JPH11147300A - Polyester resin molding and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable excellently-designed printing by integrally laminating a polyester transparent resin layer, a polyester nonwoven fabric sheet applied printing on one side, and a non-transparent polyester resin layer, and laminating the transparent polyester resin layer so as to contact with the printed side. SOLUTION: A transparent polyester resin is cast into a mold. A sheet, where a decorative layer 3 is printed on a polyester resin nonwoven fabric 2 by using a gravure ink using a binder composed of an alkyd resin and a pyroxylin, is laminated so that the printed surface is faced to the polyester resin surface 1. A transparent polyester resin 1 diluted to a low viscosity with an organic solvent is applied for putting the polyester resin between the nonwoven fabric fiber. After drying of the solvent content, it is overlapped to contact with a non-transparent sheet molding compound(SMC) comprising an unsaturated polyester resin and glass fibers for placing in a molding tool to harden the SMC. Thus, the appearance of the molding has a deep pattern due to the diffused printing ink.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester resin molded article and a method for producing the same, and more particularly, to a method for manufacturing a polyester resin.
MC (Sheet molding compound), BMC (Bulk
The present invention relates to a fiber-reinforced plastic (FRP) molded article formed by molding compound (molding compound) or the like and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a patterned fiber reinforced plastic (FRP) molded product, a method of simultaneously forming and integrating titanium paper, nonwoven fabric, cloth, impregnated paper, and the like (for example, Japanese Patent Application Laid-Open No. 48-12876). No., JP-A-51-20
951) is known, but this method lacks the depth of the handle, is poor in design, easily breaks, has no formability, limits the shape, and has a physical anchoring effect. There is a drawback that adhesion is largely varied due to molding conditions such as temperature and pressure because of adhesion.

[0003] In some cases, a sheet printed on a polyester sheet is laminated to an uncured opaque SMC and integrally molded. However, in this method, the adhesion between the polyester film and the SMC is poor. There is a drawback that the design is poor.

Further, a method of bonding a non-woven fabric to a polyester film to improve the adhesion has been adopted. However, this method has a problem that air accumulation occurs between the non-woven fabric and the SMC, and the adhesion is partially poor. Was.

[0005]

DISCLOSURE 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 and high formability. Good polyester resin molded article with good adhesion between molded article and decorative sheet, deep pattern, good printability, and no air pocket between non-woven fabric and SMC. Is to provide.

[0006]

In order to achieve the above object, a polyester resin molded article of the present invention comprises a polyester transparent resin layer, a polyester nonwoven fabric sheet printed on one side, and an opaque polyester resin layer. The polyester-based transparent resin layer is laminated and is in contact with the printing surface.

A transparent or translucent polyester resin may be laminated between the non-printed surface of the polyester-based nonwoven fabric sheet and the opaque polyester resin layer. Further, when the opaque polyester resin layer is SMC or BMC, it becomes a polyester resin molded product of FRP.

In the above-mentioned polyester resin molded product, an incompletely cured polyester-based transparent resin is placed in a mold, and a polyester-based nonwoven fabric sheet on which one side is printed is printed. It is manufactured by arranging an opaque and uncured polyester resin on the non-printing surface and integrally molding by heat and pressure.

[0009] Alternatively, a decorative sheet is prepared by sequentially laminating a polyester-based transparent resin layer and a polyester-based nonwoven fabric sheet printed on one side.
It is simply referred to as a “sheet”. FRP such as SMC or BMC so as to be in contact with the non-printing surface side of the nonwoven fabric sheet
Are manufactured by stacking the raw materials (or intermediates) and heating and pressing them in a mold to integrate them.

Here, a transparent or translucent polyester resin may be laminated between the non-printed surface of the nonwoven fabric sheet and the opaque uncured polyester resin layer. In particular, in order to print with a deep pattern and excellent design, the polyester resin in contact with the non-printed surface of the printed polyester nonwoven sheet contains an organic solvent, has a low viscosity, and is decorated by printing. It is necessary that the layer is semi-cured. Here, any organic solvent may be used as long as it disperses a polyester resin to reduce the viscosity. For example, ethyl acetate, butyl acetate, methyl ethyl ketone,
Toluene, cyclohexanone and the like can be used. The solubility of the decorative layer printed on the nonwoven fabric sheet in an organic solvent can be adjusted by adjusting the molecular weight and the crosslinking component of the binder constituting the decorative layer.

The opaque polyester resin is SM
If it is C or BMC, it will be a method for producing a polyester resin molded product of FRP.

As described above, in the present invention, the use of the polyester-based transparent resin layer allows the sheet itself to be free from deformation, flow, tear, etc., even when subjected to heat due to molding and stress caused by SMC fluidity. In addition, the backing nonwoven sheet gives the sheet an appropriate formability, and the FRP
And a moderately compatible with each other, and can exhibit strong adhesion.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION A polyester-based transparent resin layer is formed by disposing an incompletely cured polyester-based transparent resin in a mold. This polyester-based transparent resin layer is excellent in transparency, tensile strength, heat resistance, dimensional stability, printability, stain resistance, solvent resistance, and the like. In order to provide sharpness and depth of the decorative layer, it is preferable that the surface layer composed of the polyester transparent resin layer has high transparency. Although a thickness of 10 μm to 0.7 mm can be used, it is preferably about 0.05 mm to 0.5 mm. If it is too thin, the strength and the sense of depth are reduced, and if it is too thick, moldability and cost are not good. Typical examples of the polyester-based transparent resin layer include polyethylene terephthalate, polybutylene terephthalate, ethylene terephthalate isophthalate copolymer, polyethylene naphthalate, and polyarylate.
It may be MC.

On the other hand, the transparent or translucent uncured polyester resin formed between the non-printed surface of the nonwoven fabric sheet and the opaque polyester resin layer includes polyethylene terephthalate, polybutylene terephthalate and ethylene terephthalate isophthalate copolymer. Coalescence, polyethylene naphthalate, polyarylate and the like are typical. Since these are laminated below the printed surface when the molded product is viewed, the transparency may be slightly inferior, and the material may be made translucent by adding a pigment, dye, or filler. Therefore, an SMC described later may be used. 10-20 as thickness
0 μm can be used, but preferably 20 to 100 μm.
It is about μm. If it is too thin, the strength and the sense of depth are reduced, and if it is too thick, moldability and cost are not good.

In the above-mentioned polyester-based transparent resin layer, transparent or translucent polyester resin, if necessary, benzotriazole, benzophenone, fine particles oxidized in the layer may be used to improve the weather resistance of the layer itself or the underlying FRP or the like. An ultraviolet absorber such as cerium and a light stabilizer such as a hindered amine radical scavenger may be added. The addition amount of both the ultraviolet absorber and the light stabilizer is about 0.1 to 5% by weight. Further, a coloring agent such as a dye or a pigment may be added to the polyester-based transparent resin layer, if necessary, as long as the transparency is not lost.

As the non-woven fabric sheet, a polyester-based non-woven fabric sheet is used. Melts and adheres to the polyester resin in the FRP (mainly unsaturated polyester resin) by hot pressure during molding, and can be compatible with each other. Weighing 10
200 g / m ² can be used, but preferably 20 g / m ²
１００100 g / m ² . If it is too thin, it melts too much 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. The moldability of the entire sheet is improved by moderate thermal deformation of the polyester-based transparent resin layer and the nonwoven fabric sheet.

The opaque polyester resin is used to make the back of the product invisible, and may be a resin whose transparency is reduced by an opaque filler. If the product requires transparency, it is not necessary to reduce the transparency with a filler or the like.

As the thermosetting resin which is a component of FRP, unsaturated polyester resin is preferable from the viewpoint of adhesiveness. To make a molded article from these unsaturated polyester resins, first, a monomer or prepolymer (including oligomers) of these resins to which a crosslinking agent, a polymerization initiator, or a catalyst for accelerating the reaction has been added is used. An uncured composition to which a fibrous reinforcing material such as a fiber, a woven fabric, or a non-woven fabric and other various additives are added as needed is prepared. As an uncured composition, that is, a raw material or an intermediate of FRP, for example, SM
There is a form of C or BMC.

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.

In the decoration treatment applied to the nonwoven fabric sheet, it is possible to knead and apply a coloring agent such as a dye or a pigment to the sheet itself, but in general, gravure printing, silk screen printing roll coating, offset printing, etc. The print pattern is wood pattern, stone pattern, cloth pattern, letters, geometric pattern,
The entire surface is solid. When it is necessary to cover the FRP molded product, a solid layer is entirely provided on the FRP (SMC) side of the picture, and a highly concealable pigment such as titanium dioxide or carbon black is added to the solid layer. The printing ink comprises various pigments (or dyes) and a binder resin. The binder is an alkyd resin, a two-part curable urethane resin,
An acrylic resin, a polyester resin, a vinyl chloride-vinyl acetate copolymer, a cellulose resin, a polyvinyl butyral resin, or the like is appropriately selected and used. 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. If necessary, the surface of the nonwoven fabric 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, or 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 polyester-based transparent resin layer. The protective layer is selected to be transparent (colorless or colored) so that the decorative layer can be seen through. 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, but is usually 1 to 1
It is about 00 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. Typical examples of the thermosetting resin include two-component curable polyurethane resins, epoxy resins, and unsaturated polyester resins, and examples of the ionizing radiation-curable resin include polyfunctional unsaturated (meth) acrylate monomers and prepolymers. It is a target. 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 polyester resin molded product of the present invention, in particular, the fiber reinforced polyester resin molded product is used for interior materials such as walls, floors and ceilings of buildings, bathtubs, washstands, household equipment such as kitchen appliances and windows. Fittings such as frames and doors, interior materials of vehicles such as vehicles and ships, containers, cabinets of home electric appliances and the like can be mentioned.

[0023]

FIG. 1 shows an embodiment of a polyester resin molded product of the present invention. Example 1 A transparent polyester resin was poured into a mold so as to have a thickness of 0.2 mm. A sheet in which the decorative layer 3 is printed on a polyester resin nonwoven fabric 2 (manufactured by Toyobo) weighing 60 g / m ^{2 with} a gravure ink using a binder of an alkyd resin and a nitrified cotton is arranged such that the printed surface faces the polyester resin surface. Laminate. -Apply a transparent polyester resin diluted to a low viscosity with an organic solvent (ethyl acetate, butyl acetate, methyl ethyl ketone, toluene, cyclohexanone), and put the polyester resin between the nonwoven fibers. -After the solvent is dried, it is opaque and superposed so as to be in contact with SMC (manufactured by Takeda Pharmaceutical Co., Ltd.) composed of unsaturated polyester resin and glass fiber.
The SMC was cured by heating and pressing at a molding temperature of 150 ° C. and a molding pressure of 70 kgf / cm ² for 5 minutes. In this way,
Polyester resin molded product 1 as shown in Fig. 1
0 was produced. The appearance of the molded product is the diffused printing ink 3.
With 0, the pattern had a deeper depth and the polyester resin had sufficient adhesion.

Comparative Example 1 The same as Example 1 except that a 50 μm polyester film was used instead of the nonwoven fabric of Example 1 and the printed surface was laminated so as to be disposed on the transparent polyester resin side. The appearance of the molded product was less deep than that of Example 1 and was poor in the three-dimensional appearance of the pattern. Further, the adhesion between the polyester resin and the polyester film was incomplete.

[0025]

As described above, according to the present invention,
It is free from defects such as tears and wrinkles in appearance, and can be expressed by printing excellent in design, and a product firmly bonded to FRP or the like made of polyester can be obtained. In particular, by laminating a polyester resin that has been adjusted to a low viscosity with an organic solvent, it penetrates between the nonwoven fabric fibers, preventing air biting, and partially dissolving the decorative layer (printing layer) printed on the nonwoven fabric, Decoration (printing) on the entire nonwoven fabric layer as shown in Fig. 1
The ink spreads and the depth of the pattern increases. In addition, since the polyester-based nonwoven fabric is excellent in air bleeding, it also prevents air biting. That is, the printed layer (decorative layer) spreads between the nonwoven fabric layers, the appearance depth of the pattern is increased, and the design is improved. The depth of the pattern could be improved without increasing the number of painting steps.

[Brief description of the drawings]

FIG. 1 shows an embodiment of a polyester resin molded product of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent polyester 2 Nonwoven fabric 3 Decorative layer 4 Transparent and translucent polyester 5 Opaque SMC 10 Polyester resin molded product 30 Diffused printing ink

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // B29K 67:00 105: 08 B29L 9:00

Claims (7)

[Claims] 1. A polyester-based transparent resin layer, a polyester-based nonwoven fabric sheet printed on one side, and an opaque polyester-resin layer are laminated and integrated, and the polyester-based transparent resin layer is laminated in contact with the printing surface. Polyester resin molded product characterized by being made. 2. The polyester resin molded product according to claim 1, wherein a transparent or translucent polyester resin is laminated between the non-printed surface of the polyester-based nonwoven fabric sheet and the opaque polyester resin layer. . 3. The molded polyester resin product according to claim 1, wherein the opaque polyester resin layer is SMC or BMC. 4. An incompletely cured polyester-based transparent resin in which a partially-cured polyester-based transparent resin is placed in a mold, and a polyester-based nonwoven fabric sheet printed on one side is printed thereon. A method of manufacturing a polyester resin molded product, comprising: laying an opaque uncured polyester resin on a non-printing surface, and integrally molding the same by heat and pressure. 5. A transparent or translucent polyester resin is laminated between a non-printed surface of the polyester-based nonwoven fabric sheet and an opaque uncured polyester resin layer. Production method of molded polyester resin. 6. The polyester resin in contact with the non-printed surface of the printed polyester-based nonwoven fabric sheet has a low viscosity containing an organic solvent, and the decorative layer formed by printing is semi-cured. A method for producing a polyester resin molded product according to claim 4 or 5. 7. The opaque polyester resin is SMC or BMC.
Or the manufacturing method of the polyester resin molded article of Claim 6.