JPH11292595A - Artificial stone luminescent molded body - Google Patents

Abstract

(57) [Problem] To provide an artificial stone having a luminous or fluorescent light characteristic and a deep color tone. SOLUTION: Up to 50% by weight of a resin, up to 40% by weight of a luminous or fluorescent substance having a luminous property or a luminescence accompanying ultraviolet absorption, and 10 to 65% by weight of a transparent inorganic aggregate are contained. And the artificial stone luminescent molded body.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial stone light-emitting molding. More specifically, the invention of this application is useful for building materials, landscape materials, etc. as a night decoration, a direction indication by light in a dark field environment, a position guide, and the like, and a luminous property such as a luminous property or an ultraviolet absorption. TECHNICAL FIELD The present invention relates to an artificial stone molding having properties.

[0002]

2. Description of the Related Art Conventionally, natural stone is crushed,
There is known an artificial stone obtained by mixing this with a resin or the like and solidifying the mixture. In addition, various attempts have been made to make the artificial stone have a natural stone tone such as marble or granite, and have excellent hardness and strength.

As one attempt to improve the function and performance of such artificial stones, an optical function is provided by using a luminous substance such as a phosphorescent material or a fluorescent substance such as an ultraviolet light emitting material which emits light upon absorption of ultraviolet light. It has also been suggested to do so. This attempt is
A fluorescent substance is mixed with a resin component as an artificial stone binder and solidified, or a luminous fluorescent substance such as strontium aluminate or an ultraviolet fluorescent substance is mixed with resin or glass to solidify. Artificial stones are made by using crushed materials as aggregates.

However, in the case of a conventional luminous or fluorescent artificial stone, the luminous action of the luminous material or the like by any of the above methods is due to the binder resin component or bone exposed on the surface. Except for the location of the material, there is a drawback that the phosphorescent material and the like contained inside the artificial stone compact do not act at all. Fluorescent substances such as phosphorescent materials are very expensive, and the addition of a small amount increases the total cost of artificial stone products to about 3 to 100 times. The conventional artificial stone contained therein was not practical in terms of cost.

[0005] For this reason, conventionally, there has been a problem that the use and design of artificial stones having luminous properties are extremely limited due to high cost and restrictions on luminous performance. Under these circumstances, new products that can reduce the cost of products and also have excellent luminous functionality, are luminous or fluorescent, and are useful as light guides and nighttime decorative materials in dark field environments, etc. The realization of artificial stone light-emitting molded articles has been desired.

[0006]

In order to solve the above-mentioned problems, the invention of the present application aims to solve the above-mentioned problems by providing a luminous or fluorescent substance whose main composition has a luminous property or a luminescent property due to the absorption of ultraviolet rays. And an artificial stone light-emitting molded article having an inorganic aggregate and a resin, which has a luminous property having a luminous property of up to 40% by weight together with a resin of up to 50% by weight of a total amount or a luminosity accompanying absorption of ultraviolet rays or Provided is an artificial stone luminescent molded article characterized by containing a fluorescent substance and 10 to 65% by weight of a transparent inorganic aggregate.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention of this application as described above will be described in more detail below. First, the artificial stone luminescent molded article of the invention of this application contains an inorganic aggregate and a resin together with a luminescent or fluorescent substance as main components. That is, the sum of the inorganic aggregate and the resin together with the luminous or fluorescent substance accounts for 97% by weight or more of the total amount.

Importantly, the resin component accounts for up to 50% by weight of the total weight. Of course, it goes without saying that it is permissible to add a small amount of toning components such as pigments and dyes, and other compounding components such as resin deterioration inhibitors and flame retardants. Most of the components other than the resin up to 50% by weight, except for these trace components, are inorganic skeletons and luminescent or fluorescent substances.

In this case, the inorganic aggregate can be classified as follows in the artificial stone luminescent molded article of the present invention. Transparent inorganic aggregate Other inorganic aggregate And, in the artificial stone luminescent molded article of the present invention, basically, the composition thereof is (1) a resin of up to 50% by weight, (2) a luminous property of up to 40% by weight or Fluorescent substance (3) Transparent inorganic aggregate of 10 to 65% by weight (4) It is characterized as having another inorganic aggregate within a range commonly used.

The artificial stone luminescent molded article of the present invention in which the resin is blended in a high proportion of up to 50% by weight means that, for example, the casting molding described later can be performed more easily and at a lower cost. ing. And by the combination of the luminous or fluorescent substance of the present invention and the transparent mineral bone,
Even when the resin content is large, extremely remarkable optical characteristics that enable light transmission in the entire thickness direction of the molded body can be obtained.

As for inorganic aggregates, natural stones, natural minerals,
It includes a wide range of artificially synthesized inorganic substances, glass, metals and the like. The transparent inorganic aggregate means a highly transparent inorganic substance used for relatively light transmission among these. For example, quartz or glass is a typical example. In addition, the transparent inorganic aggregate includes those having high transparency whose surface is colored by pigment or dyeing.

In containing the luminous or fluorescent substance and the transparent inorganic aggregate, generally 0.5 to 40% by weight of the luminous or fluorescent substance is based on the total amount of the artificial stone. It is appropriate that the content of the transparent inorganic aggregate is 10 to 65% by weight, and the other inorganic aggregate is 0 to 30% by weight.

When blending the luminous or fluorescent substance with the transparent inorganic aggregate, these components may be mixed with a resin, or the surfaces may be preliminarily baked with a luminous or fluorescent substance. A transparent inorganic aggregate having a coating layer may be contained. Regarding the transparent inorganic aggregate and the other inorganic aggregate, a combination of the following two types is exemplified as a preferable one in terms of the size (diameter). That is, one is a fine grain component having a size of 5 to 70 mesh (Tyler standard).

[0014] A fine particle component under 100 mesh (Tyler standard) is preferably used together with the fine particle component. Examples of the fine particle component include various natural or artificial fine particle components. For example, calcium carbonate, aluminum hydroxide, silica stone powder and the like are easily obtained fine particles.
Further, as a part of the fine particle component, components such as manganese dioxide, titanium dioxide, zirconium silicate, and iron oxide for adjusting the color tone, and antimony trioxide (pentoxide) for imparting flame retardancy / incombustibility, Components such as a boron compound and a bromine compound can also be added and blended.

The fine-grained component functions as a major factor in the appearance and physical properties of the obtained artificial stone molding. The fine-grained component is considerably finer than the 100-grain level compared to the fine-grained component. The fine-grained component is positioned so as to penetrate between the individual grains of the fine-grained component and fill the space between the grains. It contributes to obtaining properties such as hardness and flexibility.

More specifically, in the artificial stone luminescent molded article of the present invention, a transparent inorganic component is used as at least a part of the fine-grained component, and night light is used as at least a part of the fine-grained component. Sex or fluorescent substances can be used. The fine-grained component as a transparent inorganic aggregate means that it is a substantially light-transmitting inorganic component, and its transparency has various degrees,
Natural or artificially synthesized inorganic substances having relatively high light transmittance will be used in the present invention. For this reason, the transparent inorganic fine particle component may be in a colored state or in a state having a unique color.

Typically, quartz stone, silica stone, glass and the like are exemplified as the transparent inorganic fine particle component in the present invention, but are not limited thereto. Then, as a part or all of the fine particle component, it is considered to use a luminous or fluorescent component having a light storage property or a luminescence property due to ultraviolet absorption, which is under 100 mesh. Representative examples of such components include strontium aluminate-based phosphorescent materials and zinc sulfide. These various materials will be used in the present invention.

With respect to each of the above-mentioned inorganic components, the mixing ratio is considered together with the size. That is, in the artificial stone composition of the present invention, the weight (W ₁ )
And the weight of the fine particle component (W ₂ ) and the weight of the luminous or fluorescent component (W ₃ ) is W ₁ / (W ₂ + W ₃ ).
Is allowed in a wide range of 1/10 to 100 times or more, but more preferably about 1/1 to 4/1.

Regarding the ratio between the inorganic fine particle component and the luminous or fluorescent component, the latter may occupy the whole, or the inorganic fine particle component may be in a ratio of 100 times by weight or more. Good. Further, for the inorganic fine component, the ratio of transparency inorganic fine component of which is (0.3 to 1.0) is desirable to be in the relation of W _1.

The above is considered to be suitable for realizing physical properties such as strength, hardness and density as artificial stones, and realizing an optical function such as luminous or fluorescent. In addition, the size of each component is specifically selected appropriately according to the size and the mixing ratio of each component to be combined, but the fine component is generally about 150 to 250 mesh. Is more preferable.

To further explain the light function of the artificial stone, in the artificial stone of the present invention, the light function is that the light emission is made possible by the thickness. It emits light over the entire thickness of the artificial stone, instead of emitting light only at the surface layer as in the past, and has excellent luminous performance, and is also economical due to the use of expensive luminous or fluorescent components. It will be.

This is because the use of the transparent inorganic fine-grain component as a transparent aggregate allows the light irradiated from the outside to penetrate and penetrate into the artificial stone, and the light energy is efficiently luminous or fluorescent. Absorbed by light components, and
Since the luminescent layer composed of a phosphorescent material or the like in which the luminous or fluorescent components are dispersed is secured as a large thickness including the inside of the artificial stone, it is possible to maintain high luminosity for a long time. is there. At the time of light emission, the transparent inorganic fine particle component has high luminous intensity due to good light transmittance.

The proportion of the transparent component in the whole fine grain component is 30 to 100% by weight as described above. However, depending on the physical performance such as the strength of the artificial stone and the appearance and design, it should be 100%. However, it is natural that it is preferable from the viewpoint of the optical function. Of course, it is not limited to this, but if it is less than 30%, it will be difficult to obtain the required optical function.

When a transparent inorganic aggregate surface-baked with a luminous or fluorescent substance is used as a part of the inorganic aggregate, in the present invention, at least a part of the fine-grain component is transparent. It can be used as a product obtained by baking a luminous substance such as a luminous substance or a fluorescent substance which emits light due to ultraviolet absorption on its surface. That is, a part or all of the fine particle component is a transparent inorganic aggregate whose surface is coated with a luminescent substance or a fluorescent substance. Suitable examples of such fine-grained components as the inorganic aggregate having transparent light include glass and silica stone.

With respect to the fine-grained component to be incorporated in the composition, it is preferable that 10 to 100% (by weight) of the fine-grained component is a transparent inorganic aggregate having a surface coating layer of the luminous substance or the fluorescent substance. . In the case of transparent inorganic aggregates, especially baking coating of fine-grained components, several μm to
Tens of μm, for example, 5 to 50 μm, more preferably 20
A coating of about 40 μm is applied. More specifically, the coating can be applied by baking at a high temperature of about 120 to 1200 ° C.

The fluorescent substance to be baked may be any of fluorescent substances such as strontium aluminate, zinc sulfide and the like which emit light upon irradiation with ultraviolet light or ultraviolet rays. The baking is not a conventionally known various method.For example, a transparent inorganic aggregate, for example, the above-mentioned fine particle component is dispersed in a dispersion or a paste in which powder particles of a phosphorescent material such as strontium aluminate are dispersed. Can be mixed, dried and baked.

In the present invention, as described above, it is desirable that the size of the inorganic fine particle component is also specified. That is, as described above, the inorganic fine particle component is 5 to 70.
The size of the mesh. It is conceivable to change the size of fine particles depending on the presence or absence of color, etc. when it is desired to add color to the top or bottom using colored and non-colored ones. Mass use of some,
It should not be used as it will reduce the strength of the product.

On the other hand, the particle size of the fine component is set to 100 mesh under as described above. It must be able to penetrate between the particles of the fine component. More specifically, those having a size of about 150 to 250 mesh are preferable. What is important in the high-density artificial stone of the present invention is that it is basically desirable that these inorganic aggregate components are uniformly dispersed in any part of the product.

The resin component can be selected from a wide range of thermosetting resins. For example, acrylic resin, methacrylic resin, unsaturated polyester resin, epoxy resin and the like are exemplified. Above all, methacrylic resin is shown to be suitable in terms of transparency, hardness, strength and the like. The mixing ratio of such a resin component is 5% of the entire artificial stone.
0% by weight or less. This resin component wraps the fine-grained component and fine-grained component, which are the components that form the aforementioned skeleton, and contributes to binding the whole, and when the artificial stone is completed, the product has elasticity or tensile strength. There is a function to give. It is also considered to provide an optical function such as optical transparency.

If the resin component exceeds 50% by weight, the product becomes too plastic. On the other hand, if the resin component is excessively reduced, the appearance of the product close to the natural color may be increased, but the product becomes brittle and unsuitable for use. From such a viewpoint, it is more preferable that the resin component is 7 to 50% by weight, more preferably 12 to 50% by weight of the whole artificial stone.

If necessary, a curing agent or a curing accelerator up to about 2% of the resin amount, a silane coupling agent up to about 2% of the resin amount, and the like can be added to the resin. . The exterior surface of the artificial stone product can be polished or roughened. In practice, it is preferable that the broken fine grain component is exposed.

Polishing is a practically convenient method for exposing the surface of the dense texture of the high-density artificial stone having a sense of depth according to the present invention. Of course, a part of the surface of the artificial stone molded body may be polished to expose the fine-grained component, and a difference between the surface and the other part of the same surface may be used as a pattern. In the case of an artificial stone molded product, it is an important matter how to achieve a desired color tone and design. Granite and marble are one of the goals because natural products are difficult to obtain and the color and luster are beautiful. In the present invention, a glossy material such as granite or marble can be obtained by using a transparent fine particle component. This is because fine particles obtained by grinding quartz-based natural stone can be used as the fine particle component.

Fine particles obtained by grinding quartz-based natural stone are often colorless and transparent. Many are not transparent, but still retain some transparency. By adding an inorganic pigment, an organic pigment such as an azo pigment or a phthalocyanine pigment, or various dyes, it is possible to have a uniform color and a unique color tone with depth and gloss.

In the artificial stone composition of the present invention, a color can be imparted to a product by using a mixture of a fine colored component and a granular colored component having substantially the same size as the fine component.
In any case, color reproducibility can be secured much more easily than conventional artificial stones, and there is no discoloration, and a product excellent in depth and gloss can be obtained. The artificial stone luminescent molded body of the present invention, which also has excellent color tone characteristics as well as luminous properties and ultraviolet luminescent properties, can be formed into any shape such as plate, rod, cylinder, or special designed shape. It can be.

The artificial stone luminescent molded article of the present invention as described above can be manufactured, for example, by the following method. As a typical production method, a luminous or fluorescent substance having a luminous property or a luminescent property due to ultraviolet absorption as at least a part of the inorganic aggregate in a molding die and a transparent inorganic aggregate, or the luminous property described above. Or, inject a molding mixture with a resin containing a transparent inorganic aggregate whose surface is baked with a fluorescent substance and allow it to cure naturally, or remove the mold by injecting the upper mold and press-curing after injection. Further, a method for producing a light-emitting artificial stone molded body by polishing or, if necessary, roughening the surface with a water jet or the like is shown.

In the case of curing not by natural curing but by heating and compression together with the upper mold, for example, 5 to 100 kgf / cm
Press and compress with about ² surface pressures. In this molding, during compression, heating is performed at a temperature of approximately 90 to 140 ° C. for approximately 5 to 20 minutes. Such a method by compression molding is effective in mass production by using a relatively simple shape like a flat molded product as a molding method, and is excellent in economical efficiency because there is almost no loss of material.

In the production by the casting method described above,
The following embodiment is also possible. <1> A light emitting portion as a surface layer or a projection is formed only on the surface of an artificial stone or a resin plate or the like which has been formed in advance by using the artificial stone light emitting resin composition of the present invention. Integration with an artificial stone or resin plate as a substrate is also possible. <2> The artificial stone luminescent resin composition of the present invention is injected and integrated only into a preformed artificial stone or a groove provided in a resin plate.

All of these embodiments are included in the artificial stone luminescent molded article of the present invention. In addition,
The means for polishing the surface is not particularly limited, and the polishing can be performed using a tool such as a grindstone, a polishing cloth, a polishing belt, or an abrasive such as a buffing abrasive or a rubbing compound.

As the abrasive, diamond, boron carbide, corundum, alumina, zirconia mainly having a polishing action, tripoly, dolomite, alumina, chromium oxide, cerium oxide having a polishing action, etc. are appropriately used. . Then, in the present invention, the surface of the molded body after molding may be subjected to a roughening process so that the fine particle component is exposed on the surface portion.

As a method for this, first, a method for selectively removing the resin component is employed. That is, for example, after the mold is released from the mold, it is effective to blow the high-pressure water onto the surface of the molded article to perform the background processing. This processing is
Although it is not limited because it depends on various conditions such as a thickness, a distance from a nozzle, and a processing form, it is usually 2 to 20 c
In the case of a thickness of m, a water pressure of about 50 to 1400 kg / cm ² can be obtained from a nozzle height of about ² to 50 cm. This pressure is a lower water pressure condition than when natural stone is targeted.

That is, the presence of the resin makes it easier to perform high-quality processing. There is no particular limitation on the nozzle and system for jetting high-pressure water. Various things are adopted. By this ground surface processing, flattening or roughening by a water jet is realized, and an artificial stone having a deep texture is manufactured.

Due to the presence of the resin component, the surface does not become cloudy, and the treatment of the waste liquid becomes easier as compared with the etching method using a chemical. Of course, if necessary, the surface portion can be treated with an organic solvent to soften or melt the resin component to partially remove the resin component. The organic solvent in this case may be selected according to the resin component to be used. For example, halogenated hydrocarbons such as methylene chloride and chloroform, carboxylic acids such as acetic anhydride, ethyl acetate and butyl acetate, and ester compounds thereof. Or acetone, tetrahydrofuran, DMF, DMSO and the like.

The molded body is immersed in these organic solvents or
Or spray or flow down these organic solvents,
Surface irregularities can be formed by removing the softened or molten resin component from the surface. Alternatively, the unevenness may be formed by scraping a resin component having low hardness from the surface with a wire brush, cutting means, or the like.

After the surface is roughened by the various means described above and subjected to background processing, and the surface is polished as described above, a unique depth and glossy surface texture can be realized.
For example, in any of the above methods, when a transparent inorganic aggregate surface-coated with a luminescent or fluorescent substance is used as a resin molding mixture, the cross-section of the particles and the coating layer thereof is polished or the like. Is exposed.

By doing so, an artificial stone having excellent texture and texture as well as excellent light-emitting characteristics can be manufactured. That is, for example, assuming that the surface of the fine particle component is coated with a luminous or ultraviolet light-emitting substance, the fine particle component particles and the coating are exposed as a cross section by polishing the surface of the artificial stone. In this way, the light emitted from the outside enters from the exposed surface of the transparent fine particles and reaches the baked coating material inside.

In the case of a highly transparent methacrylic resin or the like, light transmission is generally improved. For this reason, the incident light penetrates into the inside of the light emitting section, and also emits light from inside. Therefore, light can be stored in a short time, and the luminous efficiency increases.

Hereinafter, embodiments will be described. Of course, the present invention is not limited by the following embodiments.

[0048]

EXAMPLES (Example 1) A resin molding mixture having the following composition was injected into a molding die. -30% by weight of transparent silica having an average particle size of 10 mesh-10% by weight of aluminum hydroxide having an average particle size of 250 mesh-10% by weight of strontium aluminate phosphorescent material having an average particle size of 325 mesh-Methyl methacrylate (MMA) (0 .15% peroxide-based curing agent) 45% by weight Yellow pigment 5% by weight The upper mold was placed, and the pressure was 15 kgf / cm ^{2 and} the pressure was 120%.
Pressed at a temperature of ° C for 20 minutes to cure.

A molded body having a thickness of 12 mm was obtained. This had luminous luminous properties over the entire thickness, and had an effect of being excellent in nighttime decorativeness and guideability in a dark field. In the daytime, it was a good artificial stone with a deep color tone. Example 2 A resin molding mixture having the following composition was injected into a molding die.

50% by weight of transparent silica having an average particle size of 14 mesh having a surface baking layer at a thickness of approximately 30 μm at about 1000 ° C. using a strontium aluminate phosphorescent material. 10% by weight of aluminum hydroxide having an average particle diameter of 250 mesh 10% by weight of methyl methacrylate (MMA) (containing 0.15% of peroxide-based curing agent) 30% by weight ^At a pressure of ² , 120
Pressed at a temperature of ° C for 20 minutes to cure.

Thereafter, the mold was removed to obtain an artificial stone light-emitting molded body having a thickness of 12 mm. The surface of this molded body was polished using a diamond grindstone. The obtained molded article had luminous light-emitting properties over its entire thickness, and had excellent functions as decoration and a position guide sign in a dark field environment. (Example 3) In Example 2, molding was carried out in the same manner by using the following composition as a resin molding mixture.

• 30% by weight of silica having an average particle diameter of 16 mesh provided at about 1000 ° C. with a thickness of 30 μm using a strontium aluminate luminous material • 10% by weight of silica powder having an average particle diameter of 250 mesh Strontium aluminate phosphorescent material powder with a particle size of 325 mesh under 20% by weight ・ Methyl methacrylate (MMA) (containing 0.2% by weight of peroxide-based curing agent) 40% by weight Diamond whetstone and silicon carbide agnesia whetstone Polishing using water jet pressure of 1200 kg / cm ² (nozzle diameter 0.8 mm, injection distance 35 mm)
Thus, only the resin portion on the surface was removed.

The resulting artificial stone had a depth at normal times and a non-slip function, and was visible for a long time in the entire thickness direction at night due to its light storage property. It could be used as an effective artificial stone as a building material for luminous guidance signs during an emergency blackout. (Example 4) In Example 1, a mixture having the following composition was used as a resin molding mixture and molded in the same manner.

-Transparent silica stone having an average particle size of 9 mesh 40% by weight-Aluminum hydroxide powder having an average particle size of 250 mesh 10% by weight-Strontium aluminate phosphorescent material having an average particle size of 325 mesh under 30% by weight-Methyl methacrylate (MMA) (Containing 0.15% peroxide-based curing agent) 20% by weight In the same manner, a molded article excellent in light emitting performance was obtained.

[0055]

As described above, the present invention provides an artificial stone having excellent light characteristics such as luminous properties, and having an excellent color depth and gloss. Moreover, the production of such excellent products can be realized at a much lower cost than conventional products.

Claims (5)

[Claims] 1. An artificial stone luminescent molded article comprising a luminous or fluorescent substance having a luminous property or a luminescence accompanying absorption of ultraviolet rays, and an inorganic aggregate and a resin, comprising:
It is characterized by containing up to 40% by weight of a resin, up to 40% by weight of a luminous or fluorescent substance having a luminous property or a luminescence accompanying ultraviolet absorption, and 10 to 65% by weight of a transparent inorganic aggregate. Artificial stone light-emitting molded body. 2. The ratio of the inorganic aggregate is 50 to 8 of the total weight.
The artificial stone luminescent molded article according to claim 1, wherein the molded article is 8% by weight and the proportion of the resin is 12 to 50% by weight of the total weight. 3. The artificial stone luminescent molded article according to claim 1, wherein the inorganic aggregate comprises a fine particle component having a size of 5 to 70 mesh and a fine particle component having a size of 100 mesh under. 4. An artificial stone luminescent molded article according to claim 1, wherein the luminous or fluorescent substance is a phosphorescent material. 5. The artificial stone luminescent molded article according to claim 1, wherein the resin is at least one of methacrylic resin, unsaturated polyester resin, epoxy resin and a mixture thereof.