JP2001064338A - Resin composition for production of artificial marble - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rein composition that can give an artificial marble excellent in heat resistance, impact resistance, and light resistance by dissolving a vinyl ester resin in a styrene monomer and mixing the obtained solution with an acrylic monomer. SOLUTION: This composition comprises a mixture obtained by dissolving a vinyl ester resin being a bisphenol epoxy resin/acid adduct in a styrene monomer and mixing the obtained solution with an acrylic monomer having at least two reactive functional groups and a weight-average molecular weight of 200-300. The bisphenol epoxy resin used is desirably a bisphenol A epoxy resin, and the acid used to form the adduct is usually an unsaturated monobasic acid [e.g. (meth)acrylic acid]. It is desirable that 1-20 wt.%, based on the vinyl ester resin, acrylic monomer and 30-60 wt.%, based thereon, styrene monomer are used. It is desirable that the composition contains a benzotriazole-type ultraviolet absorber.

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 Conventionally, resins and fillers, internal release agents,
2. Description of the Related Art A resin composition containing an additive such as a curing agent is cast into a mold having a desired shape, and the cast is cured to form artificial marble.

[0003]

However, as resins used as raw materials for producing artificial marble, polyester-based, acrylic-based, vinyl-ester-based resins and the like have hitherto been used. Marble had poor heat resistance. On the other hand, when trying to increase the heat resistance by controlling the cross-linking state and molecular weight of the resin, the toughness of the entire resin decreases, and artificial marble using such a resin is excellent in heat resistance, but the impact resistance decreases. It was a mess.

[0004] In particular, since ordinary polyester-based and vinyl ester-based resins have poor light resistance due to their molecular structure, the use of artificial marble using them is limited in places where they are affected by light such as sunlight. There was also a problem that there were many.

SUMMARY OF THE INVENTION The present invention has been made in view of the above points, and it is an object of the present invention to improve the toughness without impairing the heat resistance of artificial marble, improve the impact resistance, and further improve the light resistance. It is an object of the present invention to provide a resin composition for producing artificial marble that can be used.

[0006]

According to a first aspect of the present invention, there is provided a resin composition for producing artificial marble, wherein a vinyl ester resin obtained by adding an acid to a bisphenol type epoxy resin is dissolved in a styrene monomer. It is characterized by comprising a mixture obtained by blending an acrylic monomer having a weight average molecular weight of 200 to 300 having two or more reactive functional groups.

The invention of claim 2 is characterized in that, in addition to the constitution of claim 1, the acrylic monomer is contained in an amount of 1 to 20% by weight based on the blending amount of the vinyl ester resin. .

According to a third aspect of the present invention, in addition to the constitution of the first or second aspect, a benzotriazole-based ultraviolet absorber is contained.

[0009]

Embodiments of the present invention will be described below.

The vinyl ester resin used in the present invention is an addition reaction product of a bisphenol type epoxy resin and an acid, and has a reactive unsaturated group only at both ends.

As the bisphenol type epoxy resin,
Various types such as bisphenol A type, bisphenol AD type, bisphenol S type and bisphenol F type can be used, but the use of bisphenol A type epoxy resin can particularly improve the impact resistance of artificial marble. And preferred.

As the acid to be added to the bisphenol type epoxy resin, an unsaturated monobasic acid is usually used, and acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate / malate, hydroxyethyl Ethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, dicyclopentadiene malate and the like can be used.

Specifically, as the bisphenol A type epoxy resin, those represented by the following general formula (1) can be used. Here, n in the general formula (1) represents a positive integer.

[0014]

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[0015] Styrene monomers and acrylic monomers are used as crosslinking agents for vinyl ester resins. Here, as the acrylic monomer, one having two or more reactive functional groups in one molecule is used.If the number of reactive functional groups is less than two, the toughness of artificial marble, that is, the impact resistance, is reduced. It is difficult to improve. Here, the upper limit of the number of reactive functional groups in one molecule is actually five. As the acrylic monomer, a mixture of various acrylic monomers having different molecular weights can be used.
When the average molecular weight is less than this range or exceeds this range, the weight average molecular weight does not contribute to the improvement of the impact resistance of the artificial marble in any case.

Examples of such an acrylic monomer include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, dipropylene glycol dimethacrylate,
4-butanediol dimethacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4
-Butanediol diacrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, trimethylolpropane dimethacrylate,
Examples include dimethacrylates or acrylates of alkane polyols having 2 to 12 carbon atoms, such as glycerin dimethacrylate, pentaerythritol dimethacrylate, and trimethylolpropane diacrylate.

Still further, for example, a compound having 3 carbon atoms such as trimethylolpropane trimethacrylate, glycerinpropane trimethacrylate, dipentaerythritol hexamethacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.
Polymethacrylates or polyacrylates of alkane polyols having -12.

The resin composition for producing artificial marble of the present invention (hereinafter sometimes abbreviated as "resin composition") contains a mixture of the above-mentioned vinyl ester resin, a styrene monomer and an acrylic monomer. Therefore, the toughness, that is, the impact resistance can be improved without impairing the heat resistance of the artificial marble. When the amount of the acrylic monomer in this mixture is 1 to 20% by weight based on the amount of the vinyl ester resin, the impact resistance can be further improved without impairing the heat resistance. If the compounding amount of the acrylic monomer is less than this range, the effect of improving the impact resistance may not be sufficiently obtained, and if the compounding amount of the acrylic monomer exceeds this range, the heat resistance may decrease. The amount of the styrene monomer is preferably 30 to 60% by weight based on the amount of the vinyl ester resin.

Such a mixture can be prepared by dissolving a vinyl ester resin in a liquid styrene monomer and further blending an acrylic monomer.

In order to stabilize the light resistance and stabilize the quality of artificial marble, the resin composition of the present invention preferably contains a benzotriazole ultraviolet absorber as a light resistance stabilizer. As an ultraviolet absorber,
Others such as triazine, benzoate, salylate, cyanoacrylate, anilide oxalate and benzophenone can also be used. Can be significantly improved, and coloring due to ultraviolet absorption can be effectively prevented. As this benzotriazole-based ultraviolet absorber, for example, 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2-
(2'-hydroxy-3 ', 5'-di-t-amylphenyl) benzotriazole, 2 (2'-hydroxy-3
-5-bis (α, α'dimethylbenzyl) phenyl) benzotriazole, 2-2'-methylenebis (4-
(1,1,3,3-tetramethylbutyl) -6-((2
H-benzotriazol-2-yl) phenol)),
2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-
(2'-hydroxy-3'-t-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (5-
Methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3-5-bis (α, α'dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3,5-t-butyl-2) -Hydroxyphenyl) benzotriazole, 2- (3-t-butyl-5-
Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole,
2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-
5'-t-octylphenyl) benzotriazole, condensate of methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol, hydroxy And phenylbenzotriazole derivatives. When a benzotriazole-based ultraviolet absorber is blended in the resin composition, the blending ratio is 0.05.
It is preferably set to 1.0 phr.

The resin composition may further contain a filler, a curing agent, a viscosity reducing agent, a release agent, a glass fiber, a colorant, and the like.

It is preferable to use a filler having a large heat capacity from the viewpoint of improving the heat resistance of artificial marble. For example, aluminum filler can be added. The mixing ratio is 180 parts per 100 parts by weight of the mixture of the vinyl ester resin and the crosslinking agent.
It is preferable to set it in the range of 300 parts by weight. In addition, since aluminum hydroxide has a refractive index close to that of a vinyl ester-based resin, the transparency of artificial marble can be improved and the appearance can also be improved. Here, in order to produce artificial marble having a desired transparency, it is preferable to blend a plurality of types of aluminum hydroxide having different particle sizes.

As the curing agent, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate (1,1,3,3-tetramethylbuthil peroxy-2-ethyl hexanoa)
te), t-hexyl peroxy 2-ethyl hexanoate, and the like. The mixing ratio of this curing agent is the same as that of the above mixture 1
The amount is preferably 1 to 5 parts by weight with respect to 00 parts by weight.

As a viscosity reducing agent, for example, a product number "W996" manufactured by BKY, as a release agent, for example, a product name "Separ" manufactured by Chukyo Yushi, and as a glass fiber, a product number "RES03X-BM" manufactured by Nippon Sheet Glass, for example. ] Can be used.

In preparing the resin composition, a filler, a curing agent, and various additives are blended in a predetermined ratio with the above mixture, and the mixture is mixed and stirred by a stirrer or the like.

In producing artificial marble from the resin composition, the resin composition is first defoamed by stirring under reduced pressure of about 3 to 50 Torr for 5 to 30 minutes. The degassed resin composition is opened from a reduced pressure state and injected into a predetermined mold.
By heating at a temperature of 30 ° C. for 30 to 120 minutes, a vinyl ester resin in the resin composition, a styrene monomer,
And the copolymerization reaction of the acrylic monomer is advanced to perform curing molding. The artificial marble produced in this way is
It has good heat resistance and excellent impact resistance. When a benzotriazole-based ultraviolet absorber is added to the resin composition, the resin composition has excellent light resistance, is prevented from being colored due to ultraviolet absorption, and has excellent transparency in appearance.

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

[0028]

The present invention will be described below in detail with reference to examples. (Examples 1 to 4 and Comparative Examples 1 to 4) A mixture obtained by mixing an acrylic monomer with a styrene monomer solution of a vinyl ester resin was mixed with a filler (a spherical aluminum hydroxide having an average particle diameter of 8 μm and γ- (Methacryloyloxypropyl) treated with a silane coupling agent with trimethoxysilane; manufactured by Sumitomo Chemical Co., Ltd .;
-308B "), a benzotriazole-based ultraviolet absorber (2-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole; manufactured by Ciba-Geigy; product number" TINUVIN 326 "), a curing agent (1 , 1,3,3-tetramethylbutylperoxy-2
-Ethylhexanoate; manufactured by NOF CORPORATION; trade name "Percure WO") and mixed and stirred using a stirrer to obtain a resin composition. Table 1 shows the amount of each component in the resin composition in each of Examples and Comparative Examples in parts by weight.

As the styrene monomer solution of the bisphenol A type vinyl ester resin, a solution containing 45% by weight of a styrene monomer was used. In Examples 1 and 2 and Comparative Examples 1 to 4, Takeda Pharmaceutical Company Limited The product name "Prominate P-311" manufactured by Takeda Pharmaceutical Co., Ltd. was used in Examples 3 and 4 by using the product name "Prominate P-311" manufactured by the company.

As the acrylic monomer, Example 1 was used.
In Comparative Examples 3 and 4, the following components were used, and in Comparative Examples 3 and 4, no acrylic monomer was blended. <Example 1> shown below general formula (2) average value of about 3 polyethylene glycol diacrylate of n in (weight average molecular weight _{251) CH 2 = CHCO- (OCH} 2 CH 2) n -OCOCH = CH 2 ( 2) <Example 2> A polypropylene glycol diacrylate having an average value of n in the following general formula (3) of about 2 (weight average molecular weight: 24)
_{5) CH 2 = CHCO- (OC} 3 H 6) n -OCOCH = CH 2 (3) < Example 3> Trimethylolpropane triacrylate (weight average molecular weight 296) <Example 4> Pentaerythritol triacrylate ( (Weight average molecular weight 298) <Comparative Example 1>-Polyethylene glycol diacrylate having an average value of n in the general formula (2) of about 1.3 (weight average molecular weight 18)
6) <Comparative Example 2>-Polyethylene glycol diacrylate having an average value of n in the general formula (2) of about 8 (weight average molecular weight 522) Next, the resin composition obtained as described above was added to 20 To
The mixture was stirred under a reduced pressure of rr for 30 minutes, degassed in vacuo, and then the reduced pressure was released. Next, this resin composition was applied to a thickness of 1
The mixture was poured into a mold having a cavity capable of molding a flat plate of 0 mm, and cured by heating the mold at a temperature of 90 ° C. for 30 minutes. After the curing was completed, the mold was opened and the cured molded product was taken out to obtain a flat artificial marble. (Evaluation Test) The Charpy impact strength of the artificial marble of each of the examples and comparative examples obtained as described above was measured to evaluate the impact resistance.

A pot containing oil at 270.degree. C. was placed on artificial marble. Heat resistance was evaluated as "pass" if no discoloration or cracking occurred.

UV irradiation apparatus (manufactured by Suga Test Instruments Co., Ltd .; Sunshine Weather Meter; WEL-300)
Was used to evaluate the light resistance by measuring the color change (discoloration / fading; ΔE) after irradiating with ultraviolet rays for 200 hours.

Table 1 shows the above results.

[0034]

[Table 1]

As can be seen from Table 1, in each of the examples, artificial marble excellent in both impact resistance and heat resistance and excellent in light resistance was obtained. On the other hand, Comparative Examples 1 to 4 had low impact resistance, and Comparative Example 4 had low light resistance.

[0036]

As described above, the resin composition for producing artificial marble according to claim 1 of the present invention is obtained by dissolving a vinyl ester resin obtained by adding an acid to a bisphenol type epoxy resin to a styrene monomer, Furthermore, it is a mixture obtained by blending an acrylic monomer having a weight average molecular weight of 200 to 300 having two or more reactive functional groups, and is excellent by curing and molding this resin composition for producing artificial marble. It can produce artificial marble having heat resistance and impact resistance.

In addition, the invention of claim 2 is characterized in that, in addition to the constitution of claim 1, the acrylic monomer is contained in an amount of 1 to 20% by weight based on the blending amount of the vinyl ester resin, thereby impairing the heat resistance of the artificial marble. It is possible to further improve the impact resistance.

The invention of claim 3 further comprises, in addition to the constitution of claim 1 or 2, a benzotriazole-based ultraviolet absorber, which is excellent by curing and molding the resin composition for producing artificial marble. It is possible to manufacture artificial marble having light resistance.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Shinji Yamaguchi 18-family, Yasuse, Wakamatsu-ku, Kitakyushu-shi, Fukuoka Prefecture F-term (reference) 4F071 AA22 AA42 AA78 AB18 AC08 AE02 AE05 AE17 AG05 AG12 AG23 AG28 AH03 BA03 BB01 BC03 4J027 AE02 BA05 BA19 BA20 BA21 BA25 BA26 BA27 CA14 CA25 CB03 CC02 CD01 4J036 AA02 AF19 CA21 DB29 EA01 EA02 FA12 FB03

Claims (3)

[Claims] 1. A vinyl ester resin obtained by adding an acid to a bisphenol epoxy resin is dissolved in a styrene monomer, and an acrylic monomer having a weight average molecular weight of 200 to 300 having two or more reactive functional groups is further compounded. A resin composition for producing artificial marble, characterized by comprising a mixture obtained by the above method. 2. The resin composition for producing artificial marble according to claim 1, wherein the acrylic monomer is contained in an amount of 1 to 20% by weight based on the amount of the vinyl ester resin. 3. The resin composition for producing artificial marble according to claim 1, further comprising a benzotriazole-based ultraviolet absorber.