JP2720496B2 - Molded body with handle - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded body with a handle that can be used as a material for a bathtub, a bathroom wall material, a counter, a waterproof pan, a kitchen counter, a table counter, and the like.

2. Description of the Related Art Conventionally, fiber-reinforced plastics using an unsaturated polyester resin have been used for bathtubs, ships, tanks, and the like. These have been used merely for the purpose of increasing the mechanical strength, and in order to design aesthetic and other various applications,
Various laminated structures using fiber reinforced plastics are being studied. For example, a laminated structure has been invented using a transparent range concrete hardened with an unsaturated polyester resin to prevent warping of the molded product and cracks at the corners (Japanese Patent Publication No. 60-49426). Furthermore, a molded product made of range concrete in which a pattern layer and a gel coat layer are sequentially laminated on the surface side of the front side reinforcing layer has been devised (Japanese Utility Model Application Laid-Open No. 63-125530).

Problems to be Solved by the Invention Generally, in a plastic material using an unsaturated polyester resin, powders such as calcium carbonate, hydrated alumina, and clay are used as fillers to improve the performance and increase the amount of the filler, or It is known to use fine powder of silica, mica and the like. However, when an inorganic substance or metal having a certain size that is not powdery and is added as a filler for the purpose of providing a pattern or the like is not uniformly dispersed in the unsaturated polyester resin,
There was a problem that it settled and became inhomogeneous. On the other hand, if the filler is made too light, there is a problem that the filler floats on the illegal polyester resin. Furthermore, since the molded body cured by mixing a particulate substance as a filler into the unsaturated polyester resin has low mechanical strength such as tensile strength and bending strength, it is reinforced by some method and used for various practical purposes. It was necessary to be able to withstand the use. Further, it is a problem to provide a pattern or the like without deteriorating the aesthetic appearance in terms of design.

Means for Solving the Problems In consideration of the above problems, the present invention forms a surface layer by molding a reinforcing layer made of a transparent fiber reinforced plastic on the back surface of the transparent gel coat layer, and forms the surface layer. Form a back layer made of fiber reinforced plastic through the gap,
A molded article with a handle formed by injecting and curing a mixture of a liquid thermosetting resin and a colored particulate resin between the surface layer and the back layer.

In the above-described structure, when a particulate resin obtained by coating a resin with a color pigment or a particulate resin composed of a resin which is internally colored in advance is injected and cured, for example, when the particulate resin is dispersed in an unsaturated polyester resin, Can be substantially uniformly dispersed in the unsaturated polyester resin without settling. This is because the particulate resin used is composed of a resin, and is very close to the specific gravity of the unsaturated polyester resin.

Furthermore, by providing a reinforcing layer made of fiber reinforced plastic and a gel coat layer on the surface of the unsaturated polyester resin layer containing the particulate resin, and providing a reinforcing layer made of fiber reinforced plastic on the back surface, the molded article has a tensile strength,
It is possible to obtain a molded article having a laminated structure that has large mechanical strength such as bending strength and impact strength and is practically satisfactory.

On the other hand, by laminating a reinforcing layer composed of a transparent fiber-reinforced plastic and a gel coat layer composed of a transparent resin on the surface of the unsaturated polyester resin layer containing the particulate resin, the appearance of the particulate resin through these two layers is improved. Can be seen. Therefore, various designs can be realized depending on the color and shape of the particulate matter.

Embodiment FIG. 1 shows a partial cross-sectional view of a molded article having a laminated structure of the present invention. A resin layer 4 containing at least a particulate resin 3 obtained by coating a resin with a coloring pigment via a gel coat layer 1 and a reinforcing layer 2 made of a transparent fiber-reinforced plastic.
There is a structure in which a reinforcing layer 5 made of fiber reinforced plastic is further laminated on the back surface.

Phenol resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, furan resin, polyimide, polyethylene, polypropylene, ABS resin, acrylic resin, polyethylene terephthalate, polybutylene terephthalate, At least one of the group consisting of polycarbonate, polyethersulfone, polyetheretherketone, and the like can be used. Preferably, a resin having a heat distortion temperature of 150 ° C. or higher and relatively high heat resistance is preferably used. This is because the resin mixed with the particulate resin is cured, and it is necessary to avoid thermal deformation of the particulate resin due to a temperature rise at that time.

The particulate resin of the present invention refers to one containing at least a particle having a particle size of 0.5 mm or more, and preferably 80% of the particulate resin.
It means that the weight% or more is composed of particles of 0.5 mm or more. That is, even if the particulate resin contains fine particles of the same substance on the order of microns, it is within the scope of the particulate resin of the present invention. By using a particulate resin having a size of 0.5 mm or more, it is possible to visually judge that the resin is particulate and the design such as a pattern is increased, and various patterns can be produced. On the other hand, when the average particle diameter of the particulate resin exceeds 3 mm, it is not preferable because the production process such as mixing of the particulate resin with the unsaturated polyester resin and injection of the mixture is hindered.

A particulate resin in which a resin is coated with a coloring pigment can be obtained as follows. The resin is crushed by passing resin pellets of an arbitrary color through a predetermined mesh using a crusher such as a cut mill or a hammer mill. If necessary, by further classifying, a particulate resin composed of an uncolored resin can be obtained. These are coated with a thermosetting resin such as a polyurethane resin or an acrylic resin on the surface of the particulate resin using a pigment of a desired color. Its thickness is about 1 to 100 microns. If the thickness is less than 1 micron, the coloring is insufficient, and if it exceeds 100 microns, problems such as peeling occur. In the particles obtained by this method, the coloring pigment is strongly fixed only on the surface of the particles, and the inside remains as a non-colored resin.

In the case of a thermoplastic resin, the resin which has been internally colored in advance can be colored by a known rudder process. In the case of a thermosetting resin, a colorant can be mixed before curing and then cured to obtain a uniformly colored resin. The resin is pulverized by passing them through a predetermined mesh using a pulverizer such as a cut mill or a hammer mill, so that a particulate resin composed of a resin that is internally colored in advance can be obtained.

The reinforcing layer made of transparent fiber-reinforced plastic is made by applying a glass fiber coating or a non-woven fabric and impregnating the fiber with a transparent unsaturated polyester resin layer by hand lay-up method or spray-up method. is there.

The gel coat layer made of a transparent resin is made of a bisphenol-based or isophthalic acid-based unsaturated polyester resin having various properties such as hot water resistance by a spray-up method or the like. The transparency of the two layers on the surface of the unsaturated polyester resin layer means that the unsaturated polyester resin layer can be visually observed through these two layers. It is possible to color to such an extent that the properties are not lost.

The reinforcing layer made of fiber-reinforced plastic on the back surface is made of fiber-reinforced plastic in which glass fiber or the like is impregnated with an unsaturated polyester resin.

 Hereinafter, specific examples and comparative examples will be described.

Example 1 A gel coat resin composed of a bisphenol-based transparent unsaturated polyester resin was applied in a thickness of 0.5 mm. After that, a reinforcing layer made of a fiber-reinforced plastic consisting of a transparent unsaturated polyester resin layer with a glass fiber non-woven fabric is laminated by hand lay-up method (thickness 0.8 mm),
A surface layer was created. On the other hand, a reinforcing layer made of a fiber-reinforced plastic made of an iso-unsaturated polyester resin and glass fiber was formed as a back layer by a hand lay-up method. A mixture of the following ratios with respect to 100 parts by weight of the unsaturated polyester resin was injected into the middle of these front and back layers.

Black pigment coated urea resin 30 parts by weight (average particle diameter 1 mm) Uncolored white urea resin 10 parts by weight (average particle diameter 1 mm) Brown urea resin 10 parts by weight (average particle diameter 1 mm) Calcium carbide 100 parts by weight (average particle diameter 1 μm) After mixing these, a curing agent and a curing accelerator were added, and the mixture was poured into a mold and cured. When the particulate resin composed of the resin was dispersed in the unsaturated polyester resin, the particulate resin was substantially uniformly dispersed in the unsaturated polyester resin without settling (Table 1). By applying a reinforcing layer made of fiber-reinforced plastic and a gel coat layer on the surface of the unsaturated polyester resin layer containing the particulate resin made of resin, and providing a reinforcing layer made of fiber-reinforced plastic on the back surface, the tensile strength and A molded article having a laminated structure having high mechanical strength such as bending strength and satisfying practical conditions was obtained (Table 1). By laminating a reinforcing layer made of a transparent fiber reinforced plastic and a gel coat layer made of a transparent resin on the surface of an unsaturated polyester resin layer containing a particulate resin made of a resin, the appearance of the particulate matter is reduced through these two layers. The resin could be seen. Therefore, it was possible to realize a design pattern by the color and shape of the particulate resin (Table 1).

Example 2 A gel coat resin composed of an isophthalic acid-based unsaturated polyester resin was applied in a thickness of 0.3 mm. Thereafter, a reinforcing layer composed of a fiber-reinforced plastic composed of a transparent unsaturated polyester resin layer and mounted with a nonwoven fabric of glass fiber was laminated by a hand lay-up method (1.0 mm in thickness) to form a surface layer. On the other hand, a reinforcing layer made of a fiber-reinforced plastic made of an iso-unsaturated polyester resin and glass fiber was formed as a back layer by a hand lay-up method. A mixture of the following ratios with respect to 100 parts by weight of the unsaturated polyester resin was injected into the middle of these front and back layers.

Black pigment-coated unsaturated polyester resin 30 parts by weight (average particle diameter 1 mm) White pigment-coated unsaturated polyester resin 30 parts by weight (average particle diameter 1 mm) Brown pigment-coated unsaturated polyester resin 10 parts by weight (average particle diameter 1 mm) 100 parts by weight of aluminum (average particle size: 1 μm) Unsaturated polyester specific gravity: 1.5 After mixing these, a curing agent and a curing accelerator were added, and the mixture was poured into a mold and cured. The molded article having the laminated structure obtained in this way had the performance shown in Table 1 and was satisfactory.

Example 3 A gel coat resin composed of an isophthalic acid-based unsaturated polyester resin was applied to a thickness of 0.3 mm. Thereafter, a reinforcing layer composed of a fiber-reinforced plastic composed of a transparent unsaturated polyester resin layer and mounted with a nonwoven fabric of glass fiber was laminated by a hand lay-up method (1.0 mm in thickness) to form a surface layer. On the other hand, a reinforcing layer made of a fiber-reinforced plastic made of an iso-unsaturated polyester resin and glass fiber was formed as a back layer by a hand lay-up method. A mixture of the following ratios with respect to 100 parts by weight of the unsaturated polyester resin was injected into the middle of these front and back layers.

Black internally colored polyester resin 30 parts by weight (average particle diameter 1 mm) White internally colored polyester resin 30 parts by weight (average particle diameter 1 mm) Brown internally colored polyester resin 10 parts by weight (average particle diameter 1 mm) Aluminum hydroxide 100 parts by weight (average Polyester (polyethylene terephthalate) Specific gravity 1.5 After mixing these, a curing agent and a curing accelerator were added, and the mixture was poured into a mold and cured. The molded article having the laminated structure obtained in this way had the performance shown in Table 1 and was satisfactory.

Example 4 A gel coat resin was applied with a thickness of 0.5 mm from an isophthalic acid-based unsaturated polyester resin. Thereafter, a reinforcing layer made of a fiber-reinforced plastic made of a transparent unsaturated polyester resin layer and mounted with a nonwoven fabric of glass fiber was laminated (hand thickness: 0.8 mm) by a hand lay-up method to form a surface layer. On the other hand, a reinforcing layer made of a fiber-reinforced plastic made of an iso-based unsaturated polyester resin and glass fiber was formed as a back layer by a hand lay-up method. An unsaturated polyester resin is placed between the front and back layers.
What was mixed at the following ratio with respect to 100 parts by weight was injected.

Black internally colored acrylic resin 30 parts by weight (average particle diameter 1 mm) White internally colored acrylic resin 30 parts by weight (average particle diameter 1 mm) Brown internally colored acrylic resin 10 parts by weight (average particle diameter 1 mm) Aluminum hydroxide 100 parts by weight (average Acrylic resin specific gravity 1.5 After mixing these, a curing agent and a curing accelerator were added, and the mixture was poured into a mold and cured. The molded article having the laminated structure obtained in this way had the performance shown in Table 1 and was satisfactory.

Comparative Example 1 A gel coat resin composed of an isophthalic acid-based unsaturated polyester resin was applied in a thickness of 0.5 mm. Thereafter, a reinforcing layer made of a fiber reinforced plastic made of a transparent unsaturated polyester resin layer and mounted with a nonwoven fabric of glass fiber was laminated (hand thickness: 0.8 mm) by a hand lay-up method to form a surface layer. On the other hand, a reinforcing layer made of a fiber-reinforced plastic made of an iso-unsaturated polyester resin and glass fiber was formed as a back layer by a hand lay-up method. A mixture of the following ratios with respect to 100 parts by weight of the unsaturated polyester resin was injected into the middle of these front and back layers.

Natural black pebble 30 parts by weight (average particle diameter 1 mm) Natural white pebble 30 parts by weight (average particle diameter 1 mm) Natural brown pebble 10 parts by weight (average particle diameter 1 mm) Aluminum hydroxide 100 parts by weight (average particle diameter 1 μm) Natural pebble After mixing these, a curing agent and a curing accelerator were added, and the mixture was poured into a mold and cured. As shown in the following Table 1, pebbles settled in the thus obtained molded article having a laminated structure, and only a heterogeneous molded article was obtained.

Comparative Example 2 A laminate having no fiber-reinforced plastic layer on the back surface in Example 1 was produced.

Comparative Example 3 A laminate having no fiber-reinforced plastic layer on the surface in Example 1 was prepared.

Comparative Example 4 In Example 1, a laminate having no fiber-reinforced plastic layers on the back and front surfaces was prepared.

As shown in Table 2 below, Comparative Examples 2 to 4 had low mechanical strength and were not practically usable. On the other hand, Example 1
The laminate had sufficient mechanical strength and was durable for practical use.

Effect of the Invention As is clear from the description of the above-described embodiment, the present invention incorporates a particulate resin formed by coating a resin with a colored pigment or a particulate resin formed of a resin which is internally colored in a resin such as an unsaturated polyester. When dispersed, the particulate resin can be substantially uniformly dispersed in a resin such as an unsaturated polyester without settling. Further, by providing a reinforcing layer and a gel coat layer made of a fiber reinforced plastic on the surface of a resin layer such as an unsaturated polyester containing a particulate resin, and providing a reinforcing layer made of a fiber reinforced plastic on the back surface, a mechanically molded body is obtained. A molded product having a laminated structure with high strength and practically satisfactory can be obtained, and a reinforcing layer made of a transparent fiber-reinforced plastic and a transparent resin are formed on the surface of a resin layer such as an unsaturated polyester containing a particulate resin. By laminating with the gel coat layer, the particulate resin can be seen through these two layers in appearance, and the design can be improved.

[Brief description of the drawings]

FIG. 1 is a partial sectional view showing a laminated structure of a molded article of the present invention. 1 ... Gel coat layer, 2 ... Reinforcing layer made of transparent fiber reinforced plastic, 3 ... Particulate resin obtained by coating resin with colored pigment, 4 ... Unsaturated polyester resin layer, 5 ... Fiber Reinforcement layer made of reinforced plastic.

Claims (6)

(57) [Claims] 1. A surface layer is formed by forming a reinforcing layer made of a transparent fiber reinforced plastic on the back surface of a transparent gel coat layer, and a back layer made of a fiber reinforced plastic is formed through a gap between the surface layer and the surface layer. And a molded body obtained by injecting and hardening a mixture of a liquid resin and a colored particulate resin into a gap between the front surface layer and the back surface layer. 2. The molded article with a handle according to claim 1, wherein the particulate resin contains particles having a particle size of at least 0.5 mm or more. 3. The molded article with a handle according to claim 1, wherein 80% by weight or more of the particulate resin comprises particles of 0.5 mm or more. 4. A liquid resin mixed with a particulate resin is a phenol resin, urea resin, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, furan resin, polyimide, polyethylene, polypropylene, ABS resin, acrylic resin, 2. The molded article with a handle according to claim 1, comprising at least one of the group consisting of polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyether sulfone, and polyether ether ketone. 5. A resin to be injected and cured containing at least a particulate resin comprises an unsaturated polyester resin layer, and the surface of the unsaturated polyester resin layer comprises a reinforcing layer comprising a transparent fiber reinforced plastic and a transparent resin. A bathtub having a laminated structure, wherein the bathtub is constituted by a gel coat layer, and the back surface is constituted by a reinforcing layer made of fiber reinforced plastic. 6. An unsaturated polyester resin layer containing at least a particulate resin composed of a resin internally colored in advance.
The surface of the unsaturated polyester resin layer is composed of a reinforcing layer composed of a transparent fiber reinforced plastic and a gel coat layer composed of a transparent resin, and the back surface is composed of a reinforcing layer composed of a fiber reinforced plastic. A bathtub with a characteristic laminated structure.