JP6717321B2 - Laminated panel and method for manufacturing molded article thereof - Google Patents

Description

The present invention provides a laminated panel comprising a laminate of a fiber reinforced thermoplastic resin layer and a metal plate layer, which has high rigidity and impact strength and is capable of plastic working (sheet metal working) such as bending, pressing and roll forming. , A method of manufacturing the molded article.

In recent years, from the viewpoint of environmental protection and energy saving, weight reduction of these products has been desired in the fields of automobiles, railways, aviation, transportation equipment such as robots, electronic equipment, furniture, building materials and the like. Therefore, attempts have been made to reduce the weight of metal parts by using a fiber-reinforced resin material.

Among them, the carbon fiber reinforced resin composite material, the glass fiber reinforced resin composite material and the like are superior in specific strength and specific rigidity as compared with the metal material, and thus can contribute to weight reduction.

However, these fiber-reinforced resin composite materials are not only higher in material cost than metal, but also the range of utilization of existing molding equipment is limited, and investment of dedicated molding processing equipment is required, resulting in a large cost. Therefore, the current situation is that it has not been popularized for more than 30 years. Further, any fiber-reinforced resin composite material using a thermoplastic resin or a thermosetting resin as a matrix has a problem in that the molding cycle is long.

Patent Document 1 proposes a resin composite-type vibration-damping steel sheet excellent in press workability and has been put into practical use. However, it has low impact strength and is limited to applications that do not require strength. Patent Document 2 describes a press-molding method in which a steel plate and a fiber-reinforced plastic plate body containing a thermosetting resin are integrally joined after preforming a fiber-reinforced resin layer. In addition, there is a problem in mass productivity (a molding cycle of about 5 minutes), although a rapid thermosetting thermosetting resin is applied. In Patent Document 3, as a metal-resin composite having excellent rigidity and impact resistance, a fiber-reinforced resin layer is sandwiched and fixed between metal plates, and at least one edge of the metal plates is bent and sewn. The method of integration is described by. This composite has excellent rigidity and impact resistance, but has poor productivity and does not have mass productivity.

Patent Document 4 proposes a frame member for a seat, which is a laminated body in which a woven fabric is sandwiched between metal plates and fixed with a thermosetting resin. The fiber reinforced woven fabric layer has excellent impact resistance, and the impact resistance can be improved by causing delamination at the interface between the metal and the fiber reinforced woven fabric layer. Since peeling occurs and the fiber-reinforced fabric layer breaks, there is a problem that the impact strength itself during use of the product decreases. Moreover, since a thermosetting resin is used for adhesion, it takes a long time for thermosetting, and therefore it does not combine mass productivity.

JP-A-5-138800 Japanese Patent No. 5633989 JP, 2013-15919, A Patent No. 5669288

INDUSTRIAL APPLICABILITY The present invention can utilize existing molding equipment without expensive equipment investment, has high rigidity and high impact strength, and is capable of plastic working (sheet metal working) such as bending, pressing and roll forming. An object of the present invention is to provide a reinforced resin composite laminate and a method for producing a molded article thereof.

The laminated panel of the present invention comprises a non-woven fabric or a fiber-reinforced thermoplastic resin layer containing chopped fibers having an average fiber length of 10 mm or more and a thermoplastic resin, and a metal plate layer bonded to the fiber-reinforced thermoplastic resin layer. Then, in the laminated panel in which the outermost layer is the metal plate layer, the peel strength is 2.5 kN/m or more when tested by the “floating roller method peel test” method of JIS K6854-4:1999. Moreover, the breakage occurs in the fiber-reinforced thermoplastic resin layer, and the calculated value Z of the formula (1) showing the following lamination constituent factors is 1 or more, a laminated panel.

Z=(σm·tm·εm)/(σc·tc·εc) (1)
σm: Tensile strength (MPa) of the metal plate layer at room temperature
tm: Thickness of metal plate layer (mm)
εm: Tensile elongation (%) of the metal plate layer at room temperature
σc: Tensile strength (MPa) of the fiber-reinforced thermoplastic resin layer at room temperature
tc: Thickness of fiber reinforced thermoplastic resin layer (mm)
εc: Tensile elongation (%) of the fiber-reinforced thermoplastic resin layer at room temperature

In one aspect of the present invention, the fiber-reinforced thermoplastic resin layer is a dynamic viscoelasticity test (JIS K 7244-4:1999 (Plastic-Dynamic Mechanical Property Test Method) of the fiber-reinforced thermoplastic resin layer unit test piece. , Frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.), the ratio of the storage elastic modulus E′ to the specific gravity ρ of the fiber-reinforced thermoplastic resin layer (specific storage elastic modulus value: E′/ρ) is 1.0 GPa. That is all.
Here, the specific gravity ρ (dimensionless) of the fiber-reinforced thermoplastic resin layer is obtained by applying a measured value at room temperature (23° C.) as a representative value.

In one aspect of the present invention, the fiber-reinforced thermoplastic resin layer has a puncture impact test (strike diameter 1/2 inch, impact velocity 4.4 m/s, support base inner diameter: 3 inch) using the fiber-reinforced thermoplastic resin layer unit test piece. , Test temperature: 23° C.), the maximum impact strength per unit thickness is 0.5 kN/mm or more.

In one aspect of the present invention, the fibers in the fiber-reinforced thermoplastic resin layer are non-woven fabrics, and the average fiber length thereof is 25 mm or more.

The laminated panel of one aspect of the present invention has a three-layer structure in which the metal plate layer is adhered to both surfaces of the fiber reinforced thermoplastic resin layer.

The laminated panel of one aspect of the present invention has an adhesive layer between the fiber-reinforced thermoplastic resin layer and the metal plate layer.

In one aspect of the present invention, the fibers in the fiber-reinforced thermoplastic resin layer are organic fibers, and the difference between the melting point of the organic fibers and the melting point or glass transition temperature of the thermoplastic resin is 40° C. or more.

In one aspect of the present invention, the fibers in the fiber-reinforced thermoplastic resin layer are organic fibers, and the melting point of the organic fibers is 160° C. or higher.

In one aspect of the present invention, the organic fiber is a nonwoven fabric having an average fiber length of 25 to 300 mm, an average fineness of ^{2 to} 20 dtex, and a basis weight of 50 to 1000 g/m ² .

In one aspect of the present invention, the laminated panel of the present invention is used for plastic working.

One embodiment of the method for producing a molded article of the present invention is a method for producing a molded article by plastically working the laminated panel of the present invention, wherein a dynamic viscoelasticity test of the fiber-reinforced thermoplastic resin layer single-piece test piece ( Ratio of storage elastic modulus E′ to specific gravity ρ of the fiber-reinforced thermoplastic resin layer in JIS K 7244-4:1999 (Plastic-Determination of dynamic mechanical properties, frequency 100 Hz, test piece thickness 2 mm) (specific storage elastic modulus Value: E′/ρ value is characterized by performing plastic working at any temperature in a temperature range of 1.0 GPa or more.

Another embodiment of the method for producing a molded article of the present invention is a method for producing a molded article by plastically working the laminated panel of the present invention, which is plastic working at any temperature in a temperature range of 10 to 40°C. Is characterized by.

In one aspect of the present invention, the plastic working is press working, roll forming, or bending.

The laminated panel of the present invention has a peel strength of 2.5 kN/m or more according to the "floating roller method peel test" method of JIS K6854-4:1999, and has a property of causing base material fracture in the fiber reinforced thermoplastic resin layer. Since it has, peeling does not occur at the bonding (bonding) interface during plastic working such as press working, the fiber-reinforced thermoplastic resin layer and the metal plate layer undergo plastic deformation at the same time, and the softening temperature range of the fiber-reinforced thermoplastic resin layer It is possible to process the sheet metal at the temperature (below the melting processing temperature) or at room temperature.

At this time, the fiber-reinforced thermoplastic resin layer is softened in a semi-molten state below the melting point of the thermoplastic resin or below the glass transition temperature without being heated to a melt processing temperature range where resin fluidity such as injection molding is exhibited. Sheet metal processing is possible in the cold from the temperature range to room temperature. Although it depends on the type of the thermoplastic resin, the mold temperature can be shaped in a temperature range from room temperature to about 200° C., so that the cooling time, which is the rate-determining rate of the molding cycle, can be shortened.

In particular, in the case of a laminated panel in which a fiber reinforced thermoplastic resin layer is sandwiched between metal plate layers, the heat exchange by the metal plate layers is fast, so that the cooling time can be significantly shortened to several seconds. This makes it possible to shorten the molding cycle.

The fiber reinforced thermoplastic resin layer has a thickness of 0.2 mm or more, and a puncture impact test (ASTM D3763, striker diameter 1/2 inch, impact velocity 4.4 m/s, by a fiber reinforced thermoplastic resin layer single-piece test piece, When the maximum impact strength per unit thickness is 0.5 kN/mm or more under the conditions of the support base inner diameter: 3 inch and the test temperature: 23° C., not only the impact strength during use but also bending and It is possible to facilitate plastic working (sheet metal working) such as press molding (drawing).

According to the present invention, a laminated panel comprising a metal plate layer and a fiber reinforced thermoplastic resin layer having sheet metal workability, light weight, high rigidity, impact resistance, and mass productivity, and a molded product formed by plastically processing the laminated panel. Will be provided.

FIG. 1 is a sectional view of a laminated panel of the present invention. FIG. 2 is a sectional view of a molded product manufactured in the example. 3a is a perspective view of a molded product manufactured in the embodiment, and FIG. 3b is a sectional view taken along line IIIb-IIIb of FIG. 3a.

FIG. 1 shows an example of the laminated panel of the present invention. The laminated panel 1 is one in which metal plate layers 3 are bonded to both surfaces of a fiber reinforced thermoplastic resin layer 2.

This laminated panel has a peel strength (23° C.) of 2.5 kN/m or more, preferably 3 kN/m or more, particularly preferably 5 kN/m, according to the “floating roller method peeling test” method of JIS K6854-4:1999. That is all. When the peel strength is 2.5 kN or more, breakage easily occurs in the fiber-reinforced thermoplastic resin layer, and the metal plate layer and the fiber-reinforced thermoplastic resin layer easily follow each other, so that cold working is performed. It will be easier. In addition, in this laminated panel, the breakage occurs in the fiber reinforced thermoplastic resin layer during the peel test. The upper limit of the peel strength is usually 20 kN/m, preferably 10 kN/m.

In the present invention, the metal plate forming the metal plate layer preferably has a yield ratio of 92% or less, and the yield ratio of 92% or less facilitates deep drawing.

The yield ratio is a ratio of proof stress to tensile strength of a metal plate, and is calculated from proof stress and tensile strength obtained by a tensile strength test. The lower the yield ratio, the better the fitting to a press die or the like and the better forming shape can be obtained. Therefore, it is widely used as an index for the formability of press forming and drawing.
The yield ratio of the metal plate constituting the metal plate layer used in the present invention is more preferably 85% or less and 40% or more, and further preferably 80% or less and 45% or more.

The material of the metal plate forming the metal plate layer 3 is at least selected from the group consisting of steel plates such as iron and stainless steel, aluminum, magnesium, titanium, and alloys containing them, depending on the purpose, application, and physical properties. One kind is used. Among them, iron, aluminum and alloys containing them, and stainless steel are preferable from the viewpoint of lightness (balance of specific gravity and rigidity), and iron, aluminum and alloys containing these are more preferable from the viewpoint of cost.

Further, as the material of the metal plate, the tensile strength measured at room temperature (23° C.) of the metal plate layer unit test piece according to JIS Z2241:2011 (metal material tensile test method) is preferably 200 to 1500 MPa, and 250 ˜1000 MPa is more preferable, and 280 to 600 MPa is further preferable. By using a metal plate having such tensile strength, the thickness of the metal plate layer can be made as thin as possible while ensuring cold workability such as cold deep drawability, and the laminate panel can be made more It tends to be lightweight, which is preferable. The tensile elongation at room temperature (23° C.) is preferably 10 to 80%, more preferably 12 to 80%, and further preferably 20 to 80%. By using a metal plate having such a tensile elongation, the metal plate layer is less likely to break during cold plastic working such as cold deep drawing, and cold plastic workability tends to be favorable, which is preferable.

The thickness t ₃ of the metal plate layer is usually 0.05 to 1 mm in the case of a steel plate, preferably 0.08 to 0.6 mm, more preferably 0.1 to 0.4 mm, and usually 0 in the case of an aluminum alloy. It is preferably from 1 to 2 mm, preferably from 0.15 to 1 mm, and more preferably from 0.2 to 0.5 mm from the viewpoint of rigidity and lightness of the laminated panel. By appropriately selecting the thickness of the fiber reinforced thermoplastic resin layer (core layer) and the thickness of the metal plate layer according to the application and its required characteristics, the equivalent rigidity and equivalent strength of steel and aluminum materials can be set arbitrarily. Is.

As the metal plate, an aluminum alloy having a thickness of 0.1 to 2 mm is preferable from the viewpoints of lightness and high rigidity, although it depends on the type and thickness of the fiber-reinforced thermoplastic resin layer. A1060, A1100-O, A2011, A2014, A2017 , A2024, A2025, A2117, A2219, A3003-O, A3004, A3105, A4032, A5005-O, A5052, A5056, A5086, A5154, A5182, A5254, A5544, A5652, A6061, A6063, A6066, A6101, 6N01, A7001. , A7003, A7050, A7075, A7178, 7N01, A7475, etc. can be used.

Among them, from the viewpoint of availability, A5182 (O, H34, H38), A6061 (T6, T651, T8), A6063 (T6, T83, T832) and the like can be utilized.

In addition to aluminum alloys, cold-rolled steel sheets such as SPCC, SPCD and SPCE, hot-dip galvanized steel sheets such as SGCC, electrogalvanized steel sheets such as SECC and stainless steel alloys can be used.

The metal plate forming the metal plate layer is preferably a plate-shaped one, but is not limited to a plate-shaped one as long as the laminated panel of the present invention can be formed and processed, and may be curved. , It may be bent. Further, it may have a shape having unevenness such that the surface is not flat. As the concavo-convex shape, an array in which concavo-convex shapes such as a lens shape, a cone, a triangular pyramid, a quadrangular pyramid, and a swastika are continuously arranged is preferable.

The fiber-reinforced thermoplastic resin layer of the present invention may be a thermoplastic resin containing a nonwoven fabric or chopped fibers having an average fiber length of 10 mm or more. By including such a fiber in the thermoplastic resin, when performing a forming process such as a plastic process described later using the laminated panel of the present invention, friction due to friction between the fibers and friction due to the shift between the fiber and the thermoplastic resin. Energy (friction heat) is generated, the fiber-reinforced thermoplastic resin layer is easily softened, and there is an advantage that plastic working becomes easier even at a low working temperature.

Fiber-reinforced thermoplastic resin with short glass fibers is usually a thermoplastic resin composition used in injection molding and extrusion molding, which can be obtained by compounding with a kneading extruder, and can be used after injection molding or extrusion molding. The residual fiber length of the reinforcing fiber such as glass fiber is usually 1 mm or less, and is not suitable for the present laminated panel.

A fiber-reinforced thermoplastic resin made of long-fiber chopped fibers is a thermoplastic resin composition that is usually used in injection molding or extrusion molding. However, during injection molding or extrusion molding, reinforced fibers such as glass fibers become 1 mm or less and physical properties deteriorate. Therefore, in some cases, a step of directly compounding continuous fibers of reinforcing fibers such as glass fibers into a composite is provided so that the residual fiber length is intentionally set to several mm or more. Typical examples of these include LFT (Long Fiber Thermoplastic) and D-LFT (Direct Long Fiber Thermoplastic) using a thermoplastic resin such as PP, PA or PPS as a base resin.

Although these depend on the manufacturing process, the residual fiber length of 10 to several tens of mm can be secured by suppressing the cutting of the glass fiber by the kneading process at the time of injection molding or extrusion molding. It is possible. Typical examples of such an LFT are trade names Funkster (manufactured by Nippon Polypro Co., Ltd.), Plastron (manufactured by Daicel Co., Ltd.), Mostron-L (manufactured by Prime Polymer Co., Ltd.), and quick foam (manufactured by Toyobo Co., Ltd.). Etc.

When chopped fibers are used, any chopped fibers may be used as long as the average fiber length in the fiber-reinforced thermoplastic resin layer is 10 mm or more, preferably 20 mm or more, more preferably 30 mm or more. The chopped fiber is usually used as a reinforcing fiber (strand) obtained by bundling monofilaments cut into a predetermined length. For example, a long fiber pellet cut into a predetermined length by impregnating the strand with a thermoplastic resin is used. Used as a form. In the fiber-reinforced thermoplastic resin layer, these are usually present in an opened state, but in the present invention, in addition to the chopped fibers thus opened, unopened fibers are also included.

When the fiber used for the fiber-reinforced thermoplastic resin layer is a non-woven fabric, the web forming method includes a dry method, a wet method, a spunbond method, a meltblown method, and an airlaid method, and a fiber-bonding method includes a needle punch method and a chemical bond method. Methods (immersion method/spray method), thermal bond method, hydroentangling method, and the like, and a non-woven fabric prepared by a combination thereof can be suitably used. Among the non-woven fabrics, a non-woven fabric manufactured by a needle punching method in which fibers are intertwined with each other is particularly preferable.

Typical examples of the fiber reinforced thermoplastic resin using a non-woven fabric are GMT (Glass MAT Thermoplastic: manufactured by Quadrant Plastic Composites Japan Co., Ltd.), GMtex (Glass Mat texlastoplastic Plastic Qrastic Plastic Co., Ltd.). Manufactured)) and the like. In addition, in the present invention, in addition to the fiber-reinforced thermoplastic resin using the above-mentioned nonwoven fabric, the use of a fiber-reinforced thermoplastic resin material using a woven fabric or a knitted fabric is not hindered. A typical example of the fiber-reinforced thermoplastic resin using a woven fabric is Q-Tex (manufactured by Quadrant Plastic Composites).

Among the non-woven fabrics, a non-woven fabric manufactured by needle punching in which fibers are intertwined with each other is particularly preferable. A fiber-reinforced thermoplastic resin layer obtained by combining a non-woven fabric and a woven fabric as the reinforcing fiber is also suitable. In each case, since the fibers are bound to each other, high impact resistance can be secured, cutting of fibers during plastic working and uneven distribution of fibers can be suppressed, and deterioration of physical properties during use can be easily suppressed.
These can be applied to the present laminated panel, since the residual fiber length of at least 5 mm or more, usually 25 mm or more, preferably 40 mm or more can be secured, depending on the conditions of the needle punching process. The average fiber length of the fibers in the fiber-reinforced thermoplastic resin layer is preferably 25 mm or more, more preferably 40 mm or more, and further preferably 70 mm or more. It is also preferably in the form of continuous fibers.
As the average fiber length in the present invention, the number average value of the fiber lengths measured for the fibers in the residue obtained by ashing the fiber-reinforced thermoplastic resin layer is adopted.

The thickness t2 of the fiber reinforced thermoplastic resin layer 2 is usually 0.2 to 4 mm, preferably 0.3 to 3 mm, and particularly preferably 0.4 to ₂ mm. By setting the thickness of the fiber-reinforced thermoplastic resin layer 2 within the above range, deformation due to spring back during cold plastic working is easily suppressed, which is preferable.

As the fibers constituting the fiber-reinforced thermoplastic resin layer 2, one or more kinds of reinforcing fibers such as inorganic fibers, organic fibers and metal fibers can be used. Among them, inorganic fibers are preferable from the viewpoints of lightness and elasticity, and organic fibers are preferable from the viewpoints of lightness, elongation and cold workability.

Examples of the inorganic fiber include glass fiber, carbon fiber, boron fiber, silicon carbide fiber, alumina fiber and the like. Examples of the organic fiber include aramid fiber, polyparaphenylene benzoxazole fiber (PBO fiber), high-strength polyethylene fiber, polypropylene fiber, polyamide fiber, polyester fiber, and self-reinforced fiber obtained by stretching and strengthening these fibers. Examples of metal fibers include aluminum fibers, alumina fibers, SUS fibers, and copper fibers.
Examples of the form of the reinforcing fiber include non-woven fabric, chopped fiber (average fiber length of 10 mm or more), and a combination of non-woven fabric and woven or knitted fabric, and among them, non-woven fabric and chopped fiber are preferable. From the balance of cost, impact resistance, and moldability, glass fiber or carbon fiber, particularly nonwoven fabric made of glass fiber, and chopped fiber having an average fiber length of 10 mm or more are preferable.

The organic fiber preferably used is one having a difference of 40° C. or more between the melting point of the organic fiber and the melting point or the glass transition temperature of the thermoplastic resin used for the fiber-reinforced thermoplastic resin layer, and the organic resin is impregnated with the thermoplastic resin. It is preferable from the viewpoint of maintaining the morphology of the organic fiber at the time. The temperature difference is more preferably 50 to 200°C, and further preferably 60 to 150°C. For the calculation of the temperature difference, the melting point is adopted when the thermoplastic resin used for the fiber reinforced thermoplastic resin layer is crystalline, and the glass transition temperature is adopted when it is amorphous.
When a plurality of thermoplastic resins are used in the fiber reinforced thermoplastic resin layer, the average value of the melting points or glass transition temperatures of these resins is adopted. When using a plurality of organic fibers, the average value of the melting points of these organic fibers is adopted. The melting point and glass transition temperature are measured using a differential scanning calorimeter (DSC). The melting point is the temperature at the peak top of the endothermic peak of the obtained DSC curve. Specifically, the temperature is raised from 25°C to 10°C/min to the expected melting point +50°C, held at the same temperature for 1 minute, and then lowered to 25°C at 10°C/min. , Hold at the same temperature for 1 minute. Then, it can be determined from the DSC curve when the temperature is raised again under the temperature rising condition of 10° C./min.

The organic fiber is preferably a crystalline thermoplastic resin having a melting point of preferably 160° C. or higher, more preferably 200° C. or higher, even more preferably 220° C. or higher, and particularly preferably 250° C. or higher. When the melting point is 160° C. or higher, the heat distortion temperature (heat resistance) of the fiber-reinforced thermoplastic resin layer is improved to near the melting point of the crystalline thermoplastic resin or the glass transition temperature of the amorphous thermoplastic resin. As a result, the heat resistance of the laminated panel tends to be improved, which is preferable.

The form of the organic fibers may be any of filaments, staples, flat yarns and the like, and it is preferable to use them as a non-woven fabric composed of one or more of these. The form of the filament is a long fiber (continuous fiber), and the staple is a short fiber obtained by cutting a staple tow in which filaments are bundled into a cotton shape, and usually has a fiber length of 35 to 100 mm. The flat yarn is a flat yarn obtained by cutting (slitting) a film of a thermoplastic resin or the like into a strip shape and stretching the film to give strength.

In particular, in the case of a non-woven fabric by the needle punch method using organic fibers, the morphology of the organic fibers is preferably 5 to 400 mm in average fiber length, more preferably 25 to 300 mm, and more preferably 40 to 200 mm. Is more preferable. It is also preferably in the form of continuous fibers. With such a fiber length, the fibers are homogeneously dispersed and easily entangled with each other, which is preferable because the mechanical strength and heat resistance of the fiber-reinforced thermoplastic resin layer tend to be improved.
The average fineness is preferably 1 to 30 dtex, more preferably 2 to 20 dtex, and further preferably 3 to 15 dtex. Such an average fineness is preferable because the interface between the thermoplastic resin and the organic fiber increases, and the mechanical strength and heat resistance of the fiber-reinforced thermoplastic resin layer tend to improve.
Preferably the basis weight is 50 to 1500 g / ^{m 2,} and more preferably 100 to 1000 g / ^{m 2.} By changing the thickness of the fiber reinforced thermoplastic resin layer by setting such a basis weight, it is easy to adjust the rigidity of the laminated panel required for each application as needed, and the cold plastic workability is ensured. It tends to be easy and is preferable.

Further, an organic fiber-reinforced thermoplastic resin layer in which a nonwoven fabric and a woven fabric are combined as the organic fiber is also suitable. In each case, since the fibers are bound to each other, high impact resistance can be secured, cutting of fibers during cold plastic working, uneven distribution of fibers, and opening of openings can be suppressed, and deterioration of physical properties during use can be suppressed. it can.

Examples of the thermoplastic resin include PP (polypropylene), PVC (polyvinyl chloride), PA (polyacrylonitrile), PC (polycarbonate), PPS (polyphenylene sulfide), PEEK (polyether ether ketone), and PET (polyethylene terephthalate). , Polyester such as PBT (polybutylene terephthalate), PES (polyether sulfone) and the like are preferable, and among them, crystalline resins such as PP, PA, PBT, PPS and PEEK are preferable, and PP, PA and PBT are more preferable. PP is more preferable in terms of heat resistance, moisture absorption resistance, hydrolysis resistance, and cost.

The volume content Vf of the fibers in the fiber-reinforced thermoplastic resin layer is preferably 10 to 80% by volume, more preferably 15 to 70% by volume. When the volume content Vf is less than 10% by volume, the reinforcing effect by the fiber is difficult to appear, and when it exceeds 80% by volume, voids are formed in the fiber-reinforced thermoplastic resin layer, and the stress strength is likely to be lowered due to stress concentration. It is not preferable because it may be easily broken during processing such as hot working.
The weight volume content Wf of the fibers in the fiber reinforced thermoplastic resin layer is preferably 20 to 80% by weight, more preferably 25 to 75% by weight. When the volume content Wf is less than 20% by weight, the reinforcing effect by the fibers is difficult to appear, and when it exceeds 80% by weight, voids are formed in the fiber reinforced thermoplastic resin layer, and the stress concentration is apt to reduce the impact strength, or It is not preferable because it tends to crack during processing such as hot working.

The method for producing the fiber-reinforced thermoplastic resin layer is not particularly limited, and a conventionally known method can be adopted.
When the fiber used for the fiber-reinforced thermoplastic resin layer is chopped fiber, for example, the resin pellet containing the chopped fiber is heat-melted to directly form the fiber-reinforced thermoplastic resin layer of the laminated panel, or the resin pellet is heat-melted. Then, a sheet is preliminarily formed into a sheet, and the sheet and the metal plate layer are laminated by heat fusion or the like. Further, by the D-LFT method, in a state where the fiber length is 30 mm or more, the fiber-reinforced thermoplastic resin discharged from the die of the extruder is directly laminated and formed into a sheet while suppressing the cutting of the fiber.

When the fiber used for the fiber reinforced thermoplastic resin layer is a non-woven fabric, for example, the thermoplastic resin is charged into an extruder and melted, and then extruded into a sheet having a desired thickness, and the extruded sheet It can be manufactured by supplying and laminating a nonwoven fabric on at least one side, preferably both sides. On the surface of the obtained laminate, a thermoplastic resin sheet may be further supplied to the front and back to be laminated. When laminating, heat and pressurize using a laminator etc. to impregnate the non-woven fabric with a thermoplastic resin, and then cool and solidify to form a sheet-like (so-called stampable sheet) to produce a fiber reinforced thermoplastic resin layer. You can Further, from the viewpoint of shortening the process, it is also possible to laminate a nonwoven fabric and a thermoplastic resin sheet and thermoform them together with a metal plate to form the fiber-reinforced thermoplastic resin layer of the laminated panel of the present invention.

Further, the fiber-reinforced thermoplastic resin layer may contain a component other than the thermoplastic resin and the non-woven fabric or the chopped fiber having an average fiber length of 10 mm or more within a range not impairing the object of the present invention. Other components include, for example, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, impact modifiers, flame retardants, release agents, lubricants, antiblocking agents, antistatic agents, reinforcing fibers. Other additives such as inorganic fillers other than

The fiber reinforced thermoplastic resin layer has a thickness of 0.2 mm or more, and a puncture impact test (ASTM D3763, striker diameter 1/2 inch, impact velocity 4.) with a single test piece of the fiber reinforced thermoplastic resin layer single layer. When the maximum impact force per thickness of the test piece is 0.5 kN/mm or more under the conditions of 4 m/s, support table inner diameter: 3 inch, test temperature: 23° C., not only the impact strength during use is improved. It is preferable because it can facilitate plastic working (sheet metal working) such as bending and press molding (drawing). This maximum impact force is preferably 0.7 to 10 kN/mm, and more preferably 0.8 to 5 kN/mm.

The fiber reinforced thermoplastic resin layer is a dynamic viscoelasticity test of the fiber reinforced thermoplastic resin layer unit test piece (JIS K 7244-4:1999 (Plastic-Dynamic mechanical property test method, frequency 100 Hz, test piece When the ratio (specific storage elastic modulus value: E′/ρ) of storage elastic modulus E′ to specific gravity ρ of the fiber-reinforced thermoplastic resin layer at a thickness of 2 mm and a test temperature of 23° C. is 1.0 GPa or more, The reinforced thermoplastic resin layer is less likely to be excessively plasticized, and the fiber-reinforced thermoplastic resin layer is likely to be deformed while following the plastic deformation of the metal plate layer, which is preferable because the plastic working tends to be easier.

Here, the specific storage elastic modulus of the fiber-reinforced thermoplastic resin layer is determined by using a dynamic viscoelasticity measuring device (for example, FT Rheospectler manufactured by Rheology Co., Ltd.). It can be determined by measuring the temperature dependence from room temperature to 200° C. under the conditions of the test (JIS K 7244-4:1999 (Plastic-Test method for dynamic mechanical properties, frequency 100 Hz, test piece thickness 2 mm)). .. The specific gravity ρ (dimensionless) of the fiber reinforced thermoplastic resin layer also has temperature dependency, but here, the value calculated from the measured values of weight and volume at room temperature (23°C) should be applied as a representative value. You can

The specific storage elastic modulus value (E′/ρ) value of the fiber-reinforced thermoplastic resin layer is more preferably 1.5 GPa or more, and further preferably 1.8 GPa or more. On the other hand, from the elastic modulus of the fiber-reinforced thermoplastic resin, this value is usually 50 GPa or less, preferably 30 GPa or less, more preferably 20 GPa or less. By setting the upper limit to 50 GPa or less, the metal plate layer is broken by the fiber reinforced thermoplastic resin during cold plastic working, or the transfer mark is generated on the metal plate surface by the reinforcing fiber when the high hardness reinforcing fiber is used. Is easily suppressed, which is preferable.

There are no particular restrictions on the method of joining (adhesion) the fiber-reinforced thermoplastic resin layer and the metal plate layer, and various methods can be applied, but so much that the base material is destroyed in the fiber-reinforced thermoplastic resin layer during the peel strength test. It is essential that the peel test strength be strong. According to the floating roller method peel test of JIS K6854-4:1999, the peel strength is 2.5 kN or more, and the bonding (adhesion) method does not cause interfacial peeling and causes the base material to break in the fiber reinforced thermoplastic resin layer. If there is no particular limitation, a known method can be suitably applied.

As a method for achieving a bondability (adhesiveness) in which a peeling strength in a floating roller peeling test is 2.5 kN/m or more and a base material is broken in a fiber reinforced thermoplastic resin layer, for example, an adhesive is used. In addition to the method of providing the adhesive layer used, the method of anodizing or etching the surface of the metal plate, NMT treatment developed by Taisei Plus Co., Ltd., or KO treatment developed by UACJ Co., Ltd. A method of providing an anchor layer with fine and complex irregularities on the surface, a triazine thiol modified compound by New Technology Research Institute Co., Ltd. or Toa Denka Co., Ltd. is chemically modified on the metal surface, and the metal surface and thermoplastic resin and various curing Examples include a method of improving the adhesiveness with an adhesive such as a hydrophilic resin, a method developed by Daicel Co., Ltd., and a method of forming a complicated three-dimensional mesh-like porous anchor layer called a stitch anchor on a metal surface by laser irradiation. .. As described above, when the surface treatment of the metal plate is appropriately selected, the adhesive strength with the fiber-reinforced thermoplastic resin layer serving as the core material may be sufficiently obtained, so the adhesive layer is not always necessary. However, in order to easily secure the adhesive strength between the two layers, the metal plate layer and the fiber reinforced thermoplastic resin layer are joined via an adhesive layer such as an adhesive or an adhesive resin (adhesive film). Is desirable.

Examples of the adhesive include a thermosetting adhesive of a type that has improved adhesiveness to a polyolefin resin based on an epoxy adhesive, a urethane adhesive, a polyester adhesive, and the like. Alternatively, in the laminating step, an easily adhering primer layer is provided on the surface of the fiber reinforced thermoplastic resin layer side to be laminated with the metal plate layer, and a normal thermosetting epoxy type, urethane type or polyester type is used. Alternatively, it may be bonded to the metal plate layer using an acrylic adhesive or the like.

As the adhesive resin, a commercially available maleic anhydride-PP copolymer resin film (trade name: Modic P555 manufactured by Mitsubishi Chemical Co., Cranbetter P6700 manufactured by Kurabo Industries, etc.) can be preferably used. A modified polyolefin adhesive resin film (Admer VE300 manufactured by Mitsui Chemicals Tohcello Co., Ltd.) is used as the PP film, and a heat seal type PET film (Mylar 850 manufactured by Teijin DuPont Films Co., Ltd.) and a film-shaped hot melt type are used as the PET film. As the adhesive (Cranbetter G13 manufactured by Kurabo Industries), as the nylon film, a film-shaped hot-melt adhesive (Cranbetter CN-1003 manufactured by Kurabo Industries) can be used. Alternatively, a metal composite plate (Hishimetal, Alset (both manufactured by Mitsubishi Plastics Co., Ltd., etc.) in which a film of a resin similar to the fiber-reinforced thermoplastic resin layer is laminated in advance may be used. In this case, HISHIMETAL PO, ALSET 1P, ALSET HP, etc. in the PP resin layer, ALSET 1Y, ALSET 3Y, ALSET AR, etc. in the polyamide resin layer, and ALSET in the PET resin layer. EG, Alset EH and the like can be preferably used.

It is preferable that the metal plate of the metal plate layer is subjected to a surface treatment because improvement in adhesion (bonding) strength can be expected. Examples of the surface treatment method include various chemical conversion treatments such as plasma treatment, UV treatment, corona treatment, etching treatment, alkaline electrolysis treatment and chromate treatment.

Examples of the method for adhering the metal plate layer and the fiber-reinforced thermoplastic resin layer include a method of selecting an adhesive or an adhesive resin layer according to the type of the thermoplastic resin of the fiber-reinforced thermoplastic resin layer, and interposing it at the bonding interface. Can be mentioned. Specifically, the thermoplastic resin film is fused to the metal plate layer, and the metal plate layer with the thermoplastic resin film layer and the fiber-reinforced thermoplastic resin layer are superposed and heated to form a metal plate layer. A method of adhering the fiber-reinforced thermoplastic resin layer is suitable. Further, a method in which a thermoplastic resin film is interposed between the metal plate layer and the fiber-reinforced thermoplastic resin layer, and these are pressure-heated to bond the metal plate layer and the fiber-reinforced thermoplastic resin layer to each other is also preferable. ..
As the fiber-reinforced thermoplastic resin layer used for manufacturing the laminated panel, a fiber-reinforced thermoplastic resin sheet manufactured in advance as described above may be used, or from the viewpoint of shortening the process, the nonwoven fabric and the thermoplastic resin may be used. A laminate of the resin sheet or a chopped fiber-containing resin pellet may be directly used to form the fiber-reinforced thermoplastic resin layer of the laminated panel of the present invention by thermoforming with a metal plate at once.

In the laminated panel of the present invention, the number of laminated layers is not particularly limited as long as the fiber-reinforced thermoplastic resin layer and the metal plate layer described above are laminated in combination and the outermost layer of the panel is the metal plate layer. Of these, a three-layer structure of a metal plate layer/fiber-reinforced thermoplastic resin layer/metal plate layer is preferable from the viewpoints of lightness, rigidity, and productivity. Further, the laminate panel may include layers other than the metal plate layer and the fiber-reinforced thermoplastic resin layer of the present invention, as long as the object of the present invention is not impaired.

The laminated panel obtained by adhesion has a peel strength of 2.5 kN/m or more, preferably 3 kN/m or more, when tested by the “floating roller method peel test” method of JIS K6854-4:1999. It is more preferably 5 kN/m or more, and the fracture occurs in the fiber-reinforced thermoplastic resin layer.

In the laminated panel of the present invention thus obtained, the calculated value Z of the formula (1) showing the following lamination constituent factors is 1 or more, preferably 2 or more, more preferably 3 or more, and further preferably 5 That is all. It is preferable that the lamination constituent factor Z is equal to or more than the above value from the viewpoint of workability described below. The layer constituent factor Z is preferably 2000 or less, more preferably 500 or less, further preferably 100 or less, and particularly preferably 50 or less. It is preferable that the lamination constituent factor Z is equal to or less than the above value in terms of weight reduction.
Z=(σm·tm·εm)/(σc·tc·εc) (1)
σm: Tensile strength (MPa) of the metal plate layer at room temperature
tm: Thickness of metal plate layer (mm)
εm: Tensile elongation (%) of the metal plate layer at room temperature
σc: Tensile strength (MPa) of the fiber-reinforced thermoplastic resin layer at room temperature
tc: Thickness of fiber reinforced thermoplastic resin layer (mm)
εc: Tensile elongation (%) of the fiber-reinforced thermoplastic resin layer at room temperature

Here, the tensile strength (MPa) of the metal plate layer at room temperature (23° C.) and the tensile elongation rate (%) of the metal plate layer at room temperature (23° C.) are JIS Z2241:2011 (metal Material tensile test method).
The tensile strength (MPa) of the fiber-reinforced thermoplastic resin layer at room temperature (23° C.) and the tensile elongation (%) of the fiber-reinforced thermoplastic resin layer at room temperature (23° C.) are as follows: Is measured according to JIS K7164:2005 (Plastics-Testing method for tensile properties-Part 4: Test conditions for isotropic and orthogonal row anisotropic fiber reinforced plastics).
The thickness of the metal plate layer and the fiber-reinforced thermoplastic resin layer means the average thickness, and when the metal plate layer and the boss have a partially protruding convex portion, such as a rib and a boss, the average thickness of the portion excluding these convex portions.

The value of (σm·tm·εm) in the above formula (1) is calculated by calculating the value of tensile strength×thickness×tensile elongation ratio for each of the outermost metal plates, and calculating the total value of both metal plate layers. (Σm·tm·εm). Similarly, when a metal plate layer is provided in addition to the outermost layer, the tensile strength×thickness×tensile elongation rate is calculated for each metal plate layer, and the total value of each metal plate layer is defined as (σm·tm·εm). ..
Similarly, in the case of a structure in which two or more fiber reinforced thermoplastic resin layers are present, the tensile strength×thickness×tensile elongation of each fiber reinforced thermoplastic resin layer is calculated, and the total of those fiber reinforced thermoplastic resin layers is calculated. The value is (σc·tc·εc).

The calculated value Z is an index indicating the selection of the laminated structure capable of plastic working of the laminated panel of the present invention and the plastic working characteristics thereof. If the energy required for the deformation of both layers of the metal plate layer and the fiber-reinforced thermoplastic resin layer is ideally balanced, and the energy required for the deformation of both layers is balanced, the metal plate layer and the fiber-reinforced thermoplastic resin layer are Assuming that either layer does not break, the energy required to deform both layers is the maximum tensile force of each layer of the metal plate layer and the fiber reinforced thermoplastic resin layer, and the thickness ( It can be represented by the product of cross-sectional area) and tensile elongation (strain), and can be represented by a calculated value Z (equation (1)). When Z is smaller than 1, the metal plate layer is likely to be broken or cracked during plastic working such as deep drawing and bending.

The laminated panel of the present invention can be applied to various molding processing methods, but since it has the above-mentioned properties, it can exert a remarkable effect particularly when used for plastic processing. .. As a plastic working (sheet metal working) method for producing a molded product from the laminated panel of the present invention, a conventionally known method can be mentioned. In particular, it can be preferably applied to press working (including simple press working, drawing, deep drawing, overhanging, stretch flange working, etc.), roll forming and bending, and is particularly suitable for deep drawing. Among them, it can be suitably used for the production of deep drawn products having a limiting drawing ratio of 1.6 or more, especially 2-3. The limiting drawing ratio (LDR) is defined by the maximum blank diameter (Dmax) and the diameter of the cylinder (internal diameter of drawn product: d) with which a cylinder that does not break can be drawn in one drawing. It is calculated as the ratio (Dmax/d).

The laminated panel of the present invention has a dynamic viscoelasticity test (JIS K 7244-4:1999 (Plastic-Dynamic mechanical property test method, frequency 100 Hz, test piece thickness 2 mm, The ratio of the storage elastic modulus E′ to the specific gravity ρ of the fiber reinforced thermoplastic resin layer at a test temperature of 23° C. (specific storage elastic modulus value: E′/ρ) is 1.0 GPa or more, preferably 1.5 GPa or more, for example. It can be suitably processed at any temperature in the temperature range of 1.5 to 3 GPa (mold temperature or preheating temperature of laminated panel), that is, the specific storage elastic modulus value (E'/ρ) is 1.0 GPa. The above temperature can be used as an index for selecting the preheating temperature of the laminated panel, and it is particularly preferable to process the laminated panel after preheating it to any one of the above temperature ranges.

The method for processing in the processing temperature range where the specific storage elastic modulus value (E′/ρ) shows such a value is as follows: room temperature or the melting point of the thermoplastic resin constituting the fiber reinforced thermoplastic resin layer of the laminated panel or glass. After preheating the laminated panel to a softening temperature (semi-melting temperature) below the melting temperature below the transition temperature, press working at room temperature from the glass transition temperature of the thermoplastic resin or below the melting point temperature (simple press, deep press) Suitable methods include plastic working (sheet metal working) such as drawing, etc.), bending, roll forming and the like. Although depending on the structure of the laminated panel, the laminated panel at room temperature may be cold worked by a mold at room temperature from the viewpoint of shortening the cooling cycle. In the present invention, when the organic fiber having a higher tensile elongation than the inorganic fiber is used, the fiber-reinforced thermoplastic resin layer easily follows the deformation of the metal plate layer during the cold plastic working, and the laminated panel at room temperature is cooled to room temperature. It becomes easier to perform cold working with the die.

When the thermoplastic resin forming the fiber-reinforced thermoplastic resin layer is a crystalline resin, the softening temperature is not lower than room temperature and not higher than the melting point in the DSC curve, and preferably not higher than the crystallization temperature. In the case of an amorphous resin, the softening temperature is in the range of room temperature or higher and glass transition temperature+50° C. or so, and is preferably the glass transition temperature or lower. The measuring method of the melting point and the glass transition temperature is as described above.

When the thermoplastic resin that constitutes the fiber reinforced thermoplastic resin layer is a crystalline resin, plastic processing may be possible even at room temperature without preheating, and the temperature range between the crystallization start temperature and the crystal melting temperature of the thermoplastic resin It is preferable to select and heat the above-mentioned temperature from the viewpoint of the physical properties of the obtained molded product, but from the viewpoint of the molding cycle at the time of molding, it is desirable not to provide the preheating step as much as possible. When heating is performed, if the heating temperature is lower than the crystallization start temperature, it becomes difficult to plastically deform the fiber reinforced thermoplastic resin layer and the metal plate layer may be cracked. On the other hand, if the temperature is higher than the crystal melting temperature of the thermoplastic resin, the fiber reinforced thermoplastic resin layer excessively softens and the metal plate layer in the deformation process during the molding process bites into it, which may cause wrinkles. is there.

The mold temperature is preferably set between room temperature and the crystallization temperature of the thermoplastic resin, and room temperature is particularly preferable from the viewpoint of shortening the cooling time, but it is appropriately selected depending on the broken state of the reinforcing fiber due to shearing during processing. It is possible.

When the thermoplastic resin constituting the fiber-reinforced thermoplastic resin layer is an amorphous resin, sheet metal processing may be possible even at room temperature without preheating, and the glass transition temperature (Tg) or more and the glass transition temperature +50 of the thermoplastic resin may be used. From the viewpoint of the molding cycle at the time of molding, it is preferable to provide a preheating step, although it is preferable to select and heat the temperature in the range of not higher than C, that is, in the range of Tg to Tg+50°C. Not desirable. When this heating temperature is lower than the glass transition temperature of the thermoplastic resin, it becomes difficult to plastically deform the fiber reinforced thermoplastic resin layer, which may cause cracking of the metal plate layer. On the other hand, if the temperature is higher than the glass transition temperature +50°C of the thermoplastic resin, it will be in the melting processing temperature region, so the fiber reinforced thermoplastic resin layer will be excessively softened and fluidized, and the metal plate layer in the deformation process during molding processing will be As it cuts into the ground, it may cause cracks and wrinkles.

As the mold temperature, it is preferable to set the temperature above room temperature and below the glass transition temperature of the thermoplastic resin, and room temperature is particularly preferable from the viewpoint of shortening the cooling time, but depending on the breaking state of the reinforcing fiber and the metal plate layer due to shearing during processing. It can be selected appropriately.

Since the laminated panel of the present invention has the above-mentioned performance, by appropriately selecting the type, configuration, thickness, tensile strength, and tensile elongation of the metal plate layer and the fiber-reinforced thermoplastic resin layer, the laminated panel of 10 to 40 can be obtained. It becomes easy to perform plastic working even in a low temperature region such as ℃, and the cooling time is shortened, so that the molding cycle can be effectively shortened.

The molded product obtained by the present invention can be used for automobile parts, electronic parts, building materials, and other various products, if necessary, by subjecting it to various coatings and surface decorations such as film lamination.

Automotive parts include body, door inner, side panel, bonnet (engine hood), roof, floor, cab lower cover, trunk lid, reinforcement parts, side sills, cross members, brackets, various pillar parts, various beam parts, A floor reinforcing plate etc. are illustrated.
Examples of electronic components include TVs, PCs, mobile devices, and other housings.

Other products include helmets, aluminum sash frames, elevator gate frames (beams), blade vests, travel bags, gables, roofs, and the like.

Hereinafter, examples and comparative examples will be described. In the following examples and comparative examples, deep drawing shown in FIG. 2 or press forming shown in FIG. 3 was performed as plastic working. In FIG. 2, a circular plate-shaped laminated panel having a diameter of 98 mm and a thickness of 2 mm is deep-drawn by a high-power press tester (Amino's double-acting hydraulic press TM200 special specification) to obtain the shape shown in FIG. A molded product having a drawing ratio of 1.7) was prepared. In FIG. 3, a rectangular laminated panel having a size of 400×600 mm and a thickness of 2 mm was press-molded with a mold to obtain a molded product shown in FIG.

The materials applied to the fiber reinforced thermoplastic resin layer are shown below. The various physical properties were measured according to the methods described above. Moreover, "room temperature" means 23 degreeC.

GMT40: Quadrant Composite Plastics Japan P4020-BK31
Stampable sheet consisting of non-woven fabric made of glass fiber and polypropylene resin by needle punch method Polypropylene resin content: 60% by weight
Glass fiber content: 19% by volume (40% by weight)
Average fiber length: 101 mm
Specific gravity: 1.2
Specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 3.0 GPa
Maximum impact strength by puncture test (test piece thickness 2 mm, test temperature 23°C): 2.2 kN
Maximum impact strength per unit thickness: 1.1 kN/mm

GMT65: Quadrant Composite Plastics Japan Co., Ltd. A stampable sheet consisting of a non-woven fabric made of glass fiber and polypropylene resin by the needle punch method Polypropylene resin content: 35% by weight
Glass fiber content: 40% by volume (65% by weight)
Average fiber length: 98 mm
Specific gravity: 1.53
Specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 3.4 GPa
Maximum impact strength by puncture test (test piece thickness 2 mm, test temperature 23°C): 3.1 kN
Maximum impact strength per unit thickness: 1.55 kN/mm

GMTex: Quadrant Composite Plastics Japan P6538-BK31
A stampable sheet made of a polypropylene resin and a laminated body of glass fiber woven fabric and non-woven fabric subjected to needle punching. Polypropylene resin content: 40% by weight (65% by volume)
Glass fiber non-woven fabric content: 14% by volume
Glass fiber woven fabric content: 21% by volume
Glass fiber content: 35% by volume (60% by weight)
Average fiber length: 101 mm (nonwoven fabric), continuous fiber (woven fabric)
Specific gravity: 1.45
Specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 6.9 GPa
Maximum impact strength by puncture test (test piece thickness 2 mm, test temperature 23°C): 2.7 kN
Maximum impact strength per unit thickness: 1.35 kN/mm

CFRTP: manufactured by Yuho Co., Ltd. A stampable sheet obtained by melt impregnating a PAN-based carbon fiber nonwoven fabric with a polycarbonate resin by a needle punch manufacturing method. Polycarbonate resin content: 35% by weight
Carbon fiber content: 55% by volume (65% by weight)
Average fiber length: 60 mm
Specific gravity: 1.53
Specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 12.4 GPa
Maximum impact strength by puncture test (test piece thickness 2 mm, test temperature 23°C): 4.0 kN
Maximum impact strength per unit thickness: 2.0 kN/mm

LFT: LR24A manufactured by Japan Polypro Co., Ltd.
Sheet made by long-term chopped glass fiber and polypropylene resin pellets hot-pressed at 220°C Glass fiber content of pellets: 13% by volume (40% by weight)
Polypropylene resin content of pellets: 60% by weight
Glass fiber average fiber length in pellets: 10 mm
Specific gravity of pellets: 1.2
Specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 2.9 GPa
Maximum impact strength by puncture test (test piece thickness 2 mm, test temperature 23°C): 1.6 kN
Maximum impact strength per unit thickness: 0.8 kN/mm

Organic fiber non-woven fabric 1: BT-1812W manufactured by Unicell Corporation
Nonwoven fabric made of polyester continuous fiber (melting point 265° C.) by melt blown method Average fiber length: continuous fiber Unit weight: 80 g/m ²
Fiber reinforced thermoplastic resin layer unit test piece (polypropylene resin content 70% by weight, polyester fiber content 22% by volume (30% by weight), specific gravity obtained by impregnating organic fiber nonwoven fabric 1 with polypropylene resin (melting point 165° C.) 1.0) specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 1.4 GPa
・Maximum impact strength by puncture test (test piece thickness 2mm, test temperature 23℃): 4.2kN
Maximum impact strength per unit thickness: 2.1 kN/mm

Organic fiber non-woven fabric 2: Eco punch made by Watanabe Industry Co., Ltd. Non-woven fabric made of recycled polyethylene terephthalate resin staple (melting point 265° C.) by needle punch method Average fiber length: 51 mm
Average fineness: 10 dtex
Unit weight: 300g/m ²
Fiber-reinforced thermoplastic resin layer unit test piece (polypropylene resin content 70% by weight, polyester fiber content 22% by volume (30% by weight), specific gravity obtained by impregnating organic fiber nonwoven fabric 2 with polypropylene resin (melting point 165° C.) 1.0) specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 1.4 GPa
・Maximum impact strength by puncture test (test piece thickness 2mm, test temperature 23℃): 2.4kN
Maximum impact strength per unit thickness: 1.2 kN/mm

Organic fiber non-woven fabric 3: manufactured by Misawa Textile Co., Ltd. Non-woven fabric made of polyethylene terephthalate resin staple (melting point 265° C.) by needle punch method Average fiber length: 51 mm
Average fineness: 3.3 dtex
Unit weight: 300g/m ²
Fiber reinforced thermoplastic resin layer unit test piece (polypropylene resin content 70% by weight, polyester fiber content 22% by volume (30% by weight), specific gravity obtained by impregnating organic fiber nonwoven fabric 3 with polypropylene resin (melting point 165° C.) 1.0) specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 1.4 GPa
・Maximum impact strength by puncture test (test piece thickness 2mm, test temperature 23℃): 1.6kN
Maximum impact strength per unit thickness: 0.8 kN/mm
Fiber reinforced thermoplastic resin layer unit test piece (polypropylene resin content 30% by weight, polyester fiber content 60% by volume (70% by weight), specific gravity obtained by impregnating organic fiber nonwoven fabric 3 with polypropylene resin (melting point 165° C.) 1.19) of specific storage elastic modulus value E′/ρ (frequency 100 Hz, test piece thickness 2 mm, test temperature 23° C.): 2.8 GPa
・Maximum impact strength by puncture test (test piece thickness 2mm, test temperature 23℃): 3.0kN
Maximum impact strength per unit thickness: 1.5 kN/mm

A6061-T6: Aluminum plate manufactured by Nippon Light Metal Co., Ltd. Thickness: 0.5 mm
Tensile strength: 310MPa
Tensile elongation: 12%
Yield ratio: 89%

A5052-H34: Aluminum alloy plate made by UACJ Co., Ltd. Thickness: 0.6 mm
Tensile strength: 260MPa
Tensile elongation: 10%
Yield ratio: 83%

A5182-H38: Aluminum alloy plate manufactured by Mitsubishi Aluminum Co., Ltd. Thickness: 0.25 mm
Tensile strength: 380MPa
Tensile elongation: 9%
Yield ratio: 83%

A5182-O: Mitsubishi Aluminum Co., Ltd. aluminum alloy plate Thickness: 0.25 mm
Tensile strength: 290MPa
Tensile elongation: 21%
Yield ratio: 56%

A5182-O: Aluminum alloy plate made by UACJ Co., Ltd. Thickness: 0.4 mm
Tensile strength: 290MPa
Tensile elongation: 21%
Yield ratio: 56%

A1100-H16: Aluminum alloy plate manufactured by Mitsubishi Aluminum Co., Ltd. Thickness: 0.15 mm
Tensile strength: 145MPa
Tensile elongation: 6%
Yield ratio: 94%

SPCD: Cold-rolled steel sheet manufactured by Nippon Steel & Sumitomo Metal Co., Ltd. Thickness: 0.4 mm
Tensile strength: 300MPa
Tensile elongation: 48%
Yield ratio: 50%

[Example 1] (Fig. 1)
As the metal plate layer, two A6061-T6 aluminum plates having a thickness of 0.5 mm, a tensile strength of 310 MPa and a tensile elongation of 12% were used. An adhesive resin layer (Model P555 manufactured by Mitsubishi Chemical Corporation, thickness 20 μm) was heat-fused to one surface of the aluminum plate in advance at a surface pressure of 3.9 MPa and 180° C.

As the fiber-reinforced thermoplastic resin layer, GMT40 having a thickness of 3.8 mm was used.

A fiber reinforced thermoplastic resin layer is sandwiched between two metal plate layers, and press molding is performed at a surface pressure of 3.9 MPa and 180° C. for 10 minutes to bond the metal plate layer and the fiber reinforced thermoplastic resin layer to each other to obtain a thick layer. A 2 mm thick laminated panel was obtained.

The peel strength, flexural modulus, and maximum impact strength of this laminated panel were measured, and the deep drawing shown in FIG. 2 was performed at 120° C. to evaluate the deep drawing property and the molding cycle. The results are shown in Table 1. ..
In addition, the unit thickness of the material used as the fiber reinforced thermoplastic resin layer by the puncture impact test (ASTM D3763, striker diameter 1/2 inch, impact speed 4.4 m/s, support base inner diameter: 3 inch, test temperature: 23° C.) Table 1 also shows the maximum impact strength per hit and the calculated value Z of the formula (1) representing the lamination constituent factor.

The peel strength of the laminate panel was measured at room temperature (23° C.) according to the “floating roller method peel test” method of JIS K6854-4:1999. In the peel test, "A" indicates that the fiber-reinforced thermoplastic resin composition layer breaks (breaks the base material), and "Peels at the interface between the fiber-reinforced thermoplastic resin composition layer and the metal plate layer (interfacial peeling)". It was set to "B".
The bending elastic modulus of the laminated panel was measured at room temperature by a bending tester (precision universal material tester manufactured by Intesco) based on JIS K7017:1999.
Regarding the deep drawability during deep drawing, "A" is used when deep drawing is possible and the resulting molded product has no cracks. Deep drawing is possible and there are slight cracks in the metal plate layer. The evaluation was evaluated as "B" when the level of the molded product was not problematic, and "C" when the molded product obtained by deep drawing could not be cracked.
The molding cycle at the time of deep drawing was evaluated by measuring the time required for deep drawing (the time from placing the laminated panel on the mold until releasing it) and the cooling time.

The specific storage elastic modulus value E′/ρ (GPa) at the preheating temperature of the fiber reinforced thermoplastic resin layer is within a temperature range of 25 to 200° C. by a dynamic viscoelasticity measuring device (FT Rheospectler manufactured by Rheology Co., Ltd.). It was measured.
Further, the maximum impact strength of the laminated panel and the fiber reinforced thermoplastic resin layer was measured by an impact tester manufactured by IMATEK.
The specific storage elastic modulus value E′/ρ(GPa) of the fiber reinforced thermoplastic resin layer during plastic working (preheating temperature of the laminated panel or mold temperature) is preferably 1.0 GPa or more, and the fiber reinforced thermoplastic resin The maximum impact strength per unit thickness of the layer is preferably 0.5 kN/mm or more.

[Example 2]
A laminated panel was formed in the same manner as in Example 1 except that GMT65 having a thickness of 3.8 mm was used as the fiber-reinforced thermoplastic resin layer, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 1.

[Example 3]
A laminated panel was molded in the same manner as in Example 1 except that GMtex having a thickness of 3.8 mm was used as the fiber-reinforced thermoplastic resin layer, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 1.

[Example 4]
A laminated panel was molded in the same manner as in Example 1 except that CFRTP having a thickness of 1.3 mm was used as the fiber-reinforced thermoplastic resin layer, and its characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 1.

[Example 5]
A laminated panel was molded in the same manner as in Example 1 except that the preheating temperature was 35° C. and the mold temperature was 30° C., and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 2.

[Example 6]
A laminated panel was formed in the same manner as in Example 1 except that one of the metal plate layers was an aluminum alloy plate A5182-H38 (thickness: 0.25 mm, tensile strength: 380 MPa, tensile elongation: 9%). The characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 2.

[Example 7]
The two metal plate layers were aluminum alloy plates A5052-H34 (thickness: 0.6 mm, tensile strength: 260 MPa, tensile elongation: 10%), and the adhesive resin layer was a metal plate layer and a fiber-reinforced heat. The metal plate layer and the fiber reinforced thermoplastic resin layer were adhered to each other by interposing them between the plastic resin layer and the laminated panel, the plastic working was the press molding of FIG. 3, and the mold temperature was room temperature (23 C.) was used to form a laminated panel in the same manner as in Example 1 and the characteristics were measured. The results and Z values are shown in Table 2.

[Example 8]
A laminated panel was molded in the same manner as in Example 7 except that the preheating temperature and the mold temperature at the time of press molding were 160° C., and the characteristics were measured. The results and Z values are shown in Table 2.

[Example 9]
A laminated panel was formed in the same manner as in Example 1 except that aluminum alloy plates A5182-O (thickness: 0.25 mm, tensile strength: 290 MPa, tensile elongation: 21%) were used as the two metal plate layers. Then, the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 3.

[Example 10]
Laminating in the same manner as in Example 1 except that cold-rolled steel sheets for deep drawing SPCD (thickness: 0.4 mm, tensile strength: 300 MPa, tensile elongation: 48%) were used as the two metal plate layers. The panel was molded, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 3.

[Example 11]
A laminated panel was molded in the same manner as in Example 1 except that the LFT having a thickness of 2 mm was used as the fiber-reinforced thermoplastic resin layer, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 3.

[Example 12]
A laminated panel was formed in the same manner as in Example 1 except that aluminum alloy plates A5182-O (thickness: 0.4 mm, tensile strength: 290 MPa, tensile elongation: 21%) were used as the two metal plate layers. Then, the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 3.

[Example 13]
As the metal plate layer, two A6061-T6 aluminum plates having a thickness of 0.5 mm, a tensile strength of 310 MPa and a tensile elongation of 12% were used. An adhesive resin layer (Model P555 manufactured by Mitsubishi Chemical Corporation, thickness 20 μm) was heat-fused to one surface of the aluminum plate in advance at a surface pressure of 3.9 MPa and 180° C.

As a material for the fiber-reinforced thermoplastic resin layer, an organic fiber non-woven fabric 1 and a polypropylene resin (melting point 165° C.) sheet were laminated so as to be 30% by weight of organic fiber and 70% by weight of polypropylene resin.

A polypropylene resin sheet/organic fiber nonwoven fabric 1/polypropylene resin sheet is sandwiched between two metal plate layers in this order, and press-molded to a total thickness of 2 mm at a surface pressure of 3.9 MPa and 180° C.×10 minutes, The metal plate layer and the fiber reinforced thermoplastic resin layer (polypropylene resin/organic fiber nonwoven fabric 1) were adhered to each other to obtain a laminated panel having a thickness of 2 mm.
The laminated panel thus obtained was molded in the same manner as in Example 1, and its characteristics were measured and deep drawing was performed. The results and the Z value are shown in Table 4.

[Example 14]
Using the organic fiber nonwoven fabric 2 as the material of the fiber reinforced thermoplastic resin layer, aluminum alloy plates A5182-O (thickness: 0.4 mm, tensile strength: 290 MPa, tensile elongation: 21%) are used as the two metal plate layers. A laminated panel was molded in the same manner as in Example 13 except that it was used, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 4.

[Example 15]
Using the organic fiber nonwoven fabric 3 as the material of the fiber reinforced thermoplastic resin layer, aluminum alloy plates A5182-O (thickness: 0.4 mm, tensile strength: 290 MPa, tensile elongation: 21%) are used as the two metal plate layers. A laminated panel was molded in the same manner as in Example 13 except that it was used, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 4.

[Example 16]
Using the organic fiber nonwoven fabric 3 as the material of the fiber reinforced thermoplastic resin layer, aluminum alloy plates A5182-O (thickness: 0.4 mm, tensile strength: 290 MPa, tensile elongation: 21%) are used as the two metal plate layers. A laminated panel was molded in the same manner as in Example 13 except that the organic fiber was 70% by weight and the polypropylene resin was 30% by weight, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 4.

[Comparative Example 1]
The aluminum plate was surface-treated (specifically, MEC Corporation AMALFA treatment (chemical etching) for porosity treatment (microporous treatment)) without using the adhesive PP film, fiber-reinforced thermoplastic resin layer and metal A laminated panel was formed in the same manner as in Example 1 except that the resin in the fiber-reinforced thermoplastic resin layer was adhered to the plate layer by fusion bonding, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 5. As shown in Table 5, in Comparative Example 1, since the adhesive strength between the fiber-reinforced thermoplastic resin layer and the metal plate layer was low, interfacial peeling occurred between the two and cracking occurred due to deep drawing.

[Comparative example 2]
A laminated panel was molded in the same manner as in Example 1 except that 100% PP (0% reinforcing fiber) was used instead of the fiber reinforced thermoplastic resin layer, and the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 5. As shown in Table 5, in Comparative Example 2, the tensile strength of the PP layer was as low as 40 MPa and the tensile elongation rate was as high as 600%. Therefore, the value of the formula (1) indicating the lamination constituent factor is 0.16, which is less than 1. And the specific storage elastic modulus at the preheating temperature became 0.6 GPa and less than 1.0 GPa, interfacial peeling occurred, and cracking occurred by drawing.

[Comparative Example 3]
The same procedure as in Comparative Example 2 was performed except that the preheating temperature of the laminated panel was 35° C. and the mold temperature was 30° C. for deep drawing. The results and Z values are shown in Table 5. As shown in Table 5, in Comparative Example 3, since the PP layer had a low tensile strength of 40 MPa and a high tensile elongation of 600%, the Z value indicating the lamination constituent factor was 0.16, which was less than 1, and Interfacial peeling occurred and cracking occurred due to drawing.

[Comparative Example 4]
A laminated panel was formed in the same manner as in Example 1 except that aluminum alloy plates A1100-H16 (thickness: 0.15 mm, tensile strength: 145 MPa, tensile elongation: 6%) were used as the two metal plate layers. Then, the characteristics were measured and deep drawing was performed. The results and Z values are shown in Table 5. As shown in Table 5, in Comparative Example 4, since the thickness of the metal plate layer was thin at 0.15 mm, the tensile strength was 145 MPa, and the tensile elongation was low at 6%, the Z value indicating the lamination constituent factor was 0.77. And the value was less than 1, and cracking occurred in the metal plate layer by deep drawing.

As is clear from the above examples, the laminated panel of the present invention has high rigidity, high peel strength and impact strength, is excellent in deep drawability and press workability, and can be plastically worked.

Although the invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention.
This application is based on Japanese Patent Application No. 2015-229810 filed on November 25, 2015, which is incorporated by reference in its entirety.

1 Laminated Panel 2 Fiber Reinforced Thermoplastic Resin Layer 3 Metal Plate Layer

Claims (13)

A non-woven fabric or a fiber-reinforced thermoplastic resin layer containing chopped fibers having an average fiber length of 10 mm or more and a thermoplastic resin, and a metal plate layer adhered to the fiber-reinforced thermoplastic resin layer, the outermost layer being the metal. In a laminated panel that is a board layer,
The peel strength is 2.5 kN/m or more when the test is performed by the "floating roller method peel test" of JIS K6854-4:1999, and the breakage occurs in the fiber-reinforced thermoplastic resin layer, A laminated panel characterized in that a calculated value Z of the formula (1) showing the following lamination constituent factors is 1 or more.
Z=(σm·tm·εm)/(σc·tc·εc) (1)
σm: Tensile strength (MPa) of the metal plate layer at room temperature
tm: Thickness of metal plate layer (mm)
εm: Tensile elongation (%) of the metal plate layer at room temperature
σc: Tensile strength (MPa) of the fiber-reinforced thermoplastic resin layer at room temperature
tc: Thickness of fiber reinforced thermoplastic resin layer (mm)
εc: Tensile elongation (%) of the fiber-reinforced thermoplastic resin layer at room temperature In Claim 1, the said fiber reinforced thermoplastic resin layer is the dynamic viscoelasticity test of this fiber reinforced thermoplastic resin layer single-piece test piece (JIS K 7244-4:1999 (Plastics-test method of dynamic mechanical property, frequency. The ratio (specific storage elastic modulus value: E′/ρ) of the storage elastic modulus E′ to the specific gravity ρ of the fiber-reinforced thermoplastic resin layer at 100 Hz, test piece thickness 2 mm, and test temperature 23° C.) is 1.0 GPa or more. A laminated panel characterized in that In Claim 1 or 2, the said fiber reinforced thermoplastic resin layer WHEREIN: The puncture impact test (strike diameter 1/2 inch, impact velocity 4.4m/s, support stand inner diameter) by this fiber reinforced thermoplastic resin layer single test piece: A laminated panel having a maximum impact strength per unit thickness of 0.5 kN/mm or more at 3 inches and a test temperature of 23° C.). The laminated panel according to any one of claims 1 to 3, wherein the fibers in the fiber-reinforced thermoplastic resin layer are non-woven fabrics and have an average fiber length of 25 mm or more. The laminated panel according to any one of claims 1 to 4, which has a three-layer structure in which the metal plate layers are adhered to both surfaces of the fiber-reinforced thermoplastic resin layer. The laminated panel according to any one of claims 1 to 5, further comprising an adhesive layer between the fiber-reinforced thermoplastic resin layer and the metal plate layer. The fiber in the fiber-reinforced thermoplastic resin layer according to claim 1, wherein the fiber is an organic fiber, and a difference between the melting point of the organic fiber and the melting point or the glass transition temperature of the thermoplastic resin is 40° C. The laminated panel characterized by the above. The laminated panel according to any one of claims 1 to 6, wherein the fiber in the fiber-reinforced thermoplastic resin layer is an organic fiber, and the melting point of the organic fiber is 160°C or higher. The laminated panel according to claim 7 or 8, wherein the organic fiber is a nonwoven fabric having an average fiber length of 25 to 300 mm, an average fineness of ^{2 to} 20 dtex, and a basis weight of 50 to 1000 g/m ² . The laminated panel according to any one of claims 1 to 9, which is used for plastic working. A method for producing a molded product by plastically working the laminated panel according to any one of claims 1 to 10, comprising a dynamic viscoelasticity test (JIS K 7244) of the fiber-reinforced thermoplastic resin layer single-piece test piece. -4: 1999 (Plastic-Dynamic mechanical property test method, frequency 100 Hz, test piece thickness 2 mm), the ratio of the storage elastic modulus E'to the specific gravity ρ of the fiber-reinforced thermoplastic resin layer (specific storage elastic modulus value: E A method for producing a molded product, characterized in that plastic working is performed at any temperature in a temperature range in which ′/ρ) is 1.0 GPa or more. A method for producing a molded product by plastically working the laminated panel according to any one of claims 1 to 10, wherein the plastic working is performed at any temperature in a temperature range of 10 to 40°C. And a method of manufacturing a molded article. The method for manufacturing a molded product according to claim 11 or 12, wherein the plastic working is press working, roll forming, or bending.

Images