JPH05330883A - Ornamental molded product - Google Patents

Abstract

PURPOSE:To improve weather resistance, hot water resistance and impact resistance by mixing an inorg. filler and radical hardening agent to a specified base resin, polymerizing the mixture and hardening. CONSTITUTION:Acrylate or methacrylate monomer (A) is selected and mixed by 100-50wt.% of component (A) with 0-50wt.% of styrene monomer (B) to obtain mixture monomer, (C). Then, acryl or methacryl polymer or styrene polymer (D) is dissolved by 25-40wt.% in 60-75wt.% of component (A) or (C) to obtain a polymerizable resin liquid (E). Then, 50-95wt.% of component (E), 2.5-25wt.% of trifunctional acryl or methacryl monomers (F), and 2.5-25wt.% bifunctional acryl or methacryl-modified epoxy (G) expressed by formula are compounded in a manner that the amt. of the component (F) does not exceed the amt. of the component (G). The obtd. base resin is mixed with an inorg. filler and radical hardening agent, and polymerized and hardened to produce the ornamental molded products. In formula, R1 and R2 are H or CH3, and R3 and R4 are CH3 or CF3.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION This invention is applicable to artificial stones, terrazzoes,
The present invention relates to a decorative molded article used as a surface layer of a molded article such as a fiber reinforced resin molded article having an appearance similar to natural stone such as granite or marble, and a specific trifunctional acrylic or methacrylic monomer and 2 By using a base resin mixed with a functional acrylic or methacrylic modified epoxy, a decorative molded article having high weather resistance, high hot water resistance and high impact resistance is obtained.

[0002]

2. Description of the Related Art Conventionally, as the above-mentioned decorated molded product,
Known are those consisting of acrylic or methacrylic resin such as methacryl methacrylate and inorganic filler, those consisting of polyester resin such as unsaturated polyester resin and inorganic filler, and those consisting of methacrylic resin-epoxy resin and inorganic filler. There is.

[0003]

However, the one comprising the acrylic or methacrylic resin and the inorganic filler has good weather resistance but poor hot water resistance, and conversely,
A resin comprising an unsaturated polyester resin and an inorganic filler has good hot water resistance but poor weather resistance. In addition, in the case of using the methacrylic resin-epoxy resin and the inorganic filler, yellowing due to epoxy becomes a problem. The present invention has been made in view of the above circumstances, and provides a decorative molded article which is made of an acrylic or methacrylic resin having excellent weather resistance and has improved hot water resistance.

[0004]

The decorative molded article of the present invention comprises:
For a polymerizable resin liquid obtained by dissolving an acrylic or methacrylic polymer or a styrene polymer in an acrylic or methacrylic acid ester monomer or a mixed monomer of an acrylic or methacrylic acid ester monomer and a styrene monomer, a trifunctional acrylic or Polymerization by mixing an inorganic filler and a radical curing agent into a base resin prepared by mixing a methacrylic monomer and a bifunctional acrylic or methacryl-modified epoxy represented by the following general formula (I) or general formula (II) Curing was the means for solving the above-mentioned problems.

[0005]

[Chemical 3]

[0006]

[Chemical 4]

[0007]

The decorated molded product containing the trifunctional acrylic or methacrylic monomer has high hot water resistance but low impact resistance. Since the decorative molded article of the present invention contains the bifunctional acrylic or methacryl-modified epoxy in combination with the trifunctional acrylic or methacrylic monomer, the impact resistance is decreased while maintaining high hot water resistance. Hold down.

[0008]

The present invention will be described in detail below. The decorative molded article of the present invention is a polymerizable resin liquid obtained by dissolving an acrylic or methacrylic polymer or a styrene polymer in an acrylic or methacrylic acid ester monomer or a mixed monomer of an acrylic or methacrylic acid ester monomer and a styrene monomer. On the other hand, an inorganic filler is added to a base resin obtained by mixing a trifunctional acrylic or methacrylic monomer with a difunctional acrylic or methacrylic modified epoxy represented by the general formula (I) or the general formula (II). And a radical curing agent are mixed and polymerized and cured.

First, the polymerizable resin liquid will be described.
The polymerizable resin liquid is an acrylic or methacrylic acid ester monomer or a mixed monomer of an acrylic or methacrylic acid ester monomer and a styrenic monomer,
It is an acrylic or methacrylic polymer or a styrene polymer dissolved therein.

Methyl methacrylate (hereinafter referred to as MMA) is used as the acrylic or methacrylic acid ester monomer.
Methacrylic acid esters such as ethyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, propyl methacrylate, acrylic acid esters and the like are preferably used. In addition to styrene, styrene derivatives such as methylstyrene and vinylstyrene can be used as the styrene-based monomer.

The mixed monomer is a mixture of the acrylic or methacrylic acid ester monomer and the styrene monomer, and the mixing ratio is 100 to 5 for the acrylic or methacrylic acid ester monomer.
It is preferable that the amount of the styrene-based monomer is 0% by weight and the amount of the styrene-based monomer is 0 to 50% by weight. When the content of the styrene-based monomer is more than 50% by weight, the weather resistance of the obtained decorative molded product deteriorates, which is not preferable.

As the acrylic or methacrylic polymer, polymethylmethacrylate (PMMA),
A copolymer of an acrylic ester monomer such as an MMA-styrene copolymer and a styrene-based monomer is preferably used, and as the styrene-based polymer, an acrylonitrile-styrene copolymer (AS) or the like is preferably used. The ratio of copolymerization in the MMA-styrene copolymer and the acrylonitrile-styrene copolymer (AS) is preferably about 20 to 50% by weight of the styrene-based monomer. When the content of the styrene-based monomer exceeds 50% by weight, the weather resistance of the obtained decorative molded product decreases, and when it is less than 20% by weight, the transparency of the obtained decorative molded product decreases, which is not preferable in appearance.

In the above polymerizable resin liquid, about 60 to 75% by weight of the acrylic or methacrylic acid ester monomer or the mixed monomer of the acrylic or methacrylic acid ester monomer and the styrene monomer is added to the acrylic or methacrylic polymer or the styrene polymer. Is preferably dissolved in about 25 to 40% by weight. When the amount of the acrylic or methacrylic polymer or the styrene polymer exceeds 40 parts by weight, the weather resistance of the obtained decorative molded article decreases, and when it is less than 25 parts by weight, the transparency of the obtained decorative molded article decreases. Then, it is not preferable in appearance.

The base resin is a mixture of a polymerizable resin liquid having the above-described composition with a trifunctional acrylic or methacrylic monomer and a bifunctional acrylic or methacrylic modified epoxy.

As the above-mentioned trifunctional acrylic or methacrylic monomer, trimethylolpropane trimethacrylate (TMPT), trimethylolpropane triacrylate (A-TMPT) and the like are preferably used.

As the above-mentioned bifunctional acryl or methacryl modified epoxy, those represented by the above general formula (I) or general formula (II) are used. Specifically, EMA1020, BPE1300 (these trade names; manufactured by Shin Nakamura Chemical Co., Ltd.) and the like are used.

The compounding amount of the trifunctional acrylic or methacrylic monomer and the bifunctional acrylic or methacrylic modified epoxy is 50 to 95% by weight in the polymerizable resin liquid.
2.5 to 25% by weight of trifunctional acrylic or methacrylic monomer and 2.5 to 25% by weight of bifunctional acrylic or methacrylic modified epoxy relative to the degree
It is preferable to set it to a degree. However, the blending amount of the trifunctional acrylic or methacrylic monomer is preferably equal to or less than the blending amount of the bifunctional acrylic or methacrylic modified epoxy.

Next, the inorganic filler and the radical curing agent added to the base resin will be described.

The above-mentioned inorganic filler has a particle diameter of 10 μm.
Aluminum hydroxide, magnesium hydroxide, calcium carbonate, glass powder, etc. which have been subjected to a silane coupling treatment of about 1 to 100 μm are preferably used. This inorganic filler is 100 to 2 with respect to 100 parts by weight of the base resin.
It is preferable to add about 00 parts by weight. If the amount of the inorganic filler is less than 100 parts by weight, the shrinkage becomes large at the time of molding and curing, and the obtained molded product is apt to be distorted or cracked. It is not preferable because it cannot be molded because of its high viscosity.

The radical curing agent is used to polymerize and cure the polymerizable resin liquid, and organic peroxides such as benzoyl peroxide and lauroyl peroxide are preferably used. The amount of the radical curing agent added is preferably about 0.3 to 5 parts by weight with respect to 100 parts by weight of the base resin.

Further, in the decorated molded article of the present invention, a curing accelerator can be further added. An amine compound is used as the curing accelerator. The curing accelerator is
About 0 to 1 part by weight can be added to 100 parts by weight of the base resin.

Next, an example of the method for producing the decorative molded product of the present invention will be described. First, a trifunctional acryl or methacrylic monomer and a bifunctional acryl or methacryl modified epoxy are dissolved in a polymerizable resin liquid to prepare a base resin liquid. To this base resin liquid, inorganic filler,
A radical curing agent is added and stirred until they are uniform to obtain a polymerizable resin liquid mixture.

After degassing the polymerizable resin liquid mixture under vacuum, the mixture is poured into, for example, a square mold to obtain 60 to 70.
Primary heating is performed by heating at ℃ for 1-2 hours. After the primary curing, it is demolded and further heated at 120 to 150 ° C. for about 4 hours to be secondary cured to obtain a decorative molded product.

Further, the surface of this decorative molded product can be subjected to polishing to produce a pseudolith such as so-called marborone.

Further, the polymerizable resin liquid mixture is applied to the inner wall of the mold and gelled, and then a fiber reinforced resin molded product is formed by a usual hand layup method or a spray up method, and a gel coat layer is added. It is possible to obtain a fiber-reinforced resin molded product that is a decorative molded product. Further, the polymerizable resin liquid mixture can be applied to the surface of the desired object and cured to form a decorated molded product, or it can be poured into a mold and cured and molded to form a molded product.

[0026]

Example A polymerizable resin liquid mixture was prepared according to the following six formulation examples. These were respectively poured into a mold, subjected to primary curing and molding, then taken out from the mold and subjected to secondary curing to obtain a decorative molded product. (Example 1) MMA 63.75 PMMA 21.25 TMPT 7.5 EMA1020 7.5 (methacryl modified epoxy manufactured by Shin-Nakamura Chemical Co., Ltd.) Coupling treated aluminum hydroxide 150 Kayaester 1 (manufactured by Kayaku Akzo) (unit The primary curing was performed at 70 ° C. for 1 hour, and the secondary curing was performed at 120 ° C. for 4 hours.

(Example 2) MMA 37.5 PMMA 12.5 TMPT 25 EMA1020 25 (methacryl modified epoxy manufactured by Shin-Nakamura Chemical Co., Ltd.) Coupling treated aluminum hydroxide 150 Kayaester 1 (manufactured by Kayaku Akzo) (unit: % By weight) Primary curing was performed at 70 ° C. for 1 hour, and secondary curing was performed at 150 ° C. for 4 hours.

(Example 3) MMA 37.5 PMMA 12.5 TMPT 25 BPE1300 25 (methacryl modified epoxy manufactured by Shin Nakamura Chemical Co., Ltd.) Coupling treated aluminum hydroxide 150 Kayaester 1 (manufactured by Kayaku Akzo) (unit: % By weight) Primary curing was performed at 70 ° C. for 1 hour, and secondary curing was performed at 150 ° C. for 4 hours.

Example 4 MMA 25.5 Styrene 25.5 PMMA-Styrene Polymer 34 TMPT 7.5 EMA1020 25 (methacryl modified epoxy manufactured by Shin Nakamura Chemical Co., Ltd.) Coupling treated aluminum hydroxide 150 Kayaester 4 (chemical agent) (Manufactured by Akzo Co., Ltd.) (Unit: wt%) Primary curing was performed at 70 ° C. for 1 hour and secondary curing was performed at 120 ° C. for 4 hours.

(Comparative Example 1) MMA 75 PMMA 25 Coupling-treated aluminum hydroxide 150 Kayaester 1 (manufactured by Kayaku Akzo Co., Ltd.) (unit:% by weight) Primary curing is at 70 ° C. for 1 hour, and secondary curing is , 120 ° C. for 4 hours.

(Comparative Example 2) MMA 56.25 PMMA 18.75 TMPT 25 Coupling-treated aluminum hydroxide 150 Kayaester 1 (manufactured by Kayaku Akzo Co., Ltd.) (unit: wt%) The primary curing was 1 at 70 ° C. Second curing was performed at 120 ° C. for 4 hours.

A boiling test, a hot / cold water cycle test, and an impact test were conducted on the 6 types of decorative molded products obtained above. In the boiling test, each of the above-mentioned decorated molded products was heated to 100 ° C.
After 30 minutes of exposure to the above water vapor, the boiling resistance was examined depending on the presence or absence of whitening, and ◯ indicates no whitening, Δ indicates slight whitening, and X indicates whitening. The results are shown in Table 1.

In the hot / cold water cycle test, 5 to 10
It was repeated for 3 minutes in cold water at 0 ° C. and left for 3 minutes in warm water at 90 to 95 ° C. as one cycle, and this was repeated to examine the presence or absence of whitening. The results are also shown in Table 1.

Furthermore, in the impact test, JIS K691
The Izod impact test (without notch) was performed according to 1. The results are also shown in Table 1.

[0035]

[Table 1]

From the results shown in Table 1, a base resin prepared by mixing only TMPT as a trifunctional acrylic or methacrylic monomer in a polymerizable resin liquid composed of MMA and PMMA without blending a bifunctional acrylic or methacrylic modified epoxy. The decorative molded article of Comparative Example 2 prepared from
Compared with the decorative molded article of Comparative Example 1 prepared from the base resin containing only A and PMMA, the hot water resistance is improved, but the impact resistance is significantly reduced.

On the other hand, in addition to the trifunctional acrylic or methacrylic monomer in the polymerizable resin liquid, the addition of Examples 1 to 4 prepared from a base resin compounded with a bifunctional acrylic or methacrylic modified epoxy was also added. The decorative molded article can suppress a decrease in impact resistance while improving hot water resistance. Among them, the decorative molded article obtained in Example 3 was good in both hot water resistance and impact resistance.

[0038]

As described above, the decorative molded article of the present invention has the acrylic or methacrylic acid ester monomer or the mixed monomer of the acrylic or methacrylic acid ester monomer and the styrene type monomer, the acrylic or methacrylic type polymer or the styrene type monomer. A trifunctional acryl or methacrylic monomer and a bifunctional acryl or methacryl modified epoxy represented by the above general formula (I) or general formula (II) are mixed with a polymerizable resin liquid obtained by dissolving a polymer. The obtained base resin is mixed with an inorganic filler and a radical curing agent and polymerized and cured.

Therefore, the hot water resistance can be improved without lowering the high impact resistance of the decorative molded product made of the acrylic or methacrylic resin.

Claims (2)

[Claims] 1. A polymerizable resin liquid obtained by dissolving an acrylic or methacrylic polymer or a styrene polymer in an acrylic or methacrylic acid ester monomer or a mixed monomer of an acrylic or methacrylic acid ester monomer and a styrene monomer, Trifunctional acrylic or methacrylic monomer and the following general formula (I)
Alternatively, a decorative molded article obtained by mixing an inorganic filler and a radical curing agent into a base resin obtained by mixing a bifunctional acrylic or methacryl modified epoxy represented by the general formula (II), and polymerizing and curing the mixture. [Chemical 1] [Chemical 2] 2. The base resin contains 50 to 95% by weight of the polymerizable resin liquid, 2.5 to 25% by weight of a trifunctional acrylic or methacrylic monomer, and 2 to 2% of a bifunctional acrylic or methacrylic modified epoxy. 0.5 to 25% by weight
The decorative molded article according to claim 1, wherein the compounded amount of the trifunctional acrylic or methacrylic monomer does not exceed the compounding amount of the bifunctional acrylic or methacryl-modified epoxy.