JP2003127150A - Method for producing artificial marble - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing artificial marble which can disperse/knead/mix a large granule patterning material uniformly into a resin composition for molding the artificial marble and can fit a high design pattern having a high-grade feel or a granite pattern to the artificial marble without lowering the strength of a product. SOLUTION: In the method, the patterning material is added into a compound in which additives such as a filler, an internal mold releasing agent, and a curing agent are incorporated into a thermosetting resin to obtain the resin composition for molding the artificial marble, and the composition is molded and cured to obtain the artificial marble. The large granule patterning material, after being mixed with a polymerizable solvent, is kneaded with the compound to obtain the composition containing the patterning material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing artificial marble used as a furniture member or a building material.

[0002]

2. Description of the Related Art Conventionally, thermosetting resins, fillers, handle materials,
Reinforcing an artificial marble molding resin composition containing additives such as a reinforcing material, an internal release agent, and a curing agent into a desired casting mold,
It is known to form artificial marble by heating and hardening.

As a thermosetting resin which is a raw material for producing artificial marble, polyester resins, vinyl ester resins, acrylic resins and the like have been conventionally used.
Artificial marble moldings that make use of these are widely used in bathroom counters, kitchen counters, bathtubs, and washbasins.

[0004] Usually, in order to obtain an artificial marble product having a high design pattern or a granite pattern, it has been practiced to obtain an artificial marble molding resin composition containing several types of pattern materials having different shapes and color tones. In particular, it is required to add and mix a large grain pattern as a high quality pattern having a more natural feeling. However, the larger the grain pattern, the more difficult it is to add and mix the pattern material to the compound and to disperse it uniformly. That is, the pattern material added and compounded in the compound did not easily disintegrate even when kneaded, and the pattern materials could not be uniformly dispersed in the compound.

The artificial marble molded product obtained in such a state is far from the desired pattern expression in which the solidified portion and the non-solidified portion are scattered.

Further, if the pattern materials are molded while they are stuck to each other, the compound component does not exist between the pattern materials, so that the artificial marble molded article will have a crack (crack) inside, which is extremely extreme. There was a problem that the strength was reduced.

Under the circumstances, therefore, there is a strong demand for a method for producing artificial marble in which a large grain pattern material is added and uniformly dispersed so as not to reduce the product strength.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and it is possible to uniformly disperse and knead a large grained patterning material into an artificial marble molding resin composition and to reduce the product strength. It is an object of the present invention to provide a method for producing an artificial marble having a high design pattern or a granite pattern with a high quality.

[0009]

In order to solve the above-mentioned problems, the method for producing an artificial marble according to the present invention is a compound in which additives such as a filler, an internal mold release agent and a hardening agent are mixed with a thermosetting resin. In the method for producing an artificial marble in which the artificial marble molding resin composition is obtained by adding a pattern material to the artificial marble molding resin, the artificial marble molding resin composition is molded and cured to obtain an artificial marble. It is characterized in that it is mixed with a solvent and then kneaded with a compound to obtain a resin composition for artificial marble molding containing a large grain pattern material. By adopting such a method, even if a large-sized pattern material is added and mixed to the artificial marble molding resin composition, the pattern materials do not stick to each other and can be uniformly kneaded and mixed. Further, the compound component does not exist between the large grain pattern materials, and the product strength is not deteriorated.

Further, a pattern material is added to a compound in which a thermosetting resin is mixed with additives such as a filler, an internal mold release agent, and a curing agent to obtain a resin composition for artificial marble molding. In a method for producing an artificial marble by molding and curing a resin composition for use in manufacturing, an artificial marble molding resin composition containing a large-sized pattern material after being mixed with a large-sized pattern material in advance with a thermosetting resin and kneaded with a compound. It may be a thing characterized by being a thing. By adopting such a method, even if a large-sized pattern material is added and mixed to the artificial marble molding resin composition, the pattern materials do not stick to each other and can be uniformly kneaded and mixed. Further, the compound component does not exist between the large grain pattern materials, and the product strength is not deteriorated.

The thermosetting resin is one of polyester resin, vinyl ester resin and acrylic resin,
Alternatively, a mixture of two or more kinds is preferable.

Also, the average thickness of the large grain pattern material is 0.1-3.
It is preferable that the diameter is 0 mm and the average particle diameter is 1 mm or more.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below based on the embodiments shown in the accompanying drawings.

The method for producing an artificial marble of the present invention is a resin composition for forming an artificial marble in which a pattern material is added to a compound in which a thermosetting resin is mixed with additives such as a filler, an internal release agent and a curing agent. In the method for producing an artificial marble in which the artificial marble molding resin composition is obtained by molding and curing, the large grain handle material is mixed with a polymerizable solvent (crosslinking agent) or a thermosetting resin in advance. After that, it is kneaded with a compound to obtain a resin composition for artificial marble molding with a large grain pattern material, and this resin composition for artificial marble molding with a large grain pattern material is poured into a casting mold and heat-cured to form an artificial marble molding. You get the goods.

The large-diameter pattern material used in the present invention has an average thickness of 0.1 to 3.0 mm, but if the average particle thickness is 0.1 mm or less, the pattern materials adhere strongly to each other even in the method of the present invention, and the individual pattern materials are easily separated. It is difficult for the particles to be uniform, and conversely, when the particle diameter is 3.0 mm or more, the particles are dispersed and uniformly dispersed without using the method of the present invention. Further, the average particle size is set to 1 mm or more, but if the average particle size is 1 mm or less, the particles are dispersed and cannot be uniformly dispersed without using the method of the present invention.

Before mixing these large grain handle materials into the compound, they are previously mixed with a polymerizable solvent (crosslinking agent) or a thermosetting resin. As a method of mixing, a large grain handle material can be gradually added into a container containing a polymerizable solvent (crosslinking agent) or a thermosetting resin while stirring.

Since the polymerizable solvent (crosslinking agent) or the thermosetting resin to be mixed is a single system, it can be carried out with an extremely low viscosity as compared with the case where it is added to a usual resin composition. By this operation, the large grain pattern material is disintegrated and dispersed, and the entire surface of each large grain pattern material is a polymerizable solvent (crosslinking agent).
Alternatively, it will be wet and covered with a thermosetting resin. In such a state, it may be added to the compound and kneaded. If the surface of the large grain pattern material is wet, remove the excess polymerizable solvent (crosslinking agent) or thermosetting resin (liquid It may be cut and added and kneaded.

As described above, the large grain pattern material added while the entire surface is wet is kneaded in the compound and easily dispersed uniformly. Also, even if a part of the compound is dispersed in a state of sticking in the compound, a polymerizable solvent (crosslinking agent) or thermosetting resin is present at the interface of the large-sized handle material that is stuck. Therefore, since the polymerization reaction proceeds by the subsequent heat-curing operation to cause a crosslinking reaction with the resin composition, cracks are not formed between the handle materials as in the conventional case.

The thermosetting resin of the resin composition constituting the large grain pattern material and the thermosetting resin constituting the resin composition for artificial marble molding obtained by adding the large grain pattern material are of the same kind. It is preferable to use, and the thermosetting resin may be a polyester resin, a vinyl ester resin, an acrylic resin alone, or a mixed system of two or more of these.

The polyester resin is a thermosetting resin, which is synthesized by subjecting an unsaturated dibasic acid such as maleic anhydride and a saturated dibasic acid such as phthalic anhydride to a condensation reaction with glycols to produce an intramolecular compound. It has an unsaturated bond and an ester bond. Usually, a styrene monomer, an acrylic monomer, etc. are blended as a cross-linking agent in this resin, and a so-called unsaturated polyester resin is used, but its form is not particularly limited.

The vinyl ester resin may be a bisphenol type vinyl ester resin, a novolac type vinyl ester resin, or a mixture of both.

Here, the bisphenol type vinyl ester resin is an addition reaction product of a bisphenol type epoxy resin and an acid, and each has a reactive unsaturated group only at both ends. Further, as the bisphenol type epoxy resin, bisphenol A type, bisphenol AD
Type, bisphenol S type, bisphenol F type and the like can be used. Further, a styrene monomer, an acrylic monomer, etc. are usually blended in the vinyl ester resin as a cross-linking agent, but the form is not particularly limited.

As the acrylic resin, what is called a thermosetting type acrylic syrup which is usually composed of a methylmethacrylate monomer, a polyfunctional acrylic monomer, a prepolymer, or a mixture of two or more kinds of polymers, respectively. However, the form is not particularly limited.

When a mixture of two or more kinds of polyester resin, vinyl ester resin and acrylic resin is used, the purpose is to be determined by the characteristics of each resin and the interaction with the filler or the additive compound. The optimum blending that matches the product quality is required, but the blending amount is not particularly limited.

The filler is aluminum hydroxide, silica,
It can be used as one kind of glass powder or a mixture of two or more kinds. The blending amount of the filler is
The amount is preferably 100 to 300 parts by weight with respect to 100 parts by weight of the thermosetting resin. If the amount is less than this range, the impact resistance of the product is excellent, but the heat resistance may not be sufficiently exhibited. If it exceeds the range, the heat resistance is excellent, but the impact strength may decrease.

The smaller the particle size of the filler is, the more the impact resistance of the artificial marble product can be improved, but the viscosity of the resin composition sharply increases and the manufacturing becomes difficult. Therefore, the lower limit of the average particle size is set. It is preferably 5 μm.

On the other hand, when the particle size of the filler is large, the viscosity of the resin composition 1 is low and the problem in production is eliminated.
The impact resistance of the artificial marble product tends to decrease. Therefore, the upper limit of the average particle size is preferably 50 μm.

When the surface of the filler is silane-coupling treated, the adhesion between the filler and the resin can be improved and the impact resistance of the artificial marble product can be improved.

The polymerizable solvent is usually used as a cross-linking agent for the thermosetting resin, and as described above, it is a styrene monomer (SM) or an acrylic monomer (MMA). It is preferable to use the polymerizable solvent contained in the casting resin composition from the viewpoint of stability of physical properties, but the invention is not particularly limited thereto.

Other polymerizable solvents include paramethylstyrene (vinyltoluene), monochlorostyrene, and t.
-Butylstyrene, phenoxyethyl (meth) acrylate, 1,6-hexanediol (meth) acrylate, trimethylolpropane tri (meth) acrylate, 2-hydroxyethyl (meth) acrylate, dicyclopentenyloxyethyl methacrylate, etc. .

Further, a curing agent is added to the artificial marble molding resin composition.

As the curing agent, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate or t-hexylperoxy-2-ethylhexanoate can be used. For example, in the case of a vinyl ester resin, the mixing ratio of this curing agent is 1 total amount of the resin and the crosslinking agent.
It is preferably 0.5 to 5 parts by weight with respect to 00 parts by weight.

Further, the artificial marble molding resin composition may be blended with an ultraviolet absorber, a viscosity reducer, a release agent, glass fibers and a colorant.

The artificial marble molding resin composition is prepared by mixing these compounds containing a large grain pattern material at a predetermined ratio and stirring them with a stirrer or the like.

In producing artificial marble from the artificial marble molding resin composition, the blended and prepared artificial marble molding resin composition is subjected to vacuum defoaming treatment under a reduced pressure of about 20 to 50 Torr. The artificial marble molding resin composition that has been degassed in this way is released from the depressurized state and poured into a casting mold of a predetermined shape, and the casting mold is made to have a volume of 50 to 1
The mixture is heated at a temperature of 10 ° C. for 30 to 120 minutes to promote a copolymerization reaction between the reactive unsaturated group in the thermosetting resin of the resin composition for artificial marble molding and the polymerizable monomer in the resin. The resin composition for artificial marble molding is cured and molded.

The molded article of artificial marble containing a large grain pattern material obtained as described above is one in which the large grain pattern materials are uniformly dispersed, and crack formation due to the influence of the large grain pattern materials remaining stuck to each other, There is no reduction in strength due to this, and an artificial marble molded product having a highly designed granite pattern can be obtained.

Such an artificial marble molded article can be easily commercialized as a wash counter, a kitchen counter, a bathtub, a wash bowl, or the like.

[0038]

EXAMPLES The present invention will be described in detail below with reference to examples. (Example 1) A polyester resin (Polymer 5450 manufactured by Takeda Pharmaceutical Co., Ltd.) was used as a thermosetting resin, and 100 parts by weight of this resin was used as a filler of aluminum hydroxide (H-310 manufactured by Showa Denko KK). Average particle size 17
μm) in an amount of 130 parts by weight, to which 0.5 part by weight of black toner as a colorant was added, and further 3.0 parts by weight of a curing agent (Percure HO manufactured by NOF CORPORATION) was added. The compound used as the resin composition for materials was obtained. 20 this
After stirring and mixing under vacuum defoaming treatment under reduced pressure of Torr for 60 minutes, the mixture is poured into a mold for pattern material molding and the mold temperature is set to 1
The mixture was heated at 00 ° C. for 120 minutes for curing, crushed with a crusher and classified to obtain a black large-sized handle material having an average thickness of 0.5 mm and an average particle diameter of 3.5 mm. The obtained large grain pattern material was mixed into a styrene monomer solution while stirring, and after the mixing was completed, the large grain pattern material was scooped up on a wire net to remove excess styrene monomer. On the other hand, a compound similar to the above, but without addition of a coloring agent was prepared separately, and 5.0 parts by weight of the above-mentioned large grain pattern material was added to this compound to obtain a resin composition for artificial marble molding. After stirring and mixing this under vacuum degassing treatment for 20 minutes under a reduced pressure of 20 Torr, it is poured into a casting mold having a predetermined shape and a thickness of 12 mm, and the mold temperature is heated at 100 ° C. for 120 minutes. It was cured to obtain a granite-like artificial marble containing a large black pattern material. (Example 2) A vinyl ester resin (Prominate P-311 manufactured by Takeda Pharmaceutical Co., Ltd.) was used as a thermosetting resin, and 100 parts by weight of this resin was used as a filler of aluminum hydroxide (manufactured by Showa Denko KK). H-308B (average particle size: 8 μm) was mixed in an amount of 150 parts by weight, 0.3 part by weight of black toner was added as a colorant, and a curing agent (Percure HO manufactured by NOF CORPORATION) was added to 2.0 parts. A compound to be a resin composition for pattern material was obtained by adding parts by weight. After stirring and mixing this under vacuum defoaming treatment for 20 minutes under a reduced pressure of 20 Torr, it is poured into a mold for pattern material molding, heated at a mold temperature of 100 ° C. for 120 minutes to cure, and crushed with a crusher. And classified to obtain a large-sized black pattern material having an average thickness of 0.6 mm and an average particle diameter of 4.5 mm. The obtained large grain pattern material was mixed into a vinyltoluene solution while stirring, and after the mixing was completed, the large grain pattern material was scooped up on a wire net to remove excess vinyltoluene. On the other hand, a compound similar to the above, but without the addition of a coloring agent was prepared separately, and 5.5 parts by weight of the above-mentioned large grain pattern material was added to this compound to obtain a resin composition for artificial marble molding. 20 Torr
After stirring and mixing under reduced pressure for 60 minutes under vacuum degassing treatment, the mixture is poured into a casting mold having a predetermined shape and a thickness of 11 mm, and the mold temperature is heated at 100 ° C. for 110 minutes to be cured, A granite-like artificial marble containing a large black pattern material was obtained. (Example 3) Acrylic syrup resin (AC-02 manufactured by Nippon Fellow Co., Ltd.) was used as a thermosetting resin, and 100 parts by weight of this resin was used as a filler for silica (CRYSTALITE M- manufactured by Tatsumori Co., Ltd.). 130 parts by weight of 3K average particle size 20 μm) was added, 0.6 parts by weight of a gray toner as a colorant was added thereto, and a curing agent (Perkadox 16 manufactured by Kayaku Akzo Co., Ltd.) was added. 6
A compound to be a resin composition for pattern material was obtained by adding parts by weight. After stirring and mixing this under vacuum defoaming treatment for 20 minutes under a reduced pressure of 20 Torr, it is poured into a mold for pattern material molding, heated at a mold temperature of 100 ° C. for 120 minutes to cure, and crushed with a crusher. And classified to obtain a large grain pattern material having a gray color and an average thickness of 1.0 mm and an average particle diameter of 4.0 mm.
The obtained large grain pattern material is methyl methacrylate (MMA)
This was mixed into the solution with stirring, and after the completion of the mixing, this large grain handle was scooped up on a metal net to remove excess methyl methacrylate (MMA). On the other hand, a compound similar to the above, but without addition of a coloring agent was prepared separately, and 6.5 parts by weight of the above-mentioned large grain handle material was added to this compound to obtain a resin composition for artificial marble molding. This is 20 Tor
After stirring and mixing under vacuum defoaming treatment for 60 minutes under a reduced pressure of r, the mixture is poured into a casting mold having a predetermined shape and a thickness of 15 mm and heated at 90 ° C. for 120 minutes to cure. A granite-like artificial marble containing a large-sized gray colored pattern material was obtained. (Example 4) As a thermosetting resin, vinyl ester resin (Lipoxy R-804 manufactured by Showa Highpolymer Co., Ltd.) and polyester resin (Polymer 525 manufactured by Takeda Pharmaceutical Co., Ltd.)
0) is mixed at a compounding ratio of 60/40, and the mixed resin 10
Aluminum hydroxide (H-320 manufactured by Showa Denko KK, average particle size 10 μm) was added to 1 part by weight of 0 parts by weight.
50 parts by weight were added, and 0.6 part by weight of a brown toner was added as a colorant to the mixture, and further 3.0 parts by weight of a curing agent (Percure HO manufactured by NOF CORPORATION) was added to the pattern material. A compound to be a resin composition was obtained. 20 this
After stirring and mixing under vacuum defoaming treatment for 60 minutes under a reduced pressure of Torr, the mixture is poured into a pattern material molding die and the mold temperature is set to 9
The mixture was heated at 0 ° C. for 120 minutes to be hardened, crushed with a crusher and classified to obtain a large grain pattern material of brown color having an average thickness of 1.5 mm and an average particle diameter of 4.0 mm. The obtained large grain pattern material was mixed into the thermosetting resin solution while stirring, and after the mixing was completed, the large grain pattern material was scooped up on the wire netting to remove the excess thermosetting resin solution. On the other hand, a compound similar to the above, but without addition of a coloring agent was prepared separately, and 6.5 parts by weight of the above-mentioned large grain handle material was added to this compound to obtain a resin composition for artificial marble molding. After stirring and mixing this under vacuum degassing treatment for 60 minutes under a reduced pressure of 20 Torr, it was poured into a casting mold having a predetermined shape and a thickness of 12 mm, and the mold temperature was heated at 90 ° C. for 120 minutes. After curing, a granite-like artificial marble containing large brown-colored pattern material was obtained. (Example 5) As thermosetting resins, vinyl ester resin (Lipoxy R-804 manufactured by Showa Highpolymer Co., Ltd.) and acrylic syrup resin (XE924-Mitsui Chemicals Co., Ltd.)
1) was mixed at a compounding ratio of 75/25, and the mixed resin 10
Aluminum hydroxide (Showa Denko KK H-320 average particle size 10 μm) and glass powder (Nippon Frit GF-2-30) are used as fillers based on 0 parts by weight.
A average particle size of 30 μm) was mixed at a ratio of 80/20 to 160 parts by weight, to which 0.5 part by weight of a brown toner was added as a colorant, and a curing agent (manufactured by NOF CORPORATION). 3.0 parts by weight of Percure WO) was added to obtain a compound to be a resin composition for a pattern material. 20 this
After stirring and mixing under vacuum defoaming treatment for 60 minutes under a reduced pressure of Torr, the mixture is poured into a pattern material molding die and the mold temperature is set to 9
The mixture was heated at 0 ° C. for 120 minutes to be cured, crushed with a crusher and classified to obtain a large grain pattern material of brown color having an average thickness of 0.8 mm and an average particle diameter of 5.0 mm. The obtained large grain pattern material was mixed into the thermosetting resin solution while stirring, and after the mixing was completed, the large grain pattern material was scooped up on the wire netting to remove the excess thermosetting resin solution. On the other hand, a compound similar to the above, but without addition of a coloring agent was prepared separately, and 10.0 parts by weight of the above-mentioned large grain handle material was added to this compound to obtain a resin composition for artificial marble molding. 20 Torr
After stirring and mixing under vacuum degassing for 60 minutes under reduced pressure, the mixture is poured into a casting mold having a predetermined shape and a thickness of 10 mm, and the mold temperature is heated at 90 ° C. for 120 minutes to be cured, A granite-like artificial marble containing large brown-colored pattern material was obtained.

[0039]

As described above, according to the present invention, a pattern material is added to a compound in which a thermosetting resin is mixed with an additive such as a filler, an internal mold release agent, and a curing agent for artificial marble molding. Obtaining a resin composition and molding and curing this resin composition for artificial marble to obtain an artificial marble. In a method for producing an artificial marble, after mixing a large grain pattern material with a polymerizable solvent or a thermosetting resin in advance. Since it is kneaded with the compound to make a resin composition for artificial marble molding containing a large grain pattern material, even if a large pattern material is added to the resin composition for artificial marble molding, the pattern materials do not stick to each other and are dispersed uniformly. As a result of kneading and mixing, as a result, there is no possibility that large grain pattern materials will not be molded while sticking to each other and there will be no compound component between the large grain pattern materials, and cracks will not form inside These results, in which it is possible to produce the artificial marble high design pattern or granite pattern feeling of luxury does not cause a decrease in product strength uniformly dispersed by adding a handle member having a large particle.

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Claims (4)

[Claims] 1. An artificial marble molding resin composition is obtained by adding a pattern material to a compound in which a thermosetting resin is mixed with an additive such as a filler, an internal mold release agent, and a curing agent. In the method for producing an artificial marble by molding and curing the resin composition for use in manufacturing an artificial marble, the resin composition for artificial marble molding containing a large grain pattern material after mixing the large grain pattern material in advance with a polymerizable solvent and kneading with the compound. A method for producing an artificial marble, which is characterized by being a product. 2. A resin composition for artificial marble molding is obtained by adding a pattern material to a compound in which a thermosetting resin is mixed with an additive such as a filler, an internal release agent, and a curing agent, and the artificial marble molding is obtained. In a method for producing an artificial marble by molding and curing a resin composition for use in manufacturing an artificial marble, a resin composition for forming an artificial marble containing a large pattern material, which is obtained by previously mixing a large grain pattern material with a thermosetting resin and then kneading with a compound. A method for producing an artificial marble, which is characterized by being a product. 3. The artificial marble according to claim 1, wherein the thermosetting resin is one kind of a polyester resin, a vinyl ester resin and an acrylic resin, or a mixture of two or more kinds. Production method. 4. The average thickness of the large grain pattern material is 0.1 to 3.0 m.
The method for producing an artificial marble according to claim 1 or 2, wherein m and the average particle size are 1 mm or more.