KR100190819B1 - Encapsulated bleaching actuator - Google Patents

Abstract

The present invention is to granulate the metal (II) -substituted zeolite, which is an oxygen-based bleach activator, and then encapsulate a water soluble roll and improve the storage stability of the bleach by coating with an oil component, and sufficiently activating ability for the bleach during washing. It relates to a new type of oxygen-based bleach activator designed to be exerted, and a detergent composition containing the bleach activator of the present invention as an active ingredient together with the bleach.

Description

Encapsulated Bleach Activator

The present invention relates to a new type of oxygen-based bleach activator prepared through granulation, encapsulation and coating process and a detergent composition containing the same. More specifically, the present invention granulates the metal (II) -substituted zeolite, an oxygen-based bleach activator, and then encapsulates with a water-soluble binder (encapsulating agent) (molecular weight of 1,000 or more) and hydrophobic oil component (not mixed with water). Oil-based bleaching activator, together with a new type of oxygen-based bleach activator and oxygen-based bleach, designed to improve the storage stability of the oxygen-based bleach by washing with an oil-based bleach. It relates to the detergent composition to contain.

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 ). It is not easy to pack or store together and suffer from problems such as damaging or yellowing the fibers by reacting with a specific dye during washing.

In order to overcome the disadvantages of the chlorine bleach, oxygen-based bleaches such as percarbonate, perborate, peracetic acid, and perbenzoic acid have been used. They show very strong bleaching power and have excellent stability to fibers compared to chlorine bleaches and have contributed a lot as bleaching agents. However, oxygen-based bleaching agents are more expensive than chlorine-based bleaching agents and have little problem in that the temperature of water during washing is not high enough to activate oxygen-based bleaching agents. For example, sodium perborate can exhibit sufficient bleaching performance at temperatures above 70 ° C, which is much higher than the usual washing temperature, especially in domestic low temperature washing where the water source itself is used as washing water without heating. Considering the situation, it can be said that the bleaching effect 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 what is used for this purpose is a bleach activator.

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'-tetraacetylenediamine (TAED), sodium p-acylbenzine sulfonate, and paraheptanoyloxybenzene sulfonate (sodium p -heptanoyloxybenzene sulfonate) may be mentioned. In addition to these, a series of divalent metal ions such as Mn (II), Cd (II), Cu (II), Fe (II) and Zn (II) have excellent activating ability against oxygen-based bleaching agents such as sodium percarbonate and sodium perborate. In particular, Mn (II) is known to have an excellent effect (article: US Pat. Nos. 4, 481, 129).

However, when the Mn (II) cation is used as a bleach activator, there is a problem of contaminating the fiber with brown due to oxidation at a higher valence state, so that US Patent No. 4, 536, 183 has solved this problem. The substitution of the Mn (II) cation with a silicone retardant (ie, zeolite) was intended to prevent direct attachment or contact with the fiber. In addition, US Pat. Nos. 4, 7331 and 196 attempt to increase convenience and simplify the manufacturing process by granulating Mn (II) -substituted zeolites and applying them to powdered 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 contains about 10% by weight of water when the product is packaged, and also absorbs a considerable amount of water by contact with moisture in the atmosphere while the consumer opens and uses the package. Especially during the rainy season, the humidity of the earth is close to 90%, which is even more so, it is inevitable that the bleach activator contained in the detergent meets the moisture. However, when water is present, the oxygen-based bleach is mostly 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 the oxygen-based bleach is stored in the coexistence, in spite of the water content of the detergent, oxygen-based bleach does not decompose and activates the oxygen-based bleach only during washing only to exert an excellent bleaching ability Intensive studies have been conducted to find that as a result, a certain amount of bleach activator granules are encapsulated with a water-soluble binder and coated with a hydrophobic oil component (oil component that does not mix with water) to remove the bleach activator from contact with water when stored. The present invention has been found to be able to suppress the decomposition of oxygen-based bleach during storage, as well as to completely dissolve the encapsulating agent at the time of washing, thereby fully exhibiting the activation ability for the oxygen-based bleach.

Hereinafter, the configuration of the present invention will be described in detail.

The present invention relates to a bleach activator, which is prepared by encapsulating a bleach activating component (bivalent metal ion applied to a carrier) of an oxygen-based bleach with a water-soluble binder and coating with a hydrophobic oil component.

Preferred bleaching activating components of the oxygen-based bleaching agent in the present invention are metal (II) -substituted zeolite powders, which are replaced by an aqueous solution of sodium zeolite with divalent metal ions and washed to remove excess divalent metal ions. Prepared by spray drying or drying and grinding. At this time, Mn (II), Cd (II), Fe (II) or Zn (II) may be used as the divalent metal ion, preferably Mn (II) and the degree of substitution is 1, 2 or 3 It is assumed to be a unit. In addition, usable zeolites include A, X, Y, L, Omega, Zelon mordenite, ZSM-5, F, W and the like, preferably A, X, Y Use ZSM-5.

Water-soluble binders usable for encapsulating the bleaching activating component of the oxygen-based bleach prepared as above according to the present invention include albumin, gelatin, aramid gum, agarose, alginate, cellulose, cellulose acetate phthalate, Selected from methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, silicone polymer, soluble starch, dextrin, soap, nonylphenyl ether, polyethylene glycol, fatty acid, fatty alcohol and chitosan One or more kinds may be mentioned. In addition, as a hydrophobic oil component for coating the bleaching activating component of the encapsulated oxygen-based bleach, silicone 100-5000, silicone 10000-100000 dissolved in silicone 100-5000, 0.1-5 wt% wax solution in silicone 100-5000 , Liquid paraffin, soybean oil, olive oil, sesame oil, and the like.

In order to prepare the encapsulated and coated bleach activator according to the present invention using the above-mentioned ingredients, the process as shown in the following scheme is shown, and will be described in detail for each process below. However, the granulation and encapsulation process in the following process uses a fluidized bed (POWREX, LAB-1).

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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 cohesion. In general, the particle size is too small to be encapsulated immediately by using a fluidized bed, and thus, the granules have a suitable size. In some cases it may be necessary to grow the particles.

The granulation process adds 1000 parts by weight of the metal (II) -substituted zeolite into the fluidized bed vessel and operates 10 to 1000 parts by weight, preferably 20 to 500 parts by weight, through the spray nozzle at the side or bottom of the vessel while operating the fluid. By spraying the binder solution. If the binder is used in an amount less than 10 parts by weight, the granules are too small to be suitable for the encapsulation process, and when used in excess of 1000 parts by weight, the granules are excessively large, making it difficult to achieve dense encapsulation when proceeding to the desired particle size for the encapsulation process. Problems may arise.

Usable as binders include albumin, gelatin, gum arabic, agarose, alginate, cellulose, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, Cyrylcone polymers, soluble starch, soaps, nonylphenylethers, polyethyleneglycols, fatty acids, fatty alcohols, chitosan, or mixtures thereof, which are prepared in water at a concentration of 5 to 30% by weight in water. . The temperature of the hot air at the time of granulation is 40 ~ 200 ℃, preferably 40 ~ 100 ℃, the resulting size of the final granules is 10 ~ 2000㎛, preferably 50 ~ 1000㎛.

Granulated bleaching agents can be encapsulated in succession in the same fluidized bed vessel. To encapsulate, 1000 parts by weight of granules are added to the fluidized bed vessel and the machine is operated to provide 20 to 2000 parts by weight, preferably 20 to 1000 parts by weight, of water-soluble binder through the spray nozzle at the side or bottom of the container while flowing the granules with hot air. Spray it. If the water-soluble binder (encapsulating agent) is used in less than 20 parts by weight it is difficult to encapsulate enough, and when used in excess of 2000 parts by weight the particles may be too large to form a fluidized bed.

The water-soluble binder (encapsulating agent) can be used as already mentioned, and prepared in a solution of 2 to 50% by weight, preferably 5 to 30% by weight in water, the rate of the solution injection pump is a granule Slows you down during the process. The temperature of the hot air during encapsulation is 50 ~ 200 ℃, preferably 50 ~ 100 ℃, the size of the resulting encapsulated granules are adjusted to 100 ~ 3000㎛, preferably 300 ~ 2000㎛.

When the encapsulated metal (II) -substituted zeolite is applied directly to the product, the water contained in the product dissolves the encapsulating material partially and contacts the oxygen-based bleach to destroy it. Therefore, the oil coating process is performed to compensate for these disadvantages by applying a thin film to the encapsulated bleach activator to give hydrophobicity. That is, the encapsulated particles are immersed in oil and gently stirred for a period of time, and then the dispersion solution is filtered under vacuum through a filter of a certain size and dried at room temperature. At this time, as the hydrophobic oil component can be used already mentioned, the stirring speed is adjusted to 10 ~ 500rpm, preferably 10 ~ 100rpm, the air pressure during vacuum filtration is adjusted to 0 ~ 500torr, preferably 10 ~ 100torr .

On the other hand, in the case of manufacturing the bleach activator desired in the present invention through the granulation, encapsulation and coating process, it is also possible to mass-produce in a short time depending on the capacity of the fluidized bed container used.

The present invention also provides a detergent composition containing the bleach activator according to the present invention as an active ingredient together with a conventional oxygen-based bleach.

In the detergent composition of the present invention, the oxygen-based bleach and the bleach activator may be used in the same amount as conventionally used, except that various additives added in the process of granulating, encapsulating and coating the bleach-activating component of the oxygen-based bleach are used. Considering the amount, it is preferable to adjust so that the actual bleach activating ingredient is 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, and the scope of the present invention in any sense is not limited to these examples.

Example 1 Granulation of Bleach Activators

1000 parts by weight of Mn (II) -substituted zeolite 4A was added into the fluid bed vessel and the binder solution was sprayed through the spray nozzle on the side 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 Encapsulation of Bleach Activator Granules

The encapsulation process was carried out continuously in the fluid bed vessel used in Example 1. The fluidized bed machine was operated to spray encapsulated material through a spray nozzle at the bottom of the vessel while flowing 1000 parts by weight of the granulated bleach activating component in the vessel with hot air. At this time, the type, concentration and detailed reaction conditions of the encapsulated material are as described in Table 2 below.

Table 2. Encapsulation Conditions

Example 3 Oil Coating of Encapsulated Bleach Activator Granules

The bleaching activating component encapsulated according to the process of Example 2 was separated from the fluidized bed vessel and coated with an oil component according to one of four methods selected below.

Process A:

100 g of the encapsulated powder was soaked in 500 ml of silicon-200 and stirred at 50 rpm for 10 minutes. The filter paper was placed on the strainer, and the dispersion solution was poured thereon and filtered under reduced pressure of 20 torr. When the silicone oil no longer drained, the vacuum pump was stopped and the product was obtained.

Process B:

200 g of silicon-10000 was dissolved in 400 g of silicon-200. 100 g of the encapsulated powder was soaked in the silicone solution and stirred at 50 to 100 rpm for 15 minutes. The filter paper was placed on the filtering device and filtered under vacuum of 20 torr while pouring the dispersion solution thereon. When the silicone oil no longer drained, the vacuum pump was stopped and the product was obtained.

Process C:

2.5 g of Carnauba wax was added to 500 g of silicon-200 and stirred at 200 rpm for 30 minutes while heating to a temperature of 70 to 80 ° C. When the camova wax was completely dissolved, the temperature was lowered to 40 ° C., 100 g of encapsulated powder was added at constant temperature, and then stirred at 100 rpm at 40 ° C. for 30 minutes. The filter paper was placed on the filtering device and filtered under vacuum of 20 torr while pouring the dispersion solution thereon. If the solution no longer drained, the vacuum pump was stopped and the product was obtained.

Process D:

100 g of the encapsulated powder was soaked in 500 ml of silicon-400 and stirred at 50 rpm for 10 minutes. The filter paper was placed on the strainer, and the dispersion solution was poured thereon and filtered under reduced pressure of 20 torr. When the silicone oil no longer drained out, the vacuum pump operation was neutralized to yield the product.

Experimental Example 1: Evaluation of Storage Stability

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

0.8 part by weight of detergent base (30% by weight of surfactant, 20% by weight of soda ash, 20% by weight of sodium silicate, 10% by weight of water-soluble polymer, 10% by weight of forget-me-not, 10% by weight of fluorescent dye), 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, the term at 40 ° C and 90% relative humidity is stored in a humidifier for 10 days and then in each case using the encapsulated bleach activator of this invention or an unencapsulated conventional bleach activator. Remaining free radical values were measured and compared by titration. In the test of active oxygen, the KS method was adopted, and the reagents and manipulation 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 liter of water.

2) 0.02M KMnO ₄ solution

2. Operation

1) Accurately quantitate 1 g of the sample to 0.0001 g and place it in a Erlenmeyer flask to fill the bismuth sulfate solution with enough melt.

2) While stirring continuously, add 0.02M KMnO ₄ solution until the pink color lasts for 30 seconds, and calculate the amount of free radicals (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 results of comparative comparison of the active oxygen values are shown in Table 3 below.

TABLE 3

The amount of Mn (II) -zeolite 4A in Table 3 is different because it was adjusted to contain the same bleaching agent 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, but when the encapsulated bleach activator was used in the same conditions, the active oxygen remained at 92 to 97% level. Therefore, it can be said that the effect of increasing the storage stability by the 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 wt% surfactant, 20 wt% soda ash, 20 wt% sodium silicate, 10 wt% water-soluble polymer, 10 wt% forget-me-not, 10 wt% fluorescent dye), sodium percarbonate (PC), TAED, encapsulated Mn ( II) -zeolite 4A, unencapsulated Mn (II) -zeolite 4A was weighed exactly by the content ratios shown in Table 4 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 finished, the dirt was taken out and dried. The bleaching degree of each dried 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 4.

TABLE 4

In Table 4, 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, from the above results, even though the amount of Mn (II) -zeolite 4A was added less than that of TAED, the activation ability of Mn (II) -zeolite 4A was decreased; It can be seen that the encapsulated activator exhibits a bleaching activating ability close to the unencapsulated activator, so that the encapsulation and coating have no inhibitory effect on the activating ability due to the excellent solubility of the coating material during washing.

Taken together, the new type of bleach activator according to the present invention simultaneously satisfies two mutually opposite conditions of maintaining stability against moisture and having complete solubility during washing. It is thought that it shows the bleach activating ability.

Claims (5)

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 the carrier were granulated to a size of 10 to 200 μm, and 20 to 2000 parts by weight of 1000 parts by weight of a bleaching activation component. A bleach activator prepared by encapsulation with parts by weight of water-soluble binder and coated with a hydrophobic oil component which is not mixed with water. The method of claim 1 wherein the water-soluble binder is albumin, gelatin, gum arabic, agarose, alginate, cellulose, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl Bleach activators selected from pyrrolidone, silicone polymers, soluble starch, soaps, nonylphenyl ethers, polyethylene glycols, fatty acids, fatty alcohols and chitosan. The bleach activator according to claim 1, wherein the divalent metal ion applied to the carrier is a metal ion selected from divalent metal ions of Mn, Cu, Fe, and Zn with zeolite. The process of claim 1 wherein the granulation and encapsulation process is carried out in a fluidized bed and the aqueous encapsulating material is encapsulated by spraying it into a solution at a concentration of 2 to 50% by weight, followed by dipping the encapsulated particles into an oil component and stirring gently. Bleach activator, wherein the dispersed solution was vacuum filtered through a filter and dried. The hydrophobic oil component according to claim 1, wherein the hydrophobic oil component is a silicone 100-5000, silicone 10000-100000 dissolved in silicone 100-500, 0.1-5 wt% wax solution in silicone 100-5000, liquid paraffin, soybean oil bleach activator selected from soybean oil, olive oil and sesame oil