JPH0852811A - Fiber reinforced resin molded body with gelcoat layer and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide the fiber reinforced resin molded body wherein smoothness of a surface is excellent, and the surface layer is free from peeling off. CONSTITUTION:A surface of fiber reinforced resin having urethane modified unsaturated polyester resin and/or urethane modified vinyl ester resin as a matrix is coated with a gelcoat layer consisting of unsaturated polyester and/or vinyl ester as main constituents.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber reinforced resin molded product and a method for producing the same, and more particularly to a fiber reinforced resin molded product having a gel coat layer on its surface and a method for producing the same.

[0002]

2. Description of the Related Art In order to finish the surface of a fiber reinforced resin molded article beautifully, conventionally, surface polishing and coating are performed. There are undercoat, middle coat, top coat, etc. for painting,
Intermediate polishing is performed if necessary. Polishing these,
The cost of painting is high. As another method for finishing the surface of the fiber reinforced molded article beautifully, after forming a gel coat layer on the surface of the mold, a fiber reinforced resin layer is formed by a hand layup method, a resin transfer molding (RTM) method or the like. There is a way.

[0003]

However, this method has a limited production rate. In addition, polyurethane, polyurea,
SRI using polyisocyanurate, epoxy resin, etc.
When the fiber reinforced resin layer is formed by the M method, the productivity is high, but there is a problem that the adhesiveness between the gel coat layer and the fiber reinforced resin layer is low.

[0004]

Means for Solving the Problems In view of such circumstances, the inventors of the present invention have made diligent studies, and as a result, after forming a gel coat layer, a urethane-modified unsaturated polyester resin or a urethane-modified vinyl ester resin was used. It has been found that by forming the fiber reinforced resin layer by the SRIM method, it is possible to obtain a fiber reinforced resin molded article having good adhesiveness with the gel coat layer and a beautiful surface finish at a high production rate, and completed the present invention. That is, according to the present invention, a gel coat layer whose main component is unsaturated polyester and / or vinyl ester is applied to the surface of a fiber-reinforced resin having a urethane-modified unsaturated polyester resin and / or urethane-modified vinyl ester resin as a base material. The present invention relates to a fiber reinforced molded article with a gel coat layer and a method for producing the same.

The present invention will be described in more detail below. The gel coat layer referred to in the present invention means corrosion resistance, weather resistance, hardness,
The term refers to a resin layer containing no fibers, which is attached to the surface of the fiber-reinforced resin for the purpose of improving surface characteristics such as appearance (smoothness, colored design). The resin composition used is mainly composed of unsaturated polyester and / or vinyl ester and a curing agent, and a colorant may be appropriately blended as necessary. For example, “Granuron” manufactured by Formica and the like are known as unsaturated polyester type. In addition, in the molded product of the present invention, a back coat layer may be appropriately provided between the gel coat layer and the fiber reinforced resin in consideration of thermal expansion coefficient and the like in order to improve adhesiveness, heat resistance and the like.

The fiber-reinforced resin referred to in the present invention is a resin reinforced with fibers, and the fiber is made of a material selected from inorganic and organic materials, for example, glass fiber, carbon fiber,
Alumina fiber, boron fiber, SiC fiber, aromatic polyamide fiber, polyester fiber and the like can be mentioned. The length of the fiber is not limited, but it is preferably long in order to increase the mechanical strength. As the form of the fiber reinforcing material, a mat, a woven fabric, or a combination thereof is usually used.

As the urethane-modified unsaturated polyester resin used in the present invention as the main component of the above-mentioned fiber-reinforced resin matrix resin, a styrene monomer is added to the unsaturated polyester polyol as the liquid A (for example, AJ International Chemical Company "AG
U-2000F "), and as the liquid B, a mixture of a diphenylmethane diisocyanate (MDI) prepolymer (for example," ISONATE143L "manufactured by Mitsubishi Kasei Dow Co., Ltd.) and a radical polymerization initiator (for example," Percure O "manufactured by NOF Corporation). Further, as the urethane-modified vinyl ester resin, a bisphenol A-type epoxy acrylate resin added with a styrene monomer as the liquid A (for example, "Neopol 8000" manufactured by Nippon Yupica Co., Ltd.), and a carbodiimide-modified diphenylmethane diisocyanate (MDI) prepolymer as the liquid B are used. (For example, Mitsubishi Kasei Dow "IS
ONATE112 ") and a radical polymerization initiator (for example, NOF Corporation" Perhexa 3M ").
Since the resin contains a urethane bond due to a reaction between an isocyanate group and an OH group, curing shrinkage is reduced and adhesion with the gel coat layer is good. The mixing ratio of these may be a known ratio according to a conventional method, and a collision mixing method is used as a mixing method.

Collision mixing in the present invention is a method of mixing liquid resins used in reaction injection molding (RIM), in which liquid resins separated into two liquids or three liquids are placed under high pressure through orifices arranged to face each other. It passes through the bottom and mixes instantly. This device is usually called a mixing head.

Next, a typical method for producing the fiber-reinforced molded article with the gel coat layer of the present invention will be described. Gel coat resin is sprayed onto the product side surface of the mold, dried and cured. Further, the back coat resin is sprayed, dried and cured. The gel coat layer has a thickness of 0.1 to 10 mm, preferably 0.5 to 2 mm, and the back coat layer has a thickness of 0.0.
It is preferably about 1 to 1 mm. Then, the fiber reinforcement is placed in the mold and the mold is closed.
As a solution A, a mixture of an unsaturated polyester polyol and / or a bisphenol A type epoxy acrylate resin and a styrene monomer, and as a solution B, a mixture of an isocyanate prepolymer and a radical polymerization initiator are collision-mixed at high speed and high pressure, and the inside of the mold And impregnate the fiber reinforcement. The temperature of the mold is 40 to 90 ° C. in the case of urethane-modified unsaturated polyester resin, preferably 50 to 8 ° C.
0 ° C, 80 for urethane-modified vinyl ester resin
~ 150 ° C, preferably 100-130 ° C.
After completion of the impregnation, it is preferable to increase the resin pressure before the resin is cured, since voids at the interface between the fiber-reinforced resin base material and the gel coat layer are reduced and the adhesion is improved. Resin pressure is 0.5 kg weight / cm ² or more, preferably 1 kg weight / cm
cm ² G or more is preferable. After curing, the mold can be opened to take out the molded body to which the gel coat layer is attached.

[0010]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to the examples as long as the gist thereof is not exceeded.

(Example 1) As the mold, a metal mold having a board surface of 300 mm in length and 300 mm in width and a cavity depth of 3 mm was used. A gate was provided at one end and a liquid reservoir was provided at the other end across the cavity. The mold temperature was maintained at 70 ° C. for both the upper mold and the lower mold. Fo for gel coat resin
"Granuron" manufactured by rmica was used. Further, a back coat resin was used. As the resin, as a liquid A, a styrene monomer was added to an unsaturated polyester polyol ("AGU-2000F" manufactured by AJ International Chemical Co., Ltd.), and as a liquid B, diphenylmethane diisocyanate (MDI) prepolymer ("Mitsubishi Chemical Dow" (ISONATE143L ”) and a radical polymerization initiator (NOF CORPORATION“ Percure O ”) were used. The mixing ratio of the liquid A and the liquid B was set to 77:23 by weight.
As the fiber reinforcing material, a glass fiber mat having a length of 295 mm, a width of 295 mm and a basis weight of 1800 g / m ² was used.

A gel coat resin was sprayed on the surface of the mold, and dried and cured in about 15 minutes. Further, the back coat resin was sprayed, and dried and cured in about 15 minutes. Place the above-mentioned glass mat in the above mold and set about 20 tons.
The mold was clamped with the mold clamping force of. The liquid resin was impinged and mixed under high pressure with an RIM injecting machine, injected into the mold, and impregnated into the fiber reinforcing material. Immediately after the injection was completed, pressurized air was introduced to adjust the pressure to 3 kg / cm ² G, and the value was kept constant until the curing was completed. Open the mold after curing is complete,
The molded body was taken out. The adhesiveness between the fiber-reinforced resin layer and the gel coat layer of the obtained molded product was good, and the surface shape was extremely smooth.

(Embodiment 2) As a die, the size of the board surface is 300 mm in length and 300 mm in width, and the depth of the cavity is 3
The one made of metal of mm was used. A gate was provided at one end and a liquid reservoir was provided at the other end across the cavity. Mold temperature is upper mold,
Both lower molds were kept at 100 ° C. For the gel coat resin, For
“Granuron” manufactured by Mica was used. Further, a back coat resin was used. As the resin, a bisphenol A type epoxy acrylate resin added with a styrene monomer as the liquid A (“Neopole 80” manufactured by Japan Yupica Co., Ltd.)
00 ”), and a mixture of a carbodiimide-modified diphenylmethane diisocyanate (MDI) prepolymer (“ ISONATE 112 ”manufactured by Mitsubishi Kasei Dow Co., Ltd.) and a radical polymerization initiator (“ Perhexa 3M ”manufactured by NOF CORPORATION) as the B liquid. The mixing ratio of the liquid A and the liquid B was 70:30 by weight. As a fiber reinforcement material, length 295 mm, width 295 mm
A glass fiber mat having a basis weight of 1800 g / m ² was used.

The surface of the mold was sprayed with a gel coat resin, dried and cured in about 10 minutes. Further, the back coat resin was sprayed, and dried and cured in about 10 minutes. Place the above-mentioned glass mat in the above mold and set about 20 tons.
The mold was clamped with the mold clamping force of. The liquid resin was impinged and mixed under high pressure with an RIM injecting machine, injected into the mold, and impregnated into the fiber reinforcing material. Immediately after the injection was completed, pressurized air was introduced to adjust the pressure to 3 kg / cm ² G, and the temperature was kept constant until the curing was completed. After the curing was completed, the mold was opened and the molded body was taken out. The adhesiveness between the fiber-reinforced resin layer and the gel coat layer of the obtained molded product was good, and the surface shape was extremely smooth.

[0015]

EFFECT OF THE INVENTION By using the fiber-reinforced resin molded product with the gel coat layer and the method for producing the same according to the present invention, a molded product having good adhesion between the fiber reinforced resin and the gel coat layer can be easily obtained.

Continuation of front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical display location // B29K 67:00 105: 08 B29L 9:00 (72) Inventor Manabu Fujitani Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa No. 1000 Sanryo Kasei Co., Ltd. Research Institute (72) Inventor Yasuhiro Omura 1-1-12 Ueno, Taito-ku, Tokyo Kodama Chemical Industry Co., Ltd.

Claims (3)

[Claims] 1. A gel coat layer whose main component is unsaturated polyester and / or vinyl ester is applied to the surface of a fiber-reinforced resin having a urethane-modified unsaturated polyester resin and / or urethane-modified vinyl ester resin as a base material. Fiber reinforced molding with gel coat layer. 2. A gel coat layer whose main component is unsaturated polyester and / or vinyl ester is formed on the surface of the mold and cured, and then a fiber reinforcing material is placed and the mold is closed. A method for producing a fiber-reinforced resin molding with a gel coat layer, which comprises injecting a curable liquid resin composed of a urethane-modified unsaturated polyester resin and / or a urethane-modified vinyl ester resin to cure the resin. 3. A curable liquid resin comprising a urethane-modified unsaturated polyester resin and / or a urethane-modified vinyl ester resin is separated into two or three components, which are mixed by collision mixing and poured into a mold. The method for producing a fiber-reinforced resin molded body with a gel coat layer according to claim 2, wherein the fiber-reinforced resin molded body is cured by curing.