JP2763558B2 - Stone-grain artificial stone - Google Patents

Description

The present invention relates to a stone-grain artificial stone having a deep color tone and excellent strength and heat resistance.

(B) Conventional Art Conventionally, many granite-like terrazzos made of fine crushed natural stone (eg, granite, marble, etc.) as cement aggregate are commercially available as granite-grain artificial stone.

However, these lack the depth of natural granite,
Poor realism.

Therefore, the present inventors have conducted intensive studies to improve such disadvantages, and as a result, colored natural stone crushed as a filler with a specific coloring agent, or replaced a part of this colored stone with slag. By using an aluminum hydroxide powder and an unsaturated polyester resin as a binder, we succeeded in inexpensively producing a natural granite with the same depth, gloss, and strength as or higher. ,
Such artificial stone is disclosed in Japanese Patent Publication No. 62-22939.

(C) Problems to be solved by the invention However, such artificial stone still has the following problems to be solved.

That is, such artificial stones are still not sufficient in physical or chemical strength. For example, if a load is applied to the surface of the artificial stone counter due to insufficient bending strength, the surface will be damaged or cracked, etc.On the other hand, a hot pot etc. will be mistakenly placed on the surface of the counter. When placed, the placed portion was liable to crack or discolor due to high heat, which significantly impaired the beauty of the counter.

An object of the present invention is to provide an artificial stone capable of solving the above problems.

(D) Means for Solving the Problems The present invention provides: a) a transparent gel coat layer made of an unsaturated polyester resin, b) a colored stone, a magnesium hydroxide powder, a glass powder, and a calcium aluminate powder. The present invention relates to a stone-grain artificial stone composed of at least one kind of filler and a base layer made of unsaturated polyester.

In such stone-grain artificial stone, a part of the colored stone forming the base layer can be replaced by slag.

As the filler for forming the base layer, magnesium hydroxide powder, glass powder or calcium aluminate powder whose surface is subjected to silane treatment can also be used.

Further, a colored stone forming a base layer, a filler made of magnesium hydroxide powder, glass powder, or calcium aluminate powder, or at least a part of the filler subjected to silane treatment on the surface was subjected to aluminum hydroxide or silane treatment on the surface. It can be replaced by aluminum hydroxide.

The base layer is preferably formed of a mixture of 10 to 70% by weight of a colored stone, 15 to 70% by weight of a filler, and 10 to 40% of an unsaturated polyester resin.

And various products, such as a stone-grain artificial stone counter, a table top, and a wall material, can be manufactured from the stone-grain artificial stone having the above-mentioned composition by a desired manufacturing method.

The thickness of the surface layer and the base layer is about 0.1 mm to 1.0 mm for the former and about 5 to 50 mm for the latter, and can be arbitrarily determined according to the product using the artificial stone.

Using this artificial stone, counter, table top,
It can be used for products such as wall materials.

 Hereinafter, the present invention will be described in more detail.

First, as the unsaturated polyester resin gel coat (paint) used to form the surface layer in the present invention, all known gel coats can be used equally. However, when a coating film is formed, a material that is kept transparent is used.
This type is readily available on the market.

Further, such a paint can be applied by brush painting or spraying.

The natural stone used as the filling stone in the present invention includes all natural stones that can be colored according to the purpose, and is preferably hydrated stone.

Generally, packing stones having an average particle size in the range of 0.5 mm to 5 mm can be used, preferably about 1 mm in average particle size. The proportion of the filling stone used is 15 to 68% by weight, preferably 31 to 56% by weight, based on all components of the base layer.

Magnesium hydroxide powder, glass powder, calcium aluminate powder or aluminum hydroxide powder used in the present invention, or the particle size of the filler composed of those obtained by subjecting them to cyan treatment is generally in the range of 2 to 90 μm, and 20 to 90 μm. 70μ
The range of m is preferred.

The use of particles having such a particle size has the advantage that the resulting artificial stone has a greater depth and fills the gaps between the packing stones having a larger particle size, thereby reducing the number of pinholes.

Also, such magnesium hydroxide powder, glass powder,
The filler made of calcium aluminate powder or aluminum hydroxide powder, or those obtained by subjecting them to silane treatment, adheres firmly to the unsaturated polyester resin used as the binder, so that the strength of the resulting artificial stone increases.

The proportion of magnesium hydroxide powder, glass powder, calcium aluminate powder or aluminum hydroxide powder, or those obtained by silane treatment thereof, is 15 to 58% by weight, preferably 28 to 46% by weight, based on all components of the base layer. weight%
It is.

In the above filler, magnesium hydroxide powder and calcium aluminate have a crystallization water release temperature of about 30.
0 ° C. to 350 ° C., which is effective for heat whitening resistance.

Further, as the glass powder, a known glass powder used for an enamel or the like can be used.

The silane treatment is performed to promote a chemical bond between the unsaturated polyester resin and an inorganic material such as glass powder. When performing the cyan treatment, vinyl silane, acrylic silane, epoxy silane, amino silane, titanium-based Silane or the like can be used.

In the present invention, the unsaturated polyester resin forming a part of the base layer is used as a binder of the base layer, and a known unsaturated polyester resin can be used.
To impart depth to the resulting artificial stone, it is preferable to use an unsaturated polyester resin having a refractive index similar to that of a filler made of magnesium hydroxide, glass, calcium aluminate, aluminum hydroxide, or the like.

In addition, this unsaturated polyester resin is economical because it is less expensive than acrylic resin and the like.

The usage ratio of these binders is 14 to 30% by weight, preferably 16 to 26% by weight, based on all components of the base layer.

Next, coloring of the filling stone will be described. The colorant composition used in coloring the packing stone must have no affinity for the binder and have a micro-coating effect.

When the filling stone is colored with a paint having an affinity for the unsaturated polyester resin (for example, lacquer, urethane, or the like), when the colored filling stone is dried and kneaded with the unsaturated polyester resin, or After kneading, the paint dissolves into the unsaturated polyester resin, and the pigment disperses, so that the entire base layer is colored. Thus, the grain of the colored filler stone is blurred.

Therefore, in the present invention, as the colorant composition that satisfies the above properties, a composition comprising water glass or linseed oil and a pigment is used.

The component is preferable in that it satisfies the above-mentioned properties, easily dissolves the powder pigment, has excellent drying properties, and firmly binds the filler stone and the pigment.

 Further, inorganic pigments are preferred as the pigment used.

Multicolored filler stones can be made by arbitrarily selecting the coloring composition, or by combining two or more colored filler stones, or by changing the mixing ratio thereof,
It is possible to reproduce the colors of various natural stones.

 Filling stones, for example cold water stones, are colored as follows.

Formulation A Chilled stone (average particle size 1 mm) 100.0 parts by weight Water glass 6.6 parts by weight Inorganic pigment 1.0 part by weight Formulation B Chilled stone (average particle size 1 mm) 100.0 parts by weight Linseed oil 9.5 parts by weight Inorganic pigment 1.2 parts by weight or more The compound A or B having the component constitution is put into a mixer, mixed sufficiently homogeneously, colored, and dried to obtain a colored cold water stone.

The above mixing examples are merely exemplifications, and various kinds of colored packing stones can be easily obtained by appropriately selecting the types and mixing ratios of components and inorganic pigments according to a desired color tone.

A part of the colored natural stone used in the present invention, that is, less than 100% by weight of slag (for example, iron slag,
Nickel slag, copper slag, tin slag, zinc slag, etc.) can also provide a desired artificial stone.

The base layer of the stone-grain artificial stone of the present invention is a colored filler stone,
Magnesium hydroxide, glass, fillers such as calcium aluminate or aluminum hydroxide and the unsaturated polyester resin are charged into a mixer, and after kneading,
It is obtained by casting and curing.

Hereinafter, an example of a method for manufacturing a washbasin counter using cold water stones will be described.

A predetermined amount of the unsaturated polyester resin is weighed and placed in a stirring can, and after the catalyst is charged, the colored cold water stone and glass are weighed in a predetermined amount and charged into the stirring can, followed by stirring for several minutes.

Then, this is cast on a surface of the surface of the surface mold which has been cured by spraying an unsaturated polyester resin gel coat in advance.

 After shaking and defoaming, assemble the back mold and cure at room temperature.

After curing, the back mold is released, the product is taken out, and placed in a curing chamber (for example, about 40 to 60 ° C.) for a predetermined time (for example, about 3 hours).
Perform curing for 12 hours.

Then, after deburring the periphery, sanding and buffing of the surface are performed to obtain a deep stone-grain artificial stone, which can be used as a wash counter.

As the catalyst, all known catalysts for the curing reaction of unsaturated polyester can be used.

For example, methyl ethyl ketone peroxide (MEKPO), benzoyl peroxide-dimethylaniline (BPO-DMA), methyl ethyl ketone peroxide-cobalt naphthenate (RM-
Co) type.

By the way, when forming the base layer, if the viscosity of the cast material is too low, the colored stone (or the mixture of the colored stone and the slag) is separated due to the difference in specific gravity, and particularly the vertical portion of the product is unsightly in appearance. Become.

On the other hand, when the viscosity is high, it becomes a paste and cannot be cast.

The appropriate viscosity at the time of casting can be adjusted by appropriately selecting the amounts of the colored stone (or partially replaced by slag), glass, and unsaturated polyester resin within the above ranges.

Next, an example of the present invention will be described. However, this example is given for illustrative purposes only and does not limit the scope of the present invention. The artificial stones described in the following examples were made according to the above-mentioned manufacturing method, and the surface layer used in all the examples had the following composition.

Composition of Surface Layer Unsaturated polyester resin 93 parts by weight Styrene monomer 5 parts by weight Curing accelerator 1 part by weight Catalyst (Nippon Yushi Co., Ltd., Permec N) 1 part by weight (e) Examples The artificial stone will be specifically described with reference to examples.

[First Example (Kuroishime artificial stone)] Composition of base layer Unsaturated polyester resin 22 parts by weight Glass powder (particle diameter 50 μm) 36 parts by weight Colored chilled stone (particle diameter 0.6 mm) (gray) 11 parts by weight Colored chilled water Stone (particle size 0.6mm) (white) 6 parts by weight Slag (particle size 0.6mm) (black) 4 parts by weight Slag (flow type 0.6mm) (black) 21 parts by weight Catalyst (55% MEKPO) 0.2 part by weight Was used to obtain a black stone-grain artificial stone. This was observed to be excellent in both depth and gloss and equivalent to natural stone.

The bending strength of conventional black sandstone artificial stone is 365 kg / cm.
^In contrast to the value of ² , in the present example, the value was 404 kg / cm ² , and the strength was improved.

This is considered to be due to the fact that the inclusion of the glass powder increased the adhesion between the colored stone or the filler and the unsaturated polyester resin and improved the bonding strength.

Furthermore, in the oil pan heat resistance test, the temperature exceeded 200 ° C to 230 ° C, and the heat crack resistance was greatly improved. Also, almost no discoloration due to high temperature was observed.

[Second Example (Kuroishime Artificial Stone)] Composition of Base Layer Unsaturated polyester resin 22 parts by weight Glass powder treated with acrylsilane (particle size: 50 μm) 36 parts by weight Colored cold water stone (particle size: 0.6 mm) (gray) 11 6 parts by weight Colored fluorite (particle size 0.6 mm) (white) 6 parts by weight Slag (particle size 0.6 mm) (black) 4 parts by weight Slag (particle size 0.6 mm) (black) 21 parts by weight Catalyst (55% MEKPO) 0.2 Part by weight Using the above components, a black stone-grain artificial stone was obtained according to the above-mentioned production method. This was observed to be excellent in both depth and gloss and equivalent to natural stone.

The bending strength of conventional black sandstone artificial stone is 365 kg / cm.
^In contrast to ² , it was 420 kg / cm ² in the present example, and the strength was significantly improved.

This is considered to be because the adhesion of the colored stone or filler to the unsaturated polyester resin was further increased by the inclusion of the glass powder (acrylsilane-treated product), and the bonding strength was significantly improved.

In addition, in the oil pan heat resistance test, the temperature exceeded 200 ° C to 230 ° C, and the heat crack resistance was greatly improved. Also,
Almost no discoloration due to high temperature was observed.

[Third Example (Kuroishime Artificial Stone)] Composition of Base Layer Unsaturated polyester resin 23 parts by weight Magnesium hydroxide (particle size: 30 μm) 35 parts by weight Colored cold water stone (particle size: 0.6 mm) (gray) 11 parts by weight Sparstone (particle size 0.6 mm) (white) 6 parts by weight Slag (particle size 0.6 mm) (black) 4 parts by weight Slag (particle size 0.6 mm) (black) 21 parts by weight Catalyst (55% MEKPO) 0.2 parts by weight Using the components, a black stone-grain artificial stone was obtained according to the above-mentioned production method. This was observed to be excellent in both depth and gloss and equivalent to natural stone.

The bending strength of conventional black sandstone artificial stone is 365 kg / cm.
^In contrast to ² in the present example, it is 400 kg / cm ² , which is an improvement in strength.

This is considered to be because the adhesion of the colored stone or filler to the unsaturated polyester resin was further increased by the addition of magnesium hydroxide, and the bonding strength was improved.

In addition, in the oil pan heat resistance test, the temperature exceeded 200 ° C to 230 ° C, and the heat crack resistance was greatly improved. Also,
Almost no discoloration due to high temperature was observed.

[Fourth Example (Kuroishime Artificial Stone)] Composition of Base Layer Unsaturated polyester resin 25 parts by weight Calcium aluminate (particle size: 30 μm) 33 parts by weight Sparstone (particle size 0.6 mm) (white) 6 parts by weight Slag (particle size 0.6 mm) (black) 4 parts by weight Slag (particle size 0.6 mm) (black) 21 parts by weight Catalyst (55% MEKPO) 0.2 parts by weight Using the components, a black stone-grain artificial stone was obtained according to the above-mentioned production method. This was observed to be excellent in both depth and gloss and equivalent to natural stone.

The bending strength of conventional black sandstone artificial stone is 365 kg / cm.
^In contrast to ² , it is 401 kg / cm ² in the present embodiment, and the strength is improved.

This is considered to be due to the fact that the inclusion of calcium aluminate increased the adhesion between the colored stone or the filler and the unsaturated polyester resin and improved the bonding strength.

In addition, in the oil pan heat resistance test, the temperature exceeded 200 ° C to 230 ° C, and the heat crack resistance was greatly improved. Also,
Almost no discoloration due to high temperature was observed.

[Fifth Example (Brown-tone artificial stone)] Composition of base layer Unsaturated polyester resin 26 parts by weight Glass powder (particle size: 50 μm) 36 parts by weight Colored cold water stone (particle size: 0.6 mm) (green) 4 parts by weight Coloring 10% by weight of colored waterstone (particle diameter 0.6mm) (yellow) 8 parts by weight Colored waterstone (particle diameter 0.6mm) (brown) 14 parts by weight Slag (particle diameter 0.6mm) ) (Brown) 2 parts by weight Catalyst (55% MEKPO) 0.3 parts by weight Using the above components, a brown stone-like artificial stone was obtained according to the production method. This was observed to be excellent in both depth and gloss and equivalent to natural stone.

The bending strength of conventional sandstone artificial stone is 365 kg / cm.
^In contrast to ² , it is 401 kg / cm ² in the present embodiment, and the strength is improved.

This is presumably because the inclusion of the glass powder increased the adhesion between the colored stone or filler and the unsaturated polyester resin, and improved the bonding strength.

In addition, in the oil pan heat resistance test, the temperature exceeded 200 ° C to 230 ° C, and the heat crack resistance was also improved. Also, almost no discoloration due to high temperature was recognized.

Sixth Example (Shiraishi-grain artificial stone) Composition of base layer Unsaturated polyester resin 22 parts by weight Aluminum hydroxide surface-treated product (particle size 20 μm) 17 parts by weight Glass powder (particle size 50 μm) 17 parts by weight (Particle diameter 0.6 mm) (white) 24 parts by weight Colored fluorite (particle diameter 0.6 mm) (gray) 4 parts by weight Calcium carbonate 2 parts by weight Catalyst (55% MEKPO) 0.3 parts by weight , Shiraishi-grain artificial stone was obtained. This was observed to be excellent in both depth and gloss and equivalent to natural stone.

The bending strength of conventional black sandstone artificial stone is 380 kg / cm.
^In contrast to ² , it is 420 kg / cm ² in the present embodiment, and the strength is improved.

This is considered to be because the adhesion of the colored stone or filler to the unsaturated polyester resin was increased by the inclusion of the surface-treated product of glass powder and aluminum hydroxide, and the bonding strength was significantly improved.

In addition, in the oil pan heat resistance test, the temperature exceeded 200 ° C to 230 ° C, and the heat crack resistance was greatly improved. Also,
Almost no discoloration due to high temperature was observed.

(F) Effect In the present invention, the stone-grain artificial stone is prepared by: a) a transparent gel coat layer made of an unsaturated polyester resin, b) a colored stone, a magnesium hydroxide powder, a glass powder, and a calcium aluminate powder. A filler that is at least one of
The artificial stone having a deep natural stone tone was obtained by being composed of the base layer composed of the unsaturated polyester resin. In addition, magnesium hydroxide powder and the like have a release temperature of crystal water of about
Since the temperature is as high as 300 ° C. to 350 ° C., a counter or the like having high heat whitening resistance can be manufactured.

In addition, by performing the silanization treatment on the filler described above, the filler is firmly adhered to the unsaturated polyester resin used as the binder, and the strength of the generated artificial stone can be increased, and the heat crack resistance can be improved. it can.

Further, when the colored stone is colored with a coloring agent composed of water glass or linseed oil and a pigment, it has no affinity for the unsaturated polyester resin as a binder, but has a microscopic coating effect, so that it is distinct. A natural stone pattern can be exhibited, and the commercial value of the artificial stone can be enhanced from an aesthetic point of view.

In addition, when part of colored stones is replaced with slag, in cooperation with unsaturated polyester resin used as a binder, artificial stones with the same depth, gloss and strength as natural granite are manufactured in cooperation with natural granite. can do.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C04B 111: 54 (72) Inventor Makoto Mizuguchi 4-1-1 Yukawa, Kokuraminami-ku, Kitakyushu-shi, Fukuoka References JP-A-49-115194 (JP, A) JP-A-60-65059 (JP, A) JP-A-2-102156 (JP, A) JP-A-1-261252 (JP, A) 63-196647 (JP, A) JP-B 62-22939 (JP, B2) JP-B 60-20417 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) C04B 26/18 C04B 14/02 C04B 14/22 C04B 14/36 C08L 67/06 C08K 3/22 C08K 3/40 C04B 111: 54 C04B 14:02 C04B 14:22 C04B 14:36

Claims (5)

(57) [Claims] A) a transparent gel coat layer made of an unsaturated polyester resin; b) a colored stone, a magnesium hydroxide powder, a glass powder, and a filler which is at least one of calcium aluminate powder; Stone-grain artificial stone composed of a base layer made of unsaturated polyester resin. 2. A stone-grain artificial stone comprising: a) a transparent gel coat layer composed of an unsaturated polyester resin; b) a colored stone, a silane-treated filler, and a base layer composed of an unsaturated polyester resin. . 3. A filler according to claim 2, wherein the filler is at least one or more of magnesium hydroxide powder, glass powder and calcium aluminate powder.
The described stone-grain artificial stone. 4. The colored stone is colored with a colorant comprising water glass or linseed oil and a pigment.
The stone-grained artificial stone according to claim 3. 5. The artificial stone according to claim 1, wherein a part of the colored stone is replaced by slag.