JP2002012462A - Resin composition for manufacturing artificial marble - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for manufacturing artificial marble which can obtain artificial marble with high antifouling property capable of keeping clean for long term with little labor for cleaning. SOLUTION: Thermosetting resin is blended with filler and curing agent, and added with silicone resin together. The artificial marble formed from this resin composition can be improved in the antifouling property by included silicone resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[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]

Here, when artificial marble products are used in areas called water areas such as toilets, bathrooms, kitchen areas, etc., contamination by use, contamination by detergents, food, oil, cosmetics, etc. There has been a situation in which dirt and the like are easily attached, and it is difficult to remove dirt even when cleaning, or dirt is not removed even when cleaning. Therefore, it is often performed to strongly remove dirt with a cleaning agent containing an abrasive, or to use a strong cleaning agent such as a mold remover. In such a case,
There is a problem that the surface of the product may be damaged, or the generated chemical substance may cause anxiety about health damage.

[0005] For these reasons, there is an urgent need for an artificial marble having a high antifouling property, which makes it difficult to remove dirt and remove dirt easily.

The present invention has been made in view of the above points, and provides an artificial marble which has high antifouling performance and can be kept clean for a long period of time by reducing the trouble of cleaning for cleaning dirt. It is an object of the present invention to provide a resin composition for producing artificial marble that can be used.

[0007]

The resin composition for producing artificial marble according to claim 1 of the present invention is a resin composition used for producing artificial marble by molding and curing,
It is characterized in that a filler and a curing agent are blended into a thermosetting resin and a high-viscosity type silicone resin is internally added.

The invention of claim 2 is characterized in that the high-viscosity type silicone resin has a viscosity of 10,000 to 1,000,000 cSt.

The invention of claim 3 is characterized in that at least one of straight silicone oil and modified silicone oil is used as the silicone resin.

According to a fourth aspect of the present invention, the amount of the silicone resin is 0.05 to 30 parts by mass based on 100 parts by mass of the thermosetting resin.

The invention of claim 5 is characterized in that the thermosetting resin is at least one selected from vinyl ester resin, acrylic resin and polyester resin.

Further, in the invention according to claim 6, the compounding amount of the filler is 180 to 3 with respect to 100 parts by mass of the thermosetting resin.
100 parts by mass.

The invention according to claim 7 is characterized in that the filler has an average particle size of 3 to 50 μm.

[0014]

Embodiments of the present invention will be described below.

In the present invention, a vinyl ester resin, an acrylic resin, a polyester resin, or the like can be used as the thermosetting resin. These may be used alone or in combination of two or more. it can.

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 and bisphenol F type. 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.

The acrylic resin is usually a thermosetting resin such as methyl methacrylate monomer or
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 subjecting an unsaturated dibasic acid such as maleic anhydride and a saturated dibasic acid such as phthalic anhydride to a condensation reaction 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 mixing ratio is set to match the desired product quality due to the characteristics of each resin and the interaction with the filler. The mixing ratio is not particularly limited.

As the high-viscosity type silicone resin to be internally added to the resin composition of the present invention, straight silicone oil and modified silicone oil can be used, and either one of them can be used alone. Alternatively, they can be used as a mixture of both. The straight silicone oil and the modified silicone oil are classified according to the type of the organic substituent bonded to the silicon atom.

That is, the straight silicone oil has a methyl group, a phenyl group and a hydrogen atom group as substituents, and includes dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil and the like. There are various kinds of these having different molecular weights, but they can be used without any particular limitation.

The modified silicone oil is classified into a reactive silicone oil and a non-reactive silicone oil, and is further classified according to the type of the organic group to be introduced or the position and the number of the introduced organic group. For example, reactive silicone oils include amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified,
There are types such as mercapto-modified and phenol-modified, and non-reactive silicone oils include polyether-modified,
There are types such as methylstyryl modification, alkyl modification, higher fatty acid ester modification, alkyl / aralkyl modification, alkyl / polyether modification, and fluoroalkyl modification.
In the present invention, any of the modified silicone oils can be used by being internally added, and the type thereof is not particularly limited.

In the present invention, any of these silicone resins can be used.
The one using 100,000 cSt (centistokes = mm ² / s) is used. Normally, the viscosity is determined by its molecular weight, so it can be paraphrased to use a silicone resin having a viscosity of 10,000 to 1,000,000 cSt.
A silicone resin having a viscosity of less than 10,000 cSt has a small molecular weight, so that it becomes extremely finely dispersed or distributed in the internally added resin composition, and is buried in the resin composition. There is a possibility that the effect of antifouling performance cannot be sufficiently obtained. The viscosity is 1
If it exceeds 100,000 cSt, the viscosity of the resin composition to which the silicone resin is added becomes high, and uniform mixing becomes difficult. Similarly, the effect of the antifouling performance by the addition of the silicone resin may not be sufficiently obtained. .

The amount of the silicone resin added internally is not particularly limited, but if the amount is small, it is difficult to obtain the desired antifouling performance, and if the amount is too large, the antifouling performance can be secured. However, there is a possibility that the strength of the formed artificial marble may be reduced and the product strength may not be secured. For this reason, the addition amount of the silicone oil is 0.00.0 parts by mass per 100 parts by mass of the thermosetting resin (including the crosslinking agent).
A range of 5 to 30 parts by mass is preferred. Further, although not particularly limited, in order to uniformly mix and disperse the silicone resin in the resin composition, the addition of the silicone resin is usually performed after adding the silicone resin to the thermosetting resin and mixing.
It is preferable to add and mix a compound such as another filler.

The resin composition of the present invention contains a filler. As the filler, silica, calcium carbonate, aluminum hydroxide, glass powder, clay and the like can be used. The amount of the filler is preferably in the range of 180 to 300 parts by mass based on 100 parts by mass of the thermosetting resin (including the crosslinking agent). 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. 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 of the present invention. Examples of the curing agent include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexaate and t
-Hexyl peroxy 2-ethylhexanoate and 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 based on 100 parts by mass of the total amount of the resin and the crosslinking agent.

The resin composition of the present invention may contain, in addition to the above components, an ultraviolet absorber, a viscosity reducing agent, an internal mold release agent, a glass fiber, a colorant, and the like.

In preparing the resin composition of the present invention, first, a predetermined amount of a silicone resin is added to a thermosetting resin, and then a filler, a curing agent, and each of the above additives are added to a predetermined amount. The mixing can be carried out by mixing them in a ratio 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 defoaming under reduced pressure of about 0.4 to 6.7 kPa (3 to 50 Torr). After the resin composition subjected to the treatment and the 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 can be improved in antifouling performance by the contained silicone resin. It is possible to keep it clean. And dirt due to use, contamination from detergent, dirt from food, oil, cosmetics, etc. are hard to adhere,
The dirt attached will be easier to remove, and its use in the area of water supply such as toilets, bathrooms, kitchens, etc. will be expanded. .

[0033]

Next, the present invention will be described specifically with reference to examples.

Example 1 As a thermosetting resin, a vinyl ester resin ("Prominate P-31" manufactured by Takeda Pharmaceutical Co., Ltd.)
1)), dimethyl silicone oil ("KF96H" manufactured by Shin-Etsu Chemical Co., Ltd .: viscosity: 10,000 cSt) was added as a silicone resin. At this time, vinyl ester resin 1
Dimethyl silicone oil was added in an amount of 0. 00 parts by mass.
5 parts by mass, 1.0 part by mass, 2.5 parts by mass, and 5.5 parts by mass were added. Further, 210 parts by mass of aluminum hydroxide (“CW-308B” manufactured by Sumitomo Chemical Co., Ltd.) as a filler is mixed with 100 parts by mass of the vinyl ester resin.
In addition, 2.5 parts by mass of a curing agent ("Percure WO" manufactured by NOF Corporation) is added, and mixed with a stirrer to obtain
A resin composition was prepared.

This resin composition was used at 2.7 kPa (20 To
rr) Vacuum defoaming treatment under reduced pressure for 35 minutes, injection into a mold, and heating the mold at 90 ° C. for 75 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
Dimethyl silicone oil ("KF96H" manufactured by Shin-Etsu Chemical Co., Ltd .: viscosity 100,000 c)
St) was added. At this time, acrylic syrup resin 1
1 part by weight of dimethyl silicone oil was added to 100 parts by mass.
6 parts by mass, 3.3 parts by mass, 5.8 parts by mass, and 10.8 parts by mass were added. In addition, silica (Tatsumori Co., Ltd.)
"CRYSTALITE 2105-30") was compounded in an amount of 200 parts by mass with respect to 100 parts by mass of the acrylic syrup resin, and 2.8 parts by mass of a curing agent ("PARCADOX 16" manufactured by Kayaku Akzo Co., Ltd.) was added. The resin composition was prepared by mixing with a stirrer.

This resin composition was used at 2.7 kPa (20 To
rr) Vacuum defoaming treatment under reduced pressure for 35 minutes, injection of this into a mold, and heating the mold at 90 ° C for 60 minutes to cure the resin composition and form a 10 mm thick flat plate Got marble.

Example 3 Polyester resin ("Polymer 5450" manufactured by Takeda Pharmaceutical Co., Ltd.) as a thermosetting resin
Dimethyl silicone oil (“KF96H” manufactured by Shin-Etsu Chemical Co., Ltd .: viscosity 1,000,000 cSt) was added as a silicone resin. At this time, the polyester resin 10
Dimethyl silicone oil is added to
Parts by mass, 3.5 parts by mass, 6.5 parts by mass, and 9.5 parts by mass were added. Further, 220 parts by mass of aluminum hydroxide (“H-310” manufactured by Showa Denko KK) as a filler is mixed with 100 parts by mass of the polyester resin, and a curing agent (“Percure HO” manufactured by NOF Corporation) is used. ") Was added and mixed with a stirrer to prepare a resin composition.

This resin composition was added at 2.7 kPa (20 To
rr) A vacuum degassing treatment was performed under reduced pressure for 35 minutes, this was poured into a mold, and the mold was heated at 90 ° C. for 70 minutes to cure the resin composition, thereby forming a 12 mm thick flat plate. Got marble.

(Example 4) As a thermosetting resin, a vinyl ester resin ("Ripoxy R-80" manufactured by Showa 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 a fluorine-modified silicone oil (" FL100 "manufactured by Shin-Etsu Chemical Co., Ltd.) is used as the silicone resin. ": 10,000 c
St ") was added. At this time, 0.3 parts by mass, 0.9 parts by mass, 1.8 parts by mass, and 3.3 parts by mass of the fluorine-modified silicone oil were added to 100 parts by mass of the thermosetting resin. Further, aluminum hydroxide (“H-320” manufactured by Showa Denko KK) is used as a filler, and thermosetting resin 100 is used.
A resin composition was prepared by mixing 200 parts by mass with respect to parts by mass, adding 2.6 parts by mass of a curing agent (“Percure HO” manufactured by NOF Corporation) and mixing with a stirrer.

This resin composition was added at 2.7 kPa (20 To
rr) Degassing under reduced pressure for 35 minutes under reduced pressure, injecting this into a mold and heating the mold at 90 ° C. for 80 minutes to cure the resin composition and form a 10.5 mm thick flat plate Obtained artificial 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 ") and polyester resin (Takeda Pharmaceutical Co., Ltd.)
Manufactured by "Polymer 5250") in a mass ratio of 70:15:15. As silicone resins, dimethyl silicone oil (“KF96H” manufactured by Shin-Etsu Chemical Co., Ltd .: 1,000,000 cSt) and fluorine-modified silicone oil (“FL100” manufactured by Shin-Etsu Chemical Co., Ltd.): 1
10,000 cSt) at a mass ratio of 60:40. Then, 1.3 parts by mass, 2.5 parts by mass, 4.3 parts by mass, and 7.2 parts by mass of the silicone resin were added to 100 parts by mass of the thermosetting resin. Further, as a filler, aluminum hydroxide (“H-320” manufactured by Showa Denko KK) and a glass filler (“CF002-” manufactured by Nippon Frit Co., Ltd.)
100 "in a ratio of 90:10 by mass was mixed with 210 parts by mass of 100 parts by mass of the thermosetting resin, and a curing agent (" Percure WO "manufactured by NOF Corporation) was 2.8. By adding 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) A vacuum degassing treatment was performed for 35 minutes under reduced pressure, and this was poured into a mold, and the mold was heated at 90 ° C. for 90 minutes to cure the resin composition. Marble molded.

Comparative Example 1 A resin composition was prepared in the same manner as in Example 1 except that the silicone resin was not used. 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 silicone resin was not used. 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 the silicone resin was not used. 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 the silicone resin was not used. 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 the silicone resin was not used. The resin composition was molded in the same manner as in Example 5 to obtain artificial marble.

With respect to the artificial marbles of Examples 1 to 5 and Comparative Examples 1 to 5 obtained as described above, black tea and curry were applied as pollutants on the surfaces thereof, and then left for one day. And, when this thing is washed with tap water,
The detergency upon washing with a neutral detergent was evaluated, and the degree of remaining contaminants was visually scored according to the following five levels to evaluate the antifouling performance.

5 = Pollutant is completely removed 4 = Pollutant remains very slightly 3 = Pollutant remains slightly noticeable 2 = Pollutant remains noticeable 1 = Pollutant is almost removed Absent

[0051]

[Table 1]

As shown in Table 1, each of the examples in which the silicone resin was added had higher water washability and detergency than those of the comparative examples in which no silicone resin was added, and the antifouling performance was higher. Was excellent.

[0053]

As described above, the resin composition for producing artificial marble according to claim 1 of the present invention comprises a thermosetting resin in which a filler and a curing agent are added and a high-viscosity silicone resin is added. Therefore, the artificial marble molded from this resin composition can improve the antifouling performance by the contained silicone resin, and can reduce the trouble of cleaning for cleaning the dirt, and can be used for a long time. It is possible to keep it clean throughout.

The invention of claim 2 is characterized in that the high-viscosity type silicone resin has a viscosity of 10,000 to 1,000,000 cSt, so that the effect of antifouling performance can be enhanced by the addition of the silicone resin. Can be done.

The invention of claim 3 is characterized in that at least one of a straight silicone oil and a modified silicone oil is used as the silicone resin, so that a high antifouling performance can be obtained by the straight silicone oil or the modified silicone oil. Things.

According to a fourth aspect of the present invention, the addition amount of the silicone resin is 0.05 to 100 parts by mass of the thermosetting resin.
Since the amount is で あ 30 parts by mass, the antifouling performance can be improved while ensuring the product strength of the artificial marble.

The invention of claim 5 is characterized in that the thermosetting resin is at least one selected from a vinyl ester resin, an acrylic resin and a polyester resin. Marble can be obtained.

According to the sixth aspect of the present invention, the compounding amount of the filler is 180 to 300 with respect to 100 parts by mass of the thermosetting resin.
Since it is a mass part, artificial marble excellent in both heat resistance and impact resistance can be obtained.

Further, the invention of claim 7 is characterized in that the filler has an average particle size of 3 to 50 μm, so that artificial marble excellent in impact strength can be obtained without lowering the dispersibility of the filler. What you can get.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 67/06 C08L 67/06 101/00 101/00 // (C08L 101/00 (C08L 101/00 83 : 04) 83:04) (72) Inventor Shinji Yamaguchi 1-18 Yasuse, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture F-term in Kitakyushu Matsushita Electric Works Co., Ltd. 4J002 BG041 BG061 CD201 CF221 CP032 CP042 CP072 CP092 DE146 DE236 DJ016 DJ036 DL006 EK037 EK057 FD016 FD147

Claims (7)

[Claims] Claims: 1. A resin composition used for producing an artificial marble by molding and curing, wherein a thermosetting resin comprises:
A resin composition for producing artificial marble, comprising a filler and a curing agent, and a high-viscosity silicone resin. 2. The high viscosity type silicone resin has a viscosity of 10,000 to 1,000,000 cSt.
2. The resin composition for producing artificial marble according to item 1. 3. The resin composition for producing artificial marble according to claim 1, wherein at least one of straight silicone oil and modified silicone oil is used as the silicone resin. 4. The artificial marble production according to claim 1, wherein an addition amount of the silicone resin is 0.05 to 30 parts by mass with respect to 100 parts by mass of the thermosetting resin. Resin composition. 5. The resin composition for producing artificial marble according to claim 1, wherein the thermosetting resin is at least one selected from a vinyl ester resin, an acrylic resin, and a polyester resin. object. 6. The compounding amount of the filler is 100 parts of the thermosetting resin.
The resin composition for producing artificial marble according to any one of claims 1 to 5, wherein the amount is 180 to 300 parts by mass with respect to parts by mass. 7. The resin composition for producing artificial marble according to claim 1, wherein the filler has an average particle size of 3 to 50 μm.