JPH0687185A - Laminated molding - Google Patents

Abstract

PURPOSE:To obtain a laminated molding, light in weight and large in shock- absorbing capacity, by a method wherein a part causing slip deformation by an external force is provided on a lamination plane on the occasion of lamination molding of reinforcing fibers impregnated with thermoplastic resin. CONSTITUTION:Resin sheets each of which contains reinforcing fibers impregnated with thermoplastic resin and making up 20vol.% and is made to be 0.1 to 1mm thick are molded in lamination. At this time, a part causing slip deformation by an external force is provided on a lamination plane. It is preferable that an interlayer adhesion of the part causing this slip deformation is designed to be 80 or more when the interlayer adhesion of another lamination plane not causing the slip deformation is made 100. One of the means for this purpose is to provide a nonadhesive part on the lamination plane by disposing a film or the like. It is preferable, besides, that the area on the lamination plane of the non-adhesive part in a part W of a molded body to be subjected to a shock is made to be 5 to 60% when the area on the lamination plane of the part W is made 100%. The lamination plane of the part W to be subjected to shock is formed preferably with a lamination angle having a curvature of a radius 5 to 20mm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated molded article which absorbs impact energy due to collision, drop and the like and exerts a cushioning effect, and a method for producing the same.

[0002]

2. Description of the Related Art In a collision of an automobile or a traveling device, a cushioning body that exhibits a cushioning effect absorbs the collision energy,
It plays the role of protecting the equipment body or the driver. Conventionally used shock absorbers are those in which resin foam is attached to the surface of the structure, metal cylinders and plates that are bent into shapes such as coil springs and bellows, or air pressure and hydraulic pressure. It is a cylindrical shock absorber used. When the shock absorber itself has a device fixing force, for example, when a handle and a shaft are fixed and held, a metal shock absorber, a cylindrical shock absorber, a coil spring, or the like is used. In the case of a metal shock absorber, it is necessary to give a characteristic to the shape of the bent portion that absorbs energy, and the structure and molding of the bent portion are complicated and difficult. On the other hand, the cylindrical shock absorber has a drawback of being heavy in weight, and the coil spring has a drawback of accumulating impact energy and releasing the energy after a collision to destroy a collision object.

[0003]

[PROBLEMS TO BE SOLVED BY THE INVENTION]
Attempts have been made to use a molded body obtained by laminating a resin plate having a thickness of 0.1 to 1 mm impregnated with 20% by volume or more of reinforcing fiber as a buffer. In this case, the molded body is lighter in weight than metals and is used as a lightweight cushioning body for various purposes. However, there is a problem that the molded body has a lower elastic modulus than that of metal, the molded body is destroyed by a slight deformation, and the collision energy absorbed by the molded body is small. Therefore, when an impact force exceeding the limit strain amount of the laminated molded product is applied, the laminated molded product is broken and the impact force cannot be completely buffered. Since the amount of elastic deformation of the conventional laminated molded product is small, it is difficult to absorb a large impact force, so that there is a problem that it is not possible to cope with a wide range of impact forces. Therefore, it is a technical object of the present invention to provide a laminated molded product that is lightweight, has a simple structure, and has a large impact absorbing power.

[0004]

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that conventional fiber-reinforced resin plate laminated molded articles have air bubbles, peeling, vapor deposition defects, etc. between the laminated layers. In the presence of defects, we recognized that when deformed under load, peeling and cracks develop from the defective parts, interlaminar fracture and partial breakage of reinforcing fibers occur, and displacement increases without increasing load capacity. . In the prior art, it was the first technical problem to perform molding so that there was no defect between the stacked layers, but the present inventors have found that such load-displacement characteristics cause a large accumulation of elastic energy. In view of the fact that it is a preferable fracture behavior in buffering the impact force in view of the fact that the absorption amount of buffer energy can be adjusted by positively controlling the interlaminar strength of the composite laminate, the present invention was found. It has come. That is, the present invention is a thermoplastic resin impregnated with 20% by volume or more of reinforcing fiber thickness 0.1 to 1 m
A molded article obtained by laminating and molding a resin plate of m, wherein a laminated surface forming the molded article is provided with a portion that is displaced and deformed by an external force. .

In the above-mentioned present invention, the interlayer adhesive force of the laminated surface which is displaced and deformed by an external force is designed to be 80 or less when the interlayer adhesive force of the laminated surface which is not displaced and deformed is 100. preferable. One means of embodying the above design is to provide a non-bonded portion on the stacking surface that undergoes a shear deformation due to an external force. A preferred embodiment of the above means is that the laminated surface area of the portion of the laminated molded body to be impacted is 1
When 00 is set, the laminated surface area of the non-adhesive part of the part to be impacted is in the range of 5 to 60%. In this case, when the non-adhesive part is molded in multiple layers, the adhesion of each layer It is the total of the area. In a more preferable embodiment than the laminated molded body, the laminated portion is molded with a laminating angle having a radius of 5 mm or more, preferably 20 mm or less.
According to the above-described present invention, by using a composite material in which prepregs are laminated and controlling the interlaminar strength between the laminations, the deformation amount is large, the fracture starts with a relatively low force, and the buffer with large energy absorption in the fracture is used. It has the effect of gaining a body.

The resin plate of the present invention is the above-mentioned reinforcing fiber impregnated with the above-mentioned resin, and its thickness is usually 0.1 to 1 mm.
It is in the range of. When resin plates are laminated to form a molded product, the thickness of the molded product is usually about 3 to 10 mm, and more generally about 3 to 5 mm. As a method of controlling the interlaminar strength between the laminated layers, it is possible to introduce a structure and a shape that are easily rubbed by an external force applied to a part between the laminated layers. This can be achieved more efficiently by positively creating a portion in which particularly large deformation occurs when an external force is applied. One method of controlling the strength between laminated layers is to provide a portion where peeling can easily occur in a part between laminated layers. The part that can easily peel off means a part where the resin between the laminates is prevented from contacting and the adhesive strength is remarkably reduced. Specifically, a resin film having poor adhesiveness with the used resin is arranged. Applying a varnish, grease, or mold release agent that has poor adhesiveness with resin, placing a foaming agent in a part of the layers at the molding temperature of the prepreg, or placing a woven cloth not impregnated with resin between the layers. Obtained by

The lamination of the non-bonded portion is determined by the relationship between the strength of the resin plate containing the reinforcing fibers to be used and the impact force to be absorbed. Normally, the area of the face receiving the impact force is preferably 60% or less. It is preferably in the range of 5 to 60%. When the area of the non-bonded portion with respect to the area of the surface receiving the impact force is outside the range of 5 to 60%, the impact force buffering effect of the molded product cannot be sufficiently obtained. The preferred number of release layers is appropriately selected depending on the purpose, but is usually in the range of 2 to 5 layers per 3 mm of the thickness of the molded product. When a plurality of release layers are provided, they are preferably provided in adjacent release layers. Further, the relational position between the peeling portion and the non-peeling portion in the same peeling layer can be set to an appropriate position as shown in FIGS. 2 and 6, and when the peeling portion is provided in a plurality of layers, it is almost the same. .

As another preferable method, a glass fiber woven fabric may be arranged between the layers to reduce the adhesive strength. The area of the glass fiber woven fabric in this case is also determined by the relationship between the strength of the resin plate containing the reinforcing fibers used and the impact force to be absorbed, but normally the area of the surface receiving the impact force is
It is preferably 60% or less, and can be designed in the same manner as in the above case. However, it is not necessary to stick to the woven fabric, and it is possible to arrange them appropriately by utilizing the directionality of the fibers.

As a more preferable method for controlling the peel strength between layers, in addition to adopting the above-mentioned control method, there is provided a portion laminated at a laminating angle at which delamination occurs preferentially when a load is applied. Since the deformation in the case of this method occurs not in the laminating plane but in the direction perpendicular to the laminating direction, the difference in curvature between the front surface and the back surface of the laminated molded product causes a shift in the laminating surface, such as a wall. This can be achieved by partially providing a corrugated or zigzag folded structure that does not form a balanced surface with respect to the load direction to a portion, specifically, for example, the surface W in FIG. 1 or the portion 10 in FIG. It At this time,
If the corner of the folded-back portion is a sharp angle, the load is concentrated and applied to that portion, and the corner of the folded-back portion is bent prior to the occurrence of displacement between the stacked layers. Depending on the situation, corners have a radius of 5
It is preferable to form at a lamination angle having a curvature of not less than mm, preferably not more than 20 mm.

As a method for molding the laminated plate, after a resin plate is cut into a predetermined shape and superposed, a molding method which is usually adopted by an autoclave, a molding method by a heating press and the like are adopted. The laminated molded body of the present invention has such a structure that when an external force is applied to the molded body, the interlayer adhesive force of a part of the laminated portion is weaker than that of the other laminated portion. Destruction begins around the point. This breakage first causes a gap between the stacked layers, which leads to breakage while absorbing external force. In this case, the shock absorbing power of the molded body is larger than that of the original molded body, and the elastic modulus at the time of breaking is low, so the shock at the time of impact is small and the human body is protected from the shock at the time of impact. The effect is great.

In the present invention, the reinforcing fibers are glass fibers, carbon fibers, boron fibers, titanium fibers, alumina fibers, nylon fibers, tetron fibers, polyethylene fibers,
It means a fibrous material capable of exerting an effect of improving the strength such as aramid fiber, natural fiber such as jute, metal fiber such as stainless fiber, and the material is not particularly limited as long as it is a fibrous material.
The form of the reinforcing fiber may be a continuous fiber roving yarn, a yarn known as a tow arranged in one direction, a woven fabric, a chopped strand mat, or a combination thereof. These reinforcing fibers are usually made by converging 200 to 12000 filaments of 3 to 50 μm as one unit, and the fiber content is a factor that determines the strength of the laminated product, and the practically usable amount is 20 volumes. % Or more, and preferably 30% by volume or more. The content of the reinforcing fiber depends on the required strength and the buffering effect of the application to which it is applied, but from the point of use as a structure, it is generally in the range of 20 to 70% by volume, preferably 40 to 60% by volume. . In addition, it is preferable that the surface of the reinforcing fiber is treated with a surface treatment agent such as a silane coupling agent alone or a sizing agent containing the silane coupling agent in order to improve the adhesion to the resin.

In the case of glass fiber, it is necessary to select the most suitable coupling agent according to the resin to be combined, and specific examples thereof will be given below. For nylon resin, γ-
Aminopropyl-trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-trimethoxytran and the like are used. If it is a polycarbonate resin, γ-aminopropyl-trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-trimethoxysilane and the like are used. If it is 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, γ-aminopropyl-trimethoxysilane 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 in addition, N -(Β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-aminophenyltriethoxysilane and the like can be used.

When a material other than glass fiber is used, a sizing agent or a coupling agent may not be used when the physical properties are considered first, but since the workability is deteriorated, an amine-curable epoxy resin is used as a coupling agent. In many cases, a bisphenol A type epoxy resin, an epoxy novolac resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or a glycidyl ester type resin can be used. The method of applying the coupling agent to the fiber surface is as follows. That is, the fiber from which the sizing agent has been removed is completely impregnated with a solution in which 0.1 to 3% by weight of the coupling agent is dissolved by means such as dipping or spray coating. The fiber containing the coupling agent solution is dried at 60 to 120 ° C. to allow the coupling agent to react with the surface of the fiber. The drying time is sufficient to evaporate the solvent, which is about 15 to 20 minutes. The solvent that dissolves the coupling agent depends on the pH used, depending on the surface treatment agent used.
There are cases where water adjusted to 2.0 to 12.0 is used, and cases where organic solvents such as ethanol, toluene, acetone, and xylene are used alone or as a mixture. To the impregnating resin, it is significant to add a modifier that enhances the affinity with the surface treatment agent, for example, polypropylene grafted with maleic anhydride.

The resin of the present invention may be either a thermoplastic resin or a thermosetting resin. Examples of the thermoplastic resin include polystyrene, styrene-acrylonitrile resin, ABS resin, polyethylene, polypropylene, polycarbonate, polyethylene terephthalate and polybutylene terephthalate. , Nylon resin, polyphenylene ether,
Polyphenylene sulfide, polyether imide, polysulfone, polyether sulfone, polyimide,
Polyether nitrile, polyether ketone, etc. are typical, and as the thermosetting resin, unsaturated polyester resin, vinyl ester resin, urethane resin, epoxy resin, phenol resin, etc. are typical. As the above, a combination of resins or a combination of other resins, for example, a plurality of rubber-based elastomer resins can be applied. Further, it is possible to use a resin in which an inorganic filler such as whiskers, talc, mica, short glass fibers, short carbon fibers, or graphite is added to adjust the elastic modulus of the resin.

[0015]

The details of the present invention will be described below with reference to typical examples. Example 1 A sheet in which 1800 glass fibers bundled with γ-aminopropyl-trimethoxysilane and having a diameter of 1800 glass filaments having a diameter of 13 μm are bundled into one direction and 80 fibers are arranged in one direction is impregnated with a polypropylene resin, and the glass fiber content is 50. A 0.2 mm prepreg sheet 1 adjusted to volume% was manufactured. Using the prepreg sheet 1, set the fiber direction of the prepreg to 0 °.
, 0 ° / 90 ° / 0 ° / 90 ° / 0 ° from top to bottom
/ 0 ° / 0 ° / 90 ° / 0 °
10 layers are piled up, and a nylon film (thickness: 50 μm) with a width of 10 mm and a length of 30 mm is respectively placed at the positions shown in FIGS. 2A, 2B and 2C from the upper side to the third layer, the fifth layer and the seventh layer. Place it
Make a non-bonded part, put the laminated body in a mold heated to 200 ℃, pressurize at 10kg / cm ² for 10 minutes, and then keep the pressure and cool to 50 ℃ at 10 ℃ / min. After cooling, demolding,
A molded product shown in was obtained. The area of the non-bonded part at this time is the first
It was 18% of the area of the vertical wall portion W that absorbs the impact shown in the figure. As shown in FIG. 8, the flange portion of this molded product is
150 mm long, 150 mm wide, 20 mm thick, fixed to an iron plate with bolts,
An iron plate having a length of 100 mm, a width of 100 mm and a thickness of 20 mm was placed on the center of the molded product, and a load-displacement behavior was measured by applying a compressive load to the upper surface using an Instron material testing machine Model 1125. As shown in the load-displacement curve of FIG. 3, the results of the test explained that the normal state where the fracture stress is constant is maintained and the energy absorption is large regardless of the increase of the deformation amount. The strain energy is defined as the area of the portion surrounded by the vertical seat-like baseline (usually defined as the X-axis) and the load-displacement curve in FIG. 3, and is defined as the strain energy. It can be judged that the buffering force against the force is large. The strain energy in this case was 61 J (joule). Table 1 shows the breaking force, deformation utilization at the time of breaking, and strain energy.

Comparative Example 1 In the molded product used in Example 1, a molded product having no non-bonded portion was prepared and evaluated in the same manner as in Example 1. As shown in FIG. 4, the fracture initiation force was high and the strain energy was as small as 20 J, which was not suitable for a buffer. Table 1 shows the breaking force, the amount of deformation at the time of breaking, and the strain energy. Comparative Example 2 The molded product shown in FIG. 1 was molded in the same manner as in Example 1. However, the size of the non-bonded portion was 40 mm in width and 26 mm in length. The area of the non-bonded portion at this time was 62.4% of the area of the vertical wall portion W shown in FIG. This molded product was evaluated in the same manner as in Example 1. However, as shown in FIG. 5, the fracture initiation force was low and the strain energy was as small as 3 J, which was not used as a buffer. Table 1 shows the breaking force, the amount of deformation at the time of breaking, and the strain energy.

Example 2 A prepreg sheet 1 was laminated in the same manner as in Example 1 and silicone grease (KF-manufactured by Shin-Etsu Silicone Co., Ltd.) was used instead of the nylon film at the portions A, B and C shown in FIG.
54) was applied to a thickness of 20 μm. Molding was carried out in the same manner as in Example 1 and a load test was conducted. A molded body having a large strain energy and an ability to be used as a buffer body was obtained.
Cost 1 shows the breaking force, the amount of deformation at the time of breaking, and the strain energy together.

Example 3 Lamination was carried out in the same manner as in Example 1 to obtain a molded product. However, A, B,
In the portion C, 102 g of glass cloth per square meter was used instead of the nylon film. Molding was carried out in the same manner as in Example 1 and a load test was conducted. A molded body having a large strain energy and an ability to be used as a buffer body was obtained. Table 1 shows the breaking force, the amount of deformation at the time of breaking, and the strain energy.

Example 4 Lamination was carried out in the same manner as in Example 1 to obtain a molded product. However, A, B,
In the part C, a non-woven cloth made of polyester of 30 g per square meter was used instead of the nylon film. Molding was carried out in the same manner as in Example 1 and a load test was conducted. A molded body having a large strain energy and an ability to be used as a buffer body was obtained. Table 1 shows the breaking force, the amount of deformation at the time of breaking, and the strain energy.

Example 5 Lamination was performed in the same manner as in Example 1 to obtain a molded product. However, A, B,
In the portion C, instead of the nylon film, α, α'-azobisisobutylnitrile, which is a foaming agent, was sprayed to a thickness of 10 μm.

Molding was carried out in the same manner as in Example 1 and a load test was conducted. A molded body having a large strain energy and an ability to be used as a buffer body was obtained. Table 1 shows the breaking force, the amount of deformation at the time of breaking, and the strain energy.

Example 6 A laminate was prepared by stacking 10 layers of the prepreg sheet 1 in the dimensions shown in FIG. 6 so that the fiber directions of the layers of the prepreg were the same as in Example 1. However, in this embodiment, the non-bonded portion D
The size is 23mm and 10mm, which is 51% of the vertical wall area under load. As shown in 10 of Fig.7, the shape with corrugated plate shape on the vertical wall is used as a shape that makes it easy for the layers to shift when an external force is applied. After pressurizing at a pressure of 10 mm / mm for 10 minutes, the pressure was maintained, the temperature was cooled to 50 ° C. at a cooling rate of 10 ° C./minute, and the mold was removed to obtain a molded product shown in FIG. The radius of curvature of the corner of the folded portion 11 of the liquid plate of the molded product obtained at this time was 6 mm. A load test was conducted in the same manner as in Example 1. A molded body having a large strain energy and an ability to be used as a buffer body was obtained.
Table 1 shows the breaking force, the amount of deformation at the time of breaking, and the strain energy.

Comparative Example 3 A molded product was obtained in the same manner as in Example 6. However, the energy of the corners of the folded-back portion 11 of the corrugated sheet of the molded product was small and was not used as a buffer. Table 1 shows the breaking force, the amount of deformation at the time of breaking, and the strain energy.

Example 7 When the fiber direction of the prepreg was set to 0 ° using the prepreg sheet 1, 0 ° / 90 ° / 0 ° / 90 ° /
0 ° / 90 ° / 0 ° / 90 ° / 0 ° / 90 ° / 90 ° / 90 ° / 90
° / 0 ° / 90 ° / 0 ° 90 ° / 0 ° / 90 ° / 0 ° 90 ° / 0
Twenty-two layers were laminated with the dimensions shown in FIG. However, in the case of this example, the non-bonded portion was provided only between the 11th and 12th layers from the top. Molding was performed under the same conditions as in Example 1 to obtain a molded product shown in FIG. As a result of the load test in the same manner as in Example 1, the interlayer displacement occurred only between the 11th and 12th layers from the top, but the displacement did not occur between the other layers.
A molded body having a large strain energy and an ability to be used as a buffer body was obtained. Table 1 shows the breaking force and the amount of deformation at the time of breaking.
The strain energy is shown collectively.

[0025]

The laminated molded product according to the present invention is lightweight, has a simple structure, and has a large impact absorbing power, and is useful as a buffer.

[Brief description of drawings]

FIG. 1 shows a molded body according to one embodiment of the present invention.

FIG. 2 is a developed view of the molded body shown in FIG.

FIG. 3 shows a relationship between a deformation layer and a breaking force at the time of compression failure of a molded body.

FIG. 4 shows the relationship between the amount of deformation and the breaking force at the time of compression failure of a molded body.

FIG. 5 shows the relationship between the amount of deformation and the breaking force during compression failure of a compact.

6 shows a developed view of the molded body shown in FIG.

FIG. 7 shows a molded body according to another embodiment of the present invention.

FIG. 8 is a diagram showing a method of fixing a flange portion in a compression test of a molded body.

Front Page Continuation (72) Inventor Hideo Sakai Kanagawa Gon 1190 Kasama-cho, Sakae-ku, Yokohama Mitsui Toatsu Chemical Co., Ltd.

Claims (9)

[Claims] 1. A molded body obtained by laminating a resin plate having a thickness of 0.1 to 1 mm in which a thermoplastic resin is impregnated with 20% by volume or more of a reinforcing fiber, and an external force is applied to a laminating surface constituting the molded body. A laminated molded article, characterized in that it is provided with a portion that causes a shear deformation. 2. An interlayer adhesive force of a laminated surface which causes a shear deformation due to an external force, and an interlayer adhesive force of a laminated surface which does not cause a shear deformation.
The laminated molded body according to claim 1, which is designed so that when it is 00, it is 80 or less. 3. The laminated molded body according to claim 1, wherein a non-adhesive portion is provided on a laminated surface which is displaced and deformed by an external force. 4. The laminate according to claim 1, wherein the laminated surface area of the non-adhesive portion of the impacted portion is in the range of 5 to 60% when the laminated surface area of the cushioned portion of the laminated molded body is 100. Molded body. 5. The laminated molded body according to claim 1, wherein when the non-adhesive portion is formed in a plurality of layers, it is the sum of the areas of the non-adhesive portions. 6. The laminated molded body according to claim 1, which is obtained by molding the laminated surface of a portion of the laminated molded body which receives an impact with a laminating angle having a curvature in the range of 5 to 20 mm in radius. 7. The laminated molded body according to claim 1, wherein the amount of the reinforcing fibers in the laminated molded body is in the range of 20 to 70% by volume. 8. The laminated molded product according to claim 1, wherein the surface of the reinforcing fiber is treated with a silane coupling agent or a sizing agent containing the silane coupling agent. 9. The laminated molded article according to claim 1, wherein the thermoplastic resin is a polypropylene resin.