JPH01135838A - Fiber-reinforced resin molding material - Google Patents

Abstract

PURPOSE:To provide the present molding material, extremely high in tensile strength in the longer direction, outstanding in transparency, useful as a transparent plate, etc., having such a construction that continuous filaments paralleled in the longer direction are incorporated, as the reinforcing material, in a synthetic resin as the matrix. CONSTITUTION:The objective molding material <=0.2mm (pref. 0.2-0.1mm) thick with the ratio: width/thickness = 25-200, having such a construction that continuous filaments paralleled in the longer direction are incorporated, as the reinforcing material, in a synthetic resin as the matrix. Preferably, said continuous filaments is a glass fiber roving, while said synthetic resin a thermoplastic one.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a fiber-reinforced resin molding material made by using continuous fibers as reinforcing materials and melting a layer of impregnated synthetic resin.

[Prior Art] Various molding materials made of fiber-reinforced resins are known. Typical examples of such molding materials include FRP pellets made of thermosetting resin containing glass fibers, prepregs such as BMC and SMC, and FRT made of thermoplastic resin containing glass fibers.
Various forms such as P pellets, sheets, and tapes are in practical use.

Top+ic! Although some of the fibers contained in molding materials made of fiber-reinforced resins are woven fabrics, most use chopped strands obtained by cutting continuous roving fibers. Therefore, the fibers are not continuous;
There is also the problem that the molded product obtained by molding cannot be expected to have sufficient strength.Furthermore, the impregnation of the synthetic resin into the fibers in the molded product is not necessarily sufficient. In particular, when a thermoplastic resin is used, even if the synthetic resin is transparent, it will be opaque.

On the other hand, continuous roving fibers such as those shown in 1″rlI are impregnated with an emulsion containing a synthetic resin polymer, dried, and then compressed while heating, so that the fibers are aligned in a certain direction. thickness
Fiber-reinforced resin molding materials in the form of thin sheets or tapes of 0.3 to I mm are in practical use. As a method for producing such a material, for example, a method for producing a sheet is disclosed in Japanese Patent Publication No. 47-13218, in which glass fiber roving is impregnated with an emulsion containing a vinyl chloride resin polymer, dried, and then heated and compressed into a thin plate. It is publicly known by the publication No. Further, JP-A-61-40113 discloses a resin-containing ribbon-shaped body obtained by a melt extrusion method in which a thermoplastic resin is flowed in a molten state from an extrusion head into a continuous fiber bundle under tension, and a method for manufacturing the same. There is.

"Problems to be Solved by the Invention" The sheet-like or tape-like fiber-reinforced resin molding material in which the fibers are aligned in a certain direction is such that the resin is attached to the surface of the roving fibers. The resin easily peels off and falls off, resulting in areas where the resin is not attached. Therefore, when obtaining molded products using the above materials, it is necessary to ensure that the resin is sufficiently impregnated between the fibers during the heating compression process. Coupled with the fact that the resin is not uniformly applied, it is difficult to obtain a molded product with a homogeneous resin layer.Furthermore, it has been difficult to obtain a molded product with a homogeneous resin layer.Furthermore, it has been difficult to obtain a molded product with a homogeneous resin layer. For example, a method of spreading the resin-impregnated roving fibers under pressure between compression rolls is also adopted as a means of obtaining the resin, but such a method may cause the fibers to break or become fluffy, resulting in a decrease in the strength of the molded product. Therefore, as a fiber-reinforced resin molding material in which continuous fibers are aligned in a certain direction, its thickness is naturally limited to 0.2 mm.
There are no thin ones like the one below.

Furthermore, in the case of resin-containing ribbon-like bodies obtained by melt extrusion, the high viscosity of the melted resin during production causes uneven flow resistance within the fiber bundle and polarity of the fiber surface. The flow of resin into the fiber bundle is not necessarily sufficient, and there is a tendency for the resin to be unevenly distributed only around the fiber bundles of the ribbon-like body. Therefore, as a molding material, it is far from being thin and sufficiently impregnated with resin.

Therefore, in fiber-reinforced resin molding materials, the fibers are continuously aligned in a certain direction, and the thickness is extremely thin.
Moreover, in the case of products containing a large amount of resin, the molded product obtained by molding the resin remains transparent even if it contains fiber reinforcing materials, and the molded product obtained by laminating and molding these materials by arranging them alternately has a high strength. It is recognized that there are some advantages such as significantly improved performance. An invention relating to a method for manufacturing a tape-like material as a molding material has been filed as an invention by the present inventors (Japanese Patent Application No. 156477/1982). In this method for producing a tape-like product, the thickness of the tape as a molding material and the width/thickness ratio are not particularly limited, but it is possible to produce a thin product by expanding the roving. Ta.

The present inventors studied suitable shapes and dimensions for a tape-shaped molding material manufactured by the above manufacturing method. As a result, we have found the most suitable ranges for the thickness and width/thickness ratio of the conventionally sought after molding material, and have completed the present invention.

Therefore, the present invention aims to provide a new fiber-reinforced resin molding material that solves the conventional problems and has a specific thickness and width/thickness ratio that provides various strongly desired advantages. This is the purpose.

[Means for Solving the Problems] That is, the present invention provides a fiber-reinforced resin molding material in which continuous fibers are used as reinforcing materials and a synthetic resin is impregnated and adhered thereto, in which the continuous fibers are aligned in the longitudinal direction, and The thickness of the resin molding material is 0.2 mm or less, and the width/thickness ratio is 25.
The present invention provides a fiber-reinforced resin molding material characterized in that the fiber-reinforced resin molding material has a molecular weight of 200 to 200.

In the present invention, the continuous fibers as a reinforcing material contained in the resin are made from roving, and include inorganic fibers such as glass fibers, carbon fibers, ceramic fibers, metal fibers, polyamide fibers, and polyimide fibers. Fibers (filaments) such as organic fibers such as polyamide-imide fibers are bundled with a binding agent. Here, it is preferable to use glass fiber roving in that the molding material of the present invention and the molded product using the molding material have transparency.

Rovings are usually made up of multiple fibers (filaments) with a fine diameter bound together by a binding agent. For example, a typical glass fiber roving with a diameter of about 2 mm has 4,500 filaments with a diameter of about 12 μm. It is something that is focused to some degree. If the diameter of the roving used is large, the thickness and width/thickness ratio of the present invention cannot be obtained in the Kaito expansion of the molding material manufacturing method, and the resin may not be sufficiently impregnated into the fibers. The result will be uneven.

The synthetic fiber in the molding material of the present invention is a thermoplastic resin. Since the roving as a continuous fiber is impregnated with resin in the form of an emulsion in the manufacturing method, it is desirable that the resin is capable of forming an emulsion and preferably has transparency. In consideration of this point, for example, vinyl chloride, vinylidene chloride, vinyl acetate, acrylic ester, methacrylic ester, styrene, acrylonitrile, ethylene, propylene, j-domopolymers such as fluorine-containing yarn jiimer, and others. Together! These include copolymers obtained by copolymerizing with monomers that can be polymerized. and,
Among these, vinyl chloride alone, or vinyl acetate, vinylidene chloride, acrylic ester, methacrylic ester, acrylonitrile, maleic anhydride, maleic ester, etc. in an amount that does not deteriorate the properties of vinyl chloride, etc. In addition, materials known to be difficult to impregnate into fibers, such as a vinyl chloride copolymer obtained by Kogane Co., Ltd., may also be used. It goes without saying that the thermoplastic resin may be opaque or colored. The amount of resin used as a molding material is preferably as large as possible, but the so-called ignition loss (Ig 1oss) is 30
% or more is desirable.

As described above, the fiber-reinforced resin molding material of the present invention is manufactured according to the method for manufacturing a fiber-reinforced resin tape invented by the present inventors.

In order to keep the thickness and width/thickness ratio of the molding material within the range of the present invention, the tensile stress applied to the roving, which is the condition for Kaito expansion after impregnating the roving with a resin emulsion, must be obtained. This is done by adjusting the desired thickness of the molded product and the ratio of width to thickness. By such unbundling and expansion, the roving is expanded into a tape-like shape, and the filaments are aligned in the length direction.

Therefore, in the normal Kaito expansion of one roving,
For example, if 3,000 filaments with a diameter of 12 μm are bundled together and the diameter is 2 mmφ, by appropriately adjusting the tensile stress of the roving and unfolding the filament, the thickness will be about 0.1 mm and the width will be about 1 Omm. A tape-shaped molding material having a width/thickness ratio of 100 is obtained.

Here, the molding material of the present invention has a thickness of 0.2 mm or less.

The width/thickness ratio is said to be 25 to 200, but if it is less than 25, the amount of resin is small and tends to be non-uniform, and molded products made using this have poor transparency and are particularly difficult to mold. The molded material used as the material has low strength. On the other hand, a range exceeding 200 is difficult to put into practical use. For example, in the case of the above-mentioned film according to the present invention, which has a thickness of about 0.1 mm and a width/thickness ratio of 100 and a width of 20 mm, a cross-sectional examination shows that there are about 5 filaments in the thickness direction and about 50 filaments in the width direction.
The filaments are arranged almost uniformly, and the resin is densely filled between the filaments. Moreover, it has transparency, and the strength of molded products made using it is sufficiently increased. on the other hand,
For example, even if similar rovings are used, the thickness is 0.
When the width is 4 mm and the width/thickness ratio is 20, the filaments are extremely unevenly distributed in the thickness direction, and the resin is not sufficiently affected between the filaments, is extremely heterogeneous, and is not transparent. is also inferior. Also, the thickness is 0.
If it is extremely thin, such as 1 mm or less, the molding conditions will be film-like, making it difficult to handle, and even if it contains fibers, it will not work as a reinforcing material, making it unsuitable as a molding material. These are based on experimental facts, and based on these, the suitable thickness and width /
The thickness ratio has been determined. This will be made clearer in more detail in the Examples.

The fiber-reinforced resin molding material of the present invention, in which roving fibers (filaments) as a reinforcing material are aligned in a certain direction and contained in the resin, and has a specific thickness and width/thickness ratio, is as follows. It is made into molded products. For example, the fibers are aligned in a certain direction by cutting them to a certain length, arranging them in parallel, placing flat plates made of the same or different types of resin on the top and bottom surfaces, and pressurizing and heating forming them. It can be made into a molded article. In addition, as another example, a molded product with increased strength can be obtained by cutting pieces to a certain length and arranging them in a vertical and horizontal manner and molding them in the same manner. In particular, in its application as a molding material, it is expected to have a wide range of applications, such as by freely selecting its arrangement or by making it into a woven fabric, which can increase strength and create molded products with excellent aesthetics. be.

[Example] Examples 1 to 7 Glass fiber (filament) with a diameter of approximately 13 μm was
The tensile stress of the roving during Kaito expansion was adjusted so that a molding material having the thickness and width shown in Table 1 was obtained by impregnating a glass fiber roving made of 00 fibers in a bundle with a vinyl chloride resin emulsion. After opening and developing the bundle, heat treatment was performed to obtain a tape-shaped molding material containing glass fiber as a reinforcing material in the vinyl chloride resin and having the thickness and width shown in Table 1.

Measurement of the shape (thickness, width, width/thickness ratio) of the obtained molding material, investigation of the filament using a cross-sectional magnifying glass, Ig 1o
ss measurement, transparency investigation, and tensile strength measurement in the longitudinal direction were carried out, and the results are shown in Table 1.

Ratio 1 Bite Examples 1 to 2 Chloride was prepared in the same manner as in the example except that the tensile stress of the roving in the opening of the bundle was adjusted to obtain a molding material having the thickness and width shown in Table 1. A tape-shaped molding material containing glass fiber as a reinforcing material in a vinyl resin and having the thickness and width shown in Table 1 was obtained.

Their shapes, properties, etc. were investigated and measured in the same manner as in the Examples, and the results are shown in Table 1.

Table 1 Examples 8 to 10 Instead of the vinyl chloride resin emulsion in Examples 1.4 and 7, a composite of vinyl chloride and acrylic ester (vinyl chloride/acrylic ester: 95/5) was used.
A tape-shaped molding material having the thickness and width shown in Table 2 was obtained in the same manner as in the above Example, except that an emulsion obtained by emulsifying and mixing ) with an emulsifier was used.

The shape, properties, etc. of this molding material were investigated and measured in the same manner as in the above Examples, and the results are shown in Table 2.

Examples 11 to 13 Instead of the vinyl chloride resin emulsion in Examples 1.4 and 7, an emulsicon prepared by using an emulsifier to prepare a latex containing a polymer (solid content 48%) obtained by emulsion polymerization of methyl methacrylate was used. A tape-shaped molding material having the thickness and width shown in Table 2 was obtained in the same manner as in the above Example except that the material was used.

The shape, properties, etc. of this molding material were investigated and measured in the same manner as in the above Examples, and the results are shown in Table 2.

Table 2 Example I4 Using the tape-shaped molding material obtained in Example 4, 12 pieces of wood were arranged in parallel in the length direction with a spacing of 1 Omm, and on top of them 30 x 30 mm thick. A 0.1 mm vinyl chloride resin plate is placed and heated, and a 15 kg
A glass fiber-containing transparent laminate having a thickness of about 0.2 mm was obtained by applying a pressure of /mm2. The physical properties of the thus formed laminate were measured for tensile strength, bending strength, and bending elastic modulus in the longitudinal direction of the fibers.

The results of these physical property measurements are shown in Table 3.

Examples 15 to 16 Using the tape-shaped molding materials obtained in Examples 9 and 12, 12 tapes were arranged in parallel in the length direction with an interval of 1 Omm, and a 3Q x 30 mm thick film was placed on top of the tape-shaped molding materials obtained in Examples 9 and 12. 2mm
A polymethyl acrylate plate was placed on the plate, heated and molded by applying a pressure of 20 kg/mm2 to a thickness of approximately 2 mm.
A glass fiber-containing transparent laminate was obtained. The physical properties of the thus formed laminate were measured in the same manner as in Example 14.

The results are shown in Table 3.

Table 3 Example 17 The tape-shaped molding material obtained in Example 4 was knitted alternately vertically and horizontally, and five pieces of this knitted fabric were stacked and laminated by compression molding to have almost no directionality. Approximately 1mm thick, 30X3
A glass fiber-containing laminate with a thickness of 0 mm was obtained.

When the physical properties of this laminate were measured, the tensile strength was 19.1
1 to 24.8 kg/mm2, bending strength 22.2 to 25.
The elastic modulus was 1 kg/mm2 and the bending elastic modulus was 1720 kg/mm2.

Ratio 1 bite example 3 The physical properties of a transparent vinyl chloride resin plate with a thickness of 1 mm were measured, and the tensile strength was 5.7 kg/mm, and the bending strength was 9.8 kg.
/mm2. The flexural modulus was 280 kg/mm''.

"Effects of the Invention" The fiber-reinforced resin molding material of the present invention has transparency by itself, and since the fibers are aligned in the length direction, the tensile strength in the length direction is extremely large. It has the following characteristics. In particular, by using Ijl as a molding material, it is possible to obtain transparent plates and other molded products, and by selecting various arrangements of Ijl, strength can be improved, and plates and other molded products with excellent aesthetics can be obtained. It is recognized that this method has the effect of providing

procedure manual January 2-7, 1985

Claims (4)

[Claims] (1) In a fiber-reinforced resin molding material containing continuous fibers as reinforcing materials in a synthetic resin, the continuous fibers are aligned in the length direction, and the thickness of the resin molding material is 0.2
A fiber-reinforced resin molding material having a width/thickness ratio of 25 to 200. (2) The resin molding material according to claim 1, wherein the resin molding material has a thickness of 0.2 to 0.1 mm. (3) The resin molding material according to claim 1, wherein the continuous fibers are glass fiber rovings. (4) The resin molding material according to claim 1, wherein the synthetic resin is a thermoplastic resin.