KR19980053424A - Encapsulated Bleach Activator - Google Patents

Abstract

The present invention is spherical granulation of a metal (II) -substituted zeolite, an oxygen-based bleach activator, using a binder and a photo-bleaching agent, and then oil-coated using an oil-in-water emulsion composition, a water-bleaching agent and a fluorescent dye. Encapsulated in a mixed solution to improve the storage stability of the bleach, and to fully activate the activating capacity for the bleach during washing, and to apply the detergent to the metal (II) -specific color by the color of the photobleach and fluorescent dye. A novel form of oxygen-based bleach activator designed to facilitate this and a detergent composition containing such a bleach activator together with the bleach.

Description

Encapsulated Bleach Activator

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 chlorite (NaClO), and bleaching powder (Ca (OCl) ₂ ). It is not easy to pack or store together and has problems such as damaging or yellowing fibers by reacting with a specific dye during washing.

In order to overcome the disadvantages of the chlorine-based bleach, oxygen-based bleaches such as percarbonate, perborate, peracetic acid, and perbenzoic acid are 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 also more expensive than chlorine-based bleaching agents and have almost no effect unless the water temperature is high enough to activate acid-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 a sufficient bleaching function, it is necessary to lower its activation temperature, and a bleach activator is used for this purpose.

Bleach activators do not show their own bleaching function, they only serve to lower the activation temperature of acid-based bleach. Examples of conventional bleach activators include N, N, N ', N'-tetraacetylethylenediamine (TAED), sodium p-acylbenzene sulfonate, sodium paraheptanoyloxybenzene sulfonate (sodium) p-heptanoyloxybenzene sulfonate) and the like can be mentioned. In addition, a series of divalent metal ions such as Mn (II), Cd (II), Cu (II), Fe (II), and Zn (II) have excellent activating ability against acid-based bleaches such as sodium percarbonate and sodium perborate. In particular, Mn (II) is known to have an excellent effect (see US Pat. No. 4,481,129).

However, when the Mn (II) cation is used as a bleach activator, there is a problem of contaminating the fiber brown due to oxidation at a higher valence state, and therefore, US Patent No. 4,536,183 describes Mn (II) to solve this problem. The cation was replaced by a silicone support (ie zeolite) to prevent direct attachment or contact to the fiber. In addition, US Pat. No. 4,731,196 attempts to increase convenience and simplify the manufacturing process by granulating Mn (II) -substituted zeolites and applying them to powdered detergent products.

However, the Mn (II) -substituted zeolite bleach activator according to the prior art has the following serious problems when applied to the product 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. Particularly during the rainy season, the humidity in the air is close to 90%, which is more so. Therefore, it is inevitable that the bleach activator included in the detergent encounters 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 study to find a method for activating the bleach only during washing without decomposing the bleach, even when the bleach activator and the bleach are coexisted and stored, despite the water content in the detergent. As a result, after granulating the bleach activator to a certain size and then oil-coating it with an oil-in-water emulsion composition and encapsulating it with a water-soluble substance again, the bleach activator is isolated from moisture to be stored in storage. In addition to inhibiting the degradation of the bleach as well as washing the encapsulation material is completely dissolved in the discovery that it can fully exhibit the activation ability for the bleach and has been applied for a patent application (96-17063).

However, the encapsulated bleach activator according to the application 96-17063 is excellent in stability and bleach activating ability, but one disadvantage. It is a weak brown manganese peculiar to encapsulation in spite of the encapsulation, but it may give an undesired impression to the consumer when applied to the detergent, especially when the packaging of the detergent is used and rainy season due to the rainy season, The color may become a little darker when contacted.

Therefore, the present inventors conducted intensive studies to improve the color while maintaining the stability and the bleaching activity of the bleach activator by the encapsulation method, as a result of mixing the optical bleach to the binder in the three-step process granules If the encapsulation process is encapsulated by mixing a light bleach, a fluorescent dye, or a light bleach and a fluorescent dye together in a water-soluble substance during the encapsulation process, it can effectively mask the appearance of manganese-specific brown color and wash it if a general dye is used. There is a possibility of dyeing on the fiber, but the photobleach and anaerobic dye do not have such problem at all, and the photobleach or the total amount of the bleach activator in the detergent composition is used in the detergent composition. It reduces the amount of mold dyes and costs raw materials in terms of bleach detergent It revealed the surprising fact that you can earn a significant performance improvement without the color of the rising.

The present invention provides a bleaching activator prepared by encapsulating a bleaching activating component using a binder and a photobleaching agent and then encapsulating it with an oil-in-water emulsion composition and encapsulating it with a mixture of a water-soluble material, a photobleach and a fluorescent dye. It is about.

Preferably used as the bleach activating component in the present invention is a metal Mn (II) -substituted zeolite powder, which is substituted with a divalent metal ion in sodium aqueous solution and washed to remove excess divalent metal ion, followed by spraying It is prepared by 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, Y ZSM-5 is used.

As a binder used to first granulate the bleaching activating component prepared as described above according to the purpose of the present invention, at least one selected from sugar, sodium silicate, polyethylene glycol, soap, cellulose, gum arabic, and ethylene oxide-based nonionic surfactant May be mentioned. Tinolux BBS of Ciba-Geigy was used as a photobleach when mixed with the binder. Next, the oil-in-water emulsion composition for oil coating the granulated bleach activator comprises 1 to 50% by weight of oil, 0.5 to 30% by weight of emulsifier, and 50 to 90% by weight of water. Is 100 ~ 5000 of silicon, 10000 ~ 100000 of silicon dissolved in 100 ~ 5000 of silicon, 0.1 ~ 5 wt% wax solution in 100 ~ 5000 of silicon, liquid paraffin, soybean oil, olive oil, sesame oil And water insoluble solutions.

In addition, water-soluble materials which can be used to encapsulate oil-coated bleach activator granules include albumin, gelatin, aramid gum, agarose, alginate, cellulose, cellulose acetate phthalate, methylcellulose, ethylcellulose, hydride One or more selected from oxypropyl cellulose, polyvinyl alcohol, polyvinylpyrrolidone, silicone polymer, soluble starch, dextrin, soap, nonylphenyl ether, polyethylene glycol, fatty acid, fatty alcohol and chitosan may be mentioned. have. The photobleach used in combination with the water-soluble substance is Tinolux BBS manufactured by Ciba-Geigy, and stilbenes, coumarin and carbostyril compounds, and diphenyl compounds (1) as fluorescent dyes. , 3-diphenyl-2-pyrazolines), naphthalimides, benzoxazolyl substitution products of conjugated systems, and combinations of ethylene or aromatics with other heteroaromatics (combined products of other heteroaromatics with ethylene or armatic systems.

In order to prepare granulated, oil-coated and encapsulated bleach activators according to the present invention using the above-mentioned components, a process as illustrated and shown below will be described. Granulation during the following process is made using a vertical granulator, and oil coating and encapsulation are performed continuously in a fluidized bed (POWREX, 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, and in general, the particle size is too small to be encapsulated immediately by using a fluidized bed. It is necessary to grow the particles by converting them. At this time, the closer the shape of the granules, the more uniform and stable encapsulation can be achieved in the next process. Therefore, the present invention applies a vertical granulator and a new binder system to produce hard, spherical granules.

The granulation process is premixed first with 1000 parts by weight of metal (II) -substituted zeolite and 100-1000 parts by weight, preferably 200-600 parts by weight, of powdery binder in a vertical granulator vessel. Mn (II)-100 to 1000 parts by weight, preferably 100 to 500 parts by weight of a mixed solution of a solution binder and a photobleaching agent while the substituted zeolite and the powdered binder are uniformly mixed and operating only the main blade. Open and pour, close the cover and start the cross screw. If the particles grow to a suitable size, 100 to 2000, preferably 200 to 1000 parts by weight of zeolite is added in 1 to 5 times to complete the granulation. In this case, as the binder, sugar, sodium silicate, polyethylene glycol, soap, cellulose, gum arabic, ethylene oxide-based nonionic surfactants or mixtures thereof are used, and as a solution binder, the binder component is added to water in 0 to 50% by weight. Preferably, the solution is prepared in a concentration of 0 to 30% by weight, and the photobleach is used in an amount of 0.1 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the solution phase binder. The size of the final granules produced by this method is 100-300 μm, preferably 200-2000 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, thereby contacting with the acid-based bleach to destroy it. Therefore, before the encapsulation, the oil coating process is performed to compensate for this disadvantage by forming a hydrophobic layer by coating a thin oil film. The process adds 1000 parts by weight of granules into the fluidized bed vessel and operates the machine to inject 200 to 1000 parts by weight, preferably 20 to 500 parts by weight, of coating material through a spray nozzle at the top or bottom of the container while flowing the granules into the hot product. Let it be. If the coating material is used in less than 20 parts by weight of the hydrophobic lack of long-term stability in the product, and if more than 1000 parts by weight may cause a problem that the coating particles are entangled with each other due to the 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 and the temperature of the hot air is 60 to 200 ℃, preferably 60 to 100 ℃.

The oil coated bleach activator granules in this manner can be encapsulated in succession in the same fluidized bed vessel. To encapsulate, add 1000 parts by weight of oil-coated granules into the fluidized bed vessel and operate the machine to encapsulate 100 to 3000 parts by weight, preferably 100 to 2000 parts by weight, via a spray nozzle at the side or bottom of the container while flowing the granules with hot air. Spray material solution. If the encapsulation material solution is used in less than 100 parts by weight, it is difficult to encapsulate sufficiently, and when used in excess of 3000 parts by weight, the particles may become too large to form a fluidized bed.

As the encapsulating material, those already mentioned may be used, wherein the water-soluble material is in a concentration of 2 to 50% by weight, preferably 5 to 30% by weight in water, and the photobleach is used in a concentration of 0.1 to 20% by weight, Preferably, the concentration of 0.1 to 10% by weight, the fluorescent dye is prepared in an aqueous solution of 1 to 50% by weight, preferably 1 to 30% by weight concentration, wherein the optical bleach and the fluorescent dye using only one between the two. Or you can use both. At this time, the speed of the solution injection pump slows down the granulation 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 200 ~ 400㎛, preferably 300 ~ 3000㎛ or so.

On the other hand, when manufacturing a bleach activator according to the present invention compared to the method proposed in the original patent (application number 96-17063) maintains the same storage stability and bleaching activity capacity, the raw material cost when looking at the entire bleach activator composition It is possible to improve the color without rising of.

The present invention also encompasses detergent compositions containing the bleach activator according to the invention together with conventional acid based bleaches.

In the detergent composition of the present invention, the bleach and the bleach activator may be used in the same amount as conventionally used, but considering the amount of various additives added in the process of granulating, encapsulating and coating the bleach activating component. It is desirable 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 Activator

Premix with Mn (II) -substituted zeolite and powdery binder in a vertical granulator vessel. If it is mixed uniformly, open the top cover of the mixer while operating only the main blade, pour the mixed solution of the liquid binder and the optical bleach, close the cover, and operate the cross screw to granulate. When the particles grow to a suitable size, the zeolite powder is added 1 to 5 times to complete granulation.

TABLE 1 Granulation Conditions

Example 2 Oil Coating of Bleach Activator Granules

In Example 1, the granulated bleach activator was transferred to a fluidized bed coater to perform an oil coding process. The fluidized bed machine was operated to place 600 g of granulated bleach activating component into the vessel and flow through the product while spraying the coating material through the spray nozzle at the bottom of the vessel. At this time, the composition, concentration and other detailed reaction conditions of the oil-in-water emulsion used as the coating material are shown 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 600 g of oil-coated bleach activator granules in the container and to spray encapsulated material through a spray nozzle at the bottom of the container while flowing with hot air. At this time, 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 Storage Stability Evaluation

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 to test the storage stability of the bleach in the product as follows: Active oxygen titration method ) Was performed.

0.8 parts 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. Store the vial lid for 10 days in a constant temperature and humidity chamber with a temperature of 40 ° C. and a relative humidity of 80% and then remain in each case using the encapsulated bleach activator of the present invention or an unencapsulated conventional bleach activator. Reactive oxygen values were measured and compared by titration. In the test of free radicals, the KS method was adopted, and the reagents and manipulations used in this method are described in detail below.

1. Reagent

1) sulfurine bismuth manganese solution (Reinhard-Zimmermann Reagent)

5.5 g of Bi (NO ₃ ) ₃ 2 g 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 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 A.O. 0.8 for.

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

TABLE 4

This is because the amounts of the encapsulated bleach activator and the unencapsulated bleach activator in Table 4 were adjusted to contain the same bleach activator in consideration of the amount of encapsulating material. As can be seen from the results of Table 4, in the case of the unencapsulated bleach activator, the remaining active oxygen level dropped to 51-35% level, whereas using the encapsulated bleach activator under the same conditions, the activity was 94-97% level. It can be confirmed that oxygen remains, and thus, the effect of increasing storage stability by encapsulation of the bleach activator is very excellent.

Experimental Example 2 Color Improvement and Color Stability Evaluation

In order to evaluate the color improvement and color stability by the photobleach and fluorescent dye of the encapsulated bleach activator as follows.

80 g 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 dyes), 20g of sodium perborate, encapsulated bleaching activation After adding 4 g and mixing it evenly, the color of the bleach activator in the detergent was evaluated for the use of the photobleach and the fluorescent dye, and the case was not used for 14 days in a constant temperature and humidity chamber with a temperature of 40 ° C and a relative humidity of 80%. The color was then evaluated again. In the evaluation scale, aesthetic feelings were classified into the following five levels, and each score was assigned.

TABLE 5

TABLE 6

As can be seen from the results of Table 6, when the optical bleach and the fluorescent dye are not used, the color is not immediately corrected as well as after 14 days. On the other hand, when the optical bleach and the fluorescent dye are used, the mixing immediately Of course, it was confirmed through experiments that after 14 days of storage at a constant temperature and humidity conditions of temperature 40 ℃, relative humidity 80%, the color improvement effect by photobleach and fluorescent dye is very good. It can be said.

Experimental Example 3 Bleaching Activation Evaluation

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 correctly by the content ratios shown in Table 5 below. A contaminated cloth (Red Wine: EMPA) was put in a Terg-O-tometer and washed for 10 minutes at 15 ° C. mixed with each sample. After completion of washing, the contaminated cloth was taken out and dried. The bleaching degree of each dried contaminated cloth was measured and compared using a colorimeter. Repeated experiment three times in this manner and the average value is shown in Table 5.

TABLE 7

The reason why the bleach activator encapsulated in Table 5 is higher than that of the unencapsulated bleach activator is that the weight of the encapsulating material is taken into account to equalize the amount of Mn (II) -zeolite 4A. In addition, even though the amount of Mn (II) -zeolite 4A was added less than TAED, the results showed that the activating ability of Mn (II) -zeolite 4A was excellent, and the encapsulated activator was close to the unencapsulated activator. Since it shows the bleaching activating ability, it can be seen that oil coating and encapsulation have no inhibitory effect on the activating ability due to excellent solubility of the coating material during washing.

Taken together, the new type of bleach activator according to the present invention satisfies the two opposite conditions of maintaining stability against moisture in detergent and having complete solubility during washing, as well as problems in application of the product. Even the color problem is solved, and it is expected to be applied to bleach detergent.

The present invention relates to a new type of oxygen-based bleach activator prepared through granulation, coating and encapsulation and a detergent composition containing the same. More specifically, the present invention is a spherical granulation of a metal (II) -substituted zeolite, which is an oxygen-based bleach activator, using a binder and a photo-bleach, and then oil-coated with an oil-in-water emulsion composition, and again a water-soluble material. Encapsulation with a mixture of optical bleach and fluorescent dyes improves the storage stability of the bleach, fully demonstrates the activating ability of the bleach during washing, and hides the color of the metal (II) by the color of the optical bleach and fluorescent dye. It relates to a new type of oxygen-based bleach activator designed to facilitate the application of and a detergent composition containing such a bleach activator together with the bleach.

Claims (25)

A bleach activator prepared by granulating a bleach activating component using a binder and a photo bleach, followed by oil coating using an oil-in-water emulsion composition and encapsulating with a mixed solution of a water soluble substance, a photo bleach and a fluorescent dye. 2. The bleach activator according to claim 1, wherein the bleach activator is granulated to a size of 100 to 3000 mu m by combining with a binder and a photo bleach before oil coating. The bleach activator according to claim 2, wherein the binder is at least one selected from sugar, sodium silicate, polyethyleneglycol, soap, cellulose, gum arabic, and ethylene oxide based nonionic surfactant. The bleach activator of claim 2, wherein the photobleach is Tinolux BBS. The bleaching activator according to claim 1 or 2, wherein the bleaching activator is granulated using a mixed solution of 100 to 1000 parts by weight of a powdery binder, 100 to 1000 parts by weight of a solution binder and a photobleaching agent with respect to 1000 parts by weight of the bleaching activating component. The bleach activator according to claim 5, wherein the concentration of the binder in the solution phase binder is 0 to 50% by weight. 6. The bleach activator according to claim 5, wherein the concentration of the photobleach in the solution phase binder is 0.1 to 20 wt%. The zeolite bleach activator according to claim 1, wherein the bleach activating component is substituted by a divalent metal ion. The bleach activator according to claim 8, wherein the divalent metal ion is at least one selected from Mn (II), Cu (II), Fe (II), and Zn (II). 9. The bleach activator according to claim 8, wherein the zeolite is at least one selected from zeolite A, X, Y, L, omega, zelon mordenite, ZSM-5, F and W. 9. The bleach activator according to claim 8, wherein the degree of substitution of the metal is 1, 2 or 3 units. 2. The bleach activator according to claim 1, wherein an oil-in-water emulsion solution is first prepared during oil coating and sprayed into the fluidized bed using the oil coating agent. 13. The bleach activator according to claim 12, wherein the oil-in-water emulsion composition is composed of 5-50 wt% oil, 0.5-30 wt% emulsifier, and 50-90 wt% water. The oil component of the oil-in-water emulsion composition according to claim 13, wherein the oil component is dissolved in silicone 100-5000, silicone 10000-100000 in silicone 100-5000, 0.1-5 wt% wax solution in silicone 100-5000, liquid paraffin, At least one bleach activator selected from water-insoluble solutions such as soybean oil, olive oil, sesame oil. The bleach activator according to claim 12, wherein the oil-in-water emulsion coating agent is used at a ratio of 20 to 1000 parts by weight based on 1000 parts by weight of the component having a bleaching activating ability. The method of claim 1, wherein the water-soluble substance in encapsulation is albumin, gelatin, aramid gum, agarose, alginate, cellulose, cellulose acetate phthalate, methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, polyvinyl alcohol, polyvinyl Bleach activator which is at least one selected from pyrrolidone, silicone polymer, soluble starch, dextrin, soap, nonylphenyl ether, polyethylene glycol, fatty acid, fatty alcohol and chitosan. 17. The bleach activator according to claim 16, wherein in encapsulation, a water-soluble substance is used at a concentration of 2 to 50% by weight based on the entire solution phase. The method of claim 1, wherein the encapsulating photobleaching agent is Tinolux BBS, fluorescent dye is stilbene compound, comarin and carbostyryl compound, naphthalimide compound, diphenyl compound, benzoxazolyl substituent and ethylene or aromatic And at least one bleach activator selected from combinations with other heteroaromatics. 19. The bleach activator according to claim 18, wherein the photobleach is spray encapsulated at a concentration of 0.1 to 20% by weight based on the total solution phase. 19. The bleach activator according to claim 18, wherein the fluorescent dye is spray encapsulated at a concentration of 0 to 50% by weight based on the entire solution phase. The bleach activator according to claim 1, wherein the encapsulating material solution is used in a ratio of 100 to 3000 parts by weight based on 1000 parts by weight of the component having a bleaching activating ability. The bleach activator of claim 1, wherein the size of the encapsulated final product is between 200 and 4000 μm. The bleach activator according to claim 1, wherein the granulation is carried out using a vertical granulator. The bleach activator according to claim 1, wherein the oil coating and encapsulation processes are carried out continuously in a fluidized bed. A detergent composition comprising the bleach activator of claim 1 together with a conventional oxygen-based bleach.