JPH092858A - Resin composition for artificial marble - Google Patents

Abstract

PURPOSE: To produce an artificial marble having good water-resistance, appearance and transparent feeling using an inexpensive mold in a short time by using a composition composed of a specific unsaturated polyester resin and glass frit. CONSTITUTION: The resin composition for artificial marble is produced by compounding 100 pts.wt. of an unsaturated polyester resin composed of a polymerizable monomer and an unsaturated polyester obtained by the polycondensation of a polyhydric alcohol and a total acid component composed of an α, β-unsaturated dibasic acid or its anhydride and a saturated dibasic acid or its anhydride wherein the amount of the saturated dibasic acid in the total acid component is 40-60mol% and terephthalic acid accounts for >=50mol% of the total saturated dibasic acid component with 100-300 pts.wt. of glass frit surface-treated with a silane coupling agent and having a refractive index of 1.53-1.56, an average particle diameter of <=30μm and a sodium oxide content of <=5wt.%. The composition is molded by hot-casting method at 60-90 deg.C to obtain a molded artificial marble.

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 artificial marble which has a transparent and heavy feeling and is used for bathtubs, kitchen counters, wash basins and the like.

[0002]

2. Description of the Related Art Artificial marble is usually composed of a thermosetting resin such as unsaturated polyester resin, vinyl ester resin and acrylic resin as a matrix and a compound consisting of glass frit, glass powder and filler such as aluminum hydroxide. It is produced by curing a so-called resin composition.

As the molding method, a gel coat is first spray-coated on an FRP (glass fiber reinforced plastic) mold, and once cured in a curing heating furnace, a compound consisting of a thermosetting resin and a filler is used. There are two methods, a casting method in which the compound is injected and cured again in the curing furnace, and a pressing method in which the compound is thickened in advance to form BMC (bulk molding compound), which is heated and pressure-molded in the mold. Broadly divided.

In the former method, for example, the required time (molding time) from the molding process to the demolding of one artificial marble bathtub is 150 to 300 minutes, while the latter is 5 to 5.
It is a highly productive molding method that can be molded in 15 minutes. However, the latter has the disadvantage that the equipment cost is more than 10 times that of the former.

As a method for eliminating the drawbacks of these two molding methods, Japanese Patent Laid-Open No. 6-321597 discloses a thermosetting polymerizable unsaturated ester resin and aluminum hydroxide without gel coating on the mold. It is disclosed that an artificial marble molded article that can be molded in 40 to 60 minutes is obtained by casting a compound consisting of. However, it is said that the combination of unsaturated polyester resin and aluminum hydroxide cannot obtain a transparent feeling, that is, a so-called depth feeling, in a molded product because the refractive indexes of the combinations are different.

[0006]

In order to produce a good artificial marble molded article most economically, a molding method is basically established with a low equipment cost and a molding method in a time comparable to that of the pressing method. To do. For that purpose, it is first necessary to establish a casting method in which a gel coat is not applied to the mold. In addition, it is a necessary condition to raise the mold temperature to accelerate the curing speed of the compound as compared with the conventional casting method. However, if the compound begins to harden in the process of injecting the compound into the mold, the molded product will become defective, so if the compound is injected into the mold at around room temperature and the temperature of the mold is raised to a predetermined temperature, artificial marble molding will occur in the conventional technology. Good products cannot be obtained because cracks occur in the product. In this case, the compound using aluminum hydroxide as a filler is less likely to generate heat (polymerization heat) when the resin is hardened, and the molding time is longer than that of glass frit mixed in the same weight. The effect of preventing the occurrence can be expected. This is because aluminum hydroxide has water of hydration and water of crystallization and absorbs heat generated during the process of curing the resin. On the other hand, the glass frit does not absorb the heat generated by the curing of the resin, so that the curing of the compound progresses rapidly, and raising the mold temperature in a short time involves cracking of the molded product, which is extremely difficult in the conventional technology. It was difficult. It is possible to reduce the amount of polymerization initiator (curing agent) added to the resin component in the compound, or to add a polymerization inhibitor to delay the curing speed of the resin and suppress its curing heat generation. However, there is a drawback that the molding time becomes long.

An object of the present invention is to provide a resin composition capable of producing an artificial marble molded article having good water resistance, transparency and appearance with a molding time of 15 to 30 minutes using an inexpensive mold. To do.

[0008]

In the present invention, it is considered that the glass frit does not have a retarding effect on hardening of the resin unlike aluminum hydroxide, which is an advantage of improving the productivity of the artificial marble molded product, and the glass frit is molded in a short time. In addition, they have completed a resin composition for artificial marble in which cracks do not occur in a molded product.

That is, the resin composition for artificial marble of the present invention is obtained by polycondensing a polyhydric alcohol with an α, β-unsaturated dibasic acid or its anhydride and a saturated dibasic acid or its anhydride. In an artificial marble resin composition comprising an unsaturated polyester resin composed of a saturated polyester (A) and a polymerizable monomer (B) and a glass frit, all acids used for the unsaturated polyester (A) The proportion of saturated dibasic acid in the component is 40 to 60 mol%, and at least 50 mol% in the total saturated dibasic acid component.
The above is 100 parts by weight of the unsaturated polyester resin (C) which is terephthalic acid, and the glass frit (D) 1 which satisfies all the following conditions (1) to (4) as a filler.
It is characterized in that it contains 100 to 300 parts by weight.

(1) The refractive index is in the range of 1.53 to 1.56. (2) The average particle size is 30 μm or less. (3) The particle surface is treated with a silane coupling agent. 4) The content of sodium oxide is 5% by weight or less, and the polyhydric alcohol component used in producing the unsaturated polyester (A) in the unsaturated polyester resin of the present invention is ethylene glycol, propylene glycol or diethylene glycol. , Dipropylene glycol,
1,3-butanediol, 1,6-hexanediol,
Neobenzyl glycol, hydrogenated bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol A, dibromoneopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, glycerin, trimethylol Examples thereof include propane, trimethylolethane, ethylene oxide, propylene oxide and the like. Examples of the α, β-unsaturated dibasic acid or anhydride thereof include maleic acid, maleic anhydride, and fumaric acid. As the saturated dibasic acid or its anhydride, in addition to terephthalic acid, orthophthalic acid and its anhydride, isophthalic acid, tetrahydrophthalic acid and its anhydride, endomethylenetetrahydrophthalic acid and its anhydride,
Examples thereof include tetrabromophthalic acid and its anhydride, dibromotetrahydrophthalic acid and its anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, adibic acid and sebacic acid. All of these raw materials are used alone or in combination.

As the polymerizable monomer (B), styrene,
p-methylstyrene, chlorostyrene, vinyltoluene, divinylbenzene and the like can be mentioned, and a part of them is diallyl phthalate, diallyl isophthalate,
It may be substituted with lower esters of acrylic acid or methacrylic acid.

The resin composition of the present invention may be mixed with a pigment for coloring, an antifoaming agent, an internal release agent, an ultraviolet absorber, and a glass or organic short fiber reinforcing material for improving strength. As the curing agent for curing the resin composition of the present invention, organic peroxides such as ketone peroxides, dialkyl peroxides, hydroperoxides and peroxycarbonates are used alone or in combination. Further, a curing accelerator such as cobalt naphthenate, dimethylaniline and dimethylparatoluidine may be used in combination.

The material of the mold used for molding by the hot casting method using the resin composition of the present invention includes FRP, Coalloy (sold by Nihon Sangyo Co., Ltd.), electroforming, metal spraying and aluminum casting. The molds of these materials are available at low cost. When molds of these materials are used, the molding temperature of the heat casting method is preferably in the range of 60 to 90 ° C.
If the molding temperature is lower than 60 ° C., the curing speed of the compound will be slow, and the productivity of molded products will not increase. On the other hand, if the temperature is higher than 90 ° C, the curing of the compound will proceed rapidly, cracks will occur in the molded product, and a good product cannot be obtained, and the life of the mold will be shortened, which is not economical.

[0014]

[Function] In addition to improving productivity by improving crack resistance during manufacturing, artificial marble moldings are mainly used for bathtubs, kitchen counters, wash basins, etc., so transparency, luster and smoothness, etc. The appearance and water resistance due to long-term contact with hot water are important.

If the proportion of the saturated dibasic acid in all the acid components used in the unsaturated polyester (A) exceeds 60 mol%, the gloss and water resistance of the molded article will be insufficient. Also, 4
If it is less than 0 mol%, the curing rate of the resin composition will be too high, and cracks will occur in the molded product, making it impossible to obtain a good product.

The reason why at least 50 mol% or more of the total saturated dibasic acid component must be terephthalic acid is that if it is less than that, good surface gloss cannot be obtained in a molded product in combination with glass frit. Is.

The unsaturated polyester (A) is obtained by subjecting a polyhydric alcohol, an α, β-unsaturated dibasic acid or its anhydride and a saturated dibasic acid containing terephthalic acid or its anhydride to a polycondensation reaction (esterification reaction). The desired liquid unsaturated polyester resin is obtained by dissolving this in the polymerizable monomer (B).

If the proportion of the polymerizable monomer (B) in the unsaturated polyester resin is less than 30% by weight, the viscosity of the unsaturated polyester resin becomes high and, as a result, the viscosity of the compound becomes too high. This is because it becomes difficult to inject it into the composition, and it is difficult to remove air bubbles in the compound, so that a good molded product cannot be obtained. On the other hand 50% by weight
If it exceeds the above range, the fluidity of the compound will be improved, but the curing shrinkage of the unsaturated polyester resin will be large, and as a result cracks will occur in the molded product and a good product cannot be obtained.

The ratio of the glass frit (D) to be mixed with 100 parts by weight of the unsaturated polyester resin (C) is 100.
The reason why the range is limited to 300 parts by weight is that if the amount is less than 100 parts by weight, curing shrinkage increases due to an increase in the ratio of the resin content in the compound, and cracks occur in the molded product, making it impossible to obtain a good product. On the other hand, if it exceeds 300 parts by weight, the viscosity of the compound becomes too high, which makes it extremely difficult to inject it into the mold, and it is difficult to defoam the compound, so that a good product cannot be obtained. Considering the fluidity of the compound during cast molding and the crack resistance during curing, the range of 150 to 250 parts by weight is particularly desirable.

The refractive index of the glass frit used as the filler is 1.53 to 1 in order to obtain a transparent feeling of the molded product.
It is necessary to be in the range of 56, and at the same time, the average particle size thereof needs to be 30 μm or less in order to obtain gloss and smoothness of the molded product. Further, D ₅₀ = 10 μm is particularly desirable. Further, the glass frit needs to be treated with a silane coupling agent in order to prevent interfacial peeling with the unsaturated polyester resin during high temperature molding. The content of sodium oxide in the glass frit must be 5% by weight or less in order to improve the hydrolysis resistance of the unsaturated polyester resin cured product and improve the water resistance of the artificial marble molded product. .

[0021]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. All "parts" shown in the examples mean "parts by weight" unless otherwise specified.

Production Example of Unsaturated Polyester Resin Production Example 1 A 5 liter reactor equipped with a stirrer, a thermometer, a nitrogen gas blowing tube and a series of partial condensers and full condensers (pressure resistance 1
0 kg / cm ² ) to 997 g (6 mol) of terephthalic acid,
Isophthalic acid 665 g (4 mol), propylene glycol 959 g (12.6 mol), neopentyl glycol 417 g (4 mol), dipropylene glycol 537 g
(4 mol) and dibutyltin oxide (reaction catalyst)
After charging 1.8 g, the inside of the reactor was replaced with nitrogen gas and further heated to 230 ° C. under a pressure of 3.5 kg / cm ² ,
After reacting for about 5 hours, when the acid value becomes 10 mgKOH / g or less, the pressure is returned to normal pressure, the internal temperature is once cooled to 150 ° C., and 1161 g (10 mol) of fumaric acid is charged. The temperature was raised to 210 ° C. again while flowing an appropriate amount of nitrogen gas under normal pressure, and the reaction was continued for about 13 hours. When the acid value became 16 mgKOH / g or less, the unsaturated polyester was cooled to 180 ° C. 27 g and 6% copper naphthenate 0.
6688 g of unsaturated polyester resin [nonvolatile content of about 6
0% by weight) (a) was obtained. Viscosity of resin (a) (25 ° C)
Was 9.5 dPa · s.

Production Example 2 In the same reactor as in Production Example 1, 1329 g (8 mol) of terephthalic acid, 807 g (10.6 mol) of propylene glycol, 417 g (4 mol) of neopentyl glycol, 805 g (6 mol) of dipropylene glycol and After charging 1.7 g of dibutyltin oxide (reaction catalyst), the inside of the reactor was replaced with nitrogen gas, the temperature was further raised to 230 ° C. under a pressure of 3.5 kg / cm ² , and the reaction was performed for about 4.5 hours to obtain an acid value. Returns to normal pressure when becomes less than 10 mgKOH / g,
Once the internal temperature was cooled to 150 ° C, maleic anhydride 117
Charge 7 g (12 mol). The temperature was raised to 210 ° C again while flowing an appropriate amount of nitrogen gas under normal pressure, and the reaction was continued for about 12 hours. When the acid value became 16 mgKOH / g or less, the unsaturated polyester was cooled to 180 ° C. 5925 g of unsaturated polyester resin (nonvolatile content: about 68% by weight) dissolved in 1896 g of styrene monomer containing 0.24 g of hydroquinone and 0.12 g of 6% copper naphthenate
(B) was obtained. Resin (b) viscosity (25 ° C) is 32 dP
It was a.s.

Production Example 3 In the same reactor as in Production Example 1, 1661 g (10
Mol), 296 g (2 mol) of phthalic anhydride, 1263 g (16.6 mol) of propylene glycol, 417 g (4 mol) of neopentyl glycol and 1.8 g of dibutyltin oxide (reaction catalyst), and charged with nitrogen gas in the reactor. After replacement with 23 under a pressure of 3.5 kg / cm ^2.
Raise the temperature to 0 ° C and react for about 6 hours to obtain an acid value of 10mgKO
When the pressure falls below H / g, the pressure is returned to normal pressure and the internal temperature is once set to 15
Cool to 0 ° C. and charge 929 g (8 mol) of fumaric acid. 210 ℃ again while flowing an appropriate amount of nitrogen gas under normal pressure
To room temperature and react for about 14 hours to give an acid value of 16 mg KO
When the H / g or less is reached, the unsaturated polyester is
Styrene monomer 258 cooled to 80 ° C. and containing 0.26 g of hydroquinone and 0.13 g of 6% copper naphthenate
It was dissolved in 7 g to obtain 6468 g of unsaturated polyester resin (nonvolatile content: about 60% by weight) (c). The viscosity (25 ° C.) of the resin (c) was 8.5 dPa · s.

Production Example 4 In the same reactor as in Production Example 1, 997 g (6 mol) of terephthalic acid, 807 g (10.6 mol) of propylene glycol, 417 g (4 mol) of neopentyl glycol, 805 g (6 mol) of dipropylene glycol and After charging 1.5 g of dibutyltin oxide (reaction catalyst), the inside of the reactor was replaced with nitrogen gas, the temperature was further raised to 230 ° C. under a pressure of 3.5 kg / cm ² , and the reaction was performed for about 4.5 hours to obtain an acid value. Was reduced to 101 mgKOH / g or less, the pressure was returned to normal pressure and the internal temperature was once cooled to 150 ° C.
Charge 373 g (14 mol). The temperature was raised again to 210 ° C. while flowing an appropriate amount of nitrogen gas under normal pressure, and the reaction was continued for about 11 hours. When the acid value became 16 mgKOH / g or less, the unsaturated polyester was cooled to 180 ° C. and hydroquinone 0 577 when dissolved in 1849 g of a styrene monomer containing 0.23 g and 0.12 g of 6% copper naphthenate
8 g of unsaturated polyester resin (nonvolatile content about 68% by weight) (d) was obtained. The viscosity of resin (d) (25 ° C) is 3O
It was dPa · s.

Production Example 5 In the same reactor as in Production Example 1, 1827 g (11
Mol), 296 g (2 mol) of phthalic anhydride, 1263 g (16.6 mol) of propylene glycol, 417 g (4 mol) of neopentyl glycol and 1.9 g of dibutyltin oxide (reaction catalyst), and charged with nitrogen gas in the reactor. After replacement with 23 under a pressure of 3.5 kg / cm ^2.
Raise the temperature to 0 ° C and react for about 6 hours to obtain an acid value of 10mgKO
When the pressure falls below H / g, the pressure is returned to normal pressure and the internal temperature is once set to 15
Cool to 0 ° C. and charge 812 g (7 mol) of fumaric acid. 210 ℃ again while flowing an appropriate amount of nitrogen gas under normal pressure
The reaction mixture is heated up to about 15 hours and the acid value is 16mgKO.
When the H / g or less is reached, the unsaturated polyester is
Styrene monomer 262 cooled to 80 ° C. and containing hydroquinone 0.26 g and 6% copper naphthenate 0.13 g
It was dissolved in 1 g to obtain 6552 g of unsaturated polyester resin (nonvolatile content: about 60% by weight) (e). The viscosity (25 ° C.) of the resin (e) was 9 dPa · s.

Production Example 6 In the same reactor as in Production Example 1, 665 g (4 mol) of terephthalic acid, 997 g (6 mol) of isophthalic acid, 959 g (12.6 mol) of propylene glycol, 417 g (4 mol) of neopentyl glycol, and diamine. Propylene glycol (537 g (4 mol)) and dibutyltin oxide (reaction catalyst) (1.8 g) were charged, the inside of the reactor was replaced with nitrogen gas, and the temperature was further raised to 230 ° C. under a pressure of 3.5 kg / cm ² . After reacting for about 5 hours, when the acid value becomes 10 mgKOH / g or less, the pressure is returned to normal pressure, the internal temperature is once cooled to 150 ° C., and 1161 g (10 mol) of fumaric acid is charged. While flowing an appropriate amount of nitrogen gas under normal pressure, raise the temperature again to 210 ° C. This unsaturated polyester is cooled to 180 ° C. when the acid value becomes 16 mgKOH / g or less after reacting for about 13 hours, and dissolved in 2675 g of styrene monomer containing 0.27 g of hydroquinone and 0.13 g of 6% copper naphthenate. Then, 6688 g of an unsaturated polyester resin (nonvolatile content: about 60% by weight) (f) was obtained. Resin (f) viscosity (2
5 ° C.) was 9 dPa · s.

Liquid unsaturated polyester resin (a)
1% by weight of benzoyl peroxide as a curing agent was added to each of the 6 types of (f) and cured at 100 ° C. for 2 hours, and the refractive index of each cured product was measured. Table 1 summarizes the results.
Shown in

[0029]

[Table 1] Properties of Filler Table 2 shows the properties of the filler used in describing Examples and Comparative Examples.

[Table 2] Examples 1 to 6 and Comparative Examples 1 to 6 From the liquid unsaturated polyester resins (a) to (f) shown in Production Examples 1 to 6, the filler shown in Table 2, the curing agent and, in some cases, the accelerator. Table 3 shows the composition of the constituent compounds.

[0030]

[Table 3] Each of these components is stirred and mixed under reduced pressure, and then the actual bath (1
200 kg) male / female mating mold 1.5 kg / cm
Pressed in at ² . The mold temperature is used as the curing condition, and the evaluation of the molded product is the time until demolding (holding time in the mold), the presence or absence of cracks, surface gloss, surface smoothness, transparency (depth feeling) and water resistance (1500 hours / 90 ° C). ) Was investigated. The results are summarized in Table 3.

As shown in Examples 1 to 6, in all cases, the product (bath) without cracks could be molded with the demolding time (loose when held in the mold) within 30 minutes. In addition, the surface gloss, surface smoothness, and transparency (depth feeling) were all good.After hot water of 90 ° C was put in these baths and kept for 1500 hours, presence of blisters and ΔE (color difference) were examined. As a result, no blister occurred and the color difference was 3 or less.

In Comparative Example 1, since the reactivity of the resin was high (the ratio of unsaturated acid in the total acid components was high), cracks were generated in the molded product and a good product could not be obtained. In Comparative Example 2, since the reactivity of the resin was low (the ratio of unsaturated acid in the total acid component was low), no crack was generated in the molded product, but the surface gloss and surface smoothness were poor. In Comparative Example 3, the molded product did not crack, but the surface gloss was poor. In Comparative Example 4, the average particle size of the glass frit (c) exceeds 30 μm and the content of sodium oxide exceeds 5% by weight, so that the surface smoothness and water resistance are poor. In Comparative Example 5, since aluminum hydroxide was used as the filler, cracks did not occur in the molded product, but the demolding time (holding time in the mold) was as long as 80 minutes (low productivity), and The transparency (depth) was poor. In Comparative Example 6, aluminum hydroxide was used as in Comparative Example 5, and the demolding time was intentionally set to 4
Although it was shortened to 0 minutes, cracks were generated in the molded product, and the surface gloss and the feeling of transparency (feeling of depth) were poor.

[0033]

According to the present invention, the following effects can be obtained.

(1) By molding by the heat casting method, a semi-transparent artificial marble molded article having good water resistance, gloss and smoothness and resembling marble can be manufactured at low cost and with high productivity.

(2) It is possible to produce a marble-like product having excellent water resistance, which is particularly useful for bath applications.

[Procedure amendment]

[Submission date] March 28, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0003

[Correction method] Change

[Correction contents]

[0003] As the molding method, FRP after the first gel coat (glass fiber reinforced plastic) type cured once curing oven and spray paint, the type of compound comprising a thermosetting resin and the filler There are two methods, a casting method in which the compound is injected and cured again in the curing furnace, and a pressing method in which the compound is thickened in advance to form BMC (bulk molding compound), which is heated and pressure-molded in the mold. Broadly divided.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction contents]

[0004] The former method is, for example, the required time for the single artificial marble bathtub from the molding start until demolding from the mold (molding time) whereas takes 150-300 minutes, the latter 5
It is a highly productive molding method that can be molded in 15 minutes. However, the latter has the disadvantage that the equipment cost is more than 10 times that of the former.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0006

[Correction method] Change

[Correction contents]

[0006]

In order to produce a good artificial marble molded article most economically, a molding method is basically established with a low equipment cost and a molding method in a time comparable to that of the pressing method. To do. For that purpose, it is first necessary to establish a casting method in which a gel coat is not applied to the mold. In addition, it is a necessary condition to raise the mold temperature to accelerate the curing speed of the compound as compared with the conventional casting method. However, if the compound begins to harden in the process of injecting the compound into the mold, the molded product will become defective, so if the compound is injected into the mold at around room temperature and the temperature of the mold is raised to a predetermined temperature, artificial marble molding will occur in the conventional technology. Good products cannot be obtained because cracks occur in the product. In this case, the compound using aluminum hydroxide as the filler suppresses the heat generation (polymerization heat) during resin curing and increases the molding time as compared with the compound in which the same weight of glass frit is mixed. The effect of preventing cracking of the molded product can be expected. This is because aluminum hydroxide has water of hydration and water of crystallization and absorbs heat generated during the process of curing the resin. On the other hand, the glass frit does not absorb the heat generated by the curing of the resin, so that the curing of the compound progresses rapidly, and raising the mold temperature in a short time involves cracking of the molded product, which is extremely difficult in the conventional technology. It was difficult. It is possible to reduce the amount of polymerization initiator (curing agent) added to the resin component in the compound, or to add a polymerization inhibitor to delay the curing speed of the resin and suppress its curing heat generation. However, there is a drawback that the molding time becomes long.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

(1) The refractive index is in the range of 1.53 to 1.56. (2) The average particle size is 30 μm or less. (3) The particle surface is treated with a silane coupling agent. 4) The content of sodium oxide is 5% by weight or less, and the polyhydric alcohol component used in producing the unsaturated polyester (A) in the unsaturated polyester resin of the present invention is ethylene glycol, propylene glycol or diethylene glycol. , Dipropylene glycol,
1,3-butanediol, 1,6-hexanediol,
Neopentyl glycol, hydrogenated bisphenol A, propylene oxide adduct of bisphenol A, ethylene oxide adduct of bisphenol A, dibromoneopentyl glycol, 1,4-cyclohexanedimethanol, 1,4-butanediol, glycerin, trimethylolpropane , Trimethylolethane, ethylene oxide, propylene oxide and the like. Examples of the α, β-unsaturated dibasic acid or anhydride thereof include maleic acid, maleic anhydride, and fumaric acid. As the saturated dibasic acid or its anhydride, in addition to terephthalic acid, orthophthalic acid and its anhydride, isophthalic acid, tetrahydrophthalic acid and its anhydride, endomethylenetetrahydrophthalic acid and its anhydride,
Tetrabromophthalic acid and its anhydride, dibromo tetrahydrophthalic acid and its anhydride, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, adipate pins acid, and sebacic acid. All of these raw materials are used alone or in combination.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0023

[Correction method] Change

[Correction contents]

Production Example 2 In the same reactor as in Production Example 1, 1329 g (8 mol) of terephthalic acid, 807 g (10.6 mol) of propylene glycol, 417 g (4 mol) of neopentyl glycol, 805 g (6 mol) of dipropylene glycol and After charging 1.7 g of dibutyltin oxide (reaction catalyst), the inside of the reactor was replaced with nitrogen gas, the temperature was further raised to 230 ° C. under a pressure of 3.5 kg / cm ² , and the reaction was carried out for about 4.5 hours to obtain an acid value of When the pressure falls below 10 mgKOH / g, return to normal pressure,
Once the internal temperature was cooled to 150 ° C, maleic anhydride 117
Charge 7 g (12 mol). The temperature was raised to 210 ° C again while flowing an appropriate amount of nitrogen gas under normal pressure, and the reaction was continued for about 12 hours. When the acid value became 16 mgKOH / g or less, the unsaturated polyester was cooled to 180 ° C. 5925 g of unsaturated polyester resin (nonvolatile content: about 68% by weight) dissolved in 1896 g of styrene monomer containing 0.24 g of hydroquinone and 0.12 g of 6% copper naphthenate
(B) was obtained. Resin (b) viscosity (25 ° C) is 32 dP
It was a.s.

[Procedure correction 6]

[Document name to be amended] Statement

[Name of item to be corrected] 0024

[Correction method] Change

[Correction contents]

Production Example 3 In the same reactor as in Production Example 1, 1661 g (10
Mol), 296 g (2 mol) of phthalic anhydride, 1263 g (16.6 mol) of propylene glycol, 417 g (4 mol) of neopentyl glycol and 1.8 g of dibutyltin oxide (reaction catalyst), and charged with nitrogen gas in the reactor. After replacement with 23 under a pressure of 3.5 kg / cm ^2.
Raise the temperature to 0 ° C and react for about 6 hours to obtain an acid value of 10mgKO
When the pressure falls below H / g, the pressure is returned to normal pressure and the internal temperature is once set to 15
Cool to 0 ° C. and charge 929 g (8 mol) of fumaric acid. 210 ℃ again while flowing an appropriate amount of nitrogen gas under normal pressure
Until the temperature was raised, allowed to react for about 14 hours acid value is 16mgKO
When the H / g or less is reached, the unsaturated polyester is
Styrene monomer 258 cooled to 80 ° C. and containing 0.26 g of hydroquinone and 0.13 g of 6% copper naphthenate
It was dissolved in 7 g to obtain 6468 g of unsaturated polyester resin (nonvolatile content: about 60% by weight) (c). The viscosity (25 ° C.) of the resin (c) was 8.5 dPa · s.

[Procedure amendment 7]

[Document name to be amended] Statement

[Name of item to be corrected] 0025

[Correction method] Change

[Correction contents]

Production Example 4 In the same reactor as in Production Example 1, 997 g (6 mol) of terephthalic acid, 807 g (10.6 mol) of propylene glycol, 417 g (4 mol) of neopentyl glycol, 805 g (6 mol) of dipropylene glycol and After charging 1.5 g of dibutyltin oxide (reaction catalyst), the inside of the reactor was replaced with nitrogen gas, the temperature was further raised to 230 ° C. under a pressure of 3.5 kg / cm ² , and the reaction was performed for about 4.5 hours to obtain an acid value of When the pressure became 101 mgKOH / g or less, the pressure was returned to normal pressure and the internal temperature was once cooled to 150 ° C.
Charge 373 g (14 mol). The temperature was raised again to 210 ° C. while flowing an appropriate amount of nitrogen gas under normal pressure, and the reaction was continued for about 11 hours. When the acid value became 16 mgKOH / g or less, the unsaturated polyester was cooled to 180 ° C. and hydroquinone 0 577 when dissolved in 1849 g of a styrene monomer containing 0.23 g and 0.12 g of 6% copper naphthenate
8 g of unsaturated polyester resin (nonvolatile content about 68% by weight) (d) was obtained. The viscosity of resin (d) (25 ° C) is 3O
It was dPa · s.

[Procedure amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0031

[Correction method] Change

[Correction contents]

As shown in Examples 1 to 6, in all cases, the product (bath) without cracks could be molded with the demolding time (loose when held in the mold) within 30 minutes. Moreover, the surface gloss, surface smoothness and transparency (depth feeling ) were all good. After hot water of 90 ° C. was placed in these baths and held for 1500 hours, the presence or absence of blisters and ΔE (color difference) were examined. As a result, no blisters occurred and the color difference was 3 or less.

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Claims (1)

[Claims] 1. An unsaturated polyester obtained by polycondensing a polyhydric alcohol with an α, β-unsaturated dibasic acid or an anhydride thereof and a saturated dibasic acid or an anhydride thereof. A resin composition for an artificial marble comprising an unsaturated polyester resin composed of (A) and a polymerizable monomer (B) and a glass frit, wherein all acid components used in the unsaturated polyester (A) Unsaturated polyester resin (C) 1 in which the proportion of saturated dibasic acid is 40 to 60 mol% and at least 50 mol% or more of the total saturated dibasic acid component is terephthalic acid.
00 parts by weight and 100 to 300 parts by weight of a glass frit (D) satisfying all of the following conditions (1) to (4) as a filler are compounded. (1) Refractive index is in the range of 1.53 to 1.56 (2) Average particle size is 30 μm or less (3) Particle surface is treated with silane coupling agent (4) Oxidation The sodium content should be 5% by weight or less.