JPH07178859A - Laminate and production thereof - Google Patents

Abstract

PURPOSE:To produce a lightweight laminate having high rigidity by stacking two or more combinations each formed by laminating resin foam and a prepreg to thermally bond them. CONSTITUTION:Two or more combinations each formed by laminating resin foam and a prepreg are stacked to be thermally bonded. The prepreg pref. contains 30-85vol.% of a reinforcing fiber. This reinforcing fiber is pref. composed of a long fiber continuous in one direction. Further, the reinforcing fiber is a glass fiber and a thermoplastic resin and foam are composed of a polypropylene resin or a polystyrene resin. Prepreg laminates 2-6 may be the same laminated constitution and the same wall thickness and laminated constitution and wall thickness may be changed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention comprises a laminate of one or more prepregs impregnated with a thermoplastic resin and a resin foam, which are formed by aligning continuous reinforcing fibers in one direction and melt-integrating them. The present invention relates to a molded product and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, it has been known that a fiber reinforced resin plate is attached to the upper and lower surfaces of a resin foam to make a plate that is lightweight and has high surface rigidity. It is manufactured by integrating a fiber reinforced plate having a thermosetting resin such as an unsaturated polyester resin as a matrix with a hard urethane foam obtained by foaming a thermosetting polyurethane resin. As a method of integrating, while the matrix resin of the fiber reinforced plate is in a liquid state before being cured, it is superposed on the resin foam, and is pressed by a press machine or the like to remove the liquid matrix resin from the surface of the resin foam. When the resin that has penetrated into the foam is solidified when it is allowed to penetrate and harden, and when it is physically joined while it penetrates into the foam, or when the fiber reinforced plate is preformed and the adhesive is used to join with the foam. There are cases. As another method, it is also known that a fiber reinforced thermoplastic resin plate is attached to the upper and lower surfaces of a foam made of a thermoplastic resin.

[0003]

However, although the plate manufactured by the above method has high surface rigidity as described above,
When a local bending load or impact load is applied, the fiber-reinforced resin plates on the upper and lower surfaces are not destroyed, but only the foam directly under the load is partially collapsed and the function as a plate is lost. It is a frequent problem. On the other hand, it has been pointed out that the joint surface between the fiber-reinforced resin plate and the foam is easily peeled off when it is subjected to a large deformation due to the load on the entire surface, and the reliability is poor for use as a structural member. Further, in the above-mentioned manufacturing method, a bad odor when handling the thermosetting resin and the scattering of the reinforcing fibers deteriorate the working environment, and it is pointed out that there is a problem in hygiene.

Further, since the fiber-reinforced resin plate is molded and joined to the resin foam, there is a problem that process control such as curing, application of adhesive, pressure bonding and curing is required, resulting in high processing cost. Also, in the case of a fiber-reinforced thermoplastic resin plate that is laminated on the upper and lower surfaces of a foam made of a thermoplastic resin, there is no suitable adhesive, and the thickness of the foam does not change even when joining by heat fusion. There are problems that it is difficult to work while holding them uniformly, and there are many variations in performance. Therefore, an object of the present invention is to use a foam made of a thermoplastic resin and a fiber reinforced plate having a thermoplastic resin as a matrix, and to firmly bond the fiber reinforced plate and the foam without using an adhesive. Another object of the present invention is to provide a laminate having a high surface rigidity and a foam that does not change its thickness, and a method for producing the same at low cost in a hygienic work environment.

[0005]

The present inventors have completed the present invention as a result of intensive studies to achieve the above object. That is, the laminate according to the present invention is a molded product obtained by laminating one or more prepregs impregnated with a thermoplastic resin and resin foams by aligning continuous reinforcing fibers in one direction and laminating the resin foams and prepregs. It is characterized in that two or more layers of the laminated combination are overlapped and the layers are thermally bonded. It is recommended that the prepreg contains 30% or more and 85% or less by volume content of reinforcing fibers, and that the reinforcing fibers are unidirectionally continuous filaments. Further, the reinforcing fiber is a glass fiber, the thermoplastic resin and the foam is a polypropylene-based resin or polystyrene-based resin, further the expansion ratio of the foam present near the surface of the load is the center, The present invention can be preferably applied to the case where the expansion ratio of the foam close to the layer is lower.

Further, in the production method according to the present invention for producing the above-mentioned laminated molded article, one or more prepregs in which continuous reinforcing fibers are aligned in one direction and impregnated with the thermoplastic resin are used. Heating to above the melting temperature to degas the air contained in the layers; heating the prepreg above the melting temperature, heating the resin foam below the melting temperature, simultaneously without contacting each other; A step of heat-bonding the prepreg and the resin foam overlaid on each other and applying pressure; cooling the heat-bonded laminate;
It is characterized in that the steps of solidifying and integrating are sequentially executed. The above-mentioned production method can be suitably applied when the reinforcing fiber contains 30% or more and 85% or less by volume content of the reinforcing fiber and is composed of continuous fibers in one direction, and particularly, the reinforcing fiber. Is a glass fiber, the thermoplastic resin and the foam is a polypropylene-based resin or polystyrene-based resin, further the foaming ratio of the foam existing near the surface of the load is closer to the center layer The present invention can be suitably applied to the case where the expansion ratio is lower than the above.

The thermoplastic resin used in the prepreg obtained by impregnating the unidirectionally arranged fibers with the thermoplastic resin used in the present invention is, for example, polystyrene, polypropylene, polyethylene, AS resin, ABS resin, ASA.
Resin (polyacrylonitrile / polystyrene / acrylic acid ester), polymethylmethacrylate, nylon, polyacetal, polycarbonate, polyethylene terephthalate, polyphenylene oxide, fluororesin, polyphenylene sulfide, polysulfone, polyethersulfone, polyetherketone, polyetherether Examples include ketones, polyimides, polyarylates and the like.

Typical fibers used in a prepreg in which fibers arranged in one direction are impregnated with a thermoplastic resin are, for example, glass fibers, carbon fibers, aramid fibers and silicon carbide fibers. A prepreg obtained by impregnating fibers arranged in one direction with a thermoplastic resin usually has a thickness of 3
A yarn obtained by bundling 200 to 12000 monofilaments of -25 μm or a roving in which a predetermined number of rovings are arranged in one direction is impregnated with a thermoplastic resin.

Glass fiber is usually subjected to various surface treatments,
The adhesion with the resin is improved. The surface treatment is performed by combining a sizing agent and a coupling agent. A sizing agent is usually used to focus the monofilaments. The sizing agent needs to be selected depending on the thermoplastic resin to be combined. Generally, a resin that is softened at the melting temperature of the resins to be combined and easily impregnated with the thermoplastic resin in the fiber bundle is selected. Therefore, a sizing agent whose main component is a resin of the same kind as the thermoplastic resin to be combined is often used. The glass fiber used as the fiber of the prepreg is one that is treated with a silane-based, titanate-based, or zirconium-based coupling agent to improve the adhesion to the resin.

In the case of glass fiber, it is necessary to select the most suitable coupling agent according to the resin to be combined, and specific examples thereof will be given below. For nylon resin, γ-
Aminopropyl-trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-trimethoxysilane and the like are used. If it is a polycarbonate resin, γ-aminopropyl-trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-trimethoxysilane and the like are used. If polyethylene terephthalate or polybutylene terephthalate, then β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane,
γ-glycidoxy-propyltrimethoxysilane, γ-
Aminopropyl-trimethoxysilane or the like is used. If polyethylene or polypropylene is used, vinyltrimethoxysilane, vinyl-tris- (2-methoxyethoxy) silane, γ-methacryloxy-propyltrimethoxysilane, or the like is used. Polyphenylene oxide,
As long as it is polyphenylene sulfide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyimide, polyarylate, or a fluororesin, the above-mentioned coupling agent can be used, but N- (β -Aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-aminophenyltriethoxysilane and the like can be used.

When a fiber other than glass fiber is used as the reinforcing fiber, an amine-curing type epoxy resin is often treated as a coupling agent, and specific examples thereof include bisphenol-A-epichlorohydrin resin, epoxy novolac resin and alicyclic compounds. Epoxy resins, aliphatic epoxy resins, and glycidyl ester type resins may be used, but since thermoplastic resins generally have high melting temperatures, ordinary coupling agents undergo thermal decomposition, so no coupling agents are used. It may not be used.

The method of applying the coupling agent to the fiber surface is as follows. That is, as one method, when the fiber is melted and the monofilament is pulled out, a sizing agent and a coupling agent are added to the surfactant to prepare an aqueous solution.
After spraying on the monofilament, it is dried and treated at a temperature of about 100 ° C. As another method, 0.1 to 3% by weight of a sizing agent and a coupling agent is added to the fiber from which the sizing agent is removed.
The dissolved liquid is completely impregnated by means such as dipping and spray coating. 60 fibers containing this coupling agent solution
Dry at ~ 120 ° C to allow coupling agent to react with fiber surface. The drying time is sufficient to evaporate the solvent, which is about 15 to 20 minutes. The solvent for dissolving the coupling agent has a pH of 2.0 to 1 depending on the surface treatment agent used.
There are cases where water adjusted to 2.0 is used, and cases where organic solvents such as ethanol, tolueneacetone and xylene are used alone or as a mixture. There are various methods for impregnating the reinforcing fibers unidirectionally aligned with the thermoplastic resin to form the prepreg, but the most general method is as follows. First, if the resin is soluble in the solvent,
This is a method in which the resin is made into a solution and impregnated into reinforcing fibers, and then the solvent is removed while defoaming to obtain a prepreg.

The other is a method of heating and melting a resin to impregnate a reinforcing fiber, defoaming, and cooling to obtain a prepreg. As a method of manufacturing a prepreg, for example, Japanese Patent Publication No. 02-
The method disclosed in Japanese Patent No. 042168 can be mentioned. By this method, for glass fiber, for example, thickness 1
The surface of a 3μ monofilament is γ-methacryloxy-
Treated with propyltrimethoxysilane and treated with 1800
This bundle is made into a twist-free yarn, 80 yarns are aligned in one direction while pulling with a uniform tension, the resin is entangled with the yarn, and the resin is squeezed with a hot roll,
The yarn can be impregnated to produce a prepreg. The prepreg manufactured in this manner has excellent adhesion between the fiber and the thermoplastic resin and has a fiber content of 30-90% by weight.
And it can be changed according to the requirements, and the thickness is 0.1-1.
It can be manufactured with 0 mm, but the glass content is 30
It is desirable to use it in a range of 85% by volume and a thickness of 0.1 to 0.6 mm. When the glass fiber content is 30% by volume or less, the strength is low because the amount of fibers is small, and 85% by volume.
The above is not preferable because the amount of resin with respect to the fiber is small and the adhesion between the fiber and the resin is reduced, resulting in low strength.

Examples of the foamed resin used in the present invention include polyethylene foam, polypropylene foam, polystyrene foam or polystyrene foam having polypropylene foam as an outer layer. From the viewpoint of processing industrial waste, a composite structure in which the resin used for the resin foam and the resin used for the prepreg are both made of a thermoplastic resin is preferable, and a composite structure made of the same thermoplastic resin is preferable. Structures are more preferred. The foam may be either closed cells or open cells. The strength is improved by using closed cells. A foaming ratio of 100 or less is used, and the ratio is selected from the balance of weight reduction and moldability, and is preferably 2 to 50 times. Further, the foam may be a crosslinked body or a non-crosslinked body.

Examples of the surface material used in the present invention include foamed or non-foamed sheets such as polypropylene and polystyrene, sheets such as polyvinyl chloride, and woven and non-woven fabrics made of various fibers. By applying such a surface material, it is possible to improve the appearance of the surface, improve the touch, improve the stain resistance, improve the peelability from other materials, and improve the ultraviolet resistance.

As a method of integrating the prepreg and the foam by heat welding, the laminated prepreg is heated to a melting temperature or higher and the resin foam is heated to a temperature lower than the melting temperature at the same time, and then the prepreg and the foam are superposed on each other, and then 60 to 60 In a press heated to 80 ° C., pressure is applied at a pressure of 3 kg / cm ² or less, cooling is performed, and integration is performed to form a laminated body. At this time, it is necessary to deaerate the air existing between the prepreg layers of the prepreg laminate. Usually, the prepreg is heated by heating it to a temperature higher than the melting point of the resin constituting the prepreg and pressurizing it with a pressure of 3 kg / cm ² or less. . If the pressure is within this range, the resin foam will not be crushed, so this degassing can be performed in the step of integrating with the foam. As a matter of course, there is no problem in using a laminated plate that is deaerated in advance and cooled. The prepreg and the foam can be heated without contacting the prepreg and the foam with each other, or can be heated with the prepreg placed on the foam and in contact with each other. When the expansion ratio of the foam is high, the foam is easily melted by heat, so the surface of the foam can be easily melted and integrated by the heat accumulated in the molten prepreg, so the heating conditions without contacting the prepreg and the foam It is desirable to change and heat separately. On the other hand, when the expansion ratio is low, the heat is difficult to conduct to the foam, so the surface of the foam cannot be melted by the heat accumulated by the molten prepreg.Therefore, the prepreg and the foam are brought into contact and heated at the same time to foam. It is desirable to take a method of heating while melting the body surface.

Since the prepreg and the foam must be integrated with each other while the prepreg is in a molten state, it is necessary to devise a device so that the step of heating and the step of integrating may be completed in a short time. Is. As an example of such a device, in a press that integrates prepreg and foam, a device that clamps and supports the prepreg and foam that can move in and out of the press, and the prepreg and foam that can move in and out of the press are heated. There is a facility equipped with a hot plate to operate. The procedure for forming a laminate using this equipment is:
After pulling the clamp out of the press platen and mounting the prepreg and foam, put the clamp device in the press platen surface, then put the hot plate in the press platen surface to heat the prepreg and foam, and after heating is completed, press it out of the press platen surface. The hot plate is drawn out, and the press is tightened to bring the prepreg and the foam into contact with each other to melt and integrate them. At this time, it is necessary for the clamp to have a mechanism for sequentially releasing the material while touching the surface of the press platen and retracting the material to the outside of the press platen surface. The integration of the surface material and the prepreg can be performed while the prepreg is in a molten state, like the integration of the foam and the prepreg.

Embodiments of the present invention will be described in detail below with reference to the drawings. FIG. 1 is an external view of a laminate obtained by the manufacturing method according to the present invention. FIG. 2 is a conceptual diagram showing a state in which a prepreg and a foam are installed in the apparatus for manufacturing the laminated body shown in FIG. 1, and FIG. 3 is a system in which the heat source is retracted from the apparatus shown in FIG. FIG. 4 is a schematic view showing a first step of integrating the prepreg and the foam holding the prepreg and the supporting member out of the state shown in FIG. 3, and the prepreg and the foam are cooled and integrated by pressing. It is a conceptual diagram of a state. 5 and 6 are conceptual diagrams showing another embodiment of the present invention. FIG. 7 is an external arrow view showing a laminate in which a surface material is attached to one surface, and FIG. 8 is a prepreg, a foam and a surface material attached to the inside of the apparatus to form a laminate in which the surface material is attached to one surface. The conceptual diagram which shows the state currently being shown is shown. Reference numeral 1 shown in FIG. 1 denotes a laminate obtained by the present invention. 2, 3, 4, 5, and 6 represent prepreg laminates, and 2
6 to 6 may have the same laminated constitution and plate thickness, or may be changed depending on the intended use. Reference numerals 10, 11, 12, 13, and 14 denote resin foams. The foams 10 to 14 may have the same foaming ratio and thickness, but the foaming ratio and the plate thickness may be changed depending on the intended use.

In the laminated body 1, air existing between the layers of the prepreg laminated body is eliminated in the heating step at the time of molding,
Moreover, the prepreg laminate is provided with a sufficient amount of heat to melt the surface of the foam, and the prepreg laminate and the foam are firmly bonded. Foam 10 close to the surface of the laminate
It is desirable for the expansion ratio of 14 to be smaller than the foams 11, 12, and 13 of the central layer in order to improve the load bearing performance because the foams do not collapse when a load is applied. Reducing the expansion ratio of all foams is not preferable because the weight of the laminate increases. As described above, decreasing the foaming ratio as it gets closer to the surface layer is a point for improving load bearing performance and preventing an increase in weight.

FIG. 2 shows a schematic view of the molding apparatus for the laminated body. The release film 4 mounted on the upper and lower surfaces of the press.
Between 0, the clamp 20 supporting the prepreg laminate and the foam has a mechanism for adjusting the interval and the tension at which the heated prepreg and the foam do not hang down and contact each other. A mechanism is provided for retracting in the directions 33 and 34 outside the board when touched.
A hot plate 30 is provided with a mechanism that can be inserted into the press platen surface and retracted in a direction 35 outside the press platen surface. The hot plate heats the prepreg and the foam, but it is necessary to raise the temperature of the resin of the prepreg to melt in a short time and to raise the foam to a temperature near the melting temperature. For that purpose, a mechanism for adjusting the distance from the prepreg. And a temperature control mechanism must be provided.

When the prepreg and the foam are heated at the same time, in the case of a foam having a high expansion ratio, the resin of the foam will be melted first, so the foam is inserted after the prepreg is in a molten state, and the prepreg and the foam are foamed. It is desirable to change the heating time of the body. After the prepreg and the foam are heated to a predetermined temperature, as shown in FIG. 3, the hot plate is evacuated to the outside of the press platen, the press is activated, and the prepreg laminate and the foam are generated in response to the lowering of the upper plate surface. At the same time as the body disengages from the clamp and retreats from the surface of the press board, the prepreg laminate and the foam come into contact with each other, the surface of the foam is melted by the heat accumulated in the prepreg, and the prepreg and the foam are melted and integrated. As shown in, a laminate containing the foam is obtained by cooling and solidifying in a press.

FIG. 5 shows another method for producing a laminate, in the case where the foam 10 near the surface layer has a low expansion ratio of 7 times or less and the center layer has a high expansion ratio of 15 times. Since the foams having different expansion ratios and the prepreg laminates are not simultaneously heated to a predetermined temperature in the same heating time, the foams 10 and 14 having a low expansion ratio and the prepreg laminates 1 and 2 and 5 and 6 are not heated. It shows a method of stacking and clamping in advance and then directly contacting the heating plate for heating. (However, the clamp is omitted in FIG. 5.) FIG. 6 shows another method of manufacturing a laminated body, in which the foaming ratio of the foamed body 10 close to one of the surface layers is as low as 7 times or less. , When the expansion ratio of other layers is as high as 15 times,
Since the foams having different expansion ratios and the prepreg laminate are not simultaneously heated to a predetermined temperature in the same heating time, the foam 10 having a low expansion ratio and the prepreg laminates 1 and 2 are preliminarily overlapped and clamped. It shows a method of heating by directly contacting a hot plate. (However, the clamp is omitted in FIG. 6.) Further, the present invention will be described in detail with reference to specific examples.

[0023]

EXAMPLE The prepreg used in this example has a width of 200
mm was manufactured by the method disclosed in Japanese Patent Publication No. 02-042168. Thickness 13 for glass fiber
The surface of the monofilament of μ was treated with γ-methacryloxy-propyltrimethoxysilane, 1800 filaments were bundled into a twist-free yarn, and the yarn was aligned in one direction while pulling 80 yarns with a uniform tension. Entangling the resin in the yarn and squeezing the resin with a hot roll,
The yarn was impregnated to produce a prepreg. In the case of carbon fibers, without using a sizing agent, 12,000 monofilaments with a thickness of 7μ are gathered in one direction while pulling 80 tows with a uniform tension, and the resin is entangled with the yarn. Was squeezed with a hot roll to impregnate the yarn to produce a prepreg. The prepreg manufactured in this manner has excellent adhesion between the fiber and the thermoplastic resin, and the fiber content can be changed according to the requirement of 30 to 90% by weight, and the thickness is 0.1 to 1.0 mm. However, the glass content is 30-85% by volume and the thickness is 0.
It is desirable to use it at a distance of 1 to 0.6 mm. When the volume content of the fiber is 30% by volume or less, the strength is low because the amount of the fiber is small, and when the volume content of the fiber is 85% by volume or more, the amount of the resin is small with respect to the fiber and the adhesion between the fiber and the resin is reduced, which is not preferable. .

The prepreg of unsaturated polyester and glass fiber is a resin liquid prepared by adding 1 part by weight of t-butylperoxybenzoate and 5 parts by weight of magnesium oxide to 100 parts by weight of unsaturated polyester ester ML1805 manufactured by Mitsui Toatsu Chemicals, Inc. Was impregnated into glass fibers aligned in one direction by a conventional method using a sheet molding compound manufacturing machine, and aged at 40 ° C. for 24 hours to manufacture.

Table 1 shows the constitution of prepregs manufactured for use in the examples of the present invention and the comparative examples. Table 2 shows the properties of the resin foam used in the present invention.

Example 1 When the fiber direction of the prepreg A was set to 0 degree, four sheets of 0 degree, 90 degree, 90 degree, and 0 degree were laminated from the top 50.
6 sets of 0 mm square laminates and 500 mm square resin foam P
Prepared 5 sheets. The laminated body was clamped to 1 to 6 and the resin foam was clamped to 10 to 14 of the device shown in FIG.
The resin foam is clamped and retracted to the outside of the press board, the hot plate 30 heated to 200 ° C. is introduced into the press board, the prepreg laminate is heated for 2 minutes, and then the resin foam is introduced into the press board. After a few seconds, the hot plate 30 was retracted to the outside of the press platen and 0.3 kg / c of the prepreg and the foam between the press upper platen surface 31 and the press lower platen surface 32 heated to 60 ° C.
A laminate was obtained by cooling while heating at a pressure of m2. The thickness and weight of this laminate were measured, and the surface condition and appearance of the laminate were observed. The weight of the laminate was divided by (thickness × 50 × 50) to calculate the density of the laminate. Further, this laminated body was cut into strip-shaped test pieces having a length of 150 mm and a width of 50 mm,
A three-point bending test was performed at a loading speed of 50 mm / min to determine bending strength and bending elastic modulus. The ratio of support span to plate thickness was 16: 1. In addition, this laminated body has a length of 300 mm,
Cut into 50 mm wide strip-shaped test pieces, loading speed 50 m
A three-point bending test was performed at m / min to observe the fractured state, and the bending strength and bending elastic modulus were obtained. FIG. 9 shows a state where the bending test is being performed. The bending strength and the bending elastic modulus were divided by the density, and the specific bending strength and the specific bending elastic modulus were calculated.
The above results are shown in Table 3.

Example 2 When the fiber direction of the prepreg A was set at 0 degree, four sheets of 0 degree, 90 degree, 90 degree and 0 degree were laminated from the top 50.
6 sets of 0 mm square laminates and 500 mm square resin foam Q
Were prepared, and three foams P were prepared. In the apparatus shown in FIG. 5, 1 to 6 are laminated bodies, and 10 and 14 are resin foam Q, respectively.
The resin foam P was clamped and attached to 1, 12, and 13.
The resin foam P is retracted outside the press board in a clamped state, the hot plate 30 heated to 200 ° C. is introduced into the press board surface, the prepreg laminate is heated for 2 minutes, and then the resin foam P is introduced into the press board surface. Then, after 5 seconds, the hot plate 30 is retracted to the outside of the press platen surface, and 0.3 kg of the prepreg and the foam are pressed between the press upper platen surface 31 and the press lower platen surface 32 heated to 60 ° C.
A laminate was obtained by cooling while heating at a pressure of / cm ² . In the same manner as in Example 1, the thickness, weight, surface state and appearance were observed, and the bending properties were evaluated. The results are shown in Table 3.

Example 3 When prepreg A has a fiber direction of 0 degree, four sheets of 0 degree, 90 degree, 90 degree and 0 degree are laminated from the top 50.
6 sets of 0 mm square laminates and 500 mm square resin foam Q
1 and 4 foams P were prepared. In the apparatus shown in FIG. 6, 1 to 6 are laminated bodies, 10 is a resin foam Q, and 11 and 1 are the laminated bodies.
The resin foam P was clamped and attached to Nos. 2, 13 and 14.
The resin foam P is retracted outside the press board in a clamped state, the hot plate 30 heated to 200 ° C. is introduced into the press board surface, the prepreg laminate is heated for 2 minutes, and then the resin foam P is introduced into the press board surface. Then, after 5 seconds, the hot plate 30 is retracted to the outside of the press platen surface, and 0.3 kg of the prepreg and the foam are pressed between the press upper platen surface 31 and the press lower platen surface 32 heated to 60 ° C.
A laminate was obtained by cooling while heating at a pressure of / cm ² . In the same manner as in Example 1, the thickness, weight, surface state and appearance were observed, and the bending properties were evaluated. The results are shown in Table 3.

Example 4 When the fiber direction of prepreg A was set to 0 degree,
4 layers of 0 degree, 90 degree, 90 degree, 0 degree
6 sets of 0 mm square laminates and 500 mm square resin foam P
Was prepared, two foams R, two foams N, and one foam N were prepared. Figure
Laminates 1 to 6 of the equipment shown in 5 and trees 10 and 14
Resin foam P is used for 11 and 13 and resin foam P is used for 12
The fat foam N was clamped and attached. Resin foam R and N
Retract out of the press board in the clamped state, 200 ℃
The hot plate 30 heated to the inside is introduced into the surface of the press board and pre-treated for 2 minutes.
After heating the prepreg laminate, the resin foams P and N are pressed onto the press surface.
5 seconds after introducing the heat plate, retract the hot plate 30 to the outside of the press platen.
Press upper platen surface 31 and press lower platen surface heated to 60 ° C
0.3kg / cm of prepreg and foam between 32 ²of
A laminate was obtained by cooling while heating with pressure. Same as Example 1
Similarly, observe the thickness, weight, surface condition and appearance, and
The physical properties were evaluated. The results are shown in Table 3.

Example 5 When prepreg A has a fiber direction of 0 °, four sheets of 0 °, 90 °, 90 °, and 0 ° are laminated from the top 50.
6 sets of 0mm square laminates and 500mm square resin foam S
Were prepared, and three foams P were prepared. In the apparatus shown in FIG. 5, 1 to 6 are laminated bodies, and 10 and 14 are resin foam S.
The resin foam P was clamped and attached to 1, 12, and 13.
The resin foam P is retracted outside the press board in a clamped state, the hot plate 30 heated to 200 ° C. is introduced into the press board surface, the prepreg laminate is heated for 2 minutes, and then the resin foam P is introduced into the press board surface. Then, after 5 seconds, the hot plate 30 is retracted to the outside of the press platen surface, and 0.3 kg of the prepreg and the foam are pressed between the press upper platen surface 31 and the press lower platen surface 32 heated to 60 ° C.
A laminate was obtained by cooling while heating at a pressure of / cm ² . In the same manner as in Example 1, the thickness, weight, surface state and appearance were observed, and the bending properties were evaluated. The results are shown in Table 3.

Example 6 A laminate was obtained in the same manner as in Example 5 except that prepreg C was used instead of prepreg A. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 7 Lamination was performed in the same manner as in Example 5 except that prepreg B was used instead of prepreg A, resin foam U was used instead of resin foam S, and resin foam T was used instead of resin foam P. Got the body This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 8 Lamination was performed in the same manner as in Example 5 except that prepreg D was used instead of prepreg A, resin foam U was used instead of resin foam S, and resin foam T was used instead of resin foam P. Got the body This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 9 Lamination was performed in the same manner as in Example 5 except that prepreg E was used instead of prepreg A, resin foam W was used instead of resin foam S, and resin foam V was used instead of resin foam P. Got the body This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 10 In the same manner as in Example 1, when the fiber direction of the prepreg A was set to 0 degree, four pieces of a 500 mm square, which were 0 degree, 90 degree, 90 degree and 0 degree from the top, were superposed. 6 sets and 50 stacks
Five pieces of 0 mm square resin foam P were prepared. The laminated body was clamped to 1 to 6 and the resin foam was clamped to 10 to 14 of the device shown in FIG. Furthermore, vinyl chloride laser 39 lined with a 2 mm thick polyurethane foam sheet
Was placed on the release film 40 with the surface of the vinyl chloride laser being in contact with the release film. With the resin foam clamped, retract it to the outside of the press board,
The hot plate 30 heated to 0 ° C. is introduced into the press platen surface, the prepreg laminate is heated for 2 minutes, the resin foam is introduced into the press platen surface, and 5 seconds later, the hot plate 30 is evacuated to the outside of the press platen 60 ° C. Pressed upper surface 31 and pressed lower surface 3
Between the two, the prepreg and the foam were cooled while being heated at a pressure of 0.3 kg / cm ² to obtain a laminate. A laminate having a good appearance and a good feel of vinyl chloride leather was obtained.

Comparative Example 1 When the fiber direction of the prepreg F is 0 degree, 0 degree, 90 degree, 0 degree, 90 degree, 0 degree, 90 degree, 90 degrees from the top.
Two sets of 500 mm square laminates were stacked by stacking 12 sheets of 0 °, 90 °, 0 °, 90 °, and 0 °, and one resin foam X of 500 mm square was prepared. This laminated body and the foam are superposed in the order of laminated body / foamed body / laminated body from the top, and the temperature is 150 ° C.
Put into a press equipped with a heating plate heated to 0.3 kg
After being heated at a pressure of / cm ² for 10 minutes, it was taken out to obtain a laminated body. Since the prepreg F was treated at a high temperature of 150 ° C. to cure it, the foam partly broke under pressure, and the surface condition of the cured prepreg was poor due to insufficient molding pressure. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Comparative Example 2 When the fiber direction of the prepreg A is 0 degree, 0 degree, 90 degree, 0 degree, 90 degree, 0 degree, 90 degree, 90 degrees from the top.
Two sets of 500 mm square laminates, which were a stack of 12 sheets of 0 °, 90 °, 0 °, 90 °, and 0 °, and one resin foam O of 500 mm square were prepared. 1 and 2 of the device shown in FIG.
The laminated body was attached to, and the resin foam was clamped and attached to 10.
(In the case of this example, the laminated bodies 3 to 6 and the foaming bodies 11 to 14 are not attached.) The resin foam O is retracted to the outside of the press board in a clamped state, and the hot plate 30 heated to 200 ° C. is pressed to the press board surface. After heating the prepreg laminate for 2 minutes and introducing it into the resin foam O press board surface, the hot plate 30 is evacuated to the outside of the press board surface 5 seconds later, and the press upper board surface 31 and the press bottom surface heated to 60 ° C. The prepreg and the foam were cooled while being heated at a pressure of 0.3 kg / cm ² between the board surfaces 32 to obtain a laminate. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Comparative Example 3 A laminate was obtained in the same manner as in Example 5 except that prepreg G was used instead of prepreg A. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Comparative Example 4 A laminate was obtained in the same manner as in Example 5 except that prepreg H was used instead of prepreg A. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0040]

[Table 1]

[0041]

[Table 2]

[0042]

[Table 3]

[0043]

According to the method of the present invention, a lightweight and highly rigid laminate in which a resin foam and a thermoplastic resin prepreg are firmly integrated can be manufactured.

[Brief description of drawings]

FIG. 1 is an external view of a laminate obtained by a manufacturing method according to the present invention.

FIG. 2 is a conceptual diagram showing a state in which a prepreg and a foam are installed in an apparatus for producing a laminate of the present invention.

FIG. 3 is a schematic diagram showing a first stage in which the heat source is retracted from the apparatus shown in FIG. 2 to integrate the prepreg and the foam.

FIG. 4 is a conceptual diagram of a state in which the support holding the prepreg and the foam is removed from the state shown in FIG. 3 and the prepreg and the foam are cooled and integrated by a press.

FIG. 5 is a conceptual diagram showing a state at the time of molding a laminate in which the foaming ratio of the foam near the front surface layer and the back surface layer is lower than the foaming ratio of the foam in the central layer.

FIG. 6 is a conceptual diagram showing a state at the time of molding a laminate in which the foaming ratio of the foam near the surface layer is lower than the foaming ratio of the foam in the central layer.

FIG. 7 is an external arrow view showing a laminated body in which a surface material is attached to one surface.

FIG. 8 is a conceptual diagram showing a state in which a prepreg, a foam, and a surface material are mounted in an apparatus to form a laminate in which a surface material is attached to one surface.

FIG. 9 shows a state in which bending strength of the laminate is being performed.

[Explanation of symbols]

 1 ... Laminated body 2 ... Prepreg laminated body 3 ... Prepreg laminated body 4 ... Prepreg laminated body 5 ... Prepreg laminated body 6 ... Prepreg laminate 10 ... Resin foam 11 ... Resin foam 12 ... Resin foam 13 ... Resin foam 14 ... Resin foam 20.・ ・ ・ ・ Clamp 30 ・ ・ ・ Hot plate 31 ・ ・ ・ Press upper plate surface 32 ・ ・ ・ Press lower plate surface 33 ・ ・ ・ Right side clamp retracting direction 34 ・ ・ ・ Left side clamp Retracting direction 35 ... Retracting direction of hot plate 39 ... Surface material 40 ... Release film

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] February 16, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be amended] Detailed explanation of the invention

[Correction method] Change

[Correction content]

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention comprises a laminate of one or more prepregs impregnated with a thermoplastic resin and a resin foam, which are formed by aligning continuous reinforcing fibers in one direction and melt-integrating them. The present invention relates to a molded product and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, it has been known that a fiber reinforced resin plate is attached to the upper and lower surfaces of a resin foam to make a plate that is lightweight and has high surface rigidity. It is manufactured by integrating a fiber reinforced plate having a thermosetting resin such as an unsaturated polyester resin as a matrix with a hard urethane foam obtained by foaming a thermosetting polyurethane resin. As a method of integrating, while the matrix resin of the fiber reinforced plate is in a liquid state before being cured, it is superposed on the resin foam, and is pressed by a press machine or the like to remove the liquid matrix resin from the surface of the resin foam. When the resin that has penetrated into the foam is solidified when it is allowed to penetrate and harden, and when it is physically joined while it penetrates into the foam, or when the fiber reinforced plate is preformed and the adhesive is used to join with the foam. There are cases. As another method, a plate in which a fiber-reinforced thermoplastic resin plate is laminated on the upper and lower surfaces of a foam made of a thermoplastic resin is also known.

[0003]

However, although the plate manufactured by the above method has high surface rigidity as described above,
When a local bending load or impact load is applied, the fiber-reinforced resin plates on the upper and lower surfaces are not destroyed, but only the foam directly under the load is partially collapsed and the function as a plate is lost. It is a frequent problem. On the other hand, it has been pointed out that the joint surface between the fiber-reinforced resin plate and the foam is easily peeled off when it is subjected to a large deformation due to the load on the entire surface, and the reliability is poor for use as a structural member. Further, in the above-mentioned manufacturing method, it is pointed out that the bad odor and the scattering of the reinforcing fibers when handling the thermosetting resin deteriorates the working environment and causes a hygiene problem.

Further, since the fiber-reinforced resin plate is molded and joined to the resin foam, there is a problem that process control such as curing, application of adhesive, pressure bonding and curing is required, resulting in high processing cost. Also, in the case of a fiber-reinforced thermoplastic resin plate that is laminated on the upper and lower surfaces of a foam made of a thermoplastic resin, there is no suitable adhesive, and the thickness of the foam does not change even when joining by heat fusion. There are problems that it is difficult to work while holding them uniformly, and there are many variations in performance. Therefore, an object of the present invention is to use a foam made of a thermoplastic resin and a fiber reinforced plate having a thermoplastic resin as a matrix, and to firmly bond the fiber reinforced plate and the foam without using an adhesive. Another object of the present invention is to provide a laminate having a high surface rigidity and a foam that does not change its thickness, and a method for producing the same at low cost in a hygienic work environment.

[0005]

The present inventors have completed the present invention as a result of intensive studies to achieve the above object. That is, the laminate according to the present invention is a molded product obtained by laminating one or more prepregs impregnated with a thermoplastic resin and resin foams by aligning continuous reinforcing fibers in one direction and laminating the resin foams and prepregs. It is characterized in that two or more layers of the laminated combination are overlapped and the layers are thermally bonded. It is recommended that the prepreg contains 30% or more and 85% or less by volume content of reinforcing fibers, and that the reinforcing fibers are unidirectionally continuous filaments. Further, the reinforcing fiber is a glass fiber, the thermoplastic resin and the foam is a polypropylene-based resin or polystyrene-based resin, further the expansion ratio of the foam present near the surface of the load is the center, The present invention can be preferably applied to the case where the expansion ratio of the foam close to the layer is lower.

Further, in the production method according to the present invention for producing the above-mentioned laminated molded article, one or more prepregs in which continuous reinforcing fibers are aligned in one direction and impregnated with the thermoplastic resin are used. Heating to above the melting temperature to degas the air contained in the layers; heating the prepreg above the melting temperature, heating the resin foam below the melting temperature, simultaneously without contacting each other; A step of heat-bonding the prepreg and the resin foam overlaid on each other and applying pressure; cooling the heat-bonded laminate;
It is characterized in that the steps of solidifying and integrating are sequentially executed. The above-mentioned production method can be suitably applied when the reinforcing fiber contains 30% or more and 85% or less by volume content of the reinforcing fiber and is composed of continuous fibers in one direction, and particularly, the reinforcing fiber. Is a glass fiber, the thermoplastic resin and the foam is a polypropylene-based resin or polystyrene-based resin, further the foaming ratio of the foam existing near the surface of the load is closer to the center layer The present invention can be suitably applied to the case where the expansion ratio is lower than the above.

The thermoplastic resin used in the prepreg obtained by impregnating the unidirectionally arranged fibers with the thermoplastic resin used in the present invention is, for example, polystyrene, polypropylene, polyethylene, AS resin, ABS resin, ASA.
Resin (polyacrylonitrile / polystyrene / acrylic acid ester), polymethylmethacrylate, nylon, polyacetal, polycarbonate, polyethylene terephthalate, polyphenylene oxide, fluororesin, polyphenylene sulfide, polysulfone, polyethersulfone, polyetherketone, polyetherether Examples include ketones, polyimides, polyarylates and the like.

Typical fibers used in a prepreg in which fibers arranged in one direction are impregnated with a thermoplastic resin are, for example, glass fibers, carbon fibers, aramid fibers and silicon carbide fibers. A prepreg obtained by impregnating fibers arranged in one direction with a thermoplastic resin usually has a thickness of 3
A yarn obtained by bundling 200 to 12000 monofilaments of -25 μm or a roving in which a predetermined number of rovings are arranged in one direction is impregnated with a thermoplastic resin.

Glass fiber is usually subjected to various surface treatments,
The adhesion with the resin is improved. The surface treatment is performed by combining a sizing agent and a coupling agent. A sizing agent is usually used to focus the monofilaments. The sizing agent needs to be selected depending on the thermoplastic resin to be combined. Generally, a resin that is softened at the melting temperature of the resins to be combined and easily impregnated with the thermoplastic resin in the fiber bundle is selected. Therefore, a sizing agent whose main component is a resin of the same kind as the thermoplastic resin to be combined is often used. The glass fiber used as the fiber of the prepreg is one that is treated with a silane-based, titanate-based, or zirconium-based coupling agent to improve the adhesion to the resin.

In the case of glass fiber, it is necessary to select the most suitable coupling agent according to the resin to be combined, and specific examples thereof will be given below. For nylon resin, γ-
Aminopropyl-trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-trimethoxysilane and the like are used. If it is a polycarbonate resin, γ-aminopropyl-trimethoxysilane, N-β- (aminoethyl) -γ-aminopropyl-trimethoxysilane and the like are used. If polyethylene terephthalate or polybutylene terephthalate, then β- (3,4-epoxycyclohexyl) ethyl-trimethoxysilane,
γ-glycidoxy-propyltrimethoxysilane, γ-
Aminopropyl-trimethoxysilane or the like is used. If polyethylene or polypropylene is used, vinyltrimethoxysilane, vinyl-tris- (2-methoxyethoxy) silane, γ-methacryloxy-propyltrimethoxysilane, or the like is used. Polyphenylene oxide,
As long as it is polyphenylene sulfide, polysulfone, polyether sulfone, polyether ketone, polyether ether ketone, polyimide, polyarylate, or a fluororesin, the above-mentioned coupling agent can be used, but N- (β -Aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropyltrimethoxysilane, p-aminophenyltriethoxysilane and the like can be used.

When a fiber other than glass fiber is used as the reinforcing fiber, an amine-curing type epoxy resin is often treated as a coupling agent, and specific examples thereof include bisphenol-A-epichlorohydrin resin, epoxy novolac resin and alicyclic compounds. Epoxy resins, aliphatic epoxy resins, and glycidyl ester type resins may be used, but since thermoplastic resins generally have high melting temperatures, ordinary coupling agents undergo thermal decomposition, so no coupling agents are used. It may not be used.

The method of applying the coupling agent to the fiber surface is as follows. That is, as one method, when the fiber is melted and the monofilament is pulled out, a sizing agent and a coupling agent are added to the surfactant to prepare an aqueous solution.
After spraying on the monofilament, it is dried and treated at a temperature of about 100 ° C. As another method, 0.1 to 3% by weight of a sizing agent and a coupling agent is added to the fiber from which the sizing agent is removed.
The dissolved liquid is completely impregnated by means such as dipping and spray coating. 60 fibers containing this coupling agent solution
Dry at ~ 120 ° C to allow coupling agent to react with fiber surface. The drying time is sufficient to evaporate the solvent, which is about 15 to 20 minutes. The solvent for dissolving the coupling agent has a pH of 2.0 to 1 depending on the surface treatment agent used.
There are cases where water adjusted to 2.0 is used, and cases where organic solvents such as ethanol, tolueneacetone and xylene are used alone or as a mixture. There are various methods for impregnating the reinforcing fibers unidirectionally aligned with the thermoplastic resin to form the prepreg, but the most general method is as follows. First, if the resin is soluble in the solvent,
This is a method in which the resin is made into a solution and impregnated into reinforcing fibers, and then the solvent is removed while defoaming to obtain a prepreg.

The other is a method of heating and melting a resin to impregnate a reinforcing fiber, defoaming, and cooling to obtain a prepreg. As a method of manufacturing a prepreg, for example, Japanese Patent Publication No. 02-
The method disclosed in Japanese Patent No. 042168 can be mentioned. By this method, for glass fiber, for example, thickness 1
The surface of a 3μ monofilament is γ-methacryloxy-
Treated with propyltrimethoxysilane and treated with 1800
This bundle is made into a twist-free yarn, 80 yarns are aligned in one direction while pulling with a uniform tension, the resin is entangled with the yarn, and the resin is squeezed with a hot roll,
The yarn can be impregnated to produce a prepreg. The prepreg manufactured in this manner has excellent adhesion between the fiber and the thermoplastic resin and has a fiber content of 30-90% by weight.
And it can be changed according to the requirements, and the thickness is 0.1-1.
It can be manufactured with 0 mm, but the glass content is 30
It is desirable to use it in a range of 85% by volume and a thickness of 0.1 to 0.6 mm. When the glass fiber content is 30% by volume or less, the strength is low because the amount of fibers is small, and 85% by volume.
The above is not preferable because the amount of resin with respect to the fiber is small and the adhesion between the fiber and the resin is reduced, resulting in low strength.

Examples of the foamed resin used in the present invention include polyethylene foam, polypropylene foam, polystyrene foam or polystyrene foam having polypropylene foam as an outer layer. From the viewpoint of processing industrial waste, a composite structure in which the resin used for the resin foam and the resin used for the prepreg are both made of a thermoplastic resin is preferable, and a composite structure made of the same thermoplastic resin is preferable. Structures are more preferred. The foam may be either closed cells or open cells. The strength is improved by using closed cells. A foaming ratio of 100 or less is used, and the ratio is selected from the balance of weight reduction and moldability, and is preferably 2 to 50 times. Further, the foam may be a crosslinked body or a non-crosslinked body.

Examples of the surface material used in the present invention include foamed or non-foamed sheets such as polypropylene and polystyrene, sheets such as polyvinyl chloride, and woven and non-woven fabrics made of various fibers. By applying such a surface material, it is possible to improve the appearance of the surface, improve the touch, improve the stain resistance, improve the peelability from other materials, and improve the ultraviolet resistance.

As a method of integrating the prepreg and the foam by heat welding, the laminated prepreg is heated to a melting temperature or higher and the resin foam is heated to a temperature lower than the melting temperature at the same time, and then the prepreg and the foam are superposed on each other, and then 60 to 60 In a press heated to 80 ° C., pressure is applied at a pressure of 3 kg / cm ² or less, cooling is performed, and integration is performed to form a laminated body. At this time, it is necessary to deaerate the air existing between the prepreg layers of the prepreg laminate. Usually, the prepreg is heated by heating it to a temperature higher than the melting point of the resin constituting the prepreg and pressurizing it with a pressure of 3 kg / cm ² or less. . If the pressure is within this range, the resin foam will not be crushed, so this degassing can be performed in the step of integrating with the foam. As a matter of course, there is no problem in using a laminated plate that is deaerated in advance and cooled. The prepreg and the foam can be heated without contacting the prepreg and the foam with each other, or can be heated with the prepreg placed on the foam and in contact with each other. When the expansion ratio of the foam is high, the foam is easily melted by heat, so the surface of the foam can be easily melted and integrated by the heat accumulated in the molten prepreg, so the heating conditions without contacting the prepreg and the foam It is desirable to change and heat separately. On the other hand, when the expansion ratio is low, the heat is difficult to conduct to the foam, so the surface of the foam cannot be melted by the heat accumulated by the molten prepreg.Therefore, the prepreg and the foam are brought into contact and heated at the same time to foam. It is desirable to take a method of heating while melting the body surface.

Since the prepreg and the foam must be integrated with each other while the prepreg is in a molten state, it is necessary to devise a device so that the step of heating and the step of integrating may be completed in a short time. Is. As an example of such a device, in a press that integrates prepreg and foam, a device that clamps and supports the prepreg and foam that can move in and out of the press, and the prepreg and foam that can move in and out of the press are heated. There is a facility equipped with a hot plate to operate. The procedure for forming a laminate using this equipment is:
After pulling the clamp out of the press platen and mounting the prepreg and foam, put the clamp device in the press platen surface, then put the hot plate in the press platen surface to heat the prepreg and foam, and after heating is completed, press it out of the press platen surface. The hot plate is drawn out, and the press is tightened to bring the prepreg and the foam into contact with each other to melt and integrate them. At this time, it is necessary for the clamp to have a mechanism for sequentially releasing the material while touching the surface of the press platen and retracting the material to the outside of the press platen surface. The integration of the surface material and the prepreg can be performed while the prepreg is in a molten state, like the integration of the foam and the prepreg.

Embodiments of the present invention will be described in detail below with reference to the drawings. FIG. 1 is an external view of a laminate obtained by the manufacturing method according to the present invention. FIG. 2 is a conceptual diagram showing a state in which a prepreg and a foam are installed in the apparatus for manufacturing the laminated body shown in FIG. 1, and FIG. 3 is a system in which the heat source is retracted from the apparatus shown in FIG. FIG. 4 is a schematic view showing a first step of integrating the prepreg and the foam holding the prepreg and the supporting member out of the state shown in FIG. 3, and the prepreg and the foam are cooled and integrated by pressing. It is a conceptual diagram of a state. 5 and 6 are conceptual diagrams showing another embodiment of the present invention. FIG. 7 is an external arrow view showing a laminate in which a surface material is attached to one surface, and FIG. 8 is a prepreg, a foam and a surface material attached to the inside of the apparatus to form a laminate in which the surface material is attached to one surface. The conceptual diagram which shows the state currently being shown is shown. FIG. 10 is a conceptual diagram showing a method for producing a laminated body in the case where the press hot plate is equipped with a heating and cooling mechanism and is a cooling press. Reference numeral 1 shown in FIG. 1 denotes a laminate obtained by the present invention. Reference numerals 2, 3, 4, 5, and 6 represent prepreg laminated bodies, and 2 to 6 may have the same laminated constitution and plate thickness, or the laminated constitution and plate thickness may be changed depending on the intended use. You can change it. 10, 11, 12, 13, 1
Reference numeral 4 represents a resin foam. The foams 10 to 14 may have the same foaming ratio and thickness, but the foaming ratio and the plate thickness may be changed depending on the intended use.

In the laminated body 1, air existing between the layers of the prepreg laminated body is eliminated in the heating step at the time of molding,
Moreover, the prepreg laminate is provided with a sufficient amount of heat to melt the surface of the foam, and the prepreg laminate and the foam are firmly bonded. Foam 1 close to the surface of the laminate
The expansion ratios of 0 and 14 are the same as those of the central layer foams 11, 12, and 1.
A value less than 3 is desirable from the viewpoint of improving load bearing performance because the foam does not collapse when a load is applied. Reducing the expansion ratio of all foams is not preferable because the weight of the laminate increases. As described above, decreasing the foaming ratio as it gets closer to the surface layer is a point for improving load bearing performance and preventing an increase in weight.

FIG. 2 shows a schematic view of the molding apparatus for the laminated body. The release film 4 mounted on the upper and lower surfaces of the press.
Between 0, the clamp 20 supporting the prepreg laminate and the foam has a mechanism for adjusting the interval and the tension at which the heated prepreg and the foam do not hang down and contact each other. A mechanism is provided for retracting in the directions 33 and 34 outside the board when touched.
A hot plate 30 is provided with a mechanism that can be inserted into the press platen surface and retracted in a direction 35 outside the press platen surface. The hot plate heats the prepreg and the foam, but it is necessary to raise the temperature of the resin of the prepreg to melt in a short time and to raise the foam to a temperature near the melting temperature. For that purpose, a mechanism for adjusting the distance from the prepreg. And a temperature control mechanism must be provided.

When the prepreg and the foam are heated at the same time, in the case of a foam having a high expansion ratio, the resin of the foam will be melted first, so the foam is inserted after the prepreg is in a molten state, and the prepreg and the foam are foamed. It is desirable to change the heating time of the body. After the prepreg and the foam are heated to a predetermined temperature, as shown in FIG. 3, the hot plate is evacuated to the outside of the press platen, the press is activated, and the prepreg laminate and the foam are generated in response to the lowering of the upper plate surface. At the same time as the body disengages from the clamp and retreats from the surface of the press board, the prepreg laminate and the foam come into contact with each other, the surface of the foam is melted by the heat accumulated in the prepreg, and the prepreg and the foam are melted and integrated. As shown in, a laminate containing the foam is obtained by cooling and solidifying in a press.

FIG. 5 shows another method for producing a laminate, in the case where the foam 10 near the surface layer has a low expansion ratio of 7 times or less and the center layer has a high expansion ratio of 15 times. Since the foams having different expansion ratios and the prepreg laminates are not simultaneously heated to a predetermined temperature in the same heating time, the foams 10 and 14 having a low expansion ratio and the prepreg laminates 1 and 2 and 5 and 6 are not heated. It shows a method of stacking and clamping in advance and then directly contacting the heating plate for heating. (However, the clamp is omitted in FIG. 5.) FIG. 6 shows another method of manufacturing a laminated body, in which the foaming ratio of the foamed body 10 close to one of the surface layers is as low as 7 times or less. , When the expansion ratio of other layers is as high as 15 times,
Since the foams having different expansion ratios and the prepreg laminate are not simultaneously heated to a predetermined temperature in the same heating time, the foam 10 having a low expansion ratio and the prepreg laminates 1 and 2 are preliminarily overlapped and clamped. It shows a method of heating by directly contacting a hot plate. (However, the clamp is omitted in FIG. 6.) FIG. 10 shows a method for manufacturing a laminated body using a hot-cold press. At a temperature at which the laminate and the resin foam are heat-sealed, first, as shown in FIG. 10-1, the laminates 1 and 2 are fused and integrated on the upper and lower surfaces of the resin foam 10, and then the press and the laminate are joined together. Place a heat-resistant body on the lower hot plate while it is not cooled, remove the release film on the upper side of the laminated body that is heat-sealed thereon, stack a new resin foam 11 and laminated body 3 and heat and melt them. Wear and integrate. Next, after releasing the press pressure, the upper release film is removed, and a new resin foam 12 and the laminated body 4 are stacked and hot pressed to perform fusion and integration. This process is repeated until a predetermined number of foams are stacked. In the last step, after cooling the refrigerant 42 without cooling the press pressure, the press pressure is released and the laminate is taken out. When this step is completed, the heat insulating material 41 has a heat insulating property and a thickness that prevent the temperature of the laminated body 1 and the resin foam 2 from rising above their melting temperature, and molding for integrating the laminated body and the resin foam. It must have the ability to withstand pressure. Such materials include gypsum board, asbestos board, plywood and the like. Further, the present invention will be described in detail with reference to specific examples.

[0023]

EXAMPLE The prepreg used in this example has a width of 200
mm was manufactured by the method disclosed in Japanese Patent Publication No. 02-042168. Thickness 13 for glass fiber
The surface of the monofilament of μ was treated with γ-methacryloxy-propyltrimethoxysilane, 1800 filaments were bundled into a twist-free yarn, and the yarn was aligned in one direction while pulling 80 yarns with a uniform tension. Entangling the resin in the yarn and squeezing the resin with a hot roll,
The yarn was impregnated to produce a prepreg. In the case of carbon fibers, without using a sizing agent, 12,000 monofilaments with a thickness of 7μ are gathered in one direction while pulling 80 tows with a uniform tension, and the resin is entangled with the yarn. Was squeezed with a hot roll to impregnate the yarn to produce a prepreg. The prepreg manufactured in this manner has excellent adhesion between the fiber and the thermoplastic resin, and the fiber content can be changed according to the requirement of 30 to 90% by weight, and the thickness is 0.1 to 1.0 mm. However, the glass content is 30-85% by volume and the thickness is 0.
It is desirable to use it at a distance of 1 to 0.6 mm. When the volume content of the fiber is 30% by volume or less, the strength is low because the amount of the fiber is small, and when the volume content of the fiber is 85% by volume or more, the amount of the resin is small with respect to the fiber and the adhesion between the fiber and the resin is reduced, which is not preferable. .

The prepreg of unsaturated polyester and glass fiber is a resin liquid prepared by adding 1 part by weight of t-butylperoxybenzoate and 5 parts by weight of magnesium oxide to 100 parts by weight of unsaturated polyester ester ML1805 manufactured by Mitsui Toatsu Chemicals, Inc. Was impregnated into glass fibers aligned in one direction by a conventional method using a sheet molding compound manufacturing machine, and aged at 40 ° C. for 24 hours to manufacture.

Table 1 shows the constitution of prepregs manufactured for use in the examples of the present invention and the comparative examples. Table 2 shows the properties of the resin foam used in the present invention.

Example 1 When the fiber direction of the prepreg A was set to 0 degree, four sheets of 0 degree, 90 degree, 90 degree, and 0 degree were laminated from the top 50.
6 sets of 0 mm square laminates and 500 mm square resin foam P
Prepared 5 sheets. The laminated body was clamped to 1 to 6 and the resin foam was clamped to 10 to 14 of the device shown in FIG.
The resin foam is clamped and retracted to the outside of the press board, the hot plate 30 heated to 200 ° C. is introduced into the press board, the prepreg laminate is heated for 2 minutes, and then the resin foam is introduced into the press board. After a few seconds, the hot plate 30 was retracted to the outside of the press platen and 0.3 kg / c of the prepreg and the foam between the press upper platen surface 31 and the press lower platen surface 32 heated to 60 ° C.
A laminate was obtained by cooling while heating at a pressure of m2. The thickness and weight of this laminate were measured, and the surface condition and appearance of the laminate were observed. The weight of the laminate was divided by (thickness × 50 × 50) to calculate the density of the laminate. Further, this laminated body was cut into strip-shaped test pieces having a length of 150 mm and a width of 50 mm,
A three-point bending test was performed at a loading speed of 50 mm / min to determine bending strength and bending elastic modulus. The ratio of support span to plate thickness was 16: 1. In addition, this laminated body has a length of 300 mm,
Cut into 50 mm wide strip-shaped test pieces, loading speed 50 m
A three-point bending test was performed at m / min to observe the fractured state, and the bending strength and bending elastic modulus were obtained. FIG. 9 shows a state where the bending test is being performed. The bending strength and the bending elastic modulus were divided by the density, and the specific bending strength and the specific bending elastic modulus were calculated.
The above results are shown in Table 3.

Example 2 When the fiber direction of the prepreg A was set at 0 degree, four sheets of 0 degree, 90 degree, 90 degree and 0 degree were laminated from the top 50.
6 sets of 0 mm square laminates and 500 mm square resin foam Q
Were prepared, and three foams P were prepared. In the apparatus shown in FIG. 5, 1 to 6 are laminated bodies, and 10 and 14 are resin foam Q, respectively.
The resin foam P was clamped and attached to 1, 12, and 13.
The resin foam P is retracted outside the press board in a clamped state, the hot plate 30 heated to 200 ° C. is introduced into the press board surface, the prepreg laminate is heated for 2 minutes, and then the resin foam P is introduced into the press board surface. Then, after 5 seconds, the hot plate 30 is retracted to the outside of the press platen surface, and 0.3 kg of the prepreg and the foam are pressed between the press upper platen surface 31 and the press lower platen surface 32 heated to 60 ° C.
A laminate was obtained by cooling while heating at a pressure of / cm ² . In the same manner as in Example 1, the thickness, weight, surface state and appearance were observed, and the bending properties were evaluated. The results are shown in Table 3.

Example 3 When prepreg A has a fiber direction of 0 degree, four sheets of 0 degree, 90 degree, 90 degree and 0 degree are laminated from the top 50.
6 sets of 0 mm square laminates and 500 mm square resin foam Q
1 and 4 foams P were prepared. In the apparatus shown in FIG. 6, 1 to 6 are laminated bodies, 10 is a resin foam Q, and 11 and 1 are the laminated bodies.
The resin foam P was clamped and attached to Nos. 2, 13 and 14.
The resin foam P is retracted outside the press board in a clamped state, the hot plate 30 heated to 200 ° C. is introduced into the press board surface, the prepreg laminate is heated for 2 minutes, and then the resin foam P is introduced into the press board surface. Then, after 5 seconds, the hot plate 30 is retracted to the outside of the press platen surface, and 0.3 kg of the prepreg and the foam are pressed between the press upper platen surface 31 and the press lower platen surface 32 heated to 60 ° C.
A laminate was obtained by cooling while heating at a pressure of / cm ² . In the same manner as in Example 1, the thickness, weight, surface state and appearance were observed, and the bending properties were evaluated. The results are shown in Table 3.

Example 4 When the fiber direction of prepreg A was set to 0 degree,
4 layers of 0 degree, 90 degree, 90 degree, 0 degree
6 sets of 0 mm square laminates and 500 mm square resin foam P
Was prepared, two foams R, two foams N, and one foam N were prepared. Figure
Laminates 1 to 6 of the equipment shown in 5 and trees 10 and 14
Resin foam P is used for 11 and 13 and resin foam P is used for 12
The fat foam N was clamped and attached. Resin foam R and N
Retract out of the press board in the clamped state, 200 ℃
The hot plate 30 heated to the inside is introduced into the surface of the press board and pre-treated for 2 minutes.
After heating the prepreg laminate, the resin foams P and N are pressed onto the press surface.
5 seconds after introducing the heat plate, retract the hot plate 30 to the outside of the press platen.
Press upper platen surface 31 and press lower platen surface heated to 60 ° C
0.3kg / cm of prepreg and foam between 32 ²of
A laminate was obtained by cooling while heating with pressure. Same as Example 1
Similarly, observe the thickness, weight, surface condition and appearance, and
The physical properties were evaluated. The results are shown in Table 3.

Example 5 When prepreg A has a fiber direction of 0 °, four sheets of 0 °, 90 °, 90 °, and 0 ° are laminated from the top 50.
6 sets of 0mm square laminates and 500mm square resin foam S
Were prepared, and three foams P were prepared. In the apparatus shown in FIG. 5, 1 to 6 are laminated bodies, and 10 and 14 are resin foam S.
The resin foam P was clamped and attached to 1, 12, and 13.
The resin foam P is retracted outside the press board in a clamped state, the hot plate 30 heated to 200 ° C. is introduced into the press board surface, the prepreg laminate is heated for 2 minutes, and then the resin foam P is introduced into the press board surface. Then, after 5 seconds, the hot plate 30 is retracted to the outside of the press platen surface, and 0.3 kg of the prepreg and the foam are pressed between the press upper platen surface 31 and the press lower platen surface 32 heated to 60 ° C.
A laminate was obtained by cooling while heating at a pressure of / cm ² . In the same manner as in Example 1, the thickness, weight, surface state and appearance were observed, and the bending properties were evaluated. The results are shown in Table 3.

Example 6 A laminate was obtained in the same manner as in Example 5 except that prepreg C was used instead of prepreg A. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 7 Lamination was performed in the same manner as in Example 5 except that prepreg B was used instead of prepreg A, resin foam U was used instead of resin foam S, and resin foam T was used instead of resin foam P. Got the body This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 8 Lamination was performed in the same manner as in Example 5 except that prepreg D was used instead of prepreg A, resin foam U was used instead of resin foam S, and resin foam T was used instead of resin foam P. Got the body This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 9 Lamination was performed in the same manner as in Example 5 except that prepreg E was used instead of prepreg A, resin foam W was used instead of resin foam S, and resin foam V was used instead of resin foam P. Got the body This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Example 10 In the same manner as in Example 1, when the fiber direction of the prepreg A was set to 0 degree, four pieces of a 500 mm square, which were 0 degree, 90 degree, 90 degree and 0 degree from the top, were superposed. 6 sets and 50 stacks
Five pieces of 0 mm square resin foam P were prepared. The laminated body was clamped to 1 to 6 and the resin foam was clamped to 10 to 14 of the device shown in FIG. Furthermore, vinyl chloride laser 39 lined with a 2 mm thick polyurethane foam sheet
Was placed on the release film 40 with the surface of the vinyl chloride laser being in contact with the release film. With the resin foam clamped, retract it to the outside of the press board,
The hot plate 30 heated to 0 ° C. is introduced into the press platen surface, the prepreg laminate is heated for 2 minutes, the resin foam is introduced into the press platen surface, and 5 seconds later, the hot plate 30 is evacuated to the outside of the press platen 60 ° C. Pressed upper surface 31 and pressed lower surface 3
Between the two, the prepreg and the foam were cooled while being heated at a pressure of 0.3 kg / cm ² to obtain a laminate. A laminate having a good appearance and a good feel of vinyl chloride leather was obtained.

Example 11 When the fiber direction of the prepreg A was set to 0 degree, four sheets of 0 degree, 90 degree, 90 degree, and 0 degree were laminated from the top 50.
6 sets of 0 mm square laminates and 500 mm square resin foam P
Prepared 5 sheets. As shown in FIG. 10-1, the press hot plate is heated to 180 ° C., and the laminates 1 and 2 are formed on the upper and lower surfaces of the foam 10.
The layered product is sandwiched by a release film, put into a hot press plate, and heated at a pressure of 0.3 Kg / cm ² for 1 minute for heat fusion. Next, the press pressure is released, and as shown in FIG. 10-2, the heat insulating plate 41 is placed on the lower heating plate 32, the heat-sealed laminate is further placed thereon, and the upper release film is removed. The new foam 11 and the laminated body 3 are superposed, and heat fusion is carried out by applying a pressure of 0.3 Kg / cm ² through the release film for 1 minute. Then, as shown in FIG.
After releasing the pressing pressure, the upper release film is removed, a new resin foam 12 and a layered product 4 are overlaid, and 0.3 kg /
Heat fusion is performed by applying a pressure of 1 cm ² for 1 minute. This process was repeated twice more. In the last step, 0.3 kg /
After pressurizing with a pressure of cm ² for 1 minute, while maintaining the press pressure, the refrigerant 42 is placed in the upper and lower heating plates as shown in FIG. 10-4.
Then, after cooling to room temperature, the press pressure was released to obtain a laminate, and the thickness, weight and surface condition were observed in the same manner as in Example 1, and the bending properties were evaluated. The results are shown in Table 3.

Comparative Example 1 When the fiber direction of the prepreg F is 0 degree, 0 degree, 90 degree, 0 degree, 90 degree, 0 degree, 90 degree, 90 degrees from the top.
Two sets of 500 mm square laminates were stacked by stacking 12 sheets of 0 °, 90 °, 0 °, 90 °, and 0 °, and one resin foam X of 500 mm square was prepared. This laminated body and the foam are superposed in the order of laminated body / foamed body / laminated body from the top, and the temperature is 150 °
Put into a press equipped with a heating plate heated to 0.3 kg
After being heated at a pressure of / cm ² for 10 minutes, it was taken out to obtain a laminated body. Since the prepreg F was treated at a high temperature of 150 ° C. to cure it, the foam partly broke under pressure, and the surface condition of the cured prepreg was poor due to insufficient molding pressure. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Comparative Example 2 When the fiber direction of the prepreg A is 0 degree, 0 degree, 90 degree, 0 degree, 90 degree, 0 degree, 90 degree, 90 degrees from the top.
Two sets of 500 mm square laminates, which were a stack of 12 sheets of 0 °, 90 °, 0 °, 90 °, and 0 °, and one resin foam O of 500 mm square were prepared. 1 and 2 of the device shown in FIG.
The laminated body was attached to, and the resin foam was clamped and attached to 10.
(In the case of this example, the laminated bodies 3 to 6 and the foaming bodies 11 to 14 are not attached.) The resin foam O is retracted to the outside of the press board in a clamped state, and the hot plate 30 heated to 200 ° C. is pressed to the press board surface. After heating the prepreg laminate for 2 minutes and introducing it into the resin foam O press board surface, the hot plate 30 is evacuated to the outside of the press board surface 5 seconds later, and the press upper board surface 31 and the press bottom surface heated to 60 ° C. The prepreg and the foam were cooled while being heated at a pressure of 0.3 kg / cm ² between the board surfaces 32 to obtain a laminate. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Comparative Example 3 A laminate was obtained in the same manner as in Example 5 except that prepreg G was used instead of prepreg A. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

Comparative Example 4 A laminate was obtained in the same manner as in Example 5 except that prepreg H was used instead of prepreg A. This laminate was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 3.

[0041]

[Table 1]

[0042]

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[0043]

[Table 3]

[0044]

According to the method of the present invention, a lightweight and highly rigid laminate in which a resin foam and a thermoplastic resin prepreg are firmly integrated can be manufactured.

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FIG. 1 is an external view of a laminate obtained by a manufacturing method according to the present invention.

FIG. 2 is a conceptual diagram showing a state in which a prepreg and a foam are installed in an apparatus for producing a laminate of the present invention.

FIG. 3 is a schematic diagram showing a first stage in which the heat source is retracted from the apparatus shown in FIG. 2 to integrate the prepreg and the foam.

FIG. 4 is a conceptual diagram of a state in which the support holding the prepreg and the foam is removed from the state shown in FIG. 3 and the prepreg and the foam are cooled and integrated by a press.

FIG. 5 is a conceptual diagram showing a state at the time of molding a laminate in which the foaming ratio of the foam near the front surface layer and the back surface layer is lower than the foaming ratio of the foam in the central layer.

FIG. 6 is a conceptual diagram showing a state at the time of molding a laminate in which the foaming ratio of the foam near the surface layer is lower than the foaming ratio of the foam in the central layer.

FIG. 7 is an external arrow view showing a laminated body in which a surface material is attached to one surface.

FIG. 8 is a conceptual diagram showing a state in which a prepreg, a foam, and a surface material are mounted in an apparatus to form a laminate in which a surface material is attached to one surface.

FIG. 9 shows a state in which bending strength of the laminate is being performed.

FIG. 10 is a conceptual diagram showing a method for forming a laminate by using a heat-cooled breath.

[Explanation of reference numerals] 1 ... Laminated body 2 ... Prepreg laminated body 3 ... Prepreg laminated body 4 ... Prepreg laminated body 5 ... Prepreg laminated body 6 ... prepreg laminate 10 ... resin foam 11 ... resin foam 12 ... resin foam 13 ... resin foam 14 ... Resin foam 20 ... Clamp 30 ... Hot plate 31 ... Press upper surface 32 ... Press lower surface 33 ... Right side clamp retracting direction 34 ...・ ・ ・ Retracting direction of left clamp 35 ・ ・ ・ Retracting direction of hot plate 39 ・ ・ ・ Surface material 40 ・ ・ ・ Release film 41 ・ ・ ・ Insulation material 42 ・ ・ ・ ・ ・Direction of refrigerant flow

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

Claims (21)

[Claims] 1. A molded article obtained by laminating one or more sheets of prepreg impregnated with a thermoplastic resin and a resin foam, in which continuous reinforcing fibers are aligned in one direction, and a combination of the resin foam and the prepreg is laminated in two. A laminated body, characterized in that at least one layer is overlaid and the layers are thermally bonded. 2. The laminate according to claim 1, wherein a surface material is attached to one side or both sides. 3. The laminate according to claim 1, wherein the prepreg contains reinforcing fibers in a volume content of 30% or more and 85% or less. 4. The laminate according to claim 1, wherein the reinforcing fiber of the prepreg is a glass fiber and the thermoplastic resin is a polypropylene resin. 5. The reinforcing fiber of the prepreg is a glass fiber and the thermoplastic resin is a polystyrene resin.
The laminated body according to. 6. The laminate according to claim 1, which is a prepreg in which continuous fibers are bundled and each bundle is aligned in one direction. 7. The laminate according to claim 1, wherein the resin constituting the prepreg and the resin of the foam are of the same type. 8. The laminate according to claim 1, wherein the expansion ratio of the resin foam is 2 times or more and 50 times or less. 9. The laminate according to claim 1, wherein the foaming ratio of the resin foam near both the front surface and the back surface or one of the surfaces is lower than that of the resin foam near the central layer. . 10. The laminate according to claim 1, wherein the layers are thermally bonded together under a pressure of 3 kg or less per 1 cm ² of the bonding area between the pair of prepregs and the resin foam. 11. The laminate according to claim 2, wherein the surface material is a woven or non-woven fabric made of a resin film and a fibrous material. 12. A step of degassing air contained in layers by heating one or more prepregs in which continuous reinforcing fibers are aligned in one direction and impregnated with a thermoplastic resin to a temperature equal to or higher than a melting temperature of the thermoplastic resin. And heating the prepreg to a melting temperature or higher and the resin foam to a melting temperature or lower at the same time in a state where they do not contact each other, and heating the prepreg and the resin foam are overlapped with each other and pressure applied to perform thermal bonding. A method for manufacturing a laminated body, comprising sequentially performing a step and a step of cooling and solidifying the thermally bonded laminated body to integrate them. 13. The prepreg has a volume content of 30.
The method for producing a laminate according to claim 10, wherein the reinforcing fibers are contained in an amount of not less than 85% and not more than 85%. 14. The method for producing a laminate according to claim 10, wherein the reinforcing fibers of the prepreg are glass fibers and the thermoplastic resin is a polypropylene resin. 15. The method for producing a laminate according to claim 10, wherein the reinforcing fiber of the prepreg is glass fiber, and the thermoplastic resin is polystyrene resin. 16. The method for producing a laminated body according to claim 10, wherein the continuous fibers are bundled, and each bundle is a prepreg aligned in one direction. 17. The method for producing a laminate according to claim 10, wherein the resin constituting the prepreg and the resin of the foam are the same type. 18. The foaming ratio of the resin foam is 2 times or more 50.
The method for producing a laminate according to claim 10, wherein the number of times is not more than double. 19. The laminate according to claim 10, wherein the foaming ratio of the resin foam near both the front surface and the back surface or one of the surfaces is lower than that of the resin foam near the central layer. Manufacturing method. 20. When the expansion ratio of the resin foam on both the front surface and the back surface or on one of the two surfaces is 2 times or more and 7 times or less, the prepreg and the foam are superposed and further directly applied to the hot plate. The method for producing a layered product according to claim 10, wherein heating is performed by bringing them into contact with each other. 21. The method for producing a laminate according to claim 10, wherein the layers are thermally bonded together under a pressure of 3 kg or less per 1 cm ² of the bonding area between the pair of prepregs and the resin foam.