JPH11292597A - Artificial stone formed body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the formed body which is excellent in luminescence performance in a dark field, e.g. at night and a luminescent section of which, in combination with the other non-luminescent base section of the body, normally provides a monolithic feeling as a whole and also which has excellent properties with respect to landscape and appearance. SOLUTION: This formed body 1 is provided with a luminescent section 4 used as a luminous or fluorescent indication guide, pattern, or the like, in at least a part of the body 1. The luminescent section 4 contains a transparent inorganic aggregate and a phosphorescent material or a luminous or fluorescent material capable of exhibiting luminescence with the absorption of ultraviolet rays, or contains transparent inorganic aggregate provided on its surface with a baked coating film of the above luminous or fluorescent material and also, is colored with an additive blend consisting of pigments or dyes so that the luminescent section 4 and the other non-luminescent section can not be discriminated from each other in a normal bright field.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The invention of this application relates to an artificial stone 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 stone, an optical function has been achieved 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 proposed to grant. This attempt involves mixing a resin component as a binder for artificial stone with a fluorescent substance and solidifying it, or mixing a resin, glass, etc. with a luminous fluorescent substance such as strontium aluminate or an ultraviolet fluorescent substance. It is made as an artificial stone by using solidified and crushed material as aggregate.

However, in the case of conventional luminous or fluorescent artificial stones, the phosphorescent action of the phosphorescent material or the like by any of the above methods is due to the binder exposed on the surface of the artificial stone. Except for the location where the resin component and the aggregate are arranged, there is a disadvantage that the phosphorescent material and the like contained in the artificial stone molded body 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 containing it was not practical in terms of cost.

Further, in the conventional case, since most of the light emitting layer covers the entire surface, only the guide figure or pattern indicating the direction and position required in a dark field environment at night is used as the light emitting layer. And almost none.
On the other hand, it has been considered that only such a guide figure or pattern is used as a light emitting layer. However, in the case of a conventional light emitting layer, adhesion to a substrate is poor, and the light emitting layer itself has poor wear resistance. Therefore, there is a problem that a required function is not performed due to peeling, falling off, abrasion and the like of the light emitting layer especially in floor use. In addition, when the conventional light-emitting layer is provided only as a guide figure or pattern, the color tone of the base material and the light-emitting layer at normal time is remarkably different. From the viewpoint of the landscape, there is a great restriction on the use and place of use of the artificial stone in which such a guide figure or pattern can be visually recognized normally.

For this reason, conventionally, the use and design of artificial stones having luminous or luminous properties are extremely limited due to high cost, luminous performance and physical performance, and further restrictions on the color tone composition. there were. Under these circumstances, luminous or fluorescent substances such as luminous materials are used only for the required figures and patterns to reduce the cost of the product, and also have excellent light-emitting functionality, and In addition to having excellent physical performance such as close contact with the base material and abrasion resistance, figures and patterns are not distinguished from the base material in normal times and are not visually recognized. A luminous or fluorescent light guide or night decoration, etc. in a dark field environment in which luminous or exothermic solids or patterns are clearly luminous and visible only at predetermined times such as dark field. It has been desired to realize a new artificial stone molded body which is useful as a material and has excellent design and landscape.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an artificial stone molded product having a main composition of an inorganic material and a resin, at least a part of which is intended to solve the above-mentioned problems. Is provided with a luminescent portion as a luminous or fluorescent instruction guide or a pattern, etc. This luminescent portion has a luminous or fluorescent substance having a luminous property or a luminescent property due to absorption of ultraviolet rays. It contains a transparent inorganic aggregate, or a transparent inorganic aggregate having the surface luminous or fluorescent substance baked on the surface, and the light-emitting portion and the other non-light-emitting portions have a normal bright field. Provided is an artificial stone molded product characterized by being toned by the addition and blending of a pigment or a dye so as to be indistinguishable below.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The invention of this application will be described in more detail below. The artificial stone molded object aimed at by the present invention can be exemplified and described with reference to, for example, FIGS. 1 and 2 in the drawings. In the case of FIG. 1, the artificial stone molded body (1) has a projection (3) on the plane of the substrate (2), and the projection (3) has a predetermined figure or pattern. It is arranged and formed so that it becomes. The protruding portion (3) is also a luminous or fluorescent light emitting portion having a luminous property or a luminous property due to ultraviolet absorption. The substrate part (2) itself does not have a light emitting property.

In the case of FIG. 2, the light emitting section (4) is embedded in the substrate section (2). In the daytime, the projection (3) as a light emitting unit as shown in FIG. 1 has a function of, for example, a Braille block, and in the nighttime, a direction and a position for guidance in a dark field environment and further for evacuation guidance. And the like can be provided with a function of a guide sign. FIG. 2 is also useful as a guide sign. Of course, it is also possible to configure nighttime decoration and the like.

An important point of the present invention is that the projection (3) as a light emitting portion or the embedded portion is provided under a normal bright field, that is, at a normal time when the field of view is bright due to illumination of sunlight or a fluorescent lamp. The light emitting part (4) and the substrate part (2) are in a state where they cannot be distinguished from each other as the color tone of the artificial stone. In the case of FIG. 1, even when the projection (3) as the shape is visually recognized, the projection (3) and the substrate (2) are normally visually recognized as an integrated artificial stone. .

In the case of FIG. 2, the embedded light-emitting portion (4) is normally distinguished neither in shape nor color tone, but is visually recognized as an artificial stone integrated with the substrate portion (2). It is. As described above, only the protrusion (3) and the embedded light-emitting portion (4) are selectively used as light-emitting portions, and under a normal bright field, the protrusion (3) and the embedded light-emitting portion (4). 4) is an essential feature of the present invention in that the color tone cannot be distinguished from the substrate portion (2) and can be visually recognized as an integrated artificial stone.

Of course, the present invention is not limited to the examples shown in FIGS. Needless to say, the artificial stone molded product of the present invention is provided as various application forms such as civil engineering building materials, interior materials, furniture materials, disaster prevention and the like. Various shapes, sizes, and colors are possible. For example, even in the case of a braille block having a protrusion as shown in FIG. 1, a light emitting portion is not provided on the protrusion (30), but a band-like embedded light emitting device is provided on the substrate (2) as shown in FIG. A part (20) may be provided.

Further, as shown in FIG. 4, the step board of the stage is made of artificial stone, and is embedded at its tip or provided with a light emitting portion (20) of a minute ridge, or as shown in FIG. It may be in various forms, such as a figure for guiding to a wall or the like, or a figure for evacuation guidance, or a letter formed by embedding as a light emitting part (20). In any case, the light emitting section (20)
In the dark field such as at night, light or light is emitted, and in the bright field, the substrate (2) and the light-emitting portion cannot be visually distinguished from each other, and are toned as an integral color tone.

This is extremely difficult in the prior art. The light-emitting unit has poor adhesion with the substrate,
Another major reason is that the light-emitting part itself has poor abrasion resistance.In addition, the idea that the normal color tone of artificial stone is integrated between the light-emitting part and the substrate part, and technical clues for that. There was a reason for that. In the present invention, such disadvantages of the prior art are overcome, the cost can be reduced by selective formation of the light-emitting portion, and peeling, falling off, and abrasion of the light-emitting portion as an instruction guide figure or pattern are suppressed. The present invention provides a new artificial stone molded product that is capable of integrating color tone as an artificial stone under a bright field and enabling night light or light emission under a dark field.

As for the composition of the artificial stone, in the present invention, as a basic component, any of the substrate portion (2) and the projection portion (3) of FIG. 1 and FIG. 2 and the embedded light emitting portion (4) are used. Contains an inorganic material and a resin. What is important in the present invention is that the luminous or fluorescent substance and the transparent inorganic aggregate or the luminous or fluorescent substance are used in the protrusion (3) as the luminous part and the buried luminous part (4).
It is intended to contain a transparent inorganic aggregate having a surface coating layer made of a luminescent or fluorescent substance.

As is clear from the above definition, the phrase "inorganic material" used in the present invention includes, as an inorganic substance which is a non-organic substance, <1> an inorganic material as an aggregate; Transparent inorganic aggregates and other inorganic aggregates <2> Luminescent or luminescent phosphorescent materials are included in the meaning.

In the "light emitting portion" of the present invention, <1
> A transparent inorganic material as an aggregate and <2> a luminous or luminescent phosphorescent material are always contained as at least a part of the "inorganic material". On the other hand, the non-light-emitting portion that does not emit light or emits light does not contain <2> a luminous or luminous luminous substance. In the artificial stone phosphorescent building and furniture material of the present invention including the light emitting portion, the suitable composition range is 50 to 95% by weight of inorganic material and 5 to 50% by weight of resin as a whole. The light emitting portion is preferably composed of a transparent inorganic material of less than 10 to 65% by weight, a luminous substance of 40% by weight or less, and other inorganic aggregates of 0 or 30% by weight or less based on the whole amount.

The composition may contain a small amount of a curing agent, a curing accelerator, or a curing retarder, if necessary.
Needless to say, a coloring agent, an antioxidant, a light stabilizer, an antibacterial agent, a flame retardant and the like may be further added. Examples of the inorganic aggregate include natural stones such as granite and metamorphic rock, minerals such as silica stone and mica, artificial inorganic substances such as aluminum hydroxide, calcium carbonate, silica, and alumina;
There are glass, metal, and the like, and among them, silica stone, glass, and the like are representative of the transparent inorganic skeleton. A typical example of the phosphorescent substance is a strontium aluminate-based substance. Those containing a rare earth element are also known, and these various phosphorescent substances as inorganic substances are used in the present invention.

The sum of the luminous or fluorescent substance and the transparent inorganic aggregate should be 50 to 95% by weight, more preferably 65 to 90% by weight of the whole composition of the light emitting portion. Appropriate. The same applies to the case where the light-emitting portion contains a transparent inorganic aggregate having a coating baked with a luminous or fluorescent substance.

Regarding the transparent inorganic aggregate and the other inorganic aggregate, a combination of the following two types is preferably exemplified. That is, one is a fine grain component having a size of 5 to 70 mesh (Tyler standard). 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 particles, components such as manganese dioxide, titanium dioxide, zirconium silicate, and iron oxide for adjusting the color tone, and trioxide (pentoxide) for imparting flame retardancy / incombustibility are provided. ) Components such as antimony, boron compounds and bromine compounds may be added and blended. Handles, handrails, doors, counters, easy to touch as building materials and furniture materials
For chairs, tables, toilets, etc., for example, Ag
Antibacterial components such as (silver), AgO, and Ag ion-supporting zeolite may be added and blended.

The above 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.

When the artificial stone molded body of the present invention is configured as a combination of a fine particle component and a fine particle component, the configuration of the light emitting portion can be considered as follows. <A> When a mixture of a luminous or fluorescent substance and a transparent inorganic aggregate is used, a transparent inorganic component is used as at least a part of the fine-grain component, and a luminescent material is used as at least a part of the fine-grain component. It is contemplated that luminescent or luminescent fluorescent materials will be used.

The fine-grain component as a transparent inorganic aggregate means that it is an inorganic component having substantially high light transmittance, 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. In the artificial stone molded product of the present invention, a luminous or fluorescent component having a luminous property of 100 mesh under or a luminescent property due to ultraviolet absorption is contained as a part of the fine particle component. Representative examples of such components include strontium aluminate-based phosphorescent materials and zinc sulfide. These various materials will be used in the present invention.

The size of the inorganic fine-grain component serving as an aggregate of artificial stone is assumed to be in the range of 5 to 70 mesh as described above. This is due to the combination with the inorganic fine-grain component. It is an indispensable requirement in. In the case of the luminous or fluorescent component, the luminous or fluorescent component has the same function as the fine particle component, and the luminous or fluorescent property is imparted to the artificial stone. It is preferable that the size of the luminous or fluorescent component is 100 mesh under, similarly to the fine particle component.

With respect to each of the above-mentioned inorganic components, the size and the mixing ratio are considered as important requirements. That is, in the artificial stone composition of the present invention, the weight of the fine component (W ₁ ), the weight of the fine component (W ₂ ),
The relationship with the weight of the luminous or fluorescent component (W ₃ )
As W ₁ / (W ₂ + W ₃ ), it is permissible in a wide range from 1/10 to 100 times or more, more preferably 1/1 to 100 times.
It is about 4/1.

As for 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 proportion of 100 times or more by weight. Is also 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 necessary for realizing physical properties such as strength, hardness, density and the like as artificial stone, and realizing an optical function such as luminous or fluorescent. In addition, the size of each component is specifically selected appropriately depending on the size and the mixing ratio of each component to be combined, but the fine component and the luminescent or fluorescent component are generally Is more preferably less than 200 mesh.

To further explain the light function of the artificial stone, in the artificial stone of the present invention, the light function is that light emission is enabled as thick light. 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 means that the use of the transparent inorganic fine-grain component as the 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. Since the luminescent layer, which is absorbed by the luminous luminous component and in which the luminous or fluorescent component composed of luminous material or the like is dispersed, is secured as a large thickness including the inside of the artificial stone, it can be used for a long time. This is because the luminous intensity can be maintained. 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, but it may be 100% depending on the physical performance such as the strength of the artificial stone and the appearance and design. 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. <B> In the case of using a transparent inorganic aggregate whose surface is baked with a luminous or fluorescent substance, in the present invention, the fine-grained component is at least partially transparent and has a luminous property on its surface. Or a luminous substance such as a luminescent substance or a luminescent substance that emits light due to ultraviolet absorption. 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, 10% to 100% (by weight) of the fine-grained component should be a transparent inorganic aggregate having a surface coating layer of the luminous substance or the fluorescent substance. preferable. In the case of transparent inorganic aggregates, especially baking coating of fine-grained components, several μm
To several tens μm, for example, 5 to 50 μm, more preferably 2
A coating of about 0 to 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 light. 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, about 150 to 250 mesh is preferable. What is important in the high-density artificial stone of the present invention is that, except for special cases, it is 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. It is considered that the mixing ratio of the resin component is 50% by weight or less, for example, 20% by weight or less, or 12% by weight or less based on the whole composition. 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.

On the other hand, if the resin component exceeds about 50%, the product becomes plastic, and the artificial stone is no longer just an apparent name. 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, the resin component is more preferably 5 to 5.
It should be 50% by weight.

In addition, a curing agent or a curing accelerator, a silane coupling agent, or the like up to about 2% of the resin amount can be added to the resin, if necessary. Also,
Although not particularly described, the resin may be not only a homopolymer but also various copolymers. For example, the artificial stone molded body of the present invention having luminous or luminous properties is produced by the composition as described above. In the present invention,
The light emitting part and the other non-light emitting part, for example, the projection part (3) and the substrate part (2) in the example of FIG. 1, and the embedded light emitting part (4) and the substrate part (2) in the example of FIG. In addition, it is an essential requirement that the toner be toned by the addition and blending of a pigment or a dye so that it cannot be distinguished in a bright field by ordinary sunlight or illumination. Only in a dark field at night or the like, a light-emitting portion such as an instruction guide figure or pattern, that is, a light-emitting portion as a figure or pattern whose area or spatial arrangement is divided from the substrate emits light (night light) and is illuminated during the daytime or illuminated In the bright field in a state where the light is emitted, these light emitting portions are toned so as to be indistinguishable from other substrate portions.

This toning is enabled by, for example, the following means. Addition and blending of pigments or dyes Toning by adding and blending pigments or dyes under the conditions and applications where the artificial stone molded product is used, that is, under bright-field conditions. After a predetermined amount is added, a predetermined amount is added and compounded during the production of the molded article. For example, the toning is performed under a bright field condition of 200 Lux. To explain this toning, for example, referring to the example of FIG. 2, a sample of the substrate portion (2) having an embedded groove is prepared in advance, and a mixture (resin, inorganic material) having a composition corresponding to the light emitting portion (4) is prepared. The selection of a pigment or dye for color matching with the sample of the substrate part (2) and the determination of the addition amount thereof are performed under a bright field of 200 Lux.

The required amount of the required pigment or dye determined in this manner is added and used at the time of actual production of a molded article. Pigments and dyes can be appropriately selected from conventionally known various inorganic or organic substances. It is needless to say that it is desirable that these have high transparency in the thickness direction of the molded article in view of the purpose and function of the artificial stone molded article of the present invention.

Examples of pigments and dyes include the following. As inorganic pigments, white zinc oxide, zirconium oxide, titanium oxide, calcium carbonate, barium sulfate; yellow chrome yellow (PbCr)
O ₄ ), cadmium yellow (CdS.nZnS); red iron oxide cadmium red (CdS.nCdS)
e), molybdenum red, blue-based potassium ferrocyanide, cobalt blue (CoO.nAl ₂ O ₃ ); organic pigments and dyes include azo-based compounds; cumarone-based compounds; phthalocyanine-based compounds; and the like.

Since the amounts of these additions differ depending on the type and the size of the required portion of the molded article, they may be determined at the stage of the toning. Regarding the artificial stone molded product of the present invention, which is formed by being toned as described above, it is desirable that the outer surface of the product is 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 artificial stone having a deep feeling of the present invention. Of course, a part of the surface of the product can be polished to expose fine-grained components, and the difference from other parts of the same surface can be used as a pattern. In the case of obtaining artificial stone, what the target color tone and design property are is an important problem in relation to the toning.
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 grains obtained by grinding quartz-based natural stones 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, it is also possible to give a color to a product by mixing and using, as a color component, a granular colored component having substantially the same size as the fine particle 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 high-density artificial stone of the present invention, which has excellent color tone characteristics as well as luminous properties and ultraviolet light-emitting properties, can have any shape, such as a plate, a rod, or a cylinder.

The artificial stone molded product of the present invention as described above can be manufactured, for example, by the following method. <I> Molded Body Using Projection as Light-Emitting Part FIG. 6 illustrates a typical manufacturing method of the artificial stone molded body (1) as illustrated in FIG. 1 using the projection (3) as the light-emitting part. It is a process drawing.

That is, FIG. 6 shows that a projection (3) for a figure or a pattern is integrally formed on a plane portion of a substrate portion (2), and the main composition is made of an inorganic material and a resin. At least a part of 3) shows a method for manufacturing an artificial stone molded body which is a luminous or fluorescent light emitting portion. The groove (51) of the molding die (5) having a groove (51) corresponding to the molded body projection (3) on the inner bottom surface has a light storing property or a light emitting property due to ultraviolet absorption as at least a part of the inorganic aggregate. Injection of a resin molding mixture (6) containing a luminous or fluorescent substance and a transparent inorganic aggregate having the luminous or fluorescent substance or a transparent inorganic aggregate whose surface is baked with the luminous or fluorescent substance; Next, the resin molding mixture (7) containing the inorganic aggregate is poured into the molding die (5) and naturally cured, or the mixture is demolded by press-curing under conditions such as heating and pressing. Manufactures an artificial stone molding (1) having a light-emitting portion only in the projection (3) by polishing or roughening the surface by a water jet or the like as necessary.

In the curing together with the upper mold (8), compression is performed by pressing with a surface pressure of, for example, about 5 to 100 kgf / cm ² . In this molding, approximately 90 to 14
Heat to 0 ° C. for about 5-20 minutes. Projection (3)
A resin molding mixture (6) forming a light emitting portion as
The resin molding mixture (7) forming the substrate part (2)
It will be integrally molded by the above-mentioned hardening process by compression. Therefore, there is no peeling or falling off of the light emitting portion projection (3). Moreover, the projection (3) is also formed as having excellent wear resistance due to its composition. In the above molding, the toning of the sample is performed in advance, for example, under a bright field condition of 200 Lux, the resin molding mixture (6) for the protrusion (3) and the substrate (2)
With the resin molding mixture (7) so that the projections (3) and the substrate (2) have an integral shape that cannot be distinguished in their color tone under a 200 Lux bright field after the curing molding. Be colored. This toning is performed by adding pigments and dyes.

The method of natural hardening or compression molding is effective in mass production by molding a relatively simple shape such as a flat molded product, and has excellent economical efficiency because there is almost no loss of material. It is. 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, high quality processing can be easily performed by the presence of the resin component. 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 and ground by the above-described various means, and the surface is polished as described above, a unique depth and glossy surface texture can be realized. <II> Molded Body Using Buried Groove Portion as Light-Emitting Part FIG. 7 illustrates a typical method of manufacturing an artificial stone molded body (1) as illustrated in FIG. 2 using the embedded light-emitting portion (4) as a light-emitting portion. FIG.

That is, FIG. 7 shows that the embedded light emitting portion (4) for a figure or pattern is integrally formed in the plane portion of the substrate portion (2), and the main composition is composed of an inorganic material and a resin. Part (4) shows a method for producing an artificial stone molded body having luminous or fluorescent properties. A resin molding mixture (7) containing an inorganic aggregate is injected into a molding die (5) having a projection (52) corresponding to the molded body embedded light emitting part (4) on the inner bottom surface, and cured or semi-cured to remove. A luminous or fluorescent substance and a transparent inorganic aggregate having a luminous property or a luminous property due to ultraviolet absorption with respect to the groove formed on the surface of the molded article, or the luminous or fluorescent substance described above. A resin molding mixture (6) containing a transparent inorganic aggregate whose surface has been baked is injected and cured to produce an artificial stone molded body (1) having a light emitting portion only in the embedded light emitting portion (4). To manufacture.

In the case of this method as well, the curing by compression molding can be carried out in the same manner as in the above-mentioned method, and the molded body (1) is finally polished or roughened as appropriate. Is done. Mixture for resin molding (6) (7)
Will be similarly integrated. In the above-mentioned molding, the resin molding mixture (6) (7) is, for example, in a 200 Lux bright field under the substrate (2).
And the light-emitting portion (4) are integrated so as to be integrated without being distinguished in the color tone.

For example, in any of the above methods <I> and <II>, when a transparent inorganic aggregate whose surface is coated with a luminescent or fluorescent substance is used as the resin molding mixture (6), The cross section of the particles and the coating layer is exposed by a treatment such as polishing. 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-grained component is coated with a luminous or ultraviolet-emitting substance, the fine-grained component particle and its 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. Light can be stored in a short time, and luminous efficiency also increases. Hereinafter, examples will be described. Of course, the present invention is not limited by the following embodiments.

[0062]

(Example 1) An artificial stone molding was manufactured according to the method shown in FIG. That is, first, the following composition <A> was prepared as a sample for the resin molding mixture (6) for forming the projections (3) as the light emitting part.

-50% by weight of transparent silica stone having an average particle size of 10 mesh-25% by weight of aluminum hydroxide having an average particle size of 250 mesh-25% by weight of strontium aluminate phosphorescent material having an undersize of 325 mesh-Methyl methacrylate (MMA) (Containing 0.15% of peroxide-based curing agent) 10% by weight The following composition <B> was prepared as a sample for the resin molding mixture (7) forming the substrate (2).

-60% by weight of transparent silica having an average particle size of 10 mesh-10% by weight of silica powder having an average particle size of 250 mesh-20% by weight of aluminum hydroxide having an average particle size of 250 mesh-Methyl methacrylate (MMA) (peroxide 10% by weight The composition <A> and <B> were color-matched under a bright field of 200 Lux. For color matching, zirconium oxide was used as a white pigment. 0.0005% by weight of the total amount for the composition <A> and 0.001% by weight of the total amount for the composition <B>. It has been found that the formulation is optimal for forming a unity of color tone.

Therefore, an artificial stone molded product was manufactured using the resin molding mixtures (6) and (7) in which the pigments were blended in the above manner. In this production, first, the resin molding mixture (6)
Was injected into a groove (51) having a depth of 6 mm in the mold (5). Next, the resin molding mixture (7) was injected into the molding die (5).

The upper die (8) is placed, and 12 kgf / cm
Pressed at a pressure of ² at a temperature of 120 ° C. for 20 minutes to cure. After that, it was released from the mold, and the thickness of the substrate (2) was 20 m.
m, a protrusion (3) and an artificial stone molded product (1) having a height of 6 mm were obtained. The surface of the projection (3) of this molded body (1) was polished using a diamond-based grindstone, and the height was 5 mm.
And

The molded article (1) obtained had the polished projections (3) having a luminous luminescent property and an excellent function as a position guide sign in a dark field environment. In a bright field environment of about 200 Lux, the molded article (1) has no difference in color tone between the projection (3) and the substrate (2), and has an integral shape, and is excellent in decorativeness. It was beautiful even in the daytime. In addition, the protrusion (3) could be used as a Braille block for a blind person due to its shape characteristics.

In a test according to Japanese Industrial Standard JIS K-7112, the specific gravity was 2.28. The water absorption is
0.13%. As shown in Table 1, the properties of the protrusion (3) in the region where the substrate (2) and the protrusion (3) were integrated were excellent in hardness, wear resistance, and the like.

[0069]

[Table 1]

Also, acid resistance by soaking in a 3% aqueous solution of hydrochloric acid for 8 hours and soaking in a 3% aqueous solution of sodium hydroxide for 8 hours,
No abnormality was found in the alkali resistance test. (Example 2) In Example 1, a mixture having the following composition was used as the resin molding mixture (6) and molded in the same manner.

50% by weight of silica having an average particle size of 10 mesh and 50% by weight of silica powder having an average particle size of 250 mesh provided at a temperature of about 1000 ° C. with a thickness of 30 μm by using a strontium aluminate phosphorescent material. Strontium aluminate luminous material powder having an average particle size of 220 mesh 20% by weight ・ Methyl methacrylate (MMA) 10% by weight (containing 0.2% by weight of peroxide-based curing agent) Polished using a silicon carbide agnesia grindstone, and further 1200 kg / cm ²
At a water jet pressure of (nozzle diameter 0.8 mm, injection distance 35 mm), only the resin portion on the surface was removed.

The obtained artificial stone usually had a depth and a non-slip function, and at night, it was visible for a long time in the entire thickness direction due to its light storage property. In a bright-field environment, there was no difference in color tone between the projection (3) and the substrate (2), and the projections (3) and (2) were integrated. It could be used as an effective artificial stone as a building material for luminous guidance signs during an emergency blackout. (Example 3) The resin molding mixture of Example 1 (6) (7)
By using the method shown in FIG. 4, an artificial stone molded body having a thickness of 16 mm and having the embedded light-emitting portion (4) having a depth of 4 mm as a light-emitting portion was obtained by the method of FIG.

The surface was polished with a diamond grindstone. A molded article excellent in both physical performance and light emission performance was obtained.
Under the bright field, the embedded light emitting portion (4) was not visible at all, and the sense of unity with the substrate (2) was excellent.

[0074]

As described above, according to the present invention, excellent physical properties such as luminous properties, and excellent color tone with depth and gloss, and good physical properties without problems such as peeling, falling off, and abrasion of the light emitting portion. Artificial stones with special characteristics are provided. What is most characteristic is that, in the artificial stone molded body of the present invention, the light-emitting portion as a guide figure or pattern has excellent visibility due to the night light or light emission under a dark field such as at night, In addition to being excellent in instruction guide functions such as position, direction, display, etc., and decorativeness, on the other hand, under bright field, the color tone of the light emitting part is completely indistinguishable from the substrate and has a sense of unity, It is also extremely excellent in landscape and appearance design. Moreover, the production of such excellent products can be realized at a much lower cost than conventional products.

[Brief description of the drawings]

FIG. 1 is a cross-sectional perspective view illustrating a molded body having a projection (3).

FIG. 2 is a cross-sectional perspective view illustrating a molded body having an embedded light emitting unit.

FIG. 3 is a plan view showing an example different from FIG. 1 and having a projection and a strip-shaped embedded light emitting unit.

FIG. 4 is a perspective view illustrating an example of an arrangement of a light emitting unit on a stair tread.

FIG. 5 is a plan view showing an example in which a display figure and a character have a light emitting portion.

FIG. 6 is a manufacturing process diagram of the example of FIG. 1;

FIG. 7 is a manufacturing process diagram of the example of FIG. 2;

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Molded body 2 Substrate part 20 Light emitting part 3 Projecting part 30 Projecting part 4 Light emitting part 5 Mold 51 Groove 52 Projecting part 6, 7 Mixed resin for resin molding 8 Upper mold

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Claims (8)

[Claims] 1. An artificial stone molded body having a main composition of an inorganic material and a resin, at least a part of which is provided with a luminous or fluorescent light emitting portion, and the light emitting portion has Is
It contains a luminous or fluorescent substance and a transparent inorganic aggregate having a luminous property or a luminous property accompanying ultraviolet absorption, or a transparent inorganic aggregate in which the luminous or fluorescent substance is baked on the surface. The artificial stone molded body is characterized in that the light-emitting portion and the other non-light-emitting portion are toned by the addition and mixing of a pigment or a dye so that they cannot be distinguished in a normal bright field. 2. The artificial stone molding according to claim 1, wherein the luminous or fluorescent substance is a phosphorescent material. 3. The artificial stone molding according to claim 1, wherein the transparent inorganic aggregate is glass, quartz stone or silica stone. 4. The resin according to claim 1, wherein the resin is a methacrylic resin.
Or the artificial stone molded body according to any one of the above-mentioned items 3 to 3. 5. The artificial stone molded product according to claim 1, further comprising 5 to 50% by weight of a resin and 50 to 95% by weight of an inorganic material. 6. The artificial stone molded product according to claim 1, wherein the light emitting portion contains up to 40% by weight of a luminescent or fluorescent substance. 7. The artificial stone molded body according to claim 1, wherein the light emitting section is visually recognized only in a dark field as an instruction guide figure or pattern. 8. The artificial stone molding according to claim 1, which is toned by adding a pigment or a dye.