JPH024419B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Application The present invention relates to a novel synthetic resin-impregnated glazed inorganic porous body and a method for producing the same. More specifically, in the present invention, a glazed inorganic porous body is partially impregnated densely and loosely with a polymer (densely impregnated on the back side of the glaze layer).
The present invention relates to a relatively lightweight porous body that has excellent decorative properties, frost damage resistance, impact resistance, bending strength, etc.

Prior Art and Problems Inorganic porous blocks are relatively inexpensive, lightweight, and have excellent fire resistance and heat insulation properties, so they are useful as building materials. However, due to its porous nature,
There were problems such as easy staining and low strength.
The strength is temporarily improved by making it a polymer-impregnated composite. However, in conventional polymer composites, the resin component is uniformly dispersed and impregnated into the inorganic porous body, so that the efficiency of improving the strength of the polymer is low. In particular, the strength of materials treated with low polymer impregnation cannot be expected to increase, and materials treated with high polymer impregnation are expensive.
Detracts from the fire resistance and insulation properties. Therefore, its long-term strength as a building material could not be expected.

Below are examples of typical block products conventionally used as building materials and their problems.

(a) Lightweight concrete (ALC) This is made by adding metal powder such as aluminum powder or zinc powder as a foaming agent to cement, generating hydrogen gas to make it porous, and curing and hardening in an autoclave. Lightweight, fireproof, heat-insulating, sound-absorbing,
It has excellent workability (sawing, planing, drilling, nailing, etc.) and waterproof properties, but it is weak against bending and requires surface finishing. The surface can be painted with organic or inorganic paints, but the durability of the paint is poor and dirt is difficult to remove, so the lifespan is only a few years.

(b) Perlite board This is a cement molded body mixed with perlite (for example, a very light artificial aggregate with air-tight small air bubbles inside that is made by crushing pearlite or groutite and rapidly heating and expanding it). Ultra-lightweight and fire-resistant
It has excellent sound absorption and heat insulation properties, but has the drawbacks of being weak against bending and absorbing a lot of water. As for surface finishing methods, it is necessary to apply transparent water-repellent paint for the exterior and alkali-resistant paint made of vinyl or synthetic rubber for the interior. There is only one lifespan.

(c) Firestone This is a natural stone cut from porous lava of soda flow type. It is lightweight and has excellent fire resistance, heat insulation, acid resistance, and waterproofness (it can be cut into any shape), but it is also susceptible to bending. The surface has the calm feel of natural stone, but since it is natural stone,
The colors and patterns are uneven, and weathering is inevitable.

As mentioned above, it can be said that the conventional products have major drawbacks in various strengths such as bending due to porosity, surface stains, and durability. Therefore, the main object of the present invention is to provide an inorganic porous material that solves these problems and maintains other properties.

Means for Solving the Problems According to the present invention, a resin-impregnated inorganic porous body having an inorganic glaze layer on a required surface as shown in FIG. Provided is a synthetic resin-impregnated glazed inorganic porous body 1 characterized by a structure in which a synthetic resin component is densely present, and a synthetic resin component is sparsely present in at least an intermediate porous body portion 4 remote from the glaze layer surface. be done.

The above-mentioned novel resin-impregnated porous body is produced by impregnating the porous body 2 with a required amount of liquid resin component from the part of the porous body where the glaze layer surface of the glazed inorganic porous body does not exist, and then centrifugal treatment and It can be easily manufactured by a manufacturing method characterized by a step of substantially transferring the liquid resin component to the glazed layer side by heat treatment from the non-glazed side. The liquid resin component and the individualization of the component will be described later.

Note that the resin liquid is impregnated from the non-glazed surface of the porous body and transferred to the back side of the glaze layer by heating, evaporation, vaporization or centrifugal treatment of the resin liquid, but the resin liquid is sucked into the porous body. Because of its effect, it hinders movement a little. In particular, it tends to remain in the narrow pores between particles due to capillarity. In other words, since the resin liquid does not move completely and remains in the narrow pores in the middle of movement, an independent pore layer can also be effectively formed.

The above-mentioned inorganic porous body refers to a liquid-impregnated substance made of an inorganic component and conventionally used as a building material (for example, a block body, a board, a tile, a roof tile, etc.). Typical examples include (a) molded bodies made of inorganic binders such as inorganic cement, calcium silicate, and gypsum, and fillers such as aggregate and reinforcing fibers as needed; (b) earthenware, ceramic, and mulchite materials. Examples include ceramic products such as (c) porous natural stone, etc.

The glaze layer is applied by applying an ordinary inorganic glaze to the desired surface of the porous body and firing it. The glaze layer can be applied to one surface or all surfaces except one surface of the porous body.

The liquid resin component typically refers to a liquid component that is relatively low in viscosity during impregnation and transfer to the glaze layer side, and that forms a higher molecular weight resin through polymerization, etc. . For example, liquid monomers or prepolymers having one or many ethylenic double bonds (e.g., vinyl or allyl monomers or oligomers),
A resin liquid in which an ethylenically unsaturated resin having a large number of ethylenic double bonds (for example, unsaturated polyester resin, allyl resin, vinyl ester resin, etc.) is dissolved in a liquid vinyl monomer or oligomer;
Examples include acid anhydrides, amines, etc., and resin liquids made of polyfunctional resins (eg, glycidyl-based epoxide resins) that are addition-polymerizable with these. The liquid resin component generally contains a polymerization catalyst such as a radical catalyst or a redox catalyst. Polymerization is easily accomplished by heating and/or irradiation with high energy ionizing radiation. When the process of transferring the liquid component to the glaze layer is carried out by heat treatment from the non-glazed surface, when the porous body impregnated with resin liquid is heated to about 100°C to 200°C, the resin liquid first becomes glazed. It has been found that the resin liquid substantially migrates to the layer side and then polymerization of the resin liquid proceeds intensively. In this transfer due to heating, a thin layer in which the synthetic resin is densely present also tends to be formed on the non-glazed surface on the heating side. When transferring by centrifugal force treatment, polymerization can be achieved, for example, by heating at about 100° C. or by irradiation with ionizing radiation. Note that it is also possible to use a resin liquid obtained by dissolving a soluble highly polymerized resin in a volatile solvent as the liquid resin component, to transfer the resin liquid after impregnation, and to remove the solvent by heating.

Furthermore, the resin-impregnated inorganic porous body of the present invention contains a coupling agent (for example, a silane coupling agent) containing an inorganic group having affinity with the inorganic body and an organic group having affinity with the synthetic resin. By using it, its strength can be significantly increased. Such a coupling agent may be added to the liquid resin component, or the inorganic porous body may be pretreated with a coupling agent and then impregnated with the resin liquid. The strength of ceramic products, cement molded bodies, etc. is mostly determined by the state of the pores. The reason why the bending strength and other properties are increased by resin impregnation is that the resin fills the pores and eliminates areas where breakage is likely to occur. If the inorganic particles and resin are combined at the molecular level using a silane coupling agent or the like, the pores will be strengthened and the strength will be further improved. Furthermore, according to the present invention, since the resin is concentrated on the back surface of the glaze layer, the tensile surface during three-point bending is strengthened, which is very effective in terms of strength.

As illustrated in the cross section of FIG. 1, according to the present invention, the synthetic resin 7 is densely present in the porous body part 3 close to the glaze layer surface 5, and the synthetic resin 7 is densely present in the porous body part 4 distant from the glaze layer surface 5. A novel synthetic resin having a structure in which synthetic resin 7 is sparsely present and substantially independent pores 8 are present between inorganic particles 6 and the scattered synthetic resin 7 in the porous body portion 4. An impregnated and glazed inorganic porous body 1 is provided. This structure achieves the following functions and effects.

Effects of the Invention According to the present invention, an inorganic glaze layer is applied to a required surface of an inorganic porous body, a synthetic resin is concentrated and densely present in a portion of the porous body close to the glaze layer surface, and A synergistic effect is obtained in which deterioration of this dense synthetic resin portion is protected by the glaze layer and the loosely impregnated porous body portion. That is, the resin-impregnated porous material according to the present invention has a glaze layer on the surface of the inorganic porous material, and the back surface is densely impregnated with the polymer and the entire interior is moderately impregnated with the polymer, so it is different from the conventional method as described below. have different characteristics.

(1) Since it has a glaze layer on its surface, various durable colors and glossy colors can be obtained, and it has excellent architectural beauty.

(2) Because the porous body contains resin (especially concentrated on the back side of the glaze layer), physical strength such as impact resistance and bending strength is improved compared to conventional inorganic porous bodies. .

(3) The majority of the glaze layer other than the back surface is impregnated with a moderate amount of resin, changing the continuous pores in the porous material to independent pores, resulting in no water absorption and excellent frost damage resistance. ing. Also, since there is no air permeability, it has heat insulating properties.

(4) Since the surface has a glaze layer, the polymer densely impregnated on the back side will not deteriorate due to heat, light, chemicals, etc.

(5) The major drawback of inorganic porous materials, which is their weakness to bending, is overcome by resin impregnation. The bending strength can be doubled by impregnating with MMA alone, and more than 4 times by adding 1 part of a silane coupling agent.

(6) Moreover, since the polymer is concentrated on the back side of the glaze layer, the amount of impregnation can be kept to less than 20% of the total pores, and there is no significant difference in fire resistance.

(7) Even if the glaze layer itself tends to peel off or crack due to poor fusion between the glaze and the molded object, this can be prevented by impregnating it with resin.

Examples The present invention will be further explained below with reference to Examples. In each example, amounts are by weight. In addition,
MMA stands for methyl methacrylate, TMPTMA stands for trimethylolpropane trimethacrylate, and BPO stands for benzoyl peroxide. Test results for each strength represent the average of three samples.

Example 1 According to the process illustrated in Fig. 2, a ceramic tile board A with a thickness of about 10 mm, which has been given a glaze layer, is mixed with 45 parts of styrene.
It was immersed for 15 minutes in a resin solution containing 45 parts of MMA, 10 parts of TMPTMA, and 1 part of BPO (B). Then heat on a hot plate at 200℃ for 30 minutes from the side without the glaze layer (C)
As a result, the structure shown in Figure 1 was obtained. However, in this case, a thin layer of styrene polymer was also formed on the back surface of the porous body (FIG. 2F). The thickness of the dense resin-impregnated layer 3 was approximately 0.5 mm.

A bending test (span 7 cm, head speed 1 mm/min) and impact test were carried out using a sample of the above product measuring 80 x 40 x 10 mm according to the test method described below. Bending strength is 207Kg without impregnation.
f/ ^cm2 , but when impregnated with resin, it became 382Kgf/ ^cm2 . When a falling ball test was performed using a 65g iron ball in an impact resistance test, the tiles themselves broke at 59cm for the unimpregnated tiles and at 73cm for the resin-impregnated tiles.

Example 2 According to the process illustrated in Fig. 2, a calcium silicate plate with a thickness of about 25 mm, which has been given a glaze layer, is made of 100 parts of MMA.
It was immersed for 15 minutes in a liquid with a composition of 1 part BPO. after that
From the side without the glaze layer on a hot plate at 200℃
After heating for 30 minutes, a structure as illustrated in FIG. 1 was obtained. The thickness of the dense resin-impregnated layer 3 was approximately 1 mm (Fig. 2E). In addition, by using a porous body with a glaze layer applied not only to the surface but also to the side surfaces and impregnating it with resin in the same manner, a structure in which the polymer was more densely gathered on the back surface of the glaze layer was obtained. Resin liquid composition
When impregnated in the same manner using 100 parts of MMA, 1 part of BPO, and 1 part of silane coupling agent, a product with particularly excellent physical strength was obtained, although the amount and distribution of impregnation were the same. The bending strength has more than doubled.

A bending test (span 8 cm, head speed
0.5 mm/min) and impact tests were conducted. The bending strength was 16.3 Kgf/cm ² without impregnation, but became 32.5 Kgf/cm ² with resin impregnation. Furthermore, if you use resin with added silane coupling agent, it will weigh 73.8Kg.
f/cm ² summer. When a falling ball test was conducted using a 35g iron ball, it was 7cm for the unimpregnated ball and 17cm for the impregnated ball.
cm, 1 cm for those with silane coupling agent added
So, cracks got into the glaze layer.

Example 3 In this example, centrifugation was performed according to the steps shown in FIG. A lightweight concrete (ALC) plate with a glaze layer is made of 45 parts styrene, 45 parts MMA,
It was immersed in a resin solution containing 10 parts of TMPTMA and 1 part of BPO for 30 minutes. Then centrifuge (20 at 4000rpm)
minutes) to move the resin toward the back side of the glaze layer. Next, heat it on a hot plate at 100℃ for 1 hour from the side without the glaze layer (see Figures 1 and 2).
A structure like this was obtained.

In addition, in the above strength test, the bending strength is
Measured according to JIS. Impact strength was measured as follows. That is, the sample should be placed face up.
Set it horizontally in the center of the wooden box filled with sand. Use a 65g (diameter 25mm) or 35g steel ball and let it fall naturally to approximately the center of the test specimen. The head difference starts from just before the test piece breaks or cracks, increases in 1cm intervals, and the falling ball height (cm) at which the test piece breaks or cracks is taken as the falling ball impact strength.

[Brief explanation of drawings]

FIG. 1 is a partial cross-sectional view schematically showing the structure of a synthetic resin-impregnated and glazed inorganic porous body according to the present invention.
FIG. 2 is a process diagram illustrating the method for producing the impregnated porous body according to the present invention. 1... Resin-impregnated porous body, 2... Porous body, 3
... Densely impregnated part, 4... Loosely impregnated part, 5... Glaze layer.

Claims (1)

[Scope of Claims] 1. A resin-impregnated inorganic porous body having a glaze layer on a required surface, in which the impregnated synthetic resin is densely present in a portion of the porous body close to the glaze layer surface, and the impregnated synthetic resin is densely present in a portion of the porous body that is close to the glaze layer surface, and A resin-impregnated, glazed inorganic porous body characterized by a structure in which the synthetic resin is sparsely present in at least a middle portion of the porous body. 2. The resin-impregnated porous body according to claim 1, wherein the impregnated synthetic resin is strongly bonded to the porous body by the presence of a coupling agent. 3. In a method of impregnating a porous body with a liquid resin component and solidifying the resin component, a required amount of the liquid synthetic resin component is added to the porous body from a portion of the porous body where the glaze layer surface of the glazed inorganic porous body does not exist. Dense resin impregnation on the glaze layer side, characterized by a step of substantially transferring the liquid resin component to the glaze layer side by centrifugal force treatment and/or heat treatment from the non-glazed side. A method for producing a glazed inorganic porous body.