JP2001233648A - Method for producing artificial marble - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an artificial marble capable of improving impact strength of artificial marble, dispensing with attaching a reinforcing plate, etc., to a product made from an artificial marble, thinning and lightening the product and improving appearance by raising transparency. SOLUTION: This method for producing an artificial marble comprises molding and curing a resin composition containing a resin component and a filler. A filler containing at least alumina is used as the filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Conventionally, a resin composition comprising a resin and additives such as a filler, a reinforcing material, an internal release agent, and a curing agent is injected into a casting mold having a desired shape, and is cured by heating. It was known that they formed artificial marble.

[0003] As a resin as a raw material for producing such artificial marble, a polyester-based resin, an acrylic-based resin, a vinyl ester-based resin and the like have been conventionally used.

[0004] Artificial marble moldings utilizing these are:
It is used for wash counters, kitchen counters, bathtubs, washbasins, etc.

Usually, in order to improve the impact strength (toughness) of artificial marble, the amount of glass fiber as a reinforcing material is increased. However, when the blending amount of the glass fiber is increased, the flow of the pattern or pattern formed on the artificial marble is significantly impaired, the mixing and dispersing properties become uneven, the transparency of the product is reduced, and In addition, a uniform product cannot be obtained, for example, due to fluffing of glass fibers, and therefore, there is a limit in improving the product strength.

Therefore, in order to solve such a problem, a wooden reinforcing plate is provided on the back of the artificial marble,
The thickness of a product has been increased by providing a reinforcing layer of P (fiber reinforced plastic) or the like.

[0007]

However, in order to reinforce the back surface of the artificial marble as described above, it takes time and effort to process and leads to an increase in cost.
Further, since the thickness of the reinforcing plate or the like is added to the product, it is difficult to reduce the thickness of the product, and accordingly, the weight of the product increases, and the burden on the transportation and construction of the product increases. In addition, the provision of a reinforcing plate or the like impairs the transparency of the product and deteriorates the appearance.

[0008] The present invention has been made in view of the above points, it is possible to improve the impact resistance of artificial marble, eliminate the need to provide a reinforcing plate or the like to the product formed from artificial marble, product It is an object of the present invention to provide a method for producing artificial marble, which can achieve a reduction in thickness and weight of the artificial marble as well as enhance transparency and improve appearance.

[0009]

According to a first aspect of the present invention, there is provided a method for producing artificial marble, comprising molding and curing a resin composition containing a resin component and a filler. As a material, a material containing at least alumina is used.

According to a second aspect of the present invention, in addition to the first aspect, the amount of the filler in the resin composition is 180 to 300 parts by mass with respect to 100 parts by mass of the resin component. It is characterized by the following.

According to a third aspect of the present invention, in addition to the constitution of the first or second aspect, a filler having an average particle diameter of 3 to 50 μm is used.

According to a fourth aspect of the present invention, in addition to the structure of any one of the first to third aspects, a filler treated with a silane coupling agent is used as the filler. .

[0013]

Embodiments of the present invention will be described below.

The resin composition used for producing artificial marble contains a resin component, a filler, a reinforcing material, an internal mold release agent, a curing agent, and the like.

The resin component comprises a thermosetting resin and a cross-linking agent blended as required. As the thermosetting resin, any one of a vinyl ester resin, an acrylic resin, and a polyester resin may be used. Alternatively, two or more kinds can be used in combination.

As the vinyl ester resin, either one or both of a bisphenol type vinyl ester resin and a novolak type vinyl ester resin can be used.

Here, the bisphenol type vinyl ester resin is an addition reaction product of a bisphenol type epoxy resin and an acid, and the novolak type epoxy resin is an addition reaction product of a novolak type epoxy resin and an acid. Also have reactive addition reactants at both ends only.

As the bisphenol type epoxy resin for obtaining the bisphenol type vinyl ester resin, various types such as bisphenol A type, bisphenol AD type, bisphenol S type and bisphenol F type can be used.

The acid to be added to the epoxy resin is usually an unsaturated monobasic acid, such as acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid,
Hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate and the like can be used.

Usually, a styrene monomer, an acrylic monomer, or the like is blended in the vinyl ester resin as a cross-linking agent, but is not particularly limited to such a form.

The acrylic resin is usually referred to as a methyl methacrylate monomer, a polyfunctional acrylic monomer, or a prepolymer thereof, or an ordinary acrylic syrup resin containing two or more of these polymers. A thermosetting type can be used, but it is not particularly limited to such a form.

The polyester resin 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 form an unsaturated bond in the molecule. A thermosetting type having an ester bond can be used. Usually, as the polyester resin, a resin called an unsaturated polyester resin in which a styrene monomer, an acrylic monomer, or the like is blended as a crosslinking agent is used, but it is not particularly limited to such a form.

When the thermosetting resin is a mixed type of two or more of vinyl ester resin, acrylic resin, and polyester resin, the characteristics of each resin, the characteristics and purpose of alumina used as a filler, It is blended at an appropriate ratio suitable for the physical properties of the product to be prepared, and the blending ratio is not particularly limited.

As the curing agent, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexaate,
For example, t-hexylperoxy-2-ethylhexanoate can be used. The mixing ratio of this curing agent is, for example, when a vinyl ester resin is used as the thermosetting resin, with respect to 100 parts by mass of the total amount of the thermosetting resin and the resin component composed of the crosslinking agent to be compounded as necessary. , 0.
It is preferably 5 to 5 parts by mass.

In the present invention, as the filler,
Since alumina is used, the impact resistance of artificial marble formed of a resin composition is dramatically improved. As the filler, only this alumina may be used, or alumina and another filler may be used in combination.

Examples of fillers that can be used other than alumina include ordinary fillers such as silica, calcium carbonate, aluminum hydroxide, glass powder, and clay.

The total amount of the filler is 180 to 300 parts by mass with respect to 100 parts by mass of the total amount of the resin component comprising the thermosetting resin and the optional crosslinking agent. preferable. If the compounding amount is less than this range, the impact resistance of the obtained artificial marble can be improved, but sufficient heat resistance may not be obtained, and if it exceeds this range, sufficient heat resistance will not be obtained. Although it can be
There is a possibility that the impact resistance cannot be sufficiently improved.

The amount of alumina in the total amount of the filler is not particularly limited. As the amount of alumina increases, the impact resistance (toughness) of the artificial marble obtained increases, while the hardness of the product decreases. It is preferable to appropriately design the blending amount of alumina in order to obtain artificial marble having desired properties, since it tends to increase and the machinability tends to decrease. In particular, in order to obtain artificial marble having improved impact resistance and machinability in a well-balanced manner, it is preferable to mix 1 to 70 parts by mass of alumina with respect to 100 parts by mass of the filler.

It is preferable to use a filler having an average particle size of 50 μm or less. In this case, the toughness of the artificial marble can be improved, and the impact resistance can be effectively improved. On the other hand, if the average particle size is too small, the dispersibility of the filler in the resin composition may be reduced and the filler may be aggregated. Therefore, the lower limit of the average particle size is preferably 3 μm.

When the surface of the filler is previously treated with a silane coupling agent, the adhesion between the filler and the resin component in the resin composition can be improved, and the dispersibility of the filler is also improved. The impact resistance of the resulting artificial marble can be further improved. As the silane coupling agent, γ- (methacryloyloxypropyl) trimethoxysilane or the like can be used.

Further, if necessary, an ultraviolet absorber, a viscosity reducing agent, a release agent, a glass fiber, a colorant, and the like can be added to the resin composition.

As the viscosity reducing agent, for example, a product number “W” manufactured by BKY
996 "as the internal release agent, for example," Separ "(trade name, manufactured by Chukyo Yushi), and as the glass fiber, for example, product number" RES03X-BM ", manufactured by Nippon Sheet Glass.

As the ultraviolet absorber, benzotriazole, triazine, benzoate, salylate, cyanoacrylate, oxalic anilide, benzophenone and the like can be used.

The resin composition is prepared by blending a filler with the resin component, further blending a curing agent and other various additives at a predetermined ratio, and stirring and mixing with a stirrer or the like.

In producing artificial marble from the resin composition, first, the resin composition is defoamed by stirring under reduced pressure of 4.0 to 66.5 hPa for 5 to 30 minutes.

The resin composition thus defoamed is
The pressure is released from the reduced pressure state and injected into a predetermined mold. At this time, as described above, the viscosity of the resin composition is reduced by blending aluminum hydroxide having an oil absorption of 25 ml / 100 g or less as a filler in the resin composition,
Since the fluidity is improved, the injection speed of the resin composition into the mold is reduced, and the production efficiency is improved. In addition, when the fluidity of the resin composition is improved in this way, the occurrence of unfilled resin molds in the mold is suppressed, and the occurrence of molding defects is prevented.

Then, the mold into which the resin composition has been injected
By heating at a temperature of 0 to 110 ° C. for 30 to 120 minutes, the polymerization reaction of the thermosetting resin in the resin composition proceeds to perform curing molding.

The artificial marble thus produced is
It has excellent impact resistance, and it is not necessary to form a wooden reinforcing plate or FRP reinforcing layer on the back of artificial marble to supplement the strength, and can exhibit high impact resistance (toughness). . Further, it is possible to reduce the weight of a product formed of the artificial marble and to obtain an artificial marble excellent in appearance, particularly transparency.

This artificial marble can be formed into, for example, a plate shape and used as a top plate of a kitchen counter or the like.

[0040]

The present invention will be described below in detail with reference to examples.

Example 1 As a resin component, a vinyl ester resin (manufactured by Takeda Pharmaceutical Co., Ltd .; trade name “Prominate P-311”) was used.

As the filler, alumina having an average particle size of 50 μm (manufactured by Sumitomo Chemical Co., Ltd .; trade name “A-21”)
Was used in an amount of 180 parts by mass based on 100 parts by mass of the resin component.

As a curing agent, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (manufactured by NOF Corporation; trade name "Percure WO") is used per 100 parts by mass of the resin component. 3.1 parts by mass.

These components were blended and stirred and mixed by a stirrer to prepare a resin composition.

This resin composition was subjected to vacuum defoaming treatment under reduced pressure of 26.7 hPa for 30 minutes. Further, the resin composition was poured into a mold having a cavity capable of molding a flat plate having a thickness of 11 mm, and heated at a mold temperature of 90 ° C. for 70 minutes to form a flat artificial marble.

(Example 2) As a resin component, an acrylic syrup resin (manufactured by Nippon Fellow Co., Ltd .; trade name "AC-
02 ") was used.

As a filler, alumina having an average particle size of 50 μm (Sumitomo Chemical Co., Ltd .; trade name “A-26”)
Aluminum hydroxide having an average particle size of 8 μm (manufactured by Sumitomo Chemical Co., Ltd .; trade name “CW-30”) with respect to 50 parts by mass.
8)) A blend of 50 parts by mass was used in an amount of 200 parts by mass per 100 parts by mass of the resin component.

As a hardening agent, 4.2 parts by mass of Parkadox 16 (trade name, manufactured by Kayaku Akzo Co., Ltd.) was used per 100 parts by mass of the resin component.

These components were blended and stirred and mixed by a stirrer to prepare a resin composition.

This resin composition was subjected to a vacuum degassing treatment under a reduced pressure of 26.7 hPa for 30 minutes. Further, this resin composition was poured into a mold having a cavity capable of molding a flat plate having a thickness of 11 mm, and heated at a mold temperature of 90 ° C. for 50 minutes to form a flat artificial marble.

Example 3 As a resin component, a polyester resin (manufactured by Takeda Pharmaceutical Co., Ltd .; trade name “Polymer 5450”) was used.

As the filler, alumina having an average particle size of 6.5 μm (manufactured by Showa Denko KK; trade name “A-42-
6 ") Aluminum hydroxide having an average particle diameter of 10 μm (manufactured by Sumitomo Chemical Co., Ltd., product number“ H31
0 ") A mixture containing 70 parts by mass was used, and this filler was used in an amount of 210 parts by mass with respect to 100 parts by mass of the resin component.

As a curing agent, t-hexyl peroxy-2-ethylhexanoate (manufactured by NOF CORPORATION; trade name "Percure HO") is used for 2.8 parts by mass based on 100 parts by mass of the resin component. Was.

These components were blended and stirred and mixed by a stirrer to prepare a resin composition.

This resin composition was subjected to a vacuum degassing treatment under a reduced pressure of 26.7 hPa for 30 minutes. Further, this resin composition was poured into a mold having a cavity capable of molding a flat plate having a thickness of 11 mm, and heated at a mold temperature of 90 ° C. for 80 minutes to form a flat artificial marble.

(Example 4) As a resin component, a vinyl ester resin (manufactured by Showa Polymer Co., Ltd .; trade name: Lipoxy R)
−804 ”) 50 parts by mass and a polyester resin (manufactured by Takeda Pharmaceutical Co., Ltd .; trade name“ Polymer 5250 ”) 5
A mixture of 0 parts by mass was used.

As the filler, alumina having an average particle size of 4 μm (manufactured by Showa Denko KK; product number “AL-43PC”) 4
Calcium carbonate having an average particle size of 2.1 μm with respect to 0 parts by mass (“NS- # 100” manufactured by Nitto Powder Chemical Co., Ltd.) 6
A mixture of 0 parts by mass was used in an amount of 200 parts by mass based on 100 parts by mass of the resin component.

As a curing agent, t-hexyl peroxy 2-ethylhexanoate (manufactured by NOF CORPORATION; trade name "Percure HO") was used in an amount of 40 parts by mass based on 100 parts by mass of the resin component.

These components were blended and stirred and mixed by a stirrer to prepare a resin composition.

This resin composition was subjected to a vacuum degassing treatment under a reduced pressure of 26.7 hPa for 30 minutes. Further, this resin composition was poured into a mold having a cavity capable of molding a flat plate having a thickness of 11 mm, and heated at a mold temperature of 90 ° C. for 80 minutes to form a flat artificial marble.

(Example 5) As a resin component, a vinyl ester resin (manufactured by Showa Polymer Co., Ltd .; trade name: Lipoxy R
-806 ") and 35 parts by mass of an acrylic syrup resin (manufactured by Mitsui Chemicals, Inc .; trade name" XE924-1 ") were used.

As the filler, alumina having an average particle size of 3.4 μm (manufactured by Nippon Light Metal Co., Ltd .; trade name “LS-2”)
1)) 10 parts by mass of aluminum hydroxide having an average particle size of 10 μm (manufactured by Showa Denko KK; trade name “H-320”)
A mixture of 60 parts by mass and 30 parts by mass of a glass filler having an average particle diameter of 5 μm (manufactured by Nippon Frit Co., Ltd .: product number “CF”) was used in an amount of 180 parts by mass based on 100 parts by mass of the resin component.

As a curing agent, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (manufactured by NOF Corporation; trade name “Percure WO”) is used per 100 parts by mass of the resin component. 3.6 parts by mass.

These components were blended and mixed by stirring with a stirrer to prepare a resin composition.

This resin composition was subjected to a vacuum degassing treatment under a reduced pressure of 26.7 hPa for 30 minutes. Further, this resin composition was poured into a mold having a cavity capable of molding a flat plate having a thickness of 11 mm, and heated at a mold temperature of 90 ° C. for 80 minutes to form a flat artificial marble.

(Example 6) As resin components, 60 parts by mass of a vinyl ester resin (manufactured by Takeda Pharmaceutical Co., Ltd .; trade name "Prominate P-310") and an acrylic syrup resin (manufactured by Mitsui Chemicals, Inc .; trade name " XE924-1 ")
A mixture of 10 parts by mass and 30 parts by mass of a polyester resin (manufactured by Takeda Pharmaceutical Co., Ltd .; trade name “Polymer 5250”) was used.

As the filler, alumina having an average particle diameter of 3.0 μm (manufactured by Nippon Light Metal Co., Ltd .; trade name “LS-2”)
4)) 50 parts by mass of aluminum hydroxide having an average particle size of 25 μm (manufactured by Sumitomo Chemical Co., Ltd .; product number “CW-
325LV ") and silica having an average particle diameter of 10 µm (manufactured by Shiraishi Industry Co., Ltd .; trade name" MILLISILL ").
M10 ") was used in which 20 parts by mass were blended. This filler was used in an amount of 200 parts by mass based on 100 parts by mass of the resin component.

As the curing agent, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (manufactured by NOF CORPORATION; trade name “Percure WO”) is used per 100 parts by mass of the resin component. 3.8 parts by mass.

These components were blended and stirred and mixed by a stirrer to prepare a resin composition.

This resin composition was subjected to a vacuum degassing treatment under a reduced pressure of 26.7 hPa for 30 minutes. Further, this resin composition was poured into a mold having a cavity capable of molding a flat plate having a thickness of 11 mm, and heated at a mold temperature of 90 ° C. for 80 minutes to form a flat artificial marble.

(Comparative Example 1) As a filler, an average particle diameter of 8 μm was used.
Example 1 except that only m. aluminum hydroxide (manufactured by Sumitomo Chemical Co., Ltd .; trade name "CW-308") was used.
In the same manner as in the above, artificial marble was formed.

(Evaluation) Table 1 shows the results of measuring the Charpy impact strength of the artificial marble obtained in each of the examples and comparative examples.

[0073]

[Table 1]

[0074]

As described above, the method for producing artificial marble according to the first aspect of the present invention is characterized in that the method for producing artificial marble obtained by molding and curing a resin composition containing a resin component and a filler comprises the steps of: Since the material containing at least alumina is used as the material, artificial marble having excellent impact strength can be manufactured, and a wooden reinforcing plate or an FRP reinforcing layer is formed on the back surface of the artificial marble to supplement the strength. It is possible to exhibit high impact resistance without any need, and it is possible to reduce the weight of the product formed of the artificial marble and to improve the appearance, particularly the transparency.

According to a second aspect of the present invention, in addition to the first aspect, the amount of the filler in the resin composition is 180 to 300 parts by mass with respect to 100 parts by mass of the resin component. It is possible to obtain artificial marble having a good balance of impact strength and heat resistance.

According to a third aspect of the present invention, in addition to the structure of the first or second aspect, since a filler having an average particle diameter of 3 to 50 μm is used, the impact resistance is effectively improved. It is possible to obtain marble and to suppress a decrease in dispersibility of the filler in the resin composition, thereby preventing aggregation of the filler.

According to a fourth aspect of the present invention, in addition to any one of the first to third aspects, a filler treated with a silane coupling agent is used as the filler, so that the filler in the resin composition is used. The dispersibility of the material can be further improved, and the impact resistance of the artificial marble can be more effectively improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 9/06 C08K 9/06 C08L 101/00 C08L 101/00 // C04B 111: 54 C04B 111: 54 ( 72) Inventor Shinji Yamaguchi 18-family, Yasuse, Wakamatsu-ku, Kitakyushu-shi, Fukuoka F-term in Kitakyushu Matsushita Electric Works Co., Ltd. 4J002 AA001 BG061 CD201 CF211 DE146 FB096 FD016 FD140 GL02

Claims (4)

[Claims] 1. A method for producing artificial marble obtained by molding and curing a resin composition containing a resin component and a filler, characterized in that a filler containing at least alumina is used as the filler. Method. 2. The method for producing artificial marble according to claim 1, wherein the amount of the filler in the resin composition is 180 to 300 parts by mass based on 100 parts by mass of the resin component. 3. The method for producing artificial marble according to claim 1, wherein a filler having an average particle size of 3 to 50 μm is used. 4. The method for producing artificial marble according to claim 1, wherein a filler subjected to a silane coupling agent treatment is used as the filler.