JP2507658B2 - Thermosetting synthetic resin laminated molding - Google Patents

Description

TECHNICAL FIELD The present invention relates to a thermosetting synthetic resin laminate molded body having a laminated structure which can be used as a material for bathtubs, bathroom wall materials, counters, waterproof pans and the like. It is a thing.

(Prior Art) Conventionally, a fiber reinforced plastic using an unsaturated polyester resin has been used for bathtubs, ships, tanks and the like.
These have been used merely for the purpose of increasing the mechanical strength, and in recent years, a laminated structure using fiber reinforced plastic has been studied for designing for various uses such as aesthetics. For example, there has been proposed a laminated structure for preventing warpage of a molded body and cracks at the corners of the bend by using a transparent resin concrete solidified with an unsaturated polyester resin (Japanese Patent Publication No. 60-49426). In addition, a mica layer is provided on the surface layer for coloring (Japanese Patent Publication No. Sho 61-25542).
No. 25543) and a molded body made of resin concrete in which a pattern layer and a gel coat layer are sequentially laminated on the surface side of a surface side reinforcing layer (Shokai Sho 63-125530).

(Problems to be Solved by the Invention) However, in the case of attaching a pattern pattern having an excellent surface design property like the latter, it is necessary to add an inorganic substance or metal having a certain size that is not powder as a filler. However, there is a problem in that the filler does not disperse uniformly in the unsaturated polyester resin but precipitates and becomes heterogeneous. On the other hand, if the weight of the filler is too light, there is a problem that the filler floats on the unsaturated polyester resin. Therefore,
In the synthetic resin molded body, how to impart an excellent pattern or the like without impairing the appearance is an issue.

(Means for Solving the Problems) In order to solve the above problems, the present inventors have earnestly studied, and as a result, formed a synthetic resin molded body as a laminate, and 1) seeing through the surface of the first layer and the second layer. The layer thickness is adjusted to be a possible layer, and then 2) the size of the colored pieces mixed in the first layer and the second layer is adjusted from small to large, and 3) the first layer and the second layer. Adjust the mixing ratio of colored pieces from small to large,
More preferably, a colored layer serving as a colored bottom is introduced below the colored piece-mixed layer of 4), and 5) the thickness is provided between the upper mold having at least the first layer and the lower mold having at least the lowermost layer. It was found that the formation of an intermediate layer with a pattern creates a centrifugal feeling in a patterned pattern, a deep color pattern is formed, and a synthetic resin molded article with an excellent aesthetic appearance can be constructed, and the present invention has been completed. On the side, a transparent first resin layer, in which 100 parts by weight of a transparent resin or a light blue resin is mixed with 0.05 to 1 parts by weight of colored pieces having a particle size of 0.02 to 1.0 mm, and a transparent resin is continuously formed on the first layer. Alternatively, 100 parts by weight of the light colored resin has a larger grain size and mixing ratio than the first layer, and the grain size is 0.5 to 5 mm.
While having a transparent second layer having a layer thickness greater than that of the first layer mixed with 0.5 to 20 parts by weight of colored pieces selected from the range
A laminated body having a non-transparent reinforcing layer on the back surface side,
Thermosetting, characterized in that it is produced by cast molding the second layer as an intermediate layer between the first layer formed on one mold and the back surface reinforcing layer formed on the other mold. Synthetic resin laminated molding.

In the present invention, the surface first layer is usually a gel coat layer (a thin synthetic resin layer that forms the surface of the product by mixing colored pieces in a transparent resin, is transparent or almost transparent, and is made of only a normal resin, and is a filler. Is not mixed in.) To give the product gloss, heat resistance, stain resistance, water resistance, and scratch resistance.

As the transparent resin, an unsaturated polyester resin, particularly a bisphenol-based or isophthalic acid-based unsaturated polyester resin having various performances such as hot water conventionally used depending on the application may be used. The colored pieces may be those that form a pattern or pattern by being mixed with a transparent resin or a light colored resin, and usually have a size (about 0.02 to 5.0 mm) where particles can be visually confirmed,
Foil-shaped, needle-shaped, and granular shapes are adopted, and they have some strength and heat resistance, and have the physical properties that the specific gravity is close to that of matrix resin. For example, scale-like mica powder is coated with titanium dioxide or iron oxide. The pearl pigment, pearl grace, saturated polyester film, crushed thermosetting plastic molded product, etc. can be used.

The second layer is a compound layer with a pattern in which the colored pieces are mixed in a transparent resin (a layer containing a large amount of filler for the purpose of providing strength, forming a considerably thick layer, opaque or slightly transmitting light). Is adjusted as. As the transparent resin, an unsaturated polyester resin may be used similarly to the surface layer.
The same material as that for the surface layer can be used for the colored piece, but it is particularly preferable to use a colored organic filler as the colored piece. As this kind of filler, thermosetting resin, such as phenol resin, urea resin, alkyd resin, epoxy resin, furan resin, polyimide resin, or the like, or thermoplastic resin, such as polyethylene resin, polypropylene resin, ABS resin,
Acrylic resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin,
Polyethersulfone resin, polyetherketone resin,
Although a polyimide resin or the like can be used, it is preferable to use a resin having a heat distortion temperature of 150 ° C. or higher and relatively high heat resistance. This is to avoid thermal deformation during curing of the transparent resin as the matrix.

The grain size and the mixing ratio are adjusted to be larger than those of the surface layer. For example, the grain size is preferably 0.02 to 1.0 mm for the surface layer, while the second layer is preferably 0.5 to 5 mm. That is, the grain size of the second layer is 5 with respect to the surface layer.
It should be about 30 times different.

The mixing ratio of 100 parts by weight of the transparent resin is preferably 0.05 to 1 part for the surface layer, while the second layer is
Suitably 0.5 to 20 parts. That is, the mixing ratio of the second layer and the second layer is preferably 10 to 20 times that of the surface layer, and when the difference in particle size is large, the mixing ratio does not have to be so large.

The second layer preferably contains not only the colored pieces but also a transparent or semitransparent filler. As the filler, glass frit, aluminum hydroxide, or the like can be used.

The back reinforcing layer is usually formed from a fiber reinforced plastic obtained by impregnating an unsaturated polyester resin into glass fiber or the like, but is not limited to such a reinforcing layer, and other reinforcing layers, for example, a heat containing no fibers. Curable resin,
Wood, metal plates, etc. may be used.

Therefore, in the present invention, in particular, the first layer is a gel coat layer, the second layer is a compound layer containing the colored pieces and a transparent or translucent filler, and the back reinforcing layer is a colored fiber reinforced plastic. The present invention is intended to provide a thermosetting synthetic resin laminated molding which is a layer.

Further, this intermediate layer has a gel coat layer containing a colored piece having a larger particle size and / or a larger mixing ratio than the above-mentioned surface layer as a second layer, and a colored or translucent compound layer containing no colored piece is formed by casting. You may comprise.

A colored layer is preferably formed below the second layer into which the colored pieces are mixed, and when the semitransparent compound layer is used, it is preferable to color the back surface reinforcing layer.

That is, the present invention, on the surface side, in 100 parts by weight of a transparent or pale colored resin, particle size 0.02 ~ 1.0 mm colored pieces 0.05 ~
A transparent first layer containing 1 part by weight, and 100 parts by weight of a transparent or light colored resin in succession to the first layer have a larger particle size and a larger mixing ratio than the first layer.
A laminate having a transparent second layer having a layer thickness greater than that of the first layer mixed with 0.5 to 20 parts by weight of colored pieces selected from the range of 0.5 to 5 mm, while having a non-transparent reinforcing layer on the back surface side. The first and second layers are gel coat layers, and the first layer and the second layer are laminated and formed on one mold, while the back surface reinforcing layer is formed on the other mold, and a gel coat layer is formed between them. The present invention provides a thermosetting synthetic resin laminate molded article, which is produced by casting a colored or translucent compound layer as an intermediate layer.

As above, the embodiment of the present invention includes the following modes.

1. Small pattern G / large pattern G / colored C / FRP 2. Small pattern G / large pattern G / translucent C / colored FRP 3. Small pattern G / large pattern C / colored FRP where G is the gel coat layer, C is compound layer, FR
P means fiber reinforced plastic.

(Advantageous Effects of the Invention) According to the present invention, a transparent intermediate layer in which a colored piece having a particle size and a mixing ratio larger than this is mixed in a lower layer of a surface layer in which transparent foil is mixed with foil-shaped or granular colored pieces. Since it is formed, a sense of perspective is created and a deep color pattern can be created. In particular, it is manufactured by forming at least the first layer on one mold while forming the back surface reinforcing layer on the other mold, and casting the intermediate layer between them to give a predetermined thickness. And, through the transparent first and second layers, the colored pieces that become larger can be seen in sequence, and since the colored pieces that are lower than that can back up the colored pieces, a pattern with a deep pattern can be seen. Can be realized.

Further, since the grain size and / or the mixing ratio can be changed, it is easy to manufacture various design patterns.

 Hereinafter, examples according to the present invention will be described in detail.

(Example 1) Transparent unsaturated polyester resin (gel coat resin) 10
To 0 part by weight, 0.2 parts by weight of a pearl pigment (average diameter 20 to 30 microns) obtained by coloring the fine mica powder with titanium oxide was added and uniformly dispersed by stirring. A predetermined amount of a curing agent (Perkadox 16) and a curing accelerator (NLF-10) was added to this, and uniformly applied to the upper mold by a spray-up method to a thickness of 0.4 mm to form a surface layer.

On the other hand, on the lower mold, a backside reinforcing layer made of ortho-based unsaturated polyester resin containing a large amount of white pigment and glass fiber (containing 30% by weight) was laminated by hand lay-up method to a thickness of 0.8 mm.

Here, fit the upper mold and the lower mold with a gap of about 10 mm,
100 parts by weight of iso-unsaturated polyester resin, 200 parts by weight of glass frit, 10 parts by weight of colored pieces (white spherical unsaturated polyester resin (average particle size 1 mm)) and a predetermined amount of curing agent and curing accelerator are mixed. Then, the mixture was injected and cured to form a casting intermediate layer.

The above-mentioned synthetic resin laminate molding (see FIG. 1) has an appearance that allows colored pieces contained in the intermediate layer to be visually observed through a layer having a pearly feeling, and a patterned molded article having a very deep feeling can be obtained. did it. Further, the appearance differs from the above depending on the angle at which it is visually observed, so that a molded article with a very high-grade feeling is obtained.

In addition, by using the colored pieces, they were uniformly dispersed in the casting layer. This is probably because the density of the colored pieces was 1.5, which was close to that of the rest of the mixture (1.8), so there was no sedimentation or floating.

(Example 2) Upper mold coating thickness is 0.3 mm, lower mold unsaturated polyester resin is ortho-based, coating thickness is 1.0 mm, distance between upper mold and lower mold is 8 mm, colored pieces are scale-like unsaturated Polyester resin (average diameter 1m
A synthetic resin laminated body was produced in the same manner as in Example 1 except that m) was used. The appearance was the same as in Example 1 except that the colored pieces were in a scaly state.

(Example 3) Surface layer Clear gel coat layer 100 parts Pearl pigment (titanium oxide-coated mica foil, particle size 20 to 20)
0μ, coverage 14%: silver color 0.2 parts Resin powder (multi-layered film of saturated polyester and acrylic resin in flake shape of 0.1 to 5 mm: rainbow color) 0.05 to 0.07 parts Curing agent and accelerator prescribed amount Note Mold intermediate layer Unsaturated polyester resin 100 parts Filler (glass frit or aluminum hydroxide) 180 parts Resin powder (saturated polyester film 12μ, diameter 0.5mm
10 parts glass fiber (diameter 10μ, length 0.15 mm) 4 parts, colorant (white, brown, lavender, etc.) 0.1 part Other than using specified curing agent, curing accelerator and UV absorber A synthetic resin laminated body was manufactured in the same manner as in Example 1.

Example 4 A surface gel coat layer having the following composition for the upper mold, second
A gel coat layer is laminated to form a casting intermediate layer (coloring compound layer) below between the upper mold and the lower mold.

Surface gel coat layer Clear gel coat layer (same as Example 3) 100 parts Pearl pigment (same as Example 3) 0.2 parts Resin powder (same as Example 1) 0.1 part Curing agent and accelerator Predetermined amount Second gel coat layer Clear gel coat Layer (same as in Example 3) 100 parts Resin powder (saturated polyester film thickness 12μ, diameter approximately
0.5 mm, colored with white pigment) 1 part Curing agent and accelerator Predetermined amount Casting intermediate layer Unsaturated polyester resin 100 parts Filler (same as Example 3) 180 parts Colorant (same as Example 3) 0.1 parts Predetermined A synthetic resin laminated body is manufactured in the same manner as in Example 1 except that the curing agent, the curing accelerator and the ultraviolet absorber are used to obtain the structure shown in FIG.

The structure shown in Fig. 2 has a layer with higher transparency (two gel coats) than the structure shown in Fig. 1, and the depth is increased by changing the particle size of the first layer and the second layer. It is possible to express it sensitively. (1) It is easy to give a stone tone closer to natural stone. (2) It is easier to give a sense of luxury.

[Brief description of drawings]

FIG. 1 is a partial sectional view of a three-layer laminated molded body according to the present invention, and FIG. 2 is a partial sectional view of a four-layer laminated molded body according to the present invention. 1 ... surface gel coat layer, 1 '... second gel coat layer,
2 …… Cast compound layer, 3 …… Backside reinforcing layer, 4 ……
Fine mica powder, 5 ... Colored pieces

Claims (3)

(57) [Claims] 1. A transparent resin or a pale colored resin 10 on the surface side.
A transparent first layer, in which 0 to 1 part by weight of 0.05 to 1 part by weight of colored pieces having a particle size of 0.02 to 1.0 mm are mixed, and 100 parts by weight of a transparent resin or a pale colored resin, continuously to the first layer, The grain size and mixing ratio are larger than those of the first layer, and the grain size is
A laminate having a transparent second layer having a layer thickness greater than that of the first layer mixed with 0.5 to 20 parts by weight of colored pieces selected from the range of 0.5 to 5 mm, while having a non-transparent reinforcing layer on the back surface side. And is manufactured by casting the second layer as an intermediate layer between the first layer formed in one mold and the back surface reinforcing layer formed in the other mold. And a thermosetting synthetic resin laminated molded body. 2. The first layer is a gel coat layer, the second layer is a compound layer containing the colored pieces and a transparent or translucent filler, and the back reinforcing layer is a colored fiber reinforced plastic layer. The thermosetting synthetic resin laminate molding according to claim 1. 3. A transparent first layer in which 100 parts by weight of a transparent or light colored resin is mixed with 0.05 to 1 part by weight of colored pieces having a particle size of 0.02 to 1.0 mm, and the first layer is continuous with the transparent layer. do it,
100 parts by weight of a transparent or pale colored resin has a larger grain size and mixing ratio than the first layer, and a grain size of 0.5 to 5 mm.
While having a transparent second layer having a layer thickness greater than that of the first layer mixed with 0.5 to 20 parts by weight of colored pieces selected from the range
A laminated body having a non-transparent reinforcing layer on the back surface side,
The first and second layers are gel coat layers, and the first layer and the second layer are laminated and formed on one mold, while the backside reinforcing layer is formed on the other mold, and an intermediate layer is colored between them. Alternatively, a thermosetting synthetic resin laminate molding is produced by casting a semitransparent compound layer.