JPH0446072A - Production of porous material - Google Patents

Abstract

PURPOSE:To obtain a water impermeable porous material with micropores of a uniform diameter in the surface by wetting inorg. powder or granules with a curable resin soln. and curing the resin while or after applying pressure to the wetted powder or granules with a roller. CONSTITUTION:Inorg. powder or granules are mixed with a curable resin soln. and wetted with the soln. The resin is then cured while or after applying pressure to the wetted powder or granules with a roller. The inorg. powder or granules are bonded with the resin and a water impermeable porous material with micropores of a uniform diameter in the surface is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing a porous material that is particularly suitable for use as flooring material in wet areas.

(Prior Art) It is known to use a porous material in which inorganic powder and granules are bonded with a curable resin such as an unsaturated polyester resin as a flooring material for a place that gets wet with water such as a bathroom.

This type of porous material is generally produced by pressure-molding a mixture of inorganic powder and curable resin liquid such as unsaturated polyester resin using a room temperature press machine or a hot press machine. (For example, see Utility Model Application Publication No. 2-11937).

(Problem B to be solved by the invention) However, in the case of a powder made by mixing an inorganic powder and a curable resin liquid and moistening it with the resin liquid, the particle size generally varies widely due to secondary aggregation. It has become. When such powder and granules are pressure-molded using a press machine consisting of an upper mold and a lower mold, etc., without using rollers, the large spaces existing between the powder and granules cannot be filled satisfactorily.

As a result, the pore diameters of the resulting porous material become uneven,
It is not easy to adjust the pore diameter within a certain range, and it may not be possible to sufficiently prevent slipping or staining when wet with water.

The present invention solves these problems with conventional methods, and its purpose is to have a large number of fine pores with uniform diameters, and to ensure prevention of slipping and staining even when wet with water. An object of the present invention is to provide a method for manufacturing a porous material that can be carried out.

(Means for Solving the Problems) In the present invention, a method for producing a porous material according to claim 1 is characterized in that a curable resin liquid is mixed with an inorganic powder and granules are wetted with the resin liquid. The method for producing a porous material according to claim 2, characterized in that the resin is cured while or after the body is pressurized by a roller. The method is characterized in that the granular material moistened with a liquid is pressed through a sheet-like material that can be elastically or plastically deformed with a roller, or after being pressed, the resin is cured.

In the present invention, inorganic powders include inorganic powders such as quartz, kaolin, clay, silica sand, and crushed natural stone powder, natural mineral fibers, glass milled fibers, alumina short fibers,
Powders of inorganic short fibers such as potassium titanate short fibers, carbon short fibers, and voice car are used.

The maximum particle size of the inorganic powder is preferably 1000μ or less,
In addition, in the case of powder of inorganic short fibers, it is desirable that the average thickness of the fibers is 300 μm or less. When the maximum particle size exceeds 1000 μm, the pores formed on the surface of the resulting porous material become large, and dirt and the like easily enter the pores and become dirty.

In addition, as the curable resin, unsaturated polyester resin,
Room-temperature curable or thermosetting resins are blended with diallyl phthalate resins, epoxy resins, phenolic resins, urethane resins, acrylic resins, etc., and conventional curing agents and catalysts such as organic peroxides, amines, and acid anhydrides. A curing accelerator is added if necessary.

The curable resin is used in liquid form, and its viscosity is preferably adjusted to 100 voids or less at room temperature using a solvent or the like. If the viscosity is higher than 100 voids at room temperature, secondary aggregation of the powder particles will increase, the resulting porous material will have large and non-uniform pore diameters, and dirt will easily enter the pores and become dirty.

The method of mixing the curable resin liquid with the inorganic powder is to add a small amount of the curable resin liquid to the inorganic powder and stir it, or to spray a small amount of the curable resin liquid onto the inorganic powder. Generally, the method of impregnating the In this case, both may be mixed and then put into a mold, or both may be mixed within the mold.

When mixing the curable resin liquid with the inorganic powder, the mixing amount is such that the inorganic powder is moistened with the resin liquid and maintains the powder state. It is determined by taking into consideration factors such as the particle size, type and viscosity of the curable resin liquid, and pressure molding conditions.

Generally, the bulk volume ratio is 1 part of inorganic powder to 0 part of curable resin liquid.
．． It is prepared in the range of 0.05 to 0.5. At this time, it may be colored by mixing various pigments. In this way, a powder or granule in which the inorganic powder or granule is moistened with the curable resin liquid is produced.

This granular material is placed in a desired mold such as a peelable plate-shaped mold or a flat box-shaped mold at a temperature of, for example, room temperature to 150°C,
It is pressurized by a roller press at a pressure of 150 kg/c111. A roller press machine generally consists of one or more sets of rotationally driveable press rolls arranged one above the other, with the upper roll being heatable and capable of pressing the lower roll with a constant pressure using a pneumatic or hydraulic cylinder. In some cases, a press machine consisting of an upper roll and a lower die may be used.

The mold containing the granular material is transferred between the upper and lower rolls of the roller press machine as described above, and is pressurized at a constant pressure and temperature using a pneumatic or hydraulic cylinder. The curable resin may be cured while being pressurized by a roller, or may be cured by heating after being pressurized by a roller.

When pressurizing with a roller press machine, there is a risk that inorganic powder or curable resin liquid may adhere to the roll of the roller press machine, so use a release-treated roll or remove the powder in the mold. It is preferable to cover it with a releasable sheet such as a polyester sheet or a nylon sheet.

Furthermore, in the present invention, in addition to the above-mentioned releasable sheet, a sheet-like material that can be elastically or plastically deformed is placed on top of the powder in the mold, and this sheet-like material is It is effective to apply pressure with a roll through the pores in order to further align the pore diameters. In addition, after applying pressure and curing the resin,
This sheet-like material is usually peeled off, but if it is adhered to the resulting porous material, this sheet-like material becomes the back side of the porous material, and therefore there is no need to peel and remove it.

Examples of sheet materials that can be elastically deformed include rubber sheets, plastic foam sheets, nonwoven fabrics, felt, etc. Examples of sheets that can be plastically deformed include plastic sheets filled with highly viscous fluid, and paste materials such as clay paste. A sheet or the like is used.

In this way, the curable resin liquid is cured at room temperature or by heat 1, and the inorganic powder and granules are bonded by the curable resin, and a large number of pores with uniform diameters are formed on the surface (the surface in contact with the mold surface). A porous material with micropores is obtained.

(Function) In the method of the present invention, when a curable resin liquid is mixed with an inorganic powder and the powder is wetted with the resin liquid and is pressed by a roller, the rotation of this roller causes the powder to By being pressed one after another, the powder and granules move well not only vertically but also horizontally. As a result, the large spaces between the powder particles are filled well, and a porous material with well-uniformed pore diameters is obtained.

In addition, when the above-mentioned powder and granules are pressed by rolls through a sheet-like material that can be elastically or plastically deformed, the deformation action of this sheet-like material equalizes the pressing force applied to the powder and granules, and the pore diameter is reduced. A more well-ordered porous material is obtained.

(Example) Examples and comparative examples of the present invention are shown below.

1” 1 special potassium titanate short fiber (300 mensiva) 400
0 parts by weight and room temperature curable epoxy resin (30 voids) (
2,000 parts by weight of Nisdyne 3120 (manufactured by Miki Kagaku Co., Ltd.) were uniformly mixed at a bulk volume ratio of 1 to 0.25 of the latter to prepare wet powder.

Spread this powder uniformly in a flat mold, cover it with a polyester sheet, pass it through a roller presser, set the pressure of the hydraulic cylinder to 50 kg/cal, pressurize, and then cure the resin at room temperature. The polyester sheet was removed and demolded to form a porous material with a thickness of 6111111, which is made of a water-impermeable porous material in which inorganic powder and granules are bonded with a curable resin and fine pores of uniform pore size are opened on the surface. produced a synthetic material.

Regarding this porous material, the slip resistance, stain resistance, pore diameter, and pore volume were measured and evaluated using the following methods. The results are shown in Table 1.

(1) Slip resistance was measured by placing a 30mm x 50B piece of synthetic leather on the surface of a porous material in a water-wet state, placing a 2kg load on it, and measuring the friction coefficient using the slope method.
．． 8 or more is represented by 0, less than 0.8 to 0.6 is represented by Δ, and less than 0.6 is represented by ×.

(2) Stain resistance is determined by talc powder (particle size of 10 μm or less)
is dispersed in water at a ratio of 0.2 g/cc, and 50 cc of this dispersion is sprinkled on the surface of a porous material of 100 s x 100++ ua. If the talc powder remains on the surface and can be washed off later, mark as ○. , The case where the talc powder caused clogging in the pores on the surface was indicated by ×.

(3) The diameter of the pores was measured using a mercury porosimeter, and the case where 95% or more of the pores had a pore diameter of 20 μm or less was represented by an x, and the case where the percentage of pores with a pore diameter of 20 μm or less was less than 95% was represented by an “×”.

(4) The volume of the pores was measured with a mercury porosimeter, and 0.05 cc/g or more was represented by ○, and less than 0.05 cc/g was represented by ×.

1 application 1 Spread wollastonite (400 mesh bath) evenly in a flat mold, and apply room temperature curing epoxy resin (
Nisdyne 3120 (manufactured by Sekido Kagaku Co., Ltd.) was sprayed and impregnated at a bulk volume ratio of 1 to 0.15 of the latter.

The top is covered with a polyester sheet, and this is passed through a roller pressure machine with a hydraulic cylinder pressure set to 70 kg / cffl, the resin is cured at room temperature, the polyester sheet is removed, the mold is removed, and the inorganic material is A porous material with a thickness of 6 mm was produced, which was made of a water-impermeable porous body in which powder and granules were bonded with a curable resin and fine pores with uniform pore sizes were opened on the surface.

Regarding this porous material, the slip resistance, stain resistance, pore diameter, and pore volume were measured and evaluated using the following methods. The results are shown in Table 1.

Fu Shijun 1 Alumina powder (200 mesh baths) and a styrene solution (1 void) of thermosetting unsaturated polyester resin containing 2% by weight of a hardening agent (methyl ethyl ketone peroxide) were mixed in bulk volume ratio to 1 volume of the former. The latter were uniformly mixed at a ratio of 0.25 to produce a wet powder.

This granular material is evenly spread in a flat mold, covered with a polyester sheet, passed through a roller press heated to 80°C, pressurized with a hydraulic cylinder pressure of 50kg/C-, and then the resin is Cured at a temperature of 80°C,
The polyester sheet is removed and demolded, and the inorganic powder and granules are bonded with a curable resin to form a porous material with a thickness of 6 cm, which is made of a water-impermeable porous material with fine pores of uniform pore size on the surface. manufactured the material.

Regarding this porous material, the slip resistance, stain resistance, pore diameter, and pore volume were measured and evaluated using the following methods. The results are shown in Table 1.

Implementation ■± Carbon milled fiber (average fiber length 300 μm) and thermosetting epoxy resin (30 voids) (resin GY25
7 and a curing agent) IY905 (manufactured by Nippon Chiha Geigy Co., Ltd.) were uniformly mixed at a bulk volume ratio of 1 to 0.15 of the latter to prepare wet powder.

Spread this powder uniformly in a flat mold, cover it with a polyester sheet, place wool felt (10-thickness) on top, and pass it through a roller press heated to 120°C to make a 30 kg / After pressurizing with CT11's hydraulic cylinder pressure, the resin is cured at a temperature of 120°C, the polyester sheet and wool felt are removed and demolded, the inorganic powder is bonded with a hardening resin, and the pore size is formed on the surface. A porous material having a thickness of 6 mm and consisting of a water-impermeable porous body having fine pores with uniform numbers was produced.

Regarding this porous material, the slip resistance, stain resistance, pore diameter, and pore volume were measured and evaluated using the following methods. The results are shown in Table 1.

1 out of 1 Marble crushed powder (200 mesh bath), thermosetting epoxy resin (30 voids) (resin GY257 and hardening agent 1 (Y
A mixture of 2O2 (manufactured by Nippon Ciba Geigy) (12 poise) was uniformly mixed in a bulk volume ratio of 1 to 0 and I5 of the latter to prepare wet rice granules.

Spread this powder uniformly in a flat mold, cover it with a polyester sheet, place a nitrile rubber sheet (thickness 70) on top of it, and pass it through a roller press heated to 120°C to produce 20kg/ After pressurizing with a hydraulic cylinder pressure of C4, the resin is cured at a temperature of 120°C.
The polyester sheet and nitrile rubber sheet were removed and demolded, and the inorganic powder was bonded with a curable resin to form a 6 m thick impermeable porous body with fine pores of uniform diameter on its surface. A porous material was produced.

Regarding this porous material, the slip resistance, stain resistance, t
The diameter of aFL and the volume of pores were measured and evaluated by the following method. The results are shown in Table 1.

Spread white mica (200 mesh) evenly in a flat mold, and add thermosetting epoxy resin (40 voids) (resin Epicoat 828 and hardening agent Ebicure Yl (-
306 (manufactured by Dioilka Shell Epoxy Co., Ltd.) was sprayed and impregnated at a bulk volume ratio of 1 to 0.25 of the latter.

Cover the top with a polyester sheet, place a sheet of clay paste on top of it, and apply it with hydraulic cylinder pressure for 50 minutes.
After applying pressure through a roller pressure machine set at 0 kg/cffl, it is heated to 120°C to harden the resin, and the polyester sheet and clay paste are removed and demolded to harden the inorganic powder. A porous material with a thickness of 6 mm was produced, which was made of a water-impermeable porous body bonded with a plastic resin and having fine pores of uniform pore size on the surface.

This porous material was evaluated by measuring its slip resistance, stain resistance, pore diameter, and pore volume using the following methods. The results are shown in Table 1.

Comparison ■↓ The same procedure as in Example 1 was carried out except that the pressure using the roller press was replaced with the press using the press.

The same procedure as in Example 2 was carried out except that the pressurization using the Uenen Kyutsuji 201ler press machine was replaced with pressurization using a press machine.

The same procedure as in Example 3 was carried out except that the pressure by the upper fl main roller pressure machine was replaced by the pressure by a press machine.

Table 1 (Effects of the Invention) As mentioned above, according to the production method of the present invention, the powder and granules, which are made by mixing a curable resin liquid with an inorganic powder and making it wet with this resin, are processed by a roller. Since the resin is cured by pressure, the inorganic powder is bonded with the curable resin, and a water-impermeable porous material with fine pores of uniform diameter on the surface is obtained.

When the pore diameters on the surface are uniform in this way, it is easy to set the pore diameter within a certain range, and the method of the present invention has these advantages. have

Therefore, the porous material obtained by the method of the present invention is
Suitable for use in bathrooms, toilets, galleys, entrances, balconies, shower rooms, poolsides, sidewalks, etc., for flooring, counters, tables, moisture absorbing/releasing wall materials, soundproofing building materials, etc. can.

Claims (1)

[Claims] 1. Mixing a curable resin liquid with an inorganic powder and granular material and curing the resin while pressing the powder and granular material moistened with the resin liquid with a roller or after applying pressure. A method for producing a porous material characterized by: 2. A curable resin liquid is mixed with an inorganic powder and the powder is wetted with the resin liquid while being pressed by a roller through a sheet-like material that can be elastically or plastically deformed. A method for producing a porous material, characterized by curing the resin after applying pressure.