of the sample to 0.0001 g and place it in a Erlenmeyer flask and fill with bismuth sulfate solution to the extent that it is sufficiently dissolved.

2) While stirring continuously, add 0.02M KMnO ₄ solution until the pink color lasts for 30 seconds, and calculate the amount of active oxygen (c) based on the following equation.

In the above formula,

A represents the amount of KMnO ₄ added,

f represents the KMnO ₄ concentration coefficient,

S represents the sample weight,

K is 0.8 in A.O.

The comparative results of the active oxygen values are shown in Table 4 below.

TABLE 4

The amounts of the encapsulated bleach activator and the unencapsulated bleach activator in Table 4 are different because they are adjusted to contain the same bleach activator in consideration of the amount of encapsulating material. As can be seen from the results of the above table, in the case of the unencapsulated bleach activator, the residual free oxygen level dropped to 55% level, while using the encapsulated bleach activator under the same conditions, the active oxygen remained at 94 to 97% level. It can be confirmed that the effect of increasing the storage stability by encapsulation of the bleach activator is very excellent.

Experimental Example 2: Evaluation of Bleaching Activation Capacity

In order to evaluate the bleaching activation ability of the encapsulated metal (II) -zeolite during washing, the following experiment was carried out.

First detergent (30% by weight surfactant, 20% by weight soda ash, 20% by weight soda silicate, 10% by weight water soluble polymer, 10% by weight forgetful dye, 10% by weight fluorescent dye), sodium percarbonate (PC), TAEI), encapsulated Mn (II) -zeolite 4A and unencapsulated Mn (II) -zeolite 4A were weighed correctly by the content ratios shown in Table 5 below. Red wine (EMPA) was put in a Terg-O-tometer, mixed with each sample, washed at 15 ° C. for 10 minutes, and after the washing was completed, the dirt was taken out and dried. The bleaching degree of each dried contaminated cloth was measured and compared using a colorimeter. The experiment was repeated three times in this manner and the average value is shown in Table 5.

TABLE 5

In Table 5, the amount of the bleach activator encapsulated by soap and PVA is higher than that of the unencapsulated bleach activator because the weight of the encapsulating material is taken into account to equalize the amount of Mn (II) -zeolite 4A. to be. In addition, despite the addition of less Mn (II) -zeolite 4A than TAED from the above results, Mn (II) -zeolite 4A has excellent activation ability, and the encapsulated bleach activator is close to the unencapsulated bleach activator. Since it shows the activating ability, it can be seen that the oil coating and encapsulation have no inhibitory effect on the activating ability because of excellent solubility of the coating material during washing.

From the above results, it is determined that the novel type of bleach activator according to the present invention exhibits long-term storage stability and excellent bleaching activating ability by simultaneously satisfying two conditions of maintaining stability against moisture in detergent and completely dissolving during washing.

Claims (5)

1000 parts by weight of the bleaching activating component and 10 to 1000 parts by weight of the water-soluble binder of the oxygen-based bleach composed of divalent metal ions applied to the carrier were granulated to a size of 10 to 2000 μm in a fluidized bed, and to 1000 parts by weight of the bleaching activating component. A bleach activator prepared by coating with 20 to 1000 parts by weight of an oil-in-water coating, followed by encapsulation with a water-soluble encapsulating material in a proportion of 20 to 2000 parts by weight. The method of claim 1 wherein the water-soluble binder is albumin, gelatin, gum arabic, agarose, alginate, cellulose, cellulose oacetate phthalate, methyl cellulose, ethyl cellulose, hydroxy phytophyllulose, polyvinyl alcohol, Bleach activator which is polyvinylpyrrolidone, silicone polymer, soluble starch, dextrin, soap, nonylphenyl ether, polyethylene glycol, fatty acid, fatty alcohol, chitosan or mixtures thereof. The bleach activator according to claim 1, wherein the divalent metal applied to the carrier is substituted with a zeolite with a metal ion selected from Mn, Cu, Fe and Zn. The solution according to claim 1, wherein the oil-in-water emulsion composition is guosiodine with 1 to 50% by weight of oil, 0.5 to 30% by weight of emulsifier and 50 to 90% by weight of water and is continuously sprayed with an oil coating agent into the fluidized bed. Bleaching activator, re-encapsulated by spraying an aqueous binder material into a solution phase at a concentration of 2-50% by weight. The hydrophobic oil component of the oil-in-water emulsion composition according to claim 4, wherein the hydrophobic oil component of the oil-in-water emulsion composition is dissolved in silicon 100 to 5000, silicon 10000 to 100000 in silicon 100 to 5000, 0.1 to 5 wt% wax solution in silicon 100 to 5000, liquid paraffin, At least one bleaching agent selected from the group consisting of soybean oil, olive oil and sesame oil. The method of claim 1, wherein the water-soluble encapsulating material is albumin, gelatin, gum arabic, agarose, alginate, cellulose, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinylpyrroli Bleach activator which is money, silicone polymer, soluble starch, dextrin, soap, nonylphenylether, polyethylene glycol, fatty acid, fatty alcohol, chitosan or mixtures thereof.