JPH08118354A - Fiber reinforced thermoplastic resin impregnated sheet and production thereof - Google Patents

Abstract

PURPOSE: To obtain a molded product good in moldability and having a good surface smoothness by forming a noncrystalline thermoplastic resin layer containing no reinforcing fiber on at least the single surface of a fiber reinforced thermoplastic resin impregnated sheet material and having a specific thickness. CONSTITUTION: A fiber reinforced thermoplastic resin impregnated sheet material 2 is produced by sufficiently impregnating a reinforcing fiber base material with a noncrystalline thermoplastic resin. This sheet material 2 is heated to temp. higher than the secondary transition point of the thermoplastic resin and a film 3 of a crystalline thermoplastic resin heated in the same way is bonded to the heated sheet material 2 under pressure. The temp. at this time is pref. made higher than the secondary transition point of a thermoplastic resin to be used by about 5-70 deg.C, pref., about 20-40 deg.C. The press bonding method may be a press method or a press roll method. On the surface having the film 3 laminated thereto of the impregnated sheet 1 thus obtained, a non-crystalline thermoplastic resin layer containing no reinforcing fiber is provided in a thickness of 20-200μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced thermoplastic resin-impregnated sheet in which reinforcing fibers and a thermoplastic resin are integrated, and particularly in compression molding such as deep drawing, the surface smoothness is good, and the machine is lightweight. TECHNICAL FIELD The present invention relates to a fiber-reinforced thermoplastic resin-impregnated sheet that enables a molded product with good physical properties.

[0002]

Description of the Related Art A sheet material of a thermoplastic resin reinforced with short glass fibers and a sheet material of a thermoplastic resin reinforced with a continuous glass fiber mat are known as stampable sheet materials. Further, a thermoplastic resin sheet material reinforced with reinforcing fibers aligned in one direction and a thermoplastic resin sheet material in which the reinforcing material is reinforced with a woven fabric made of glass fiber, carbon fiber or aramid fiber are also known. When deep drawing is performed using these thermoplastic resin sheet materials, as shown in FIG. 2, there are a portion A in which the sheet material is greatly stretched and a portion B in which the sheet material gathers on the contrary. As a result, in the stretched portion A, the reinforcing fibers are in a protruding shape, and the thermoplastic resin is extruded from between the protruding reinforcing fibers to form the resin uneven layer 7 in FIG. The concavo-convex layer 7 remains on the surface of the molded product and deteriorates the surface smoothness, and in some cases post-processing such as polishing is required. In particular, this tendency tends to occur remarkably in the case of a molded product having a thin layer.

[0003]

When the conventional thermoplastic resin molding material is subjected to deep drawing, the reinforcing fibers are likely to be extruded on the surface of the molded product, and the resin is extruded from between the embossed reinforcing fibers. As a result, there is a problem that the surface of the molded product becomes uneven, the surface smoothness deteriorates, and the appearance defect easily occurs. Therefore, the object of the present invention is to obtain a molded article having good moldability and good surface smoothness,
Moreover, it is an object of the present invention to provide a molding material that enables a molded product that is lightweight and has excellent mechanical properties.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, a fiber-reinforced thermoplastic resin-impregnated sheet in which an amorphous thermoplastic resin is reinforced with a base material composed of reinforcing fibers. By reinforcing the material into a fiber-reinforced thermoplastic resin-impregnated sheet having a reinforcing fiber-free amorphous thermoplastic resin layer having a thickness of 20 to 200 μm on at least one side, the material is reinforced with a base material composed of reinforcing fibers. The thermoplastic resin of the fiber-reinforced thermoplastic resin-impregnated sheet material is amorphous, the impregnated sheet material is laminated in a plurality of layers, and the amorphous thermoplastic resin does not contain reinforcing fibers having a thickness of 20 μm or more between the layers. A fiber-reinforced thermoplastic resin-impregnated sheet having a layer and having an amorphous thermoplastic resin layer having a thickness of 20 to 200 μm and containing no reinforcing fiber on at least one surface of the impregnated sheet material. It has found that it is possible to solve problems by.

Further, as a method for producing the above-mentioned fiber-reinforced thermoplastic resin-impregnated sheet, a non-crystalline thermoplastic resin is reinforced with a base material made of reinforcing fibers, and at least one surface of the fiber-reinforced thermoplastic resin-impregnated sheet material is A method for producing a fiber-reinforced thermoplastic resin-impregnated sheet by laminating and crimping a crystalline thermoplastic resin film, and a fiber-reinforced thermoplastic resin-impregnated sheet material in which an amorphous thermoplastic resin is reinforced with a base material made of reinforcing fibers. When laminating a plurality of layers, a fiber-reinforced heat for inserting an amorphous thermoplastic resin layer between the layers, and laminating an amorphous thermoplastic resin film on at least one surface of the laminate to perform pressure bonding and integration. A method for producing a plastic resin-impregnated sheet has been found. Further, in the above-mentioned production method, when laminated and pressure-bonded, it is possible to obtain the fiber-reinforced thermoplastic resin-impregnated sheet of the present invention by thermocompression bonding at a temperature higher than the softening point of the amorphous thermoplastic resin film. It started.

The impregnated sheet of the present invention is shown in FIG. FIG.
(A) shows the impregnated sheet 1 of claim 1, 2 is a fiber-reinforced thermoplastic resin-impregnated sheet material, and 3 is a thermoplastic resin layer containing no reinforcing fiber of the skin layer. In FIG. 1A, the skin layers are provided on both sides, but it is also possible to have only one side. FIG. 1 (b) shows an impregnated sheet 1'of claim 2 and 2
Is a fiber-reinforced thermoplastic resin-impregnated sheet material, 4 is a core layer, 3 is a skin layer, and both the core layer and the skin layer are thermoplastic resin layers containing no reinforcing fiber. In FIG. 1 (b),
The skin layers are provided on both sides, but it is also possible to have only one side, and the two impregnated sheet materials are two layers, but three or more layers are also possible.

The thickness of the skin layer of the impregnated sheet of the present invention is
If the thickness is 20 to 200 μm and is thinner than 20 μm, a molded product with a smooth surface cannot be obtained when deep drawing,
When it is thicker than m, the strength of the obtained molded article decreases.
Moreover, the thickness of the core layer in FIG. 1B may be 20 μm or more, but in order to more effectively exhibit the effects of the present invention, the thickness is preferably 100 to 600 μm. As the thermoplastic resin used in the impregnated sheet of the present invention, an amorphous resin such as acrylic acid ester resin, polycarbonate, polysulfone, polyetherimide, or polyethersulfone is used alone or as a blend. In addition, these thermoplastic resins include stabilizers, plasticizers, flame retardants,
Additives such as UV absorbers can also be added.
As the reinforcing fiber used in the present invention, glass fiber, carbon fiber, alumina fiber, aramid fiber or the like can be used. Examples of the form of the reinforcing fiber include woven fabric, knitted fabric, non-woven fabric and mat. Particularly, in the case of a woven fabric, deep drawing is difficult, and the present invention works effectively. When a woven fabric is used as the reinforcing material, a woven fabric having a satin weave or a twill weave is desirable. When a glass fiber woven fabric is used as the woven fabric, it is desirable to use a glass fiber woven fabric that has been surface-treated with a silane coupling agent. As the silane coupling agent, γ-aminopropyltriethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane.
Hydrochloride, N-phenyl-γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-
Methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, etc. are used and are selected according to the type of matrix resin.

Next, a method for producing the impregnated sheet of the present invention will be described. First, a fiber-reinforced thermoplastic resin-impregnated sheet material is prepared by sufficiently impregnating a reinforcing fiber base material with an amorphous thermoplastic resin. This sheet material is heated to a temperature higher than the second-order transition point of the thermoplastic resin, and similarly heated amorphous thermoplastic resin films are laminated and pressure-bonded. The temperature at this time is 5 to 70 from the second-order transition point of the thermoplastic resin used.
It is good to carry out pressure bonding at a temperature higher by 20 ° C., preferably 20-40 ° C. The pressure bonding method may be a press method or a press roll method. The pressure bonding of the film may be performed on one side or both sides of the sheet material. On the film-laminated surface of the impregnated sheet obtained by this method, the resin layer containing no reinforcing fibers is 20 to 200.
It is provided with a thickness of μm.

Further, in the method for producing an impregnated sheet having a resin layer as a core layer, similarly, a fiber-reinforced thermoplastic resin-impregnated sheet material is prepared by sufficiently impregnating an amorphous thermoplastic resin with a reinforcing fiber base material. To do. An amorphous thermoplastic resin sheet and a thermoplastic resin film are prepared. These materials are heated to a temperature higher than the second-order transition point of the thermoplastic resin, the thermoplastic resin sheet is sandwiched between the sheet materials, and a thermoplastic resin film is further laminated on at least one side of this laminate, and pressure-bonding is integrated. To do. The temperature at this time is 5 to 70 ° C, preferably 20 to 40 ° C from the second-order transition point of the thermoplastic resin used.
It is good to crimp at high temperature. As the pressure bonding method, it is possible to obtain a single pressure bonding by a pressing method, or a method in which the pressure bonding can be repeated successively by a press roll method. The impregnated sheet thus obtained has a core layer made of a resin layer having a thickness of 20 μm or more, and further has a resin layer having a thickness of 20 to 200 μm on the surface on which the films are laminated.

[0010]

The function of the impregnated sheet of the present invention is
It is preheated to a moldable temperature and then inserted into the mold 5. As shown in FIG. 2, as the male die 8 descends, the sheet material 6 is stretched at the portion A. However, in the case of the impregnated sheet of the present invention, since the surface has a resin layer with a constant thickness, the reinforcing fibers do not rise, and as a result, the resin is extruded from between the reinforcing fibers found in conventional sheet materials. The phenomenon of fracturing does not occur, and a deep-drawn molded product with good surface smoothness can be obtained. Further, since the impregnated sheet of the present invention has a resin layer on the surface, the resin layer serves as a cushioning material at the time of molding, and thus has an advantage of good moldability. In particular, in the case of an impregnated sheet having a resin layer in the core layer, since the resin layer is provided on both sides of the reinforcing fiber layer, the moldability is further improved.

Further, the impregnated sheet having a resin layer in the core layer is inferior in absolute strength as compared with a sheet material having the same sheet thickness and having no resin layer in the core layer, but it is high in terms of the volume% ratio of the reinforcing fiber. It was found to show a value. The fiber-reinforced thermoplastic resin-impregnated sheet of the present invention uses an amorphous resin. This is because in the case of an amorphous resin, it is possible to perform bonding and molding operations at a temperature of the second-order transition point or higher. In addition, the workable temperature range can be relatively wide. In the case of a crystalline resin, the temperature difference between the second-order transition point and the melting point is small, and if the temperature exceeds the melting point, the fluidity of the resin becomes large and the handleability becomes poor. Further, in the case of an amorphous resin, at a temperature higher by 5 to 70 ° C. than the second-order transition point, depending on the resin,
Preferably, when the temperature is higher by 20 to 40 ° C., the fluidity of the resin itself is not so great, but the adhesiveness of the resin surface is increased, so that the lamination pressure-bonding work is facilitated. Table 1 shows the second-order transition points of the amorphous thermoplastic resin. Further, the shape capable of deep drawing when using the impregnated sheet of the present application is at least as shown in FIG.
It is possible to have a hemispherical shape as shown in.

[0012]

[Table 1]

[0013]

【Example】

<Example 1> (1) Manufacture of impregnated sheet Manufacture of impregnated sheet material (b) Yarn used for glass cloth ECG75 1/0 Density of warp 44 yarns / 25mm Weft 33 yarns / 25mm Weaving texture 4 pieces Suzaku Weight 209g / m ² surface treatment γ-aminopropyltriethoxysilane (adhesion rate 0.5%) (b) Polycarbonate film (hereinafter abbreviated as PC) Thickness 100 μm (c) (a) glass cloth and (b) PC film The layers were laminated as follows and heat-molded to prepare an impregnated sheet material. PC film / Glass cloth / PC film / Glass cloth / PC film / Glass cloth / PC film / Glass cloth / PC film Manufacture of impregnated sheet A PC film having a thickness of 100 μm is superposed on both sides of the impregnated sheet material obtained by 210 ℃, pressure 10kg / c
It was molded with m ² to obtain the impregnated sheet shown in FIG. (2) Deep drawing test The impregnated sheet obtained in (1) is placed in a far infrared oven and heated and softened under the conditions of a temperature of 300 ° C. and a heating time of 90 seconds. This impregnated sheet was deep-drawn by a molding die (FIG. 2) having a hemispherical male mold and a female mold heated to 100 ° C. Molding conditions are pressure 100kg, pressure holding time 2
It was set to 0 seconds. The appearance of the deep-drawn product is shown in Table 2.

<Example 2> (1) Production of impregnated sheet Production of impregnated sheet material (a) Glass cloth The same glass cloth as in Example 1 was used. (B) Polyetherimide (hereinafter abbreviated as PEI) Thickness 100 μm ( (C) The glass cloth of (a) and the PEI film of (b) were laminated as follows and heat-molded to prepare an impregnated sheet material. PEI film / Glass cloth / PEI film / Glass cloth / PEI film / Glass cloth / PEI film / Glass cloth / PEI film Manufacture of impregnated sheet A PEI film having a thickness of 100 μm is superposed on both sides of the impregnated sheet material obtained at 250 ° C, pressure 10kg /
It was molded with a cm ² to obtain an impregnated sheet shown in FIG. When the cross section of the obtained impregnated sheet was measured by an engineering microscope, a PEI resin layer having a thickness of 100 μm was found in the skin layer. (2) Deep drawing test The impregnated sheet obtained in (1) is placed in a far infrared oven and heated and softened under the conditions of a temperature of 320 ° C. and a heating time of 90 seconds. This impregnated sheet was deep-drawn by a molding die (FIG. 2) having a hemispherical male mold and a female mold heated to 150 ° C. Molding conditions are pressure 100kg, pressure holding time 3
It was set to 0 seconds. The appearance of the deep-drawn product is shown in Table 2.

<Example 3> (1) Preparation of impregnated sheet Preparation of impregnated sheet material (a) Glass cloth The same glass cloth as in Example 1 was used. (B) Polycarbonate film (hereinafter abbreviated as PC film) PC having a thickness of 50 μm Film (c) The glass cloth of (a) and the PC film of (b) were laminated as follows and heat-molded to prepare an impregnated sheet material. PC film / Glass cloth / PC film Polycarbonate sheet Use a PC sheet with a thickness of 500 μm Insert the PC sheet between the impregnated sheet materials obtained in the preparation of the impregnated sheet,
Further, a PC film having a thickness of 50 μm was laminated on both sides of the laminate, and molded at a temperature of 250 ° C. and a pressure of 10 kg / cm ² to obtain an impregnated sheet shown in FIG. 1 (b). When the cross section of the obtained impregnated sheet was measured by an engineering microscope, a resin layer of 50 μm in the skin layer and 500 μm in the core layer was recognized. (2) Deep Draw Molding Experiment The impregnated sheet obtained in (1) was deep draw molded under the same conditions as in Example 1, and the results are shown in Table 2.

<Example 4> (1) Preparation of impregnated sheet Preparation of impregnated sheet material (a) Glass cloth The same glass cloth as in Example 1 was used (b) Polyetherimide film (hereinafter abbreviated as PEI film) Thickness 50 μm PEI film of (C) The glass cloth of (A) and the PEI film of (B) were laminated as follows and heat-molded to prepare an impregnated sheet material. PEI film / glass cloth / PEI film Polyetherimide sheet Use a PEI sheet with a thickness of 500 μm Insert a PEI sheet between the impregnated sheet materials obtained in the preparation of the impregnated sheet, and further with a thickness of 50 μm on both sides of the laminate. PEI films were stacked and molded at a temperature of 250 ° C. and a pressure of 10 kg / cm ² to obtain an impregnated sheet shown in FIG. 1 (b). When the cross section of the obtained impregnated sheet was measured with an engineering microscope, a PEI resin layer of 50 μm in the skin layer and 500 μm in the core layer was recognized. (2) Deep Drawing Molding Experiment The impregnated sheet obtained in (1) was deep drawn under the same conditions as in Example 2 and the results are shown in Table 2.

<Comparative Example 1> For comparison, the impregnated sheet material obtained in Example 1 was subjected to cross-sectional observation and deep drawing forming experiments. Cross-section observation shows that the skin layer is 5-10 μm
The resin layer was observed. The results of the deep drawing experiment are shown in Table 2. Comparative Example 2 For comparison, the impregnated sheet material obtained in Example 2 was subjected to cross-sectional observation and deep drawing forming experiment. A cross-sectional observation showed a resin layer of 5 to 10 μm in the skin layer. The results of the deep drawing experiment are shown in Table 2. Bending strengths of the impregnated sheets of Examples 1 to 4 and Comparative Examples 1 and 2 were measured, and the results are shown in Table 2.

[0018]

[Table 2]

[0019]

The fiber-reinforced thermoplastic resin-impregnated sheet of the present invention has good moldability as a molding material for deep drawing,
Enables molded products with good surface smoothness. Further, the fiber-reinforced thermoplastic resin-impregnated sheet having a resin layer in the core layer enables a molded product having excellent surface smoothness, light weight and good mechanical properties. In particular, the above-mentioned effects are exhibited in the case of a thin-layer deep-drawn molded product.

[Brief description of drawings]

FIG. 1 shows a cross-sectional view of an impregnated sheet of the present invention.

FIG. 2 is a sectional view showing a state of deep drawing when a conventional molding material is used.

[Explanation of symbols]

 1,1 '. Fiber reinforced thermoplastic resin impregnated sheet 2. Fiber reinforced thermoplastic resin impregnated sheet material 3. Thermoplastic resin film 4. Thermoplastic resin sheet 5. Mold for molding 6. Molding material 7. Uneven portion of resin 8. Male 9. Female A. Stretched portion of molding material B. Part of resin of molding material

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Claims (5)

[Claims] 1. An amorphous thermoplastic resin layer containing no reinforcing fibers on at least one surface of a fiber-reinforced thermoplastic resin-impregnated sheet material in which an amorphous thermoplastic resin is reinforced with a base material composed of reinforcing fibers, and the amorphous thermoplastic resin layer has a thickness of 20 to 200 μm. And a fiber-reinforced thermoplastic resin-impregnated sheet. 2. A thermoplastic resin of a fiber-reinforced thermoplastic resin-impregnated sheet material reinforced with a base material made of reinforcing fibers is amorphous, and the impregnated sheet material is laminated in a plurality of layers, and a thickness between the layers is increased. Having a thickness of 20 μm or more on at least one surface of the impregnated sheet material having an amorphous thermoplastic resin layer containing no reinforcing fiber and having a thickness of 20 to 200 μm.
A fiber-reinforced thermoplastic resin-impregnated sheet having an amorphous thermoplastic resin layer containing no reinforcing fiber of m. 3. An amorphous thermoplastic resin film is laminated and pressure-bonded onto at least one surface of a fiber-reinforced thermoplastic resin-impregnated sheet material in which an amorphous thermoplastic resin is reinforced with a base material composed of reinforcing fibers. A method for producing a fiber-reinforced thermoplastic resin impregnated sheet. 4. When laminating a plurality of fiber-reinforced thermoplastic resin-impregnated sheet materials in which an amorphous thermoplastic resin is reinforced with a base material composed of reinforcing fibers, an amorphous thermoplastic resin layer is provided between the layers. A method for producing a fiber-reinforced thermoplastic resin-impregnated sheet, which comprises inserting and laminating an amorphous thermoplastic resin film on at least one surface of the laminate, and press-bonding and integrating. 5. The method for producing a fiber-reinforced thermoplastic resin-impregnated sheet according to claim 3 or 4, wherein, when laminating and pressure-bonding, heat-pressing is performed at a temperature higher than the softening point of the amorphous thermoplastic resin film.