WO2017090676A1 - Laminated panel and method for manufacturing article molded therefrom - Google Patents

Abstract

[Problem] To provide: a fiber-reinforced resin composite laminate that has high rigidity and impact strength and that can be subjected to bending, press working, roll forming, and other forms of plastic working (plate working), it being possible to use preexisting molding facilities to manufacture the fiber-reinforced resin composite laminate without investing in expensive facilities; and a method for manufacturing a molded article of said fiber-reinforced resin composite laminate. [Solution] Provided is a laminate panel 1 having a fiber-reinforced thermoplastic resin layer 2 that includes a thermoplastic resin and either a non-woven fabric or chopped fibers measuring 10 mm or more in average length, and a metal plate layer 3 bonded to the fiber-reinforced thermoplastic resin layer 2, the outermost layer of the laminate panel 1 being the metal plate layer, wherein the laminate panel 1 is characterized in that: when testing is carried out in accordance with the "floating roller peel test" method of JIS K 6854-4:1999, the peel strength is 2.5 kN/m or higher, destruction occurs in the fiber-reinforced thermoplastic resin layer, and the following value Z calculated from formula (1), which indicates the lamination construction factor, is at least 1. Z=(σm·tm·εm)/(σc·tc·εc) ... (1)

Description

Laminated panel and method for producing molded product

The present invention relates to a laminated panel composed of 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. The present invention relates to a method for producing the molded product.

In recent years, from the viewpoint of environmental conservation and energy saving, it is desired to reduce the weight of these products in the fields of transportation equipment such as automobiles, railways, aviation, robots, electronic equipment, furniture, and building materials. For this reason, attempts have been made to reduce the weight by using fiber reinforced resin materials for metal parts.

Among them, carbon fiber reinforced resin composite materials, glass fiber reinforced resin composite materials, and the like can contribute to weight reduction because they are superior in specific strength and specific rigidity compared to metal materials.

However, these fiber reinforced resin composite materials are not only more expensive than metals, but also limit the scope of use of existing molding equipment, necessitating the investment of these dedicated molding equipment, and the cost is high. Therefore, the current situation has not been popularized over the past 30 years. Moreover, the fiber reinforced resin composite material which uses a thermoplastic resin or a thermosetting resin as a matrix has a subject that a molding cycle is long.

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

Patent Document 4 proposes a frame member for a seat that is a laminated body in which a woven fabric is sandwiched between metal plates and fixed with a thermosetting resin. The fiber reinforced fabric layer is excellent in impact resistance, and the impact resistance can be improved by causing delamination at the interface between the metal and the fiber reinforced 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 is lowered. In addition, since a thermosetting resin is applied for bonding, it takes a long time for thermosetting, so that it does not have mass productivity.

JP-A-5-138800 Japanese Patent No. 5633989 JP 2013-159019 A Japanese Patent No. 5669288

The present invention is a fiber that can utilize existing molding equipment without expensive capital investment, has high rigidity and impact strength, and is capable of plastic working (sheet metal working) such as bending, press working, and roll forming. It aims at providing the manufacturing method of a reinforced resin compound laminated body and its molded article.

The laminated panel of the present invention has a nonwoven 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. In a laminated panel in which the outermost layer is the metal plate layer, the peel strength is 2.5 kN / m or more when a test according to the “floating roller method peel test” method of JIS K6854-4: 1999 is performed. And destruction occurs in a fiber reinforced thermoplastic resin layer, The calculated value Z of Formula (1) which shows the following lamination constituent factors is 1 or more, The laminated panel characterized by the above-mentioned.

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

In one embodiment 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) for a single specimen of the fiber reinforced thermoplastic resin layer. 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) at a frequency of 100 Hz, a test piece thickness of 2 mm, and a test temperature of 23 ° C. is 1.0 GPa. That's it.
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 embodiment of the present invention, the fiber reinforced thermoplastic resin layer is formed by a puncture impact test using a single specimen of the fiber reinforced thermoplastic resin layer (strike diameter 1/2 inch, impact speed 4.4 m / s, support base inner diameter: 3 inch). , Test temperature: 23 ° C.), the maximum impact strength per unit thickness is 0.5 kN / mm or more.

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

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

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

In one embodiment 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 higher.

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

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

Another aspect of the method for producing a molded article of the present invention is a method for producing a molded article by plastic working the laminated panel of the present invention, wherein the plastic working is performed at any temperature in a temperature range of 10 to 40 ° C. It is characterized by.

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

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 a base material breakage in a fiber reinforced thermoplastic resin layer. Therefore, no peeling occurs at the bonding (bonding) interface during plastic processing such as press processing, and the fiber reinforced thermoplastic resin layer and the metal plate layer are simultaneously plastically deformed, and the softening temperature range of the fiber reinforced thermoplastic resin layer. Sheet metal processing at room temperature (however, less than the melt processing temperature) or room temperature becomes possible.

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 heating to a melt processing temperature range where the resin fluidity is developed such as injection molding. Sheet metal processing is possible in the cold from the temperature range to room temperature. Although depending 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 that is the rate limiting 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 a metal plate layer and a metal plate layer, the heat exchange by the metal plate layer is fast, so the cooling time is 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 speed 4.4 m / s, with 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 inner diameter of the support base: 3 inches and the test temperature: 23 ° C., not only the impact strength during use is improved, Plastic processing (sheet metal processing) such as press molding (drawing) can be facilitated.

According to the present invention, a laminated panel composed of 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 obtained by plastically processing the laminated panel Is provided.

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

FIG. 1 shows an example of the laminated panel of the present invention. The laminated panel 1 is obtained by bonding metal plate layers 3 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 peel test” method of JIS K6854-4: 1999. That's it. When the peel strength is 2.5 kN or more, breakage is likely to occur in the fiber reinforced thermoplastic resin layer, and the metal plate layer and the fiber reinforced thermoplastic resin layer easily follow, thereby cold working. It becomes easy. In addition, this laminated panel is one in which breakage during the peel test occurs in the fiber reinforced thermoplastic resin layer. The upper limit of the peel strength is usually 20 kN / m, preferably 10 kN / m.

In the present invention, it is preferable that the metal plate constituting the metal plate layer has a yield ratio of 92% or less, and the deep drawing process becomes easier when the yield ratio is 92% or less.

The yield ratio is a ratio of the yield strength to the tensile strength in the metal plate, and is calculated from the yield strength and tensile strength obtained by the tensile strength test. The lower the yield ratio, the better the fit to the press die and the like, and the better the molded shape is obtained. Therefore, it is widely used as an index for the moldability of press molding 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 constituting the metal plate layer 3 is at least selected from the group consisting of steel, 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 these, iron, aluminum, an alloy including these, and stainless steel are preferable from the viewpoint of lightness (balance between specific gravity and rigidity), and iron, aluminum, and an alloy including these are more preferable from the viewpoint of cost.

As the material of the metal plate, it is preferable that the tensile strength measured at room temperature (23 ° C.) according to JIS Z2241: 2011 (metal material tensile test method) for the metal plate layer unit test piece is 200 to 1500 MPa, 250 More preferably, it is ˜1000 MPa, more preferably 280 to 600 MPa. 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. 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 still more preferably 20 to 80%. It is preferable to use a metal plate having such a tensile elongation rate because the metal plate layer is difficult to break during cold plastic working such as cold deep drawing, and the cold plastic workability tends to be good.

The thickness _{t 3} of the metal plate layer is usually 0.05 ~ 1 mm in the case of the steel sheet, preferably 0.08 ~ 0.6 mm, more preferably 0.1 ~ 0.4 mm, usually in the case of aluminum alloy 0 The thickness is preferably 1 to 2 mm, preferably 0.15 to 1 mm, more preferably 0.2 to 0.5 mm, from the viewpoint of the rigidity and light weight 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 the required characteristics, the equivalent rigidity and equivalent strength of the steel material and aluminum material can be set arbitrarily. It is.

Although the metal plate depends on the type and thickness of the fiber reinforced thermoplastic resin layer, an aluminum alloy having a thickness of 0.1 to 2 mm is preferable from the viewpoint of lightness and high rigidity. A1060, A1100-O, A2011, A2014, A2017 , A2024, A2025, A2117, A2219, A3003-O, A3004, A3105, A4032, A5005-O, A5052, A5056, A5086, A5154, A5182, A5254, A5454, A5652, A6061, A6063, A6066, A6101, 6N01, A7001 , A7003, A7050, A7075, A7178, 7N01, A7475, etc. can be used.

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

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

The metal plate constituting the metal plate layer is preferably a plate-like one, but is not limited to a plate-like one as long as it can shape the laminated panel of the present invention, and may be curved. , May be bent. Moreover, the shape etc. which have the unevenness | corrugation whose surface is not flat may be sufficient. As the irregular shape, an array in which irregularities such as a lens shape, a cone, a triangular pyramid, a quadrangular pyramid, and a bowl shape are continuously arranged is preferable.

The fiber reinforced thermoplastic resin layer of the present invention may be any material that includes a nonwoven fabric or chopped fibers having an average fiber length of 10 mm or more in the thermoplastic resin. By including such fibers in the thermoplastic resin, when performing molding processing such as plastic processing, which will be described later, using the laminated panel of the present invention, friction between fibers and friction due to displacement between the fibers 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 processing becomes easier even at a low processing temperature.

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

Fiber reinforced thermoplastic resin with long chopped fibers is a thermoplastic resin composition that is usually used in injection molding and extrusion molding. However, when injection molding or extrusion molding, reinforced fibers such as glass fibers are 1 mm or less, resulting in deterioration of physical properties. Therefore, there is a type in which a step of directly combining continuous fibers of reinforcing fibers such as glass fibers at the time of molding is provided so that the remaining fiber length is intentionally set to several mm or more. Typical examples of these include LFT (Long Fiber Thermoplastic), D-LFT (Direct Long Fiber Thermoplastic), etc. using a thermoplastic resin such as PP, PA, or PPS as a base resin.

Although these depend on the manufacturing process, the remaining fiber length of about 10 to several tens of millimeters can be secured by minimizing the glass fiber cutting in the kneading process during injection molding and extrusion molding. Is possible. Typical examples of such LFTs include the trade names Funkster (Nippon Polypro Co., Ltd.), Plastron (Daicel Co., Ltd.), Mostron-L (Prime Polymer Co., Ltd.), Quick Form (Toyobo Co., Ltd.) Etc.

When using chopped fibers, 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 reinforced fiber (strand) in which monofilaments are bundled and cut into a predetermined length. For example, a chopped fiber is made of a long fiber pellet cut into a predetermined length by impregnating the strand with a thermoplastic resin. 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 fibers used in the fiber reinforced thermoplastic resin layer are non-woven fabrics, examples of the web forming method include dry type, wet type, spun bond method, melt blown method, and airlaid method, and fiber bonding methods include needle punch method and chemical bond method. Examples include a method (dipping method / spray method), a thermal bond method, a hydroentanglement method, and the like, and a nonwoven fabric prepared by a combination thereof can be suitably used. Particularly preferred among the nonwoven fabrics is a nonwoven fabric produced by a needle punch method in which fibers are intertwined with each other.

Typical examples of fiber reinforced thermoplastic resins using nonwoven fabric include the trade names GMT (Glass MAT Thermoplastic: Quadrant Plastic Composites Japan), GMTex (Glass Matsplastic Plastic Co., Ltd.). Manufactured)) and the like. In addition, in this invention, in addition to the fiber reinforced thermoplastic resin using said nonwoven fabric, it does not prevent using the fiber reinforced thermoplastic resin material using a textile fabric or a knitted fabric. A typical example of a fiber reinforced thermoplastic resin using a woven fabric is Q-Tex (manufactured by Quadrant Plastic Composites).

Among the nonwoven fabrics, a nonwoven fabric produced by a needle punch in which fibers are intertwined with each other is particularly preferable. A fiber reinforced thermoplastic resin layer in which a nonwoven fabric and a woven fabric are combined as the reinforcing fiber is also suitable. In any case, since the fibers are mutually constrained, high impact resistance can be secured, fiber cutting during fiber processing and fiber uneven distribution can be suppressed, and deterioration of physical properties during use can be easily suppressed.
Although depending on the conditions of the needle punching process, these can be applied to the present laminated panel because a minimum remaining fiber length of 5 mm or more, usually 25 mm or more, and preferably 40 mm or more can be secured. 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. Moreover, it is also preferable that it is a form of continuous fiber.
In addition, the average fiber length in this invention employ | adopts the number average value of the fiber length measured about the fiber in the residue obtained by ashing a fiber reinforced thermoplastic resin layer.

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

As the fibers constituting the fiber-reinforced thermoplastic resin layer 2, one or more reinforcing fibers such as inorganic fibers, organic fibers, and metal fibers can be used. Among these, inorganic fibers are preferable from the viewpoint of light weight and elastic modulus, and organic fibers are preferable from the viewpoint of light weight, elongation, and cold workability.

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

The organic fiber preferably used has a difference between the melting point of the organic fiber and the melting point of the thermoplastic resin used for the fiber-reinforced thermoplastic resin layer or the glass transition temperature of 40 ° C. or more, and impregnates the organic fiber with the thermoplastic resin. It is preferable from the viewpoint of maintaining the shape of the organic fiber. The temperature difference is more preferably 50 to 200 ° C., and further preferably 60 to 150 ° C. In calculating the temperature difference, the melting point is employed when the thermoplastic resin used for the fiber-reinforced thermoplastic resin layer is crystalline, and the glass transition temperature is employed when the thermoplastic resin is amorphous.
Moreover, when using a some thermoplastic resin for a fiber reinforced thermoplastic resin layer, the average value of melting | fusing point or glass transition temperature of these resin is employ | adopted. When using a plurality of organic fibers, the average melting point of these organic fibers is employed. 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. And hold at the same temperature for 1 minute. Then, it can obtain | require from the DSC curve at the time of heating up again on temperature rising conditions of 10 degree-C / min.

The organic fiber is preferably made of a crystalline thermoplastic resin having a melting point of preferably 160 ° C. or higher, more preferably 200 ° C. or higher, further preferably 220 ° C. or higher, particularly preferably 250 ° C. or higher. When the melting point is 160 ° C. or higher, the thermal deformation temperature (heat resistance) of the fiber-reinforced thermoplastic resin layer is improved to the vicinity of the melting point of the crystalline thermoplastic resin and the glass transition temperature of the amorphous thermoplastic resin. As such, the heat resistance of the laminated panel tends to be improved.

The form of the organic fiber may be any of filaments, staples, flat yarns and the like, and is preferably used as a nonwoven fabric composed of one or more of these. Filaments are long fibers (continuous fibers). Staples are staple fibers formed by cutting staple tows in which the filaments are converged to form cotton. Usually, the fiber length is 35 to 100 mm. The flat yarn is a flat yarn that has a strength by cutting (slit) a film of a thermoplastic resin or the like into a strip shape and stretching it.

In particular, in the case of a nonwoven fabric by needle punching using organic fibers, the form of the organic fibers is preferably an average fiber length of 5 to 400 mm, more preferably 25 to 300 mm, and more preferably 40 to 200 mm. More preferably. Moreover, it is also preferable that it is a form of continuous fiber. By setting it as such fiber length, since a fiber disperse | distributes uniformly and it becomes easy to mutually entangle, it tends to improve the mechanical strength and heat resistance of a fiber reinforced thermoplastic resin layer, and is preferable.
The average fineness is preferably 1 to 30 dex, more preferably 2 to 20 dtex, and further preferably 3 to 15 dtex. By setting it as such an average fineness, the interface of a thermoplastic resin and organic fiber increases, and the mechanical strength and heat resistance of a fiber reinforced thermoplastic resin layer tend to improve, and it is preferable.
The basis weight is preferably 50 to 1500 g / m ² , more preferably 100 to 1000 g / m ² . By setting the weight per unit area, it is easy to adjust the rigidity of the laminated panel required for each application by changing the thickness of the fiber reinforced thermoplastic resin layer, ensuring cold plastic workability. 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 an organic fiber is also suitable. In both cases, the fibers are constrained to each other, so that high impact resistance can be ensured, fiber cutting, uneven fiber distribution, and opening during cold plastic working can be suppressed, and deterioration in physical properties during use can be suppressed. it can.

As thermoplastic resins, PP (polypropylene), PVC (polyvinyl chloride), PA (polyacrylonitrile), PC (polycarbonate), PPS (polyphenylene sulfide), PEEK (polyether ether ketone), PET (polyethylene terephthalate) Polyester such as PBT (polybutylene terephthalate), PES (polyethersulfone), and the like are preferable, and crystalline resins such as PP, PA, PBT, PPS, and PEEK are preferable, and PP, PA, and PBT are more preferable. PP is more preferable from the viewpoints of heat resistance, moisture absorption resistance, hydrolysis resistance, and cost.

The fiber volume content Vf in the fiber reinforced thermoplastic resin layer is preferably 10 to 80% by volume, more preferably 15 to 70% by volume. If the volume content Vf is less than 10% by volume, the reinforcing effect due to the fibers is difficult to appear. Since it may become easy to break at the time of processing, such as inter-processing, it is not preferred.
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 fiber is hardly exhibited. It is not preferable because it is easy to break during processing such as inter-processing.

The manufacturing method of a fiber reinforced thermoplastic resin layer is not specifically limited, A conventionally well-known method is employable.
When the fiber used in the fiber reinforced thermoplastic resin layer is chopped fiber, for example, the resin pellet containing the chopped fiber is heated and melted to directly form the fiber reinforced thermoplastic resin layer of the laminated panel, or the resin pellet is heated and melted. Then, a method of forming a sheet in advance and laminating it and a metal plate layer by heat fusion or the like can be mentioned. Further, there is a method in which a fiber reinforced thermoplastic resin discharged from a die of an extruder is directly laminated and formed into a sheet while suppressing fiber cutting by the D-LFT method with a fiber length of 30 mm or more.

When the fiber used for the fiber reinforced thermoplastic resin layer is a non-woven fabric, for example, after the thermoplastic resin is put into an extruder and melted, it is extruded into a sheet having a desired thickness, and the extruded sheet It can be produced by supplying and laminating a nonwoven fabric on at least one side, preferably both sides. A thermoplastic resin sheet can also be supplied to the front and back of the laminate to obtain a laminate. When laminating, a fiber reinforced thermoplastic resin layer is produced by heating and pressurizing using a laminator or the like, impregnating the thermoplastic resin into the nonwoven fabric, and then solidifying by cooling to form a sheet (so-called stampable sheet). Can do. Further, from the viewpoint of shortening the process, it is also possible to form a fiber reinforced thermoplastic resin layer of the laminated panel of the present invention by laminating a nonwoven fabric and a thermoplastic resin sheet and thermoforming the metal plate at once.

Further, the fiber reinforced thermoplastic resin layer may contain other components other than the thermoplastic resin and the nonwoven 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, mold release agents, lubricants, antiblocking agents, antistatic agents, and reinforcing fibers. Various additives, such as inorganic fillers other than, are mentioned.

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

Further, the fiber reinforced thermoplastic resin layer is composed of a dynamic viscoelasticity test (JIS K 7244-4: 1999 (plastic-dynamic mechanical property test method, frequency 100 Hz, test piece). When the ratio of the storage elastic modulus E ′ to the specific gravity ρ of the fiber-reinforced thermoplastic resin layer (thickness 2 mm, test temperature 23 ° C.) (specific storage elastic modulus value: E ′ / ρ) is 1.0 GPa or more, the fiber Plasticization of the reinforced thermoplastic resin layer is unlikely to be excessive, and the fiber reinforced thermoplastic resin layer is also easily deformed while following the plastic deformation of the metal plate layer, which is preferable because plastic processing tends to be easier.

Here, the specific storage elastic modulus of the fiber-reinforced thermoplastic resin layer is determined based on the dynamic viscoelasticity of the fiber-reinforced thermoplastic resin layer single specimen using a dynamic viscoelasticity measuring apparatus (for example, FT Rheospectr manufactured by Rheology). It can be obtained by measuring the temperature dependence from room temperature to 200 ° C. under the test conditions (JIS K 7244-4: 1999 (Plastic—Dynamic mechanical property test method, frequency 100 Hz, test piece thickness 2 mm)). . The specific gravity ρ (dimensionless) of the fiber reinforced thermoplastic resin layer is also temperature-dependent, but here, the values calculated from the measured weight and volume at room temperature (23 ° C.) are applied as representative values. Can do.

The specific storage elastic modulus (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, destruction of the metal plate layer by the fiber reinforced thermoplastic resin during cold plastic processing, or generation of transfer marks on the surface of the metal plate by the reinforcing fiber when using high-strength reinforcing fibers Is easy to be suppressed, which is preferable.

There are no particular restrictions on the bonding (adhesion) method between the fiber reinforced thermoplastic resin layer and the metal plate layer, and various methods can be applied. However, the base material breaks down in the fiber reinforced thermoplastic resin layer during the peel strength test. It is essential that the peel test strength is strong. JIS K6854-4: Joining (adhesion) method in which the peeling strength is 2.5 kN or more in the floating roller method peeling test of 1999, and no interface peeling occurs and the base material breaks down 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 the bondability (adhesiveness) in which the peel strength in the floating roller method peel test is 2.5 kN / m or more and the base material breaks down in the fiber reinforced thermoplastic resin layer, for example, an adhesive is used. In addition to the method of providing the used adhesive layer, the method of, for example, anodizing and etching the surface of the metal plate, metals such as NMT treatment recently developed by Taisei Plus Co., Ltd. and 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 Laboratory Co., Ltd. or Toa Denka Co., Ltd. is modified on the metal surface by chemical reaction, the metal surface and thermoplastic resin and various curing A method to improve the adhesiveness with adhesives such as adhesive resins, and a complex three-dimensional mesh-like surface on a metal surface by laser irradiation developed by Daicel Corporation. A method in which a porous layer, called the pitch anchor the like. As described above, if the surface treatment of the metal plate is appropriately selected, the adhesive strength with the fiber reinforced thermoplastic resin layer 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 an epoxy adhesive, a urethane adhesive, a polyester adhesive, and the like, and a thermosetting adhesive of a type having improved adhesion to a polyolefin resin. Alternatively, in the lamination process, an easy-adhesive primer layer is provided on the surface of the fiber reinforced thermoplastic resin layer laminated with the metal plate layer, and a normal thermosetting epoxy system, urethane system, polyester system is provided. Alternatively, the metal plate layer may be bonded using an acrylic adhesive or the like.

As the adhesive resin, commercially available maleic anhydride-PP copolymer resin films (trade names: Modic P555 manufactured by Mitsubishi Chemical Corporation, Clanbetter P6700 manufactured by Kurabo Industries, etc.) can be suitably used. In addition, a modified polyolefin adhesive resin film (Mitsui Chemicals, Inc., Admer VE300, manufactured by Mitsui Chemicals, Inc.) 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-like hot melt type are used. An adhesive (Kurabo Clam Better G13), a film-like hot melt type adhesive (Kurabo Clan Better CN-1003) and the like can be used as the nylon film. Alternatively, a metal composite plate (Hishimetal, Alset (both manufactured by Mitsubishi Plastics Co., Ltd.) or the like) in which a film of a resin similar to the fiber reinforced thermoplastic resin layer is previously laminated may be used. In this case, Hishi Metal PO, Alset 1P, Alset HP, etc. in the PP resin layer, Alset 1Y, Alset 3Y, Alset AR, etc. in the polyamide resin layer, Alset in the PET resin layer EG, Alset EH, etc. can be used suitably.

The surface of the metal plate of the metal plate layer is preferably subjected to a surface treatment because an improvement in adhesion (bonding) strength can be expected. Examples of the surface treatment method include various chemical treatments such as plasma treatment, UV treatment, corona treatment, etching treatment, alkali electrolysis treatment, chemical treatment such as chromate treatment, and the like.

As a method for adhering the metal plate layer and the fiber reinforced thermoplastic resin layer, there is 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 joining 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 the metal plate layer. A method of bonding the fiber reinforced thermoplastic resin layer is preferable. Also suitable is 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 pressed and heated to bond the metal plate layer and the fiber reinforced thermoplastic resin layer. .
In addition, as a fiber reinforced thermoplastic resin layer used for manufacture of a laminated panel, you may use the fiber reinforced thermoplastic resin sheet manufactured previously as mentioned above, and a nonwoven fabric and thermoplasticity from a viewpoint of process shortening. It is good also as a fiber reinforced thermoplastic resin layer of the laminated panel of this invention by thermoforming at once with a metal plate using what laminated | stacked the resin sheet and the chopped fiber containing resin pellet directly.

In the laminated panel of the present invention, the number of laminated layers is not particularly limited as long as the above-described fiber reinforced thermoplastic resin layer and the metal plate layer are laminated and the outermost layer of the panel is the metal plate layer. Among these, a three-layer structure of metal plate layer / fiber reinforced thermoplastic resin layer / metal plate layer is preferable in terms of lightness, rigidity, and productivity. Moreover, in the range which does not impair the objective of this invention, layers other than a metal plate layer and the fiber reinforced thermoplastic resin layer of this invention may be included in the laminated body panel.

The laminated panel obtained by bonding 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. More preferably, it is 5 kN / m or more, and the breakage 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 factor is 1 or more, preferably 2 or more, more preferably 3 or more, and still more preferably 5 That's it. It is preferable from the viewpoint of workability described below that the lamination component factor Z is equal to or greater than the value. Further, the lamination component factor Z is preferably 2000 or less, more preferably 500 or less, still more preferably 100 or less, and particularly preferably 50 or less. It is preferable from the point of weight reduction that the lamination | stacking component factor Z is below the said value.
Z = (σm · tm · εm) / (σc · tc · εc) (1)
σm: Tensile strength (MPa) of the metal plate layer at room temperature
tm: Metal plate layer thickness (mm)
εm: Tensile elongation at room temperature of metal plate layer (%)
σc: Tensile strength at room temperature (MPa) of the fiber reinforced thermoplastic resin layer
tc: thickness of the fiber-reinforced thermoplastic resin layer (mm)
εc: Tensile elongation at room temperature (%) of the fiber reinforced thermoplastic resin layer

Here, the tensile strength (MPa) at room temperature (23 ° C.) of the metal plate layer and the tensile elongation (%) at room temperature (23 ° C.) of the metal plate layer are JIS Z2241: 2011 (metal Based on measured values according to the 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. For JIS K7164: 2005 (Plastics-Test method for tensile properties-Part 4: Test conditions for isotropic and orthotropic anisotropic fiber reinforced plastics).
The thicknesses of the metal plate layer and the fiber reinforced thermoplastic resin layer refer to the average thickness, and in the case of having protruding portions such as ribs and bosses that partially protrude, the thickness refers to the average thickness of the portion excluding these protruding portions.

In addition, the value of (σm · tm · εm) in the above formula (1) is calculated by calculating the value of tensile strength × thickness × tensile elongation for each outermost metal plate, and calculating the total value of both metal plate layers. (Σm · tm · εm). Similarly, in the case of having a metal plate layer other than the outermost layer, the tensile strength × thickness × tensile elongation is calculated for each metal plate layer, and the total value of each metal plate layer is (σm · tm · εm). .
Similarly, in the case of a configuration in which two or more fiber reinforced thermoplastic resin layers exist, the tensile strength × thickness × tensile elongation of each fiber reinforced thermoplastic resin layer is calculated, and the total of each fiber reinforced thermoplastic resin layer is calculated. The value is (σc · tc · εc).

This calculated value Z is an index indicating the selection of a laminated structure capable of plastic working of the laminated panel of the present invention and its plastic working characteristics. If the energy required for deformation of both layers is balanced on the assumption that both the metal plate layer and the fiber reinforced thermoplastic resin layer are ideally joined, the metal plate layer and the fiber reinforced thermoplastic resin layer Assuming that deformation does not occur in either layer, the energy required for deformation of both layers is the maximum tensile force and thickness of each of the metal plate layer and the fiber reinforced thermoplastic resin layer ( Cross-sectional area) and tensile elongation (strain), and can be represented by a calculated value Z (formula (1)). When Z is less than 1, the metal plate layer is likely to break or crack during plastic working such as deep drawing or bending.

Although the laminated panel of the present invention can be applied to various forming methods, since it has the above-described properties, a remarkable effect can be exhibited particularly by using it for plastic working. . As a plastic working (sheet metal working) method for producing a molded product from the laminated panel of the present invention, conventionally known methods can be mentioned. In particular, it can be preferably applied to press working (including simple press working, drawing, deep drawing, overhanging, stretch flange processing, etc.), roll forming, and bending, and is particularly suitable for deep drawing. Among these, it can be suitably used for producing deep-drawn products having a limit drawing ratio of 1.6 or more, particularly 2 to 3. The limit drawing ratio (LDR) is the maximum blank diameter (Dmax) and the diameter of the cylinder (inner diameter of the drawn product: d) that can squeeze a cylinder that does not break with a single drawing. Calculated as the ratio (Dmax / d).

The laminated panel of the present invention comprises 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. It can be suitably processed at any temperature in the temperature range of 1.5-3 GPa (mold temperature or preheating temperature of the 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 to any temperature in the above temperature range.

As a method of processing in the processing temperature region in which the specific storage elastic modulus value (E ′ / ρ) shows such a value, it is room temperature or below 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 processing is performed from room temperature to the mold temperature set below the glass transition temperature or melting temperature of the thermoplastic resin (simple pressing, deep A method of plastic working (sheet metal working) such as bending and roll forming is preferable. Depending on the configuration of the laminated panel, a room temperature laminated panel may be cold worked with a room temperature mold from the viewpoint of shortening the cooling cycle. In the present invention, when organic fibers having a higher tensile elongation than inorganic fibers are used, the fiber-reinforced thermoplastic resin layer easily follows the deformation of the metal plate layer during cold plastic processing, and the room temperature laminated panel is changed to room temperature. It becomes easier to cold work with this mold.

When the thermoplastic resin constituting the fiber-reinforced thermoplastic resin layer is a crystalline resin, the softening temperature is not less than room temperature and not more than the melting point, preferably not more than the crystallization temperature, in the DSC curve. In the case of an amorphous resin, the softening temperature is in the range of room temperature to glass transition temperature + 50 ° C., preferably below the glass transition temperature. The measuring method of melting | fusing point and glass transition temperature is as having mentioned above.

When the thermoplastic resin constituting 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 of the thermoplastic resin and the crystal melting temperature It is preferable from the viewpoint of the physical properties of the obtained molded product to select and warm the temperature, but from the viewpoint of the molding cycle at the time of molding, it is desirable not to provide a preheating step as much as possible. When heating, if the heating temperature is lower than the crystallization start temperature, plastic deformation of the fiber-reinforced thermoplastic resin layer becomes difficult and the metal plate layer may be cracked. Conversely, if the temperature is higher than the crystal melting temperature of the thermoplastic resin, the fiber reinforced thermoplastic resin layer is excessively softened, and the metal plate layer in the deformation process at the time of 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. However, it is appropriately selected depending on the breaking state of the reinforcing fiber due to shear 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, the glass transition temperature (Tg) of the thermoplastic resin or higher, and the glass transition temperature +50. It is preferable from the viewpoint of the molding cycle during molding to provide a preheating step as much as possible from the viewpoint of the physical properties of the molded product obtained by selecting and heating at a temperature not higher than ° C., that is, in the range of Tg to Tg + 50 ° C. Desirably not. When this heating temperature is lower than the glass transition temperature of the thermoplastic resin, the plastic deformation of the fiber-reinforced thermoplastic resin layer becomes difficult, and the metal plate layer may be cracked. Conversely, if the glass transition temperature of the thermoplastic resin is higher than + 50 ° C., it becomes the melt processing temperature range, so the fiber reinforced thermoplastic resin layer is excessively softened and fluidized, and the metal plate layer in the deformation process at the time of molding processing becomes this. It may cause cracks and wrinkles.

The mold temperature is preferably set to room temperature or more and below the glass transition temperature of the thermoplastic resin, and room temperature is particularly preferable because of shortening of the cooling time. It is possible to select appropriately.

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

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

Auto parts include body, door inner, side panel, bonnet (engine / hood), roof, floor, cab lower cover, trunk lid, reinforcement parts, side sill, cross member, bracket, various pillar parts, various beam parts, A floor reinforcement board etc. are illustrated.
Examples of the electronic component include a housing such as a TV, a PC, and a mobile device.

Other products include helmets, aluminum sash frames, elevator gate frames (beams), anti-blade waistcoats, travel bags, gusts, roofs, etc.

Hereinafter, examples and comparative examples will be described. In the following examples and comparative examples, the deep drawing shown in FIG. 2 or the press forming shown in FIG. 3 was performed as plastic working. In FIG. 2, the shape shown in FIG. 2 is obtained by deep drawing a circular plate-like laminated panel having a diameter of 98 mm and a thickness of 2 mm using a high-power press tester (special specification of the double-acting hydraulic press TM200 manufactured by Amino Co., Ltd.) The molded product had a drawing ratio of 1.7). 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. Various physical properties were measured according to the method described above. “Room temperature” refers to 23 ° C.

GMT40: Quadrant Composite Plastic Japan Co., Ltd. P4020-BK31
Stampable sheet made of glass fiber nonwoven fabric 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: 101mm
Specific gravity: 1.2
Specific storage modulus E ′ / ρ (frequency 100 Hz, specimen 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 Plastic Japan Co., Ltd. Stampable sheet made of glass fiber nonwoven fabric and polypropylene resin by needle punch method Polypropylene resin content: 35% by weight
Glass fiber content: 40% by volume (65% by weight)
Average fiber length: 98mm
Specific gravity: 1.53
Specific storage elastic modulus value E ′ / ρ (frequency 100 Hz, specimen 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: P6538-BK31 made by Quadrant Composite Plastic Japan Co., Ltd.
Stampable sheet consisting of a laminate of a glass fiber woven fabric and nonwoven fabric subjected to needle punching treatment and polypropylene resin Polypropylene resin content: 40% by weight (65% by volume)
Glass fiber nonwoven 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, specimen 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 in which a polycarbonate resin is melt-impregnated with a PAN-based carbon fiber nonwoven fabric by a needle punch manufacturing method. Polycarbonate resin content: 35% by weight
Carbon fiber content: 55% by volume (65% by weight)
Average fiber length: 60mm
Specific gravity: 1.53
Specific storage elastic modulus value E ′ / ρ (frequency 100 Hz, specimen 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: Nippon Polypro Co., Ltd. LR24A
Sheets obtained by hot press molding pellets made of long fiber chopped glass fibers and polypropylene resin 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 the pellet: 10 mm
Specific gravity of pellet: 1.2
Specific storage modulus E ′ / ρ (frequency 100 Hz, specimen 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 nonwoven fabric 1: BT-1812W manufactured by Unicel Corporation
Polyester continuous fibers by melt-blown method (melting point 265 ° C.) nonwoven fabric average fiber length: Continuous Fiber basis weight: 80 g / ^{m 2}
Fiber reinforced thermoplastic resin layer single-piece test piece (polypropylene resin content 70% by weight, polyester fiber content 22% by volume (30% by weight), specific gravity impregnated with an 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 2 mm, test temperature 23 ° C.): 4.2 kN
Maximum impact strength per unit thickness: 2.1 kN / mm

Organic fiber nonwoven fabric 2: Eco punch made by Watanabe Kogyo Co., Ltd. Recycled polyethylene terephthalate resin staple (melting point 265 ° C.) nonwoven fabric by needle punch method Average fiber length: 51 mm
Average fineness: 10 dtex
Basis weight: 300 g / m ²
Fiber reinforced thermoplastic resin layer single-piece test piece (polypropylene resin content 70% by weight, polyester fiber content 22% by volume (30% by weight), specific gravity impregnated with an 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 2 mm, test temperature 23 ° C.): 2.4 kN
Maximum impact strength per unit thickness: 1.2 kN / mm

Organic fiber non-woven fabric 3: manufactured by Misawa Fiber 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
Basis weight: 300 g / m ²
Fiber reinforced thermoplastic resin layer single-piece specimen impregnated with an organic fiber nonwoven fabric 3 with a polypropylene resin (melting point 165 ° C.) (polypropylene resin content 70% by weight, polyester fiber content 22% by volume (30% by weight), specific gravity 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 2 mm, test temperature 23 ° C.): 1.6 kN
Maximum impact strength per unit thickness: 0.8 kN / mm
Fiber reinforced thermoplastic resin layer single-piece specimen impregnated with polypropylene fiber (melting point 165 ° C.) in organic fiber nonwoven fabric 3 (polypropylene resin content 30% by weight, polyester fiber content 60% by volume (70% by weight), specific gravity 1.19) ・ Specific storage elastic modulus value E ′ / ρ (frequency 100 Hz, specimen thickness 2 mm, test temperature 23 ° C.): 2.8 GPa
・ Maximum impact strength by puncture test (test piece thickness 2 mm, test temperature 23 ° C.): 3.0 kN
Maximum impact strength per unit thickness: 1.5 kN / mm

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

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

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

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

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

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

SPCD: Cold rolled steel sheet manufactured by Nippon Steel & Sumitomo Metal Corporation Thickness: 0.4mm
Tensile strength: 300 MPa
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 previously heat-sealed to one surface of the aluminum plate at a surface pressure of 3.9 MPa and 180 ° C.

As the fiber reinforced thermoplastic resin layer, GMT 40 having a thickness of 3.8 mm was used.

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

The laminate panel was measured for peel strength, flexural modulus, and maximum impact strength, and the deep drawing shown in FIG. 2 was performed at 120 ° C. to evaluate the deep drawability and molding cycle. The results are shown in Table 1. .
Moreover, the unit thickness by the puncture impact test (ASTM D3763, striker diameter 1/2 inch, impact speed 4.4 m / s, support stand inner diameter: 3 inch, test temperature: 23 degreeC) of the material used as a fiber reinforced thermoplastic resin layer Table 1 also shows the maximum impact strength per hit and the calculated value Z of equation (1) representing the lamination component 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, the case where the fiber reinforced thermoplastic resin composition layer breaks (base material breakage) is “A”, and the case where the fiber reinforced thermoplastic resin composition layer peels off at the interface between the metal plate layer (interface peel). “B”.
The flexural modulus of the laminated panel was measured at room temperature using a bending tester (a precision universal material tester manufactured by Intesco) based on JIS K7017: 1999.
Regarding the deep drawability at the time of deep drawing, “A” indicates that deep drawing can be performed and there is no crack in the resulting molded product, while deep drawing is possible and there are slight cracks in the metal plate layer. Evaluation was made with “B” for a case where there was no problem as a molded product, and “C” for a case where cracking occurred in a molded product obtained because deep drawing could not be performed.
The forming 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 to releasing the mold) 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 25 to 200 ° C. in a temperature range of 25 to 200 ° C. using a dynamic viscoelasticity measuring machine (FT Leospectr manufactured by Rheology) It was measured.
Moreover, 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 at the time of plastic working (preheating temperature or mold temperature of the laminated panel) 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 GMT 65 having a thickness of 3.8 mm was used as the fiber reinforced thermoplastic resin layer, and the characteristics were measured and deep-drawn. The results and Z values are shown in Table 1.

[Example 3]
A laminated panel was formed 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-drawn. The results and Z values are shown in Table 1.

[Example 4]
A laminated panel was formed 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 characteristic measurements and deep drawing were performed. The results and Z values are shown in Table 1.

[Example 5]
A laminated panel was formed in the same manner as in Example 1 except that deep drawing was performed at a preheating temperature of 35 ° C. and a mold temperature of 30 ° C., and characteristic measurements and deep drawing were 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 aluminum alloy plate A5182-H38 (thickness: 0.25 mm, tensile strength: 380 MPa, tensile elongation: 9%), Characteristic measurement and deep drawing. The results and Z values are shown in Table 2.

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

[Example 8]
In Example 7, a laminated panel was molded in the same manner except that the preheating temperature and the mold temperature during press molding were set to 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 metal plate A5182-O (thickness: 0.25 mm, tensile strength: 290 MPa, tensile elongation: 21%) was used as the two metal plate layers. Then, characteristic measurement and deep drawing were performed. The results and Z values are shown in Table 3.

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

[Example 11]
A laminated panel was formed in the same manner as in Example 1 except that LFT having a thickness of 2 mm was used as the fiber-reinforced thermoplastic resin layer, and characteristic measurement and deep drawing were 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 metal plate A5182-O (thickness: 0.4 mm, tensile strength: 290 MPa, tensile elongation: 21%) was used as the two metal plate layers. Then, characteristic measurement and deep drawing were 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 previously heat-sealed to one surface of the aluminum plate at a surface pressure of 3.9 MPa and 180 ° C.

As the material of the fiber reinforced thermoplastic resin layer, the organic fiber nonwoven 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 molding is performed so that the total thickness is 2 mm at a surface pressure of 3.9 MPa and 180 ° C. for 10 minutes. The metal plate layer and the fiber reinforced thermoplastic resin layer (polypropylene resin / organic fiber nonwoven fabric 1) were bonded to obtain a laminated panel having a thickness of 2 mm.
The obtained laminated panel was molded in the same manner as in Example 1 and subjected to characteristic measurement and deep drawing. The results and Z values are shown in Table 4.

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

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

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

[Comparative Example 1]
Without using a PP film for bonding, the aluminum plate was surface-treated (specifically, porous treatment (microporous treatment) by MAL Corporation AMALFA treatment (chemical etching)), fiber reinforced thermoplastic resin layer and metal A laminated panel was formed in the same manner as in Example 1 except that the plate layer was bonded to the resin layer by fusing the resin in the fiber-reinforced thermoplastic resin layer, and the characteristics were measured and deep-drawn. 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 them, and cracking occurred due to deep drawing.

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

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

[Comparative Example 4]
A laminated panel is formed in the same manner as in Example 1 except that aluminum alloy plate A1100-H16 (thickness: 0.15 mm, tensile strength: 145 MPa, tensile elongation: 6%) is used as the two metal plate layers. Then, characteristic measurement and deep drawing were performed. The results and Z values are shown in Table 5. As shown in Table 5, in Comparative Example 4, the thickness of the metal plate layer is as thin as 0.15 mm, the tensile strength is 145 MPa, and the tensile elongation is as low as 6%. The value was less than 1 and the metal sheet layer was cracked by deep drawing.

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

Although the present 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)

1. A non-woven fabric or a fiber reinforced thermoplastic resin layer containing a chopped fiber 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, the outermost layer being the metal In laminated panels that are plate layers,
   When a test according to the “floating roller method peel test” method of JIS K6854-4: 1999 is performed, the peel strength is 2.5 kN / m or more, and the breakage occurs in the fiber-reinforced thermoplastic resin layer. The calculated value Z of Formula (1) which shows the following lamination constituent factors is 1 or more, The laminated panel characterized by the above-mentioned.
   Z = (σm · tm · εm) / (σc · tc · εc) (1)
   σm: Tensile strength (MPa) of the metal plate layer at room temperature
   tm: Metal plate layer thickness (mm)
   εm: Tensile elongation at room temperature of metal plate layer (%)
   σc: Tensile strength at room temperature (MPa) of the fiber reinforced thermoplastic resin layer
   tc: thickness of the fiber-reinforced thermoplastic resin layer (mm)
   εc: Tensile elongation at room temperature (%) of the fiber reinforced thermoplastic resin layer
2. The fiber reinforced thermoplastic resin layer according to claim 1, wherein the fiber reinforced thermoplastic resin layer has a dynamic viscoelasticity test (JIS K 7244-4: 1999 (plastic-dynamic mechanical property test method, frequency 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) at 100 Hz, test piece thickness 2 mm, and test temperature 23 ° C. is 1.0 GPa or more. A laminated panel characterized by that.
3. 3. The fiber reinforced thermoplastic resin layer according to claim 1, wherein the fiber reinforced thermoplastic resin layer is a puncture impact test (strike diameter 1/2 inch, impact speed 4.4 m / s, support base inner diameter: A laminated panel having a maximum impact strength per unit thickness of 0.5 kN / mm or more by 3 inches and a test temperature of 23 ° C.
4. 4. The laminated panel according to any one of claims 1 to 3, wherein the fibers in the fiber-reinforced thermoplastic resin layer are nonwoven fabrics, and the average fiber length is 25 mm or more.
5. 5. The laminated panel according to claim 1, wherein the laminated panel has a three-layer structure in which the metal plate layer is bonded to both surfaces of the fiber reinforced thermoplastic resin layer.
6. 6. The laminated panel according to claim 1, further comprising an adhesive layer between the fiber-reinforced thermoplastic resin layer and the metal plate layer.
7. In any 1 item | term of the Claims 1 thru | or 6, the fiber in the said fiber reinforced thermoplastic resin layer is an organic fiber, and the difference of melting | fusing point of this organic fiber, melting | fusing point of the said thermoplastic resin, or glass transition temperature is 40 degreeC. A laminated panel characterized by the above.
8. 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.
9. 9. The laminated panel according to claim 7, 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 .
10. 10. A laminated panel according to claim 1, wherein the laminated panel is used for plastic working.
11. A method for producing a molded product by plastic processing of the laminated panel according to claim 1, wherein a dynamic viscoelasticity test (JIS K 7244) of the fiber-reinforced thermoplastic resin single-piece test piece is performed. -4: ratio of storage elastic modulus E 'to specific gravity ρ of the fiber-reinforced thermoplastic resin layer in 1999 (plastic-dynamic mechanical property test method, frequency 100 Hz, test piece thickness 2 mm) (specific storage elastic modulus value: E A method for producing a molded article, wherein the plastic working is performed at any temperature in a temperature range of '/ ρ) of 1.0 GPa or more.
12. A method for producing a molded product by plastic 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. A method for manufacturing a molded product.
13. The method for manufacturing a molded product according to claim 11 or 12, wherein the plastic working is press working, roll forming work, or bending work.

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