JPH0446073A - 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 lamellarly coating inorg. powder or granules wetted with a curable resin soln. with a sheet and/or powder or granules absorbing the soln. and then curing the resin under pressure. CONSTITUTION:Inorg. powder or granules are mixed with a curable resin soln., wetted with the soln. and lamellarly coated with a sheet and/or powder or granules absorbing the soln. The resin is then cured while or after applying pressure to the coated powder or granules. 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 a flooring material for wet areas.

(Prior Art) It is known to use a porous material in which inorganic powder is bonded with a curable resin such as an unsaturated polyester resin as a flooring material for wet areas such as bathrooms.

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 to be Solved by the Invention) However, the powder and granules that have been wetted with the resin by mixing the inorganic powder and the curable resin liquid in this way have a hardening effect on the resin due to secondary aggregation. There are areas where there is an excess of liquid,
There is a large variation in particle size.

Such powder and granules are produced using a press! 'JI] When pressure forming, the pore diameters of the resulting porous material will be 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) The method for producing a porous material of the present invention is to mix a curable resin liquid and apply the inorganic powder and granules moistened with the resin liquid to a sheet capable of absorbing the resin liquid. The method is characterized in that it is covered in a layered form with a granular material or a granular material, or both materials, and the resin is cured while or after the material is pressurized, thereby achieving the above object.

In the present invention, the inorganic powders to be mixed with the curable resin liquid include inorganic powders such as quartz, kaolin, clay, silica sand, crushed natural stone powder, natural mineral fibers, glass milled fibers, alumina staple fibers, and titanic acid. Powders of inorganic short fibers such as potassium 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 um 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 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 polymerizability, the polymerization degree of the resin, etc. 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 of curable resin to 1 part of inorganic powder; M
o, prepared in the range of 05 to 0.5. At this time, it may be colored by mixing various pigments. In this way, inorganic powder moistened with the curable resin liquid is produced.

This inorganic powder or granular material can be formed into a sheet-like material or powdery material capable of absorbing the resin liquid, or this sheet-like material and powdery material in a desired mold such as a peelable plate-like mold or a flat box-like mold. Both the body and the body are covered in layers.

As the sheet-like material capable of absorbing resin liquid, chopped glass strand cloak, cotton fabric, kraft paper, valve seat, cotton felt, wool felt, etc. are preferably used. In addition, as the granular material capable of absorbing the resin liquid, whitebait powder, Seviolite, glass milled fiber, etc. are preferably used.

The granular material covered in a layer with the above-mentioned sheet material, granular material, or both materials is transferred to a press machine or a roller press machine, and is heated at a temperature of, for example, room temperature to 150° C., 1 to 150 k.
g/co! Pressurized at a pressure of

The curable resin may be cured during pressurization using a press or roller press, or it may be cured by heating to room temperature or a temperature of 150'C or less after pressurization using a press or roller press. be.

As the press, a conventional device that moves up and down with a hydraulic cylinder is used. In addition, a roller press machine generally consists of one or more sets of rotationally driveable press rolls arranged above and below, the upper roll being able to be heated and the lower roll being able to be pressed by a hydraulic cylinder. However, in some cases, a press machine consisting of an upper roll and a lower die may be used. In particular, it is preferable to use a roller presser.

A sheet-like material that can be elastically deformed or plastically deformed on top of a sheet-like material that can absorb the resin liquid that covers the inorganic powder or granular material, or both materials during pressure molding. It is preferable to place the sheet and press-mold it through this sheet-like material.

Rubber sheets, plastic foam sheets, non-woven fabrics, etc. are used as sheet materials that can be elastically deformed. Examples of sheets that can be plastically deformed include plastic sheets filled with highly viscous fluid, paste-like materials such as clay paste, etc. A sheet or the like is used.

In addition, if the sheet-like material, powder or granular material, or both of these materials capable of absorbing the resin liquid are adhered to the resulting porous material, these sheet-like material, powder or granular material, or both of these materials Since this becomes the back surface of the porous material, there is no need to peel and remove it after pressure molding.

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, the inorganic granular material wetted with the resin liquid by mixing the curable resin liquid is mixed with a sheet-like material or granular material, or both materials capable of absorbing the upper rudder resin liquid. When the inorganic powder and granules are covered in a layer and this is pressurized, the excess resin liquid of the curable resin liquid mixed with the inorganic powder is absorbed by the sheet-like material that can absorb the resin liquid, the powder or granules, or both. Ru.

Therefore, the powder particles are free from the adverse effects of excess resin liquid, the large spaces existing between the powder particles are well filled, the pressing force is made uniform, and a porous material with well-uniformed pore diameters can be obtained.

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

1 Foot ■ 4000 parts by weight of silica sand powder (average particle size 300 μm) and 1400 parts by weight of room-temperature curable epoxy resin (30 voids) (Nisdyne 3120: manufactured by Chiki Kagaku Co., Ltd.) were combined in a bulk volume ratio of 1 to 1. The latter were mixed uniformly at a ratio of 0.15 to produce wet inorganic powder.

Spread this inorganic powder uniformly in a flat box-shaped mold, and cover it with a chopped glass strand mat (thickness 3
mm) and pressurized with a press machine at a temperature of 80'C and a hydraulic cylinder pressure of 30 kg/CrA to harden the resin, the inorganic powder and granules are bonded with a hardening resin, and the surface has fine pores with uniform diameters. A porous material having a thickness of 6 cylinders and consisting of an impermeable porous body with open pores 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) The difficulty of peeling can be determined by layering a 30an x 50mm piece of synthetic leather on the surface of a porous material in a wet state.
Place a load of
Less than 20% is indicated by ×.

(2) Stain resistance is determined by talc powder (particle size 10μM or less)
Dispersed in water at a ratio of 0.2 g / cc, and sprinkled 50 cc of this Yi solution on the surface of a porous material of 100 m + n x 100 mm. , 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 borozmeter, and 95% or more of the pores had a pore diameter of 20 μm or less, and the case where the percentage of pores with a pore diameter of 20 μm or less was less than 95% was indicated by a ×. .

(4) The volume of the pores was measured using a mercury porosimeter, and 0.05 cc/g or more was expressed as ◯, and less than 0.05 cc/ε was expressed as ×.

1 pulverized marble powder (180 NOON YUBAS) and a thermosetting vinyl ester resin (15 BOYS) containing 1.5% by weight of a hardening agent (penduyl bar oxide) were mixed in a bulk volume ratio of 1 and the latter at a ratio of 0.15 to produce wet inorganic powder.

This inorganic powder is spread uniformly in a flat box-shaped mold, covered with cotton felt (thickness 7+m++), and passed through a roller pressure machine with a hydraulic cylinder pressure set to 45kg/C111. After shaping, the resin is cured by heating to 90°C to form a thick, water-impermeable porous body with fine pores of uniform diameter formed on the surface by bonding the inorganic powder and granules with a curable resin. A 6 ann porous material 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.

Spread white mica powder (200 mesh) uniformly in a flat box-shaped mold, and add a styrene solution (1 void) of thermosetting polyester resin containing 2% by weight of a hardening agent (methyl ethyl ketone peroxide). The former was impregnated by spraying at a bulk volume ratio of 1 to 0.15 of the latter.

Cover it with kraft paper and press it at 60℃.
The resin is cured by applying pressure to a °C1 hydraulic cylinder at a pressure of 50 kg/cffl, and the inorganic powder is bonded with a curable resin to form an impermeable porous body with fine pores of uniform pore size on its surface. A porous material with 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.

Carbon milled fibers (average fiber length 300 μm) and thermosetting epoxy resin (40 poise) were uniformly mixed in a bulk volume ratio of 1 to 0.3 of the latter in a wet state. Inorganic powder was made.

Spread this inorganic powder uniformly in a flat box-shaped mold, and layer whitebait powder (60 mensius) on top (approximately 7
mm), further covered with a protective nylon sheet, and pressurized with a press at a temperature of 120°C and a hydraulic cylinder pressure of 30 kg/afl to harden the resin.
A 6-thick, water-impermeable porous body made of inorganic powder bound with a curable resin and with fine pores of uniform pore size on its surface.
A saliva porous material 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.

Crushed marble powder (240 mesh) and room temperature curable epoxy resin (5 voids) (Nisudyne 4o○: manufactured by Block Chemical Co., Ltd.) were mixed in a bulk volume ratio of 1 for the former and 0.27 for the latter. A wet inorganic powder was prepared by uniformly mixing the ingredients.

This inorganic powder is spread evenly in a flat box-shaped mold, covered with a layer (approximately 5 coats) of Seviolite (300 Mesosyubas), and then covered with a protective polyester sheet. is pressurized with a hydraulic cylinder pressure of 20 kg/cd using a press machine at room temperature to harden the resin, and the inorganic powder is bonded with a hardening resin to form an impermeable material with fine pores of uniform diameter on the surface. A porous material having a thickness of 6 cylinders was manufactured.

This porous material is non-slip and stain-resistant.

The hardness, pore diameter, and pore volume were measured and evaluated by the following methods. The results are shown in Table 1.

Spread 1 sieve mica powder (200 mesh baths) uniformly in a flat box-shaped mold, and add a styrene solution of thermosetting unsaturated polyester resin containing 2% by weight of a hardening agent (methyl ethyl ketone peroxide) ( 1 voice),
Impregnation was carried out by spraying at a bulk volume ratio of 1 to 0.15 of the latter.

On top of that, glass milled fiber (average fiber length 100t)
Iffl) is coated in a layer (approx. A porous material with a thickness of 61 m 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.

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.

Suutoyu carbon milled fiber (average fiber length 300μm)
and curing agent (Varcadox 60: manufactured by Kayaku Akzo)
thermosetting epoxy acrylate resin (12 voids) containing 2% by weight of the former in a bulk volume ratio of 1 to the latter 0
．． A wet inorganic powder was prepared by uniformly mixing the ingredients at a ratio of 15 to 15.

This inorganic powder is evenly spread into a flat box-shaped mold, covered with a layer (approximately 2 mm) of sepiolite, and further covered with a valve seat. Cylinder pressure 60 kg/ct
! A porous material with a thickness of 6 mm is made by applying pressure to harden the resin, bonding inorganic powder with a hardening resin, and making a water-impermeable porous body with fine pores of uniform pore size on the surface. was manufactured.

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.

Silicon nitride voice car powder (240 mesh baths) and thermosetting unsaturated polyester resin (6 voices) containing 2% by weight of a hardening agent (methyl ethyl ketone peroxide) were mixed in a bulk volume ratio of 1 to 0.15 of the latter. A wet inorganic powder was prepared by uniformly mixing the ingredients.

Spread this inorganic powder uniformly in a flat box-shaped mold, and cover it with a chopped glass strand mat (thickness 3
m), then cover it with wool felt (thickness: 10 cm), pressurize this with a press machine at a temperature of 70°C, and a hydraulic cylinder pressure of 30 kg/d to harden the resin, and the inorganic powder becomes hardenable. 61I thick, made of a water-impermeable porous body bonded with resin and having fine pores of uniform diameter on its surface.
A porous material of II11 was prepared.

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.

Wollastonite (200 mm) was uniformly spread in a flat box-shaped mold, and a styrene solution (1 l) of thermosetting unsaturated polyester resin containing 2% by weight of a hardening agent (methyl ethyl ketone peroxide) was poured into the mold. Poise) was sprayed and impregnated at a bulk volume ratio of 1 to 0.20 of the latter.

The top is covered with a layer (about 4 am) of wollastonite (300 mesosyupa), and then the chopped glass strand cloak (1 m thick) is covered, and the top is covered with a protective polyester sheet. The press machine has a temperature of 80″C1 hydraulic cylinder pressure of 50kg/cff
The inorganic powder and granules are bonded together with a curable resin, and the resin is hardened by applying pressure with a pressure of 1.5 mm to form a porous material with a thickness of 16 mm. manufactured the material.

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 performed except that the cap was not covered with a chopped glass strand cloak.

Pressure is applied using a roller pressure machine without covering it with uneven cotton felt.
The same procedure as in Example 2 was carried out except that the pressurization was performed using a press machine.

The same procedure as in Example 3 was performed except that the sample was not covered with 1 ml of kraft paper.

The same procedure as in Example 4 was carried out except that the powder was not covered with whitebait powder.

Soil flame i The same procedure as in Example 5 was performed except that it was not covered with Seviolite.

L comparison l Not covered with glass milled fiber, otherwise Example 6
I did the same thing.

1. The same procedure as in Example 7 was carried out except that the sample was not covered with Esebiolite and the valve sheet.

Stopping plate 1 The same procedure as in Example 8 was carried out except that the plate was not covered with a chigged glass strand mat and wool felt.

In comparison, the same procedure as in Example 9 was carried out except that the material was not covered with wollastonite and glass strand mat.

(Margins below) Table 1 (Effects of the Invention) As mentioned above, according to the production method of the present invention, inorganic powder particles made by mixing a curable resin liquid with inorganic powder particles and making them wet with this resin liquid. The body is covered in a layer with a sheet material, powder or both, which can absorb the resin liquid, and is pressurized to harden the resin, so that the inorganic powder is bonded with the curable resin, and the surface A water-impermeable porous material with fine pores of uniform diameter can be obtained.

When the pore diameters on the surface are uniform in this way, 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 staining due to clogging.

The method of the invention has these advantages.

Therefore, the porous material obtained by the method of the present invention is
It can be suitably used for flooring, counters, tables, moisture absorbing/releasing wall materials, soundproof building materials, etc. that are expected to have an anti-slip effect, such as in bathrooms, toilets, galleys, entrances, balconies, shower rooms, poolsides, and sidewalks.

Claims (1)

[Claims] 1. Mix a curable resin liquid and cover the inorganic powder material moistened with the resin liquid in a layer with a sheet-like material, powder material, or both materials capable of absorbing the resin liquid. A method for producing a porous material, which comprises curing a resin while or after applying pressure.