JPH0289626A - Fibre reinforced resin mold material and fibre reinforced resin laminated board as base material thereof - Google Patents

Abstract

PURPOSE:To obtain a thin tape-shaped fibre reinforced resin mold material by filling synthetic resin among fibres closely in paralleling continuous fibres in a longitudinal direction, and rendering the resin mold material to have a ratio of a specific thickness and width / thickness. CONSTITUTION:A fibre reinforced resin mold material containing continuous fibres in synthetic resin as a reinforcing material is of a type wherein continuous fibres are paralleled in a longitudinal direction and synthetic resin is filled among the fibres closely. And, the thickness of the resin mold material is 0.2mm or below and the ratio of the width / thickness is 25 - 200. The resin mold material is obtained in such a manner that the emulsion of synthetic resin is infiltrated into the continuous fibres and the continuous fibres are unbound and extended, and then dried and heated while giving tension to them. At this time, unbound and extended glass fibre roving is employed as continuous fibres and thermoplastic resin is used as synthetic resin. Furthermore, the mold material is arranged and lamination-molded on a synthetic resin board in order to form a fibre reinforced resin laminated board.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention is a thin tape-shaped fiber-reinforced resin molding in which continuous fibers are contained in a synthetic resin as a reinforcing material, and the synthetic resin is densely filled between the fibers. The present invention relates to a fiber-reinforced resin laminate formed by arranging the material and the molding material as a base material on a synthetic resin plate and laminating the same.

[Prior art] Among molding materials made of fiber-reinforced resins, FR made of thermosetting resins containing glass fibers is a typical example.
Various forms of prepregs such as P pellets, BMC, and SMC, and FRTP pellets, sheets, and tapes made of thermoplastic resin containing glass fibers are in practical use.

The fibers contained in the above-mentioned molding materials may be woven fabrics, but chopped strands, which are made by cutting continuous roving fibers, are used. Therefore, the fibers are not continuous. Moreover, there is a problem that the molded product obtained by molding cannot be expected to have sufficient strength because it tends to be non-uniform.Furthermore, in a molded product using FRTP made of thermoplastic resin,
Even when the resin is transparent, for example, vinyl chloride resin, the adhesion and impregnation of the resin onto the fibers is insufficient (as a result, the molded product has disadvantages such as poor transparency and low strength).

On the other hand, continuous roving fibers are impregnated with an emulsion containing a synthetic resin polymer, dried, and then compressed while heating, resulting in thin fibers with a thickness of 0.3 to 1 mm that are aligned in a certain direction. Fiber-reinforced resin molding materials in the form of sheets or tapes are in practical use.

As a method for producing such a material, for example, a method for producing a sheet by impregnating glass fiber roving in an emulsion containing a vinyl chloride resin polymer, drying it, heating it and compressing it into a thin plate is disclosed in Japanese Patent Publication No. 47-132.
It has become publicly known from Publication No. 18. Furthermore, JP-A No. 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.
It is disclosed in the publication No.

[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 simply a resin adhered to the surface of roving fibers. , the resin easily peels off and falls off, resulting in areas where the resin is not attached. Therefore, when obtaining a molded article using the above materials, it has been difficult to obtain a molded article having a homogeneous resin layer. In addition, as a means of obtaining a fiber-reinforced resin molding material in the form of a thin plate or tape as a molding material,
For example, a method of spreading the resin-impregnated roving fibers under pressure between compression rolls is also adopted, but such a method causes the fibers to be cut or fluffed, resulting in a decrease in the strength of the molded product. Therefore, the thickness of a fiber-reinforced resin molding material in which continuous fibers are aligned in a certain direction is naturally limited, and it has not been possible to obtain a material as thin as 0.2 mm or less and with a large amount of resin impregnated.

Furthermore, in the case of resin-containing ribbon-shaped bodies obtained by melt extrusion, the high viscosity of the melted resin during production causes flow resistance in the fiber bundle and polarity of the fiber surface, causing resin to flow between the fibers. The filling is not necessarily sufficient, and there is a tendency for the particles to be unevenly distributed only on the surface of the ribbon-like body. Therefore, as a molding material, its thickness is thin (and it is far from being sufficiently filled with resin).

Therefore, the present inventors have applied for an invention (patent application) for a method for manufacturing a tape-shaped fiber-reinforced resin molding material in which continuous fibers are aligned in a certain direction, are extremely thin, and are filled with a large amount of resin. (Sho 62-156447).

The present inventors further studied the suitable shape and dimensions of a tape-shaped molding material manufactured by the above manufacturing method. As a result, we determined the thickness and width/thickness ratio suitable for obtaining a transparent and strong laminate molded product by arranging this molding material on a synthetic resin plate as a base material and laminating it. This finding led to the completion of the present invention.

Therefore, the object of the present invention is to provide a thin tape-shaped fiber-reinforced resin molding material in which continuous fibers are aligned in the length direction and synthetic resin is densely filled between the fibers, as a fiber-reinforced resin molding material that solves the conventional problems. Our goal is to provide molding materials.

Furthermore, another object of the present invention is to form a fiber-reinforced resin laminate with excellent transparency and mechanical properties by arranging a plurality of tape-shaped fiber-reinforced resin molding materials as a base material and laminate-molding them on a synthetic resin board. The purpose is to provide a board.

[Means for Solving the Problems] That is, the present invention provides a fiber-reinforced resin molding material in which continuous fibers are impregnated in a synthetic resin as a reinforcing material, in which the continuous fibers are aligned in the longitudinal direction, and synthetic resin is formed between the fibers. The resin molding material is densely packed and the thickness of the resin molding material is 0.2 m.
A tape-shaped fiber-reinforced resin molding material having a width/thickness ratio of 25 to 200, and a plurality of tape-shaped fiber-reinforced resin molding materials formed on a synthetic resin board using the fiber-reinforced resin molding material as a base material. The object of the present invention is to provide a fiber-reinforced resin laminate having transparency, which is arranged in a plane and formed by lamination molding, and has a base material and a synthetic resin plate laminated in at least one layer.

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, polyimide fibers, etc. Fibers (filaments) such as organic fibers such as polyamide-imide fibers are bundled with a binding agent. Here, the tape-shaped fiber-reinforced resin molding material (hereinafter referred to as molding material) of the present invention and the molded product using the molding material are preferably glass fiber rovings in that they have transparency.

Roving is 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 3000 filaments with a diameter of about 12 μm. It is something that is focused to some extent. If the diameter of the roving is large, the thickness and width/thickness ratio of the present invention cannot be obtained by unbundling and expansion in the manufacturing method of the molding material, and the resin will not be sufficiently filled into the fibers. It becomes non-uniform.

The synthetic resin in the molding material of the present invention is preferably a thermoplastic resin. In the manufacturing method, the roving as continuous fibers is impregnated with resin as an emulsion and filled between the fibers, so it can become an emulsion.
More preferably, it is a transparent resin. For example, homopolymers such as vinyl chloride, vinylidene chloride, vinyl acetate, acrylic esters, methacrylic esters, styrene, acrylonitrile, ethylene, propylene, fluorine-containing monomers, and other copolymerizable monomers. Examples include copolymers obtained by copolymerizing with the same. Among these, especially vinyl chloride alone, or vinyl acetate, vinylidene chloride, acrylic ester, methacrylic ester, acrylonitrile, maleic anhydride, maleic acid in an amount that does not deteriorate the properties of vinyl chloride. A material known to be difficult to impregnate into fibers, such as a vinyl chloride copolymer obtained by polymerization with an ester or the like, may be used. Incidentally, it goes without saying that the thermoplastic resin may be opaque or colored. The amount of resin filled as a molding material is preferably as large as possible;
It is desirable that the so-called ignition loss (Ig 1oss ) be 30% or more.

The molding material of the present invention is manufactured according to the method for manufacturing a fiber reinforced resin tape invented by the present inventors as described above.The thickness and width/thickness ratio of the molding material are as follows: In order to achieve this range, the tensile stress applied to the roving during unbundling and expansion after impregnating the roving with the resin emulsion, which is the condition, must be the desired thickness and width/thickness ratio of the resulting molding material. This is done by adjusting the

Usually, the roving is made into a fiber-reinforced resin tape by the above-mentioned manufacturing method, but by making a plurality of rovings adjacent to each other, a wide tape can be obtained.

Here, unbundling and development refers to immediately after impregnating the roving with a resin emulsion, or simultaneously with the impregnation, passing the roving over the sliding surface of a member having a sliding curved surface while applying tension to the roving to concentrate the roving. This refers to unraveling the roving fiber bundle and spreading it out into a flat shape by dispersing and averaging the stress.

At this time, the fine resin particles in the emulsion are filled between the filaments, creating a wedge effect, and the resin is densely packed, making the unbundling and expansion more effective.

In the unbundling development of roving, for example, the diameter of 3000 filaments with a diameter of 12 μm is approximately 2+n.
mφ, a tape-shaped molding material with a thickness of about 0.1 mm, a width of about 10 mm, and a width/thickness ratio of 100 can be obtained by appropriately adjusting the bow tension stress of the roving and unbundling it.

The molding material of the present invention has a thickness of 0.2 + nm or less9 and a width/thickness ratio of 25 to 200, but if the ratio is less than 25, the amount of resin is small and it tends to be non-uniform. The molded product has poor transparency and low strength.

On the other hand, it is difficult to exceed 200. For example, the above thickness according to the present invention is about 0.1+n+n, and the width/thickness ratio is 1.
00, which has a width of 20+++m, has approximately 5 filaments in the thickness direction and approximately 60 filaments in the width direction in its cross-sectional investigation.
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 roving is used, the thickness is 0.4
When the width is 8 mm and the width/thickness ratio is 20 mm, the filaments are extremely unevenly distributed in the thickness direction, and the resin is extremely non-uniform without sufficient grooves between the filaments, and is not transparent. is also inferior. Also, the thickness is 0, 1
If it is extremely thin (n++n or less), it becomes film-like, difficult to handle, and unsuitable as a molding material.

By arranging a plurality of the above-mentioned molding materials in a plane on a synthetic resin board as a base material and laminating them, a fiber-reinforced laminate in which the base material and the synthetic resin board are laminated in at least one layer is obtained.

As for the form of the base material, for example, the molding material can be used in the form of fibers, but it is not limited to a specific shape (
As explained in the laminating means for obtaining a laminate described below, for example, in a multistage press method, a plurality of molding materials are arranged in parallel on a synthetic resin plate at a desired constant interval in the length direction, thereby forming a base material. It also includes adjusting the form.

In addition, in the above-mentioned arrangement of the molding material, it is possible to form a base material by arranging a plurality of molding materials densely in parallel in the length direction, or by arranging a plurality of molding materials at predetermined regular intervals or densely in the vertical and horizontal directions. Of course, it is also possible to do so.

On the other hand, synthetic material (
The greaseproof plate is preferably transparent, and the color tone and material are not restricted, but in terms of lamination, adhesion, etc., it is a resin plate made of the same type of thermoplastic resin that is impregnated with the molding material. If the resin of the molding material is a vinyl chloride resin, it is preferable that the slit is a vinyl chloride resin plate. The thickness of such a synthetic resin board may be anything from an extremely thin film-like material to a sheet-like or slightly thin plate-like material, and is not limited to a flat plate; for example, it may be a fiber-reinforced resin laminate such as a corrugated plate. It can be selected as appropriate depending on the purpose of use. Furthermore, instead of only one layer consisting of a base material and a synthetic resin, the base materials may be laminated in a sandwich shape, or synthetic resin plates may be laminated in multiple layers.

The laminating means for obtaining a laminate is not particularly limited, and may include a multi-stage press method, which is a laminating means for ordinary synthetic resin plates, etc.
A lamination method using direct pressure bonding such as a belt press method, an extrusion method, or a calendar method as a continuous method is adopted.

Lamination conditions in such a lamination method are carried out under appropriate conditions. As a specific example,
In the case of the above multi-stage press method, a transparent thermoplastic resin plate of a desired shape is set in the press, and a plurality of molding material tapes are placed on the resin plate as a base material at regular intervals in the length direction. are arranged in parallel, and then the same resin plate as above is placed on top of them and pressed while heating at a predetermined pressure. Further, as a continuous method, when using a belt press method, the thermoplastic resin plate and the molding material are continuously supplied and pressed by heating under a predetermined pressure between upper and lower belts.

In such lamination means, it is also possible to process the surface of a thermoplastic resin plate, or to process a flat plate into a corrugated shape. Also,
A multilayer laminate can also be obtained by alternately laminating thermoplastic resin plates and molding materials in multiple layers. Furthermore, the arrangement of the molding materials can be made arbitrary, and the thermoplastic resin plates can be appropriately colored to create laminates with enhanced decorativeness.
By using a thermoplastic resin plate with improved weather resistance, a fiber-reinforced resin laminate with improved weather resistance can be obtained.

The thus obtained fiber-reinforced resin laminate of the present invention can be easily cut, and can be processed into any shape using, for example, a power tool.

[Example] Examples 1 to 9 Approximately 30 glass fibers (filaments) having a diameter of approximately 12 μm were
The tensile stress of the roving during unbundling and development 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 an emulsion of vinyl chloride resin. After unbundling and expansion, the mixture was heat-treated to obtain a tape-shaped molding material containing glass fiber as a reinforcing material in a 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.

Comparative Examples 1 to 2 Vinyl chloride resin was prepared in the same manner as in the example except that the tensile stress of the roving during unbundling and expansion was adjusted so as 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 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 *) A wide roving made of four adjacent rovings.

- Two wide ropings made adjacent to each other.

Examples 10 to 12 Instead of the vinyl chloride resin emulsion in Examples 2, 6, and 9, a vinyl chloride-acrylic ester copolymer (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 13 to 15 In place of the vinyl chloride resin emulsions in Examples 2.6 and 9, emulsions prepared by using an emulsifier to prepare a latex containing a polymer (solid content 48%) obtained by emulsion polymerization of methyl methacrylate 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 following was used.

The shape, characteristics, etc. of this molding material were compared to the third example.
Arrange and arrange as shown in the table and press under the following conditions (
A 1 m×1+n fiber-reinforced resin laminate was obtained by laminating the sheets using a multistage press (multistage press).

Press temperature 180℃ Press pressure 90 kg/cm2 Press time
The properties of the fiber-reinforced resin laminate obtained by heating for 50 minutes and cooling for 50 minutes are measured, and the results are shown in Table 3.

The results are shown in Table 2.

Table 2 Examples 16 to 23 Using the tape-shaped molding materials obtained in Examples 1, 5, 6, and 8 and a vinyl chloride resin plate with a thickness of 0.1 to 0.5 mm as a synthetic resin plate. , Examples 25 to 26 Using the tape-shaped molding materials obtained in Examples 10 and 13, 12 tapes were arranged in parallel in the length direction with an interval of 10+++n, and a lm x 1m molding material was placed on top of it. Thickness 2mm
A piece of polymethyl acrylate is placed and heated, and a pressure of 20 kg/mm is applied to mold it to a thickness of approximately 2 mm.
A glass fiber-containing transparent laminate was obtained. The physical properties of the laminate thus formed were measured.

The results are shown in Table 4.

Table 4 "Effects of the Invention" The tape-shaped fiber-reinforced resin molding material of the present invention has transparency by itself, and since the fibers are aligned in the longitudinal direction, It is characterized by extremely high strength. In particular, a fiber-reinforced resin laminate can be obtained by laminating and molding synthetic resin plates using a molding material as a base material. This fiber-reinforced resin laminate has transparency by laminating transparent synthetic resin plates,
Furthermore, the effect of excellent mechanical strength is recognized.

It is also recognized that a laminated board with excellent aesthetics and decorative properties can be obtained by appropriately selecting the arrangement of the molding material as a base material or the synthetic resin plate.

Claims (8)

[Claims] (1) In a fiber-reinforced resin molding material in which continuous fibers are contained in a synthetic resin as a reinforcing material, the continuous fibers are aligned in the length direction, and the synthetic resin is densely filled between the fibers,
and the thickness of the resin molding material is 0.2 mm or less,
A tape-shaped 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 is obtained by impregnating continuous fibers with a synthetic resin emulsion, unbundling and expanding the continuous fibers while applying tension, drying, and heating. . (3) The resin molding material according to claim 1, wherein the resin molding material has a thickness of 0.2 mm to 0.1 mm. (4) The resin molding material according to claim 1, wherein the continuous fibers are formed by unbundling and expanding glass fiber rovings. (5) The resin molding material according to claim 1, wherein the synthetic resin is a thermoplastic resin. (6) In a fiber-reinforced resin molding material in which continuous fibers are contained in a synthetic resin as a reinforcing material, the continuous fibers are aligned in the length direction, and the synthetic resin is densely filled between the fibers, and The thickness of the resin molding material is 0.2 mm or less, and the width/thickness ratio is 25 to 200. Using a tape-shaped fiber-reinforced resin molding material as a base material, a plurality of tapes are arranged in a flat shape on a synthetic resin plate. A transparent fiber-reinforced resin laminate, which is formed by arranging and laminating molding, and has a base material and a synthetic resin plate laminated in at least one layer. (7) The laminate according to claim 6, wherein the synthetic resin plate is a transparent thermoplastic resin plate. (8) Claim 6, wherein the continuous fiber is a glass fiber roving.
Laminated board as described.