JPH0967155A - Hardening resin composition, formed body and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a hardening resin compsn. from which a formed body such as a floor bed, color aggregate, etc., can be efficiently produced by mixing a small amt. of a liquid hardening resin and a large amt. of a solid aggregate of a specified particle size to cover the surface of the solid aggregate with the hardening resin. SOLUTION: A liquid hardening resin (such as a novolac epoxy resin) by 100 pts.wt. and a solid aggregate (pulverized stone) of 1-50mm particle size by 1900-19900 pts.wt. are mixed to cause collision among the solid aggregate to cover the surface of the aggregate with the hardening resin. Then, a powder material having 0.1-200μm particle size is deposited by 0-3000 pts.wt. to 100 pts.wt. of the hardening resin on the hardening resin which covers the solid aggregate to obtain a hardening resin compsn. Then the obtd. hardening resin compsn. is supplied in a die and the hardening resin is hardened in the die to obtain a formed body. As for the powder material, a color pigment, alumina, active carbon, zirconia, slug, zeolite, titania, fly ash, etc., can be used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, a molded article and a method for producing the same. More specifically, a curable resin composition comprising a small amount of curable resin, a large amount of solid lumps, and powders as necessary, wherein the solid lump surface is coated with a liquid curable resin. The present invention relates to a molded body and a manufacturing method thereof. Furthermore, the present invention is a curable resin composition comprising a small amount of curable resin and a large amount of solid lumps and powders, wherein the surface of the solid lump is uniformly coated with a liquid curable resin, and the surface is powdered. TECHNICAL FIELD The present invention relates to a molded body obtained by adhering a body and a manufacturing method thereof.

The present invention provides a molded product which can be used in a variety of fields such as floorboards, colored aggregates, surface-sealed porous aggregates, high-strength gravel for cleaning polluted water, adsorbent beds and the like, and a series of techniques relating to the molded products. It is provided.

[0003]

2. Description of the Related Art In a composition of a liquid curable resin and a solid mass, a technique of coating the surface of the solid mass with a curable resin and utilizing it has been put to practical use in many fields. The obtained molded product is in a state where solid lumps are present in the cured resin. In other words, the proportion of solid mass relative to the liquid curable resin is relatively small, and even a composition in which the particle size of the solid mass is adjusted and the closest packing is filled with the liquid, generally, the solid mass per 100 parts by weight of the resin is solid. The mass is 500 parts by weight or less. As a conventional technique for obtaining a molded body, a mixing technique effective for mainly mixing a slurry composition such as a pan-type mixer equipped with a rotating stirring blade has been generally adopted.

[0004]

An object of the present invention is to provide a curable resin composition comprising a small amount of curable resin, a large amount of solid lumps and, if necessary, a powder or granules. The present invention provides a curable resin composition uniformly coated with a functional resin, a molded product made from the curable resin composition, and a method for producing the same. Furthermore, a curable resin composition comprising a small amount of curable resin and a large amount of solid lumps and powders, wherein the surface of the solid lumps is uniformly coated with a liquid curable resin, and the powders and granules are adhered to the surface. It is an object of the present invention to provide a molded body obtained at most and a manufacturing method thereof.

[0005]

According to the present invention, 100 parts by weight of a liquid curable resin, 1900 to 19900 parts by weight of a solid mass having a particle size of 1 to 50 mm, and a particle size of 0.1 are used with respect to 100 parts by weight thereof. A curable resin composition is provided which is substantially composed of 0 to 3000 parts by weight of a granular material having a particle size of 200 μm.

Further, according to the present invention, 100 parts by weight of the cured resin, 1900 to 19900 parts by weight of a solid mass having a particle size of 1 to 50 mm, and a particle size of 0.1 are used with respect to 100 parts by weight thereof.
Provided is a molded product, which is substantially composed of 0 to 3000 parts by weight of powders and granules having a particle size of 200 μm, and the solid masses are fixed to each other through the cured resin.

Further, according to the present invention, (1) 100 parts by weight of a liquid curable resin and 1100 to 19900 parts by weight of a solid mass having a particle size of 1 to 50 mm are mixed with 100 parts by weight of the curable resin, and the solid mass is mixed. To coat the surface with a curable resin, and (2) if desired, a powder or granular material having a particle diameter of 0.1 to 200 μm and having a particle diameter of 3000 parts by weight or less relative to 100 parts by weight of the curable resin, Adhering to the surface of the curable resin coated on the surface of the solid mass,
(3) A method for producing a molded article is provided, which comprises placing the composition thus obtained in a mold, and (4) curing and curing the curable resin in the mold.

Further, according to the present invention, (1) 100 parts by weight of a liquid curable resin and 1100 to 19,900 parts by weight of a solid mass having a particle size of 1 to 50 mm are mixed with 100 parts by weight of the curable resin to form a solid mass. The surface is coated with a curable resin, and (2) if desired, a powder or granular material having a particle size of 0.1 to 200 μm and having a particle size of 3000 parts by weight or less with respect to 100 parts by weight of the curable resin is applied to the surface of the solid mass. Provided is a method for producing a powder-particle-coated solid mass, which comprises adhering to a surface of a coated curable resin. Hereinafter, the present invention will be described in more detail. The curable resin composition of the present invention,
100 parts by weight of a liquid curable resin, 1900 to 19900 parts by weight of a solid mass having a particle size of 1 to 50 mm, and 0 to 300 of a granular material having a particle size of 0.1 to 200 μm.
It consists essentially of 0 parts by weight.

Further, the curable resin composition for obtaining a desired molded product by adhering solid lumps is a liquid curable resin 100.
1 part by mass of solid particles with a particle size of 1 to 50 millimeters per part by weight
900 to 19,900 parts by weight, preferably 3230 to 99
00 parts by weight, and if coloring is necessary, 1 to 30 parts by weight, preferably 2 to 20 parts by weight of the starting pigment having a particle size of 0.1 to 200 μm. The amount of solid mass is 190
If the amount is less than 0 parts by weight, resin adheres to the inside of the manufacturing equipment for cleaning,
It is not preferable because it requires frequent cleaning. The amount of solid mass is 19
If it exceeds 900 parts by weight, the adhesive strength of the solid mass is weak and the purpose of obtaining a strong molded product cannot be achieved, which is not preferable.

Further, a curable resin composition for obtaining a solid block molded product in which a powder or granular material such as a coloring pigment or an adsorbent is adhered to the surface of the solid block is a particle size based on 100 parts by weight of a liquid curable resin. 1-50 mm solid mass 1900-1
9900 parts by weight, preferably 3900 to 12400 parts by weight and a granular material 1 having a particle size of 0.1 to 200 microns
It comprises 0 to 3000 parts by weight, preferably 20 to 2000 parts by weight. If the amount of the solid mass is less than 1900 parts by weight, the resin adheres to the inside of the manufacturing apparatus and the cleaning and cleaning become frequent,
This is not preferable because the resin migrates to the powder and granules and solidifies them. If the amount of the solid mass exceeds 19,900 parts by weight, the adhesive strength of the powder or granular material as the adherend becomes weak, which is not preferable.

The curable resin of the present invention is an epoxy resin, a polyurethane resin, an unsaturated polyester resin, a vinyl ester resin or the like, and is not particularly limited, but a resin which is liquid at room temperature and hardens at room temperature is suitable. . Among these, an epoxy-based curable resin, which can be easily adjusted, is particularly preferable in terms of workability and reactivity. The viscosity of the curable resin at 200C is preferably 200 to 5000 centipoise, and more preferably 500 to 3000 centipoise.

The epoxy-based curable resin suitable for the present invention comprises an epoxy resin having one or more epoxy groups in one molecule and an epoxy resin curing agent. In the present invention, the epoxy resin is a bisphenol type epoxy resin having an epoxy equivalent (g / epoxy group: the same applies hereinafter) in the range of 165 to 5000, a novolac type epoxy resin having an epoxy equivalent of 170 to 250, and an epoxy equivalent of 160 to 350. One or more of glycidyl ester and glycidyl amine having an epoxy equivalent of 100 to 250, preferably a liquid or liquefied resin at 25 ° C. is used. The epoxy resin also includes a modified epoxy resin obtained by reacting the above epoxy resin with one or more other chemicals.

The above epoxy resin has an epoxy equivalent of 1
25-2200 glycidyl ethers of aliphatic alcohols
One or more reactive diluents having at least one epoxy group in one molecule, such as tell, can be used together for the purpose of adjusting the viscosity of the epoxy resin or liquefying.

Further, for the purpose of adjusting the viscosity of the epoxy resin or liquefying it, a solvent such as xylene or alcohol, water, and one or more low-viscosity synthetic oils such as xylene resin can be used in combination. The epoxy resin curing agent is a chain aliphatic polyamine such as polyethylene polyamine, polyalkylene ether polyamine or polymethylene polyamine, or a cycloaliphatic polyamine such as N-aminoethylpiperazine or isophorone diamine, or a fat such as m-xylene diamine. Room temperature curing type curing agents such as aromatic amines and polyamidoamines, or aromatic polyamines or phthalic anhydride, trimellitic anhydride, tetrahydrophthalic anhydride,
Acid anhydrides such as polyadipic anhydride, phenolic resins, melamine resins, dicyandiamide and its derivatives, latent heat-curing curing agents such as block isocyanate, 2-ethyl-4-methylimidazole, etc. imidazo -, Secondary methyl and tertiary amines such as tetramethylguanidine, triethylenediamine and the like, boron trifluoride-amine complex and one or more catalysts which are activated by ultraviolet rays or electron beams to polymerize an epoxy group are used.

Further, a solvent such as xylene or alcohol for the purpose of adjusting the viscosity or liquefying the epoxy resin curing agent,
Water and low-viscosity synthetic oil such as xylene resin, and also additives such as coupling agent, defoaming agent and thixotropic agent can be used in combination. The type and combination of the epoxy resin and the epoxy resin curing agent can be selected depending on the curable resin composition and the method for producing a molded product from the epoxy resin, but an epoxy product having a low risk of fire and low energy can be obtained. An epoxy-based curable resin composed of a resin and a room temperature curable amine is suitable.

A solvent that does not contribute to the curing reaction in the curable resin composition of the present invention, preferably the epoxy resin composition,
Components such as water and xylene resin are not included in the calculation of the composition ratio.

In the present invention, the solid mass means a particle size of 1 to 5
The material and shape are not particularly limited as long as they are substantially solid of 0 mm, and they are selected according to the purpose of use of the molded product from the curable resin composition. Examples of the solid mass include crushed brick, crushed slag, sand, gravel, crushed stone, calcined shale, sintered shale, crushed concrete, and sintered fly ash.

In the present invention, the granular material has a particle size of 0.1 to
It is at least one kind of a coloring pigment of 200 μm and an inorganic powder. As the color pigment, fine powder having an average particle size of less than 10 μm is preferably used. Specifically, minerals such as zinc white, ultramarine, carbon black, cadmium red, cobalt green, cobalt violet, cobalt blue, chrome oxide green, titanium oxide, cerulean blue, titanium yellow, Prussian blue, mars violet, red iron oxide, etc. Organic color pigments such as color pigments, permanent red, Hansa yellow, phthalocyanine green, phthalocyanine blue, benzidine yellow, lake red and the like are used. The particle size of the inorganic powder is 0.1 to 2
Those having a diameter of 00 μm, preferably 1 to 150 μm are preferably used. Specifically, alumina, kaolin, activated carbon, activated clay, glass balloons, glass beads, glass flakes, glass powder, graphite, diatomaceous earth, acid clay, silica, zirconia, aluminum hydroxide, slag, zeolite, talc, calcium carbonate, Magnesium carbonate, titania, dolomite, fly ash, bentonite, mica, magnesia, montmorillonite, barium sulfate and the like can be used, but among them, alumina, activated carbon, zirconia, slag, zeolite, titania, fly ash and magnesia are preferable. Used.

The curable resin composition of the present invention is a composition obtained by coating the surface of the solid mass with a liquid curable resin. Such a curable resin composition can be produced by a method of colliding a solid mass and coating the surface. The method of coating the surface of the solid mass with the curable resin includes a dipping method or a mixing method. The coating by dipping method is required to be a highly stable curable resin with little change in viscosity during dipping work, and a heat-curable curing agent with low reactivity at room temperature is selected. In order to obtain a molded product, it is necessary to prepare a temperature condition exceeding 100 ° C., and in the dipping method, the resin adhesion amount becomes larger than expected, which is not preferable.

In the manufacturing method by the mixing method, a conventional mixing technique such as a tilting barrel type mixer, a forced bread type mixer or a continuous mixer used for mixing a slurry composition can be applied, but a liquid curable resin is used. On the other hand, in the curable resin composition of the present invention, which is a composition with an overwhelmingly large amount of solid lumps, the solid lumps are randomly collided and the curable resin adhered to some solid lumps is mixed with other solid lumps. A method of coating all solid lump surfaces by adhering to the above and repeating this is effective, and a mixing technique using a tilting mixer is suitable.

Next, several embodiments of the molded product of the present invention and the method for obtaining the molded product will be described. In the present invention, the molded body and the first embodiment for obtaining the molded body are 1900 to 19900 parts by weight, preferably 1900 to 19900 parts by weight, of a compound in which a solid mass having a particle diameter of 1 to 50 mm is closest packed with 100 parts by weight of a liquid curable resin. 3230 to 9900 parts by weight are mixed for 5 minutes by a movable tilting mixer, cast on the floor, tamped and left to cure and cure. The reinforced floorboard molded product that is set and cured on a foundation floorboard that is laid with crushed stones, etc. has no flow deformation compared to the conventional crushed stones, and the strength can be significantly improved.
In this case, the solid mass is preferably at least one kind of sand, gravel, crushed stone, construction waste concrete, and brick.

In the present invention, a molded body and a second embodiment for obtaining the molded body are porous molded bodies for forming a gravel layer, wherein the particle size is 1 to 50 mm with respect to 100 parts by weight of a liquid curable resin. Solid mass of preferably 20-40 millimeters is 1900-19900 parts by weight, preferably 3230-9.
This is a method in which 900 parts by weight are mixed for 5 minutes by a tilting mixer, and the solid mass is adhered by hardening in a mold processed with polyolefins or a mold covered with polyolefins and curing in a mold. In this method, for example, a metal or wooden mold used when producing a concrete block is used, and the curable resin composition of the present invention can be packed and cured in the mold. In general, since it firmly adheres to these mold materials, it is difficult to isolate the molded body from the mold. For this reason, expensive surface treatment with a silicon-based or fluorine-based release agent or the like is required, which is uneconomical. On the other hand, polyolefins such as polyethylene, polypropylene, and polyfluorinated ethylene usually have very weak adhesiveness with epoxy-based curable resin and can be easily isolated from molded products. It is preferable that the mold made of the above material can withstand repeated use. In this case, the solid mass is preferably at least one kind of sand, gravel, crushed stone, construction waste concrete, and brick.

In the present invention, the molded body and the third mode for obtaining the molded body are colored aggregates, which are a liquid curable resin and a particle size of 1
-1900 to 19900 with solid mass of 10 mm
1 part by weight, preferably 3900-12400 parts by weight, is mixed in a tilting mixer for 5 minutes and a particle size of 0.1-2 is prepared separately.
One or more 00 micron color pigments and, if necessary, the inorganic powder or granules are transferred to a mixer, preferably the same volume as the solid mass, and mixed for 10 seconds, and then the excess color pigment or the color pigment and the inorganic powder or granules are mixed. This is a method of separating and removing to obtain a cured molded article. In this case, the solid mass is not particularly limited, but at least one kind of sand, gravel or crushed stone having a specific gravity of 1 or more, waste concrete for construction, and brick is preferable.

In the present invention, a molded body and a fourth mode for obtaining the molded body are lightweight aggregates obtained by sealing a thin film on the surface of a porous solid mass, and have a particle diameter of 1 to 100 parts by weight with respect to 100 parts by weight of a liquid curable resin.
50 mm porous solid mass 1900-1990
0 part by weight, preferably 2500-10000 parts by weight, is mixed for 5 minutes with a tilting mixer, and a particle size of 0.1-0.1 is prepared separately.
One or more of 200 μm color pigments and / or inorganic powders are transferred to a mixer, preferably the same volume as the porous solid mass, and mixed for 10 seconds, and then excess color pigments, etc. are separated and removed to form a porous body. It is a method of obtaining a coated solid mass in which the surface of a solid solid mass is sealed. In this case, the solid mass is
At least one type of sintered shale or calcined shale having an absolute dry specific gravity of 1.2 to 1.7 is preferable. The inorganic powder or granular material is not particularly limited, but fly ash is preferable.

In the present invention, a molded body and a fifth mode for obtaining the molded body are a coated solid mass in which an inorganic powder or granular material and, if necessary, a powder or granular material such as a coloring pigment are adhered to the surface of the solid mass, which is liquid curable. With respect to 100 parts by weight of the resin, 1900 to 19900 parts by weight, preferably 3900 to 12400 parts by weight of a solid mass having a particle size of 1 to 50 mm is mixed by a tilting mixer,
A mixer in which one or more inorganic powders having a particle size of 0.1 to 200 μm, preferably 5 to 150 μm, and optionally one or more coloring pigments, preferably the same volume as a solid mass, are filled. It is a method of obtaining a coated solid mass in which the inorganic powder particles are adhered to the surface of the solid mass by separating and removing excess inorganic powder particles and the like for 10 seconds. In this case, the solid mass is not particularly limited, but at least one kind of sand, gravel or crushed stone having a specific gravity of 1 or more, waste concrete for construction, and brick is preferable. The inorganic powder is not particularly limited, but activated alumina for forming the adsorption bed,
Activated carbon, zirconia, slag, zeolite, titania,
Magnesia is preferably used.

In the present invention, the molded body and the sixth embodiment for obtaining the molded body have a particle size of 1 with respect to 100 parts by weight of a liquid curable resin.
~ 50 mm solid mass 5000-10000 parts by weight was mixed with a tilting mixer for 5 minutes to coat the surface of the solid mass, and then the curable resin was cured to cover the surface of the solid mass with the cured resin. It is a method of obtaining a coated solid mass. In this case, the solid lump is preferably a sintered shale, a calcined shale or a brick having an absolute dry specific gravity of 1.2 to 1.7. In this mode, lightweight aggregate is suitable, and the ratio of the resin and the solid mass cannot be uniformly determined. However, by appropriately selecting the ratio, the solid mass does not adhere to each other and the surface of the solid mass is resinous. A coated solid mass coated with can be obtained. In addition, it is effective to mix the solid lumps whose surfaces are coated in a powder or granular material and cure the curable resin in order to obtain a solid lump or granular molded product. Although there is no limitation on the powder or granular material in this case, fly ash is preferable.

[0027]

EFFECTS OF THE INVENTION A composition comprising an extremely small amount of a liquid curable resin with respect to a solid mass and, if necessary, a powder or granule, wherein the surface of the solid mass is uniformly coated with the liquid curable resin. Provided are a resin composition, a molded article made from the same, and a method for producing the same. Thus, there is provided a molded product that is advantageously used in various fields such as floorboards, colored aggregates, surface-sealed porous aggregates, high-strength gravel for cleaning polluted water, and adsorbent beds.

[0028]

EXAMPLES Hereinafter, the curable resin composition according to the present invention, a molded article made from the same, and a method for producing the same will be specifically described with reference to Examples. However, the present invention is not limited to these examples.

[Embodiment 1] Particle diameters of 20 to 4 were added to the tilting barrel type mixer.
20 millimeters of 0 mm crushed stone, grain size 2.5-5
15 kilograms of crushed stone of 15 millimeters and 15 kilograms of sand having a particle diameter of 1 to 2 millimeters are charged, and 100 parts by weight of a modified bisphenol A type epoxy resin having an epoxy equivalent of 200 and a viscosity of 3800 centipoise (25 ° C.) and an active hydrogen equivalent ( g / active hydrogen: the same applies hereinafter) 70, a curable resin obtained by mixing 35 parts by weight of a m-xylenediamine-modified polyamine having a viscosity of 100 centipoise (25 ° C.), and 2 kg of the resin is added and the mixer is operated for 5 minutes to mix. Then, it was filled in a polypropylene mold and cured to obtain a test molded body of 50 × 50 × 300 mm.

[Comparative Example 1] A commercially available concrete flat plate (5
(0 × 300 × 300 mm) was cut out with a diamond cutter to obtain a test body with dimensions of 50 × 50 × 300 mm.

The test moldings obtained in Example 1 and Comparative Example 1 were subjected to a three-point bending test with a fulcrum distance of 250 mm, and the results are shown in Table 1. Bending strength calculation formula ; σ = Pl / bd ² σ: Bending strength (kgf / cm ² ) P: Maximum load (kgf) l: Distance between fulcrums (cm) b: Fracture section width (cm) d: Fracture section Height (cm)

[0032]

[Table 1]

[Embodiment 2] A tilted barrel type mixer having a particle size of 20 to 4 is used.
55 kilograms of washed and dried crushed stone of 0 mm were put in, and 100 parts by weight of a modified bisphenol A type epoxy resin having an epoxy equivalent of 200 and a viscosity of 3800 centipoise (25 ° C.) and an active hydrogen equivalent of 70, a viscosity of 100 centipoise (25 C.) polyalkylene ether diamine (manufactured by Heinzmann: EDR148) and 35 parts by weight of modified polyamine having N-aminoethylpiperazine as a main component are mixed with 1 kg of a curable resin, and the mixer is added for 5 minutes. Operate and mix, internal dimensions 100 x 100 x 1
It was filled in a polypropylene mold of 00 mm and hardened to obtain a test porous molded article to which crushed stone was adhered.

[Comparative Example 2] 4.92 kilograms of No. 6 crushed stone, 3.27 kilograms of Portland cement and 2.13 kilograms of water were added to a tilting cylinder type mixer, and this was run for 5 minutes. 30 kilograms of crushed stone of the same size as used in 2 was added and the operation was continued for another 15 minutes. This was packed in a polypropylene mold having internal dimensions of 100 × 100 × 100 mm and covered with a water retention mat to maintain the humidity, and after 7 days, a test porous molded body was obtained. The molded body was left for a further 2 weeks and subjected to the test.

The mold used for molding is filled with water and the weight of the water is measured (W0). The porous molded body for test is gently put into this to flush out the overflowed water, and the weight of the water remaining in the mold is measured. Weighing (W
1) Yes. The porosity (%) was calculated as 100 (W1) / (W0).

The test porous molded article was dropped from a height of 500 mm onto a concrete floor to examine the state of the molded article. The test results are shown in Table 2.

[0037]

[Table 2]

[Embodiment 3] The opening diameter of the tilting barrel type mixer is 2.5.
49 kg of the crushed stone obtained by fractionating into a millimeter mesh pass to 1 mm mesh on was charged, 1 kg of a curable resin having the same composition as used in Example 2 was added thereto, and the mixer was operated for 20 minutes. One kilogram of this was separately transferred to a ball mill container having an internal volume of about 5 liters, in which 1 kilogram of chromium oxide green was weighed, and the container was capped and mixed for 10 seconds. This mixture was transferred to a mesh with an opening diameter of 1 mm and surplus chrome oxide green was separated and removed to form chrome oxide green on the crushed stone surface.
Crushed stones were obtained by adhering the weight% and uniformly coloring in green. Similarly, 2.3% by weight of a homogenous dispersion consisting of 100 parts by weight of Taipaque Yellow (manufactured by Ishihara Sangyo) and 30 parts by weight of talc JA13R (manufactured by Asada Flourishing Co., Ltd.) was adhered and colored crushed stones, and further titanium oxide R820 (Ishihara Industrial product) and talc JA1
2.2% by weight of a homogenous dispersion of 3R was adhered to obtain a colored crushed stone.

The colored crushed stone obtained in this example was laid on a slate plate so as to have a pattern, and the epoxy curable resin used in this example was cast from above and solidified. The obtained molded body is rich in design without bleeding of each color,
It was suitable for flooring.

[Embodiment 4] The tilted barrel type mixer has a particle size of 5 to 15
Millimeter fired shale (made by Japan Mesalite Kogyo) 10
Equivalent Epomic R-130 with an epoxy equivalent of 180 and a viscosity of 900 centipoise (25 ° C) was added.
4 (manufactured by Mitsui Petrochemical Industry Co., Ltd.) and 38 parts by weight of m-xylenediamine-modified polyamine having an active hydrogen equivalent of 70 and a viscosity of 100 centipoise (25 ° C.) were mixed, and 0.15 kg of a curable resin was added. The mixer was run for 5 minutes. The whole amount of the fly ash was transferred to another container into which 10 kg of fly ash had been put, and the shale was obtained by separating and curing with a mesh having an opening diameter of 2.5 mm and hardening.

Table 3 shows the results of examining the weight change of the specimen dipped in water, using an uncoated calcined shale of the same kind as that used in this example as a control.

[0042]

[Table 3]

[Embodiment 5] A tilted barrel type mixer has a particle size of 3 to 10
25 kilograms of crushed millimeter stones were added, to which 0.5 kilogram of curable resin having the same composition as used in Example 2 was added, and the mixer was operated for 20 minutes. This was transferred to another mixer charged with about 20 kg of gamma-type activated alumina having an average particle size of 120 μm.
Mix for 0 seconds. This mixture was transferred to a mesh having an opening diameter of 2.51 mm, and excess activated alumina was removed by fractionation to obtain crushed stone in which 11.3% by weight of activated alumina adhered to the crushed stone surface. The molded body obtained by the above method was filled in a tube having a diameter of 150 mm and a length of 1500 mm having an inlet and an outlet at both ends, covered with a lid, and treated with an aqueous solution of sodium sulfate sulfate adjusted to pH 4. After that, raw water containing 10 ppm of phosphorus was treated at a flow rate of 100 liters per hour, and as a result, phosphorus at the outlet was less than 1 ppm.

Claims (8)

[Claims] 1. 100 parts by weight of a liquid curable resin, part 1
1 mass of solid particles having a particle size of 1 to 50 mm with respect to 00 parts by weight
A curable resin composition, which is substantially composed of 900 to 19900 parts by weight and 0 to 3000 parts by weight of a powder or granular material having a particle size of 0.1 to 200 μm. 2. 100 parts by weight of a cured resin, and a solid mass 1900 having a particle size of 1 to 50 mm with respect to 100 parts by weight thereof.
A molded product, which is substantially composed of 19,900 parts by weight and 0 to 3,000 parts by weight of a granular material having a particle size of 0.1 to 200 μm, wherein the solid lumps are fixed to each other through the cured resin. . 3. The molded product according to claim 2, wherein, when the powdery or granular material is contained, the powdery or granular material is adhered to the surface of the cured resin which is present in a form coated on the surface of the solid mass. 4. The molded product according to claim 2, wherein the cured resin is an epoxy-based cured resin. 5. The molded product according to claim 2, wherein the powdery or granular material is at least one selected from the group consisting of a coloring pigment, alumina, activated carbon, zirconia, slag, zeolite, titania, fly ash and magnesia. 6. (1) 100 parts by weight of a liquid curable resin and 1100 to 19900 parts by weight of a solid mass having a particle size of 1 to 50 mm are mixed with 100 parts by weight of the curable resin, and the solid mass is made to collide with the surface thereof. With a curable resin,
Then, (2) if desired, the surface of the curable resin in which the surface of the solid mass is coated with a powder or granular material having a particle diameter of 0.1 to 200 μm, which is not more than 3000 parts by weight with respect to 100 parts by weight of the curable resin. And (3) placing the composition thus obtained in a mold, and (4) curing the curable resin in the mold to form the molded product. 7. The method for producing a molded article according to claim 6, wherein the molding is carried out in a mold processed with polyolefins or in a mold covered with polyolefins. 8. (1) 100 parts by weight of a liquid curable resin and 1900 to 19900 parts by weight of a solid mass having a particle size of 1 to 50 mm are mixed with 100 parts by weight of the curable resin, and the surface of the solid mass is coated with the curable resin. (2) A curable resin in which the surface of the solid lump is coated with (2) a powder or granular material having a particle size of 0.1 to 200 μm, which is 3000 parts by weight or less with respect to 100 parts by weight of the curable resin, if desired. A method for producing a powder-particle-coated solid mass, which comprises adhering to a surface of a powder.