JPH0788998A - Fiber-reinforced thermoplastic resin laminated body - Google Patents

Abstract

PURPOSE:To provide a fiber-reinforced thermoplastic resin laminated body wherein it has light-weight, high strength and the coefficient of linear expansion which is lower than that of a metal, therefore, combination use with various metallic materials is possible and suitable for use of parts for which high dimensional accuracy is required. CONSTITUTION:A plurality of sheets of fiber-reinforced thermoplastic resin prepregs are laminated so that arrangement directions of fibers are identical with each other or met at right angles with each other, the coefficient of linear expansion of an arrangement direction of a fiber or the coefficient of linear expansion of a direction meeting at right angles with the arrangement direction of the fiber is taken as 0.6X10<-5>/ deg.C. It is recommendable that as a fiber of the fiber-reinforced thermoplastic resin prepreg, it is allowed to contain, for example, a glass fiber within a range of at least 40% and not exceeding 85% in volume.

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 laminate which is lightweight, has excellent mechanical strength and impact resistance and is suitably used as an industrial material such as automobiles and interiors of houses.

[0002]

2. Description of the Related Art Fiber-reinforced resin laminated moldings are used as interior materials for automobiles, houses, etc., because they are lighter in weight, easier to mold, and easier to mold than metal. The range of use of the interior materials is expanding as a fuel efficiency improvement measure.

[0003]

However, the conventional fiber-reinforced resin molding uses a thermosetting resin such as unsaturated polyester resin, vinyl ester resin, or epoxy resin.

Usually, a fiber-reinforced resin molded body is manufactured by laminating a predetermined number of reinforcing fibers impregnated with a resin. However, a fiber-reinforced resin molded body using a thermosetting resin causes a gap between layers when an impact load is applied. It peels off and causes shape destruction. Increasing the fiber content to reduce the linear expansion coefficient tends to facilitate delamination. This is said to be due to the poor toughness of the thermosetting resin. As an attempt to improve impact resistance, use of a thermoplastic resin having higher toughness than a thermosetting resin has been studied.

However, in conventional fiber-reinforced thermoplastic resin moldings, it is difficult to maintain the linearity of continuous fibers and increase the fiber content because the thermoplastic resin has a high viscosity, and the linear expansion coefficient is There was a limit to the combination use with metals such as iron, aluminum, and copper having a low linear expansion coefficient of 2.5 × 10 ⁻⁵ / ° C. or higher and low thermal expansion coefficient materials, and the integrated use.

Furthermore, there is a limitation in maintaining the dimensional accuracy even when it is used in parts where temperature changes,
The development of a fiber reinforced thermoplastic resin product having a linear expansion coefficient of a metal plate or less has been strongly desired. The present invention has been made for the purpose of meeting such a demand.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above objects can be achieved by laminating and molding a fiber-reinforced thermoplastic resin plate in order to solve these problems. The present invention has been completed.

That is, according to the present invention, a plurality of fiber-reinforced thermoplastic resin prepregs are laminated so that the arrangement direction of the fibers is the same or orthogonal to each other, and a line in the arrangement direction of fibers (hereinafter referred to as "0 degree direction"). The expansion coefficient or the linear expansion coefficient in the fiber array direction (0 degree direction) and the direction orthogonal thereto (hereinafter referred to as "90 degree direction") is set to 0.6 x 10 ^-5 / ° C or less. A fiber-reinforced thermoplastic resin laminate is provided.

The types of resin used as the thermoplastic resin for the fiber-reinforced thermoplastic resin plate according to the present invention include polyolefins such as polyethylene and polypropylene, polyamides, polycarbonates, vinyl chloride, polyesters such as polyethylene terephthalate, polystyrene, Various other thermoplastic resins such as polyacetal and nylon can be used, but polypropylene resin is the most desirable resin from the viewpoints of strength, abrasion resistance, price and easiness of recycling when it becomes waste. Recommended.

The fibers used in the fiber-reinforced thermoplastic resin prepreg of the present invention include synthetic resin fibers such as aramid fibers, natural organic fibers, metal fibers such as titanium, boron and stainless steel, glass, carbon and silicon carbide. Inorganic fibers can be mentioned, but it is recommended to use glass fibers as the most desirable fibers in terms of strength, price and coefficient of thermal expansion.

The blending ratio of the thermoplastic resin and the fibers is preferably such that the blending ratio of the fibers is 40% or more and 85% or less by volume. If it is 85% or more, the required toughness is lowered and the molding process becomes difficult. If it is 40% or less, the required rigidity and wear resistance cannot be obtained. It is recommended that these fibers be arranged in a fixed direction.

A fiber-reinforced thermoplastic resin plate obtained by impregnating fibers arranged in one direction with a thermoplastic resin usually has a thickness of 3 to 2.
A yarn obtained by bundling 200 to 12000 5 μm monofilaments or a roving in which a predetermined number of rovings are arranged in one direction is impregnated with a thermoplastic resin.

Glass fiber is usually subjected to various surface treatments,
The adhesion with the resin is improved. The surface treatment is performed by combining a sizing agent and a coupling agent. The sizing agent needs to be selected depending on the thermoplastic resin to be combined. Generally, a thermoplastic resin that is softened at the melting temperature of the combined thermoplastic resin and is easily impregnated into the fiber bundle by the thermoplastic resin is selected. Therefore, a sizing agent containing a resin of the same type as the thermoplastic resin to be combined as a main component is often used.

The glass fiber used as the fiber of the fiber reinforced thermoplastic resin plate is one which has been treated with a silane-based, titanate-based or zirconium-based coupling agent to improve the adhesion to the resin. In the case of glass fiber, it is necessary to select the optimum coupling agent according to the resin to be combined, and specific examples thereof will be listed below.

In the case of nylon resin, γ-aminopropyl-trimethoxysilane, N-β- (aminoethyl)-
γ-aminopropyl-trimethoxysilane or the like is used. If it is a polycarbonate resin, γ-aminopropyl-trimethoxysilane, N-β- (aminoethyl)-
γ-aminopropyl-trimethoxysilane or the like is used.

In the case of polyethylene terephthalate or polybutylene terephthalate, β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane, γ-
Glycidoxy-propyltrimethoxysilane, γ-aminopropyl-trimethoxysilane and the like are used.

For polyethylene or polypropylene, vinyltrimethoxysilane, vinyl-tris- (2
-Methoxyethoxy) silane, γ-methacryloxy-propyltrimethoxysilane and the like are used.

If polyphenylene oxide, polyphenylene sulfide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyimide, polyarylate or fluororesin is used, the above-mentioned coupling agent can be used, but other than that. In addition, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-aminophenyltriethoxysilane and the like can be used.

When a fiber other than glass fiber is used as the reinforcing fiber, an amine-curable epoxy resin is often treated as a coupling agent, and specific examples thereof include bisphenol-A-epichlorohydrin resin, epoxy novolac resin, alicyclic system. Epoxy resin, aliphatic epoxy resin,
Glycidyl ester type resins can be used. When the melting temperature of the thermoplastic resin is high and it is assumed that the ordinary coupling agent is thermally decomposed, the coupling agent may not be used at all.

The method of applying the coupling agent to the fiber surface is as follows. That is, as one method, when the fibers are melted and the monofilament is pulled out, a surfactant is added to the sizing agent and the coupling agent to prepare an aqueous solution, which is sprayed on the monofilament, and then the temperature is about 100 ° C. Dry and process. As another method, the fiber from which the sizing agent has been removed is completely impregnated with a solution in which the coupling agent is dissolved by 0.1 to 3% by weight by means such as dipping or spray coating.

6 fibers containing this coupling agent solution
It is dried at 0 to 120 ° C., and the coupling agent is reacted with the fiber surface. The drying time is sufficient for the solvent to evaporate, which is about 15 to 20 minutes. The solvent for dissolving the coupling agent has a pH of 2.0 to 1 depending on the surface treatment agent used.
There are cases where water adjusted to 2.0 is used, and cases where organic solvents such as ethanol, tolueneacetone and xylene are used alone or as a mixture.

There are various methods for forming a thin plate by impregnating the reinforcing fibers unidirectionally aligned with the thermoplastic resin, but the most general method is as follows. One method is to make a thin plate by dissolving the resin in a solvent and impregnating the reinforcing fiber with the resin, and then removing the solvent while defoaming. Another method is to heat and melt the resin to impregnate the reinforcing fibers, degas, and cool to form a thin plate.

The thin plate thus produced has excellent adhesion between the fiber and the thermoplastic resin, and the fiber content is 30 to 30.
It can be changed to 90% as required, and the thickness is 0.1-
Although it can be manufactured as thin as 1.0 mm, it is desirable to use it at a glass content of 40 to 85% and a thickness of 0.1 to 0.6 mm.

When the glass fiber content is 40% by volume or less, the amount of fibers is small and the strength is low. On the other hand, when the glass fiber content is 85% by volume or more, the amount of resin is small with respect to the fibers and the adhesion between the fibers and the resin is lowered, resulting in low strength. Not preferable.

A preferred continuous production method of the fiber reinforced thermoplastic resin prepreg in the present invention is carried out by the apparatus and production conditions shown in JP-B-2-48907.

When the reinforcing fiber is glass fiber, 100 yarns having 1600 bundles of 13μ monofilaments surface-treated with γ-methacryloxy-propyltrimethoxysilane are bundled together while pulling 100 yarns with a uniform tension of 200 m in width.
It was manufactured by impregnating the resin with a heat roller while squeezing the resin with a hot roll while bringing the resin into contact with a heat-melted thermoplastic resin while pulling.

The fiber reinforced thermoplastic resin laminate is obtained by laminating the above fiber reinforced thermoplastic resin prepregs so that the fiber arranging directions are the same or the fiber arranging directions are orthogonal to each other. The number of laminated layers is arbitrary depending on the application.

Any method can be used as a method for molding the laminate, for example, after heating the laminate above the flowable temperature in an oven, the laminate is heated to a glass transition temperature of the resin. If the temperature is 30 ° C. or higher, it is put into a press mold heated to at least the glass transition temperature,
If the glass transition temperature of the resin is less than 30 ° C., it is placed in a press mold at room temperature, and the mold is pressed in a short time to perform shaping, defoaming and cooling at the same time, a so-called stamping molding method,
Further, while heating the laminated body in a mold attached to a press to a temperature at which the resin cannot flow or more, the laminated body is pressed at a pressure of 1 to 300 kg per 1 m ² of the surface area of the molded product for 10 seconds to 60 minutes to make a glass transition of the resin. A so-called press molding method in which the temperature is cooled to below the temperature and then demolding, or after heating to a temperature above the resin flowable temperature under vacuum, after shaping at a pressure of 20 kg / cm ² or less, defoaming, the glass transition temperature The so-called autoclave molding method, in which the mold is cooled and then removed from the mold, is exemplified below.

The fiber-reinforced thermoplastic resin laminate produced in this manner has features such as light weight and high strength, and also has a linear expansion coefficient similar to that of a metal that has hitherto been obtained. It is possible to combine with existing materials with low linear expansion coefficient such as iron, aluminum, copper, etc., and the applications will be greatly expanded.

[0030]

EXAMPLES The present invention will be described in detail below with reference to examples. [Example 1] γ-methacryloxy-pro as reinforcing fiber
Uses glass fiber surface-treated with pyrtrimethoxysilane
Polypropylene grafted with maleic acid as resin
Use polypropylene (PP) mixed with 1 part by weight of pyrene.
1m at a width of 200mm ²Weight per 250g, thickness
180-μm fiber-reinforced thermoplastic with a fiber content of 40% by volume
A resin plate A was manufactured. And this fiber reinforced thermoplastic
A resin plate A cut into a length of 200 mm in the fiber direction
32 pieces were prepared.

This fiber-reinforced thermoplastic resin plate is 90 ° / 0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 0 in order from the top when the fiber direction is 0 °. ° / 90 ° /
1 in the direction of 0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 90 °
Two sets of 6 layers were prepared.

One set of the laminates was sandwiched between two polyimide films and placed between hot plates heated to 240 ° C., preheated at a pressure of 0.02 kg / cm ² for 5 minutes, and then the pressure was released, A laminated plate having the shape shown in FIG. 1 can be molded 60
It was put into a mold heated to 0 ° C. and cooled and shaped at a pressure of 3 kg / cm ² for 5 minutes to form a laminated plate (1) for measuring a linear expansion coefficient.

Another set of laminates is sandwiched between two polyimide films and placed between hot plates heated to 240 ° C.,
After preheating at a pressure of 0.02 kg / cm ² for 5 minutes, the pressure is released, and the mixture is put into a mold heated to 60 ° C. where a laminated plate having the shape shown in FIG. 2 can be molded, and a pressure of 3 kg / cm ² is applied. After cooling and shaping for 5 minutes, a molded body (2) for impact test was molded.

Next, from the laminated plate (1) for measuring the linear expansion coefficient shown in FIG. 1, 0 was obtained as a test piece for measuring the linear expansion coefficient.
Test pieces (1a, 1a) cut out in the ° direction and test pieces (1b, 1b) cut out in the 90 ° direction were prepared, and JI
The linear expansion coefficient was measured according to SK6911. The results are shown in Table 1.

Further, holes (2a, 2a) are opened in the flange portion of the molded body (2) for impact test shown in FIG.
As shown in, the bolts (4,
Fixed in 4). After leaving this for 60 minutes in a constant temperature bath at 100 ° C., the deformation state of the fiber-reinforced resin molded body was observed, but it was not significantly deformed compared to the state at room temperature.

Furthermore, after leaving this at room temperature overnight,
At the position of P, a 4 kg steel ball was naturally dropped from a height of 50 cm, an impact energy of 2000 J was applied, and a visual inspection and a measurement of the delamination area by ultrasonic flaw detection were performed. The results are shown in Table 1. As described above, a fiber-reinforced thermoplastic resin molded article having excellent impact resistance was obtained without significant deformation at high temperatures.

[0037]

[Table 1]

Example 2 A fiber-reinforced thermoplastic resin plate B was produced in the same manner as in Example 1 except that the fiber content was 60% by volume and the thickness was 150 μm. This was cut, laminated and molded in the same manner as in Example 1 to obtain a linear expansion coefficient measuring laminate (1).
And a molded product (2) for impact test was molded and tested. The results are shown in Table 1. A fiber-reinforced thermoplastic resin molded article having excellent impact resistance was obtained without significant deformation at high temperatures.

Example 3 A fiber-reinforced thermoplastic resin plate C was produced in the same manner as in Example 1 except that the fiber content was 85% by volume and the thickness was 130 μm. In the same manner as in Example 1,
A laminate (1) for measuring a linear expansion coefficient and a molded body (2) for impact test were molded and tested. The results are shown in Table 1. A fiber-reinforced thermoplastic resin molded article having excellent impact resistance was obtained without significant deformation at high temperatures.

Comparative Example 1 A fiber reinforced thermoplastic resin plate D was produced in the same manner as in Example 1 except that the fiber content was 35% by volume and the thickness was 200 μm. In the same manner as in Example 1,
A laminate for measuring the coefficient of linear expansion and a molded body for impact test were molded and tested. The results are shown in Table 1. A fiber-reinforced thermoplastic resin molded product was obtained that was significantly deformed at high temperatures and had poor impact resistance.

Comparative Example 2 A fiber-reinforced thermoplastic resin plate D was produced in the same manner as in Example 1 except that the fiber content was 90% by volume and the thickness was 120 μm. In the same manner as in Example 1,
A laminate for measuring the coefficient of linear expansion and a molded body for impact test were molded and tested. The results are shown in Table 1. A fiber-reinforced thermoplastic resin molded product was obtained that was significantly deformed at high temperatures and had poor impact resistance.

[Comparative Example 3] Unsaturated polyester resin ML
A glass fiber is impregnated with a resin solution obtained by adding 100 parts of 3501 (manufactured by Mitsui Toatsu Chemicals, Inc.) to 1 part of ditertiary butyl perbenzoate, and having a width of 200 mm, a weight of 250 g per 1 m ² , a thickness of 160 μm, and a fiber. A fiber reinforced resin plate E having a content rate of 40% by volume was manufactured. This fiber-reinforced resin plate E was cut into a length of 200 mm in the fiber direction to obtain 32 resin plates.

When the fiber direction of this fiber-reinforced resin plate is set to 0 °, 90 ° / 0 ° / 90 ° / 0 ° / 9 in order from the top.
0 ° / 0 ° / 90 ° / 0 ° / 0 ° / 90 ° / 0 ° / 90
Two sets of 16 layers were prepared in the direction of ° / 0 ° / 90 ° / 0 ° / 90 °. One set of the laminated bodies is put into a mold heated to 150 ° C. capable of forming the shape shown in FIG. 1 and pressed at a pressure of 70 kg / cm ² for 5 minutes to form a laminated plate for measuring a linear expansion coefficient. did.

Further, another set of laminated bodies is put into a mold heated to 150 ° C. capable of forming the shape shown in FIG. 2 for 5 minutes.
It was pressed at a pressure of 70 kg / cm ² to form a molded body for impact test. A linear expansion coefficient and an impact test were conducted in the same manner as in Example 1. The results are shown in Table 1. There was no deformation at high temperature, but the impact test caused fracture.

[0045]

EFFECT OF THE INVENTION The coefficient of linear expansion in the 0 degree direction is 0.6 × 10 ^-5 / ° C
Below or 0 ° and 90 ° direction coefficient of linear expansion 0.6 ×
The fiber-reinforced thermoplastic resin laminate according to the present invention, which is characterized by having a temperature of 10 ⁻⁵ / ° C. or less, has features such as light weight and high strength, and a linear expansion coefficient of metal or less which has not been obtained so far. Because of this, it is possible to combine with materials such as iron, aluminum, and copper, which were not possible until now, and the application to parts that require dimensional accuracy will be greatly expanded. The laminated molded body according to the present invention can be recycled and is useful in terms of resource saving.

[Brief description of drawings]

FIG. 1 is a fiber-reinforced thermoplastic resin laminate according to the present invention,
It is explanatory drawing which shows the state which cuts out the test piece for linear expansion coefficient measurement from this.

FIG. 2 is an explanatory view of a molded article for impact test produced from the fiber-reinforced thermoplastic resin laminate according to the present invention.

FIG. 3 is an explanatory view showing a state in which the molded article for impact test shown in FIG. 2 is fixed to an iron plate.

[Explanation of symbols]

 1 Fiber Reinforced Thermoplastic Resin Laminate 1a 0 ° Directional Expansion Coefficient Measurement Test Piece 1b 90 ° Directional Expansion Coefficient Measurement Test Piece 2 Impact Test Molded Product 2a Hole 3 Impact Test Molded Fixing Plate 4 Impact Test Molded product fixing bolts

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[Procedure amendment]

[Submission date] March 2, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Claim 4

[Correction method] Change

[Correction content]

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction content]

The blending ratio of the thermoplastic resin and this fiber is preferably such that the blending ratio of the fibers is 20% or more and 70% or less by volume. When it is 70% or more, the required toughness is lowered and the molding process becomes difficult. If it is 20% or less, the required rigidity and wear resistance cannot be obtained. It is recommended that these fibers be arranged in a fixed direction.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0039

[Correction method] Change

[Correction content]

Example 3 A fiber reinforced thermoplastic resin plate C was produced in the same manner as in Example 1 except that the fiber content was 70% by volume and the thickness was 130 μm. In the same manner as in Example 1,
A laminate (1) for measuring a linear expansion coefficient and a molded body (2) for impact test were molded and tested. The results are shown in Table 1. A fiber-reinforced thermoplastic resin molded article having excellent impact resistance was obtained without significant deformation at high temperatures.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

Comparative Example 1 A fiber-reinforced thermoplastic resin plate D was produced in the same manner as in Example 1 except that the fiber content was 15% by volume and the thickness was 200 μm. In the same manner as in Example 1,
A laminate for measuring the coefficient of linear expansion and a molded body for impact test were molded and tested. The results are shown in Table 1. A fiber-reinforced thermoplastic resin molded product was obtained that was significantly deformed at high temperatures and had poor impact resistance.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Tanabe 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.

Claims (4)

[Claims] 1. A plurality of fiber-reinforced thermoplastic resin prepregs are laminated so that the fiber arrangement directions are the same or orthogonal, and the linear expansion coefficient of the fiber arrangement direction or the fiber arrangement direction and the direction orthogonal thereto The linear expansion coefficient is 0.6 × 10 ^-5
/ ° C or less, a fiber-reinforced thermoplastic resin laminate. 2. The fiber-reinforced thermoplastic resin laminate according to claim 1, wherein the thermoplastic resin of the fiber-reinforced thermoplastic resin prepreg is a polypropylene resin. 3. The fiber of the fiber reinforced thermoplastic resin prepreg is a glass fiber in which the fibers are unidirectionally arranged.
The fiber-reinforced thermoplastic resin laminate according to any one of 1. 4. The fiber-reinforced thermoplastic resin laminate according to claim 3, wherein the glass content of the fiber-reinforced thermoplastic resin prepreg is in the range of 40% or more and 85% or less in terms of volume content.