JP2000140604A - Water resistant granulated material and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a granulated material excellent in dispersibility in water, free from the collapse even if receiving the shearing stress by stirring or the like and having water resistance and the producing method. SOLUTION: This water resistant granulated material is produced by granulating a powdery material with an anionic binder and further applying a cationic material thereon or by granulating the powdery material with a cationic binder and further applying an anionic material thereon or granulating the powdery material with a polyamine.epichlorohydrine resin, an aklylated amino resin as the binder.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a granulated powdery substance having water resistance and a method for producing the same. It can be used for industrial products, foods, medicines, cosmetics, fertilizers, feeds, and agricultural chemicals.

[0002]

2. Description of the Related Art Conventionally, by adding a concentrated starch wastewater solution to a general granulated material, for example, a powdered fertilizer feed, kneading the mixture, and granulating the mixture, there is no hygroscopicity during the storage period, and furthermore, it is rapidly formed in water. There was a granular fertilizer feed having the property of disintegrating and dispersing (JP-A-59-6932), but this did not require water resistance. On the other hand, silicone compounds, tin compounds,
Using a fluorine-containing olefin compound, etc., forms a cured film with excellent moisture resistance, water resistance, solvent resistance, chemical resistance, oxygen resistance, heat resistance, etc., and excellent adhesion to substrate particles. Coating method (Japanese Patent Laid-Open No. 7-22292)
0) has been proposed.

[0003]

Conventionally, granulated materials such as starch have been required to be disintegratable when poured into water. Cannot be obtained. Further, granules coated with a silicone-based or fluorine-based compound often float when poured into water, making it difficult to uniformly disperse them with other substances.

[0004]

Means for Solving the Problems In order to solve the above problems, the present inventors have conducted intensive studies and found that a powdery substance was granulated with an anionic binder and this was further coated with a cationic substance. Alternatively, the powdery substance is granulated with a cationic binder and further coated with an anionic substance, or the powdery substance is polyamine / epichlorohydrin resin, water-soluble alkylated amino resin, water-soluble methylated melamine resin It has been found that a water-resistant granulated product can be produced by granulating one or more kinds selected from the group consisting of a binder and the present invention has been completed.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The granulated material of the powdery substance used in the present invention is obtained by granulating starch by a usual granulation method. Method, extrusion granulation method, spray drying granulation method, fluidized bed granulation method, compression granulation method, melt granulation method, crush granulation method, and stirring granulation method. Among them, the spray-drying granulation method has a feature that small spherical particles can be produced. After granulation and drying by the method of the present invention,
If coating is required, use a coating machine other than a dedicated coating machine, such as one that can perform coating processing with the granulator used in the above granulation method or one that can spray liquid while drying with a dryer. Can be used.

[0006] Starch is mentioned as a powdery substance that can be used in the present invention. Specifically, potato starch, corn starch,
Natural starches such as sweet potato starch, tapioca starch, sago starch, rice starch, amaranth starch, and modified starches thereof (starch derivatives such as acid-decomposed starch, oxidized starch, etherified, esterified, cross-linked, and wet heat-treated starch). Can be In the application field of foods and the like, when granules that become transparent liquid when heated water is required, partially decomposed starches such as acid-decomposed starch and oxidized starch are suitable. Other powdery organic substances include flour such as wheat flour and corn flour, powdered cellulose, bacterial cellulose, microfibrous cellulose, water-insoluble powdered cellulose such as crystalline cellulose, wood flour and the like, and powdered inorganic substances. Examples of the filler include titanium oxide, silicates (kaolin, clay, bentonite, talc, synthetic aluminum silicate, synthetic calcium silicate, etc.), silicic acid (diatomaceous earth, silica powder, hydrated fine silica, anhydrous fine silica), calcium carbonate , Zinc oxide, magnesium carbonate, calcium magnesium carbonate, aluminum hydroxide,
Examples include barium sulfate, calcium sulfate, calcium sulfite, iron oxide and the like. Further, examples of organic pigments include azo, phthalocyanine, thioindigo, and anthraquinone pigments. Examples of the inorganic pigment include carbon black, red iron oxide (red petal), yellow iron oxide, graphite, molybdenum orange, chrome orange, gunjo, mica pigment, and the like. These powdery substances may be used alone or in combination of two or more. Further, these powdery substances can be added to the coating liquid when coating the binder.

The anionic binder used in the present invention includes alginic acid, sodium alginate, carboxymethyl cellulose, carboxymethyl starch, carboxymethyl guar gum, carboxymethyl xanthan gum,
Examples include polysaccharides having an anionic group such as carboxymethyl cod gum, low methoxyl pectin, carrageenan, polyacrylic acid, and sodium polyacrylate, or synthetic polymers having anionic group. As a cationic substance to be coated after granulation to impart water resistance to the anionic binder, a salt of a polyvalent metal ion can be used. For example, calcium, magnesium, barium, boron, aluminum, hydrochloride such as titanium,
Sulfates, carbonates, phosphates, lactates, and hydroxides. Further, as the cationic substance used in the present invention,
Cationic water-soluble polymeric substances can also be used.
Examples of the cationic water-soluble polymer include cationic polyacrylamide, polyethyleneimine, polyvinylpyrrolidone, cationic polyamide resin, polyallylamine, cationic polymer-grafted starch, cationized starch, cationized guar gum, and cationized xanthan gum. And cationized tara gum.

As the cationic binder used in the present invention, a cationic water-soluble polymer substance can be used. Examples of the cationic water-soluble polymer include cationic polyacrylamide, polyethyleneimine, polyvinylpyrrolidone, cationic polyamide resin, polyallylamine, cationic polymer-grafted starch, cationized starch, cationized guar gum, and cationized xanthan gum. And cationized tara gum. Examples of anionic substances to be coated after granulation to impart water resistance to the cationic binder include alginic acid, sodium alginate, carboxymethyl cellulose, carboxymethyl starch, carboxymethyl guar gum, carboxymethyl xanthan gum, carboxymethyl cod gum, and low methoxyl. Examples include polysaccharides having an anionic group, such as pectin, carrageenan, polyacrylic acid, and sodium polyacrylate, or synthetic polymers having an anionic group.

As described above, the method for producing a water-resistant granule according to the present invention in which a powdery substance is granulated with an anionic binder and further coated with a cationic substance, or the powdery substance is granulated with a cationic binder An anionic binder, a cationic substance, a cationic binder, and an anionic substance which can be used in the method for producing a water-resistant granule of the present invention, which is further coated with an anionic substance, are exemplified. Further, as a method for producing a water-resistant granulated product of the present invention, a powdery substance is granulated by using at least one selected from a polyamine / epichlorohydrin resin, a water-soluble alkylated amino resin, and a water-soluble methylated melamine resin as a binder. In this case, a water-resistant granulated product can be obtained only with these binders, and the coating step is not required.

In order to granulate the powdery substance in the above-mentioned various granulation methods, the above-mentioned binder can be used for the granulation under the methods and conditions commonly used in each method. Representative examples will be described in detail in Examples, but in extrusion granulation, it depends on the type and amount of the binder, but when granulation is poor, other than the above binder, hydroxypropylcellulose, methylcellulose, hydroxypropylmethylcellulose, It is improved when one or more kinds selected from binders such as hydroxyethylcellulose, oxidized starch and dextrin are simultaneously added, kneaded, and granulated by an extrusion granulator. In addition, it is a general process that the extruded granules are then subjected to sizing using a sizing machine. Although it depends on the type and amount of the binder used in the present invention, when the sizing property is poor, a surfactant and a lubricant can be added to improve the sizing property. Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to only these Examples.

[0011]

Example 1 100 parts by weight of corn starch (hereinafter "parts")
And a glue solution prepared by dissolving 1 part of sodium alginate and 1 part of hydroxypropyl cellulose in 30 parts of water, and polyoxyethylene stearyl ether 1 as a lubricant.
Was added and mixed and stirred for 10 minutes. This kneaded product was extruded and granulated by extruding a 0.5 mm-diameter columnar starch granulated product using an extrusion granulator Dome Gran manufactured by Fuji Paudal Co., Ltd. The starch granules were sized in a spherical or cocoon shape having an L / D of 3 or less using a granulator Malmerizer manufactured by Fuji Paudal Co., Ltd., and then dried. This granulated starch was put into the above marmellaizer, and sprayed with 25 parts of a 5% calcium chloride solution while tumbling, followed by drying. 50 parts of the granules were dispersed in 100 parts of water and stirred at a rotation speed of 300 rpm for 10 minutes, but did not collapse.

[0012]

Example 2 A liquid obtained by dispersing 1 part of hydroxypropylcellulose in 40 parts of water in 100 parts of spherical fine granular starch Grafau M and 20 parts of kaolin manufactured by Nisseki Kagaku Co., Ltd. and a centrifugal flow type coagulating granulator CF manufactured by Freund Corporation. And coated on the surface of the fine granular starch. Subsequently, on the kaolin layer, 20 parts of red pattern CH2-223 red (a red inorganic pigment manufactured by Nippon Red Pattern Industry Co., Ltd.) was added with polyamine.
Epichlorohydrin resin (WS5 manufactured by PMC Japan)
64) A coating liquid dispersed in 50 parts of water together with 2 parts, 5 parts of corn starch and 1 part of 10% sodium hydroxide solution was similarly coated to obtain a granular material having a particle size of 0.2 to 0.4 mm. 50 parts of the granules are dispersed in 100 parts of water,
The mixture was stirred at a rotation speed of 300 rpm for 10 minutes, but did not collapse.

[0013]

Example 3 100 parts of corn flour was replaced with polyethyleneimine (Epomin P-1000 manufactured by Nippon Shokubai Co., Ltd.) 10
A part was used as a binder and spray dried to obtain fine granular starch. The fine granular starch was treated with a mica pigment (mica coated with titanium oxide by a fluid bed granulation coating apparatus (flow coater) manufactured by Freund Corporation).
A coating solution in which 25 parts of K. iridion 100) and 2 parts of carboxymethyl starch were dispersed in 80 parts of water was subjected to fluid bed coating to obtain granules having a particle size of 0.2 to 0.5 mm. 50 parts of the granules were dispersed in 100 parts of water and stirred at a rotation speed of 300 rpm for 10 minutes, but did not collapse.

[0014]

Example 4 Fukae was prepared by mixing 100 parts of crystalline cellulose (Avicel manufactured by Asahi Kasei Kogyo Co., Ltd.) and 10 parts of zinc oxide with 30 parts of a 10% glue solution of hydroxypropyl starch (Piostarch H manufactured by Nisseki Kagaku Co., Ltd.) as a binder. Granulated and dried using a high speed mixer manufactured by Kogyo Co., Ltd. Using the granules as a nucleus, 15 parts of a coating liquid (Disperse Red SDP110T (organic pigment manufactured by Dainippon Ink and Chemicals, Inc.)) was mixed with 15 parts of a water-soluble methylated melamine resin (SU manufactured by Sumitomo Chemical Co., Ltd.) as a binder using a high-speed mixer.
MUTEX RESIN M-3) dispersed and dispersed in 10 parts of water and 30 parts of water to give a particle size of 0.3
A granular material of ~ 1.0 mm was obtained. 50 parts of this granular material is
The mixture was dispersed in 00 parts and stirred at a rotation speed of 300 rpm for 10 minutes, but did not collapse.

[0015]

Example 5 100 parts of flour and 15 parts of calcium carbonate were mixed with hydroxypropyl cellulose (Nippon Soda Co., Ltd. H
Using 10 parts of 10% size liquid of PC-L) as a binder, fluidized bed granulation is carried out with a fluidized bed granulating / coating apparatus Nummarmerizer manufactured by Fuji Paudal Co. 30 parts of black are polyamine / epichlorohydrin resin (WS564 manufactured by PMC Japan) 2
Parts, 10 parts of rice starch and 1 part of 10% sodium hydroxide solution in 50 parts of water were coated in the same manner with a fluidized bed to obtain granules having a particle size of 0.2 to 0.4 mm. 50 parts of the granules were dispersed in 100 parts of water and stirred at a rotation speed of 300 rpm for 10 minutes, but did not collapse.

[0016]

Example 6 100 parts of corn starch and yellow iron oxide 1
5 parts, 10 parts of water-soluble methylated melamine resin (SUMUTEX RESIN M-3 manufactured by Sumitomo Chemical Co., Ltd.), 30 parts of water, and polyoxyethylene stearyl ether 1
Was added and mixed and stirred for 10 minutes. This kneaded product was extruded and granulated by extruding a 0.5 mm-diameter columnar starch granulated product using an extrusion granulator Dome Gran manufactured by Fuji Paudal Co., Ltd. The starch granules were sized in a spherical or cocoon shape having an L / D of 3 or less using a granulator Malmerizer manufactured by Fuji Paudal Co., Ltd., and then dried. 50 parts of the granules were dispersed in 100 parts of water and stirred at a rotation speed of 300 rpm for 10 minutes, but did not collapse.

[0017]

Example 7 100 parts of crystalline cellulose (Avicel manufactured by Asahi Kasei Corporation), 10 parts of zinc oxide, Gunjo 15
Parts, 10 parts of a water-soluble methylated melamine resin (SUMUTEX RESIN M-3, manufactured by Sumitomo Chemical Co., Ltd.) and 25 parts of 10% glue solution of hydroxypropyl starch (Piostarch H, manufactured by Nissen Chemicals Co., Ltd.) as a binder, Particle size 0.3 with high speed mixer manufactured by Fukae Industry Co., Ltd.
Granulated to 1.0 mm and dried. 50 parts of the granules were dispersed in 100 parts of water and stirred at a rotation speed of 300 rpm for 10 minutes, but did not collapse.

[0018]

Example 8 When the product obtained in Example 1 was added to a hand-washing detergent, it was effective as a scrubbing agent, was quickly removed, and had a good feel. The feel can be adjusted by changing the amount of the binder and the particle size used. Three parts of the pulp obtained in Examples 2, 3 and 4 were added to 100 parts of pulp, and paper was internally added according to a conventional method. A quaint paper with red, silver and red dots, respectively, was obtained. When the products obtained in Examples 5, 6, and 7 were applied to white high-quality paper according to a conventional method, a quaint paper having black, yellow, and blue dots appeared was obtained.

[0019]

As described above, according to the present invention, it is possible to obtain a granulated material which has good dispersibility in water and does not collapse even when subjected to a shearing force such as stirring. These granules were shown for use in cosmetics and papermaking applications,
If the type of powdery substance / binder is selected, it can be used for food thickeners, medicines, fertilizers, feeds and agricultural chemicals not shown here.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Shigeaki Hayashi 3-3-29 Mitsuya Kita, Yodogawa-ku, Osaka City, Osaka F-term (reference) 4D075 AA01 AB07 AC00 CA38 DA11 DC30 EA06 4G004 BA00 BA02 NA01 4H061 AA01 AA02 DD01 DD04 DD18 EE06 EE12 EE13 EE18 EE27 EE35 EE41 EE62 EE63 FF08 FF12 GG26 HH02 HH25 HH32 4J038 BA011 BA041 BA121 BA131 CG031 CG171 CK031 PC011 DH001 DJ0101 DH001

Claims (6)

[Claims] 1. A water-resistant granulated product obtained by granulating a powdery substance with an anionic binder and further coating with a cationic substance. 2. A water-resistant granulated product obtained by granulating a powdery substance with a cationic binder and further coating it with an anionic substance. 3. A water-resistant granulated product obtained by granulating a powdery substance with at least one binder selected from a polyamine / epichlorohydrin resin, a water-soluble alkylated amino resin, and a water-soluble methylated melamine resin. . 4. A method for producing a water-resistant granulated product, comprising granulating a powdery substance with an anionic binder, and further coating this with a cationic substance. 5. A method for producing a water-resistant granulated product, comprising granulating a powdery substance with a cationic binder and further coating the same with an anionic substance. 6. A water-resistant granulation characterized in that the powdery substance is granulated with at least one selected from a polyamine / epichlorohydrin resin, a water-soluble alkylated amino resin, and a water-soluble methylated melamine resin as a binder. Method of manufacturing a product.