JP2002104859A - Method of producing artificial marble - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing artificial marble having high impact resistance not necessarily blended with large amount of glass fibers nor provided with a reinforcing plate or a reinforcing layer. SOLUTION: This method of producing artificial marble comprises preparing a resin composition of a thermosetting resin added by additives such as a filler and a curing agent, and molding and curing the resin composition, where liquid polybutadiene resin is added to the thermosetting resin to be compounded in the resin composition.

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 Artificial marble has been conventionally used to mold a resin composition prepared by blending a thermosetting resin with a filler, a reinforcing agent, an internal mold release agent, a curing agent, etc., into a casting mold having a desired shape. It is manufactured by injecting into a mold and curing by heating or the like. As a thermosetting resin of a resin composition as a raw material for producing such artificial marble, polyester-based, acrylic-based, and vinylester-based resins are used.

[0003] The artificial marble thus manufactured is commercialized and widely used as a wash counter, a kitchen counter, a bathtub, a wash bowl and the like.

[0004] In the production of artificial marble as described above, a resin composition prepared by blending a large amount of glass fiber as a reinforcing agent is used in order to increase the impact resistance of artificial marble and increase the toughness. It has been used.

[0005]

However, when a large amount of glass fiber is blended, the flow of artificial marble pattern or pattern may be significantly impaired, mixing and dispersion may be difficult, and the transparency of the product may be reduced. There is a possibility that the glass fiber will be reduced or fuzz of the glass fiber will be generated on the surface of the product, and as a result, a uniform product may not be obtained. Therefore, there is a problem that there is a limit in increasing strength such as impact resistance by blending glass fibers.

Therefore, in order to compensate for this, a wooden reinforcing plate or a reinforcing layer of FRP is provided on the back surface of the artificial marble, and the thickness of the product is increased. However, in this case, there is a problem that the processing time is increased and the cost is increased due to the reinforcement of the back surface, and the thinning becomes difficult, and the weight of the product increases, and the burden on the product transportation and construction is increased. Was to do.

The present invention has been made in view of the above points, and it is an object of the present invention to obtain an artificial marble having high impact resistance without the necessity of blending a large amount of glass fibers and without providing a reinforcing plate or a reinforcing layer. It is an object of the present invention to provide a method for producing artificial marble that can be used.

[0008]

According to a first aspect of the present invention, there is provided a method for producing artificial marble, wherein a resin composition is prepared by blending additives such as a filler and a curing agent with a thermosetting resin. In producing artificial marble by molding and curing a resin composition, a resin composition is prepared by adding a liquid polybutadiene resin to a thermosetting resin to form a composite type. .

Further, the invention of claim 2 is characterized in that a low molecular weight polybutadiene having an average molecular weight of 500 to 5,000 is used as the liquid polybutadiene resin.

[0010] The invention of claim 3 provides a thermosetting resin 10
0.1 to 3 parts by weight of liquid polybutadiene resin
It is characterized in that it is used by adding 0 parts by mass.

A fourth aspect of the present invention is characterized in that a filler is mixed in an amount of 150 to 300 parts by mass with respect to a total of 100 parts by mass of the thermosetting resin and the liquid polybutadiene resin.

The invention according to claim 5 is characterized in that a filler having an average particle size of 3 to 50 μm is used.

[0013]

Embodiments of the present invention will be described below.

In the resin composition of the present invention, a vinyl ester resin, an acrylic resin, a polyester resin, or the like can be used as the thermosetting resin, and these may be used alone or in combination of two or more. It can also be used.

Here, as the vinyl ester resin, a bisphenol type vinyl ester resin or a novolak type vinyl ester resin can be used, or a mixture of both can be used.

The bisphenol type vinyl ester resin is an addition reaction product of a bisphenol type epoxy resin and an acid. Examples of the bisphenol type epoxy resin include bisphenol A type, bisphenol AD type, bisphenol S type, bisphenol F type and the like. Can be used. In addition, novolak type vinyl ester resin
It is an addition reaction product of a novolak type epoxy resin and an acid,
Both bisphenol-type vinyl ester resins and novolak-type vinyl ester resins have a reactive unsaturated group only at both ends. Usually, a styrene monomer, an acrylic monomer, or the like is blended as a crosslinking agent in the vinyl ester resin, but the form is not particularly limited.

As the acrylic resin, a methyl methacrylate monomer or a thermosetting type is usually used.
A polyfunctional acrylic monomer, a prepolymer, or a polymer, which is a mixture of two or more kinds of acrylic syrup resins, is used, but the form is not particularly limited.

Further, the polyester resin is synthesized as a thermosetting resin by a condensation reaction of an unsaturated dibasic acid such as maleic anhydride and a saturated dibasic acid such as phthalic anhydride with glycols. A compound having an unsaturated bond and an ester bond in the molecule is used. Usually, a styrene monomer, an acrylic monomer, or the like is blended in this resin as a cross-linking agent, and is called an unsaturated polyester resin, but the form is not particularly limited.

Further, vinyl ester resin, acrylic resin,
When two or more of the polyester resins are used in combination, the desired product quality is achieved by the interaction of each resin with its characteristics and filler, and further with the liquid polybutadiene resin to be combined. The blending ratio is set to a suitable blending ratio, and the blending ratio is not particularly limited.

In the present invention, the above-mentioned thermosetting resin is used in the form of a composite type obtained by adding and mixing a liquid polybutadiene resin to the thermosetting resin. A liquid polybutadiene resin may be added to one kind of thermosetting resin and mixed to form a composite. Alternatively, two or more kinds of thermosetting resins may be mixed with a liquid polybutadiene resin and mixed. The shape may be taken.

This liquid polybutadiene resin is a low molecular weight polybutadiene having an average molecular weight of about 500 to 5,000, obtained by polymerizing butadiene with a specific catalyst under predetermined polymerization conditions. If the average molecular weight is less than 500, it will not be a resin having a normal polybutadiene skeleton, and if the average molecular weight exceeds 5,000, it will be rubbery and exceed the liquid range, making it difficult to form a composite with a thermosetting resin. So that the liquid polybutadiene resin has an average molecular weight of 500
A low molecular weight polybutadiene of about 5,000 is used.

Depending on the catalyst to be used, those having different butadiene bonding modes can be obtained, and various types are commercially available. That is, 1,2-bonded type and 1,4
There is a -linked type, and the 1,4-linked type further includes a trans type and a cis type. Further, copolymers of styrene and acrylonitrile, and -OH, -COOH, -CH =
Some have a functional group such as CH ₂ . [Formula 1] shows an example of the structural formula of the liquid polybutadiene resin.

[0023]

Embedded image

(Where a, b, c, and m are positive integers, X is styrene or acrylonitrile, and Y is a terminal functional group) The characteristics of the liquid polybutadiene resin have different characteristics depending on the type thereof. The form is not particularly limited. The addition amount of the liquid polybutadiene resin is preferably in the range of 0.1 to 30 parts by mass based on 100 parts by mass of the thermosetting resin (including the crosslinking agent). If the added amount of the liquid polybutadiene resin is less than 0.1 part by mass, the effect of increasing the impact resistance (toughness) of the product strength of artificial marble may be insufficient, and if it exceeds 30 parts by mass, it is prepared. The viscosity of the resin composition sharply increases, and molding tends to be difficult, and in some cases, molding may not be possible.

The resin composition used in the present invention contains a filler. As the filler, silica, calcium carbonate, aluminum hydroxide, glass powder, clay and the like can be used. The compounding amount of the filler is preferably in the range of 150 to 300 parts by mass with respect to the resin component, that is, 100 parts by mass in total of the thermosetting resin (including the crosslinking agent) and the liquid polybutadiene resin. If the amount of the filler is less than this range, the impact resistance of the molded artificial marble is excellent, but the heat resistance may not be sufficiently improved.If the amount exceeds this range, the heat resistance is excellent. Impact strength may be reduced.

The smaller the particle size of the filler, the higher the toughness of the artificial marble and the higher the impact resistance, and it is preferable to use a filler having an average particle size of 50 μm or less. However, if the particle size is too small, the dispersibility of the filler may be reduced and the filler may be aggregated.
The lower limit of the average particle size of the filler is preferably set to 3 μm.
In addition, when the surface of the filler is treated with a silane coupling agent in advance, the adhesion between the filler and the thermosetting resin can be improved, and the dispersibility of the filler can be further improved. The impact resistance of artificial marble can be further improved.

Further, a curing agent is added to the resin composition used in the present invention. As the curing agent, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexaate, t-hexylperoxy-2-ethylhexanoate, or the like can be used. When the thermosetting resin is a vinyl ester resin, for example, the mixing ratio of the curing agent is preferably in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin and the crosslinking agent.

The resin composition used in the present invention may further contain, in addition to the above-mentioned additives, an ultraviolet absorber, a viscosity reducing agent, an internal mold release agent, glass fibers, a colorant and the like.

In preparing the resin composition, first, a liquid polybutadiene resin is added to and mixed with the thermosetting resin to form a composite type. The liquid polybutadiene resin may be directly added to the thermosetting resin, or may be added in a state in which the liquid polybutadiene resin is dissolved or dispersed in a soluble resin or a solvent in advance. Then, a resin composition can be prepared by blending a filler, a curing agent, and each of the above-described additives at a predetermined ratio with the composite resin, and stirring and mixing using a stirrer or the like.

In producing artificial marble using the resin composition thus prepared, first, the resin composition is subjected to vacuum degassing under reduced pressure of about 0.4 to 6.7 kPa (3 to 50 Torr). After the resin composition subjected to the treatment and defoaming treatment is opened from a reduced pressure state, the resin composition is poured into a mold having a predetermined shape, and the mold is cooled at a temperature of 50 to 110 ° C. for 30 to 12 hours.
This can be done by heating for 0 minutes. By heating in this manner, the copolymerization reaction between the reactive unsaturated group in the thermosetting resin of the resin composition and the polymerizable monomer proceeds, and the resin composition is cured and molded to obtain artificial marble. You can do it.

The artificial marble thus obtained has a high impact resistance due to the plasticizing action of the polybutadiene resin and can be made into a product having high toughness. Therefore, a large amount of glass fiber is blended. No longer needed
The transparency of the product is not reduced, and the fuzz of glass fiber does not occur on the surface of the product,
An artificial marble having an excellent appearance, in particular, excellent transparency can be obtained. In addition, there is no need to provide a wooden reinforcing plate or FRP reinforcing layer on the back surface of the artificial marble product, or to increase the product thickness, thereby making it possible to reduce the thickness and reduce the weight of the product. It is.

[0032]

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

Example 1 As a thermosetting resin, a vinyl ester resin ("Prominate P-31" manufactured by Takeda Pharmaceutical Co., Ltd.)
1)) and a liquid polybutadiene resin ("HYCARCT polymer CTB 2000" manufactured by Ube Industries, Ltd.)
× 162 ”; average molecular weight 4800) was added to 3.5 parts by mass based on 100 parts by mass of the vinyl ester resin. Further, aluminum hydroxide (“CW-308B” manufactured by Sumitomo Chemical Co., Ltd .; average particle size: 8 μm) was added as a filler to the resin component (vinyl ester resin and liquid polybutadiene resin).
A resin composition was prepared by adding 200 parts by mass to 100 parts by mass, adding 3.0 parts by mass of a curing agent (“Percure WO” manufactured by NOF Corporation) and mixing with a stirrer.

This resin composition was used at 2.7 kPa (20 To
rr) Vacuum defoaming treatment for 40 minutes under reduced pressure, injection into a mold, and heating the mold at 90 ° C. for 80 minutes to cure the resin composition and form an 11 mm thick flat plate. Got marble.

(Example 2) Acrylic syrup resin ("AC-02" manufactured by Nippon Fellow Co., Ltd.) as a thermosetting resin
Using a liquid polybutadiene resin (“HYCAR CT Polymer CTBN 1300 × 3” manufactured by Ube Industries, Ltd.)
1 "; acrylic syrup resin 1 having an average molecular weight of 3500)
6.1 parts by mass was added to 00 parts by mass. Further, as a filler, silica (CRYSTA manufactured by Tatsumori Co., Ltd.)
LITE 2105-30 "; average particle size 6 μm) was compounded in an amount of 200 parts by mass with respect to 100 parts by mass of the resin components (acrylic syrup resin and liquid polybutadiene resin), and a curing agent (“ PERCADOX ”manufactured by Kayaku Akzo Co., Ltd.) 16 ") by adding 1.5 parts by mass and mixing with a stirrer,
A resin composition was prepared.

This resin composition was used at 2.7 kPa (20 To
rr) Vacuum defoaming treatment under reduced pressure for 60 minutes, injection into a mold, and heating the mold at 90 ° C. for 70 minutes to cure the resin composition and form an 11 mm thick flat plate Got marble.

Example 3 Polyester resin ("Polymer 5450" manufactured by Takeda Pharmaceutical Co., Ltd.) as a thermosetting resin
Using a liquid polybutadiene resin ("HYCAR CT Polymer CTBN 1300x" manufactured by Ube Industries, Ltd.)
8 "; average molecular weight of 3,500)
5.6 parts by mass was added to the parts by mass. In addition,
As a filler, 220 parts by mass of aluminum hydroxide (“H-310” manufactured by Showa Denko KK; average particle size: 17 μm) is mixed with 100 parts by mass of the resin component (polyester resin and liquid polybutadiene resin), and then cured. 3.5 parts by mass of an agent ("Percure HO" manufactured by NOF Corporation)
The resin composition was prepared by mixing with a stirrer.

This resin composition was added at 2.7 kPa (20 To
rr) A vacuum degassing treatment was performed under reduced pressure for 50 minutes, and this was poured into a mold, and the mold was heated at 90 ° C. for 100 minutes to cure the resin composition, thereby forming an 11 mm thick flat plate. Got marble.

(Example 4) As a thermosetting resin, a vinyl ester resin ("Ripoxy R-80" manufactured by Showa High Polymer Co., Ltd.) was used.
4 ") and a polyester resin (" Polymer 5250 "manufactured by Takeda Pharmaceutical Co., Ltd.) in a mass ratio of 50:50, and used as a liquid polybutadiene resin (" HY "manufactured by Ube Industries, Ltd.).
CAR VT polymer VTBNX 1300 × 3
3 "; average molecular weight 3500) was added to 6.5 parts by mass based on 100 parts by mass of the total of the vinyl ester resin and the polyester resin. Further, aluminum hydroxide ("H-320" manufactured by Showa Denko KK; average particle size: 1) was used as a filler.
0 μm) is compounded in an amount of 210 parts by mass with respect to 100 parts by mass of the resin component (vinyl ester resin, polyester resin and liquid polybutadiene resin), and 3.5 parts by mass of a curing agent (“Percure HO” manufactured by NOF Corporation). And a resin composition was prepared by mixing with a stirrer.

This resin composition was used at 2.7 kPa (20 To
rr) a vacuum degassing treatment for 40 minutes under reduced pressure, injecting this into a mold, heating the mold at 90 ° C. for 100 minutes to cure the resin composition, and forming an 11 mm thick flat plate Got marble.

(Example 5) As a thermosetting resin, a vinyl ester resin ("Ripoxy R-80" manufactured by Showa High Polymer Co., Ltd.) was used.
6 ”) and acrylic syrup resin (“ X ”manufactured by Mitsui Chemicals, Inc.)
E924-1 ") at a mass ratio of 65:35, and a liquid polybutadiene resin (" HY "manufactured by Ube Industries, Ltd.)
CAR VT polymer VTBNX 1300 × 3
3 "; average molecular weight of 3500) with respect to 100 parts by mass of vinyl ester resin and acrylic syrup resin in total of 8.2 parts.
Parts by weight were added. Further, aluminum hydroxide ("H-320" manufactured by Showa Denko KK; average particle size: 10 m) and a glass filler ("CF002-10D" manufactured by Nippon Frit Co., Ltd .; average particle size: 10 m) were added as fillers. 70:
The mixture obtained at a mass ratio of 30 was blended in an amount of 210 parts by mass with respect to 100 parts by mass of the resin components (vinyl ester resin, acrylic syrup resin and liquid polybutadiene resin), and a curing agent ("Percure WO" manufactured by NOF CORPORATION). )) To 3.0
A resin composition was prepared by adding parts by mass and mixing with a stirrer.

This resin composition was used at 2.7 kPa (20 To
rr) under a reduced pressure of 50 minutes under reduced pressure and defoaming treatment, poured into a mold and heated at 90 ° C. for 90 minutes to cure the resin composition, and the artificial marble was formed as a flat plate having a thickness of 11 mm. Molded.

Example 6 As a thermosetting resin, a vinyl ester resin ("Prominate P-3" manufactured by Takeda Pharmaceutical Co., Ltd.)
10 "), an acrylic syrup resin (" XE924-1 "manufactured by Mitsui Chemicals, Inc.) and a polyester resin (" Polymer 5250 "manufactured by Takeda Pharmaceutical Co., Ltd.) at 60:10:30.
Liquid polybutadiene resin ("HYCAR VT Polymer VTBN" manufactured by Ube Industries, Ltd.)
X 1300 × 33 ”; average molecular weight 3500) and liquid polybutadiene resin (“ HYCAR C ”manufactured by Ube Industries, Ltd.)
T polymer CTBN 1300 × 31 ”; average molecular weight 3500) were added in an amount of 3.2 parts by mass and 2.5 parts by mass, respectively, based on a total of 100 parts by mass of the vinyl ester resin, the acrylic syrup resin, and the polyester resin. Further, as a filler, aluminum hydroxide (“CW-325LV” manufactured by Sumitomo Chemical Co., Ltd .; average particle size: 25 μm) and silica (“MILLISIL M1” manufactured by Shiraishi Industry Co., Ltd.)
0 "; average particle size of 10 µm) was mixed at a mass ratio of 80:20, and 200 parts by mass were mixed with 100 parts by mass of the resin component (vinyl ester resin, acrylic syrup resin, polyester resin and liquid polybutadiene resin). And a curing agent ("Percure WO" manufactured by NOF Corporation) of 4.0
A resin composition was prepared by adding parts by mass and mixing with a stirrer.

This resin composition was added at 2.7 kPa (20 To
rr) A defoaming treatment under reduced pressure for 50 minutes under reduced pressure, and the resulting mixture is poured into a mold, and the mold is heated at 90 ° C for 110 minutes to cure the resin composition. Molded.

Comparative Example 1 A resin composition was prepared in the same manner as in Example 1 except that no liquid polybutadiene resin was added and a non-composite vinyl ester resin was used as the thermosetting resin. . The resin composition was molded in the same manner as in Example 1 to obtain artificial marble.

Comparative Example 2 A resin composition was prepared in the same manner as in Example 2 except that the liquid polybutadiene resin was not added and an acrylic syrup resin which was not complexed was used as the thermosetting resin. . The resin composition was molded in the same manner as in Example 2 to obtain artificial marble.

Comparative Example 3 A resin composition was prepared in the same manner as in Example 3, except that no liquid polybutadiene resin was added and a non-composite polyester resin was used as the thermosetting resin. Then, this resin composition was molded in the same manner as in Example 3 to obtain artificial marble.

Comparative Example 4 A resin composition was prepared in the same manner as in Example 4 except that no liquid polybutadiene resin was added and a non-composite vinyl ester resin and polyester resin were used as the thermosetting resin. Was prepared. The resin composition was molded in the same manner as in Example 4 to obtain artificial marble.

Comparative Example 5 A resin composition was prepared in the same manner as in Example 5 except that no liquid polybutadiene resin was added and a non-composite vinyl ester resin and an acrylic syrup resin were used as the thermosetting resin. Was prepared.
The resin composition was molded in the same manner as in Example 5 to obtain artificial marble.

Comparative Example 6 The procedure of Example 6 was repeated, except that no liquid polybutadiene resin was added and a non-composite vinyl ester resin, an acrylic syrup resin and a polyester resin were used as the thermosetting resin. Thus, a resin composition was prepared. Then, this resin composition was molded in the same manner as in Example 6 to obtain artificial marble.

For the artificial marbles of Examples 1 to 6 and Comparative Examples 1 to 6 obtained as described above, the Charpy impact strength was measured to evaluate the impact resistance. Table 1 shows the results.
In addition, each of Examples 1 to 6 had good transparency, and Comparative Examples 1 to 6 were almost the same as each Example.

[0052]

[Table 1]

As shown in Table 1, each of the examples in which the liquid polybutadiene resin was added to the thermosetting resin to form a composite type was different from the comparative examples in which the liquid polybutadiene resin was not added. Also, it was confirmed that the Charpy impact strength was high and the impact resistance was improved.

[0054]

As described above, in the method for producing artificial marble according to claim 1 of the present invention, a resin composition is prepared by blending additives such as a filler and a curing agent with a thermosetting resin. In producing artificial marble by molding and curing the resin composition, a liquid polybutadiene resin was added to the thermosetting resin to prepare a resin composition using a composite type, so that the liquid polybutadiene resin By adding, it is possible to obtain artificial marble having high impact resistance without having to mix a large amount of glass fibers and without providing a reinforcing plate or a reinforcing layer.

According to the second aspect of the present invention, since a low molecular weight polybutadiene having an average molecular weight of 500 to 5,000 is used as the liquid polybutadiene resin, the liquid polybutadiene resin is added without greatly increasing the viscosity of the resin composition. And does not impair moldability.

The third aspect of the present invention relates to a thermosetting resin 10
0.1 to 3 parts by weight of liquid polybutadiene resin
Since 0 parts by mass is used, artificial marble excellent in impact resistance can be obtained without impairing the formability.

According to the fourth aspect of the present invention, the filler is blended in an amount of 150 to 300 parts by mass with respect to the total of 100 parts by mass of the thermosetting resin and the liquid polybutadiene resin. An excellent artificial marble can be obtained.

According to the fifth aspect of the present invention, since a filler having an average particle size of 3 to 50 μm is used, artificial marble excellent in impact resistance without lowering the dispersibility of the filler is used. What you can get.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/00 C08L 101/00 // (C04B 26/18 (C04B 26/18 C 24:26 24:26 Z 20:00) 20:00) B (C08L 101/00 (C08L 101/00 9:00) 9:00) B29K 9:00 B29K 9:00 101: 10 101: 10 105: 16 105: 16 B29L 31 : 10 B29L 31:10 C04B 103: 60 C04B 103: 60 111: 54 111: 54 (72) Inventor Masahiko Suzuki 18 Fukuoka Prefecture, Kitakyushu City 4F204 AA20 AA46 AB03 AB11 AB16 AH44 EA03 EB01 EE12 EK13 EK24 4J002 AC032 BG031 CD201 CF211 DE146 DE236 DJ016 DJ036 DL006 EK007 GL02

Claims (5)

[Claims] 1. A resin composition is prepared by blending an additive such as a filler and a curing agent with a thermosetting resin, and the resin composition is molded and cured to produce an artificial marble. A method for producing artificial marble, characterized in that a resin composition is prepared using a compound obtained by adding a liquid polybutadiene resin to a resin. 2. The method for producing artificial marble according to claim 1, wherein low molecular weight polybutadiene having an average molecular weight of 500 to 5000 is used as the liquid polybutadiene resin. 3. The method for producing artificial marble according to claim 1, wherein 0.1 to 30 parts by mass of a liquid polybutadiene resin is added to 100 parts by mass of the thermosetting resin. 4. The artificial marble according to claim 1, wherein 150 to 300 parts by mass of a filler is blended with respect to a total of 100 parts by mass of the thermosetting resin and the liquid polybutadiene resin. Production method. 5. The method for producing artificial marble according to claim 1, wherein a filler having an average particle diameter of 3 to 50 μm is used.