JP2002254559A - Fiber-reinforced plastic moldings - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide fiber-reinforced plastic moldings with high surface smoothness and pattern depth. SOLUTION: The fiber-reinforced plastic moldings are structured of (A) a gel coat layer composed mainly of (a) a transparent resin, (B) an intermediate layer composed mainly of (b) a transparent resin and a scaly inorganic filler or a coloring material, (C) a fiber-reinforced layer composed mainly of (c) a transparent resin and a glass fiber and (D) a colored fiber-reinforced layer composed mainly of (d) a transparent resin, a glass fiber and a coloring material, laminated in that order from the surface side. The light transmissivity of the composite layer comprising the layer (A), (B) and (C) is 2% or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has an excellent surface design in which a resin layer of a transparent thermosetting resin having a smooth surface like a mirror surface is provided, and a layer below the surface layer appears to be raised. The present invention relates to a fiber-reinforced plastic molded product.

[0002]

2. Description of the Related Art A resin layer to which a decorative material is added or a colored resin layer as a pattern layer is disposed immediately below a transparent resin layer on the surface, and then the glass layer is reinforced to raise the pattern and color. A method for producing a fiber-reinforced plastic molded product is known (Japanese Patent Publication No. 2-49907).

However, in this method, since the resin layer on the surface is thickened as a result, cracks occur in the surface layer during use for a long time, and a glass fiber pattern emerges on the surface, resulting in a smooth surface. Function was sometimes impaired.

As a technique for solving such a problem, there is a method in which polymethyl methacrylate (PMMA), which is a transparent thermoplastic resin, is disposed on a surface layer, and a thermosetting resin, which is a pattern layer, is laminated on the back side. . However, in this method, if the adhesion between the PMMA and the thermosetting resin is not sufficiently considered, the interface between the PMMA and the thermosetting resin layer is peeled off during use for many years, and the function is impaired. Or
The glass fiber pattern included in the pattern layer sometimes appeared on the thin portion of PMMA.

In recent years, the surface smoothness, the designability (depth of the pattern, etc.), the durability against repeated cold and the like, etc.
Unprecedentedly high level characteristics are required, and it is becoming difficult for the above-mentioned conventional technology to meet such requirements.

[0006]

SUMMARY OF THE INVENTION In view of the above circumstances, the present invention is directed to a fiber having excellent surface design without showing any function deterioration due to a change in the mirror surface state with the lapse of time and allowing a layer below the surface layer to appear in a raised manner. It is intended to provide a reinforced plastic molded product.

[0007] The fiber-reinforced plastic molded article according to the present invention can be applied to fields requiring design properties such as bathtubs, bathroom units, wash counters, kitchen counters, signboards, wall materials, flooring materials and decorative boards.

[0008]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned objects, the present inventors have studied the structure of a fiber-reinforced plastic, including a resin layer for providing a pattern, and completed the following invention. Reached. [1] In order from the surface side, (A) a gel coat layer mainly composed of a transparent resin (a), (B) a transparent resin (b), and an intermediate layer mainly composed of a scaly inorganic filler or a coloring material, (C) A fiber reinforced plastic comprising: a transparent resin (c) and a fiber reinforced layer mainly composed of glass fiber; and (D) a transparent resin (d), a colored fiber reinforced layer mainly composed of glass fiber and a coloring material. Molding. [2] The fiber-reinforced plastic molded article according to [1], wherein the composite layer comprising the layers (A), (B) and (C) has a light transmittance of 2% or more. Molding. [3] The fiber-reinforced plastic molded product according to [2], wherein the composite layer has a light transmittance of 25% or more. [4] The fiber according to any one of [1] to [3], wherein the intermediate layer (B) or the fiber reinforced layer (C) further contains a decorating material. Reinforced plastic moldings. [5] The fiber-reinforced plastic molded product according to [4], wherein the decorating material is obtained by pulverizing a cured colored resin. [6] In the fiber-reinforced plastic molded article according to any one of [1] to [5], the thickness of the intermediate layer (B) is 0.2 to 2 mm, and the thickness of the fiber-reinforced layer (C) is 0.1 to 2 mm.
A fiber-reinforced plastic molded product having a size of 2 to 10 mm. [7] The fiber-reinforced plastic molded article according to any one of [1] to [6], further comprising: (D ′) transparent between the fiber-reinforced layer (C) and the colored fiber-reinforced layer (D). A fiber-reinforced plastic molded article comprising a colored layer mainly comprising a resin (d ') and a coloring material.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The transparent resin in the present invention means a transparent resin having a high light transmittance. The light transmittance is JI
KK means light transmittance measured by K7361-1, which allows light to pass through in the thickness direction of the cured resin body test piece, and determines the transmittance from the ratio of incident light to transmitted light. The transparent resin in the present invention preferably has a light transmittance of 70% or more when measured on a test piece having a thickness of 0.5 mm. Since the resin with low light transmittance reduces the amount of transmitted light when a decorative material or coloring material is added,
The effect of embossing the pattern may be reduced.

Specific examples of the transparent resin in the present invention include an unsaturated polyester resin, an epoxy resin, a vinyl ester resin, and an acrylic syrup in which a polymethyl methacrylate resin is dissolved in methyl methacrylate.

Unsaturated polyester resins include, for example, α, β dibasic acids such as maleic acid, maleic anhydride and fumaric acid, and optionally phthalic acid, isophthalic acid, terephthalic acid, adipic acid, tetrahydrophthalic anhydride and the like. Saturated dibasic acid and diethylene glycol, ethylene glycol, propylene glycol, 1,3-butanediol,
1,4-butanediol, 1,6-hexanediol,
A polymerizable monomer, for example, styrene, vinyltoluene, divinylbenzene, methyl methacrylate, ethylene glycol diester is added to an unsaturated polyester obtained by esterifying glycols such as neopentyl glycol and an ethylene oxide adduct of bisphenol A by an ordinary method. It can be mixed and dissolved with (meth) acrylic acid ester such as methacrylate. These polymerizable monomers may be used alone or as a mixture of several kinds. As the amount of the polymerizable monomer used,
60 to 15 with respect to 100 parts by mass of the unsaturated polyester
0 parts by mass.

The unsaturated polyester resin thus obtained can be cured by adding a curing agent and a curing accelerator. As the curing agent, for example, methyl ethyl ketone peroxide, acetylacetone peroxide, cumene hydroperoxide,
Organic peroxides such as t-butyl perbenzoate, t-butyl peroctoate, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t-hexyl peroxy-2-ethylhexanoate, etc. Is used. The amount of the curing agent used is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin. Examples of the curing accelerator include metal soaps such as cobalt naphthenate, manganese naphthenate, copper naphthenate, potassium naphthenate, calcium naphthenate, and cobalt octylate, dimethylaniline, N, N-dimethyltoluidine, N, N -Diethylaniline, N, N
Amines such as -di (hydroxy) -4-methylaniline, β-diketones such as acetylacetone, ethyl acetoacetate and N, N-dimethylacetamide, β-ketoesters, β-ketoamides, and oxides such as vanadium pentoxide. No. The amount of the curing accelerator used is 100
The amount is preferably 0.5 to 5 parts by mass with respect to parts by mass.

The epoxy resin has two epoxy groups in the molecule.
It is an epoxy compound containing two or more. There are bisphenol A type, bisphenol F type, novolak type and the like depending on the difference of the skeleton to which the epoxy group is bonded. Such an epoxy resin can be cured using an amine compound having an amino group in the molecule or a carboxylic acid compound having a carboxyl group in the molecule as a curing agent.

The vinyl ester resin is, for example, 1.0 to 0.9 with respect to 1 mole of epoxy group of the epoxy resin.
An unsaturated monobasic acid such as acrylic acid and methacrylic acid in a molar amount is subjected to an addition reaction by a conventional method, and a polymerizable monomer having a vinyl group such as styrene is diluted and mixed at 20 to 50% by mass. Such a vinyl ester resin can be cured by adding a curing agent and a curing accelerator similarly to the unsaturated polyester resin. As the curing agent and the curing accelerator, the same as the unsaturated polyester resin can be used.

An acrylic syrup in which a polymethyl methacrylate resin is dissolved in methyl methacrylate is one in which a polymethyl methacrylate resin is dissolved in methyl methacrylate and a radical polymerization catalyst is added in methyl methacrylate to cause a polymerization reaction. Some of the methacrylates are made to be polymethyl methacrylate, and the reaction is stopped when a certain amount of polymethyl methacrylate is produced, but any of them can be used. The amount of polymethyl methacrylate in methyl methacrylate is usually from 10 to 40% by mass. Such an acrylic syrup can be cured with benzoyl peroxide.

In the present invention, as the transparent resin constituting each of the layers (A) to (D), the same kind of resin or different kinds of resins may be used. The transparent resin that composes each layer is
In any case, it is desirable that the light transmittance is 70% or more. In particular, by increasing the transparency of the gel coat layer (A), the design property can be further enhanced. Conventional fiber-reinforced plastic molded articles usually include a coloring material or the like in a gel coat layer and have a colored and transparent appearance.
On the other hand, the present invention realizes a unique design by increasing the transparency of the gel coat layer (A). The gel coat layer (A) is preferably composed of only the transparent resin described above, but a small amount of a coloring material can be added to the transparent resin as long as the light transmittance of the gel coat layer (A) is not hindered.

The effect of embossing the pattern of the molded article of the present invention is as follows. The light rays entering the layers (A) to (C) are caused by the scaly inorganic filler added to the layers (B) and (C) and / or Or, the light beam reflected by the decorating material and reflected is (A) ~
Light that has passed through the layer (C) and returned to the surface of the molded article, while entering the colored fiber reinforced layer (D), is absorbed by the layer (D) and is achieved by the layer (D) having a dark background. You. The coloring material, the scaly inorganic filler, and the decorating material absorb light rays or do not transmit light rays. Therefore, when added in a large amount, they absorb or impede light rays and reduce the effect of embossing the pattern. For this reason, it is preferable that the light transmittance of the transparent resin is high,
For example, the light transmittance of each layer having a thickness of 0.5 mm is 50% or more, preferably 60% or more, and more preferably 70% or more. Further, it is desirable that the light transmittance of the composite layer obtained by integrally laminating the layers (A) to (C) is at least a certain level.
The light transmittance of the composite layer obtained by integrally laminating the layers (A) to (C) is preferably 2% or more, more preferably 25% or more,
Most preferably, it is 45% or more. In this case, (A),
The light transmittance of each of the layers (B) and (C) can be arbitrarily designed according to the combination, properties, type, amount of the coloring material, scaly inorganic filler, decorating material, etc. used in each layer. it can.

The scaly inorganic filler used in the present invention includes glass, mica, talc and the like. “Scaly” means, for example, that the average aspect ratio is 3
-8, thickness 1-10 μm, average particle size 100-30
It has a plate shape of 00 μm.

The amount of the scaly inorganic filler added is as follows:
5 to 40 parts by mass relative to 00 parts by mass is desirable. By setting the content in such a range, the effect of preventing shrinkage of the glass fiber can be sufficiently obtained, and the operability of spraying the resin layer or brushing can be well maintained.

The inorganic filler used in the present invention includes:
Examples include calcium carbonate, aluminum hydroxide, talc, clay, and silica powder. The inorganic filler is
Adding too much will reduce the light transmittance of the layer,
It is necessary to determine the limit of the amount of the inorganic filler to be used depending on the properties of the inorganic filler used. In general,
It is preferable to use the inorganic filler in an amount of 50 parts by mass or less based on 100 parts by mass of the transparent resin.

As the coloring material used in the present invention, both organic pigments and inorganic pigments can be used.

Examples of organic pigments include phthalocyanine blue, phthalocyanine green, permanent red, rhodamine lake, aniline black, anthraquinone,
Permanent yellow and the like can be exemplified.

Examples of the inorganic pigment include titanium oxide,
Examples include zinc white, lithopone, titanium yellow, cobalt blue, mineral violet, red iron oxide, yellow iron oxide, carbon black, iron black, and the like.

These pigments can be used as a paste toner by adding and kneading a plasticizer such as a phthalate ester, an unsaturated polyester resin or the like as a vehicle. The amount of the pigment is preferably 1 part by mass or less based on 100 parts by mass of the transparent resin. If the amount exceeds 1 part by mass, the transparency of the resin layer may be lost.

The glass fiber used in the present invention is used to reinforce a molded product, and may be in the form of a chopped strand mat, a chopped strand obtained by cutting a roving to a length of 1 to 3 inches, or a glass cloth. ,
A glass roving cloth, a fiber obtained by sewing a chopped strand mat and a glass roving cloth with polyethylene terephthalate fiber, and the like can be used.

In the present invention, the intermediate layer (B) and the fiber reinforced layer (C) may be configured to contain a decorative material. As decorative materials, pulverized colored unsaturated polyester resin, pulverized mixture of colored unsaturated polyester resin and inorganic filler, pulverized colored polyethylene terephthalate film, colored polyvinyl acetate film Pulverized product, colored mica pulverized product, pulverized product of inorganic or organic pigment insoluble in unsaturated polyester resin, and the like. The size of these decorative materials is usually 10 to 200 mesh, preferably 30 mesh.
１００100 mesh. Unwanted solid substances in the colored transparent resin are dispersed in the thickness direction of the fiber-reinforced plastic molded product due to differences in particle diameter, shape, and specific gravity between the thickness of the intermediate layer (B) and the fiber-reinforced layer (C). Therefore, a deep appearance which is not seen in the prior art can be obtained.

The fiber-reinforced plastic molded article of the present invention comprises:
It can be obtained by a hand lay-up molding method, a spray-up molding method, or the like.

An example of the hand lay-up molding method for obtaining the molded article of the present invention will be described below.

On a resin mold having a surface treated with a release agent, a resin for a gel coat layer prepared by adding a curing agent and a curing accelerator to an unsaturated polyester resin (transparent resin) and mixing well,
The gel coat layer (A) is formed by applying a uniform thickness on the mold surface with a spray gun for coating, or by uniformly applying and curing the mold surface with a brush. Next, a scaly inorganic filler, a coloring material and a decorating material were added to the unsaturated polyester resin (transparent resin) as necessary, and the mixture was uniformly dispersed by adding a curing agent and a curing accelerator. The resin for the intermediate layer is applied to the gel coat layer (A) with a coating spray gun to a uniform thickness, or the resin for the intermediate layer is evenly applied on the gel coat layer (A) with a brush and cured to cure the intermediate layer (B). ). Next, one layer of a glass fiber mat is placed on the intermediate layer (B), a decorating material is added to the unsaturated polyester resin (transparent resin) from above, and after uniformly dispersing, a curing agent and a curing accelerator are added. An operation of replacing the air present in the glass fiber mat with the resin for the fiber reinforced layer while applying the resin for the fiber reinforced layer prepared by mixing well with a roller, that is, so-called impregnation and defoaming, and the intermediate layer (B) Fiber reinforced layer on top (C)
To form If the thickness of the fiber reinforced layer is required according to the specifications of the molded product, the glass fiber mats are further stacked one by one and the operation of impregnation and defoaming is repeated to form the fiber reinforced layer (C). When the fiber reinforced layer (C) is cured, a glass fiber mat is placed on the fiber reinforced layer (C), and from there,
The colorant is uniformly dispersed in the unsaturated polyester resin (transparent resin), and a curing agent and a curing accelerator are added and mixed well. Is performed by replacing the air existing in the resin with the resin for the colored fiber reinforced layer, that is, performing so-called impregnation defoaming to form the colored fiber reinforced layer (D) on the fiber reinforced layer (C). If the thickness of the colored fiber reinforced layer is required depending on the specifications of the molded product, the work of impregnating and defoaming is repeated by further stacking glass fiber mats one by one. Further, if necessary, a coloring agent is uniformly dispersed in an unsaturated polyester resin (transparent resin) between the fiber reinforced layer (C) and the colored fiber reinforced layer (D), and a curing agent and a curing accelerator are further added. In addition, the coloring layer resin prepared by mixing well is applied on the fiber reinforced layer (C) to a uniform thickness by using a spray gun for coating, or the coloring layer resin is applied to the fiber reinforced layer (C) with a brush. In some cases, a colored layer (D ′) is formed by uniformly applying the composition on the substrate and curing it. When the colored fiber reinforced layer (D) is cured,
Is left in a curing furnace for 2 to 3 hours to perform post-curing. After the post-curing is completed, the resin mold is removed from the curing furnace, cooled to room temperature, and the molded article is removed from the mold to obtain the fiber-reinforced plastic molded article of the present invention.

The fiber-reinforced plastic molded article of the present invention can be molded by a spray-up molding method. The difference between the spray-up molding method and the hand lay-up molding method is that the fiber reinforced layer (C) and the colored fiber reinforced layer (D) are different. Only the method of formation is different. That is, in the spray-up molding method, while the hand lay-up method impregnates and defoams the glass fiber mat with a roller, using a spray-up molding machine, glass roving is continuously performed as glass fiber to 1-2 inches. While cutting, a curing agent and a curing accelerator are added to the unsaturated polyester resin (transparent resin), and a well-mixed resin liquid is sprayed at the same time to spray the cured resin layer on the mold. ) To form a layer.

The thickness of the gel coat layer (A) of the present invention is:
0.2 to 1.0 mm is desirable. When the thickness is 0.2 mm or more, the effect of lifting the pattern is sufficiently obtained, and a sense of depth is obtained. Further, by setting the thickness to 1.0 mm or less, the light transmittance is improved.

The intermediate layer (B) of the present invention has a thickness of 0.2 to 0.2.
2.0 mm is desirable. When the thickness is 0.2 mm or less, the effect of lifting the pattern can be sufficiently obtained. Also, 2.
By setting the thickness to 0 mm or less, the planarity of the flaky inorganic filler is improved, and a sufficient light transmittance is obtained.

[0033] The thickness of the fiber reinforced layer (C) of the present invention is 0.1.
2 to 10 mm is desirable. When the thickness is 0.2 mm or more, the effect of lifting the pattern can be sufficiently obtained. Also, 1
By setting the thickness to 0 mm or less, the light transmittance is improved.

The thickness of the colored fiber reinforced layer (D) or colored layer (D ') of the present invention is desirably 0.5 to 10 mm.
When the thickness is 0.5 mm or more, the reinforcing effect of the colored fiber reinforced layer (D) is sufficient. When the thickness is 10 mm or less, the curing shrinkage of the (D) or (D ′) layer can be suppressed, and as a result, the upper (A) to (C) layers can be formed by the layer (D) or the layer (D ′). ) Side, it is possible to prevent the unevenness of the surface of the layer (A) from being amplified and the flatness from being impaired.

[0035]

The present invention will be described in more detail with reference to the following examples.

Resin Synthesis Example 1 0.5 mol of isophthalic acid, 1.2 propylene glycol
The moles were reacted at 185 ° C. for 12 hours under a nitrogen stream by a conventional method to obtain a resin having an acid value of 8. After cooling this resin to 100 ° C., 0.5 mol of maleic anhydride was added, and the temperature was gradually raised under a nitrogen stream, and finally the reaction was carried out at 200 ° C. for 8 hours.
An unsaturated polyester having an acid value of 35 was obtained. The unsaturated polyester is cooled to 120 ° C., and 0.01 part by mass of hydroquinone is added to 100 parts by mass of the unsaturated polyester.
Styrene (70 parts by mass) was added and dissolved to obtain Resin 1.

Resin Synthesis Example 2 0.5 mol of maleic anhydride, 0.5 mol of phthalic anhydride,
Propylene glycol (0.8 mol) and diethylene glycol (0.2 mol) were subjected to a conventional method under a nitrogen stream at 195 to 205.
The mixture was reacted at 12 ° C. for 12 hours to obtain an unsaturated polyester having an acid value of 35. After cooling this unsaturated polyester to 120 ° C,
To 100 parts by mass of this unsaturated polyester, 0.01 part by mass of hydroquinone and 70 parts by mass of styrene were added and dissolved to obtain Resin 2.

(I) Measurement of light transmittance The transparent resin compound having the composition shown in Table 1 was uniformly stirred and mixed for 3 minutes, and then left under a vacuum of 1 mmHg or less for 2 minutes.
After completely removing air bubbles in the resin compound, the mixture was poured into a mold in which glass plates were opposed to each other to form a cured resin plate having a thickness of 0.5 mm. The light transmittance of this cured resin plate is J
It was measured according to IS K7361-1. Table 1 shows the results.

[0039]

[Table 1]

As shown in Table 1, the light transmittance of the transparent resin constituting each layer of the molded article of the present invention was 70% or more as shown in Resin Synthesis Examples 1 and 2.
The light transmittance of each layer can be controlled by adjusting the addition amount of the inorganic filler and the coloring material.

(Ii) Evaluation of Molded Article A molded article was prepared using Resin 1 and Resin 2 synthesized as described above and evaluated. The coloring material paste used for the molded product was adjusted as follows. First, 100 parts by mass of resin 1 was added to titanium white 98 as a coloring material.
Parts by mass and 2 parts by mass of phthalocyanine green (hereinafter sometimes referred to as PCG) are mixed with a stirrer. Thereafter, the mixture is passed through three rolls to uniformly disperse the pigment component to obtain the coloring material paste 1. When 100 parts by mass of the coloring material paste 1 is added, 50 parts by mass of the coloring material component is added.

Example 1 After a bathtub mold of type 1100 was treated with a release agent,
0.5 parts by mass of Esther EP430 (trade name) manufactured by Mitsui Chemicals, Inc., which is a light-colored cobalt-based accelerator, and 55% methyl ethyl ketone peroxide (hereinafter sometimes referred to as MEKP), which is a curing agent, are added to 0 parts by mass. Then, the mixture was stirred and uniformly dispersed, and then applied to a bathtub type with a spray coater to a thickness of 0.5 mm and cured to form a gel coat layer (A). After the gel coat layer (A) is dry to the touch, 100 parts by mass of the resin 1 has an average particle size of 45 to 300 μm.
20 parts by mass of glass flake RCF140A (trade name) manufactured by Nippon Sheet Glass Co., Ltd., in which the component of m accounts for 70%, 0.5 parts by mass of Ester EP430 (curing accelerator), and 1.0 parts by mass of MEKP as a curing agent. After the mixture was stirred and uniformly dispersed, the mixture was applied to a thickness of 0.5 mm on the gel coat layer (A) on the bathtub mold using a spray coater and cured to form an intermediate layer (B). Next, after the intermediate layer (B) is dried by touch, 100 parts by mass of the resin 1 is mixed with 0.5 parts by mass of Ester EP430 (curing accelerator) and MEKP 1.0 as a curing agent
After adding the parts by mass and stirring and uniformly dispersing, the glass fiber mat MC manufactured by Nitto Boseki Co., Ltd. is placed on the intermediate layer (B).
Using a resin adjusted to X360H2 (trade name), two plies of a glass fiber layer were manually laminated to a thickness of 1.6 mm to form a fiber reinforced layer (C).

Next, after the fiber reinforced layer (C) is cured, 20 parts by mass of the coloring material paste 1 is added to 100 parts by mass of the resin 2.
0.5 parts by mass of Esther EP430 (curing accelerator) and 1.0 part by mass of MEKP as a curing agent were added, stirred and uniformly dispersed, and then, on the fiber reinforced layer (C), Nitto Boseki Co., Ltd.
A glass fiber mat MCX360H (trade name) and a prepared resin were used to manually stack and laminate 4 ply glass fiber layers to a thickness of 3 mm to form a colored fiber reinforced layer (D). After the colored fiber reinforced layer (D) was cured, it was left in a curing oven at 60 ° C. for 3 hours, cooled to room temperature, and the bath was removed from the mold.

The gel coat layer (A) was subjected to a cold repetition test of 20 ° C for 4 hours, 70 ° C for 4 hours, and 20 times at 20 ° C. for 4 hours, at 70 ° C. for 4 hours. Was evaluated for its difficulty in generating abnormalities. Table 2 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 2.

Further, in the same manner as in the present embodiment (thickness of each layer is set in the same manner), a test of a composite layer in which the layers (A) to (C) are integrally laminated using a resin mold for flat plate molding is performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 2.

Example 2 A bath was formed and evaluated in the same manner as in Example 1 except that the amount of the glass flake RCF140A of the intermediate layer (B) was changed to 5 parts by mass. Table 2 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 2.

Further, in the same manner as in the present example (thickness of each layer is also set in the same manner), a test of a composite layer obtained by integrally laminating the layers (A) to (C) using a resin mold for flat plate molding is performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 2.

Example 3 A bath was formed and evaluated in the same manner as in Example 1 except that the glass flake RCF140A of the intermediate layer (B) was used in an amount of 40 parts by mass. Table 2 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 2.

Further, in the same manner as in the present example (thickness of each layer is also set in the same manner), a test of a composite layer obtained by integrally laminating the layers (A) to (C) using a resin mold for flat plate molding is performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 2.

Example 4 The glass flake RCF140A of the intermediate layer (B) was changed to 20 parts by mass of a glass flake RCF600A (trade name) manufactured by Nippon Sheet Glass Co., Ltd. in which a component having an average particle size of 150 to 1700 μm accounted for 80% or more. In the same manner as in Example 1, a bathtub was formed and evaluated. Table 2 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 2.

Further, in the same manner as in the present example (thickness of each layer is set in the same manner), a test of a composite layer in which the layers (A) to (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 2.

Example 5 The glass flake RCF140A of the intermediate layer (B) was treated with mica 1
Except for 5 parts by mass, a bathtub was formed in the same manner as in Example 1,
An evaluation was performed. Table 2 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 2.

Further, in the same manner as in the present embodiment (thickness of each layer is set in the same manner), a test of a composite layer obtained by integrally laminating the layers (A) to (C) using a resin mold for flat plate molding is performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 2.

Example 6 Example 2 was repeated except that 10 parts by mass of mica was added to the intermediate layer (B).
A bathtub was formed in the same manner as in Example 2 and evaluated. Table 3 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 3.

Further, in the same manner as in the present example (thickness of each layer was also set in the same manner), a test of a composite layer in which the layers (A) to (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 3.

Example 7 Example 1 was repeated except that the thickness of the intermediate layer (B) was 0.2 mm.
A bathtub was formed in the same manner as in Example 2 and evaluated. Table 3 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 3.

Further, in the same manner as in the present example (thickness of each layer is also set in the same manner), a test of a composite layer in which the layers (A) to (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 3.

Example 8 A bath was formed and evaluated in the same manner as in Example 1 except that the thickness of the intermediate layer (B) was changed to 1 mm. Table 3 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 3.

Further, in the same manner as in the present example (thickness of each layer is also set in the same manner), a test of a composite layer obtained by integrally laminating the layers (A) to (C) using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 3.

Example 9 A bath was formed and evaluated in the same manner as in Example 1 except that the thickness of the fiber reinforced layer (C) was changed to 0.8 mm. Table 3 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 3.

Further, in the same manner as in the present example (thickness of each layer was also set in the same manner), a test of a composite layer in which layers (A) to (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 3.

Example 10 A bath was formed and evaluated in the same manner as in Example 1 except that the thickness of the fiber reinforced layer (C) was 4.8 mm. Table 3 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 3.

Further, in the same manner as in the present example (thickness of each layer was also set in the same manner), a test of a composite layer in which the layers (A) to (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 3.

Example 11 Between the fiber reinforced layer (C) and the colored fiber layer (D), 100 parts by weight of the resin 2, 20 parts by weight of the coloring material paste, and 0.5 parts by weight of Esther EP430 (curing accelerator) Parts, MEKP (1.0 parts by mass) as a curing agent, was added thereto, stirred, uniformly dispersed, and then applied to the layer (C) to a thickness of 0.5 mm with a spray coater and cured to form a colored layer (D ′). A bathtub was formed and evaluated in the same manner as in Example 1 except for the formation. Table 4 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 4.

Further, in the same manner as in the present example (thickness of each layer is also set in the same manner), a test of a composite layer in which the layers (A) to (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 4.

Example 12 A bath was formed and evaluated in the same manner as in Example 1, except that 0.2 parts by mass of the coloring material paste 1 was added to the gel coat layer (A). Table 4 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 4.

Further, in the same manner as in the present example (thickness of each layer is set in the same manner), a test of a composite layer in which the layers (A) to (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 4.

Example 13 A bath was formed and evaluated in the same manner as in Example 1 except that 0.4 parts by mass of the coloring material paste 1 was added to the gel coat layer (A). Table 4 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 4.

Further, in the same manner as in the present example (thickness of each layer is also set in the same manner), a test of a composite layer obtained by integrally laminating layers (A) to (C) using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 4.

Example 14 Ester EP was added to an unsaturated polyester resin colored white.
430 (curing accelerator) 0.5 parts by mass, ME as a curing agent
2 parts by mass of a 30-mesh white solid substance obtained by adding 1.0 part by mass of KP and curing the cured product, 5 parts by mass of a 100-mesh black solid substance obtained by crushing black colored polyethylene terephthalate, and Then, 3 parts by mass of a 70-mesh tea solid substance obtained by pulverizing a cured unsaturated polyester resin colored into tea are added and stirred, and a uniformly dispersed resin liquid is applied to the fiber-reinforced layer on the intermediate layer (B). A bathtub was formed and evaluated in the same manner as in Example 1 except that the bathtub was used to form (C). Table 4 shows the contents of each layer and the evaluation results.

In the same manner as in this example, test pieces of each layer (A), (B) and (C) were molded using a resin mold for flat plate molding. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361-1.
And the results are shown in Table 4.

Further, in the same manner as in the present example (thickness of each layer is set in the same manner), a test of a composite layer in which the layers (A) to (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K736.
The measurement was performed according to 1-1, and the results are shown in Table 4.

In each of Examples 1 to 14, molded articles excellent in surface smoothness, pattern depth, and durability against repeated cold and heat were obtained.

[0087] After the bath type of Comparative Example 1 1100 type processing release agent, 10 of the resin 1
20 parts by mass of the coloring material paste 1, 0.5 parts by mass of Ester EP430 (curing accelerator), and 1.0 parts by mass of MEKP as a curing agent were added to 0 parts by mass, and the mixture was stirred and uniformly dispersed. Was applied to a bathtub mold to a thickness of 0.5 mm and cured to form a gel coat layer (A). After the gel coat layer (A) is cured, 0.5 parts by mass of Esther EP430 (curing accelerator) and 1.0 parts by mass of MEKP as a curing agent are added to 100 parts by mass of the resin 2, and the mixture is stirred and uniformly dispersed. On the gel coat layer (A), glass fiber mat MCX360H (trade name) manufactured by Nitto Boseki Co., Ltd. and 4 ply of glass fiber layers were manually laminated by adjusting the resin to a thickness of 3 mm to form a colored fiber reinforced layer. (D) was formed. After the colored fiber reinforced layer (D) was cured, it was left in a curing oven at 60 ° C. for 3 hours, cooled to room temperature, and the bath was removed from the mold. In the bathtub,
The surface smoothness was determined by the sharpness of the straight line of the fluorescent lamp, and the depth of the pattern was visually observed.
The gel coat layer (A) was evaluated for its difficulty in abnormal occurrence by repeated cold and heat tests. Table 5 shows the contents and evaluation results of each layer. Since this had no intermediate layer (B) and fiber reinforced layer (C), it had poor surface smoothness and no pattern depth.

In the same manner as in this comparative example, a test piece of the (A) layer having a thickness of 0.5 mm was molded using a resin mold for flat plate molding. The light transmittance of this test piece was measured according to JIS K7.
The measurement was carried out according to 361-1, and the results are shown in Table 5.

COMPARATIVE EXAMPLE 2 Instead of the gel coat layer (A), a 3 mm-thick polymethyl methacrylate (PMMA) plate was formed into a shape similar to the 1100 type by vacuum forming, and placed on the 1100 type. 100 parts by mass of resin 2 and 20 of colorant paste 1
Parts by mass, 0.5 parts by mass of Esther EP430 (curing accelerator), and 1.0 part by mass of MEKP as a curing agent, and stirred,
After being uniformly dispersed, a glass fiber mat MCX360H (trade name) manufactured by Nitto Boseki Co., Ltd. is placed on a PMMA plate.
4 ply glass fiber layer by 3 mm
To form a colored fiber reinforced layer (D). After the colored fiber reinforced layer (D) was cured, it was left in a curing oven at 60 ° C. for 3 hours, cooled to room temperature, and the bath was removed from the mold.

The obtained molded product was evaluated in the same manner as in Example 1. Table 5 shows the contents and evaluation results of each layer.
This one had good surface smoothness and a deep pattern depth despite the absence of the intermediate layer (B) and the fiber reinforced layer (C), but had poor durability against repeated cold and heat.

Further, (A)
A layer test piece is molded and one side is precision polished to a thickness of 0.5 m.
m. The light transmittance of this test piece was determined by JI
The measurement was performed according to SK7361-1, and the results are shown in Table 5.

Further, in the same manner as in this comparative example,
A test piece of the (A) layer was formed. The light transmittance of this test piece was measured according to JIS K7361-1, and the results are shown in Table 5.

Comparative Example 3 After the bathtub mold of type 1100 was treated with a release agent,
0 parts by mass of Ester EP430 (curing accelerator) 0.5
After adding 1.0 parts by mass of MEKP as a curing agent and stirring, the mixture is uniformly dispersed, and then applied to a bathtub type with a spray coater to a thickness of 0.5 mm and cured to form a gel coat layer (A). . After the gel coat layer (A) is cured, 0.5 parts by mass of Ester EP430 (curing accelerator) and 1.0 parts by mass of MEKP as a curing agent are added to 100 parts by mass of the resin 1, and the mixture is stirred and uniformly dispersed. On the gel coat layer (A), weighing 100 g / g from Dainippon Gravure Co., Ltd.
Two plies were manually laminated to a thickness of 1.6 mm with a resin prepared from m ² polyester nonwoven fabric Granit Black (trade name) to form a fiber reinforced layer (C). After the fiber reinforced layer (C) is cured, 20 parts by mass of the coloring material paste 1, 0.5 parts by mass of Ester EP430 (curing accelerator), 100 parts by mass of the resin 2,
After adding the parts by mass and stirring and uniformly dispersing, the glass fiber mat M manufactured by Nitto Boseki Co., Ltd. is placed on the fiber reinforced layer (C).
Using a resin adjusted to CX360H (trade name), four plies of a glass fiber layer were manually laminated to a thickness of 3 mm to form a colored fiber reinforced layer (D). After the colored fiber reinforced layer (D) was cured, it was left in a curing oven at 60 ° C. for 3 hours, cooled to room temperature, and the bathtub was removed from the mold. Evaluation was performed in the same manner as in Example 1. Table 5 shows the contents and evaluation results of each layer. This one has an insufficient depth of pattern because there is no intermediate layer (B),
In addition, since the reinforcing material of the fiber reinforced layer (C) is a nonwoven fabric,
The surface smoothness was poor, and the durability against repeated cold and heat was not good.

Further, test pieces of each layer (A) and (C) were molded using a resin mold for flat plate molding in exactly the same manner as in this comparative example. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm.
The light transmittance of this test piece was measured according to JIS K7361-1, and the results are shown in Table 5.

Further, in the same manner as in the present comparative example (thickness of each layer was also set in the same manner), a test of a composite layer in which layers (A) and (C) were integrally laminated using a resin mold for flat plate molding was performed. A piece was molded. The light transmittance of this test piece was measured according to JIS K7.
The measurement was carried out according to 361-1, and the results are shown in Table 5.

Comparative Example 4 When forming the intermediate layer (B), the amount of glass flake RCF140A (trade name) manufactured by Nippon Sheet Glass was 20
A bath was formed and evaluated in the same manner as in Example 1 except that the mass was changed from 50 parts by mass to 50 parts by mass. Table 5 shows the contents and evaluation results of each layer.

In the same manner as in this comparative example, (A), (B) and (C) were obtained using a resin mold for flat plate molding.
A test piece for each layer was formed. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361.
-1 and the results are shown in Table 5.

Further, the layers (A), (B) and (C) were integrally laminated in the same manner as in this comparative example (thickness of each layer was also set in the same manner) using a resin mold for flat plate molding. A test piece of the composite layer was formed. The light transmittance of this test piece was determined by JI
Measured according to S K7361-1, and the results are shown in Table 5.

Comparative Example 5 When forming the intermediate layer (B), the process was carried out except that 60 parts by mass of calcium carbonate was used instead of using 20 parts by mass of glass flake RCF140A (trade name) manufactured by Nippon Sheet Glass Co., Ltd. A bathtub was formed and evaluated in the same manner as in Example 1. Table 5 shows the contents and evaluation results of each layer.

Further, in the same manner as in the present comparative example, (A), (B) and (C) were obtained using a resin mold for flat plate molding.
A test piece for each layer was formed. If necessary, the surface not in contact with the resin mold was precision polished and processed into a test piece having a thickness of 0.5 mm. The light transmittance of this test piece was measured according to JIS K7361.
-1 and the results are shown in Table 5.

Further, the layers (A), (B) and (C) were integrally laminated using a resin mold for flat plate molding (thickness of each layer was also set) in exactly the same manner as in this comparative example. A test piece of the composite layer was formed. The light transmittance of this test piece is J
The measurement was performed according to IS K7361-1, and the results were shown in Table 6.
It was shown to.

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

[Table 5]

[0106]

As described above, according to the present invention, a beautiful fiber-reinforced plastic molded article having excellent surface smoothness, a deep pattern, and durability against repeated cold and heat can be obtained.

Continuing from the front page (72) Inventor Yoichi Hara 580-32 Nagaura, Sodegaura-shi, Chiba Mitsui Chemicals, Inc. (72) Inventor Yoshitaka Ito 23 Iwatsubo, Takaoka-shi, Toyama 3 Alps Chemical Co., Ltd. (72) Inventor Hideyuki Matsui 23 Alps Chemical Co., Ltd. at 23 Iwatsubo, Takaoka City, Toyama Prefecture (72) Inventor Hashi Satoshi 23 Alps Chemical Co., Ltd. at 23 Iwatsubo, Takaoka City, Toyama Prefecture F-term (reference) 4F072 AA02 AA04 AA07 AB09 AB28 AB29 AD09 AD23 AD28 AD38 AF06 AK12 AK13 AL01 AL06 AL09 AL17 4F100 AA00B AG00C AG00D AK01A AK01B AK01C AK01D AK01E AK44 BA04 BA05 BA07 BA10A BA10D CA02 CA13B00 H08 DE02 CA13D CA13D CA13E CAB JK15 JL00 JL10B JL10C JL10E JN01A JN01B JN01C JN01D JN01E JN08 JN08A JN08B JN08C YY00A YY00B YY00C

Claims (7)

[Claims] 1. A transparent resin (a) in order from the surface side
A gel coat layer mainly composed of (B) a transparent resin (b), and an intermediate layer mainly composed of a flaky inorganic filler or coloring material; (C) a fiber reinforced layer mainly composed of a transparent resin (c) and glass fiber; D) A fiber-reinforced plastic molded article characterized by being laminated with a transparent resin (d), a colored fiber-reinforced layer mainly composed of glass fiber and a coloring material. 2. The fiber-reinforced plastic molded article according to claim 1, wherein the composite layer comprising the layers (A), (B) and (C) has a light transmittance of 2% or more. Reinforced plastic moldings. 3. The fiber-reinforced plastic molded product according to claim 2, wherein the composite layer has a light transmittance of 25% or more. 4. The fiber according to claim 1, wherein the intermediate layer (B) or the fiber reinforced layer (C) further contains a decorating material. Reinforced plastic moldings. 5. The fiber-reinforced plastic molded product according to claim 4, wherein the decorating material is obtained by pulverizing a cured colored resin. 6. The fiber-reinforced plastic molded article according to claim 1, wherein said intermediate layer (B) has a thickness of 0.2 to 2 mm, and said fiber-reinforced layer (C) has a thickness of 0.1 to 2 mm. A fiber-reinforced plastic molded product having a size of 2 to 10 mm. 7. The fiber-reinforced plastic molded article according to claim 1, wherein said fiber-reinforced layer (C)
And between the colored fiber reinforced layer (D) and
(D ′) A fiber-reinforced plastic molded article comprising a colored layer mainly composed of a transparent resin (d ′) and a coloring material.