KR101861900B1 - Composition using construction materials and engineered stone chip having metal pearl pattern and Engineered stone using the same - Google Patents
Composition using construction materials and engineered stone chip having metal pearl pattern and Engineered stone using the same Download PDFInfo
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- KR101861900B1 KR101861900B1 KR1020150177500A KR20150177500A KR101861900B1 KR 101861900 B1 KR101861900 B1 KR 101861900B1 KR 1020150177500 A KR1020150177500 A KR 1020150177500A KR 20150177500 A KR20150177500 A KR 20150177500A KR 101861900 B1 KR101861900 B1 KR 101861900B1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/34—Metals, e.g. ferro-silicon
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2676—Polystyrenes
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/28—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/283—Polyesters
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Abstract
The reinforcing natural stone composition of the present invention, the reinforcing natural stone having the metal pearl texture and the reinforcing natural stone comprising the same, (A) 10 to 60% by weight of the sand type silica having an average particle diameter of 0.1 to 0.3 mm or less; (B) 5 to 40% by weight of a powdery silica having an average particle diameter of 0.1 mm or less; (C) 5 to 40% by weight of an unsaturated polyester resin; (D) 1 to 10% by weight of metallic pearl particles; And (E) 1 to 10% by weight of a styrene-based monomer.
Description
The present invention relates to a composition for reinforcing natural stone, a reinforcing natural stone having a metal pearl texture and a reinforced natural stone containing the same.
Natural stones such as granite and marble have been used as building materials since ancient times because of their beautiful surface patterns. In recent years, natural stone has attracted attention as a material showing high-quality texture, and its demand has been greatly increased in the fields of flooring, wall, and sink top plate.
On the other hand, natural stone has not been popularized due to its high price, heavy weight, and weakness in impact despite its high surface hardness and beautiful pattern. Various types of artificial stones have been developed to overcome this.
Unlike natural stones, artificial stones have a variety of images and patterns, have excellent gloss, are resistant to severe temperature changes, have low water absorption and high strength.
These artificial stones are used in luxury houses, hotels, apartments, etc., and can provide excellent interior effects, so that demand is rapidly increasing all over the world.
In general, artificial stones are classified into general artificial marble and resin-reinforced natural stone. The above-mentioned general artificial marble is produced by adding various additives such as an inorganic filler, a colorant and a curing agent to an acrylic or unsaturated polyester resin. The resin-reinforced natural stone (so-called engineered stone) is made by compressing a compound made of a mineral (silica-based) natural mineral and a binder resin by vibration or vacuum-vibration so as to express the texture of the natural stone .
The resin-reinforced natural stone can be manufactured to exhibit various colors and textures depending on the type of natural minerals to be mixed, the color of the binder resin or pigment, the stirring process, and the like. Since the resin-reinforced natural stone is made of natural minerals as a main raw material, it has a much higher natural texture than ordinary artificial marble, and the demand for the resin-reinforced natural stone has been greatly increased in recent years.
On the other hand, in recent years, the use of metal has been increasing as a material of various interior sculptures because of the cold and modern feeling unique to the metal. However, the use of metals is limited due to cost increase of materials and metal corrosion.
In addition, metal has a problem that metal texture is not clearly displayed because a pigment or a raw material having a metal texture is mixed with a specific raw material (silica, silica, etc.), and then the resin is coated by resin coating.
In addition, when a compound having a metal texture is coated on a resin surface and then hardened and crushed to produce a chip, a texture similar to a metal can be expressed. However, sharpness is significantly reduced, There is a drawback that the workability is weakened.
In order to solve the above problems, the inventors of the present invention have solved the problem of unevenness of the surface and the sharpness of the surface due to poor machinability because of excellent sharpness and hardness difference while maintaining the metal texture, Thereby completing the invention.
The background art of the present invention is disclosed in Korean Patent No. 10-0833273 (May 05, 2008).
It is an object of the present invention to provide a composition for reinforced natural stone that provides a chip having various colors and a high quality texture by raising the illuminance of a chip having a metal texture.
Another object of the present invention is to provide a reinforced natural stone chip produced using the above reinforced natural stone composition.
It is still another object of the present invention to provide a reinforced natural stone having an improved metallic pearl feel by improving the surface roughness deviation using a chip.
It is still another object of the present invention to provide a chip having a metal pearl texture improved in surface roughness deviation and hardness by applying chips to a shaped or irregular shape, and reinforced natural stone produced using the same.
The above and other objects of the present invention can be achieved by the present invention described below.
One aspect of the present invention relates to a composition for reinforced natural stone. The reinforced natural stone composition comprises (A) 10 to 60% by weight of a sand-like silica having an average particle diameter of 0.1 to 0.3 mm; (B) 5 to 40% by weight of a powdery silica having an average particle diameter of 0.1 mm or less; (C) 5 to 40% by weight of an unsaturated polyester resin; (D) 1 to 10% by weight of metallic pearl particles; And (E) 1 to 10% by weight of a styrene-based monomer.
In an embodiment, the composition for reinforcing natural stone may further comprise a sand-type silica having an average particle diameter of more than 0.3 mm but not more than 0.7 mm.
In an embodiment, the composition for reinforcing natural stone may not contain sand-type silica having an average particle diameter of more than 0.7 mm.
In the concrete examples, the amount of the curing accelerator, the curing accelerator, the crosslinking agent, the pigment, the dye, the leveling agent, the ultraviolet absorber, the storage stabilizer, the light diffusing agent, the antioxidant, the polymerization inhibitor, the flame retardant and the antistatic agent 0.01 to 5 parts by weight of at least one additive selected.
In an embodiment, the unsaturated polyester resin has a weight average molecular weight of 70,000 to 100,000 and a viscosity at 25 ° C of 500 to 600 cps.
In an embodiment, the unsaturated polyester resin may be any one or two or more selected from ortho type, iso type, bisphenol type, vinyl ester type and novolak vinyl ester.
In an embodiment, the metallic pearl particles comprise at least one natural component selected from the group consisting of core, stone, quartz, charcoal, loess, magnetite, fragrance, pearl, shellfish and mirror powder .
In an embodiment, the styrene-based monomer is at least one member selected from the group consisting of? -Methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, -Bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, and m-chlorostyrene.
Another aspect of the present invention relates to a chip for reinforced natural stone. The chip for reinforcing natural stone is formed from the composition for reinforcing natural stone described above and has a metal pearl texture.
In a specific example, the reinforced natural stone chip may have a structure in which sand type silica, powder type silica and metallic pearl particles are dispersed in a continuous phase comprising an unsaturated polyester resin and polystyrene.
In embodiments, the hardened natural stone chips may have a hardness of 75 to 85 as measured with a Barcol hardness tester (GYZJ 934-1, Barber Colman company).
Another aspect of the present invention relates to reinforcing natural stone. The reinforcing gemstones include 1 to 20% by weight of the above-mentioned reinforcing natural stone chips; 7 to 20% by weight of an unsaturated polyester resin; And 60 to 90% by weight of a silica-based inorganic material, and has a metal texture.
In an embodiment, the reinforcing natural stone may have a structure in which a reinforcing natural stone chip and a silica-based inorganic material are dispersed in a matrix containing an unsaturated polyester resin.
In an embodiment, the silica-based inorganic material has a metal texture including a sand-type silica-based inorganic material having an average particle size of 0.1 to 2.0 mm, a quartz chip having an average particle size of 1.2 to 5.6 mm, and a powder- .
In a specific example, the 100 parts by weight of the reinforcing gemstone is selected from a curing agent, a curing accelerator, a crosslinking agent, a pigment, a dye, a leveling agent, an ultraviolet absorber, a storage stabilizer, a light diffusing agent, an antioxidant, And may further contain 0.01 to 20 parts by weight of any one or two or more additives.
In the specific examples, the reinforced natural stone may have a metal pearl texture having a maximum cross-sectional depth (Rv) of 6.0 탆 or less and a maximum height Ry of 10 탆 or less as measured by JIS B 0601.
The present invention can increase the illuminance of a chip having a metal texture to have a variety of colors and a luxurious texture in addition to the original texture of natural stone. Further, according to the present invention, the difference in hardness between the chip and the reinforced natural stone is largely reduced to improve the surface processability, and the surface roughness is lowered, so that an elegant and luxurious texture closer to natural marble can be expressed. The present invention also includes a reinforced natural stone composition combined with a specific silica size and content for making the chip, a chip made using the same, and an unsaturated resin of the same category as the silica and the chip The present invention has the effect of providing a new reinforced natural stone improved in metal texture, improved surface roughness and surface uniformity by minimizing the difference in hardness between the chip and the matrix of reinforced natural stone.
Fig. 1 shows a chip for reinforced natural stone, which has been judged to be good by the embodiment of the present invention.
Fig. 2 shows a chip for reinforced natural stone, which has been judged to be defective by a comparative example of the present invention.
Fig. 3 shows reinforced natural stone, which has been judged to be good according to an embodiment of the present invention.
4 shows the reinforced natural stone which has been judged to be defective by the comparative example of the present invention.
Hereinafter, the composition for reinforcing natural stone according to the present invention, the reinforcing gemstone chip and the reinforced natural stone comprising the same will be described in detail with reference to specific examples.
The following embodiments are provided by way of example so that those skilled in the art can fully understand the spirit of the present invention. It will be apparent to those skilled in the art that, unless otherwise defined, technical terms and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, And a description of the known function and configuration will be omitted.
In addition, unless otherwise specified in the present specification, "average particle diameter" means an average value of the maximum length and the minimum length of the particles. In the present invention, the average particle size can be measured according to KS F 5102 (method for testing the sieve aggregate of coarse aggregate and fine aggregate), but not limited to KS A 5101-1 (# 16 mesh), 0.1 mm (# 150 mesh), and 0.045 mm (# 325 mesh) based on the scale size of the sieves.
Hereinafter, each component will be described in more detail.
Composition for reinforced natural stone
The reinforced natural stone composition according to the present invention comprises (A) 10 to 60% by weight of a sand-like silica having an average particle diameter of 0.1 to 0.3 mm; (B) 5 to 40% by weight of a powdery silica having an average particle diameter of 0.1 mm or less; (C) 5 to 40% by weight of an unsaturated polyester resin; (D) 1 to 10% by weight of metallic pearl particles; And (E) 1 to 10% by weight of a styrene-based monomer.
(A, B) silica
In the present invention, the silica is added in order to secure a texture close to a natural stone, to replace the use of an unsaturated polyester resin as a base resin, and to realize the mechanical properties of a chip for a reinforced natural stone produced. And powder type can be adopted.
In the present invention, the sand-type silica preferably has an average particle diameter of 0.1 to 0.3 mm, for example, 0.15 to 0.25 mm, for example, 0.18 to 0.22 mm. If the average particle diameter of the sand-type silica is less than 0.1, there is a problem that the implementation of mechanical properties through the inclusion of silica particles is insufficient. On the other hand, when the average particle size of the sand-type silica is more than 0.3, it is difficult to realize effects such as strengthening of natural stone texture and improvement of physical properties such as surface hardness.
In one embodiment of the present invention, the composition for reinforcing natural stone may further include sand-type silica having an average particle diameter of more than 0.3 mm but not more than 0.7 mm. In the above average particle diameter range, it is easy to realize the mechanical properties of the reinforced natural stone chip manufactured while replacing the use of the unsaturated polyester resin.
In another embodiment of the present invention, the composition for reinforcing natural stone may not contain sand type silica having an average particle diameter of more than 0.7 mm. When the average particle diameter is more than 0.7 mm, the specific surface area of the metal pearl decreases with an increase in the average particle diameter of the silica, thereby reducing the metal texture effect.
In the present invention, the sand-type silica may include 10 to 60% by weight, more preferably 20 to 60% by weight, and most preferably 35 to 50% by weight, based on 100% by weight of the whole reinforcing natural stone composition. When the content of the sand-type silica is less than 10% by weight, there is a problem that the effect of containing the sand-type silica becomes insufficient. On the other hand, when the content of the sand-type silica is more than 60% by weight, the bonding strength with the unsaturated polyester resin and the mechanical properties of the chips are deteriorated, and it is difficult to effectively realize a natural- .
In the present invention, the powdery silica may have an average particle size of 0.1 mm or less, for example, preferably 0.045 mm or less, for example, 0.030 mm or less. When the average particle size of the powdery silica is more than 0.1 mm, it is difficult to compaction of the reinforcing natural stone chip produced through the composition for reinforcing natural stone, the improvement of the mechanical properties is lowered, and it is difficult to secure sufficient stability in the impact etc. .
In the present invention, the powdery silica may include 5 to 40% by weight, for example, preferably 25 to 30% by weight, for example, 20 to 25% by weight, based on 100% by weight of the whole reinforcing natural stone composition. When the content of the powdery silica is less than 5% by weight, there is a problem that the effect of containing the powdery silica is insufficient. On the other hand, when the content of the powdery silica is more than 40% by weight, it is difficult to sufficiently maintain the molding and mechanical properties of the product, and it is difficult to maintain the surface hardness upon bonding with the unsaturated polyester resin required for product formation there is a problem.
(C) unsaturated polyester resin (UPE)
In the present invention, the reinforced natural stone composition and the unsaturated polyester resin used for manufacturing the reinforced natural stone may be combined with specific silica to improve the mechanical properties in the production of the reinforced natural stone or the reinforced natural stone.
Furthermore, by using the base resin used as a component of the reinforced natural stone or the base resin used in the manufacturing of the chip as the unsaturated polyester resin of the same category, the refractive index is maintained as it is, and the difference in hardness between the chip and the natural stone matrix is reduced, , The uniformity of the surface is ensured, and the effect of improving the transparency and the performance of the metal texture can be obtained.
The unsaturated polyester resin used in the present invention can be a resin commonly known in the art, and the polyvalent acid and / or polyhydric alcohol compound as an esterification reaction product of a polyhydric alcohol and a polyhydric alcohol may contain an unsaturated part have.
Examples of the polyvalent acid include polycarboxylic acid, polycarboxylic acid anhydride, polycarboxylic acid halide, and polycarboxylic acid ester. Specific examples of the polycarboxylic acid include maleic acid, maleic anhydride, fumaric acid, Maleic acid, ethyl maleic acid, itaconic acid, citraconic acid, geronic acid, mesaconic acid, aconic acid or a mixture thereof can be used. Further, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, or a mixture thereof, which are conventionally used in the production of a polyester resin, may be used, but is not limited thereto.
Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol and 1,4- , Trihydric alcohols such as pentaerythritol, and the like, or mixtures thereof. Specific examples of the unsaturated polyhydric alcohols include butenediol, pentenediol, allyl or vinyl glycerol ether, allyl or vinylpentaerythritol, or mixtures thereof.
The unsaturated polyester resin may be any one or two or more selected from ortho type, iso type, bisphenol type, vinyl ester type and novolak vinyl ester.
The molecular weight of the unsaturated polyester resin is not particularly limited, but preferably the weight average molecular weight is 70,000 to 100,000 (g / mol), and preferably 80,000 to 100,000 (g / mol). However, the present invention is not limited thereto. When the weight average molecular weight is within the above range, the bonding strength with the silica-based inorganic substance is improved, and smoothness and sanding property are excellently expressed in the process such as surface polishing. However, when the molecular weight is too low, the sedimentation of the chips or silica may proceed quickly, which may not be good. If the molecular weight is too high, it may be difficult to disperse the monomer sufficiently even if the monomer is added. That is, there may be problems in processability and composition, but this can be controlled by a person skilled in the art.
The unsaturated polyester resin may have a viscosity at 25 ° C of 500 to 600 cps, for example, 520 to 580 cps, for example, 540 to 560 cps. In the above viscosity range, the bonding strength with the silica-based inorganic substance is improved, and smoothness and sanding property are exhibited in the surface polishing process. At this time, the viscosity of the unsaturated polyester resin was measured according to ASTM D 2270 standard.
The unsaturated polyester resin may be added in an amount of 5 to 40% by weight, for example, preferably 20 to 25% by weight, for example, 22 to 24% by weight, based on 100% by weight of the whole reinforcing natural stone composition. When the content of the unsaturated polyester resin is less than 5% by weight, there is a problem that the effect of containing the unsaturated polyester resin becomes insufficient. On the other hand, when the content of the unsaturated polyester resin is more than 40% by weight, it is difficult to improve the metal texture and increase the workability.
(D) Metallic pearl particles
In the present invention, the metallic pearl particles are added in order to realize the texture of the composition. The metallic pearl particles are metallic pearl-colored particles, and conventional chips in the art may be used.
Such metallic pearl particles may, for example, be colored with chips representing gold, blue, bronze, or colored materials such as suitable pigments or dyes to apply various colors. Also, for example, those produced by surface treatment of a colored material by coating or vapor deposition can be used. Natural materials may also be used to provide adequate texture. Examples of such natural materials may include at least one selected from the group consisting of mother-of-pearl, stone, stone, quartz, charcoal, loess, magnet, fragrance, pearl, shellfish and mirror powder. However, as long as the object of the present invention can be realized, the kind thereof is not limited thereto.
The metallic pearl particles preferably have an average particle size of 5 mu m or less, for example, 3 mu m or less, though the average particle size is not limited. There is an advantage that an appropriate texture of the composition can be expressed in the above average particle diameter range.
The metallic pearl particles may be added in an amount of 1 to 10% by weight, for example, preferably 3 to 5% by weight, for example, 3.5 to 4.5% by weight, based on 100% by weight of the whole reinforcing natural stone composition. When the metallic pearl particles are contained in an amount of less than 1% by weight, metal texture development may be insufficient. On the other hand, when the metallic pearl particles are added in an amount of more than 10% by weight, the resin content is increased and it is difficult to secure physical properties of desired hardness, and the production cost of pearl may increase.
(E) a styrene-based monomer
The styrene-based monomer is used as a material for forming a matrix of a chip by adjusting the viscosity of the reinforced natural stone composition and inducing dispersion of silica to give a uniform metal texture and directly reacting. Also, by adopting styrene, transparency can be increased and the effect of making the metal texture more clear can be provided.
In the present invention, only the styrene-based monomer is limited in order to control the viscosity of the composition, but a halogenated styrene-based monomer or the like may be used depending on the type of the base resin, and the present invention is not limited thereto.
Examples of the styrene-based monomer include alkylstyrenes having the same properties as? -Methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, I-butylstyrene, t- o-bromostyrene, p-bromostyrene, m-bromostyrene, o-chlorostyrene, p-chlorostyrene, m-chlorostyrene and halogenated styrene having equivalent properties; And the like.
The styrene-based monomer may be contained in an amount of 1 to 10% by weight, preferably 2 to 5% by weight based on 100% by weight of the reinforced natural stone composition. When the styrene-based monomer is contained in an amount of less than 1% by weight, it is difficult to control the viscosity, making it difficult to produce chips. If it is added in an amount exceeding 10% by weight, the viscosity may be lowered, resulting in separation of the silica particles and the resin.
The composition for reinforced natural stone according to the present invention can be used for the reinforced natural stone in addition to the above-mentioned composition in addition to the above-mentioned composition, which is selected from a curing agent, a curing accelerator, a crosslinking agent, a pigment, a dye, a leveling agent, an ultraviolet absorber, a storage stabilizer, a light diffusing agent, an antioxidant, One or more additives may be further included.
Examples of the curing agent include benzoyl peroxide, lauroyl peroxide, butyl hydroperoxide, cumyl hydroperoxide, t-butyl peroxybenzoate, bis (butylperoxy) cyclododecane and dibutyl peroxide Organic peroxides may be used, and these may be used singly or in combination of two or more.
Examples of the curing accelerator include naphthenic acid salts such as cobalt naphthenate, copper naphthenate, and barium naphthenate; Octanoic acid salts such as cobalt octenoate, manganese octenoate, zinc octenoate and vanadium octanoate; Or the like, and more preferably a cobalt-based curing accelerator is preferably used.
The crosslinking agent is preferably a silane compound having a functional group selected from among ethoxy, alkoxy, aminoalkyl, alkyl, alkenyl and mercaptoalkyl groups, more preferably vinyltrimethoxysilane, vinyltriethoxysilane, n- (2-aminoethyl) -3-aminopropyltrimethoxysilane, n- (1,3-dimethyl (Triethoxysilyl) -3- (triethoxysilyl) -1-propanamine, 3- (glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl ) Ethyl trimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like are preferably used.
In addition, pigments, dyes, leveling agents, ultraviolet absorbers, storage stabilizers, light diffusing agents, antioxidants, polymerization inhibitors, flame retardants and antistatic agents, which are conventionally added in the art, may be further included as additives in addition to the above materials.
In the present invention, the additive may include 0.01 to 5 parts by weight, for example, 0.05 to 1 part by weight, for example, 0.1 to 0.5 part by weight, based on 100 parts by weight of the whole reinforcing natural stone composition. In the above content range, the preparation of the composition for reinforced natural stone for the object of the present invention can be easily carried out. The composition ratio of the additive may be a composition ratio of one material or may be an addition ratio of a composition in which two or more materials are mixed.
Chips for reinforced natural stone with metal pearl texture
A reinforced natural stone chip having a metal pearl texture according to the present invention is formed from the composition for reinforcing natural stone. That is, one embodiment includes: a1) preparing a reinforced natural stone composition by charging an unsaturated polyester resin, metal pearl, sand type silica and powder type silica and styrene; a2) injecting the composition into a mold and curing the composition; And a3) cutting and grinding the cured composition to produce a shaped or non-shaped chip; . ≪ / RTI >
The reinforced natural stone composition of the present invention may further contain an additional component including a curing agent, a crosslinking agent, and a curing accelerator.
Specifically, one embodiment may be further described, and the following embodiments may be included, and those skilled in the art may appropriately change the order of injection according to need. A1) mixing an unsaturated polyester resin, a curing agent, a crosslinking agent, a curing accelerator and a metal pearl; a2) adding a silica-based inorganic material and a styrene-based monomer and mixing them to prepare a composition; a3) injecting the composition into a mold and curing; And a4) cutting and crushing the cured composition to produce a shaped or non-shaped chip.
In the method for manufacturing a reinforced gemstone according to the present invention, the mixing method of steps a1) and a2) is not limited to the present invention and a known method may be applied.
The curing conditions in step a3) are not limited to the present invention, but may be carried out at 100 to 120 ° C for 15 to 20 minutes. There is an advantage in that it is easy to manufacture a reinforced natural stone chip having a metal pearl texture for realizing the object of the present invention in the above-mentioned curing condition range.
The reinforced natural stone chip may have a structure in which sand type silica, powder type silica and metallic pearl particles are dispersed in a continuous phase containing an unsaturated polyester resin and polystyrene. Through the above-described dispersion structure, the reinforced natural stone chip of the present invention improves the surface processability, exhibits an elegant and luxurious texture, minimizes the hardness difference between the chip and the reinforced natural stone matrix, and improves the metal texture, increases the surface roughness, An excellent effect of improving the performance can be realized.
The reinforced natural stone chips produced by the above method may have a hardness of 75 to 85 as measured with a Barcol hardness tester (GYZJ 934-1, Barber Colman company). When the surface hardness of the reinforced natural stone is within the above range, the present invention exhibits a desired clear metallic pearl texture. When the reinforced natural stone including chips is produced, the difference in hardness between the chip and the natural stone is reduced, Degradation can disappear.
In the present invention, the above-mentioned reinforcing natural stone chips can be used by shattering by a conventional method in the art. In order to obtain a metallic texture, the fractured reinforced natural stone chip according to the present invention has a better effect as the average particle size of the chip is larger. Therefore, it is preferably 5.0 mm or more, and more preferably 5.0 to 20.0 mm. When the crushed average particle size is less than 5.0 mm, formation of three dimensional solid texture is difficult. When the crushed average particle size is more than 20.0 mm, the mechanical properties may be deteriorated due to insufficient densification in the production of reinforced natural stone. May not be achieved.
Reinforced natural stone with a metal pearl texture
The reinforced natural stone having the metal pearl texture according to the present invention may comprise the unsaturated polyester resin and the silica-based inorganic substance in the above-mentioned reinforcing natural stone chip.
Chips for reinforced natural stone with pearl texture
As described above, the reinforced natural stone for chip according to the present invention is intended to impart a cold and modern feeling unique to metals to reinforced natural stone. The chip is used in an amount of 1 to 20% by weight, preferably 1 to 10% by weight %. If the reinforcing gemstone chip is contained in an amount less than 1% by weight, it may be difficult to form a metal texture on the surface of the product. If the amount is more than 20% by weight, an artificial texture may be produced.
Unsaturated polyester resin
The unsaturated polyester resin according to the present invention forms a matrix of reinforced natural stone, and the same or different resin as the unsaturated polyester resin used in the above-mentioned reinforced natural stone chips can be used.
The unsaturated polyester resin according to the present invention may contain 7 to 20% by weight, preferably 7 to 12% by weight, based on 100% by weight of the total reinforced natural stone composition. If it is less than 7% by weight, the strength of reinforcing natural stone may be lowered and voids may be generated on the surface, and when it is more than 20% by weight, deformation and voids of reinforcing natural stone may occur.
Silica-based inorganic material
The silica-based inorganic material according to the present invention can be added to form a natural stone-like appearance and texture and improve mechanical properties.
The silica-based inorganic material may be any of various types of silica-based inorganic materials that can be obtained in nature, and may include, for example, a sand mold, a powder-type silica-based inorganic material, and a quartz chip. And may be the same as or different from the silica contained.
In the present invention, it is most preferable that the silica-based inorganic material is most preferably mixed with a sand mold, a powder mold and a quartz chip at the same time, because the metal texture is remarkably enhanced and the transparency is also increased. That is, the present invention has a remarkable effect by adopting three kinds of silica-based inorganic materials having different particle sizes. Preferably, the composition ratio of the sand-type silica, quartz chip and powder-type silica is better for the metal appearance and transparency aimed at in the present invention.
The reinforced natural stone may have a structure in which a reinforcing natural stone chip and a silica-based inorganic material are dispersed in a matrix containing an unsaturated polyester resin. Through the dispersion structure, the reinforced natural stone of the present invention has improved surface processability, exhibits an elegant and luxurious texture, minimizes the hardness difference between the chip and the reinforced natural stone matrix, and improves the metal texture, the surface roughness and the surface uniformity Excellent effects can be realized.
The sand-type silica-based inorganic material may have an average particle size of 0.1 to 1.2 mm, and the powder-type silica-based inorganic material may have an average particle size of 0.1 mm, more preferably 0.045 mm or less. In case of quartz chips, the average particle size may be 1.2 to 5.6 mm. The use of the silica-based inorganic materials having various sizes as described above can effectively realize a three-dimensional texture such as a natural stone, and the densification of the reinforced natural stone can be effectively performed, thereby improving the mechanical properties.
The silica-based inorganic material preferably comprises 60 to 90% by weight, preferably 20 to 70% by weight of the sand-type silica-based inorganic substance, 15 to 40% by weight of the powder-type silica-based inorganic substance, 1 to 50 By weight, and most preferably 20 to 65% by weight of the sand-type silica-based inorganic substance, 22 to 32% by weight of the powder-type silica-based inorganic substance, and 2 to 45% by weight of the quartz chip. By the inclusion of the above-mentioned range, the mutual bonding force between the unsaturated polyester resin, the silica-based inorganic substance and the reinforced natural stone can be maintained and a cold and modern feeling unique to the metal can be realized.
The reinforced natural stone according to the present invention may contain any one selected from a curing agent, a curing accelerator, a crosslinking agent, a pigment, a dye, a leveling agent, an ultraviolet absorbent, a storage stabilizer, a light diffusing agent, an antioxidant, a polymerization inhibitor, And may further include two or more additives. The additive may be the same as or different from the additive used in preparing the reinforcing natural stone.
The additive may be included in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the total reinforced natural stone composition. For example, 1 to 15 parts by weight, for example, 5 to 10 parts by weight. Within the above range of content ratios, the production of reinforced natural stone for the purpose of the present invention can be easily carried out. The composition ratio of the additive may be a composition ratio of one material or may be an addition ratio of a composition in which two or more materials are mixed.
The reinforced natural stone according to the present invention comprises the steps of: a) preparing a reinforced natural stone including a composition for reinforced natural stone; b) mixing and molding the unsaturated polyester resin and the silica-based inorganic material with the reinforcing natural stone chip; And c) polishing and shaping the molded semi-finished product.
The step a) can be carried out by using the composition for reinforcing natural stone through steps a1) to a4) as described above, and a description thereof will be omitted.
The mixing method in the step b) is not limited to the present invention and a known method can be applied. It is also possible to mix them by the same or different method as the above-mentioned a1) and a2).
In the step b), the composition may be cured at the time of molding. In the present invention, the curing conditions are not limited, but the curing may be carried out at 80 to 120 ° C for 20 to 60 minutes. In addition, reinforcing natural stone can be produced by uniformly distributing it uniformly while maintaining a uniform shape by using a crushing facility at the time of molding, followed by compression molding. The compression molding can proceed in a vibration or vacuum-vibration state, but the present invention is not limited thereto.
The reinforced natural stone produced according to the present invention may have a maximum cross-sectional depth (Rv) of 6.0 mu m or less and a maximum height Ry of 10.0 mu m as measured by JIS B 0601. The surface roughness means that the hardness of the chip and the natural stone satisfies a desired range in the present invention and the surface processing is natural, and it can have a luxurious and soft metal pearl texture for the purpose of the present invention.
Hereinafter, the configuration and operation of the present invention will be described in more detail with reference to preferred embodiments of the present invention. However, the following examples are provided to aid understanding of the present invention, and the scope of the present invention is not limited to the following examples. The contents not described here are sufficiently technically inferior to those skilled in the art, and a description thereof will be omitted.
The specifications and physical properties of each component used in the following Examples and Comparative Examples are as follows.
(Surface hardness)
The surface hardness of chips and specimens prepared using a Barcol hardness tester (GYZJ 934-1, Barber Colman company) according to ASTM D2583 was measured.
(Surface roughness)
The maximum reinforcing gemstones were measured for maximum cross-sectional depth (Rv) and maximum height (Ry) using a roughness tester (SJ-301, Mitutoyo) based on JIS B 0601 (1994).
(Chip state)
The surface of the chip was visually inspected by a sensory test agent before crushing the reinforced natural stone chip manufactured through the following examples. In this case, when colors are united or severely separated and the texture is poor, it is inadequate to use as a product, or phase separation occurs between the resin and the inorganic constituting the chip, so that the pattern is not uniform and the texture is greatly deteriorated. The case was judged to be 'bad'. On the other hand, a state in which molding was impossible and the chip could not be shredded was judged as " impossible to mold ".
(Texture)
After the chips were broken (10 mm), the sensory testing staff observed more than 5 samples and judged to be 'bad' when 3 or more holes with a diameter of 1 mm or more were found on the surface.
(Judgment)
Five trained sensory test agents of the fortified natural stone prepared through Examples 9 to 11 and Comparative Examples 11 to 13 were observed with naked eyes and tactile senses, and the surface was smooth and well-formed. When the metal texture appeared well, Good ", rough surface, holes on the surface, no molding, and if color saturation or blurring were satisfied.
(Composition)
The specifications of the compositions used in the following examples are shown in Tables 1 and 2 below. Table 1 shows the chips for reinforced natural stone, and Table 2 shows the reinforced natural stone.
(2) average particle diameter 0.3 to 0.7 mm;
(3) Average particle diameter 0.7 to 1.2 mm
318M, Red 110, Y3910, Y8G, Y6R
Others
≪ Experiment of manufacturing chips for reinforced natural stone >
Example
Example 1
The reinforced natural stone chip composition comprising the sand type silica (30% by weight, 10% by weight) described in Table 1, 30% by weight of powder type silica, 25% by weight of UPE, 3% by weight of metallic pearl and 2% by weight of styrene- 0.25 parts by weight of a crosslinking agent, 0.05 parts by weight of a curing accelerator and 0.5 parts by weight of a curing agent were added to 100 parts by weight of the composition as an additive.
First, UPE, a curing agent, a curing accelerator, a crosslinking agent and a metal pearl were put into a mixer and mixed. Next, the three kinds of silica were added and mixed, and then the viscosity-controlling styrene-based monomer was further added and stirred to prepare a reinforced natural stone chip composition.
The prepared composition was placed in a plate frame and cured at 110 ° C for 15 minutes to prepare a reinforced natural stone chip material. The prepared material was crushed into a crusher and crushed to have an average particle size of 10 mm to prepare a reinforced natural stone chip. The state and texture of the manufactured chip were confirmed and are shown in Table 3.
Examples 2 to 8
A reinforced natural stone chip was prepared in the same manner as in Example 1, except that the composition ratio of the composition was changed as shown in Table 3 below. The state and texture of the manufactured chip were confirmed and are shown in Table 3.
Comparative Examples 1 to 10
A reinforced natural stone chip was prepared in the same manner as in Example 1, except that the composition ratio of the composition was changed as shown in Table 4 below. The state and the texture of the manufactured chip were confirmed and are shown in Table 4.
One
2
3
4
5
6
7
8
Silica ①
(weight%)
Silica ②
(weight%)
Silica ③
(weight%)
Silica
(weight%)
(weight%)
(weight%)
(weight%)
(Parts by weight)
(Parts by weight)
(Parts by weight)
One
2
3
4
5
6
7
8
9
10
Silica ①
(weight%)
Silica ②
(weight%)
Silica ③
(weight%)
Silica
(weight%)
(weight%)
(weight%)
(weight%)
(Parts by weight)
(Parts by weight)
(Parts by weight)
Impossible
Impossible
Impossible
Impossible
Impossible
In Examples 1 and 2 and Comparative Examples 1 to 4 in which the average particle size and the content of the silica particles are different from each other in Table 3 and Table 4 and FIGS. 1 to 4, As the particle size decreases, the chip state becomes better.
On the contrary, in the comparative example, the specific surface area of the metal pear becomes smaller as the average particle diameter of the silica increases, and the metal texture effect is lowered. It is also understood that, in the case of using only silica having an average particle diameter of 0.3 to 0.7 or more, the chip itself is not produced except for Comparative Example 9. In the case of Comparative Example 9, it can be seen that the manufacturing condition of the chip itself is 'good', but the textured state is 'poor' because the colors are clumped or severely separated and the texture is poor and the product is unsuitable for use.
When the physical properties of the chip were examined in accordance with the difference in the content of the unsaturated polyester resin (UPE) as a base resin, the chip state became better as the content of UPE was increased as in Examples 3 to 5. On the other hand, when the content of UPE is less than 20 wt% (Comparative Examples 5 and 6), it can be understood that the chip can not be formed and can not be crushed into chips, and that the UPE content is more than 20 wt% (Comparative Example 7), the chip itself is not formed, or phase separation occurs between the resin constituting the chip and the inorganic substance, so that the pattern is not uniform and the texture is greatly deteriorated and the appearance of the chip is not good. '.
When the physical properties of the chip according to the content of the metal pearl were confirmed, it can be confirmed that as the content of the metal pearl increases as in Examples 6 to 8, the chip state becomes better. However, as in Comparative Examples 8 and 9, when the content of the metallic pearl was less than 3 wt%, the metal texture was insufficient (Comparative Example 9), and the phase separation occurred between the resin and the inorganic material (Comparative Example 8) It can be seen that the molding of the chip itself is impossible as in Example 10.
Examples 9 to 11
The physical properties of the natural gypsum according to the content of the base resin in the manufacture of the reinforced natural stone including the chips prepared in Examples 3 to 5 were confirmed. First, the composition was put into a mixer and mixed as shown in Table 5 below to prepare a reinforced natural stone composition. Then, the composition was put into a mold, and then subjected to vibration and compression to uniformly distribute the composition throughout the mold. Next, the composition was compression molded by a press, and then hardened and surface polished to produce reinforced natural stone. The surface roughness and the state of the prepared reinforced natural stone were confirmed and are shown in Table 5.
Comparative Examples 11 to 13
The reinforced natural stone including the chips prepared in Comparative Examples 5 to 7 was prepared. The preparation method was the same as in Example 9, and the surface roughness and the condition of the prepared reinforced natural stone were confirmed and are shown in Table 5.
(weight%)
10
10
10
10
10
10
Silica
(weight%)
(weight%)
Silica
(weight%)
(weight%)
Surface hardness
(Not formed)
(Hole generation)
(Hole generation)
As shown in Table 5, Examples 9 to 11 prepared according to the present invention show that the surface roughnesses Rv and Ry satisfy all values. On the other hand, in Comparative Example 11 in which the content of the base resin is less than 7% by weight, both the Rv and Ry values exceed the standard value, and the surface condition of the reinforced natural stone produced is uneven, so that the workability is greatly deteriorated. . Also, in Comparative Examples 12 and 13 in which the content of the base resin exceeded 20% by weight, the roughness value was lower than that of Comparative Example 11, but the workability exceeded the reference value of the present invention and the workability was poor.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, Various modifications and variations are possible in light of the above teachings.
Therefore, the spirit of the present invention should not be construed as being limited to the described embodiments, and all of the equivalents or equivalents of the claims, as well as the following claims, are included in the scope of the present invention.
Claims (16)
(B) 5 to 40% by weight of a powdery silica having an average particle diameter of 0.1 mm or less;
(C) 5 to 40% by weight of an unsaturated polyester resin;
(D) 1 to 10% by weight of metallic pearl particles; And
(E) 1 to 10% by weight of a styrene-based monomer;
Lt; / RTI >
A composition for reinforced natural stone containing no sand-type silica having an average particle diameter of more than 0.7 mm.
Wherein the composition for reinforcing natural stone further comprises sand-type silica having an average particle diameter of more than 0.3 mm and not more than 0.7 mm.
Wherein at least one selected from a curing agent, a curing accelerator, a crosslinking agent, a pigment, a dye, a leveling agent, an ultraviolet absorber, a storage stabilizer, a light diffusing agent, an antioxidant, a polymerization inhibitor, a flame retardant and an antistatic agent is added to 100 parts by weight of the above- And 0.01 to 5 parts by weight of an additive.
Wherein the unsaturated polyester resin has a weight average molecular weight of 70,000 to 100,000 and a viscosity at 25 DEG C of 500 to 600 cps.
Wherein the unsaturated polyester resin is any one or two or more selected from ortho type, iso type, bisphenol type, vinyl ester type and novolak vinyl ester.
Wherein the metallic pearl particles comprise at least one natural component selected from the group consisting of core, stone, quartz, charcoal, loess, magnetite, fragrance, pearl, shellfish and mirror powder / RTI >
The styrene-based monomer may be at least one selected from the group consisting of? -Methylstyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, ethylstyrene, , m-bromostyrene, o-chlorostyrene, p-chlorostyrene, and m-chlorostyrene.
Characterized in that the reinforced natural stone chip has a structure in which sand type silica, powder type silica and metallic pearl particles are dispersed in a continuous phase containing an unsaturated polyester resin and polystyrene.
The chip for reinforced natural stone has a metal pearl texture having a hardness of 75 to 85 as measured by a Barcol hardness tester (GYZJ 934-1, Barber Colman company).
7 to 20% by weight of an unsaturated polyester resin; And
60 to 90% by weight of a silica-based inorganic material;
≪ / RTI >
Wherein the reinforcing natural stone has a structure in which a reinforcing natural stone chip and a silica-based inorganic material are dispersed in a matrix containing an unsaturated polyester resin.
The silica-based inorganic material has a sand-like silica-based inorganic material having an average particle size of 0.1 to 2.0 mm, a quartz chip having an average particle size of 1.2 to 5.6 mm, and a powder-type silica-based inorganic material having an average particle size of 0.1 mm or less.
One or two selected from a curing agent, a curing accelerator, a crosslinking agent, a pigment, a dye, a leveling agent, an ultraviolet absorber, a storage stabilizer, a light diffusing agent, an antioxidant, a polymerization inhibitor, a flame retardant and an antistatic agent per 100 parts by weight of the above- Reinforced natural stone having a metal texture further comprising 0.01 to 20 parts by weight of an additive.
The reinforced natural stone has a metal pearl texture having a maximum cross-sectional depth (Rv) of 6.0 탆 or less and a maximum height (Ry) of 10 탆 or less as measured by JIS B 0601.
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