JPH1170622A - Fiber reinforced plastic molded product and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the adhesion of a molded object and a decorative sheet and to apply sharp and fine printing. SOLUTION: A decorative sheet 1 wherein a biaxially stretched polyester resin layer and an ABS resin layer are successively laminated is prepared and an uncured compsn. 2 is superposed on the ABS resin layer of the decorative sheet 1 and both of them are heated and pressed within a mold consisting of upper and lower molds to be integrated mutually. By using the biaxially stretched polyester resin layer, the sheet itself does not generate deformation, flow, breakage or the like even with respect to heat at the time of molding or stress by the flowability of SMC and a printing pattern layer is protected from the flow of SMC or a styrene monomer by the lined ABS resin layer and made to be properly compatibe with FRP to develop strong adhesion.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an SMC (Seet m
olding compound), BMC (Bulk molding compoun
d) Fiber reinforced plastic (FRP)
= Fiber Reinforced Plastic) This relates to a molded product and a method for producing the same.

[0002]

Conventionally, as a method for producing a patterned fiber reinforced plastic (FRP) molded article, a method of simultaneously forming and integrating titanium paper, nonwoven fabric, cloth, impregnated paper, etc. JP-A-48-12876 and JP-A-51-20951) are known, but in this method, clear printing cannot be performed, tearing tends to occur, and the shape is limited due to lack of moldability. ,
There is a drawback that adhesion is largely varied due to molding conditions such as temperature and pressure due to the physical anchoring effect.

Further, as disclosed in Japanese Patent Application Laid-Open No. 7-60911, a nonwoven fabric is lined with a two-component curable urethane resin adhesive on a printed plastic sheet having a melting temperature not lower than the FRP molding temperature. Although a method of integrating the sheets during molding is also adopted, this method has a problem that the backing process is complicated and the quality of the nonwoven fabric is unstable due to uneven formation and the cost is high. there were.

Another method is disclosed in Japanese Patent Application Laid-Open No. 56-729.
As disclosed in JP-A No. 30 and the like, a plastic sheet or printing ink which has good adhesiveness to the SMC resin, that is, melts or softens at the temperature at the time of SMC molding or swells and dissolves with the components of the SMC is used. A method is also known in which the decorative sheet is integrated at the time of molding. However, this method has a problem in that the printed layer is caused to flow due to heat at the time of thermosetting of the SMC or stress at the time of flowing, thereby causing a defect.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has as its object to provide high flexibility and strength at the time of heating and pressurization, good moldability, good molding and decoration. It is an object of the present invention to provide a fiber-reinforced plastic molded article having good adhesion to a sheet and capable of performing clear and delicate printing, and a method for producing the same.

[0006]

In order to achieve the above-mentioned object, a fiber-reinforced plastic molded article of the present invention comprises an ABS formed on the surface of a molded article made of a cured thermosetting resin reinforced with a fibrous reinforcing material. (Acrylonitrile-butadiene-styrene copolymer) A resin layer, and a biaxially stretched polyester resin layer is sequentially laminated and integrated on the resin layer in this order.

The above fiber-reinforced plastic molded article has
A decorative sheet in which an axially stretched polyester resin layer and an ABS resin layer are sequentially laminated is prepared, and SMC or BMC or the like is contacted with the decorative sheet (hereinafter, also simply referred to as “sheet”) in contact with the ABS resin layer side. It is manufactured by laminating FRP raw materials (or intermediates), heating and pressing in a mold to integrate them.

As described above, in the present invention, by using the biaxially stretched polyester resin layer, the sheet itself may be deformed, flowed, broken, or the like against heat generated during molding or stress caused by the fluidity of the SMC. In addition, the printed pattern layer is protected from the flow of SMC and styrene monomer by the backed ABS resin layer, the sheet is given appropriate moldability, and it is compatible with FRP appropriately and expresses strong adhesion. can do.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a biaxially stretched polyester resin layer, a polyester sheet formed in advance is used. This sheet has transparency, tensile strength, heat resistance, dimensional stability,
Excellent printability, stain resistance and solvent resistance. Although a thickness of 10 to 200 μm can be used, it is preferably about 20 to 100 μm. If it is too thin, the strength and the sense of depth are reduced, and if it is too thick, printability, moldability, and cost are poor. Typical examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate isophthalate copolymer, polyethylene naphthalate, and polyarylate.

ABS (acrylonitrile butadiene)
As the (styrene copolymer) resin layer, those generally manufactured as a sheet are used. This is relatively inexpensive. FRP (mainly unsaturated polyester resin)
It melts and adheres to the styrene monomer in it due to the heat pressure during molding, and can be compatiblely bonded. At the same time, it prevents the styrene monomer in the FRP from reaching the decoration layer and flowing the decoration layer. Although a thickness of 10 to 500 μm can be used, it is preferably about 50 to 200 μm. If it is too thin, it melts during molding and cannot protect the printed layer. If the thickness is too large, the warpage of the molded product increases and the cost increases. A
The moldability of the entire decorative sheet is improved by appropriate thermal deformation of the BS resin layer.

In the biaxially stretched polyester resin layer, if necessary, benzotriazole, benzophenone,
An ultraviolet absorber such as fine cerium oxide and a light stabilizer such as a hindered amine radical scavenger may be added. 0.1 to 5% by weight of UV absorber and light stabilizer
It is about. Further, a coloring agent such as a dye or a pigment may be added to the biaxially stretched polyester resin layer as needed as long as the transparency is not lost.

The thermosetting resin which is a component of FRP includes unsaturated polyester resin, vinyl ester resin,
Examples include diallyl phthalate resin, thermosetting acrylic resin, melamine resin, guanamine resin, phenol resin, epoxy resin, and two-component curable polyurethane resin.

In order to form a molded article from these thermosetting resins, first, a monomer or prepolymer (including oligomers) of these resins is added with a crosslinking agent, a polymerization initiator, or a reaction accelerating catalyst. First, an uncured composition is prepared by adding a fibrous reinforcing material such as a short fiber, a woven fabric or a nonwoven fabric and other various additives as required. This uncured composition, ie, F
Examples of the form of the raw material or intermediate of RP include the form of SMC or BMC.

Then, as shown in FIG. 1A, the decorative sheet 1 and the uncured composition 2 are inserted into a molding die (upper die 11 and lower die 12) having a predetermined shape in a superposed manner. As shown in (b), the mold is closed, heated and pressurized, and the uncured composition 2 is cross-linked or polymerized and cured to form a solid molded article 3 and, at the same time, the decorative sheet 1 is placed on the surface of the molded article 3. By bonding and integrating, a decorative material as shown in FIG. 1 (c) is obtained. At that time, in the ABS resin in the decorative sheet 1,
The unreacted components (monomer and the like) in the FRP raw materials or intermediates penetrate and enhance the adhesive strength between the decorative sheet 1 and the molded article 3.

The SMC, which is a typical form of the uncured composition, will be described in detail. The material of the SMC is a fibrous reinforcing agent such as glass fiber, carbon fiber, asbestos, and potassium titanate, a catalyst, a filler, and a release agent. And the like. The thermosetting resin used is typically a prepolymer of an unsaturated polyester resin. As the fibrous reinforcing agent, glass fiber short fibers are usually used. The content of this glass fiber is usually 10 to 70% by weight. Powders such as calcium carbonate, barium sulfate, and aluminum hydroxide are used as the filler. As a release agent, zinc stearate or the like is used. In addition, if necessary, a reaction diluent such as a styrene monomer, a polyfunctional acrylate (or methacrylate) monomer, a crosslinking agent such as an isocyanate or an amine,
Polymerization initiators (curing catalysts) such as benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl perpenzoate, and organic sulfonates; curing accelerating catalysts such as cobalt naphthenate and manganese naphthenate; titanium dioxide, carbon black, red iron oxide, etc. Is added.

The decoration treatment applied to the sheet on which the biaxially stretched polyester resin layer and the ABS resin layer are laminated is performed by the following method.
An axially stretched polyester resin layer, one or both of the ABS resin layer itself can be kneaded with a coloring agent such as a dye or pigment, but generally, gravure printing, silk screen printing, etc. The print pattern is a wood grain pattern, a stone grain pattern, a cloth grain pattern, a character, a geometric pattern, a solid pattern, or the like. F
If it is necessary to hide the RP molded product, use the picture FRP
On the (SMC) side, a solid layer is entirely provided, and a pigment having high concealing properties, such as titanium dioxide and carbon black, is added to the solid layer. The printing ink comprises various pigments (or dyes) and a binder resin. The binder is appropriately selected from two-component curable urethane resins, acrylic resins, polyester resins, vinyl chloride-vinyl acetate copolymers, cellulose resins, polyvinyl butyral resins, and the like.
As a decoration process, a metal thin film of aluminum, chromium, or the like may be formed by vapor deposition, sputtering, or the like. In this case, the metal thin film may be in the entire surface or in a pattern. The printed pattern layer or metal thin film applied as a decoration process may be applied to the front surface or the back surface (thermosetting resin side) of the ABS resin layer as long as the entire decoration sheet is transparent. If necessary, the surface of the resin layer (sheet) on which printing is to be performed may be previously subjected to an easy-adhesion treatment such as a corona discharge treatment, a plasma treatment, and an easy-adhesion primer coating treatment.

If necessary, a protective layer made of a synthetic resin may be further formed on the surface of the decorative sheet. This protective layer is transparent (colorless or colored) so that the decorative layer can be seen through
Choose the right one. As a resin, a thermoplastic resin is used when emphasis is placed on moldability, and a curable resin such as a thermosetting resin or an ionizing radiation curable resin is used when emphasizing physical properties such as surface scratch resistance and chemical resistance. Is used. The thickness may be appropriately determined according to the required performance, and is usually about 1 to 100 μm. The above-mentioned resin is used as the thermoplastic resin. However, when used for the protective layer, the reactive component may not be added. As the thermosetting resin, two-component curing type polyurethane resin, epoxy resin, unsaturated polyester resin, etc.,
Representative examples of the ionizing radiation-curable resin include polyfunctional unsaturated (meth) acrylate monomers or prepolymers. In addition, as the ionizing radiation, an ultraviolet ray or an electron beam is usually used. In order to improve the weather resistance, an ultraviolet absorber and / or a light stabilizer as described above is added to the protective layer.

The fiber-reinforced plastic molded article of the present invention is used for interior materials such as walls, floors and ceilings of buildings, bathtubs, and the like.
Examples include household equipment such as wash basins and kitchen utensils, fittings such as window frames and doors, interior materials for vehicles such as vehicles and ships, containers, and cabinets for home electric appliances.

[0019]

【Example】

(Example) A decorative sheet was produced as follows. That is, a biaxially stretched polyethylene terephthalate sheet (diamond “T-100”, 25 μm thick) is coated with an ink using a two-component curable polyurethane resin composed of hexamethylene diisocyanate and acrylic polyol as a binder (“NL- manufactured by The Inktec”). After forming a decorative layer by printing a marble-like marble stone pattern by gravure printing using ALFA), a two-component curable polyurethane resin adhesive (“E-295” manufactured by Dainichi Seika Kogyo Co., Ltd.) is applied to the printed surface. ) Using a colored ABS sheet (“A402” manufactured by Sanbo Resin, 30μ)
m) was dry-laminated.

The decorative sheet is overlaid so that the ABS surface is in contact with an SMC (manufactured by Takeda Pharmaceutical Co., Ltd.) composed of an unsaturated polyester resin and glass fibers, and these are placed in a molding die. , Molding pressure 100k
The SMC was heated and pressurized at gf / cm ² for 5 minutes to cure the SMC, and the two were bonded and integrated. As a result, a bathroom wall panel of a high design was obtained. There was no defect such as tearing of the decorative sheet, and the adhesiveness and moldability between the molded article and the decorative sheet were good. Further, when an attempt was made to peel the decorative sheet, no peeling occurred at the interface between the sheet and the molded article.

Comparative Example 1 DAP-impregnated paper (basis weight 100 g)
/ M ² titanium paper impregnated with diallyl phthalate prepolymer) to produce a decorative sheet having the same pattern printing as in the example, and using this decorative sheet, simultaneously molding with SMC as in example 1 did. In the molded product, the decorative sheet was torn and the pattern distortion was partially generated.

(Comparative Example 2) A decorative sheet having the structure of a polymethyl methacrylate-based acrylic resin sheet / the same printed layer as in the example / a semi-rigid polyvinyl chloride resin (plasticizer DOP: 20 parts by weight) colored base sheet It was produced and simultaneously molded with SMC using this decorative sheet in the same manner as in Example 1. In the molded product, the sheet was melted, torn, wrinkled, and the pattern flow occurred. Also, the adhesion between the SMC and the sheet was not sufficient.

[0023]

As described above, according to the present invention,
There are no defects such as tears in appearance, wrinkles, pattern running, pattern distortion, etc., and it is possible to express by vivid printing in design, and to obtain a product firmly bonded to FRP.

[Brief description of the drawings]

FIG. 1 is a process chart for explaining a production procedure of a fiber-reinforced plastic molded product.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Uncured composition 3 Molded article 11 Upper mold 12 Lower mold

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/36 B29C 67/14 G // B29K 105: 06

Claims (2)

[Claims] An ABS resin layer is formed on the surface of a molded article made of a cured thermosetting resin reinforced with a fibrous reinforcing material, and a biaxially stretched polyester resin layer is further laminated and integrated on the surface in this order. A fiber-reinforced plastic molded product characterized by comprising: 2. A decorative sheet in which a biaxially stretched polyester resin layer and an ABS resin layer are sequentially laminated is prepared, and SMC or BMC is overlapped so as to be in contact with the ABS resin layer side of the decorative sheet. A method for producing a fiber-reinforced plastic molded product, wherein the two are integrated by heating and pressing.