JP2815925B2 - Method for coating particles for detergent formulation - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a method for producing coated particles for detergent blending, which are less susceptible to aging and the effects of blending agents, and have good water solubility.

[Conventional technology and its problems]

Generally, various detergent formulations are used in detergents for the purpose of enhancing the cleaning action or added value. Among them, enzymes and bleaches are easily affected by other detergent components due to their properties, and are coated for the purpose of protecting them from aging and the effects of compounding agents. Conversely, bleaches and the like may affect the quality of other detergent components, and may be coated to suppress the effects. Conversely, other detergent formulations that affect enzymes and bleaches may be coated. The solubility of a detergent formulation after coating is also one of the important points from its use.

Conventionally, various methods for coating granules have been studied. For example, there are a method of spray-coating a polymer latex (JP-A-63-305931) and a method of spray-coating a polymer film-forming substance (JP-A-50-71583). The coatings obtained by these methods have poor solubility in water, and are insufficient as coating methods for detergent formulations. On the other hand, a method of introducing a water-soluble high-melting substance and a molten wax into a stirring granulator and coating (JP-A-63-32485, JP-A-53-6484, etc.) is introduced. These methods have drawbacks such as generation of coarse particles due to agglomeration of particles, adhesion to a stirring granulator, and low yield.

[Means for solving the problem]

The present inventors have conducted intensive studies to solve the above problems, and as a result of using a coating apparatus, used a water-insoluble or poorly water-soluble fine particle having a specific range of average particle diameter and a water-soluble film-forming substance at a specific ratio. According to the method of forming a continuous film around the particles by introducing the suspension into the particles for detergent mixing and drying, the adhesion to the granulator during the coating and the generation of coarse particles are small, and the yield is low. The inventors have found that coated particles for detergent blending having a high rate and excellent water solubility can be obtained, and the present invention has been completed.

That is, the present invention provides an aqueous suspension containing water-insoluble or poorly water-soluble fine particles having an average particle diameter of 0.05 μm to 10 μm and a water-soluble film-forming substance in a weight ratio of 50:50 to 95: 5, What is provided is a method for coating detergent-containing particles, wherein the method is introduced into the detergent-containing particles that are flowing or stirred in the apparatus, and the detergent-containing particles coated with the aqueous suspension are dried. It is.

The coating agent used in the present invention is an aqueous suspension containing water-insoluble or hardly water-soluble fine particles (hereinafter referred to as hardly soluble fine particles) and a water-soluble film-forming substance in an appropriate ratio.

The average particle size of the hardly soluble fine particles is 0.05 μm to 10 μm, preferably 0.1 μm to 5 μm. Examples include calcium carbonate, titanium dioxide, magnesium carbonate, zeolites,
Clay, kaolin, metal soap, polymer beads, etc., but various hardly soluble fine particles can be used irrespective of inorganic or organic substances. When the average particle size of the hardly soluble fine particles is smaller than 0.05 μm, the bulk specific gravity is small, so that the handleability is deteriorated and the fluidity of the aqueous suspension is deteriorated. On the other hand, if the average particle diameter is larger than 10 μm, a uniform and good coating layer cannot be obtained with respect to the particles for mixing the detergent.

As the water-soluble film-forming substance, polyvinyl alcohol, carboxymethylcellulose, methylcellulose,
Examples include hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, starch derivatives, pullulan, shellac, sodium alginate, polyethylene glycol, acrylic acid polymers, etc. Any material that does not impair the effect of can be used.

The weight ratio of the hardly soluble fine particles and the water-soluble film-forming substance is
It is 50: 50: 95-5, preferably 60: 40-90: 10. If the ratio of the water-soluble film-forming substance is larger than the above ratio, the drying rate of the coating material is decreased, and when the coating particles are used in a detergent, the dissolution rate in water is undesirably low. Further, when the amount of the water-soluble film-forming substance is smaller than the above ratio, the bonding between the surface of the particles for mixing detergent and the hardly soluble particles, and the bonding between the particles of hardly soluble particles on the surface of the particles for mixing detergent become insufficient, and a good coating layer is obtained. I can't.

The concentration of the solid content in the aqueous suspension is arbitrarily determined in the range of 1 to 70% by weight so that physical properties such as viscosity are appropriately adjusted. As the solvent, water or an organic solvent can be considered, but water is preferable from the viewpoint of the stability of the detergent-mixing particles and the operation stability.

In addition, a surfactant can be added to the aqueous suspension for the purpose of improving the dispersibility of pigments, dyes such as dyes, fragrances, or hardly soluble fine particles.

Examples of the coating device used in the present invention include a fluidized bed, for example, Okawara Seisakusho Co., Ltd .; Flow Coater, Fuji Sangyo Co., Ltd .; Eromatic (fluidized granulation coating dryer), Freund Sangyo Co., Ltd .;
Coating pan, for example, Freund Corporation
High Coater, Doria Coater by Fuji Sangyo Co., Ltd., fluidized-type granulator, for example, Freund Corporation; CF-Granulator, Fuji Sangyo; Multiplex-Granulator, stirring granulator, for example, Fukae Industrial Co., Ltd .; High Speed Mixer; Fuji Sangyo Co., Ltd .; Vertical Granulator, etc. can be used.

The detergent blending particles used in the present invention are not particularly limited, but include, for example, the following substances.

Enzymes include protease, esterase, carbohydrase and the like.

Specific examples of proteases include pepsin, trypsin, chymotrypsin, collagenase, keratinase,
Esterase, splicitin, papain, aminopeptidase, carboxypeptidase and the like.

Specific examples of esterases include gastric lipase, pancreatic lipase, plant lipases, phospholipases, cholinesterases, and phosphotases.

Specific examples of carbohydrase include cellulase, mattase, saccharase, amylase, pectinase,
α and β-glucosidase and the like.

Examples of the bleaching agent include sodium percarbonate, sodium perborate, sodium prophosphate, sodium sulfate hydrogen peroxide adduct, sodium chloride hydrogen peroxide adduct and the like.

Examples of the bleaching aid include tetraacetylethylenediamine (TAED), glucose pentaacetate, tetraacetylglycolurine, sodium alkanoylokobenzenebenzenesulfonate, and a compound represented by the following general formula (I).

Wherein R ₁ represents a C _1-18 alkyl group; R ₂ and R ₃ represent
_And R ₄ represents — (CH ₂ ) _1-12 —
And L is Represents As the surfactant, any of anionic, cationic, nonionic and amphoteric surfactants can be used. Specific surfactants include the substances described in “Fatty Acid Chemistry (Koshobo, 238P, written by Inaba and Hirano, 1981)”.

Examples of the flavor include isoamyl acetate, α-pinene, β-pinene, myrcene, terpinolene, limonene, benzaldehyde, methylhexyl ketone, citronellal, linalool, benzyl acetate, linalyl acetate, anethole, citral, l-menthol, geranyl formate, and the like. . When a liquid fragrance is used, the particles are impregnated with a porous substance, for example, dextrin, β-cyclodextrin, amorphous silica derivative or the like, and then granulated to provide a coating.

As described above, in the present invention, a coating layer composed of poorly soluble fine particles and a water-soluble film-forming substance is formed on the surface of the particles for mixing detergent.

In the present invention, the water-soluble film-forming substance is used to bond between the surface of the detergent-containing particles and the hardly-soluble fine particles and between the hardly-soluble fine particles on the surface of the detergent-containing particles. According to such a coating method, it is possible to form a coating layer with a smaller amount of a film-forming substance as compared with a conventional method of coating only with a film-forming substance, to reduce the generation of coarse particles, and to adhere to the inside of a coating apparatus. Even less coating can be performed. It also improves water solubility when used as a detergent formulation.

〔Example〕

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

The enzyme particles used in Examples 1 to 5 and Comparative Examples 1 to 5 are enzyme particles having a particle diameter of 350 μm to 1000 μm prepared by the method described in JP-A-62-257990. Example 6
And Comparative Example 6 is an example in which bleaching aid particles were used as the particles for blending the detergent.

Example 1 Fluid coating equipment erotic from Fuji Sangyo Co., Ltd.
STREA-1 type was charged with 500 g of enzyme granules, and was blown with hot air at 60 ° C. to flow. Next, 25 g of a coating liquid consisting of an aqueous suspension having a composition of 17% calcium carbonate, 6% polyethylene glycol ^# 60003%, and 80% water was sprayed upward for 8 minutes from a two-fluid nozzle attached to the bottom.

After that, drying was continued for 2 minutes to obtain coated granules having a good appearance. The yield (particle size is 350
The ratio of particles of ~ 1000 μm, the same applies hereinafter) is 99.5%,
There was no loss such as formation of secondary particles and adhesion in the machine during coating. The water solubility was as good as the granules before coating. No inactivation of the enzyme by the coating was observed.

Example 2 Enzyme granules in a stirred fluidized bed FBS-1 manufactured by Okawara Seisakusho Co., Ltd.
20 kg was charged, and a coating liquid consisting of an aqueous suspension having a composition of 17% of calcium carbonate, 3% of polyvinyl alcohol, and 80% of water was sprayed with 1 kg from a two-fluid nozzle attached to a side portion of a fluidized-bed straight cylinder portion to perform coating.

Yield 98.8%, other water solubility, in-machine adhesion, etc. Example 1
The result was the same.

Example 3 The same apparatus as in Example 2 was charged with 20 kg of enzyme granules, and titanium dioxide 17%, polyethylene glycol ^# 6000 3%, water 80
1% of a coating liquid containing 0.2% of a dye was sprayed onto an aqueous suspension having a composition of 0.1% to perform coating.

Yield 98.5%, other water solubility, in-machine adhesion etc.
The result was the same as 2.

Example 4 Enzyme granules were applied to a high coater manufactured by Freund Corporation.
5 kg preparation, 250 kg of coating liquid having the same composition as in Example 1
Was sprayed.

Example 1 yield: 98.2%, other water solubility, in-machine adhesion, etc.
The results were the same as those of Nos.

Example 5 The same apparatus as in Example 4 was charged with 5 kg of enzyme granules, and 17% of calcium carbonate, 3% of hydroxymethylcellulose, a dispersant (sodium polyacrylate) poise 526 0.08%, and water 80%
250 g of a coating liquid consisting of an aqueous suspension having the following composition:

Example 1: Yield 98.5%, other water solubility, in-machine adhesion, etc.
The result was the same as that of ４4.

Comparative Example 1 Enzyme granules were spray-coated with polyethylene glycol ^# 6000 melted at 80 ° C. using the same apparatus and the same method as in Example 1. As a result, a uniform coating layer could not be formed on the surface of the granules, and mottled particles were obtained. Also, the particle size is 350-1
The yield of 000 μm particles was as low as 92%, and generation of secondary particles was observed.

COMPARATIVE EXAMPLE 2 As a result of spray coating a 10% aqueous solution of polyethylene glycol ^# 6000 using the same apparatus and the same method as in Example 1, a large amount of agglomerated coarse particles were generated due to a low drying speed.
In order to eliminate the generation of coarse particles, it was necessary to reduce the spray speed to half that of Example 1.

Comparative Example 3 As a result of spray coating a 10% aqueous solution of polyvinyl alcohol with the same apparatus and the same method as in Example 1, the same phenomenon as in Comparative Example 2 occurred. The water solubility of the resulting coating was inferior to the coatings obtained in Examples 1-5.

Comparative Example 4 As a result of spray-coating a 25% aqueous methacrylic acid copolymer solution using the same apparatus and the same method as in Comparative Example 1, granules having a glossy surface were obtained, and the yield was as high as 98.9%. Solubility was very poor.

Comparative Example 5 5 kg of enzyme granules were charged into a high-speed mixer and a high-speed mixer manufactured by Fukae Kogyo Co., Ltd., heated to 54 ° C., and then 150 g of polyethylene glycol ^# 6000 melted at 80 ° C. was supplied with stirring to perform coating. .

As a result, a coating having good water solubility was obtained, but adhesion to the inside of the machine and generation of coarse particles occurred, and the yield was as low as 88%. In addition, the surface of the coating was not shiny and roughness was observed.

Using the coating materials obtained in Examples 1 to 5 and Comparative Examples 1 to 5, solubility and storage stability were evaluated by the following methods. Table 1 shows the results.

Solubility (dissolution rate after 2 minutes) A 100 mM Na ₂ CO ₃ solution 1 is put into a 1-volume beaker, and a stirring blade having a blade diameter of 2.5 cm is set at a position of 2 cm from the center and the bottom of the beaker and stirred at 200 rpm. 0.5g sample while stirring
Was added and the mixture was stirred at a liquid temperature of 25 ° C. for 2 minutes, and the enzyme activity of the lysate was measured by the dinitrosalicylic acid method.

The enzyme activity after 2 minutes and 10 minutes was measured, and the dissolution rate after 2 minutes was calculated by the following equation.

Storage stability (activity retention rate) A predetermined amount of the coating materials prepared in Examples 1 to 5 and Comparative Examples 1 to 5 was put in a powder detergent for clothing, and 30 ° C. and relative humidity 40
Stored under ~ 80% conditions for 30 days. The enzyme activities before and after storage were measured by the dinitrosalicylic acid method, and the activity retention was calculated by the following formula.

Example 6 Mixer (Matsuzaka Trading Co., Ltd .; Ladyge Mixer M-20)
3.5 kg of TAED and polyethylene glycol ^# 6000
1.0 kg, 0.5 kg of Glauber's salt, 5.0 kg in total, jacket temperature 70 ° C, spindle speed 200 rpm, chopper speed 10
Heated to 00 rpm for 15 minutes. This mixture was extruded and granulated with a horizontal extrusion granulator (Fuji Paudal Co., Ltd., Peretta Double EXD-60 Model, screen diameter 1.0 mmφ).

This granulated product is flash milled (Fuji Paudal Co., Ltd .; F
(L-200 type) at a rotation speed of 2500 rpm. Next, the granulated product was sieved to obtain a product having a particle size of 350 to 1500 μm. The commercialization yield at this time was 86%.

As a result of coating the same as in Example 1 by using 500 g of the above granulated product as particles for detergent formulation, the yield (proportion of particles having a particle size of 350 to 1500 μm) was 99.4%. There was no loss such as formation of secondary particles or adhesion to the inside of the machine.

Comparative Example 6 As a result of coating in the same manner as in Comparative Example 1 using 500 g of the same granulated material as in Example 6, the yield (350-1500 μm) was 90.
4%, indicating the formation of secondary particles in the coating.

Using each of the coating particles obtained in Example 6 and Comparative Example 6, the dissolution rate and storage stability of each were evaluated according to the following criteria.

 The results are shown in Table 2.

Dissolution rate (dissolution rate after 5 minutes) Put 150 ml of water at 20 ° C into a 200 ml beaker, and make sure that the available oxygen is 0.1%.
After dissolving the sodium percarbonate to a concentration of 05%, the coating material was added to a concentration of 0.04% as a pure content of activator (TAED), and a mechanical stirrer with a 2 cm stirring blade was used at 100 rpm for 3 minutes. After stirring, 5 ml of a 0.3% catalase solution is added and stirred for 1 minute. 10% in this solution
Add 10 ml of potassium iodide solution and 10 ml of 20% sulfuric acid solution,
Titrate with 0.1N sodium thiosulfate solution. Titration after 10 minutes was also performed by the same method, and the dissolution rate (after 5 minutes) was calculated by the following equation.

Storage stability (residual ratio) 10 g of sodium percarbonate and the coating material are mixed at a mixing ratio of 1/1, and stored in a 50 ml plastic container at 50 ° C for 2 weeks. Using the mixed composition before and after storage, the titration constant of the mixture before storage and after storage for 10 minutes after the storage was determined by the same titration method as the above dissolution rate, and the activator (TAED) The residual rate was calculated.

[Effects of the Invention] According to the method for coating detergent-mixing particles of the present invention, the generation of coarse particles due to the aggregation of the detergent-mixing particles during coating is small, and the amount of particles attached to the coating apparatus is small. The yield of particle size particles is high, and coating with excellent operability can be achieved. Also,
High quality coated particles having good solubility and storage stability of the coated particles when used as a detergent formulation can be obtained.

──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. ⁶ , DB name) C11D 11/00 C11D 17/06 C11D 3/14 C11D 3/20-3/22 WPI / L (QUESTEL)

Claims (5)

(57) [Claims] 1. A method of preparing a water-insoluble or poorly water-soluble fine particle having an average particle diameter of 0.05 μm to 10 μm and a water-soluble film-forming substance.
A water suspension containing the mixture in a weight ratio of 0:50 to 95: 5 is introduced into the detergent blending particles which are flowing or agitated in the coating apparatus, and the detergent suspension coated with the aqueous suspension is mixed. A method for coating particles for blending a detergent, comprising drying the particles. 2. The detergent blending particles are enzyme particles, bleach particles,
The coating method according to claim 1, wherein the coating method is one or a mixture selected from bleaching aid particles, perfume particles, and surfactant particles. 3. The coating method according to claim 1, wherein the water-insoluble or hardly water-soluble fine particles are one or a mixture selected from calcium carbonate, titanium dioxide, magnesium carbonate, and zeolite. 4. The material according to claim 1, wherein the water-soluble film-forming substance is one or a mixture selected from polyvinyl alcohol, cellulose derivatives, starch derivatives, natural polymer derivatives, polyethylene glycol and acrylic acid polymers. 2. The coating method according to claim 1. 5. The coating method according to claim 1, wherein the coating apparatus is selected from a fluidized bed, a coating pan, a fluidized granulator, and a stirring granulator.