JPH07314578A - Synthetic stone with pattern and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a synthetic stone with patterns, which is provided with recesses and projections on the surface thereof, keeping the handling of natural stones and provided with characteristics such as resistance to contamination, weather proof property, water resistant property and the like, and the manufacturing method thereof. CONSTITUTION:A part of the surface of granular filler (C) is exposed and form recessed or projected parts on a part of the surface of a molded form (E), obtained by curing a thermosetting resin compound (D) containing a thermosetting resin (A) having the refractive index of 1.53-1.65 after cured, fine powder filler (B) and the granular filler (C) having the Mohs hardness of 2-7, while a transparent resin layer, having the thickness of 0.02-5mm, is formed on the surface layer thereof and the transparent resin layer is provided with the recesses and projections of 0.5-6.0mm.

Description

Detailed Description of the Invention

[0001]

[Industrial application] The present invention relates to an artificial stone used for interiors and exteriors, and relates to an artificial stone having a transparent resin layer as a protective layer on its surface.

[0002]

2. Description of the Related Art Artificial stones made from natural stone and crushed stone are
A beautiful surface having natural stone-like irregularities cannot be obtained in the cut-out state or in the state where it is formed by casting or pressing. Therefore, by polishing the surface with a method such as sharpening, a glossy artificial stone is produced,
It is used as a material for interiors, counters, and exteriors. However, in order to obtain a glossy surface, a large number of polishing steps are required, which requires a lot of time and cost. Further, the artificial stone products provided by such conventional polishing techniques have a flat surface only.

Therefore, in order to obtain a more natural appearance, it has been attempted to make the surface uneven, but as a method therefor, a method of heating the surface of natural stone with a burner to roughen the surface, and artificial stone is disclosed. A method of casting in a mold provided with engraving-like unevenness as seen in Japanese Patent Publication No. 49-33910, by burning the plastic appearing on the surface of the product as seen in Japanese Patent Publication No. 43-7637. Method of removing and exposing only crushed natural stone on the surface thereof
As disclosed in Japanese Patent Laid-Open No. 7-13039, a method of treating the surface with an acid to float the aggregate and make it uneven is proposed.
However, the method requires a step of cutting natural stone into a required size, and the use of natural stone itself is limited in terms of weight and strength. According to the method (1), since a random unevenness is simply formed on the surface, it is difficult to obtain a natural design. Also, because of casting, pinholes are likely to occur on the surface, or the mold releasability of the uneven mold tends to be a problem. In this method, the resin may be deteriorated due to high heat even in the deep part of the resin due to combustion, and it is difficult to obtain a beautiful artificial stone. In the method (1), there is a problem that the aggregate is restricted and a washing step after the acid treatment is necessary, and that the use of the acid is not desirable in terms of working environment and safety. Further, natural stones or artificial stones having an uneven surface obtained by these methods tend to have minute cracks, cracks, pinholes, etc. on the surface, and tend to be inferior in stain resistance, chemical resistance, etc. .

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a patterned artificial stone which has unevenness excellent in design property on the surface and is excellent in stain resistance, weather resistance and water resistance. is there. Further, the present invention provides a method for easily and safely producing a desired patterned artificial stone. The unevenness with excellent design here is
It is achieved by selectively processing the particulate filler (C) into convex or concave by the method described below, rather than simply forming random irregularities on the surface.

[0005]

According to the present invention, a thermosetting resin (A) having a refractive index of 1.53 to 1.65 when cured and a granular filler (C) having a Mohs hardness of 2 to 7 are used. Molded product (E) obtained by curing the thermosetting resin composition (D) containing
And a patterned artificial stone comprising a transparent resin layer (G) having a thickness of 0.02 to 5.0 mm attached to the surface thereof, and a granular filler (C ) Is exposed by forming a convex portion or a concave portion on the surface, and the depth or height of the surface to which the transparent resin layer (G) is attached is 0.
The present invention relates to a patterned artificial stone having irregularities of 5 to 6.0 mm.

The present invention further has a refractive index of 1. when cured.
A molded product obtained by curing a thermosetting resin composition (D) containing a thermosetting resin (A) of 53 to 1.65 and a granular filler (C) of Mohs hardness of 2 to 7 ( An abrasive (F) having a Mohs hardness of 7 to 10 on at least a part of the surface of E).
To form a concave portion (FIG. 4) in which the granular filler (C) is exposed, and then apply the transparent resin (G) to the surface of the molded article (E) in which the concave portion is formed. It was a finding of a method of manufacturing a patterned artificial stone.

The present invention also has a refractive index of 1.53 when cured.
~ 1.65 thermosetting resin (A) and Mohs hardness 6 ~
The thermosetting resin composition (D) containing the granular filler (C) of No. 7 is cured on at least a part of the surface of the molded article (E) to obtain an abrasive (F) having a Mohs hardness of 3 to 4 (F). ) Is applied to roughen the surface to form a convex portion (FIG. 3) in which the granular filler (C) is exposed, and then a transparent resin (G) is applied to the surface of the molded article (E) on which the convex portion is formed. This is a completed method of manufacturing a patterned artificial stone characterized by:

The thermosetting resin (A) of the present invention can be used without particular limitation as long as it is a resin which can be hardened by containing the granular filler (C). For example, polyester resin, vinyl Ester resin, acrylic resin,
Examples thereof include epoxy resin, phenol resin, urethane resin and the like. Of these, polyester resins or acrylic resins are preferable because they are excellent in weather resistance of artificial stones and have a deep appearance.

As the granular filler (C), those having a Mohs hardness of 2 to 7 and an average particle diameter of 0.5 mm or more can be used. For example,
Use resin crushed material without filler (2-3), resin crushed material with filler (2-7), glass crushed material (4-7), natural stone (2-7), ceramics, slag, etc. You can [Numerical values in parentheses indicate Mohs hardness. Above all, when natural stone is used as the granular filler (C), an artificial stone having a natural design is easily obtained, which is desirable.

The natural stones used as the granular filler (C) are, for example, granite (6-7), marble (2-3), garnet (7), mica (2-3), pumice (6), orthoclase. (6), Quartz (7) [Numerical value in () indicates Mohs hardness. ], But granite and marble are preferable in terms of design. Among them, granite has a Mohs hardness of 6 to 7
Since it is large, it is most preferable in that it is easy to select the surface irregularities.

As the granular filler (C), weight% of the particle size is used.
The distribution is preferably such that the amount of particles having a diameter of 3 to 5 mm is 25 to 65% by weight. Among them, 6 mm or more is 0 to 10% by weight, 5 to 6 mm is 1 to 20% by weight, and 4 to 5 mm is 10% by weight.
30% by weight, 3-4 mm is 15-35% by weight, 2-3 m
More preferably, m is 10 to 30% by weight, 1 to 2 mm is 15 to 35% by weight, and 1 mm or less is 0 to 10% by weight. If the number of particles having a large particle size increases, the fluidity during molding deteriorates. Further, it is not preferable because it damages the kneading equipment during kneading. On the other hand, if the number of particles having a small particle size increases, the design will be deteriorated, for example, blackening will occur.

The thermosetting resin composition (D) is a mixture of the thermosetting resin (A) and the granular filler (C), and is further hardened together with the thermosetting resin (A). It may contain a fine powder filler (B) having a Mohs hardness of 2 to 4 when pressed. In this case, when the surface of the obtained molded product (E) is processed so that a part of the surface of the granular filler (C) is exposed, the granular filler (C) is selectively processed into convex or concave. It is desirable because it is easy to do and has excellent design. When the Mohs hardness is less than 2, the surface of the thermosetting resin (A) tends to be fluffy when the above processing is performed,
It is not desirable because it impairs the design. On the other hand, when the Mohs hardness exceeds 4, cracks are easily formed on the surface, which is not desirable in terms of strength physical properties. When the thermosetting composition (D) contains the fine powder filler (B), it is desirable that the thermosetting resin (A) has a refractive index of 1.53 to 1.65 when cured. The refractive index of the resin can be changed according to the electron density of the raw material used, and the refractive index can be increased by using, for example, a resin having a benzene ring or a halogen group. When the refractive index at the time of curing is less than 1.53, the transparency is poor, and when it exceeds 1.65, the transparency is inferior and the depth is lost, so that an artificial stone having an excellent design property cannot be obtained, which is not preferable. .

The fine powder filler (B) is a fine powder filler (B) having a Mohs hardness of 2 to 4 when added to the thermosetting resin (A) and cured, and has an average particle size of Diameter is 10
If it is 0 μm or less, it can be used in the present invention. Examples thereof include aluminum hydroxide, calcium hydroxide, magnesium hydroxide, glass powder, powder silica and powder quartz. These may be used alone or may be mixed. Of these, aluminum hydroxide is preferable because it is effective in imparting flame retardancy to artificial stone and is low in cost, and glass powder is preferable from the viewpoints of transparency at the time of curing and improvement of Mohs hardness. Mohs hardness is 2 to 3 when aluminum hydroxide is used alone
Then, when the glass powder is used alone, 3 to 4 are obtained. Above all, when aluminum hydroxide and glass powder are used in combination, an artificial stone having high transparency and excellent designability and high surface hardness can be obtained, which is desirable. Fine powder filler (B)
The average particle diameter of the filler used as is preferably 1 to 100 μm, more preferably 5 to 15 μm. If the particle size is small, the wetting at the time of kneading will be poor, and whitening and deterioration of transparency will occur. In addition, if the particle size is large, the packing density will decrease, and the fluidity of the thermosetting resin composition (D) will deteriorate during molding.

The thermosetting resin composition (D) may also contain glass fibers, if necessary. Mixing a small amount of short glass fibers enhances the strength of the patterned artificial stone and is desirable.

The amount of the granular filler (C) is preferably 200 to 900 parts by weight based on 100 parts by weight of the thermosetting resin (A). If it is less than 200 parts by weight, the distribution of the granular filler (C) tends to be non-uniform, and conversely 900
If the amount is more than parts by weight, molding tends to be difficult, and both are not desirable. The particle size of the granular filler (C) is 3 to 100 parts by weight of the thermosetting resin (A).
200 mm of crushed stone of natural granite or natural marble whose 5 mm is 25 to 65% by weight of the granular filler (C).
900 parts by weight and 100 parts of aluminum hydroxide and / or glass powder as the fine powder filler (B)
When used in an amount of up to 300 parts by weight, an artificial stone having an excellent appearance very similar to natural stone can be obtained, and it is also desirable in view of flame retardancy and surface hardness.

The molded product (E) is obtained by curing the thermosetting resin composition (D) obtained by uniformly mixing the thermosetting resin (A) and the granular filler (C). For such mixing and curing, methods generally used in the industry can be used, such as casting method, pressing,
Heat and pressure molding such as injection molding can be used. Among them, a thermosetting resin composition (D) containing a thermosetting resin (A), a fine powder filler (B), a granular filler (C), and if necessary, a colorant, a thickener and the like. To B
A molding material pre-molded into an MC shape is molded at a molding temperature of 100 to 20
When press molding is performed at 0 ° C. under a pressure of 50 to 100 kgf / cm ² for 5 to 10 minutes, a molded product (E) that is dense and has few defects such as pinholes can be obtained, which is desirable. The molded product (E) thus obtained is processed so that a part of the surface of the granular filler (C) is exposed and an uneven surface is formed. Such processing can be achieved, for example, by spraying the molded product (E) with an abrasive (F) having a Mohs hardness of 3 to 10.

As a method of spraying the abrasive (F),
Examples include liquid honing and blasting. Among them, blasting is desirable because it has good work efficiency and requires less equipment and running costs. In this manner, by spraying the abrasive (F) onto the surface of the molded product (E) containing the granular filler (C) that has been previously formed into a flat plate shape, the abrasive (F) is selectively convex or It is possible to form a recess and to form a surface exposed on the surface, and it is possible to obtain a surface excellent in design.

It is desirable that the abrasive (F) is sprayed so that the surface irregularity becomes 0.5 to 6.0 mm when the transparent resin (G) is adhered to the surface. It is also possible to partially spray the abrasive (F) to form patterns or letters.

If the surface is previously carved with a diamond grindstone or the like before spraying the polishing agent (F),
A good design can be obtained by spraying for a short time.

If the surface roughness is less than 0.5 mm, a three-dimensional design cannot be obtained, which is not desirable. On the contrary, 6.0
When irregularities exceeding mm are formed, defects such as chips and cracks are likely to occur, and a long-time spraying operation is required, which is both undesirable. As the abrasive (F), alumina, silicon carbide, glass beads, plastic particles, steel grit, or the like can be used.

The transparent resin (G) is, for example, urethane resins, acrylic resins, can be a polyester resin or the like, can be allowed to adhere by a method such as coating or de _Lee mappings.

In carrying out the present invention, it is obtained by curing a thermosetting resin composition (D) containing a thermosetting resin (A) and a granular filler (C) having a Mohs hardness of 2 to 7. Mohs hardness of 7 to 1 on at least a part of the surface of the molded product (E)
When the abrasive (F) of 0 is sprayed, the granular filler (C) is selectively. It can be roughened so as to form recesses, and by applying the transparent resin (G) to the surface, a patterned artificial stone having an excellent appearance can be obtained. Further, at this time, a crushed material of natural stone is used as the granular filler (C), and the thermosetting resin composition (D) is added to the thermosetting resin (A) to cure the resin. When the fine powder filler (B) having a Mohs hardness of 2 to 4 is contained in the cured product, a patterned artificial stone having a particularly excellent appearance can be obtained. Alumina, silicon carbide or the like can be used as the abrasive (F) having a Mohs hardness of 7 to 10.

Further, the thermosetting resin (A) and Mohs hardness 6
No. 7 to No. 7 granular filler (C), and at least a part of the surface of a molded article (E) obtained by curing the thermosetting resin composition (D), an abrasive having a Mohs hardness of 3 to 4 By spraying (F), the granular filler (C) can be roughened so as to selectively form convex portions, and by applying the transparent resin (G) to the surface, an excellent appearance can be obtained. You can obtain patterned artificial stone.

Further, at this time, a crushed material of natural stone is used as the granular filler (C), and the thermosetting resin composition (D) is added to the thermosetting resin (A) to cure the resin. When the fine powder filler (B) having a Mohs hardness of 2 to 4 is obtained, the patterned artificial stone having a particularly excellent appearance can be obtained. Mohs hardness 3-4
As the abrasive (F), a crushed polyester resin or the like can be used.

[0025]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. However, the part in an example shows a weight part.

<Production Example of Molded Article> Refractive index when cured is 1.
58 unsaturated polyester resin (Epolak NH-
111 parts made by Nippon Shokubai Co., Ltd. 85 parts, shrinkage reducing agent (AT-60)
0 Nippon Shokubai 15 parts, coupling agent (KBM-5
03 Shin-Etsu Chemical Co., Ltd. 2 parts, curing agent (Kayacarnol BIC-75 Kayaku Akzo Co., Ltd.) 1 part, aluminum hydroxide as a fine powder filler (Hijilite H320)
Showa Denko KK) 250 parts {Mohs hardness of 2 when added to a thermosetting resin and cured}, natural granite (mahogany dichotomite made by Tokai Stone Co., Ltd., natural stone amount of 3-5 mm is 4)
5% by weight) and 30 parts of tempered glass fiber (Chopped Strand ECS06B-144 / P Nippon Electric Glass Co., Ltd.) were kneaded with a kneader to obtain BMC. This BMC is molded under the conditions of an upper mold temperature of 135 ° C., a lower mold temperature of 130 ° C., a press pressure of 85 kgf / cm ² , and a keeping time of 10 minutes, and the granular filler (C) is granite (a). Got Furthermore, as a granular filler (C), marble (white cold water 2 part stone)
A molded article (a) was obtained in the same manner except that the same amount of natural stone having a particle size of 3 to 5 mm and a natural stone amount of 45% by weight) was used.
Further, the above-mentioned (A) fine powder filler was changed from aluminum hydroxide to glass powder (manufactured by Konak FMB-5W001 Nitto Boseki Co., Ltd.) and similarly prepared granular filler (C).
To obtain a molded product (C) which is a granite.

<Example 1> The surface of a molded product (a) having a size of 5 x 15 cm was sandblasted by a direct pressure type (Ascon Blasting Machine BA-2 manufactured by Atsuko Tekko Co., Ltd.), and the blasting condition was a pressure of 5 kgf / cm ² . Distance 20 cm, processing time 120 min / m ² , alumina abrasive (Morundum A #
60 Showa Denko KK: Blasting with Mohs hardness 9) gave a molded product in which natural stone had recesses. In addition to this, a transparent acrylic urethane resin (Arotane 2816
By spraying 20 to 30 μm (manufactured by Nippon Shokubai Co., Ltd.) and curing it, a patterned artificial stone having irregularities of 1.5 mm and a deep grain tone was obtained.

<Example 2> The surface of a molded product (a) having a size of 5 x 15 cm was sandblasted directly using a pressure type (Ascon Blasting Machine BA-2 manufactured by Atsuko Tekko Co., Ltd.) under a blasting condition of a pressure of 5 kgf / cm ² . Molded product in which natural stones formed protrusions when blasting was performed with a distance of 5 cm, processing time of 300 min / m ² , and plastic grain abrasive (Polyplus # 60-80 US Technologie Far East Co., Ltd .: Mohs hardness 3-4) was gotten. To this, 20 parts of transparent acrylic urethane resin (Arotane 2816 manufactured by Nippon Shokubai Co., Ltd.)
~ 30μm 1.5mm by spraying and curing
A patterned artificial stone with unevenness and deep stone patterns was obtained.

<Example 3> The surface of a molded product (a) of size 5 x 15 cm was sandblasted directly using a pressure type (Ascon Blasting Machine BA-2, manufactured by Atsuko Tekko Co., Ltd.) under a blasting condition of a pressure of 5 kgf / cm ² . Distance of 20 cm, processing time 300 min / m ² , steel shot abrasive (TSH
-60 Ito Kiko Co., Ltd .: Blasting with a Mohs hardness of 4 to 5) gave a molded product in which natural stone had recesses. In addition to this, a transparent acrylic urethane resin (Arotane 2
By spraying 816 (manufactured by Nippon Shokubai Co., Ltd.) for 20 to 30 μm and curing it, a patterned artificial stone with unevenness of 1.5 mm and a deep stone pattern was obtained.

<Example 4> The surface of a molded product (c) having a size of 5 x 15 cm was sandblasted directly by pressure (Ascon Blasting Machine BA-2 manufactured by Atsuko Tekko Co., Ltd.), and the blast condition was a pressure of 5 kgf / cm ² . Distance 20 cm, processing time 120 min / m ² , silicon carbide abrasive (Green Densic GC # 60 manufactured by Showa Denko KK: Mohs hardness 9-
When blasting was performed in 10), a molded product in which natural stone had a recess formed was obtained. 20 to 3 parts of transparent acrylic urethane resin (Arotane 2816 manufactured by Nippon Shokubai Co., Ltd.)
By spraying with 0 μm and hardening, a patterned artificial stone with a rough texture and a depth of 1.5 mm was obtained.

<Comparative Example 1> The surface of a molded product (a) having a size of 50 × 50 cm was wet-polished at 450 rpm with a wet polishing machine (Isobe Iron Works Co., Ltd.) at a metal and resin diamond grindstone (M6 polishing machine: M6). 50, # 200, and # 5
No. 00 was polished, but only a smooth surface (irregularities of 0.3 mm: FIG. 6) was obtained.

[0032]

EFFECTS OF THE INVENTION According to the present invention, the surface has irregularities, the texture of natural stone is maintained, and the stain resistance, weather resistance, and
A patterned artificial stone having properties such as water resistance can be obtained. Furthermore, the manufacturing method of the patterned artificial stone is an easy and safe manufacturing method.

[Brief description of drawings]

FIG. 1 is a state in which a surface of a molded product is roughened to form concaves in a granular filler and is further coated with a transparent resin.

FIG. 2 is a molded product.

FIG. 3 shows a state where the surface of a molded product is roughened so that the granular filler becomes convex.

FIG. 4 is a state in which the granular filler is concaved by roughening the surface of the molded product.

FIG. 5 is a state in which the surface of the molded product is roughened to form the convex portion of the granular filler and further coated with the transparent resin.

6 is a surface condition of a molded product of Comparative Example 1. FIG.

[Explanation of symbols]

 a: matrix part b: granular filler c: transparent resin d: press-molded product

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Claims (6)

[Claims] 1. A thermosetting resin (A) and a Mohs hardness of 2 to 7
Molded product (E) obtained by curing a thermosetting resin composition (D) containing the granular filler (C), and a transparent film having a thickness of 0.02 to 5.0 mm attached to the surface thereof. A patterned artificial stone made of a resin (G), wherein a part of the surface of the molded article (E) is exposed by forming a convex portion or a concave portion on the surface of the granular filler (C), A patterned artificial stone having a depth or height of 0.5 to 6.0 mm on the surface of a transparent resin (G). 2. A thermosetting resin composition (D), wherein the thermosetting resin composition (D) has a refractive index of 1.53 to 1.65 when cured.
And a finely powdered filler (B) which, when added to the thermosetting resin (A) to cure the resin, has a Mohs hardness of 2 to 4 as a fine powder filler (B). stone. 3. The patterned artificial stone according to claim 1, wherein the granular filler (C) is a crushed product of natural stone. 4. Thermosetting resin (A) and Mohs hardness 2 to 7
The thermosetting resin composition (D) containing the particulate filler (C) of (1) is used to form an abrasive (F) having a Mohs hardness of 7 to 10 on at least a part of the surface of the molded article (E) obtained. ) Is sprayed to roughen the surface to form a concave portion in which the granular filler (C) is exposed, and then the transparent resin (G) is applied to the surface of the patterned artificial stone. 5. A thermosetting resin (A) and Mohs hardness of 6 to 7
Of the molded product (E) obtained by curing the thermosetting resin composition (D) containing the granular filler (C) of No. 3, the abrasive (F of Mohs hardness of 3 to 4). ) Is sprayed to roughen the surface to form convex portions in which the granular filler (C) is exposed, and then the transparent resin (G) is applied to the surface of the patterned artificial stone. 6. The granular filler (C) is a crushed product of natural stone, and the thermosetting resin composition (D) is added to the thermosetting resin (A) to cure the resin. The method for producing a patterned artificial stone according to claim 4 or 5, comprising a fine powder filler (B) having a Mohs hardness of 2 to 4 as a cured product.