JPH03111497A - Coating of particle for compounding into detergent - Google Patents

Abstract

PURPOSE:To decrease the adhesion of particles for compounding into a detergent to the inside of a machine and the generation of coarse grains and to improve the yield and the solubility in water by coating the particles with a specific aqueous suspension in a coating machine before drying. CONSTITUTION:Fine particles (a) insoluble or hardly soluble in water selected from among CaCO3, TiO2, MgCO3 and zeolite and having an average particle diameter of 0.05-10mum and a water-soluble film-forming substance (b) selected from among PVA, cellulose derivatives, starch derivatives, natural polymer derivatives, polyethylene glycol and acrylic acid polymer are suspended in water at an (a) to (b) weight ratio of (50-95):(50-5) to give an aqueous suspension (A). Particles (B) for compounding into a detergent are placed in a coating machine selected from among a fluidized bed coater, a coating pan, a fluid granulator and an agitating granulator, and component (A) is introduced into the machine while flowing or agitating component (B) to coat component (B) with component (A) before drying.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for producing coated particles for detergent formulations that are less susceptible to changes over time and to compounding agents and have good water solubility.

[Conventional technology and its problems]

Generally, various detergent formulations are used in detergents for the purpose of enhancing cleaning action or added value.

Of these, enzymes and bleaches are susceptible to the effects of detergent ingredients, and are coated to protect them from changes over time and the effects of compounding agents.

On the other hand, bleaching agents can affect the quality of other detergent ingredients, and coatings are sometimes applied to suppress this effect.

Conversely, it may also be coated with other detergent formulations that affect enzymes and bleaching agents. One of the important points for detergent formulations is their solubility after coating, depending on their intended use.

Various methods have been studied for coating granules. For example, there are a method of spray coating a polymer latex (Japanese Patent Laid-Open No. 63-305931), a method of spray coating a polymer film-forming substance (Japanese Patent Laid-Open No. 50-71583), and the like. Coatings obtained by these methods have poor solubility in water and are unsatisfactory as coating methods for detergent formulations.

On the other hand, a method of introducing a water-soluble high melting point substance, molten Wanx, into a stirring granulator and coating it (Japanese Patent Laid-Open No. 63-3248
5, Japanese Unexamined Patent Publication No. 53-6484, etc.). These methods have drawbacks such as generation of coarse particles due to mutual aggregation of particles, adhesion to the inside of the stirring granulator, and low yield.

[Means to solve the problem]

As a result of intensive research to solve the above problems, the present inventors used a coating device to form a suspension containing a specific ratio of water-insoluble or poorly water-soluble fine particles and a water-soluble film-forming substance into detergent formulation particles. According to the method in which a continuous film is formed around the particles by introducing the particles into the granulator and drying them, there is less adhesion to the inside of the granulator during coating, less generation of coarse particles, high yield, and high water solubility. The present inventors have discovered that coated particles for excellent detergent formulations can be obtained, and have completed the present invention.

That is, the present invention provides an aqueous suspension containing water-insoluble or poorly water-soluble fine particles and a water-soluble film-forming substance in a weight ratio of 50 to 95:5 to a detergent fluidized or stirred in a coating device. The present invention provides a method for coating detergent formulation particles, which comprises introducing the aqueous suspension into a formulation particle portion and drying the detergent formulation particles coated with the aqueous suspension.

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

The average particle size of the poorly soluble fine particles is 0.05s to 10-1, preferably 0.1pa to 5. +111 is appropriate. Examples include calcium carbonate, titanium dioxide, magnesium carbonate, zeolite, clay, kaolin, metal soap, polymeric polymer fuse, etc., but various poorly soluble fine particles, whether inorganic or organic, can be used. If the average particle diameter of the poorly soluble fine particles is smaller than 0.05/I11, the bulk specific gravity will be small, resulting in poor handling properties and poor fluidity of the aqueous suspension. Also, the average particle diameter is 101! If it is larger than m, a homogeneous and good coating layer cannot be obtained for particles for detergent formulation.

Water-soluble film-forming substances include polyvinyl alcohol,
Examples include carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, starch derivatives, pullulan, shellac, sodium alginate, polyethylene glycol, and acrylic acid polymers. good,
Any material can be used as long as it does not impair the effects of the present invention.

The weight ratio of the slightly soluble fine particles and the water-soluble film-forming substance is 5.
0:50-95:5, preferably 60:40-
90:10. If the amount of the water-soluble film-forming substance exceeds this ratio, the drying rate of the coated product will be slow, and when the coated particles are used in a detergent, the dissolution rate in water will be slow, which is not preferable. Furthermore, if the amount of the water-soluble film-forming substance is less than the above ratio, the bond between the surface of the detergent compounding particle and the poorly soluble fine particles, and the bonding between the sparingly soluble fine particles on the surface of the detergent compounding particle will be insufficient, resulting in a good coating layer. I can't.

The concentration of solids in the aqueous suspension is arbitrarily determined within the range of 1 to 70% by weight so that physical properties such as viscosity can be appropriately adjusted. Water or an organic solvent can be considered as the solvent, but water is preferred from the viewpoint of stability and operational stability of particles for detergent formulation.

Furthermore, a surfactant may be added to the aqueous suspension for the purpose of improving the dispersibility of pigments, dyes, and other pigments, fragrances, or poorly soluble fine particles.

The coating equipment used in the present invention includes: ■Fluidized bed, for example, ■Oyohara Manufacturing Co., Ltd.; Flow Coater, Tomito Sangyo; ■Eromatic (fluidized granulation coating dryer);
Freund Sangyo■; Spiral flow, ■Coating pan, e.g., Freund Sangyo■; Hi-coater, Tomito Sangyo■;Dria coater, ■Fluidized granulator, e.g. Freund Sangyo■;CF-Granulator-Tomito Sangyo ■；
Multiplex Granulator-1 ■ Stirring Granulator,
For example, Fukae Kogyo (2); high speed bead mixer, Tomito Sangyo (2); vertical granulator, etc. can be used.

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

Examples of 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, phospholyses, and the like.

Specific examples of carbohydrases include cellulase, maltase, saccharase, amylase, pectinase, α
and β-glucosidase.

Examples of bleaching agents include sodium percarbonate, sodium percarbonate, sodium peroxide pyrophosphate, sodium sulfate-hydrogen peroxide adduct, and sodium chloride-hydrogen peroxide adduct.

As a bleaching aid, tetraacetylethylenediamine (
TAED), glucose pentaacetate, tetraacetyl glycol urin, sodium alkanoyloxybenzenesulfonate, and a compound represented by the following formula (1).

g RINR4CL (1) 1'h
O [In the formula, R represents a C1-1s alkyl group, R2+
R3 represents a C9-2 alkyl group, and R4 represents -(CHz
)+～l□. ] Any of anionic, cationic, nonionic and amphoteric surfactants can be used as the surfactant.

For specific surfactants, see “Fatty Acid Chemistry” (Saiwai Shobo,
Inaba and Hirano, p. 238, 1982).

Fragrances include isoamyl acetate, α-pinene, β-pinene, myrcene, terpinolene, limonene, benzaldehyde, methylhexyl ketone, citronellal, linalool, benzyl acetate, linalyl acetate, anethole, citral! - Menthol, geranyl formate, etc.

When using a liquid perfume, the particles are impregnated with a porous substance such as dextrin, β-cyclodextrin, an amorphous silica derivative, etc., and then granulated and then coated.

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

In the present invention, a water-soluble film-forming substance is used to bond the surfaces of particles for detergent formulation and poorly soluble fine particles, and between the sparsely soluble fine particles on the surfaces of particles for detergent formulation. According to this coating method, compared to the conventional coating method using only film-forming substances, it is possible to form a coating layer with less film-forming substances, less generation of coarse particles, and less adhesion inside the coating equipment. Also, less coating can be applied. It also improves water solubility when used in detergent formulations.

〔Example〕

The present invention will be explained below 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 were enzyme particles having a particle size of 350 ttm to 1000 ttm and were prepared by the method described in JP-A-62-257990. Further, Example 6 and Comparative Example 6 are examples in which bleaching aid particles were used as particles for detergent formulation.

SuJLLL Fluid coating equipment manufactured by Tomito Sangyo ■Eromatic 5TR
500g of enzyme granules were placed in the EA-1 type, and 17% calcium carbonate was prepared by blowing hot air at 60°C to make it fluid.
25 g of a coating liquid consisting of an aqueous suspension having a composition of 3% polyethylene glycol and 80% water,
The mixture was sprayed upward for 8 minutes from a two-fluid nozzle attached to the bottom.

After that, drying was continued for 2 minutes, and Coachib granules with a good appearance were obtained. The yield at this time (particle size is 350~
The ratio of particles of 10,001 m (hereinafter the same) was 99.5%, and there was no loss due to formation of secondary particles or adhesion inside the machine during coating. In addition, the water solubility was good and equal to that of the granules before coating. No enzyme deactivation due to coating was observed.

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

The yield was 98.8%, and the pond water solubility, adhesion inside the machine, etc. were the same as in Example 1.

Fruit 1111 20 kg of enzyme granules were placed in the same equipment as in Example 2, and 17% titanium dioxide and polyethylene glycol "60003" were added.
%, 0.2% for an aqueous suspension with a composition of 80% water
1 kg of the coating liquid to which the pigment was added was sprayed and coated.

The yield was 98.5%, and its solubility in pond water, adhesion inside the machine, etc. were the same as in Examples 1 and 2.

5 kg of enzyme granules are placed in a Hi-Coater manufactured by Urause Masudo Freund Sangyo ■
Preparation: Coating liquid 250k with the same composition as Example 1
g was sprayed.

The yield was 98.2%, and its solubility in pond water, adhesion inside the machine, etc. were the same as in Examples 1 to 3.

5 kg of enzyme granules were placed in the same equipment as in Example 4, and 17% of calcium carbonate, 3% of hydroxymethylcellulose, and 5260.08% of dispersant (sodium polyacrylate) were added.
, 250 g of a coating solution consisting of a water suspension having a composition of 80% water was sprayed.

The yield was 98.5%, and its solubility in pond water, adhesion inside the machine, etc. were the same as in Examples 1 to 4.

Using the same equipment and the same method as in Example 1, enzyme granules were spray-coated with polyethylene glycol 6000 melted at 80°C.As a result, a uniform coating layer was not formed on the granule surface, and the particles were mottled. In addition, the yield of particles with a particle size of 350 to 1000 I!m was as low as 92%.
Generation of secondary particles was observed.

Comparative Example) As a result of spray coating a 10% aqueous solution of polyethylene glycol 6000 using the same equipment and the same method as in Example 1, a large amount of agglomerated coarse particles were generated due to the slow drying speed. It was necessary to reduce the speed to half that of Example 1.

Comparative Example U When a 10% aqueous solution of polyvinyl alcohol was spray coated using the same equipment and method as in Example 1, the same phenomenon as in Comparative Example 2 occurred. Moreover, the water solubility of the finished coated product was inferior to that of the coated products obtained in Examples 1 to 5.

Static carbon ↓ As a result of spray coating a 25% methacrylic acid copolymer aqueous solution using the same equipment and method as in Comparative Example 1, granules with a glossy surface were obtained, and the yield was as high as 98.9%. The water solubility of the particles was very poor.

Place 5 kg of enzyme granules in a high-speed mixer using a stirring granulator manufactured by Fukae Kogyo Co., Ltd., raise the temperature to 54°C, and add 1 lb of 80°C molten polyethylene glycol ``6000'' while stirring.
Coating was performed by supplying 50 g.

As a result, a coated product with good water solubility was obtained, but it adhered to the inside of the machine and generated coarse particles, and the yield was as low as 88%. Furthermore, the surface of the coated product was dull and rough.

Using the coated products obtained in Examples 1 to 5 and Comparative Examples 1 to 5, solubility and storage stability were evaluated by the method shown below. The results are shown in Table 1.

Dissolution rate (dissolution rate after 2 minutes) 1! Add 1 100mM NazCO3 solution to a beaker with a volume of 1.
and place a stirring blade with a blade diameter of 2.5cm in the center of the beaker.
Set at a position 2cn+ from the bottom and stir at 200 rpm. Add 0.5g of sample while stirring, and bring the liquid temperature to 25°.
The mixture was stirred at C for 2 minutes, and the enzyme activity of the solution was measured by the dinitrosalicylic acid method.

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

■Existence stability (activity retention rate) The coated products prepared in Examples 1 to 5 and Comparative Examples 1 to 5 were added to laundry powder detergent in a specified amount and kept at 30°C and relative humidity of 40 to 80% for 30 days. saved. The enzyme activity before and after storage was measured by the dinitrosalicylic acid method, and the activity retention rate was calculated using the following formula.

3.5 kg of TAED, polyethylene glycol "6" in a raw color mixing machine (Matsuzaka Boeki ■; Redige Mixer M-20 type)
000 to 1. Okg, 0.5kg of mirabilite (D total 5.
Charge 0kg, jacket temperature 70°C, spindle rotation speed 20Orpm, chopper rotation speed 1000rpm.
+ Stitching and heating for 15 minutes. This mixture was extrusion granulated using a horizontal extrusion granulator (Fuji Paudal Pelleta Double EXD-60 type, screen diameter 1, 0 mmφ).

This granulated material is flash milled (Fuji Baudal 14;
The particles were sized using a machine (Model FL-200) at a rotation speed of 2500 rpm. Next, this granulated material was sieved and the particle size was 350 to 1.
500- was used as a product. The product yield at this time is
It was 86%.

Using 500 g of the above productized granules as particles for detergent formulation, coating was performed in the same manner as in Example 1, and the yield (ratio of particles with a particle size of 350-1500) was 99.4.
%, and there was no loss due to formation of secondary particles or adhesion to the inside of the machine during coating.

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 to 1500 I
Im) was 90.4%, and formation of secondary particles was observed during the coating.

Using each coated particle obtained in Example 6 and Comparative Example 6, the dissolution rate and storage stability of each were evaluated according to the criteria shown below.

The results are shown in Table 2.

MMJJL (Dissolution rate after 5 minutes) Pour 150 m7 of 20°C water into a 200 m1 beaker and dissolve sodium percarbonate so that the effective oxygen content is 0.05%. After adding the pure content to 0.04% and stirring for 3 minutes at 1100 rpm using a mechanical stirrer with 2 cm stirring blades, 0.3% catalase solution 5atZ
Add and stir for 1 minute. To this solution was added 1°-10% potassium iodide solution and 1°-120% sulfuric acid solution. I
Titration is carried out with a solution of N in sodium thiosulfate. Further, titration was also performed after 10 minutes using the same method, and the dissolution rate (after 5 minutes) was calculated using the following formula.

Storage stability (survival rate) Mix 10g of sodium percarbonate and coating material at a mixing ratio of 1/1, and store 50g in a 50@l plastic container.
"C Store for 12 weeks. Using the mixed composition before and after storage, determine the titration number after 10 minutes of each mixture before and after storage by the same titration method as the dissolution rate above, and use the following formula. The residual rate of the activator (TAED) was calculated.

Table 2 [Effects of the invention] According to the method of coating particles for detergent formulation of the present invention,
Coarse particles are less likely to be generated due to agglomeration of particles for detergent formulation during coating, and particles are less likely to adhere to the inside of the coating equipment, resulting in a high yield of particles with a desired particle size.
Enables coating with excellent operability. Moreover, high-quality coated particles with good solubility and storage stability when used as detergent formulations can be obtained.

Claims (1)

[Claims] 1. An aqueous suspension containing water-insoluble or poorly water-soluble fine particles and a water-soluble film-forming substance in a weight ratio of 50:50 to 95:5 is fluidized or stirred in a coating device. 1. A method for coating detergent compounding particles, which comprises introducing the detergent compounding particles into a detergent compounding particle portion and drying the detergent compounding particles coated with the aqueous suspension. 2. The coating method according to claim 1, wherein the particles for detergent formulation are one or a mixture selected from enzyme particles, bleach particles, bleaching aid particles, perfume particles, and surfactant particles. 3 The average particle size of water-insoluble or poorly water-soluble fine particles is 0.
．． The coating method according to claim 1 or 2, wherein the thickness is 0.05 μm to 10 μm. 4. The coating method according to any one of claims 1 to 3, wherein the water-insoluble or poorly water-soluble fine particles are one or a mixture selected from calcium carbonate, titanium dioxide, magnesium carbonate, and zeolite. 5 The water-soluble film-forming substance is polyvinyl alcohol, a cellulose derivative, a starch derivative, a natural polymer derivative,
The coating method according to any one of claims 1 to 4, wherein the coating material is one selected from polyethylene glycol and acrylic acid polymer, or a mixture thereof. 6 The coating equipment includes a fluidized bed, a coating pan,
The coating method according to any one of claims 1 to 5, wherein the coating method is one selected from a fluidized granulator and an agitating granulator.