JPH03150251A - Artificial marble and frp reinforced molded article thereof - Google Patents

Abstract

PURPOSE:To obtain readily moldable artificial marble hardly cracking in artificial marble having a gel coated layer on the surface of resin concrete layer by adding a specific amount of glass fibers to the resin concrete layer. CONSTITUTION:In artificial marble having a gel coated layer on the surface of resin concrete layer, at least 2-10wt.% glass fibers having 0.05-0.5mm length are added to the resin concrete layer. FRP reinforced molded articles which are obtained by laminating FRP to molded articles using the artificial marble as is mentioned above are also usable. Unsaturated polyester resin, vinyl ester resin, epoxy resin, etc., may be cited as a thermosetting resin used in a composition for the resin concrete.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to an artificial marble to which resin concrete is applied and an FRP reinforced molded product thereof.

[Conventional technology]

Artificial marble, which has a marble-like appearance by laminating a gel coat layer on the surface of a resin concrete layer, gives a high-class appearance and has excellent water resistance and boiling resistance, so it is ideal for bathtubs, sink counters, and kitchen counters. Widely used.

Such artificial marble is molded using a concave-convex mold such as FRP or @casting. That is, a thermosetting resin composition is applied to the mold surface that will become the front side of the artificial marble product,
It is cured to form a gel coat layer. The molds are then matched, and resin concrete is injected into the gap between the molds, hardened, and shaped.

At this time, resin concrete usually uses a thermosetting resin such as unsaturated polyester resin or vinyl ester resin as a matrix, and uses aluminum hydroxide, glass powder, etc.
Fill with filler such as calcium carbonate. The type of filler and its content 9 are selected taking into account the quality, performance, and moldability of the product, but the amount of filler is usually 40 to 70 ffi.
It is blended within the range of 1%. The resin concrete composition poured into the mold is cured at a temperature of about 40 to 80°C. In this way, the gel coat layer is laminated on the resin concrete layer, and this molded product is demolded to produce an artificial marble product.

[Problem to be solved by the invention]

However, when curing the resin concrete composition in the above-mentioned molding process, the curing shrinkage is large and the mechanical strength of the cured product is also low, so the molded product tends to crack during molding. This can also occur due to careless handling or differences in temperature during transportation, installation, or use of the product.

Cracks are particularly likely to occur when the molded product is large in shape or thin-walled.

Furthermore, when producing artificial marble products, the resin concrete composition is dropped from a container into a mold by its own weight and poured into the mold. At this time, press-fitting may be performed, but since the mold material is usually FRP or electroformed material, high-pressure injection is difficult in terms of strength. Therefore, the composition for resin concrete must be adjusted to a viscosity that allows easy pouring into molds.

An object of the present invention is to provide an artificial marble that is easy to cast and less prone to cruff.

(Means for Solving the Problems) In order to solve the above problems, the present invention provides an artificial marble having a gel coat layer on the surface of the resin concrete layer. The present invention provides an artificial marble characterized by containing at least 2 to 10% by weight of glass fiber.

Next, the present invention will be explained in detail.

The artificial marble in the present invention has a gel coat layer formed on the inner surface of the mold, and a resin concrete layer laminated thereon. Resin concrete is a resin concrete compound made of thermosetting resin filled with fillers such as aluminum hydroxide and glass powder, and has a length of 0.05~
This is a cured resin concrete composition containing 2 to 10% by weight of glass fibers of 0.5 m thick, which hardly increases the viscosity of this composition, and improves the appearance, water resistance, and boiling resistance. It can be prevented from cracking without damaging it.

Glass fiber is transparent and has high strength, so it is commonly used as an FRP reinforcing material, and has been used in many bathtub units. Therefore, it is easy to think of using glass fiber to solve the problem of clumping of artificial marble products, but the glass fiber length of 1 to 25 cranes is usually used as an FRP reinforcing material. When the fibers are loaded into the artificial marble composition, the viscosity of the resulting composition increases significantly, and stirring or stirring to homogenize the composition increases
The workability during casting and defoaming becomes very poor.

In order to improve this point, the present invention has a length of 0.05~
A resin concrete composition containing 2 to 9% of 0.5 glass fibers is used. That is, by shortening the fiber length, the viscosity of the resin concrete composition can be lowered.

On the other hand, in the present invention, since glass fiber is mixed in the resin concrete composition, its reinforcement is performed,
It is difficult for cracks to get into the molded product during molding, etc., and there are benefits to using this. In other words, when producing a large artificial marble molded product such as a bathtub using the casting method, the back side of the molded product is FJ? By P? I strengthen it. Specific reinforcing methods include a method of laying FRP on the surface of the mold and then pouring the artificial marble compound into the mold to integrate it, and a method of molding the artificial marble product and then applying FRP to Jl. There is a way to reinforce one layer. The former method tends to leave internal distortion due to shrinkage during casting, so the latter method is preferable. Therefore,
In that case, the artificial marble product must be molded alone and must be free of cracks, which the present invention has made possible.

Examples of the thermosetting resin used in the resin concrete composition include unsaturated polyester resins, vinyl ester resins, epoxy resins, urea resins, melamine resins, diallyl phthalate resins, and the like.

The unsaturated polyester resin is produced by polycondensation of α, β-unsaturated dibasic acid or its acid anhydride, aromatic saturated dibasic acid or its anhydride, and glycols,
Unsaturated polyester produced using an aliphatic or alicyclic saturated dibasic acid as an acid component in some cases
80 market parts, α.

Examples include those obtained by dissolving in 70 to 20 parts by weight of a β-unsaturated monomer, but also unsaturated polyesters with vinyl-modified ends, vinyl esters with vinyl-modified ends of epoxy resin skeleton, etc. can also be mentioned.

The above α,β-unsaturated dibasic acids or their acid anhydrides include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chlormaleic acid and their esters, and aromatic saturated dibasic acids Examples of acids or acid anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, diphenic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and these. There are esters, etc., and aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid,
Examples include azelaic acid, glutaric acid, hexahydrophthalic anhydride, and esters thereof, each of which may be used alone or in combination.

Glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol. , tetraethylene glycol, 1,5-pentanediol, 1.
6-hexanediol, bisphenol A1 hydrogenated bisphenol A1 ethylene glycol carbonate, 2.
Examples include 2-di(4-hydroxypropoxydiphenyl)propane, which can be used alone or in combination,
In addition, ethylene oxide, propylene oxide F
Oxides such as can also be used in the same manner. Furthermore, polycondensates such as polyethylene terephthalate can also be used as part of the glycols and acid components.

In addition, the above α,β-unsaturated monomers include styrene,
Vinyltoluene, α-methylstyrene, chlorstyrene, dichlorostyrene, vinylnaphthalene, ethyl vinyl ether, methyl vinyl ketone, methyl acrylate,
Can be cross-linked with unsaturated polyesters and vinyl ester resins such as vinyl compounds such as ethyl acrylate, methyl methacrylate, fukurinitrile, and methacrylate trile, and allyl compounds such as diallyl phthalate, difuryl fumarate, difuryl succinate, and triallyl cyanurate. Examples include vinyl monomers and vinyl oligomers, which may be used alone or in combination, but styrene is generally used.

In addition to the above, fillers used in the resin concrete composition used in the present invention include calcium carbonate powder, clay, alumina powder, silica powder, talc, barium sulfate, silica powder, glass powder, glass peas, mica, and crushed stone powder. Cellulose-based fillers are also used, and among them, glass powder, aluminum hydroxide, barium sulfate, etc. are preferred because they provide transparency during curing.The filler is usually 100 to 9 parts by weight of the unsaturated polyester resin. It can be used in a proportion of 300 parts by weight. The particle size of the filler is 6
Preferably, it is 0 me or less.

Furthermore, natural crushed stone may be used as the filler.

Natural crushed stone includes crushed igneous rock, metamorphic rock, and aquatic rock (sedimentary rock). Igneous rocks include volcanic rocks and plutonic rocks (granite).
Among them are Komatsuishi and Teppeishi, which are generally called andesite. In addition, plutonic rocks include granites such as jimikage (generally called granite), cherry granite (red granite), red granite (red granite), black granite (referred to as gabbro), and diorite. Metamorphic rocks include serpentinite, crystalline limestone, limestone, and other marbles.

The aqueous rocks (sedimentary rocks) that are used include limestone, Indian Myone stone called sandstone, Tago stone, basalt stone called slate, Sendai stone, Oya stone called tuff, and Fukumitsu stone.

In addition, crushed stone for ceramics, porcelain, glass, stained glass, etc. is also used in combination.

Further, crushed stone can be used alone or in combination of two or more types.

The natural crushed stone preferably has an average particle size of 1 to 20 grains.

Further, in the present invention, a low shrinkage agent can also be used in combination, and the low shrinkage agent used can be a thermoplastic resin, and specific examples thereof include methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, and ethyl acrylate. Lower alkyl esters of acrylic acid or methacrylic acid such as styrene, vinyl chloride,
Homopolymers or copolymers of I-mers such as vinyl acetate,
At least one of the vinyl ML polymers and lauryl methacrylate, isovinyl methacrylate, acrylamide, methacrylamide, hydroxyalkyl acrylate or methacrylate, acrinitrile, methacrylic nitrile, acrylic acid, methacrylic acid, cetylsteryl methacrylate. Examples include copolymers of at least one monomer, cellulose acetate butyrate and cellulose acetate propionate, polyethylene, polypropylene, saturated polyester, and the like. The amount added is preferably 0 to 50 M@ parts, particularly preferably 0 to 35 parts by weight, per 9 parts of 100 parts of the thermosetting resin.

In order to obtain the resin concrete of the present invention, it is also preferable to use a curing catalyst, and examples of curing catalysts include those that act on unsaturated polyester resins, vinyl ester resins, etc., such as azo compounds such as azoisobutyronitrile, tertiary resins, etc. -Butyl perbenzoate, tertiary-
Examples include organic peroxides such as bar octoate, penzoyl peroxide, methyl ethyl ketone peroxide, and dicumyl peroxide;
It can be used generally in an amount of 0.3 to 3 parts by weight per 100 parts by weight of the ester resin.

Curing accelerators can also be used in the present invention, including
Metal salts of R#, especially cobalt salts, such as cobalt naphthenate, cobalt octylate, cobalt acetylacetone, etc., are used.

In addition, the gel coat layer in the present invention includes a composition consisting of the above-mentioned thermosetting resin, a curing catalyst, and, if necessary, a curing accelerator, or at least 14 of the above-mentioned low shrinkage agent and the following thickener. It is also possible to use a composition that uses a combination of these and cure it.

The thickener chemically bonds with the hydroxyl group, carboxyl group, ester bond, etc. possessed by unsaturated polyester, etc. to generate linear or partially cross-linked bonds, increasing the number of molecules 9, and increasing the viscosity of the unsaturated polyester resin. For example, diisocyanates such as toluene diisocyanate, metal alkoxides such as aluminum isopropoxide and titanium tetrabutoxy, divalent metal oxides such as magnesium oxide, lucium oxide, and beryllium oxide, and calcium hydroxide. Examples include hydroxides of two metals, such as hydroxides of two metals, and the like. The amount of thickener used is usually 0.2 to 5 parts by weight, preferably 0.5 to 4 parts by weight, per 100 parts by weight of the unsaturated polyester resin. And if necessary, a small amount of a highly polar substance such as water can be used as a thickening agent.

In addition, conventionally known internal M type agents such as higher fatty acids such as stearic acid and zinc stenylate, higher fatty acid esters, and alkyl phosphate esters can also be used in the gel coat layer and resin concrete compositions. Usually 0.0% per 100 parts by weight of saturated polyester resin.
It can be used at a rate of 5 to 5 degrees. Coloring pastes can also be used, and organic and inorganic dyes and pigments can be used, but among them, they have excellent heat resistance and transparency, and do not significantly interfere with the curing of thermosetting resins. Preferably.

In order to produce the artificial marble of the present invention, the gel coat layer composition described above is applied to the surface of the uneven mold and cured, then the molds are combined and the resin concrete composition described above is injected, cured, and removed from the mold. do.

It is also preferable that the artificial marble product obtained in this way has four layers of FRP II strong layers as described above to make it a product with high strength.

The artificial marble of the present invention and its FRP reinforced molded product can be used for bathtubs, washroom counters, table tops, floors, walls, building interiors, lower box tops, washstands, etc.

implementation! 141 Next, examples of the present invention will be described.

Example 1 A bathtub made of a material laminated with a gel coat layer, an artificial marble layer, and an FRP M strong layer (length: 1400 mm, width: 850 mm,
990 mm deep and 9 m thick) was molded as follows.

0 Formation of Gel Coat Layer The following composition was applied to the surface of the convex mold using a concavo-convex mold made by FlJP.

Polylite GC-530100yi weight% (unsaturated polyester resin manufactured by Dainippon Ink & Chemicals) Curing catalyst (O KPO) 0.8% by weight 9%
Curing accelerator 0.04 M amount% (6
%C0 naphthinate) The coated material was cured by heating at 60° C. for 30 minutes to form a gel coat layer.

■ Formation of artificial marble layer Next, after matching the concave and convex molds, a resin concrete composition having the following composition was cast.

Polylite TP-50040% by weight (Dainippon Ink & Chemicals Wi unsaturated polyester resin) Aluminum hydroxide 55% by weight (particle size 50-100mm) Glass fiber (length 100-200μ) 5M9%
6% C0 naphthinate 0.02% by weight
Methyl ethyl ketone peroxide 0.5% by weight (M
EKPO) Pigment (green) 1.0% by weight After casting, it was defoamed and cured at 60°C for 1 hour. Thereafter, it was cooled for 1 hour and the concave mold was removed. When observed immediately after demolding, no cracks were observed.

■Formation of FRP reinforcing layer Next, in order to provide the FRP reinforcing layer, two layers of adhesive and glass muff (300 g, 10 f) of the following composition were used to laminate on the surface of the above convex molded product and cure at 50°C for 60 minutes. The mold was removed.

Polylite Ffl-123-N 1
00% by weight (unsaturated polyester resin manufactured by Dainippon Ink and Chemicals) Pigment (green) lff
i amount % methyl ethyl ketone peroxide 0.8ff
iJin% By repeating these eight steps, six bathtubs were made, and two of these bathtubs were subjected to a repeated heating and cooling test (-20°C).
and 80°C (alternately repeated 210 times), and the remaining 4 machines were tested for cold jJ (-20°C) hole drilling, but no abnormality was observed in the molded product.

In addition, a molded product (artificial marble product) obtained by molding and demolding was performed in the same manner as above using a 20C11 square, 1olIII wall thickness flat plate concave-convex mold, and a bending test was conducted.

The results obtained above are shown in the table.

Comparative Example 1 Six bathtubs were manufactured in the same manner as in Example 1 except that glass fiber was not used in the resin concrete composition in (■), and the results of testing in the same manner as in Example 1 are shown in the table. In the test, no abnormalities were observed in 2 out of 2 machines, but cracks occurred in 2 out of 4 machines in the cold hole drilling test.

In addition, the bending strength of the artificial marble was approximately 2
It showed a 0% lower value.

Comparative Example 2 In Example 1, among the compositions for resin concrete,
A bathtub was made in the same manner except that 3M% of In fiber length was used as the glass fiber, but the resin concrete composition had a high viscosity and was highly thixotropic, so casting could not be done smoothly. It was not possible to obtain a molded product.

l (Kg/srrf), l
l, a long time ago:? ? jJIs-ni-72o3
5 pieces 760 740 j [Effects of the Invention] According to the present invention, in the artificial marble having a gel coat layer on the surface of the resin concrete layer and its FRP reinforced molded product, the composition for resin concrete has a length of 0-05 to 0.
By using 50% glass fiber, the viscosity of this composition can be prevented from becoming too high, resulting in good casting workability and maintaining the strength of the product to prevent the occurrence of graphs, etc. be able to.

November 6, 1999

Claims (1)

[Claims] 1. In the artificial marble having a gel coat layer on the surface of the resin concrete layer, the resin concrete layer has a length of 0.
．． At least 2-10 glass fibers of 0.05-0.5 mm
Artificial marble characterized by containing % by weight. 2. FRP molded product using artificial marble according to claim 1
FRP reinforced molded product obtained by laminating.