JPH031943A - Granite-like molded product with superior resistance to boiling water - Google Patents

Abstract

PURPOSE:To harden in the state of natural dispersion without disarrayed pattern generated by sedimentation of aggregates by forming a gel coat layer as a first layer, a transparent FRP layer as a second layer constituted by glass fiber or a non-woven cloth impregnated with thermosetting resin, resin concrete of opaque granite feeling as a third layer and an FRP backup layer as a fourth layer. CONSTITUTION:A transparent gel coat layer as a first layer and a transparent FRP layer as a second layer constituted of 30g - 600g/m<2> glass fiber or a non- woven cloth impregnated with thermosetting resin are formed successively on the surface of a first mold controlling one surface of a molded material. On the other hand, an FRP backup layer as a fourth layer is formed on the surface of a second mold controlling the other surface of the molded material. Then, resin concrete having thixotropy as a third layer containing 100 pts. wt. of synthetic resin and 10 - 300 pts. wt. of aggregates of 0.3 - 5mm size having two colors or more is injected into a space controlled by the first and second molds. The aggregates are not separated during molding by said process, and natural pattern can be provided.

Description

[Detailed Description of the Invention] [Industrial Field of Application] This invention relates to a method for manufacturing artificial marble that has an opaque and uniform granite-like artificial marble part that can be seen through a gel coat layer and an FRP layer and has excellent hot water resistance. be. In particular, the present invention provides a manufacturing method that gives a natural shading tone when molding a molded body having an vertical surface, such as a bathtub, using a thermosetting resin.

[Conventional technology]

Various methods have been known for manufacturing bathtubs and the like using thermosetting resins.
No. 07377 discloses a manufacturing method by pouring polyester mortar with aggregate into the mold surface. Furthermore, Japanese Patent No. 1418683 is known for producing synthetic resin molded products with transparent marble, which involves injecting a thermosetting resin containing organic or inorganic fillers and toner into a mold and curing it. discloses a method for producing a molded article exhibiting a natural marble pattern.

[Problem to be solved by the invention]

In these known techniques, there is no problem when molding is performed on a horizontal surface without vertical surfaces, or even if there is an vertical surface, if the filler or toner is fine particles or the difference in specific gravity is small and there is no separation due to gravity, molding When the body has an elevation and the specific gravity of the aggregate is high, separation of the aggregate becomes a problem. In particular, when producing a stone-grained molded body, for example, a molded body with a granite tone such as granite, uncolored and Resin concrete mixed with colored products is used to form the concrete, but in most cases there is not only a large difference in specific gravity from the compound, but also a large difference in specific gravity between the aggregates, which causes natural settling and hardening. Before the process was completed, the aggregate became unevenly distributed, making it difficult to produce a uniformly textured pattern.

Therefore, an easy solution could be to use colored plastic particles with the same specific gravity as the resin concrete compound, but this would be expensive, the color tone would be unnatural, or it would be difficult to match the specific gravity of the compound. is quite a difficult task.

In addition, when using Mikage-style artificial marble in an environment where hot water or hot water is handled, such as in a bathtub, the first layer of gel coat alone will not allow water to penetrate into the fillers and aggregate contained in the artificial marble. - There is a concern that the hot water resistance for boat fishing will deteriorate, and the gel coat will become blistered due to the expansion of air bubbles.
Problems arise that cause cracks and discoloration.

[Means to solve the problem]

The present invention overcomes these problems and provides a grain-like molded article with excellent hot water resistance and a method for producing the same.

That is, one of the aspects of the present invention is that the gel coat layer as the first layer and the thermosetting resin as the second layer are mixed in an amount of 30 g to 600 y/m.
2. Transparent FRP impregnated with glass fiber or nonwoven fabric
The object of the present invention is to provide a granite-like molded article having excellent hot water resistance, which is composed of an opaque granite-like resin concrete as a third layer, and an FRP backup layer as a fourth layer.

Furthermore, another aspect of the present invention provides a molded body having an elevational surface having a height to horizontal width ratio of 0.1/1 or more, a horizontal width of 400 mm or more, and a height of 4011 mm or more. In the manufacturing method, a transparent gel coat layer as a first layer and a thermosetting resin as a second layer are placed on the surface of a first mold that regulates one side of a molded article, in an amount of 30 g to 600 I? /m'' of transparent FRP layers impregnated with glass fiber or nonwoven fabric, and an FRP backup layer as a fourth layer is formed on the surface of the second mold, which controls the other side of the molded object. Resin concrete as a third layer is placed in the space regulated by the first and second molds] 00 parts by weight of synthetic resin and aggregates of size 0.3 to 5ii+ in two or more colors.
300 parts by weight of resin concrete having thixotropy is injected into the molded body.

The molded article of the present invention and its manufacturing method will be explained below using a bathtub as an example.

Bathtubs are basically made using a male mold that regulates the shape of the internal surface of the bathtub and a female mold that regulates the external surface.
There is a cold press method in which resin concrete is placed in a female mold and a male mold is pushed into the female mold.

In the present invention, first, a transparent gel coat is uniformly applied to the male mold (hereinafter referred to as the first layer). Any conventional coating method may be used, but transparent FRP is laminated as the 0th and 2nd N layers, for which spray painting is convenient. This method includes laminating or spraying mats using transparent resin, but spray-up molding is suitable and convenient in terms of shape. There is also a fourth
Since the layer is a back-up layer, it is not necessary to specifically use a transparent resin; any suitable resin may be used. Second
It is common to use the lamination method used for layers. Further, the fourth layer may be laminated as necessary after molding and demolding the first, second, and third layers.

Set the male mold and female mold made in the above molding process, and fill the space with 10 to 10 aggregates of size 0.3 to 5zx in two or more colors.
A resin concrete containing 300 parts by weight and having lateral modification is poured. This resin concrete is made by adding inorganic substances, fillers, and organic substances to impart lateral modification to a resin or resin having lateral modification such as unsaturated polyester.

In this state, the aggregate with a size of 0.3 to 5 cm, which forms the granite tone, does not settle downward, and a bathtub having a granite side where the aggregate and particles can be seen in a uniform manner is obtained.

This bathtub is mainly made of thermosetting resin, and has a gel coat and clear intermediate layer on the surface, and a reinforcing FRP backup layer on the back, so it has sufficient hot water resistance and mechanical strength as a bathtub. It is.

The gel coat used for the first layer of the present invention must provide smoothness and gloss to the surface of the molded product, allow the granite pattern of the third layer to be seen through, and have sufficient hot water resistance and surface hardness. No.

Such gel coat agents usually include vinyl esters,
Bisphenol and iso-based resins are good, and the coating amount is 400~
1000g/l112 and thickness 0.1-0.5III are suitable.

The resin used for the second layer is a resin that has transparency and is used to compensate for the low hot water resistance of the granite-like artificial marble, and may be ordinary FRP.

The resin concrete used for No. 3N has a thermosetting resin as its main component, plus minerals, fillers and 0.5%.
10 to 300 parts by weight of 3 to 5zx aggregate is added, and the resin concrete is made to have lateral modification. The resin for resin concrete is either lateral modified by itself, or a filler or organic substance that imparts lateral modification is added to improve the lateral modification of resin concrete. g to 10, preferably 1. It is preferable to set it in the range of g to 5.0.

The viscosity of the thermosetting resin is 1 to 30 voids, preferably 3 to 30 voids.
There are 15 voices. The curing system may be a room temperature curing system, but from the viewpoint of workability, medium temperature curing of 40 to 80°C is preferable.

The thermosetting resin used in resin concrete is preferably an unsaturated polyester resin. The unsaturated polyester that can be used in the present invention is not particularly limited, and is one synthesized from an organic polybasic acid and a polyhydric alcohol, or a modified product thereof, and has a molecular weight of 500 to 10,000, preferably 1.000. ~5,000 unsaturated polyester resin. Examples of organic polybasic acids include unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid, which are used in the production of general unsaturated polyesters, and unsaturated polybasic acids such as maleic anhydride. It contains an anhydride as an essential component and saturated acids such as pentaphthalic acid, terephthalic acid, isophthalic acid, and adipic acid as an optional component. Organic polybasic acids can be used alone or in combination.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1,3-butanediol, 1,3-butylene glycol, 1.6-hexanediol, 1.6-cyclohexanediol, Neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, hydrogenated bisphenol A, polybutadiene glycol, propylene oxide diadduct of bislaenol A, and the like are used alone or in combination.

Examples of modified unsaturated polyesters include dicyclopentadiene or its derivatives, and allyl compounds such as pentaerythritol triallyl ether, mono- or diallyl ether of glycerin, allyl glycol, and allyl glycidyl ether, which are air-drying agents. , those used as one component of unsaturated polyester can be used.

Regarding the method for producing unsaturated polyester in the present invention,
There are no restrictions and it can be produced using any known reaction method.

For example, an organic polybasic acid and a polyhydric alcohol are reacted at a reaction temperature of 100 to 230°C, and the resulting condensed water is distilled out of the system to proceed with the reaction. If necessary, the end point of the reaction is determined by adjusting the acid value, etc. demand. The acid number is preferably about 5-40.

The organic polybasic acid used in the present invention may be reacted with a polyhydric alcohol by simultaneously charging the blonde hair, or a part of the organic polybasic acid may be reacted with the polyhydric alcohol in advance, and then the remaining organic polybasic acid may be reacted with the polyhydric alcohol. A basic acid may be added to cause the reaction.

Further, if necessary, dicyclopentadiene, a derivative thereof, or an allyl compound may be added for reaction.

Usually, the unsaturated polyester thus obtained is added with polymerizable monomers such as styrene, talolostyrene, vinyltoluene, divinylbenzene, acrylic ester, etc.
Methacrylic acid ester etc., unsaturated polyester 100
It can be used in a proportion of 20 to 300 parts by weight.

As the filler, calcium carbonate, aluminum hydroxide, glass powder, glass flakes, etc. are preferably used.

Examples of inorganic aggregates include cold water, silica, ceramic, and glass. Examples of organic materials include colored thermoplastic resins such as PET, PE, PP, and acrylic polymers, and colored thermosetting resins such as area, polyester, and phenol.

The aggregate used in resin concrete consists of stones with unique combinations or crushed pieces of cured resin.
Coarse particles with a particle size of 0.3 to 51 J are preferred.

The color of the stone used as aggregate varies depending on the stone-like pattern desired for the final molded product, but in order to create a rich, natural-looking stone, it is best to use white and black stones to create a granite pattern. , suitable for the present invention. Also, resins that darken or give a dirty color cannot be used.

Examples of white stone include Kansui stone and marble scraps, but Kansui stone is the best. As the black stone, any black stone can be used, but silica stone dyed black can also be used.

The specific gravity of a stone is -m, where white stone is larger than black stone1.For example, kansuite, which is a typical example of white stone, has a specific gravity of 2.7, whereas dyed silica stone, which is an example of black stone, has a specific gravity of 2.7. , specific gravity 2
．． It is 5.

The blending amount for the thermosetting resin is 10 to 300 parts by weight, more preferably 50 to 200 parts by weight, of the aggregate based on 100 parts by weight of the thermosetting resin.

Furthermore, various pigments, fillers, and binders such as calcium carbonate, aluminum hydroxide, glass powder, and glass flakes may be added to this resin concrete depending on the color and texture required for the molded product. good.

The resin concrete also contains a curing agent and, in some cases, a curing accelerator. As the curing agent, an azo compound such as azoisobutyronitrile, or an organic peroxide such as dicumyl peroxide, benzoyl peroxide, methyl ethyl getone peroxide, t-butyl perbenzoate, t-butyl per octoate, etc. be. As curing accelerators, in addition to cobalt naphthenate, copper naphthenate, cobalt octylate, etc., dimethylaniline,
Dimethyl para-toluidine and the like are also used.

The fourth layer is a layer of unsaturated polyester reinforced with glass fiber or the like, and is applied to the inner mold of the female mold by a backup method, a spray-up method, or the like. The resin and fiber reinforcing material used in this layer are selected for the purpose of preventing deformation of the entire bathtub and providing strength.

[Effect]

Since the present invention has the above-described configuration, when molding a molded product having a structure with an vertical surface using a combination of a male mold and a female mold, two or more types of grain size 0 with a difference in specific gravity are used for the compound. Even if 3 to 5 mm of aggregate is mixed, it will not separate during molding, and a natural pattern can be obtained, as well as a granite-like artificial marble that can be seen through the gel coat layer and the FRP layer. Moreover, this molded body is 98℃-5
Even when subjected to a continuous boiling test for 00 hours, the gel coated surface was free of flakes and cracks.

[Example 1] Width approx. 90cm x length approx. 120cLI+x depth approx. 60cm
The molding was carried out using male and female molds corresponding to the size of the bathtub. The coating agents used for each layer were as follows. In addition, all compounding ratios are parts by weight.

(1st layer) Gel coat layer (manufactured by 5QOOOOP Nippon Fellow Co., Ltd.) bisphenol-based unsaturated polyester resin 2nd layer) FRP intermediate layer bisphenol-based unsaturated polyester resin (Revolac 450BTN manufactured by Showa Kobunshi) #380 chop Lamination of Dostrand mat (3rd layer) Resin concrete layer putty [Unsaturated polyester containing Aerosil (Revolac 3157T, manufactured by Showa Kobunshi Co., Ltd.)] Viscosity 8 voids, Rice quality 4.0 100 parts Kuroishi [Shinkyotou] Made by Zai Co., Ltd.] No. 20 Specific gravity 2.5 140 parts Shiroishi [
Kansuiseki, manufactured by Oshima Straisei Co., Ltd.] S old 000 specific gravity 2.7 10 parts Aluminum hydroxide (Hisilite H310, manufactured by Showa Denko) 100 parts Burriki Dox 16 (hardening agent 1) 1.0 parts NL
P-10 (curing accelerator) 0.4 parts Percure 0 (curing agent 2) 0.3 parts (4th layer)
Backing layer Rivolac 158BQT (unsaturated polyester manufactured by Showa Kobunshi Co., Ltd.) Chopped stranded polymer, #450 Permeckle (hardening agent manufactured by NOF) Using the above plastic coating agent, mold as follows. went.

(Application of Gel Coat) A gel coat agent was spray applied to the male mold surface in an amount of about 800 fI/l112 and cured.

(Coating of second layer) The resin composition for the second layer is coated on the cured gel coat of the male mold and cured.

(Coating of 4th layer) The above-mentioned resin composition between the backing layers was coated on the female mold and cured.

After assembling the male and female molds coated and prepared as described above with the bottom of the bathtub facing up and clamping the molds, the resin concrete constituting the center layer (third layer) is placed on the top plate of the female mold. It was cast through the injection port provided in the center. Thereafter, it was immediately cured in a curing oven.

When the molded product was removed from the mold after curing was completed, a natural granite-like pattern consisting of white and black patterns appeared on the inner surface of the molded product. There were no mottled patterns that could be caused by sedimentation or separation of white and black stones on the elevation of the interior side of the bathtub.

[Example 2] The first, second, and fourth layers were formed in the same manner as in Example 1, and as the resin concrete layer, putty (unsaturated polyester containing Aerosil) (Revolac 3157T-1, Showa Kobunshi Co., Ltd.) was used. (manufactured by) viscosity 8 boids, rice-wheat consistency 2゜5 100 parts colored aggregate (red) specific gravity 1
．． 4 90 parts colored aggregate (black) nl, 4
5 parts colored aggregate (brown) nl, 4 5
1 part Aluminum hydroxide (Hijirai 1~) 100 parts Parriki Dox 16 (hardening agent 1) 1 part NLP-10 (hardening accelerator) 0.4 parts Vercure 0 (hardening agent 2) 0.3 parts in the same way It was cast from the entrance.

Thereafter, it was immediately cured in a curing oven.

The results of Example 1 also showed that there was no mottled pattern and a red granite pattern appeared with good texture.

In addition, regarding the bathtub obtained in the above example, 98
When a continuous boiling test was conducted for 500 hours in hot water at ℃, a bathtub with no blisters or cracks was obtained.

[Comparative Example 1] For comparison, when the following formulation without rice-wheat properties was used, the resin [Rivolac 100g manufactured by Showa Kobunshi Co., Ltd.] had a viscosity of 1.
0 boise, rice and wheat 1. ．． 0 100 parts Kuroishi [manufactured by Shinto Tozai Co., Ltd.] No. 20 Specific gravity 2.5 140 parts Shiroishi [Kansuiseki manufactured by Oshima Seino Co., Ltd.] 5W100O specific gravity 2.7 10 parts Aluminum hydroxide (Hygielite 1 (310) 100 parts Pariki Dox 16 1 part NLP-100,
When 4 parts and 0.3 parts of Vercure 0 were cast in the same manner, stones settled and separated on the vertical surface, and an unnatural mottled pattern appeared on the surface of the molded product.

[Comparison PA2] The product molded in Example 1 without the second layer was molded for 90'
When it was boiled in hot water (C), many blisters occurred within 50 hours, and it could not be used in places such as bathtubs that require hot water resistance.

〔Effect of the invention〕

As described above, since the present invention is configured as described in item 5 or above, even when manufacturing a molded body having an elevation like a bathtub, the pattern can be naturally dispersed without disturbing the pattern due to settling of the aggregate. It is possible to obtain a hot water-resistant granite-like molded product that is cured while still being cured.

Patent applicant: Eishin Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A gel coat layer as the first layer, a transparent FRP layer in which glass fiber or nonwoven fabric is impregnated with 30 g to 600 g/m^2 of thermosetting resin as the second layer, and a third layer as the third layer. A granite-like molded body with excellent hot water resistance, consisting of an opaque granite-like resin concrete and an FRP backup layer as the fourth layer. 2. In a method for producing a molded body having an elevational surface having a height to horizontal width ratio of 0.1/1 or more, and a horizontal width of 400 mm or more and a height of 40 mm or more, 30g of gel coat layer as the first layer and thermosetting resin as the second layer on the surface of the first mold that regulates one side.
Transparent FRP layers impregnated with ~600g/m^2 glass fiber or nonwoven fabric are sequentially formed, and an FRP backup layer as a fourth layer is formed on the surface of the second mold that regulates the other side of the molded object. Then, a third layer of resin concrete is placed in the space regulated by the first and second molds.
00 parts by weight of synthetic resin and two or more colors with a size of 0.00 parts by weight.
A method for producing a granite-like molded body, which comprises injecting resin concrete containing 10 to 300 parts by weight of 3 to 5 mm aggregate and having thixotropy.