JPH08267666A - Artificial stone and its manufacture - Google Patents

Abstract

PURPOSE: To provide an artificial stone withstanding outdoor service for a long period by a method wherein a first layer in which a compound composed of respective specific pts.wt. of a hardening accelerator having a specific main component and crushed stone sand is hardened, is made a front layer, and a second layer having different pts.wt. of only the crushed stone sand is made a rear layer. CONSTITUTION: A first layer wherein a first compound composed of 100 pts.wt. of unsaturated polyester resin, 0.15-10 pts.wt. of organic peroxide, 0.1-5 pts.wt. of hardening accelerator having metallic salt of organic acid as main component, and 50-300 pts.wt. of crushed stone sand is hardened, is provided. Further, a second layer wherein a second compound composed of 100 pts.wt. of unsaturated polyester resin, 0.5-10 pts.wt. of organic peroxide, 0.1-5 pts.wt. of hardening accelerator having metallic salt of organic acid, and 200-1500 pts.wt. of crushed stone sand is hardened, is provided. The first layer is made a front layer, the second layer is made a rear layer, and they are integrally formed. Thus, a state wherein a surface of natural stone is imitated, is obtained, and though exposed in the air, the state is free from yellowing and chalking.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial stone mainly composed of unsaturated polyester resin and crushed sand and a method for producing the same.

[0002]

2. Description of the Related Art When paving a pavement in a park or garden, a plaza, a building such as a bridge, or a sidewalk, natural stones, tiles, bricks, etc. are laid on the surface to prepare a landscape.

A large amount of natural stone is used to construct embankments and facilities around the embankments in order to maintain a stone wall or the like when constructing a residential land and to maintain the scenery of the shore even when revetment works are performed.

Further, in the construction of houses, natural stones are used to cover gates, walls, entrances, outer walls, inner walls, floors, and interior decorative building materials.

Conventionally, natural stone has been widely used as a building material and a covering material because of its excellent texture and its easy availability.

[0006]

However, in recent years, natural stones are remarkably depleted of resources, and it is difficult to collect natural stones from the viewpoint of nature protection. Even if they are collected, the price is high, and natural stones are used. It has become economically difficult to adjust the landscape.

Therefore, there is a demand for an artificial stone which is inexpensive and has a texture of natural stone. So, acrylic resin,
Various artificial stones made by binding an aggregate or an inorganic powder using an epoxy resin, a furan resin, or the like as a binder, and various manufacturing methods thereof have been proposed. (For example, JP-A-59-83973)
issue)

Conventional artificial stones are not suitable for applications in which yellowing and chalking occur due to aging deterioration of a binder such as an epoxy resin, and which are exposed to a natural environment for long-term outdoor use. .

Further, since the viscosity of the binder is high, the handling becomes difficult unless the compounding ratio of the resin with respect to the aggregate is increased, and it is difficult to manufacture the artificial stone and the economy is poor. Further, since the proportion of the inorganic aggregate in the artificial stone cannot be increased, there is a problem that the flame retardancy is poor.

Furthermore, in order to use it as a surface material for secondary concrete products, it is embedded in the surface of uncured concrete,
When the effect of concrete is promoted by steam curing,
There is a drawback that the binder deteriorates.

Similarly, in the case of an acrylic resin, there is a drawback that softening occurs due to heat of direct sunlight and the binder is whitened by steam curing. Further, in the conventional method in which the resin and the aggregate are mixed and poured into the mold, many bubbles are entangled in the surface of the artificial stone, resulting in a very poor finish.

It is an object of the present invention to provide an artificial stone material which solves the above-mentioned drawbacks, can withstand outdoor use, and is excellent in economical efficiency and flame retardancy, and a method for producing the artificial stone material.

[0013]

In order to solve the above problems, 100 parts by weight of an unsaturated polyester resin, 0.5 to 10 parts by weight of an organic peroxide, and a curing accelerator containing a metal salt of an organic acid as a main component are accelerated. A first layer obtained by curing a first compound comprising 0.1 to 5 parts by weight of an agent and 50 to 300 parts by weight of crushed sand;
From 100 parts by weight of unsaturated polyester resin, 0.5 to 10 parts by weight of organic peroxide, 0.1 to 5 parts by weight of a hardening accelerator containing a metal salt of an organic acid as a main component, and 200 to 1500 parts by weight of crushed sand. And a second layer formed by curing the second compound, wherein the first layer is a front surface layer and the second layer is a back surface layer.

The amount of crushed sand contained in the first mixture is smaller than the amount of crushed sand contained in the second mixture.

Further, a mesh-like reinforcing material is inserted between the first layer and the second layer and cured, or an anchor member is exposed to the surface of the second layer opposite to the first layer. Some are planted and cured.

As a method for producing the above-mentioned artificial stone material, a first step of pouring an appropriate amount of the first compound into a required mold to evenly level it, and a period during which the first compound retains flexibility. A second step of pouring the second formulation on top of the first formulation and evenly leveling;
After the completion of the second step, it comprises a third step of integrally curing the first compound and the second compound to form a double structure.

As a method for manufacturing the above-mentioned required mold, a liquid urethane resin is cast on the surface of natural stone and cured to form a urethane mold having a natural stone pattern formed on the surface thereof. With the outer frame manufacturing process of forming an outer frame so that the liquid casting material can be filled on this surface with the surface formed upward, the above-mentioned first by using the above-mentioned mold, It has a two-layer structure in the second and third steps, and is manufactured so that the surface of one of the first layers has a pattern of natural stone.

After the completion of the first step, when the first compound is uncured, a reinforcing material is placed on the surface of the first compound. After the fourth step is performed, the process proceeds to the second step. It is also possible to manufacture artificial stone materials.

Furthermore, after the second step after the completion of the second step is uncured, a fifth step of burying the anchor member in a semi-immersed state from the surface is carried out, and then the third step is carried out, whereby the back surface is obtained. It is also possible to manufacture an artificial stone material in which the anchor member is projected.

[0020]

[Function] As described above, in the state of imitating the surface of natural stone,
Moreover, it does not cause yellowing or chalking even when exposed to the atmosphere. Further, it is not deteriorated by steam curing of concrete and can be used as a secondary concrete product.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is an explanatory view showing the manufacturing steps of the present invention in the order of steps. (A) is a cross-sectional view of a natural stone that uses the surface shape, (b) is a state diagram in which an outer frame is placed on the upper side of the natural stone,
(C) is a state diagram in which liquid urethane is thinly applied to the surface of natural stone in the outer frame, and (D) is a state diagram in which a reinforcing material such as glass cloth is placed on (C) and liquid urethane is poured into it.
(E) is a state diagram in which the required amount of liquid urethane is poured directly without using the glass cloth shown in (d), and (e) is a cross-sectional view of the urethane type removed after curing the urethane resin,
(G) is a state diagram in which the mold is placed on the urethane mold, (H) is an explanatory diagram of the first step, (L) is an explanatory diagram of the reinforcing material and the anchor, (G) is an explanatory diagram of the second step, ( (L) is a cross-sectional view of the artificial stone when the reinforcing material and the anchor are not used, and (e) is a cross-sectional view of the artificial stone when the reinforcing material and the anchor are used.

First, the general aspects of the present invention will be described in detail. The unsaturated polyester (A) used in the present invention includes an organic acid, an unsaturated dibasic acid or an anhydride thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid and citraconic acid.

As the saturated acid, benzoic acid as a base, p
-Tert-butylbenzoic acid, p-hydroxybenzoic acid, phthalic acid as a dibasic acid, isophthalic acid, terephthalic acid, het acid, het anhydride, trimellitic acid, trimellitic anhydride, oxalic acid, malonic acid, succinic acid , Azelaic acid, adipic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride and the like are used.

As glycol components, ethylene glycol, propylene glycol, neopentyl glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, trimethylolethane,
Examples thereof include polyhydric alcohols such as glycerin, pentaerythritol, dipentaerythritol, and 1,4-butanediol.

Further, it can be obtained by a known method using a styrene monomer, dicyclopentadiene or the like as a diluent. In addition, other additives may be used to impart unique properties.

The hardener (B) is an acyl peroxide such as benzoyl peroxide or acetyl peroxide, a hydroperoxide such as tertiary bityl peroxide or cumene hydroperoxide, a methyl ethyl ketone peroxide or a ketone peroxide such as cyclohexanone peroxide. Alkyl peroxides such as oxide, ditertiary butyl peroxide and dicumyl peroxide, and oxyperoxides such as tertiary butyl perbenzoate and tertiary butyl peroxyacetate are used. The above-mentioned curing agent (B)
The amount of addition is 0.5 to 10 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the unsaturated polyester (A).

The curing accelerator (C) is iron, cobalt, lead,
Naphthenates, octenoates and the like of manganese, nickel, tin and zinc are used. The amount of the curing accelerator (C) added is 0 to 5 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the unsaturated polyester (A).

The type and addition amount of the curing agent (B) and the curing accelerator (C) are, depending on the unsaturated polyester (A) used, a working time of 10 to 20 minutes and a curing time of 40 to 60 at room temperature.
There is no particular limitation as long as it is within the above range without causing large shrinkage, deterioration, discoloration and other changes, and it can be freely selected.

The crushed stone sand (D) had a particle size of 0.
It is preferably about 6 to 7 mm. If the drying is insufficient, the reaction of the unsaturated polyester (A) may be hindered or whitening may be caused.

If the particle size is less than 0.6 mm, it may cause curing inhibition during the curing reaction, causing the artificial stone surface to become sticky or whitening. Further, if the particle size exceeds 7 mm, bubbles easily enter the unsaturated polyester (A), which may cause deterioration of the finish of the artificial stone. Therefore,
It is preferable to disperse crushed stone sand having a particle size of 0.6 to 7 mm with substantially the same distribution.

Further, if necessary, an inorganic powder, silica sand or the like may be used alone or in combination instead of the crushed stone sand (D), and a pigment may be added for the purpose of coloring.

When the surface of the unsaturated polyester (A) is poorly hardened, paraffin wax can be added in an appropriate amount to suppress the stickiness of the surface. However, if the added amount is too large, the adhesive strength may be extremely reduced when the artificial stone is adhered to a floor or the like using an adhesive, so care must be taken.

As a manufacturing method, a urethane type is manufactured,
Using this mold, it can be classified as artificial stone manufacturing.

As an example of the urethane type manufacturing process, FIG.
The surface of the natural stone 1 shown in (a) is cleaned and degreased, and the outer frame 2 shown in (b) is installed. Next, a mold release agent is applied to the inner surface of the outer frame 2 and the surface of the natural stone 1 in the mold. Then, as shown in (e), a liquid urethane resin is poured and cured, and after curing, the urethane mold 3 is taken out by demolding as shown in (e).

In order to increase the strength of the urethane mold 3,
Alternatively, when manufacturing a large urethane mold 3, about half the amount of urethane resin is poured as shown in (c), and the reinforcing material 4 such as glass cloth, vinylon cloth, or metal cloth is placed on the cured urethane resin. Alternatively, the urethane resin may be poured onto the above to obtain the state shown in (d), and the mold may be removed after the urethane resin is completely cured.

Alternatively, as shown in (e), the above-mentioned reinforcing material 4 may be buried before the curing after the entire amount of the urethane resin has been poured, and then the state may be removed as shown in (d).

Next, the manufacturing method of the artificial stone is as follows.
A required mold 5 is placed on the urethane mold 3 shown in the figure as shown in (g). Next, 100 parts by weight of the unsaturated polyester (A) is mixed with the curing agent (B) and the curing accelerator (C) in the specified amounts to prepare a binder. This binder was divided into two parts by weight, and crushed sand (D) 5 was added to 100 parts by weight of the binder.
0 to 300 parts by weight (preferably 100 to 200 parts by weight)
Add and mix, pour into the above required formwork as shown in (h), and spread evenly with a spatula, trowel, brush or the like.

Next, 200 to 1500 parts by weight (preferably 400 to 1000 parts by weight) of crushed sand (D) is added to and mixed with 100 parts by weight of the remaining half of the binder, and the mixture is added to the upper side of (h). (G) Pour as shown, and uniformly evenly harden with a spatula, trowel, brush or the like.

The distribution ratio of the binder and the crushed stone (D) is adjusted so that the weight ratio is 1: 3 to 1: 5 (preferably 1: 4).

In order to make the surface of the artificial stone uniform, the mixture is divided and poured in first to spread the mixture containing a large amount of the binder to remove air bubbles as much as possible. By pouring a large amount of the compound, the crushed stone (D) sinks to the bottom surface of the form, resulting in a uniform mixing ratio of the binder and the crushed stone (D) throughout, which is the most dense (compact, compression, Bending) is high.

Further, for the purpose of improving the strength of the artificial stone, the reinforcing material 6 made of steel or the like shown in (i) is embedded in the artificial stone or embedded in the secondary concrete product for the purpose of anchoring effect. The anchor 7 can also be embedded.

Although the finish of the artificial stone surface is slightly inferior,
As described above, an artificial stone having an excellent finish can be produced even if the binder and the crushed stone (D) are mixed in the same mixing ratio without being divided, and the mixture is gently and evenly poured.

The artificial stone manufactured by the above-described manufacturing method is the one without the reinforcing material 6 and the anchor 7, and the one with the reinforcing material 6 and the anchor 7 is the one shown in (e).

Experimental Example 1 100 parts by weight of a resin (Three Longie P-290: manufactured by ThreeBond Unicom Co., Ltd.) was mixed with 1 part by weight of a curing accelerator cobalt naphthenate and 1 part by weight of paraffin wax, and methyl ethyl ketone peroxide was used as a curing agent. 2 parts by weight were mixed to obtain a binder.

To 100 parts by weight of this binder, 400 parts by weight of crushed sand having a particle size of 0.6 mm or more and less than 7 mm was mixed, poured into a required mold and hardened. It was left to stand for about 1 hour and then demolded. An artificial stone resembling a natural stone was obtained, although air bubbles appeared slightly on the surface.

Experimental Example 2 100 parts by weight of a resin (Three Longie P-290: manufactured by ThreeBond Unicom Co., Ltd.) was mixed with 1 part by weight of a curing accelerator cobalt naphthenate and 1 part by weight of paraffin wax, and methyl ethyl ketone peroxide was used as a curing agent. 2 parts by weight were mixed to obtain a binder.

To 100 parts by weight of this binder, 0.5 parts by weight of a pigment (ET 3W114 White: manufactured by Dainichiseika Kogyo Co., Ltd.) and 400 parts by weight of crushed sand having a particle size of 0.6 mm or more and less than 7 mm are mixed. It was poured into a required mold and cured. It was left to stand for about 1 hour and then demolded. Although some bubbles appeared in the surface layer, the pigment was uniformly dispersed and an artificial stone with a bright color tone was obtained.

Experimental Example 3 100 parts by weight of a resin (Three Longie P-290: manufactured by Three Bond Unicom Co., Ltd.) was mixed with 1 part by weight of a curing accelerator cobalt naphthenate, and 1.5 parts by weight of methyl ethyl ketone peroxide was added as a curing agent. And used as a binder.

This binder is divided into two parts and a part of the binder 100 is added.
200 parts by weight of crushed stone sand having a particle size of 0.6 mm or more and less than 7 mm was mixed with the parts by weight, poured into a required mold, and evened with a trowel. Next, with respect to the remaining 100 parts by weight of the binder, 800 parts by weight of crushed sand having a particle size of 0.6 mm or more and less than 7 mm is mixed, poured into the above mixture, and similarly leveled with a trowel and cured. It was No bubbles were found on the surface of the artificial stone, and the artificial stone was so smooth that the entire surface was indistinguishable from natural stone.

[0050]

EFFECT OF THE INVENTION Since the artificial stone of the present invention uses the unsaturated polyester resin as a binder for crushed stone, it does not cause yellowing, chalking, etc. as compared with the conventional binder, and can be used outdoors for a long time. It can withstand the use of.

Since the unsaturated polyester resin used has a low viscosity and the curing time can be set according to the ambient temperature, the artificial stone is demolded from the mold in a shorter time than the resin used for the conventional binder. It can be done and has excellent workability.

By changing the compounding ratio of the binder and the crushed sand in two times and pouring the mixture into two portions, it is easy to form a surface layer without bubbles on the front surface side, and the ratio of the crushed sand to the binder is large on the back surface side. By doing so, it is possible to produce artificial stone with excellent economical efficiency and flame retardancy.

Since the artificial stone of the present invention has the texture of natural stone, it is used as a building material for parks, residential areas, revetment work, etc.
It is suitable as a cover material.

The secondary concrete product using the present invention as the covering material does not cause yellowing, chalking, etc., and the binder resin does not deteriorate even if steam curing is performed to accelerate the hardening of the concrete. Withstands outdoor use for a period of time,
It has excellent economical efficiency and flame retardancy.

[Brief description of drawings]

FIG. 1 is an explanatory view showing the order of manufacturing steps of the present invention. (A) is a cross-sectional view of natural stone that uses the surface shape, (b)
Is a state diagram in which a mold is placed on the upper side of natural stone, (c) is a state diagram in which liquid urethane is thinly applied to the surface of the natural stone in the form,
(D) Place a reinforcing material such as glass cloth on (c),
Furthermore, a state diagram in which liquid urethane is poured, (e) is a state diagram in which the required amount of liquid urethane is directly poured without using the glass cloth shown in (d), and (he) is the urethane type removed after curing the urethane resin Cross-sectional view, (g) is a state diagram in which a mold is placed on a urethane mold, (h) is an explanatory view of the first step, (d) is an explanatory view of reinforcing materials and anchors, (g)
Is an explanatory view of the second step, (l) is a cross-sectional view of the artificial stone when the reinforcing material and the anchor are not used, and (e) is a cross-sectional view of the artificial stone when the reinforcing material and the anchor are used.

[Explanation of symbols]

 1 Natural stone 2 Outer frame 3 Urethane type 4 Reinforcing material 5 Form 6 Reinforcing material 7 Anchor

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C08J 5/00 CFD C08J 5/00 CFD // B29K 67:00 B29L 31:10 (72) Inventor Haruichi Ueoka 711-1 Narimi Ko, Utsu, Suda-cho, Ozu-shi, Ehime Eishin Concrete Industry Co., Ltd.

Claims (8)

[Claims] 1. 100 parts by weight of an unsaturated polyester resin, 0.5 to 10 parts by weight of an organic peroxide, 0.1 to 5 parts by weight of a hardening accelerator containing a metal salt of an organic acid as a main component, and 50 to 50 of crushed sand.
A first layer formed by curing a first compound composed of 300 parts by weight, an unsaturated polyester resin 100 parts by weight, an organic peroxide 0.5 to 10 parts by weight, and a metal salt of an organic acid as main components. 0.1-5 parts by weight of hardening accelerator and 200-15 crushed stone sand
And a second layer formed by curing a second compound consisting of 100 parts by weight, wherein the first layer is a front surface layer and the second layer is a back surface layer. Artificial stone material. 2. The artificial stone material according to claim 1, wherein the content of crushed sand in the first mixture is smaller than the content of crushed sand in the second mixture. 3. The artificial stone material according to claim 1, wherein a mesh-like reinforcing material is inserted between the first layer and the second layer and cured. 4. The artificial stone material according to claim 1, wherein an anchor member is planted and hardened so as to be exposed on the surface of the second layer opposite to the first layer. 5. A first step of pouring an appropriate amount of the first composition into a required mold to evenly level it, and the second composition while the first composition retains flexibility. Is poured onto the first compound and uniformly leveled, and after the second process is completed, the first compound and the second compound are integrally cured to form a double structure. A method for manufacturing an artificial stone material, which comprises the third step. 6. A liquid urethane resin is cast and cured on the surface of natural stone to prepare a urethane mold having a natural stone pattern formed on the surface, and the surface on which this urethane type pattern is formed faces upward. An outer frame manufacturing process that assembles an outer frame so that a liquid casting material can be filled on this surface, and has a two-layer structure by the first, second, and third steps, and the surface of one of the first layers is made of natural stone. The method for manufacturing an artificial stone material according to claim 5, wherein the manufacturing method has a pattern. 7. The method according to claim 7, wherein when the first compound after the completion of the first step is uncured, a fourth step of placing a reinforcing material on the surface of the first composition is carried out, and then the second step is performed. Item 5
Alternatively, the method for manufacturing an artificial stone material according to 6 above. 8. When the second compound after the completion of the second step is uncured, a fifth step of burying the anchor member in a semi-immersed state from the surface thereof is carried out, and then the step of transferring to the third step is performed. The method for manufacturing an artificial stone material according to claim 5, 6 or 7.