KR20220156192A - Method for producing multi-functional catalase and bleaching detergent composition containing the same - Google Patents

Abstract

The present invention relates to a method for producing particles through a coating method in order to maximize the long-term storage stability of catalase, more particularly, to a method for producing particles by impregnating/coating a liquid catalase into a seed material and then coating the seed material with a functional raw material to increase the fluidity of the particles and using a coating polymer for the outermost layer. To this end, the present invention is in the production of coated particles, comprising: a step of applying a liquid catalase enzyme to a seed material; a step of coating on the surface using a functional raw material such as a polymer component for protecting the reproduction of clothing and a component for preventing reattachment of stains in order to increase the fluidity of the applied seed material; a step of finally coating with a material such as PEG on the particles coated with the functional raw material to increase stability; and a step of drying the coated particles through the above steps to produce final particles.

Description

Method for producing multi-functional catalase and bleaching detergent composition containing the same {Method for producing multi-functional catalase and bleaching detergent composition containing the same}

The present invention relates to a method for preparing catalase and a composition for improving the performance and solubility of a bleaching detergent, and more particularly, to a functional polymer for forming particles by combining liquid catalase with powder and increasing fluidity in the formed particles. It relates to a method for maximizing the long-term stability of an enzyme to be used in a product and at the same time imparting multiple functionality by coating the particle with a polymer material and finally applying a polymer material to the surface of the particle to make it into a particle.

In general, bleaching detergents have sodium percarbonate as their main component and have the function of removing stains or special stains during the washing process of clothes. It refers to a product that plays a role in imparting a bleaching effect. Sodium percarbonate has a problem of lowering its activity during long-term storage when in contact with moisture at room temperature, so its stability is increased by coating on the outside. . In addition, in order to increase the activity of sodium percarbonate, chemicals such as TAED (Tetra Acetyl Ethylene Diamine) or OBA (Optical Bleach Activator) are sometimes used, which can damage the fabric and cause environmental problems. To solve this problem, catalase enzyme extracted from natural ingredients such as potatoes is used. Catalase enzyme reacts with sodium percarbonate to generate bubbles, which not only enhances the activity of bleaching power but also improves the solubility of sodium percarbonate. plays a role in However, catalase also has a problem in that its activity rapidly decreases when exposed to air for a long time. Catalase enzyme is generally present in liquid form, so when applied to bleaching detergents, it is manufactured in the form of powder particles and used in products.

In addition, when bleaching detergent is used for clothes, there is a risk of damaging the fabric, and in particular, in colored clothes, it provides a cause of discoloration or dyeing. In order to prevent this, it is solved by using a polymer material that prevents color transfer or discoloration. In the case of washing at a high temperature to increase the bleaching power, stains desorbed from the clothes may reattach. In particular, since the supply of drum washing machines is increasing recently, this problem needs to be solved.

[Document 1] Korean Patent Registration No. 10-1700282 It relates to a method for producing catalase for cleaning, which is proposed to be prepared by spraying liquid catalase on seed material, fluidizing it using heated air, and then spraying a coating solution on the outside, and simply using trehalose powder for coating. There is a problem in that it does not provide special functionality and its stability is also limited.

[Document 1] Choi Eun-kyung, Kim Joo-hye, Pretreatment and processing technology using enzymes, Textile technology and industry, Vol. 7 No. 3, 2003, pp. 292-302 In this paper, catalase was used to remove excess hydrogen peroxide after bleaching, which is the last step in the pretreatment process of cotton fabrics, and stabilization of the enzyme was pursued by covalently fixing catalase to alumina, and the long-term stability presented in the present invention However, it is a different technology from products in granular form.

In order to solve the above problems, it not only stabilizes catalase by using the optimal coating method and functional raw materials, but also prevents damage to clothes due to the use of sodium percarbonate, color transfer and desalination, and can occur during long-term washing at high temperatures. The purpose is to manufacture a multi-functional product that can play a role in preventing reattachment of contamination.

In addition, the present invention proposes an optimal coating method in order to maximize the stability of catalase during long-term storage, and provides additional functions along with the stability of catalase using a characteristic functional polymer component, thereby reducing the effects that may occur using sodium percarbonate. By supplementing the problems in advance, the inconvenience of having to supply additional functional raw materials in the detergent manufacturing process and the stability of functional raw materials can be secured together.

An object of the present invention is to maximize the performance by increasing the stability in the product by particulate liquid catalase in order to solve the above problems. In order to implement this, the liquid catalase is applied or impregnated to the seed material, and the functional raw material in the form of powder is applied to the impregnated/coated seed material by multiple coating methods to make it into particles, and finally to the granulated powder. It is characterized by maximizing stability by applying an external coating material.

The main seed material to be used in the present invention is sodium chloride, sugar, sodium sulfate, sodium citrate, sodium acetate, potassium sulfate, It is characterized by containing one or more of potassium acetate, urea, sodium succinate, and polyethylene glycol, but is not limited to the seed material mentioned in the present invention not. The seed material may be impregnated with a liquid catalase, maintain a powder form at room temperature, and any water-soluble material may be used.

As a functional raw material usable for the seed material coated with catalase, carboxy methyl cellulose and acryl-maleic co-polymer, which have an effect of preventing recontamination and adhesion, are suitable. Examples of the salt of carboxymethyl cellulose include alkali metal salts such as sodium and potassium, ammonium salts, and the like, and a mixture of these salts may be used. Among the above, carboxymethylcellulose sodium salt is preferable. The weight average molecular weight of the CMC is 100,000 or more, preferably 300,000 or more, more preferably 800,000 or more. As an upper limit, it is less than 2,000,000, Preferably it is less than 1,500,000, More preferably, it is less than 1,200,000. When the average molecular weight of the CMC is 800,000 or more and less than 1,200,000, the effect of preventing recontamination can be remarkably improved. The degree of etherification of the CMC is preferably from 0.2 to 1.3, more preferably from 0.2 to 0.8. The average particle size of the CMC is preferably 10 to 1500 μm, more preferably 10 to 500 μm, and still more preferably 10 to 100 μm. When the average particle diameter of the CMC is 10 to 100 μm, not only the fluidity of the particles made can be increased, but also the solubility is increased. In the case of using the above acryl-maleic copolymer, an average molecular weight of 1,000 to 80,000 is appropriate.

PVP K-30, which is produced as a product by ISP, was used in the embodiment of the present invention as an anti-migration agent used in the particleized anti-migration agent composition of the present invention, and in addition to the anti-migration agent, vinyl pyrrolidone, vinyl Additional additions may be made using one or more of the components, such as imidazole and vinyl pyridine enoxide.

A polymer material such as polyethylene glycol (PEG) is used as the coating material applied to the outermost part of the catalase particles, and the molecular weight of the PEG is suitably 1,000 or more, preferably 2,000 or more, and more preferably 3,000 or more. As the upper limit of the amount of PEG used, the molecular weight is 15,000 or less, preferably 12,000 or less, and more preferably 10,000 or less. In general, PEG exists as a solid at room temperature when its molecular weight is 1,000 or more. If it is less than that, it does not function properly as a coating material, resulting in poor storage stability, and when the molecular weight exceeds 15,000, It has relatively low solubility, so it does not dissolve well in water during washing.

In producing the Alcalase coated particles, several layers of films are formed using the above method. After applying or impregnating Alcalase based on the seed, a powder product having an anti-reattachment effect is produced. It is preferable to prepare by coating, applying an anti-migration agent, and finally dissolving and spraying PEG, but it is okay to change the order of PEG and functional powder type products to coat when preparing the particles.

The present invention can increase the stability during long-term storage of the raw material itself by forming an optimal multi-coating layer using various functional raw materials and stabilizing ingredients for the catalase enzyme to maximize the long-term stability of the catalase enzyme that improves bleaching power and solubility. have. It is possible to add various complex functionalities to the additionally used particles, so it has the advantage of reducing manufacturing cost as well as improving production efficiency through simplification of the manufacturing process.

1 is a cross-sectional example of a multi-coating layer presented in the present invention
Figure 2 is a cross-sectional example of a multi-coating layer presented in the present invention

The present invention will be described in detail with reference to the accompanying drawings in FIG.

1 is a cross-sectional view of coated particles showing a structure in which liquid catalase 20 is applied to a seed material 10, functional powder 30 is coated, and PEG 40 is coated. Applied to the final product It shows its effect as it is slowly dissolved in water from the coating layer. 2 shows a cross-sectional view of particles coated with functional powder 30 after first applying PEG 40. 1 and 2 are prepared by changing the coating order, and it can be seen that the overall manufacturing method or the role of the manufactured particles in the product is the same.

The seed material used for coating particles is impregnated with liquid catalase to form particles. As mentioned above, any material that dissolves in water such as salt or sugar can be used, but materials that inhibit the activity of catalase can be used. this is impossible In the first step for preparing the coated particles, while slowly stirring the seed material, the catalase enzyme is sprayed and the surface is slowly dried using heated air at 40 to 70 °C. At this time, it is preferable to add 15 to 40% by weight of catalase compared to the seed material. More preferably, it is appropriate to use 20 to 30% by weight. If the content is less than 15% by weight, the activity of catalase is low, making it difficult to show the effect in the final product, and if it exceeds 40% by weight, it is difficult to granulate the seed material. When the coating particles have fluidity to some extent, functional raw materials are added to increase the fluidity of the particles. As the functional raw materials used above, ingredients applied to washing clothes, which is one of the main uses of this product, are used. A clothing color protection component that greatly prevents dye transfer and desalting and a stain reattachment prevention component that prevents reattachment of stains use as With the recent increase in the supply of drum washing machines, as the high temperature washing and washing time increase, the phenomenon of water loss of colored clothes and transfer to other clothes frequently occurs, and the phenomenon that the contamination removed from clothes adheres to the clothes again. will appear To this end, detergents are generally prepared by additionally adding the above-mentioned clothing color protection component and contamination prevention component, but since each component is mainly micronized, dust is blown away during use, which is inconvenient and the components are not mixed evenly, so the effect is poor. There is a problem of non-uniformity.

In the present invention, not only can the stability of catalase be increased, but also these problems can be solved by coating the particles with the color protection and stain reattachment prevention component at the same time. In the present invention, a coating layer was formed using a powdery anti-migration component such as polyvinylpyrrolidone as the clothing color protection component. to 20% by weight. More preferably, it is good to use 8 to 15% by weight. If it is less than 5% by weight, the effect of preventing migration is insufficient, and if it exceeds 20% by weight, dust may fly during particle formation due to excessive powder. In particular, since the above components are expensive raw materials, the product cost increases. . In addition, a polymer material such as carboxymethylcellulose is used as the anti-fouling agent, and similarly, while stirring the previously prepared catalase particles, carboxymethylcellulose powder is gradually added to proceed with granulation. It is prepared by adding 30% by weight. More preferably, it is good to use 10 to 20% by weight. If it is less than 5% by weight, it is difficult to show the effect of preventing recontamination and adhesion, and if it exceeds 30% by weight, when applied to the final product after coating is completed, a film layer is formed when in contact with water due to the nature of the raw material, rather reducing solubility. There are problems that can be made.

Finally, in order to increase the stability of the catalase particles, a coating is performed using a polymer material such as PEG. As mentioned above, the PEG is solid at room temperature when the molecular weight is 1,000 or more. Then, it is prepared to form a film on the outermost layer of the particles by evenly spraying the catalase particles formed first through a spray nozzle. When the spraying is completed, the granulation is completed by stirring while gradually cooling. When the molecular weight of the PEG is high, since it can be easily hardened, it is okay to use it together with a solvent such as alcohol in order to add ease of manufacture. It is preferable to use 0.5 to 7% by weight of the catalase particles to be prepared, and more preferably 1 to 5% by weight of the PEG. When the above PEG is used in an amount of less than 0.5% by weight, it is difficult to form a coating layer, resulting in problems in securing stability when applying the product, and in the case of exceeding 7% by weight, the coating layer is too thick, resulting in low solubility when applying the product. cause problems In addition to PEG, it is also possible to use one or more materials that are solid at room temperature and have high solubility in water, such as nonionic surfactants such as Alkyl Ethoxylate having an added mole number of EO (Ethylene Oxide) of 15 or more.

As shown in FIG. 2 in the manufacturing process, in the process step for particle coating, PEG is first applied, and functional raw materials such as clothing color protection component and stain prevention component are applied to the outermost layer to form particles. free In particular, after the seed material is impregnated with catalase and applied, the remaining coating raw materials may be granulated regardless of the order, but there is no problem when applying the product in the future. That is, in the present invention, it is not limited to the coating order, but it is also possible to use it by properly adjusting it according to the type and characteristics of the functional raw material and coating agent to be used.

After all, in the method of forming a coating film of several layers in order to secure the stability of the catalase to be implemented in the present invention and simultaneously produce functional particles, even if the order is changed, it does not deviate from the scope of the present invention. The final catalase multi-coated particles prepared in this way are capable of maximizing the activity and stability of the catalase enzyme as well as imparting a multi-purpose function when applied to detergents including bleach, etc., which is the final product.

The present invention will be described in detail through the preparation of the coating agent particles and the performance evaluation results. However, the examples are for explaining the present invention in detail, and the scope of the present invention is not limited thereto.

(Examples 1 to 2, Comparative Examples 1 to 5)

In Example 1, catalase was added while slowly stirring the seed material, dried with hot air at 60 ° C for 30 minutes, functional raw material 1 was added and gradually coated, and functional raw material 2 was added to complete the first coating, followed by soluble dissolution. After spraying the coating agent, it was cooled/dried to prepare final coated particles.

Example 2 has the same component content, but in the manufacturing method, the coating agent was first coated, and then the functional raw materials 1 and 2 were added to finally prepare the coated particles.

In Comparative Example, it was prepared in the same manner as in Example 1, and was prepared while changing the content of the main components, and comparatively evaluated with Example. In the case of Comparative Example 5, it was prepared by simply coating using sodium bicarbonate without using functional raw materials or coating agents in the conventional method.

Examples and Comparative Examples for Preparation of Catalase Enzyme Particles Classification (content:% by weight) Example comparative example One 2 One 2 3 4 5 main
ingredient seed material 60 60 65 66 70 61.8 60 catalase 15 15 10 15 15 15 15 Functional raw material 1 10 10 10 4 10 10 - Functional raw material 2 13 13 13 13 3 13 - coating agent 2 2 2 2 2 0.2 - sodium bicarbonate - - - - - - 25 note Coating of functional raw materials first coating agent first Coating of functional raw materials first

Here, the seed material used refined salt sold by Hanju Gold, the catalase used Catazyme sold by Novozymes, the functional raw material 1 used PVP K-30 sold by ISP, and the functional raw material 2 was purchased from Duksan Science as a CMC product, and the coating agent was purchased from Duksan Science as a PEG-8000 product and manufactured.

Using the coating agents prepared in the above Examples and Comparative Examples, the physical properties (fluidity and solubility) of the particles and the performance when applied to the bleaching detergent were evaluated and the quality was compared. In the evaluation of the physical properties of the particles, the prepared catalase particles themselves were evaluated, and in order to evaluate the bleaching power, a bleaching detergent was prepared and evaluated with the same prescription. The basic prescription for bleaching detergent evaluation is described in detail in the following bleaching power evaluation method.

(Method for evaluating physical properties of catalase particles-liquidity)

Fluidity of each particle prepared based on Comparative Examples and Examples by measuring the time it takes for 100 g of powder to pass through a funnel with a diameter of 10 cm using a hopper for apparent specific gravity based on KS-2709 and comparing the time was compared. The smaller the time, the better the fluidity.

(Method for evaluating physical properties of catalase particles-solubility)

Solubility was determined by stirring 5 g of each particle prepared based on Comparative Examples and Examples in 1 liter of water at 25 ° C. for 5 minutes with a magnetic stirrer, and then filtering using a Buchner funnel on a black cloth. After that, measure the remaining amount. If the residual amount is large, solubility is evaluated as poor.

(Method for Evaluating Bleaching Power of Bleaching Detergent)

For comparative evaluation of bleaching power, examples and comparative examples were evaluated by preparing 93% by weight of bleach (sodium percarbonate), 5% by weight of nonionic surfactant, and 2% by weight of catalase particles. Terg-O-Tometer was used as the washing machine, the washing temperature was 25℃, the washing water hardness was 80ppm Ca/20ppm Mg, and the dirty cloth was Art No. 116 (cotton) / 117 (blend) was used, and the detergent concentration was 0.50 g / ℓ. The bleaching power was evaluated by measuring the reflectance of light before and after washing using a whiteness meter (Color Guard 2000) to evaluate how well the contamination was removed.

(Evaluation of anti-discoloration ability of bleaching detergent)

Anti-discoloration ability was evaluated based on the method according to ASTM D5548. 11 吊㎠ white cotton cloth, acid red151, direct blue1, direct blue90 dyed cloth of the same size were prepared, and water (water temperature 49℃, hardness 110ppm 3:1 = Ca:Mg ) and 1 g each of the samples prepared according to Table 1 were added. After putting three pieces of white cotton cloth and dyed cloth here, they were washed for 40 minutes, rinsed for 3 minutes at the same hardness at 20 ° C, and dried naturally. After measuring the DE of the cotton fabric before and after washing using a color difference meter, the degree of dye transfer was calculated by substituting it into the following equation.

(Equation 1)

In Equation 1, L means reflectance, a means redness/greenness, b means yellowness/blueness, w means fabric after washing, and o means fabric before washing.

(Evaluation of contamination prevention)

Prepare 2 white cotton cloths of 11 cm2, put 1 g of pollutants made of motor oil and loess in a 1:1 ratio into 1 liter of 40 ° C water, and 0.5 g of the prepared detergent sample in a Terg-O-Tometer at 100 rpm for 10 minutes. After stirring, drying is performed to determine the degree of contamination with the naked eye. In order to analyze the effect of preventing reattachment of stains, the degree of reattachment of stains is visually determined through repeated washing more than 10 times.

Performance quality evaluation result division Example comparative example One 2 One 2 3 4 5 quality
evaluation Liquidity (seconds) 18-19 19-20 19-20 21-22 21-22 22-23 25-27 Solubility (remaining amount, g) 0 0 0.1 0 0 0 0 bleaching power Early 88.23 88.31 80.51 88.21 87.59 86.99 85.78 After 4 weeks (room temperature) 82.70 81.45 69.98 77.12 75.65 55.34 37.50 otitis
prevention Acidred 151 31.9 32.0 32.1 43.5 35.7 33.3 53.2 Directblue 90 20.1 21.4 20.9 32.1 23.5 22.9 37.2 Directblue 1 19.2 20.0 19.7 25.9 22.7 21.1 29.6 Degree of adhesion of contaminants (visual identification) Good Good Good usually bad Good bad manufacturability Good Good Good usually usually usually usually

Comprehensively examining the quality evaluation results, Examples 1 and 2 corresponding to the present invention showed excellent performance in most items. In particular, in the case of bleaching power, the long-term stability evaluation result after 4 weeks showed very excellent results compared to Comparative Example 5 to which the present invention was not applied. I could see that there was a difference in the back. The contents and results presented in the above examples and comparative examples are intended to help the understanding of the present invention, but do not limit the present invention.

10: seed material 20: catalase 30: functional powder 1 or 2 40: coating agent

Claims (4)

Impregnating / applying 15 to 40% by weight of liquid catalase to the seed material to stabilize the catalase enzyme,
In order to increase the fluidity of the catalase-coated particles, firstly coating the surface with 5 to 20% by weight of a fiber color protecting agent and 5 to 30% by weight of an anti-recontamination agent as functional raw materials,
Applying 0.5 to 7% by weight of a coating agent to maximize long-term stability of the coated particles;
A method for preparing catalase enzyme particles having excellent fluidity and stability by drying the multi-layered coated particles prepared through the above steps, and a bleaching detergent composition comprising the same The method of claim 1, wherein the seed material for applying the catalase enzyme is sodium chloride, sugar, sodium sulfate, sodium citrate, sodium acetate, potassium sulfate Catalase particle composition comprising at least one of (Potassium Chloride), Potassium Acetate, Urea, Sodium Succinate, and Polyethylene Glycol In the above claim 1, as a functional raw material usable for the seed material coated with catalase, a polymer having a color protection effect for clothing such as polyvinylpyrrolidone and its derivatives is used, and carboxymethyl cellulose and its derivatives are used. Catalase particle composition characterized by coating using at least one of polymers having an effect of preventing stain reattachment such as salt and acryl-maleic copolymer (Acryl-Maleic Co-Polymer) The coating agent used to finally maximize stability according to claim 1 is a catalase particle composition using a material that is in a solid state at room temperature and has excellent water solubility, such as PEG, surfactant, etc.

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