JPH0446076A - Production of porous material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

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 a flooring material for 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. 11937/1993).

(Problem to be Solved by the Invention) However, the powder and granules obtained by mixing an inorganic powder and a curable resin liquid and moistening them with the resin liquid generally have variations in particle size due to secondary aggregation, etc. is getting bigger.

When such granular materials are pressure-molded using a press machine, the large spaces existing between the granular materials cannot be filled satisfactorily.

As a result, the pore diameters of the resulting porous material become uneven,
It is difficult to adjust the pore diameter within a certain range (or 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, wherein the resin is cured while or after the body is pressurized through a sheet-like material capable of elastic deformation or plastic deformation. A curable resin liquid is mixed into the body, the powder and granules are moistened with this resin liquid, and then covered with a gas-impermeable sheet in a mold, and after degassing the air between the powder and granules under reduced pressure, the particles are elastically deformed. Alternatively, the resin is cured while or after being pressurized through a sheet-like material that can be plastically deformed.

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 1000 μm 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 .mu.-, 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 curing made by blending diallyl phthalate resin, epoxy resin, phenol resin, urethane resin, vinyl ester resin, epoxy acrylate resin, acrylic resin, etc. with conventional curing agents and catalysts such as organic peroxides, amines, acid anhydrides, etc. A thermosetting or thermosetting resin is used, and a curing accelerator is added if necessary.

The curable resin is used in liquid form, and its viscosity is desirably adjusted to 100 voids or less at room temperature, depending on the polymerizable monomer and the degree of polymerization of the resin. 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 m machine powder. The method of impregnation is generally adopted. 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 the powder state is maintained. 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 preferable to prepare within the range of 0.05 to 0.5. At this time, various head weights may be mixed and colored. In this way, a powder or granule in which the inorganic powder or granule is moistened with the curable resin liquid is produced.

This powder or granular material is placed in a desired mold such as a peelable plate-shaped mold or a flat box-shaped mold, and a sheet-like material that can be elastically or plastically deformed is placed thereon. , for example, room temperature to 150°Cf7)in, 1 to 150 kg/
It is pressurized with a pressure machine such as a press machine at a pressure of cni.

The curable resin liquid is cured while being pressurized by a press or the like. Alternatively, after being pressurized by a press or the like, it is heated to, for example, room temperature or a temperature of 150''C or less to harden.As the press, a conventional press device that moves up and down with a pneumatic or hydraulic cylinder is used.

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

When placing a sheet-like material that can be elastically or plastically deformed onto the powder in the mold, the powder in the mold is covered with a gas-impermeable sheet and the air between the powder and granules is degassed under reduced pressure. It is preferable to keep it.

As the gas-impermeable sheet, a plastic sheet such as polyethylene, polypropylene, polyester, or nylon is used. The edge of this gas-impermeable sheet is airtightly sealed with a sealant, a sealing frame, or the like to the upper or side surface of the edge of the mold containing the powder or granules. Then, internal air is sucked in by a vacuum pump through one or more decompression holes formed in a part of the mold, thereby depressurizing and deaerating the air between the particles. Internal pressure is 400mmH
It is preferable that the pressure be less than 10 g and 1 atm or more for monomers, etc.

Note that gas-impermeable sheets and sheet-like materials that can be elastically or plastically deformed are usually peeled off after pressure forming, but if they are adhered to the resulting porous material, these sheets There is no need to peel away these sheet materials after pressing, as the material becomes the back side of the porous material.

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

(Function) In the method of the present invention, inorganic powder and granules are mixed with a curable resin liquid, and the powder and granules moistened with the resin liquid are pressed through a sheet-like material that can be elastically or plastically deformed. Even if there is a large variation in particle size due to secondary agglomeration, etc., the pressing force applied to the entire powder or granule is made uniform by the deformation effect of the sheet-like material, and the powder or granule is The large spaces that exist in between are well filled. As a result, a porous material with well-uniformed pore sizes is obtained.

In addition, in this case, if the powder and granules in the mold are covered with a gas-impermeable sheet and the air between the powder and granules is degassed under reduced pressure, it will be restored to its original state when it is released to normal pressure after pressurization. This prevents the openings from becoming larger and is more effective. Moreover, since there is almost no air (oxygen) between the particles, the curing reaction is not dominated by oxygen and the curing proceeds rapidly.

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

In practice] Carbon milled fiber fibers (average fiber length 300 μm) and thermosetting epoxy resin (40 voids) (resin Epikote 828 and curing agent Ebicure YH-306: manufactured by Yuka Shell Epoxy Co., Ltd.) were mixed in a bulk volume ratio. The former was mixed uniformly at a ratio of 1 to the latter at a ratio of 0.30 to prepare a wet powder.

This granular material was evenly spread in a flat box-shaped mold, a wool felt (thickness 20 mm) was placed on top of it, and a hydraulic cylinder pressure of 40 kg/cm was applied using a press machine at room temperature.
After pressurizing with cj, heating to 120°C to harden the resin, removing the wool felt and demolding, the inorganic powder and granules are bonded with a hardening resin, and fine pores with uniform diameter are formed on the surface. A porous material with a thickness of 6 bars consisting of an open, water-impermeable porous body was produced.

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.

(1) Slip resistance was measured by stacking 30 x 50 pieces of synthetic leather on the surface of a porous material in a wet state, placing a 2 kg load on it, and measuring the friction coefficient using the inclination method. 0.
8 or more: ○, less than 0.8 to 0.6: △, less than 0.6: ×
It was expressed as

(2) Stain resistance is determined by talc powder (particle size 10μM or less)
was dispersed in water at a rate of 0.2 g/cc, and 50 cc of this dispersion was sprinkled on the surface of a porous material of 100 dishes x 1100 ff1I, and the talc powder remained on the surface and could be washed off later. O indicates that the talc powder causes clogging in the pores on the surface.

(3) The diameter of the pores was measured with a mercury boron meter, and the case where 95% or more of the pores had a pore diameter of 20 μl or less was represented by an x, and the case where the number of pores with a pore diameter of 20 μl or less was less than 95% was represented by an x.

(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 ×.

Foothills 11 Pulverized marble powder (240 mesh passes) is evenly spread in a flat box-shaped mold, and thermosetting epoxy acrylic resin containing 1.5% by weight of a hardening agent (manufactured by Barhexa 3-2 Nippon Oil & Fats Co., Ltd.) A resin (35 voids) was sprayed and impregnated at a bulk volume ratio of 1 to 0.27 of the latter.

Cover the top with clay paste in the form of a sheet (approx. 5mm thick), and press this with a press machine at room temperature to a hydraulic cylinder pressure of 10k.
After applying pressure with g/c+fl, remove the clay paste and
The product is heated to 00°C to harden the resin, then removed from the mold, and the inorganic powder is bonded with a curable resin to form a water-impermeable porous body with fine pores of uniform diameter on the surface. 6m thick
m porous materials were produced.

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

15 copies of muscovite powder (200 mesh baths) and a styrene solution of thermosetting unsaturated polyester resin (1 void) containing 2% by weight of a hardening agent (benzoyl peroxide),
A wet granular material was prepared by uniformly mixing the former at a bulk volume ratio of 1 to 0.25 of the latter.

Spread this powder uniformly in a flat box-shaped mold, place a urethane rubber sheet (thickness 10m) on top of it, and press it with a press at a temperature of 80°C and a hydraulic cylinder pressure of 50k.
The resin is cured by applying pressure at g/c-, the urethane rubber sheet is removed and the mold is demolded, and the inorganic powder is bonded with the curable resin to form a non-woven material with fine pores of uniform diameter on the surface. A porous material made of a water-permeable porous body and having a thickness of 611II11 was produced.

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.

Thermosetting epoxy acrylate resin (12 voids) containing Fuse Masudo carbon milled fiber (average fiber length 300 μm) and 2% by weight of hardening agent (hensilver oxide)
were uniformly mixed in a bulk volume ratio of 1 to 0.15 of the latter to prepare a wet powder.

Spread this powder uniformly in a flat box-shaped mold, cover it with a nylon sheet, seal the edges with the upper edge of the mold, place wool felt (thickness 1 Oam) on top of it, and mold it. The inside of the mold is degassed under reduced pressure, and the resin is hardened by pressurizing it with a press machine at a temperature of 80°C and a hydraulic cylinder pressure of 50kg/c+J.The nylon sheet and wool felt are removed and demolded to produce inorganic powder. are combined with a curable resin,
A porous material with a thickness of 6 mm consisting of a water-impermeable porous body with fine pores of uniform pore size on its surface was produced.

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.

1 vessel ■ Five marble crushed powder (180 mensius) and a thermosetting unsaturated polyester resin (10 voids) containing 1% by weight of a hardening agent (methyl ethyl ketone peroxide), with a bulk volume ratio of 1 for the former to 0 for the latter. They were uniformly mixed at a ratio of .15 to produce a wet powder.

Spread this powder uniformly in a flat box-shaped mold, cover it with a polyester sheet, seal the edges with the upper edge of the mold, and place a nitrile rubber sheet (thickness 7
am), the inside of the mold was depressurized and degassed, and this was pressed in a press at a temperature of 60°C and a hydraulic cylinder pressure of 30 kg/
d to harden the resin, remove the polyester sheet and nitrile rubber sheet and demold, and the inorganic powder is bonded with a curable resin to form an impermeable surface with fine pores of uniform diameter. A porous material having a thickness of 6 mm was produced.

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.

Powdered muscovite mica powder (200 mesh) was evenly spread in a flat box-shaped mold, and a styrene solution of thermosetting unsaturated polyester resin containing 2% by weight of a hardening agent (benzoyl peroxide) (1 Boise) was sprayed and impregnated at a bulk volume ratio of 1 to 0.25 of the latter.

Cover it with a polyester sheet, seal its edges with the upper edge of the mold, and cover it with clay paste to form a sheet (
The inside of the mold was depressurized and degassed, and then pressed in a press machine at room temperature under a hydraulic cylinder pressure of 50 kg.
/ After pressurizing with cllN, heating to 80°C to harden the resin, removing the polyester sheet and clay and demolding, the inorganic powder and granules are bonded with a hardening resin, and the surface has a uniform pore size. A porous material with a thickness of 6 mm consisting of a water-impermeable porous body with minute pores was produced.

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.

The same procedure as in Example 1 was carried out except that the wool felt was not used on the outer surface of L.

Comparison 1 The same procedure as in Example 2 was carried out except that clay paste was not used.

Comparison Example 3 The same procedure as in Example 3 was carried out except that the urethane rubber sheet was not used.

(Margins below) Table 1 (Effects of the Invention) As mentioned above, according to the production method of the present invention, the granular material is mixed with an inorganic powder material and a curable resin liquid, and the powder material is moistened with this resin. As the resin is hardened by applying pressure through a sheet-like material that can be elastically or desirably deformed, the inorganic particles are bonded with the hardening resin, and fine pores with uniform diameters are formed on the surface. A water-impermeable porous material is obtained.

When the pore diameters on the surface are uniform as shown in 2, it becomes easy to set the pore diameter within a certain range, and it is possible to reliably prevent slipping when wet with water and prevent stains due to clogging.

Further, when the air between the powder particles is degassed under reduced pressure, there is an advantage that curing is accelerated and productivity is improved.

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, walkways, etc., for flooring, counters, tables, moisture absorbing/releasing wall materials, soundproofing building materials, etc. with anti-slip properties. can.

Claims (1)

[Claims] 1. Inorganic powder and granules are mixed with a curable resin liquid, and the powder and granules moistened with the resin liquid are processed through a sheet-like material that can be elastically or plastically deformed. A method for producing a porous material, characterized by curing the resin while or after applying pressure. 2. Mix a curable resin liquid with an inorganic powder, cover the powder moistened with the resin liquid with a gas-impermeable sheet in a mold, and degas the air between the powder and granules under reduced pressure. After that, the resin is cured while being pressurized through a sheet-like material capable of elastic deformation or plastic deformation, or after being pressurized.