JPH01161009A - Manufacture of artificial marble - Google Patents

Abstract

PURPOSE:To produce an artificial marble excellent in appearance and heat resistance, by casting a compound which contains a specific unsaturated polyester resin, trimethylolpropane tri(meth)acrylate, a filler, and a curing agent into a mold to be molded. CONSTITUTION:An acid component containing an unsaturated dibasic acid (anhydride) is reacted with a polyol component to produce an unsaturated polyester, and the product is dissolved in an unsaturated monomer (e.g., styrene) to produce an unsaturated polyester resin (A). 100 pts.wt. mixture made up of 80-95 pts.wt. component (A) and 20-5 pts.wt. trimethylolpropane tri(meth) acrylate (B) of the formula (wherein X is H or CH3) are blended with a filler (C) (e.g., CaCO3), a curing agent (e.g., azobisisobutyronitrile), and if desired, a curing promotor, an agent for keeping shrinkage low, etc., to produce a compound. This compound is cast into a mold while deaerating, reacted, and cured, thereby molding it.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a method for producing 9 artificial astronomical stones.

(Prior art) Conventionally, two-piece artificial astronomical stones are produced by adding a low-shrinkage agent as needed to a compound consisting of an unsaturated polyester resin, a filler, a hardening agent, and a hardening accelerator, and then coloring the compound, and then applying the compound to a vibrating table. It is injected into a mold while being vibrated and deaerated, and is removed from the mold after hardening. It is used in molded products such as system kitchen counters and bathroom vanity interior parts.

If a heated frying pan, kettle, etc. is placed on this artificial marble during cooking, discoloration and blistering occur, which impairs the aesthetic appearance.

In order to solve this problem, methods of using highly heat-resistant epoxy resins, vinyl ester resins, etc. are being considered, but there is a problem that the molded product becomes colored and the product value is greatly impaired, so a solution to this problem is strongly desired. was.

(Problems to be Solved by the Invention) The present invention provides a method for producing artificial marble that has excellent heat resistance without impairing its appearance, while eliminating the drawbacks of the above-mentioned conventional techniques.

(Means for Solving the Problems) The present inventors have made extensive studies in view of the above-mentioned circumstances, and as a result, the present invention has been developed to solve the problem by using an unsaturated dibasic acid and/or An unsaturated polyester obtained by reacting an acid component containing an acid anhydride with a polyhydric alcohol component and 5 to 95 parts by weight of A trimethylolpropane triacrylate or trimethylolpropane trimethacrylate. The present invention relates to a method for producing artificial marble, in which a compound containing a filler and a hardening agent is injected into a mold in an amount of 20 parts by weight for a total amount of 1 part by weight of 10C.

The compound may contain curing accelerators, low shrinkage agents, etc. as necessary.
Dyes, pigments, etc. may also be added.

Examples of the unsaturated dibasic acids and/or their acid anhydrides used in the present invention include maleic acid, fumaric acid, itaconic acid, citraconic acid, and maleic anhydride. Two or more of these may be used in combination.

In the present invention, a saturated dibasic acid and/or its acid anhydride may be used as the acid component depending on the infatuation, examples of which include phthalic acid and phthalic anhydride.

Isophthalic acid, terephthalic acid, trimellitic acid.

Trimellitic anhydride, succinic acid, azelaic acid.

Adipic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, rosin-maleic anhydride adduct, chlorendic acid, chlorendic acid anhydride, tetrachlorophthalic acid, tetrachlorophthalic anhydride Examples include acids, tetrabromophthalic acid, and tetrabromophthalic anhydride. Two or more of these may be used in combination.

Polyhydric alcohol components include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,6-hexanediol, neopentyl glycol, triethylene glycol, water-added hisphenol A, iso Pentyl crico-A/, RIJ serine, trimethylolpropane, dicyclopentadiene, pentaerythritol, etc. can be used.

React the above acid component and polyhydric alcohol component.

The manufacturing method for obtaining an unsaturated polyester resin is mainly carried out by proceeding with a condensation reaction, and the process proceeds by removing water produced when the two components are reacted to the outside of the system.

The obtained unsaturated polyester is dissolved in an unsaturated monomer such as styrene, vinyltoluene, divinylbenzene, methyl methacrylate, or vinyl acetate.

The unsaturated polyester resin used in the present invention.

Additives such as a polymerization inhibitor such as hydroquinone can be added to the resin as necessary.

Trimethylolpropane triacrylate or trimethylolpropane trimethacrylate, which is an essential component of the present invention, has a structure represented by -maximum % formula %). In the formula, X is CH3 or H, and may be the same or different.

The amount of trimethylolpropane triacrylate or trimethylolpropane trimethacrylate used is 5 parts by weight based on 80 to 95 parts by weight of the unsaturated polyester resin when the total amount with the unsaturated polyester resin is 100 mt parts.
The range is 20 parts by weight. If the amount is less than 5M parts, no improvement in heat resistance will be observed, and if it exceeds 20 parts by weight, the resin molded product will become heavily colored and molding cracks will occur, resulting in a decrease in commercial value. Trimethylolpropane triacrylate and trimethylolpropane trimethacrylate may be used in combination.

In the present invention, the unsaturated polyester resin and trimethylolpropane triacrylate or trimethylolpropane trimethacrylate are used in an amount within the range of the above-mentioned parts by weight so that the total amount thereof is 100 parts by weight.

Fillers used in the present invention include calcium carbonate, magnesium carbonate, barium sulfate, and talc.

Clay, asbestos, silica, colloidal silica.

Mica, gypsum, alumina, antimony trioxide, glass powder,
Porcelain powder, metal powder, wood powder, synthetic resin powder, etc. can be used.

Examples of curing agents include azo compounds such as azobisisobutyronitrile, tert-butyl perbenzony), tert-butyl peroctoate, benzoyl peroxide, methyl ethyl ketone peroxide,
hydroperoxide, lauroyl peroxide,
Organic peroxide catalysts such as dicumyl peroxide are used.

In addition, these curing agents can be used as necessary, such as metal soaps such as cobalt naphthenate and cobalt octenoate, quaternary ammonium salts such as dimethylbenzylammonium chloride, β-diketones such as acetylacetone, dimethylaniline, N- It can be used in combination with a curing accelerator such as amines such as ethyl metatoluidine and triethanolamine.

Low shrinkage agents that can be used as necessary include saturated polyester resin, polystyrene resin, polyvinyl acetate resin,
Polyacrylic resin etc. are used.

When coloring artificial marble, commercially available organic or inorganic dyes or pigments can be used, but they must have excellent hot water resistance and weather resistance.

It is also necessary that the curing of the unsaturated polyester resin is not inhibited.

The compound obtained as described above is vibrated on, for example, a vibration table, and poured into a mold while being degassed.

After reacting for a predetermined time, it is cured and molded into the desired marble shape.

The artificial marble obtained by the manufacturing method of the present invention is suitably used for manufacturing large-sized cast products such as countertops.

(Example) The present invention will be explained in more detail with reference to Examples.

In the Examples and Comparative Examples, all parts are by weight.

Example 1 6 moles of maleic anhydride, 4 moles of phthalic anhydride.

10 moles of propylene glycol was placed in a four-way flask equipped with a stirrer, condenser, thermometer, and inert gas inlet, and 70 parts of unsaturated polyester obtained by reacting in a conventional manner at 210°C while passing nitrogen gas was added to styrene. 30 copies of Monoma.

...Resin A was obtained by adding 100 ppm of hydroquinone.

Next, to 93 parts of resin A, TMP-A ()limethylolpropane triacrylate, Kyoeisha Yushi Kagaku Kogyo Gap) 7s,
Cobalt naphthenate (cobalt content 6N amount 96) 0.
2 parts, aluminum hydroxide (trade name Heijirai) H31
150 parts (manufactured by Showa Light Metal Co., Ltd.) and 1.0 part of a curing agent (55% solution of methyl ethyl ketone peroxide, the same solution was used in the following examples) were added and stirred with a mixer to prepare a compound.

To 251.2 parts of this compound, 20 parts of a white pigment (trade name 5T-2374W manufactured by Dainichiseika Kaisha, Ltd., the same one was used in the following examples) was added.

The pigment was dispersed unevenly by partial stirring using a mixer, and the resulting colored powder was poured into an FRP mold while being vibrated on a shaking table. After sufficient deaeration, the vibration was stopped and the mixture was left to gel. . After gelation, after-cure was performed at 50°C for 2 hours to a thickness of 15 mm.

A box-shaped artificial marble molded product measuring 300 m long, 250 m wide, and 500 m deep was obtained. Table 1 shows the moldability and properties of the molded product obtained.

Example 2 To 85 parts of the resin A obtained in Example 1, 15 parts of TMP-A, 0.2 parts of copal naphthenate, 150 parts of aluminum hydroxide, and 1.0 parts of a hardening agent were added, and the mixture was stirred with a mixer to form a compound. It was created. 2.0 parts of white pigment was added to 251.2 parts of this compound.

Casting and after-curing were performed under the same conditions as in Example 1 to obtain a molded article of artificial marble similar to that in Example. Table 1 shows the moldability and various performances of the obtained molded article.

Example 3 To 85 parts of the resin A obtained in Example 1, 15 parts of TMP-A, 0.2 parts of cobal naphthenate, and 20 parts of polystyrene resin (manufactured by Denka, 40% styrene solution) were added.

A compound was prepared by adding 150 parts of aluminum hydroxide and 1.0 part of a hardening agent and stirring with a mixer.

281.2 parts of this compound and 2.2 parts of white pigment. ．． 0 parts was added and casting and after-curing were performed under the same conditions as in Example 1 to obtain a molded article of artificial marble similar to that in Example 1.

Table 1 shows the moldability and various performances of the obtained molded article.

Comparative Example 1 10.0 parts of the resin A obtained in Example 1, 0.2 parts of cobalt naphthenate, 150 parts of aluminum hydroxide, and 1.0 parts of curing agent.
A compound was prepared by stirring with a mixer without adding TMP-A.

20 parts of white pigment was added to 251.2 parts of this compound, and casting and after-curing were performed under the same conditions as in Example 1 to obtain a molded article of artificial marble similar to that in Example. Table 1 shows the moldability and various performances of the obtained molded article.

Comparative Example 2 70 parts of resin A obtained in Example 1, 30 parts of KTMP-A, 0.2 parts of cobalt naphthenate, 150 parts of aluminum hydroxide
1.0 parts of curing agent were added and stirred with a mixer to prepare a compound.

To 251.2 parts of this compound, Lθ part of white pigment was added, and casting and after-curing were carried out under the same conditions as in Example 1 to obtain a molded article of artificial marble similar to that in Example 1. Table 1 shows the moldability and various performances of the obtained molded article.

Comparative example 3 0.2 parts of cobalt ofthenate to 100 parts of resin A.

Add 20 parts of polystyrene resin, 150 parts of aluminum hydroxide, and 1.0 part of hardening agent and stir with a mixer to create a compound.

2.0 parts of white pigment was added to 271.2 parts of this compound, and casting and after-curing were performed under the same conditions as in Example 1 to obtain a molded article of artificial marble similar to that in Example 1. Table 1 shows the moldability and various performances of the obtained molded article.

Comparative Example 4 Methacrylic acid 172.09 (2.0 mol), bisphenol epoxy resin Epicoat 828 (Shell Chemical Exhibition, epoxy equivalent 189) 151.29 (0.4 mol), Epicoat 1001 (Shell Chemical, epoxy equivalent) 475) 570.09 (0.60 mol).

Resin B was obtained by mixing 70 parts of an unsaturated ester with an acid value of 9 obtained by heating 0.409% of hydroquinone and 0.509% of trimethylbenzylammonium chloride at 120° C. and 30 parts of styrene. Add 0.1 part of dimethylaniline, 0.5 part of cobalt octenoate, 150 parts of aluminum hydroxide, and 1.0 part of a hardening agent to 100 parts of resin B, and stir with a mixer to prepare a compound.

20 parts of white pigment was added to 251.2 parts of this compound, and casting and after-curing were performed under the same conditions as in Example 1 to obtain a molded article of artificial marble similar to that in Example 1. Table 1 shows the moldability and various performances of the obtained molded article.

In Table 1, the appearance of the molded products was determined visually.

Heat resistance was determined by placing an oil pot containing oil at 250°C inside the molded product for 25 minutes and observing changes in the temperature. The presence or absence of molding cracks was determined visually.

From Table 1, the amount of TMP-A added was less than 5 parts (Comparative Example 1
), no improvement in heat resistance is observed, and if the amount exceeds 20 parts (Comparative Example 2), heat resistance improves, but coloring of the resin molding and molding cracks occur, so the amount of TMP-A added is 5 to 2 parts.
It is shown that 0 parts (Examples 1 and 2) is good. Furthermore, from Example 3 and Comparative Example 3, even when the low shrinkage agent was added, T
It is shown that the addition of MP-A improves heat resistance.

Comparative Example 4 shows that the use of epoxy resin (Resin B) improves heat resistance, but the resin molded product is significantly colored.

(Effect of the invention) According to the present invention, the product is light in color and free from molding cracks.

Excellent heat resistance. It is possible to produce artificial marble with high commercial value.

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Claims (1)

[Claims] 1. An unsaturated polyester resin containing an unsaturated monomer and an unsaturated polyester obtained by reacting an acid component containing an unsaturated dibasic acid and/or its acid anhydride with a polyhydric alcohol component. parts by weight of trimethylolpropane triacrylate or trimethylolpropane trimethacrylate in an amount of from 5 to 20 parts by weight for a total of 100 parts by weight, and further containing fillers and hardeners. A method of manufacturing artificial marble characterized by injection into a mold and molding.