JPH06297651A - Patterned semi-cured sheet and patterned frp molded product - Google Patents

Abstract

PURPOSE:To provide a patterned semi-cured sheet which allows the efficient manufacture of an FRP molded product with a pattern on the surface, and free from the generation of cracks due to the unevenness of a mold surface, with a satisfactory outer appearance when the sheet is molded in one piece with a thermally curable molding material. CONSTITUTION:The patterned semi-cured sheet consists of a thermally curable resin composition layer 2 containing a thickner and an organic peroxide, a woven cloth layer or an non-woven fabric layer 3 and a patterned semi-cured thermosetting resin layer 4. The patterned FRP molded product uses this sheet.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an F having a pattern on its surface.
The present invention relates to a patterned semi-cured sheet used for an RP molded product and a patterned FRP molded product using the same.

[0002]

2. Description of the Related Art As a method for producing an FRP molded product having a pattern on its surface, (A) a method of laminating a woven fabric or a non-woven fabric printed with a pattern on a surface mold, (B) masking the surface mold, As shown in (C) Japanese Patent Publication No. 3-47183, a method of spraying a gel coat resin, further removing the masking, placing a molding material on a mold, and integrally molding it.
On the uncured transparent resin placed in a block on one end of the mold surface,
Press the end side of the pattern printing surface of the transfer film, stretch the resin evenly on the transfer film with a roller, cure the resin, peel off the transfer film to transfer the pattern, then the transparent resin layer, colored There is known a method of producing a patterned glass fiber reinforced plastic product by laminating an opaque layer and a resin reinforcing layer containing glass fiber.

[0003]

The above method (A) is
In addition to the lamination work on the molding die, and in the method (B), since the gel coat resin is directly applied on the molding die, the productivity is reduced due to the longer occupancy time of the mold, and the work time for the masking work is reduced. In the case of the heating type, further, it was not a preferable manufacturing method because the environment was deteriorated due to long-time working in the vicinity of a high temperature type. In addition, application of the gel coat resin provided only a monotonous pattern such as a monotone or multicolor blow or a stone tone due to the inclusion of particles. Next, (C) Japanese Patent Fairness 3
In the method disclosed in Japanese Patent Publication No. 471873, since a pattern is formed by transfer, the pattern is not limited to wood grain, stone tone, abstract pattern, etc., and printing is precise, and a more accurate pattern can be obtained. In order to peel off and transfer the pattern onto the surface resin, it is necessary to cure the surface resin and the work time on the molding die becomes long, so a high cycle such as press molding using a heating die is required. It could not be used as a patterning method in some cases.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention provide a method of forming a pattern portion as a sheet in advance in the method (C), integrally forming it with SMC or BMC, and simultaneously performing curing and patterning. It is a thing. According to the present invention, the FRP having a high design property can be freely patterned.
A molded product is obtained. On the other hand, in the case of products whose appearance is enhanced due to the unevenness of the surface of the molded product as at present, a pattern sheet having a function of following the unevenness is required at the time of integral molding, but the present invention integrally molds the pattern sheet with SMC or BMC. The present invention provides a pattern sheet that follows the surface irregularities of a mold and does not cause cracks or sheet breakage, and an FRP molded product using the pattern sheet.

[0005]

The present invention is directed to a thermosetting resin composition layer containing a thickener and an organic peroxide, a woven or non-woven layer, and a semi-cured thermosetting resin patterned on the surface. The present invention relates to a patterned semi-cured sheet having layers and an FRP molded article using the same.

The patterned semi-cured sheet according to the present invention is manufactured as shown in FIG. That is, the base film 1
On which a thermosetting resin composition 2 containing a thickener and an organic peroxide is placed, on which a woven or non-woven fabric 3 is placed, and further on which an organic peroxide and a chain transfer agent are included A transfer film 6 having a pattern 5 on the surface is placed on the thermosetting resin composition 4, and the roller 7 or the like is used to press and stretch the transfer film 6 in one direction to form a woven or non-woven fabric of the resin composition. Impregnation and defoaming are performed simultaneously to form a sheet. After heating, thickening and curing this, the base film 1 and the transfer film 6 are peeled off to obtain a semi-cured sheet having a patterned surface.

Although the thermosetting resin used in the present invention is not limited, transparent or translucent unsaturated polyester resin, vinyl ester resin, acrylic resin and the like are used.

As the thickener, metal oxides or isocyanates such as magnesium oxide, diphenylmethane diisocyanate and hexamethylene diisocyanate are used, and the amount thereof is not limited.

As the organic peroxide, peroxyketals, dialkyl peroxides, diacyl peroxides and peroxyesters are used and can be selected according to the heating temperature. The amount of the organic peroxide to be added is not limited, but is 0.5 to 2.
0% by weight is preferred.

The woven or non-woven fabric used as the reinforcing material includes paper, organic fibers such as polyester and acrylic,
Inorganic fibers such as glass are used. These may be used alone or in combination.

As the thermosetting resin used in the semi-cured thermosetting resin layer having a pattern on the surface, a transparent or semi-transparent unsaturated polyester resin may be a vinyl ester resin, an acrylic resin or the like. To be In order to bring the thermosetting resin into a semi-cured state, use a combination of the compounding amount of a chain transfer agent such as 4-methyl-2,4diphenylpentene (α-methylstyrene dimer) and an organic peroxide and the heating temperature. You can The type and blending amount of the organic peroxide used are the same as those of the thermosetting resin composition layer. A semi-cured thermosetting resin layer is obtained by curing in the presence of a chain transfer agent.

The transfer film for transferring the pattern is not particularly limited as long as it has heat resistance and releasability and is insoluble in the above-mentioned thermosetting resin, but polyethylene resin, polypropylene resin, nylon, polyester resin , A plastic film such as a fluororesin, a metal foil such as an aluminum foil alone or laminated with another film, or a paper or a plastic film coated with a releasable resin is used. The thickness of the film is 10 to 100 in order to uniformly stretch the block-shaped thermosetting resin.
It is preferably about μm. The ink to be patterned needs to be soluble in the above thermosetting resin, but it is a mixture of unsaturated polyester resin, acrylic resin, nitrified cotton (nitrocellulose) resin, etc., with pigments and dyes. Are preferred. The base film is not particularly limited as long as it has heat resistance and peelability and is insoluble in the thermosetting resin, and the same material as the transfer film can be used.

A surface mold 10 in which a semi-cured sheet with a pattern is cut into a desired shape on the surface and a release agent is applied with the patterned surface facing a thermosetting fiber-reinforced molding material as shown in FIG.
The thermosetting fiber reinforced molding material 9 such as SMC or BMC is placed on the predetermined position in an overlapping manner, pressed and heat-molded, and the molding material is cured and the semi-cured resin sheet is cured at the same time to be integrated, The FRP molded product 12 has a pattern on its surface. 11 is a back surface type.

[0014]

EXAMPLES Examples of the present invention will be described below. As shown in FIG. 1, 100 parts by weight of an unsaturated polyester resin (Polyset 3715: manufactured by Hitachi Chemical Co., Ltd.) is attached to one surface of a base film 1 made of a polyester film having a thickness of 50 μm.
Perbutyl I (Nippon Yushi Co., Ltd., peroxyester)
A resin composition 2 in which 1.0 part by weight and 2.0 parts by weight of magnesium oxide are mixed is placed, and as a reinforcing material, a polyester non-woven fabric having a basis weight of 45 g / m ² (trade name of Unitika Ltd. 2
0451FLV) 3, and further, at one end thereof, polyset 3715100 parts by weight with 1.0 part by weight of Perloyl TCP (trade name of NOF CORPORATION) as a curing agent and 4-methyl-2 as a chain transfer agent in advance. Thermosetting resin 4 to which 0.5 part by weight of 4 diphenylpentene-1 (α-methylstyrene dimer) (trade name, NOFMER MSD, manufactured by NOF CORPORATION) was added was placed in a lump. on the other hand,
A transfer film 6 made of a polyester film having a thickness of 50 μm was prepared, in which one surface was patterned with an ink soluble in the thermosetting resin to form a granite pattern layer 5. The end side of the patterning surface of the transfer film 6 is pressed against the block-shaped thermosetting resin 4, and then the transfer film 6 is placed on the roller 7
By the base film 1, polyester fiber non-woven fabric 3
The thermosetting resins 2 and 4 in a lump form were uniformly stretched by pressing from one end of the resin, and at the same time, the polyester fiber non-woven fabric 3 was impregnated and the polymerization of the resin was allowed to proceed for 60 minutes in a curing oven maintained at 70 ° C. The polymerization was stopped at the curing degree (reaction rate of styrene monomer) of 80% by the action of the previously added chain transfer agent, and the first-stage curing was completed. Then, when the transfer film 6 was peeled off, a patterned semi-cured sheet 8 in which a granite pattern layer 5 was transferred to the surface of the semi-cured thermosetting resin 4 was formed. Semi-cured sheet with pattern 8 on base film
Had no surface tackiness and had a wall thickness of 0.45 mm and was excellent in handleability. After the base film 1 is peeled off and the patterned semi-cured resin sheet 8 is cut into 800 mm × 1100 mm, the patterned layer 5 is placed on the surface mold 10 as shown in FIG. SMC as the elastic fiber reinforced molding material 9 is laid on the semi-cured sheet 8 and the back surface mold 11 is tightened and pressed (100 kg / cm ² ) and heated (front surface mold 150 ° C., back surface mold 145 ° C.). Molded. The semi-cured sheet 8 was completely cured and integrated with the SMC as the SMC flowed and cured in the molding die, and the second stage curing was completed. The molded product was taken out of the mold to obtain an FRP molded product 12 shown in FIG. 2 having a granite pattern on the surface. The thus-obtained FRP molded product was free of defects that follow the irregularities on the surface of the surface mold and were not easily cracked at the irregular corners.

[0015]

EFFECTS OF THE INVENTION The patterned semi-cured sheet of the present invention can be stored in the semi-cured state for a certain period of time, so that an FRP molded product having a pattern on its surface can be efficiently produced. In addition, the degree of curing of this semi-cured sheet is adjusted by the action of the chain transfer agent, the surface is not sticky, and handling is easy,
It has the flexibility and strength to withstand press molding in the production of molded products, can be integrated with molding materials, and when molded integrally with thermosetting molding materials, it does not cause cracks due to unevenness of the mold surface and is good. It is possible to obtain an FRP molded product having a different appearance.

[Brief description of drawings]

FIG. 1 is a diagram showing a method for producing a patterned semi-cured sheet in an example of the present invention.

FIG. 2 is a diagram showing a method of manufacturing a patterned FRP molded product in an example of the present invention and a cross section of the obtained patterned FRP molded product.

[Explanation of symbols]

 1 Base Film 2 Thermosetting Resin Composition 3 Woven or Nonwoven Fabric 4 Thermosetting Resin Composition 5 Pattern 6 Transfer Film 7 Roller 8 Semi-Cured Sheet 9 Molding Material 10 Surface Mold 11 Backside Mold 12 FRP Molded Product

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoichi Kuwana 1010 Ippongki, Toyama City, Toyama Prefecture Within Hitachi Chemical Unit Co., Ltd.

Claims (2)

[Claims] 1. A patterned semi-cured sheet comprising a thermosetting resin composition layer containing a thickener and an organic peroxide, a woven or non-woven fabric layer, and a semi-cured thermosetting resin layer patterned on the surface. . 2. The semi-cured sheet with a pattern according to claim 1,
A patterned FRP molded product obtained by integrally molding the patterned surface of the thermosetting fiber-reinforced molding material toward the thermosetting fiber-reinforced molding material.