JPH0232226B2 - TAIKAJINZOSEKINOSEIZOHO - Google Patents

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method for producing fire-resistant artificial stone, and more specifically, it has a color pattern and pattern far superior to natural stone, and is different from artificial stone. This article relates to a method for producing artificial stone, which has an incredible naturalness and is particularly superior in terms of fire resistance, making it suitable for decorative wall materials for buildings, lobby walls, floorboards, etc.

[Problems to be solved by conventional technology and invention]

Conventionally, the common method for manufacturing artificial stone is to mix colored white cement with crushed natural stone and mold it. It looks like stone, and its appearance is inferior. Another drawback is that it requires a considerable process for cement curing.

On the other hand, by using synthetic resin, a composition consisting of a printed board or crushed pieces and a thermosetting resin is cast onto a flat plate, and after waiting for the crushed pieces to settle, paper, cloth, glass can be applied as it is or on top of it. A method of curing the resin by attaching a reinforcing material such as a fiber or a rigid plate has already been proposed. However, since a large amount of resin is used in this method, the resulting product lacks naturalness, does not have a sufficient filling feeling, and has the drawbacks of increased cost. In particular, the most serious drawbacks include poor fire resistance and the tendency to generate toxic gases. Furthermore, it is inconvenient to install at a construction site because the base must be sufficiently dry, and even if it is carefully installed using a special adhesive, it will not be easy to install at a later date. There is a problem that it may peel off.

Therefore, the main object of the present invention is to create a man-made structure that has extremely excellent fire resistance, can be easily and completely applied to the construction site, and has a pattern that closely resembles natural marble or natural stone. An object of the present invention is to provide a method for manufacturing stone or decorative artificial stone slabs.

Another object of the present invention is to create creatively beautiful colors, patterns, stripes, and wavy irregularities that are not found even in natural stones.
An object of the present invention is to provide a method for manufacturing artificial stone or decorative artificial stone slabs having a free shape.

Another object of the present invention is to provide a method for producing strong artificial stone or decorative artificial stone slate which has more favorable properties than natural stone in terms of physical and chemical properties such as specific gravity, strength, weather resistance and chemical resistance. There is a particular thing.

[Means to solve the problem]

According to the present invention, in order to achieve the above object, at least one kind of granular material selected from crushed natural stone, crushed ceramic pieces, and glass pieces, and 2 to 20 parts by weight of liquid heat per 100 parts by weight of the granular material are used. A composition containing a curable resin is loaded onto a substrate or a mold, vibration or centrifugal rotation is applied to the substrate or mold depending on its cross-sectional shape, and the cement composition is poured or cast in layers to harden the bond. Provided is a method for producing refractory artificial stone characterized by:

[Action/effect of the invention]

In order to enhance the fire resistance of artificial stone, it is better to use as little resin as possible to bind granular materials such as crushed stone grains. However, it is quite difficult to uniformly mix a small amount of resin, such as 2 to 20 parts by weight, with 100 parts by weight of granules such as crushed natural stone. Particularly when the amount of resin used is relatively small and/or when the granules used contain a considerable amount of fine fractions, it is difficult to adjust the mixing. Therefore, in the method of the present invention, depending on the cross-sectional shape of the substrate or mold to which the composition is loaded, vibration is applied if the substrate or mold is flat, and centrifugal rotation is applied if the cross-section is arcuate. This ensures that the resin liquid is evenly distributed between each particle and that the granules are evened out.

Furthermore, in the method of the present invention, a cement composition is further poured or cast in layers while the granules are embedded in the resin, which further improves fire resistance and makes it easier to apply the cement to the construction site. This makes it easy and reliable.

In this way, according to the method of the present invention, it is possible to easily and reliably attach artificial stone to the construction site, as well as to have extremely excellent fire resistance, and also to have a beautiful appearance and a heavy feeling. Moreover, it can be manufactured economically. Furthermore, it has better physical and chemical properties than natural stone, and has the advantage of being able to freely create beautiful colors, patterns, stripes, waves, uneven shapes, etc. that are not found even in natural stone. is obtained.

[Aspects of the invention]

Although any natural stone can be used in the method of the present invention, preferred raw stones include marble, granite, serpentine, vermiculite, and quartzite. Although the particle size of these crushed natural stone blocks is not critical, particles finer than about 1 mesh are generally used in practice. Also, to obtain an attractive product, the particle size of the crushed agglomerates is preferably coarser than about 100 meshes, although fractions of about 200 meshes or finer may be present. Rather, when relatively coarse crushed pieces are used,
The presence of fractions finer than about 200 meshes in an amount of about 5% by weight or less of the entire crushed mass initially used has the advantage of suppressing the "separation" phenomenon of the product. In the method of the present invention, glass and/or ceramic fragments of appropriate particle size can be used in addition to or in place of crushed natural stone, but it is generally not advisable to use large amounts of these. Not recommended.

Various thermosetting resins can be used in the method of the present invention. Unsaturated polyesters dissolved in vinyl or allyl monomers are among the preferred thermosetting resins that can be used in the process of the invention. Unsaturated polyesters include unsaturated dibasic acids such as maleic anhydride, fumaric acid, itaconic acid and citraconic acid or their acid anhydrides, ethylene glycol, propylene glycol,
1,3-butylene glycol, 2,3-butylene glycol, 1,4-butylene glycol, 2,
Examples include those produced by condensation with glycols such as 2-diethylpropanediol, diethylene glycol and dipropylene glycol.

In the production of unsaturated polyester, an addition compound of an unsaturated dibasic acid and a diene may be used in place of all or part of the unsaturated dibasic acid.

Succinic acid, adipic acid, sebacic acid, phthalic anhydride, isophthalic acid, chlorophthalic anhydride, cis-3,6-endomethylene-△-tetrahydrofuranic acid in place of a part of the unsaturated dibasic acid or its acid anhydride. Unsaturated polyesters prepared using saturated dibasic acids or anhydrides, such as anhydrides and HET acids, as the dibasic acid component can also be used in the process of the present invention. Furthermore, in addition to the acid component and the glycol component, the unsaturated polyester that can be used in the method of the present invention includes alcohols such as allyl alcohol, decyl alcohol, tetrahydrofurfuryl alcohol, glycerin, pentaerythritol, sorbitol, and/or benzoic acid and stearin. Acids such as acids can be included as modifying components.

These unsaturated polyesters are used dissolved in vinyl or allyl monomers, usually at a concentration of 50-90%. Examples of vinyl monomers include styrene, α-methylstyrene, vinyltoluene, divinylbenzene, vinyl acetate, and methyl methacrylate; examples of allyl monomers include diallyl phthalate, triallyl cyanurate, and diallylbenzene phosphonate. obtain.

Another group of thermosetting resins that can be effectively used in the method of the invention include epoxy resins such as 2,2-
It is a precondensation product of a phenol such as bis(4'-hydroxyphenyl)propane or bisphenol A and epichlorohydrin.

These polyester resins or epoxy resins are used with appropriate proportions of curing catalysts.
Those skilled in the art can easily select an effective curing catalyst and the proportion thereof for the resin used. Usually, curing catalysts for unsaturated polyester resins and acrylic resins include hydroxyheptyl peroxide, methyl isobutyl ketone peroxide, methyl ethyl ketone peroxide, 1-hydroxycyclohexyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, t -butyl hydroperoxide,
Methyl acyl ketone peroxide, lauroyl peroxide, benzoyl peroxide, t
-butyl permaleate, t-butyl perbenzoate, di-t-butyl di-perphthalate,
t-butyl perphthalate, p-chlorobenzoyl peroxide, dibenzal peroxide,
Di-t-butyl peroxide, 2,2-bis(t-butylperoxy)butane and 2,2'-
Compounds such as azobisisobutyronitrile can be used in proportions of up to 5% by weight, preferably at least 0.01% by weight, based on the resin. Furthermore, along with a curing catalyst,
Promoters such as cobalt naphthenate, stannous chloride, dimethylaniline, N-methylaniline, maleic anhydride, benzoin, bis(4-dimethylaminophenyl)methane, triethanolamine, dodecylmercaptan, and 1,2-diaminopropane. A small amount of agent, for example, about 3% by weight based on the resin.
It is preferable to use the following amounts together.

For epoxy resins, curing agents such as diethylaminopropylamine, dimethylaminopropylamine, diethylenetriamine, 2,3,5-tri(dimethylaminomethyl)phenol, m-phenylenediamine, dicyandiamide, diethylamine, pyridine, piperidine and melamine are used. The catalyst is used in a proportion of 3 to 20% by weight based on the amount of resin.

Furthermore, the cement that can be used in the method of the present invention may be a combination of one or more of blue cement, white cement, lime, and gypsum. Further, these cements and the like can be freely colored with pigments, dyes, etc. Further, fillers can also be mixed and used. Examples of fillers for cement include calcium carbonate, magnesium carbonate, china clay,
Preferably, one or more fillers such as talc, silica, diatomaceous earth, clay, crushed stone powder, and crushed porcelain powder are blended.

Substrates or formworks include steel plates, Alkyast, aluminum plates, wooden molds, glass plates, plaster molds, rubber plates,
Either silicone rubber or synthetic resin molds can be used depending on the size of the desired product. The partition plate is preferably a plate with high thermal conductivity for the purpose of preventing heat retention during curing and making the curing ratio uniform. Incidentally, it is also possible to draw irregular shapes, engraved patterns, etc. using the form board and the substrate.

A mold release agent (silicone resin, polyvinyl alcohol, paraffin, wax, etc.) is usually coated or baked on the substrate, formwork, and partition plate.

In the method of the present invention, first, the above-mentioned granules are
A composition is prepared containing 2 to 20 parts by weight, preferably 5 to 20 parts by weight of the resin per 100 parts by weight. Since the granulate is mixed with a relatively small amount of hydrophobic resin, it must be well dehydrated before mixing. Although dehydration can be accomplished by hot air drying, it is preferred to wet the dry surface with a vinyl monomer such as styrene. Furthermore, crushed natural stone blocks and the like can be washed with dilute acid prior to drying. Dilute hydrochloric acid or dilute sulfuric acid is suitable for cleaning crushed marble, but commercially available industrial sulfuric acid is
Particularly preferred is a mixed solution consisting of 3 parts by volume of a diluted product and 7 parts by volume of a commercially available hydrogen peroxide solution diluted about 10 times. On the other hand, for cleaning crushed granite blocks, a mixed acid of phosphoric acid and oxalic acid (approximately 6:4) or hydrofluoric acid are suitable. Generally, the effect of pre-treating crushed pieces with dilute acid is that a fairly clear pattern appears on the surface of the product even without final polishing, but the surface gloss when final polishing is Inferior to polished products that were not pretreated with dilute acid. Therefore, pretreatment with a dilute acid is preferable for products with complex surface shapes that are difficult to polish, but is preferable for products with flat surfaces that are easy to polish. Not necessarily desirable. In addition, yellowing of the resin on the surface can be eliminated by spraying and blasting a sand-like material such as iron sand, diamond sand, or silica sand onto the surface instead of polishing it to give it a decorative finish.

According to the method of the present invention, 100 parts by weight of the granules are first mixed with 3 to 7 parts by weight of resin, and then an additional amount of resin is added and mixed to give 5 to 20 parts by weight per 100 parts by weight of the granules. It is also possible to form a composition containing parts by weight of the above resin. In this case, the resin component mixed first may not contain a curing catalyst. Further, additional resin and filler to be added and mixed later can be further added and mixed or laminated in two or more operations.

The composition consisting of 100 parts by weight of granules and 2 to 20 parts by weight of resin is cast onto a substrate that has been subjected to mold release treatment or into a mold. Preferably, the substrate surface is a flat surface, a corrugated surface, or the inner surface of a cylinder. When a flat plate or an equivalent sheet plate is used as the substrate surface, the substrate or mold is vibrated after casting. This vibration usually has an amplitude of 2 to 5 mm.
This can be done by giving 100 to 500 times/minute. Furthermore, when the inner surface of a cylinder is used as the substrate surface, the cylinder is centrifugally rotated at high speed around the axis. The rotation speed also depends on the diameter of the cylinder used, but when using a cylinder with a diameter of about 20 cm, a rotation speed of about 150 to 600 rpm is suitable. During this vibration or rotation step, a large number of air bubbles are observed to form on the surface of the layer of composition on the substrate surface that is not in contact with the substrate surface, and are degassed from the surface. In this case, if the required amount of resin is mixed with the granules in two or more addition operations as described above,
The time required for defoaming is considerably reduced.

Furthermore, colorants and fillers may be added to the resin described above. Fillers that can be used in the method of the present invention include, for example, calcium carbonate, magnesium carbonate, china clay, talc, gypsum, silica, diatomaceous earth, clay, talc, asbestos, mica powder, alumina,
It is preferred to incorporate one or more fillers such as crushed stone chips, glass powder, crushed porcelain powder, glass fibers and metal powder. Further, glass powder, metal powder, stone powder, and coloring agent may be bonded with unsaturated polyester resin or acrylic resin, solidified into a single piece, and then pulverized and used as a filler. The type of filler and its blending ratio depend on the intended use or place of use of the final product. For example, calcium carbonate, magnesium carbonate, silica, diatomaceous earth, gypsum, talc, china clay, etc. help reduce the price of the product, mica powder increases electrical insulation, and alumina improves thermal conductivity and reduces heat generation during curing. Prevents cracks, fiber powder increases the mechanical strength of the product and prevents cracks from forming due to shrinkage during curing. Especially when the product requires mechanical strength, Mildoff Cyber (about 1/32 to 1/4 length) is recommended.
10 to 20% by weight of antimony oxide is added, and 5 to 10% by weight of antimony oxide is added when imparting flame resistance. Crushed natural stone, glass pieces, metal powder, crushed porcelain blocks, etc. have the function of imparting color and/or weight to the product. The maximum amount of filler that can be added will vary depending on the type and size of the filler and the desired properties of the final product, but may be as high as 95% by weight of the resin composition. It is also possible to pre-color the crushed pieces.

In the method of the present invention, it is necessary to use at least two types of granular resin compositions in order to embody a pattern on the product. However, it is sufficient that they differ in any one of the colors, the quality and quantity of the filler blended, etc.
The resin components themselves may be the same.

If the amount of filler used is relatively large, after charging the composition into each compartment, apply vibration to the entire formwork,
It is best to allow the resin to seep out to the surface.
By doing so, a product without pinholes can be obtained. Further, the interface between the two types of resin compositions to be charged does not necessarily have to be a horizontal plane. If desired, the interface can be artificially disturbed to change the pattern that is to appear on the product. It is also possible to charge the second resin composition or cement mixture composition after the surface of one resin layer has gelled.

If a reinforced product is desired, it is also possible to obtain a product in which steel wires, pipes, etc. are previously held in compartments as bone reinforcing materials and filled with them. Inserting a pipe also has the advantage of reducing the weight of the product.
It is also possible to back the resulting product with a concrete or slate board or the like with an adhesive. Incidentally, it is also possible to create an integrated product by directly combining them.

Conventionally, it has been believed that synthetic resin liquids are absolutely unable to combine with water. However, by combining it with cement liquid, the present invention has strong fire resistance and can prevent the generation of toxic gases, is considerably inexpensive, and can be completely attached to the construction site at the site. can be completed easily and quickly. In addition, on-site casting finishing can be performed directly on-site. All of this can be attributed to the bonding of the cement liquid.

To further increase the bond between the resin liquid and the cement liquid under the above conditions, use a water-soluble organic filler or adhesive such as vinyl acetate emulsion strong adhesive (BOND), BOND flame retardant CR-1004, glue, etc. If one or more types of inorganic fillers or binders such as water glass and bittern are mixed, it is highly effective in bonding the mixed resin liquid and cement liquid, and is particularly preferred when strength is required.

〔Example〕

Next, the present invention will be explained with reference to Examples. Parts represent parts by weight unless otherwise specified.

Example 1 In this example, crushed marble stone having the following grain size was used which had been thoroughly washed and dried.

2 to 3 meshes Approximately 30 parts by weight 3 to 9 meshes Approximately 30 parts by weight 9 to 25 meshes Approximately 20 parts by weight 25 to 60 meshes Approximately 10 parts by weight 60 meshes or less Small quantity Add 100 parts by weight of the above crushed stone to Epolack G110AL (Nippon Shokubai Chemical Industry Co., Ltd.) Co., Ltd. products, polyester resin)
8 parts by weight and 0.04% of promoter OCO, and further mixed with 4 parts by weight of calcium carbonate and 0.7% of catalyst CAT-M.

Next, a wooden frame of the desired size is assembled on the smooth glass plate (coated with a mold release agent and dried), the resin composition of the crushed stone particles obtained as described above is laid out on top of it, and then the crushed stone grain resin composition obtained as described above is laid out. and its substrate amplitude 3
Vibrations of approximately m/m were applied at a rate of 200 times per minute.

Continue to vibrate for about 15 minutes, then back the upper part, which will be the back side, with a cement composition (10 parts by weight of white cement, vinyl acetate emulsion strong adhesive (bond) mixture, 10 parts by weight of stone powder, a little pigment), and after hardening. The mold was released from the substrate surface, and the same cement composition was applied to the surface where there were pinholes and cavities to polish the surface. By combining the cement composition, it was possible to obtain a decorative artificial stone slab with even better fire resistance.

Example 2 In this example, crushed granite stone that had been thoroughly washed and dried with the following particle size distribution was used.

2-3 meshes Approximately 30 parts by weight 3-10 meshes Approximately 30 parts by weight 10-60 meshes Approximately 20 parts by weight 60 meshes or less Approximately 20 parts by weight Add 100 parts by weight of the above crushed stone to Epolack G155AL (product of Nippon Shokubai Chemical Co., Ltd., polyester resin) )
10 parts by weight and 0.04% of the promoter OCO, and further mixed with 5 parts by weight of calcium carbonate and 0.7% of the catalyst CAT-M.

The obtained resin composition was poured into a long and narrow L-shaped frame on a rust-free steel plate (coated with a mold release agent and dried) from the top, and then the mold was subjected to vibrations with an amplitude of about 3 m/m. was given at a rate of 200 times per minute.

The vibration was continued for about 15 minutes, and then the cement composition used in Example 1 was applied, and after hardening, the mold was released, and it was possible to freely create L-shaped and H-shaped irregular shaped products with wavy irregularities.

In this case, corrugated profiles particularly require sand blasting.

Incidentally, there are various types of natural stone such as granite, marble, serpentine, etc., but it is not necessary to select stone types of the same type, but by using a mixture of them, you can create something that cannot be seen in natural stone. In this case, ceramics and glass pieces can be used. In addition, surface coating finishing and spray finishing can be done freely, but the product value is sufficient even when released from the mold without any cosmetic surface treatment.Of course, cutting, shredding, and polishing can be applied freely, and sand-blowing can be done as needed. You can apply a dip blast finish, apply pressure to about 50 kg/cm ² , or heat at around 80°C to accelerate curing, and apply it as you wish.

Claims (1)

[Claims] 1. At least one type of granular material selected from crushed natural stone, crushed ceramic pieces, and glass pieces, and 100 pieces of the granular material.
Load a composition containing 2 to 20 parts by weight of a liquid thermosetting resin into a substrate or formwork, apply vibration or centrifugal rotation to the substrate or formwork depending on its cross-sectional shape, and then add a cement composition. A method for producing refractory artificial stone, which is characterized by pouring or layer-casting and bonding and hardening. 2 The vibration applied to the substrate or formwork has an amplitude of 2 to 5
2. The method according to claim 1, wherein the vibration frequency is 100 to 500 times/min. 3 The rotational speed of centrifugal rotation applied to the substrate or formwork is
15. The method according to claim 1, wherein the rpm is 150-600 rpm. 4 A composition containing a particulate material and a liquid thermosetting resin,
The method according to any one of claims 1 to 3, further comprising an inorganic filler. 5 A composition containing a particulate material and a liquid thermosetting resin,
Claims 1 to 4 are obtained by first adding and mixing 3 to 7 parts by weight of a liquid thermosetting resin per 100 parts by weight of the granules, and then adding an additional amount of a liquid thermosetting resin to this. The method described in any of the paragraphs. 6 Claim 1 in which the liquid thermosetting resin is a polyester resin or an epoxy resin containing a curing catalyst and/or a curing accelerator as necessary.
6. The method according to any one of items 5 to 5. 7. The method according to any one of claims 1 to 6, wherein the cement composition is a liquid composition containing one or more of adhesives, fillers, pigments, and dyes in addition to cement. 8. The method according to any one of claims 1 to 7, wherein a mold release agent is coated or baked on the inner surface of the substrate or mold. 9. The method according to any one of claims 1 to 8, in which the cement composition is poured after the composition containing the granules and the liquid thermosetting resin is cured.