JP2000190341A - Method for producing fiber-reinforced resin laminate and fiber-reinforced resin laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fiber-reinforced resin laminate in which a sufficient amount of reinforced continuous long fibers are arranged on a surface layer portion and an inner layer portion is constituted by a resin layer containing a filler. I will provide a. SOLUTION: An impregnated body 42 obtained by impregnating a continuously progressing long fiber bundle 41 with a foamable thermosetting resin composition 22 is provided from one end of a molding die 5 to all edges or facing of the molding die 5. The filler 14 containing the thermosetting resin is continuously introduced into the space formed by the impregnating body 42 along the inner surface of the molding die. And
A fiber characterized in that the impregnating body 42 and the filler 14 are foamed and cured by advancing and curing the foamable thermosetting resin composition 22 and the thermosetting resin while moving the inside of the molding die 5 to form a fiber. A method for manufacturing the reinforced resin laminate 100.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a fiber-reinforced resin laminate suitably used for sleepers, truck carriers, civil engineering materials, and the like.

[0002]

2. Description of the Related Art Conventionally, wood and concrete have been widely used as materials for civil engineering and construction. However, wood is liable to be corroded or damaged, and has problems in durability such as deterioration of physical properties due to water absorption. On the other hand, concrete has excellent durability and strength, but has problems such as being very heavy and easily cracking due to vibration.

[0003] In response to these problems, synthetic wood in which a resin foam is reinforced with unidirectional continuous long fibers has been developed.
Used for truck bed materials, civil engineering construction materials, etc. However, in applications where a strong bending load is applied, such as sleepers, the stress due to the bending load is applied exclusively to the surface layer and not much to the inner layer. However, there is a problem that the price is high for the performance.

To solve the above problem, Japanese Patent Laid-Open No.
Japanese Patent Publication No. 138797 describes a surface made of a thermosetting resin foam reinforced by long fibers along a longitudinal direction on at least one surface side and an opposite surface side of a core material made of a thermosetting resin foam containing a filler. Composite materials in which materials are laminated have been proposed. However, the method of the present proposal is batch type, has low productivity, and is not suitable for mass production.

Japanese Patent Laid-Open No. 7-32386 discloses that
As a manufacturing method, a method has been proposed in which a resin composition containing an inorganic filler is supplied into a cylindrical cavity of a moving belt that forms a cylindrical shape and continuously advances, and inorganic fibers are continuously supplied. I have.

[0006] However, the above publication does not disclose a specific method of arranging reinforcing fibers in the surface layer portion, and also describes a method of impregnating continuous filaments with the thermosetting resin composition. Absent.

Further, Japanese Patent Publication No. 4-32728 discloses that a filler and a foamed plastic material are injected into a nozzle pressurized by a blower and mixed in the nozzle. A manufacturing method has been proposed in which the material is injected into a mold as it is.

[0008] However, even in the above-mentioned publication, there is no description about the arrangement of the reinforcing fibers in the surface layer necessary for obtaining strength.

[0009]

SUMMARY OF THE INVENTION The object of the present invention is to solve such a problem. An object of the present invention is to provide a sufficient amount of reinforced continuous filaments arranged on a surface layer supporting a stress caused by a bending load. In addition, the thickness of the fiber-reinforced resin laminate, in which the thickness and the thickness are secured, is made of a resin layer containing a low-cost filler. It is to provide a manufacturing method.

[0010]

According to a first aspect of the present invention, there is provided a method for producing a fiber-reinforced resin laminate, wherein a foamable thermosetting resin composition is added to a continuous fiber bundle. The impregnated impregnated body is introduced from one end of the molding die along all the edges of the molding die or along the inner surfaces of two opposing edges,
Into the space formed by the impregnated body along the inner surface of the molding die, a filler and a thermosetting resin, or a filler containing a thermosetting resin is continuously charged, and the impregnated body and ,
The foaming thermosetting resin composition and the foaming thermosetting resin and the foaming and curing of the thermosetting resin are performed while the thermosetting resin or the filler containing the thermosetting resin is advanced in the molding die. It is characterized by being molded.

[0011] The invention according to claim 2 (hereinafter referred to as "invention 2") is characterized in that the filler is held on a carrier base material made of a porous sheet. It is a method of manufacturing the body.

The invention according to claim 3 (hereinafter referred to as invention 3) is characterized in that the filler containing the thermosetting resin is added to the filler in a state where the filler is held by a transport base material made of a porous sheet. A method for producing a fiber-reinforced resin laminate according to the first aspect of the present invention, characterized by containing a thermosetting resin.

According to a fourth aspect of the present invention (hereinafter, referred to as the fourth aspect of the present invention), the step of incorporating a thermosetting resin into the filler held on the carrier substrate made of the porous sheet comprises the step of: A method for producing a fiber-reinforced resin laminate according to the third aspect of the present invention, which is a step of passing through a resin bath.

According to a fifth aspect of the present invention, there is provided a fiber-reinforced resin laminate according to any one of the first to third aspects of the present invention, wherein the thermosetting resin is polyurethane. Is the way.

The invention according to claim 6 (hereinafter referred to as invention 6) is characterized in that the thermosetting resin of the foamable thermosetting resin composition is polyurethane.
The method for producing a fiber reinforced resin laminate according to any one of the above.

The invention according to claim 7 (hereinafter referred to as the present invention 7) provides a surface layer portion made of a thermosetting resin foam reinforced with long fibers and an inner layer portion made of a thermosetting resin containing a filler. Wherein the porous sheet is present at least at a part of the interface between the surface layer portion and the inner layer portion, and manufactured by the method according to any one of the present inventions 1 to 6. It is a fiber reinforced resin laminate. Note that the layer structure includes not only a case having three parallel layers but also a structure in which the surface layer has side surfaces and the inner layer is surrounded.

The long fibers constituting the long fiber bundle used in the present invention may be in the form of a thread obtained by entanglement of short fibers, or may be a monofilament. In short, the long fiber may be a continuous long fiber. The material of the fiber constituting the long fiber bundle is not particularly limited, and glass fiber, natural fiber, carbon fiber, synthetic fiber and the like are used. Among them, glass fibers and carbon fibers are preferable because they have a large reinforcing effect. As the synthetic fiber, for example, vinylon, polyamide, polyester, polyolefin and the like can be used. Rayon may also be used.

The diameter of the long fibers constituting the fiber bundle is preferably 2 μm or more and 100 μm or less. That is, if the diameter of the long fiber is less than 2 μm, the long fiber is cut when impregnating with the foamable thermosetting resin liquid, and if it exceeds 100 μm, the surface area of the long fiber is reduced and the rigidity of the molded body is reduced. May decrease.

The thermosetting resin of the foamable thermosetting resin composition used in the present invention is not particularly limited, and examples thereof include polyurethane resin, phenol resin, unsaturated polyester resin, urea resin, epoxy resin and the like. Can be Among them, a polyurethane resin is more preferable in terms of durability and mechanical strength.

The foaming agent contained in the resin composition may be a thermal decomposition type foaming agent or a solvent type foaming agent such as chlorofluorocarbon. When a polyurethane resin is used as the thermosetting resin, water may be used.

[0021] The resin composition may optionally contain compounding agents such as a catalyst, a foam stabilizer, a colorant, a crosslinking agent, and a filler.

The viscosity of the resin composition is 1 poise
If it is less than 1, it is difficult to impregnate the long fiber bundle into the resin composition after impregnating the resin composition, and if it exceeds 1000 poise, it becomes difficult to impregnate the long fiber bundle.
~ 1000 poise is preferred.

The impregnation amount (weight ratio) of the resin composition into the long fiber bundle in the present invention is not particularly limited, and the strength of the intended fiber-reinforced resin laminate (product) and the surface layer of the intended product The volume ratio is appropriately adjusted depending on the volume ratio of the foam layer and the inner layer portion, the foaming power of the foamable thermoplastic resin composition used, and the like. Further, as described below, in the method of excessively impregnating the foamable thermoplastic resin composition into the long fiber bundle, and including the filler impregnated with the excessively impregnated resin composition, in the method of the target product The volume ratio between the surface layer portion and the inner layer portion, the type and amount of the filler used, the foaming power of the resin composition, and the like, the above-mentioned impregnation amount is appropriately adjusted, and the surplus amount is larger than the amount necessary for forming the surface layer portion. The resin composition is impregnated into the long fiber bundle.

As a method of impregnating the above-mentioned resin composition into the above-mentioned long fiber bundle in the present invention, for example, the long fiber bundle is discharged from the upper part of the continuous long fiber bundle which is drawn substantially parallel to a predetermined interval under tension and continuously advances. Sprinkle the resin composition discharged from the nozzle of the machine, advance the long fiber bundle to which this resin composition adheres to an impregnating machine equipped with an impregnating table and a kneading plate, and move the kneading plate perpendicular to the traveling direction of the long fiber bundle. A method is preferable in which the long fiber bundle is rubbed by reciprocating motion, and the long fiber bundle is uniformly impregnated with the resin composition to obtain an impregnated body.

In the present invention, the long fiber bundle is impregnated with the resin composition at a temperature of less than 10 ° C., the viscosity of the resin composition is too high to impregnate the resin composition. The temperature is preferably from 10 to 35 ° C. because foaming easily starts.

The method of introducing the impregnated body from one end of the molding die along all the edges of the molding die or along the inner surfaces of the two opposing edges is not particularly limited. When a cylindrical cavity formed by a plurality of moving endless belts is used as a mold, the impregnated body is introduced along the conveyor belt corresponding to the edge where the fiber-reinforced surface layer is to be obtained. Is preferred.
Therefore, when it is intended to obtain a fiber reinforced surface layer on the entire periphery of the target fiber reinforced resin laminate, the fiber reinforced surface layer is formed on all the conveyor belts forming the cylindrical cavity, and on two opposing edges. In order to obtain a portion, the impregnated body may be brought into contact with a conveyor belt corresponding to the two edges and introduced along the same. For the introduction of the impregnated body, if necessary, a position regulating tool such as a guide may be provided in front of the end of the molding die to assist the impregnated body in contact with the conveyor belt.

Examples of the filler used in the present invention include inorganic powders, sludge dry powders, and fiber-reinforced resin powders. These fillers may be used alone or as a mixture of two or more.

Examples of the inorganic particles include rock particles, glass particles, calcium silicate, crushed cement concrete, amorphous particles such as silica sand, and inorganic short fiber powders such as sericite and wollastonite. And inorganic powder having a relatively small particle size such as calcium carbonate, fly ash and the like, and inorganic powder having bubbles such as vermiculite, perlite, expanded shale, and fly ash hollow powder.

Examples of the sludge dry powder include dry solids generated from a sludge treatment plant. Examples of the fiber-reinforced resin particles include a pulverized FRP and a pulverized fiber-reinforced rigid polyurethane foam.

The particle size of these fillers is 100 μm.
When it is less than m, the specific surface area of the filler becomes large, and the content of the thermosetting resin is deteriorated.

In particular, the particle size of the filler used in the present invention 4 is preferably 1 mm or more in the process of the present invention 4 if it is less than 1 mm because it is difficult to contain a thermosetting resin.

In the present invention, the above-mentioned filler is filled with a thermosetting resin or contains a thermosetting resin, and a cavity formed from one end of the molding die along an inner surface of the molding die along the inner surface of the molding die. Although it is put into the part, as the thermosetting resin to be contained in the filler, for example, polyurethane resin,
Unsaturated polyester resins, epoxy resins and the like can be mentioned. Of these, polyurethane resins are preferred because of their excellent bonding property with the filler and mechanical strength. This thermosetting resin may be the same as the foamable thermosetting resin composition used for impregnating the long fiber bundle.

The filler and the thermosetting resin may be charged as a resin-containing filler obtained by mixing the filler and the thermosetting resin in advance and adding the thermosetting resin to the filler. Alternatively, the filler and the thermosetting resin in the intact state may be separately charged into one end of a molding die, or an impregnated body obtained by excessively impregnating a long fiber bundle with the foamable thermosetting resin composition. A method in which a molding die is introduced, the filler is charged as it is, and the excessively impregnated resin composition is caused to flow out of the impregnated body in the process of foaming and curing and adhered to the filler and contained. .

According to the second aspect of the present invention, the above-mentioned filler is used while being held on a transport base material made of a porous sheet. The term “holding” as used herein refers to a state in which the filler is placed on the transport base material, or the filler is placed on the upper surface of a long strip-shaped transport base material, and the transport base material is sequentially rained while being advanced in the manufacturing direction. A state in which the filler is wrapped by being transformed from a gutter shape or a horizontal U-shape into a substantially cylindrical or rectangular tube shape may be used. In the case where the filler is wrapped, a plurality of the transfer bases may be used, for example, the upper part wrapped in a horizontal U-shape may be covered with another transfer base. It is also a preferable retention that the cross-sectional area in a state where the filler is wrapped is reduced as the progress proceeds, and the denseness of the wrapped filler is increased. The filler held by the transport base material may be a resin-containing filler containing a thermosetting resin or may be used as it is.

The transport base material used in the present invention 2 includes
It is necessary to have a performance capable of holding a filler or a resin-containing filler, and in the case of a method of containing a thermosetting resin while holding the filler, it is necessary to have a capability of transmitting the thermosetting resin. Some materials having such performance include:
For example, a porous sheet such as a glass cloth, a glass mat, a nonwoven fabric, a paper, a wire mesh, a porous plastic film or a metal foil can be used. Among them, a mesh-like porous sheet having a large tensile strength is preferable.

The above-mentioned transport base material is incorporated between the fiber-reinforced surface layer portion and the inner layer portion of the obtained fiber-reinforced resin laminate, and serves to uniform the thickness of the fiber-reinforced surface layer portion.
It is also useful for reinforcement in the direction perpendicular to the longitudinal direction of continuous continuous fibers.

When the resin-containing filler is contained in the carrier, the method of obtaining the resin-containing filler by adding the thermosetting resin to the filler includes the type of the filler used, the type of the thermosetting resin used, and the like. Although it differs depending on the kind and the amount to be contained, a conventionally known method of mixing a thermosetting resin and a filler can be employed.

According to the third aspect of the present invention, after the filler is held on the carrier, the filler contains a thermosetting resin.
As a method of causing the filler to contain the thermosetting resin, for example, a method in which the filler is sprayed on the carrier base material, the thermosetting resin is sprinkled thereon, and the thermosetting resin is introduced into the molding die together with the carrier base material may be used. However, in the present invention 4, the filler is wrapped by the transport base material, and in this holding state, the filler is passed through the thermosetting resin bath, and the thermosetting resin is wrapped by the transport base material. It is performed by a method of including a resin.

The thermosetting resin used in the present invention 4 is preferably, for example, an unsaturated polyester resin composition having no limit on the pot life at normal temperature, and has a viscosity exceeding 10,000 cps. And it is difficult to make the filler sufficiently contained, and the content is preferably 10,000 cps or less.
Further, the particle size of the filler used in the present invention is preferably 1 mm or more from the viewpoint of easy inclusion of the thermosetting resin.

The molding die used in the present invention may be, for example, a movable type comprising a plurality of endless belts or cylindrical cavities formed by slat conveyors or the like, or may be a known type in FRP drawing. It may be a fixed cylindrical body. Examples of the material of the endless belt include steel, rubber, and resin. When a polyurethane resin is used as the foamable thermosetting resin composition,
A movable type using an endless belt is preferable from the viewpoint of the adhesive force to the inner surface of the mold.

The impregnated body, the filler and the thermosetting resin or the resin-containing filler introduced and introduced into the molding die undergo foaming and curing as the molding die proceeds. In order to assist the above, it is preferable that the molding die is made temperature-adjustable. In the case of the endless belt system, it is preferable to provide a segment in contact with the belt at a predetermined position, adjust the temperature of the segment, and apply a temperature to the inside through the belt. In the case of a fixed mold, a method in which a pipe is provided in the mold and a heat medium such as steam, oil, or water is passed, or a method using an electric heater may be used.

When the molding die is installed vertically,
The other end opposite to the one end into which the impregnated body or the like is introduced is fitted with a weir plate. The dam plate is used to hold the injected filler and the thermosetting resin or the resin-containing filler so as not to leak at the start of the production, and is removed at the stage when the production is started. You.

It is preferable that the fiber reinforced resin laminate (hereinafter, referred to as a product) obtained by advancing, foaming, and curing the molding die is cooled at the other end of the molding die. The cooling of the product may be performed by rotating a cooling roll in contact with the product, or cooling water may be directly sprayed on the surface of the product.

The obtained product is taken by a take-up machine provided in front of the forming die in the traveling direction. The take-off force is appropriately selected depending on the shape and size of the product. The take-off speed is appropriately selected depending on the structure of the product, the reaction speed of the thermosetting resin used, and the temperature of the molding die.

[0045]

The method for producing a fiber-reinforced resin laminate of the present invention 1 comprises:
The impregnated body obtained by impregnating the continuous fiber bundle with the foamable thermosetting resin composition in the long fiber bundle is arranged along one of the edges of the molding die along all the edges of the molding die or the inner surface of the two opposing edges. Introduced, into the space formed by the impregnated body along the inner surface of the molding die, a filler and a thermosetting resin, or a filler containing a thermosetting resin is continuously charged, The impregnated body, a filler and a thermosetting resin, or a filler containing a thermosetting resin and the foaming thermosetting resin composition and the thermosetting resin while advancing the molding die. Because it is a method of foaming and curing and molding, a sufficient amount of reinforced continuous filament is arranged on the surface layer supporting the stress due to bending load, and the thickness and thickness that express high rigidity are The inner layer part to be given is composed of a resin layer containing a filler, ensuring the thickness and thickness. Ri, than conventional methods inexpensive and can be produced fiber-reinforced resin laminate of high performance continuously.

In the method for producing a fiber-reinforced resin laminate according to the second aspect of the present invention, since the above-mentioned filler is the method according to the first aspect of the present invention in which the filler is held on a carrier base material made of a porous sheet, the method follows the inner surface of the molding die. A desired amount of the filler is reliably introduced into the space formed by the impregnated body, and the fiber reinforced resin laminate can be stably manufactured.

The method for producing a fiber-reinforced resin laminate according to the third aspect of the present invention is characterized in that the filler containing the above-mentioned thermosetting resin is thermoset to the filler in a state where the filler is held on a carrier base made of a porous sheet. Since the method according to the first aspect of the present invention includes a thermosetting resin, the thermosetting resin passes through the porous sheet and is contained in the filler. It is possible to uniformly and sufficiently wet, and to stably produce a fiber-reinforced resin laminate of uniform quality.

In the method for producing a fiber-reinforced resin laminate according to the fourth aspect of the present invention, the step of adding a thermosetting resin to the filler held by the transport base made of the porous sheet comprises the step of forming the thermosetting resin bath. Since the method of the present invention 3 is a step of passing through the inside, the action of the present invention 3 is more effectively exhibited.

In the method for producing a fiber-reinforced resin laminate according to the fifth aspect of the present invention, the thermosetting resin is a method according to any one of the first to third aspects of the present invention, wherein the thermosetting resin is a polyurethane resin. A laminate can be manufactured.

The method for producing a fiber-reinforced resin laminate of the present invention 6 is characterized in that the thermosetting resin of the foamable thermosetting resin composition is:
Inventions 1 to 5 characterized by being a polyurethane resin
In this case, a fiber-reinforced resin laminate having more excellent physical properties can be produced.

The fiber-reinforced resin laminate of the present invention 7 is a fiber-reinforced resin having a surface layer portion made of a thermosetting resin foam reinforced with long fibers and an inner layer portion made of a thermosetting resin containing a filler. A laminate, produced by any of the methods of the present invention 1 to 6, wherein a porous sheet is present at least at a part of the interface between the surface layer portion and the inner layer portion. Therefore, the thickness of the surface layer is constant, and the fiber reinforced resin laminate is reinforced in a direction different from the longitudinal direction of the continuous filament.

[0052]

DESCRIPTION OF THE PREFERRED EMBODIMENTS One embodiment of the present invention will be described below with reference to the drawings. Figures 1-3 and 5
FIG. 3 is a schematic explanatory view showing a manufacturing apparatus used in Examples 1 to 4. FIG. 4 and FIG. 6 are schematic explanatory views illustrating the steps of Examples 3 and 4. 7 to 10 are schematic perspective views showing products obtained by Examples 1 to 4.

Example 1 In this example, a vertical manufacturing apparatus 1 shown in FIG. 1 was used. Product 1 obtained in Example 1
As shown in FIG. 7, 00 has a rectangular cross section and has a surface portion 100a reinforced with long fibers at four peripheral edges.

As shown in FIG. 1, the manufacturing apparatus 1 comprises a mixer 10, a discharger 21, an impregnator 3, a molding die 5, a cooler 7,
A take-up machine 8 and a cutting machine 9 are provided. The discharger 21 mixes each component supplied from a tank (not shown) to form a foamable thermosetting resin composition 22 and then aligns the four components from four rectifying plates (not shown) to form a tension. Foamed thermosetting resin while reciprocating in a direction perpendicular to the traveling direction of the long fiber bundle 41 on a long fiber bundle 41 (only two directions are shown in the drawing) continuously supplied with The composition 22 is discharged and sprinkled.

In this embodiment, the composition 22 has a viscosity of 500 cps / 25 ° C., a propylene oxide-added polyether (hydroxyl value 410, functional group 4) 100
A composition obtained by mixing 120 parts by weight of diphenylmethane diisocynate, 1 part by weight of silicone oil for foam control, 1 part by weight of water, and 0.05 part by weight of dibutyltin laurate (hereinafter referred to as composition A). Using. Further, as the long fiber bundle 41, a roving using 200 E-glass monofilaments having a fiber diameter of 9 μm as one strand was used.

The impregnating machine 3 includes an impregnating table 31 and a rubbing plate 32, and the rubbing plate 32 is reciprocated in a direction perpendicular to the traveling direction of the long fiber bundle 41, and the composition A 22 is transferred between the impregnating table 31 and the impregnating table 31. The sprinkled long fiber bundle 41 was rubbed, and the long fiber bundle 41 was impregnated with the composition A22 to form an impregnated body 42.
In this example, the weight ratio between the long fiber bundle 41 and the composition A22 was 1: 1.

The molding die 5 has a long side of 200 mm and a short side of 100 mm.
4 mm endless belt 5
1 (only two sheets are shown in the figure), and each belt is moved by drive rolls 53, 53... The molding die 5 is provided with a temperature adjusting segment 52 in contact with each belt 51. In the present embodiment, a molding die 5 having a length of 15 m is used, and the temperature of each belt 51 is 85 ° C. at the center in the longitudinal direction.
It was adjusted to be. In addition, the temperature control segment 52
The belt 51 is cooled in the lowermost portion 521 of the belt.

The impregnated body 42 is connected to each belt 51
The cylindrical cavity was introduced into the molding die 5 so as to be aligned along the width direction of the four peripheral edges of the cylindrical cavity without any gap.

At the upper end of the molding die 5, a mixer 1
0 is provided. The mixer 10 is provided with a filler inlet 11 and a thermosetting resin inlet 12. The filler and the thermosetting resin injected from each of the inlets are mixed in a mixing chamber 13. The content filler 14 is made. The resin-containing filler 14 falls into one end of a cylindrical cavity having a rectangular cross section formed by being surrounded by four impregnating bodies 42 in contact with and along the four belts 51. You.

In this example, No. 7 silica sand was used as a filler.
The resin-containing filler 14 was prepared using the resin composition A as the thermosetting resin, and the weight ratio between the filler and the thermosetting resin was 8: 1.

The impregnated body 42 and the resin-containing filler 14 charged into the molding die 5 advance downward as the belt 51 moves, and the heat from the belt 51 heated by the temperature controlling segment 52 Then, the foaming and curing reaction of the composition A is performed, and a fiber reinforced resin laminate (product) 100 including a surface layer reinforced with long fibers and an inner layer containing a filler is obtained. The product 100 is pre-cooled by the action of the temperature control segment 521 and comes out of the molding die 5.

Reference numeral 58 in FIG. 1 denotes a weir plate. This weir plate 58
Was inserted into the other lower end of the molding die 5 until the start of production, so that the injected resin-containing filler 14 did not leak out. The weir plate was removed at the stage when the production was started and the inside of the cylindrical cavity of the molding die 5 was filled by foaming of the resin composition A.

Next, the product 100 is sent to the cooler 7 and is sufficiently cooled by the plurality of cooling rolls 71 provided in the cooler 7. The cooled product 100 is cut into a predetermined length by a cutting machine 9 after passing through a take-up machine 8 operated at a take-up speed of 1.5 m / min.

The product 100 thus obtained has a cross section of 2
As shown in FIG.
Surface layer 100a reinforced with peripheral long fibers and inner layer 100b containing filler (inner layer size 180 mm × 80 m
m).

(Embodiment 2) In this embodiment, a horizontal manufacturing apparatus 2 shown in FIG. 2 was used. Product 2 obtained in Example 2
As shown in FIG. 8, 00 has a rectangular cross section, and has a surface portion 200a reinforced with long fibers at the top and bottom.

As shown in FIG. 2, the manufacturing apparatus 2 includes a transport base material feeding device 45, a filler sprayer 15, a resin dropping device 17, a transport device 6, a discharger (not shown), and an impregnator (not shown). ), A molding die 5, a cooling machine 7, a take-off machine 8, and a cutting machine 9.

The transport base material 46 delivered from the transport base material feeding device 45 by the transport roll 61 of the transport device 6 is
It is placed on a conveyor belt 62 and, while traveling on the belt 62, a filler spreader 15 provided thereabove.
The filler 16 is sprayed, and then the thermosetting resin 18 is filled with the filler 1 from a resin dropping device 17 provided above.
The transfer base material 46 on which the filler 16 dropped on the thermosetting resin 18 and sprinkled with the thermosetting resin 18 is supplied along the lower belt 51 of the molding die 5 described later.
Is sent to the molding die 5 in the form of being placed on the

In this embodiment, a glass mat is used as the transfer base material 46 and the average particle size is 2.5 m as the filler 16.
A composition obtained by mixing 100 parts by weight of an isophthalic acid-based unsaturated polyester resin, 1 part by weight of methyl ethyl ketone peroxide, and 0.5 part by weight of cobalt naphthenate was used as the thermosetting resin 18. And
The weight ratio of the thermosetting resin 18 dropped to the filler 16 was 6: 1.

The molding die 5 used was the same as that used in Example 1 but was placed in the horizontal position. That is,
An endless belt 51 having four cylindrical hollow cavities with a long side of 200 mm and a short side of 100 mm and a rectangular cross section (only two sheets are shown in the figure)
, And each belt is moved by driving rolls 53, 53... The upper and lower endless belts 51, 51 of the driving rolls 53, 53 are supplied with impregnating bodies 42, 42 from above and below, respectively, as shown in the figure.

The impregnated body 42 used in this embodiment is the same as that in the first embodiment.
Using the same long fiber bundle and the foamable thermosetting resin composition (composition A) as used in Example 1, the composition A was discharged from the same discharging machine as in Example 1, and the same impregnating machine as in Example 1 was used. The long fiber bundle was impregnated with the same weight ratio as in Example 1 to form an impregnated body 42.

The molding die 5 is provided with a temperature adjusting segment 52 in contact with each belt 51. In the present embodiment, a molding die 5 having a length of 15 m was used, and the temperature of each belt 51 was adjusted to 85 ° C. at the center in the longitudinal direction. The belt 51 is cooled at the forefront portion 521 of the temperature control segment 52.

The impregnated body 42 and the transfer base material 46 introduced into the molding die 5 move rightward with the movement of the belt 51, and move from the belt 51 heated by the temperature adjusting segment 52. Upon receiving the heat, the foaming and curing reaction of the resin composition A in the impregnated body 42 and the curing reaction of the thermosetting resin 18 are performed, and the fiber reinforced resin including the surface layer reinforced with long fibers and the filler-containing inner layer A laminate (product) 200 is obtained. By the action of the temperature control segment 521, the product 2
00 is precooled and comes out of the molding die 5.

Next, the product 200 is sent to the cooler 7, and the cooling water is directly sprayed on the product 200 by a plurality of cooling water spraying devices 72 provided in the cooler 7, whereby the product 200 is sufficiently cooled. The cooled product 200 is cut into a predetermined length by the cutting machine 9 after passing through the take-up machine 8 (having a speed of 1.5 m / min).

The product 200 thus obtained has a cross section of 2
As shown in FIG. 8, it has a square shape of 00 mm × 100 mm and has a filler-containing inner layer portion 200 b (the inner layer portion size 200 mm × 70 mm) sandwiched between surface layers 200 a reinforced with upper and lower long fibers. Configuration. In FIG. 8, the lower surface layer 200a and the inner layer 20
The porous sheet 20 composed of the transport base material 46
0c is present.

(Embodiment 3) In this embodiment, a horizontal manufacturing apparatus 3A shown in FIG. 3 was used. As shown in FIG. 9, the product 300 obtained in the third embodiment has a rectangular cross section, a surface layer 300 a reinforced with long fibers on four edges, an inner layer 300 b made of a filler and a thermosetting resin, and It has a configuration in which a porous sheet 300c containing a thermosetting resin exists at the interface between the surface layer portion 300a and the inner layer portion 300b.

As shown in FIG. 3, the manufacturing apparatus 3 includes transporting material feeding devices 45 and 45 ′, a filler spraying device 15, a resin dripping device 17, a molding device 63, a discharging machine (not shown),
An impregnating machine (not shown), a molding die 5, a cooling machine 7, a take-off machine 8, and a cutting machine 9 are provided.

The transporting base material 47 fed from the transporting base material feeding device 45 by the transporting roll 61 is fed to a molding device 63.
While traveling on the shaping device 63, the shape is changed from a band shape at a location as shown in FIG. 4 to a rain gutter shape, and to a horizontal U-shape with an open upper portion. Let it.
The filler 16 is sprayed from the filler sprayer 15 provided above on the transport base material 47 at an intermediate point between the resin discharge device 17 and the resin discharge device 17 provided at an intermediate point between The thermosetting resin 18 is sprayed on the filler 16 in the form of a mist, and at this point, the thermosetting resin 18 is filled with the sprayed filler 16 in a horizontal U-shape with an open top. The upper opening side of the material 47 is covered with the transporting base material 47 ′ fed from the transporting base material feeding device 45 ′ provided above, and is supplied along the lower belt 51 of the molding die 5 described later. It is sent to the molding die 5 while being placed on the impregnating body 42.

In this embodiment, the transport bases 47, 47 '
As a filling material 16, expanded shale (manufactured by Nippon Mesalite Industry Co., Ltd., "Mesalite Coarse Aggregate") was used, As the thermosetting resin 18, composition A in which the amount of water was changed to 0.7 parts by weight and dibutyltin laurate was changed to 0.15 parts by weight was used. Then, the thermosetting resin 1 sprayed on the filler 16
The weight ratio of 8 was 8: 1.

The same mold 5 as that used in Example 2 was used. That is, the long side 200 mm and the short side 10
A cylindrical cavity having a rectangular cross section of 0 mm is formed by four endless belts 51 (only two belts are shown in the figure), and each belt is moved by driving rolls 53, 53. Along the four belts, the impregnating bodies 42 are supplied from four directions, up, down, left and right, and a cylindrical cavity is formed surrounded by the impregnating bodies 42.

The impregnated body 42 used in this embodiment is the same as that in the first embodiment.
As the same long fiber bundle and foaming thermosetting resin composition as used in Example 1, composition A in which dibutyltin laurate was changed to 0.15 parts by weight was used, and the same impregnating machine as in Example 1 was used. The same impregnation method as in Example 1 was used to impregnate the long fiber bundle into the same weight ratio as in Example 1 to form an impregnated body 42.

Temperature control in the following molding process, molding die 5
Cooling, cutting, etc. after exiting from
A product 300 was obtained in the same manner as in Example 2, except for using the same apparatus as in Example 2. Product 300 is shown in FIG.
As shown in the figure, the cross section is a square shape of 200 mm × 100 mm, and the surface layer portion 300 a reinforced with four peripheral long fibers and the inner layer portion 300 b containing the filler (the inner layer portion has a size of 180 mm ×
70 mm), and a porous sheet 300c containing a thermosetting resin exists at the interface between the surface layer portion 300a and the inner layer portion 300b.

(Embodiment 4) In this embodiment, a horizontal manufacturing apparatus 4A shown in FIG. 5 was used. As shown in FIG. 10, the product 400 obtained in the fourth embodiment has a rectangular cross section and has a surface portion 400a reinforced with long fibers at the top and bottom.

As shown in FIG. 5, the manufacturing apparatus 4 includes a transport base material feeding device 45, a filler dispersing machine 15, a first shaping device 64, a resin bath 65, a second shaping device 66, and a discharging machine (shown in FIG. 5). (Not shown), an impregnating machine (not shown), a molding die 5, a cooling machine 7, a take-off machine 8, and a cutting machine 9.

The transporting base material 48 fed out of the transporting base material feeding device 45 by the transporting roll 61 is placed on a first shaping device 64, and while traveling on the shaping device 64, its shape is changed to the shape shown in FIG. As shown in the figure,
The shape is shaped like a rain gutter and the shape is roughly elliptical in section. The filler 16 is sprayed from the filler sprayer 15 provided above the transport base material 48 at an intermediate point between the above and the transport base material 4 wrapping the filler 16 into a substantially elliptical cross section at the point.
8 is introduced into a resin bath 65 containing a thermosetting resin 19, and while moving through the bath 65, the thermosetting resin 19 penetrates the carrier 48 and is sufficiently contained in the filler 16. Is done.

Next, the transport base material 46 wrapping the filler 16 containing the thermosetting resin 19 is introduced into the second shaping device 66. The second shaping device 66 has a taper in which the cross-sectional area is reduced and the cross-sectional shape becomes square as it goes in the traveling direction. The filler 16 is densified while passing through the second shaping device 66. It is being done. And
It is sent to the molding die 5 while being placed on the impregnating body 42 supplied along the lower belt 51 of the molding die 5 described later.

In the present embodiment, a glass cloth (trade name “Micro Glass Cloth YEG4
501 ", silica sand No. 1 as the filler 16 and
As the thermosetting resin 19, a composition obtained by mixing 1 part by weight of methyl ethyl ketone peroxide with 100 parts by weight of an isophthalic unsaturated polyester resin was used. The weight ratio of the thermosetting resin 19 contained in the filler 16 was 6: 1.

The same mold 5 as that used in Example 2 was used. That is, the long side 200 mm and the short side 10
A cylindrical cavity having a rectangular cross section of 0 mm is formed by four endless belts 51 (only two belts are shown in the figure), and each belt is moved by driving rolls 53, 53. The impregnated body 42 is supplied along the upper and lower two belts.

The impregnated body 42 used in this embodiment is the same as that in the first embodiment.
The same long fiber bundle and foaming thermosetting resin composition as used in Example 1 also used the same composition A as in Example 1, and the same impregnation method as in Example 1 using the same impregnation method as in Example 1. The impregnated body 42 obtained by impregnating the long fiber bundle with the same weight ratio as in Example 1 was used.

Temperature control in the following molding step, molding die 5
For cooling, cutting, etc. after exiting from the apparatus, the same apparatus as in Example 2 was used except that the maximum temperature of the temperature control segment 52 was set to 100 ° C. and the take-off speed was set to 0.5 m / min.
A product 400 was obtained in the same manner as described above.

As shown in FIG. 10, the product 400 has a rectangular cross section of 200 mm × 100 mm, and has a filler-containing inner layer 400b sandwiched between upper and lower long fiber reinforced surface layers 400a (the inner layer 400b). Size 180mm x 7
0 mm), a porous sheet 400c containing a thermosetting resin at the interface between the surface layer portion 400a and the inner layer portion 400b and on both side surfaces.
Had a configuration that existed.

[0091]

According to the present invention, the method for producing a fiber-reinforced resin laminate of the present invention has the above-mentioned structure. According to the present invention, a sufficient amount of reinforced continuous filament is disposed on the surface layer supporting the stress caused by the bending load. The inner layer that gives the thickness and thickness that expresses high rigidity is made of a resin layer containing a low-cost filler, and the thickness and thickness are secured. Inexpensive and high-performance laminates can be manufactured continuously.

The method for producing a fiber-reinforced resin laminate according to the second aspect of the present invention has the above-described structure. According to the present invention, a desired amount of filler is reliably introduced into the inner layer portion, and the fiber-reinforced resin laminate is stabilized. Can be manufactured.

The method for producing a fiber-reinforced resin laminate according to the third aspect of the present invention has the above-mentioned structure. According to the present invention, the thermosetting resin is contained in the filler through the porous sheet, and the surface of the filler is Can be uniformly and sufficiently wetted by the thermosetting resin, and a fiber-reinforced resin laminate of constant quality can be stably manufactured.

The method for producing a fiber-reinforced resin laminate according to the fourth aspect of the present invention has the above-described configuration. According to the present invention, the effects of the third aspect of the present invention are more effectively exhibited.

The method for producing a fiber-reinforced resin laminate according to the fifth aspect of the present invention has the above-described structure. According to the present invention, a fiber-reinforced resin laminate having excellent physical properties can be produced.

The method for producing a fiber-reinforced resin laminate according to the sixth aspect of the present invention has the above-described structure. According to the present invention, a fiber-reinforced resin laminate having more excellent physical properties can be produced.

The fiber-reinforced resin laminate of the present invention 7 has a surface layer portion made of a thermosetting resin foam reinforced with long fibers and an inner layer portion made of a thermosetting resin containing a filler. In the laminate, the porous sheet is present on at least a part of the interface between the surface layer portion and the inner layer portion.According to the present invention, the thickness of the surface layer portion is constant, and the longitudinal direction of the long fiber is To provide a fiber reinforced resin laminate reinforced also in the direction perpendicular to the fiber. Further, a fiber reinforced resin laminate having the function of the porous sheet can be provided.
That is, for example, when a glass cloth or the like is used as the porous sheet, reinforcement in a direction perpendicular to the longitudinal direction is particularly possible, and when a rubber-based sheet or the like is used, a vibration damping effect is exhibited. It is. If high tension remains in these porous sheets, physical properties such as bending strength can be improved.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view showing an example of a manufacturing apparatus used in the present invention.

FIG. 2 is a schematic explanatory view showing another example of the manufacturing apparatus used in the present invention.

FIG. 3 is a schematic explanatory view showing another example of the manufacturing apparatus used in the present invention.

FIG. 4 is a schematic explanatory view illustrating a part of a manufacturing process used in the present invention.

FIG. 5 is a schematic explanatory view showing another example of the manufacturing apparatus used in the present invention.

FIG. 6 is a schematic explanatory view illustrating another part of the manufacturing process used in the present invention.

FIG. 7 is a schematic perspective view showing an example of a product obtained by the present invention.

FIG. 8 is a schematic perspective view showing another example of a product obtained by the present invention.

FIG. 9 is a schematic perspective view showing another example of the product obtained by the present invention.

FIG. 10 is a schematic perspective view showing another example of the product obtained by the present invention.

[Explanation of symbols]

1, 2, 3A, 4A Manufacturing apparatus 10 Mixer 14, 16 Filler 15 Filler disperser 17 Resin dripping device 18, 19 Thermosetting resin 21 Discharger 22 Foamable thermosetting resin composition 3 Impregnator 41 Length Fiber bundle 42 Impregnated body 46, 47, 48 Transfer base material 5 Mold 51 Endless belt 52 Temperature control segment 6 Transfer device 61 Transfer roll 63, 64, 66 Molding device 65 Resin bath 7 Cooler 71 Cooling roll 72 Cooling water Spraying device 8 Take-off machine 9 Cutting machine 100, 200, 300, 400 Product 100a, 200a, 300a, 400a Surface portion 100b, 200b, 300b, 400b Inner layer portion 100c, 200c, 300c, 400c Porous sheet

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI theme coat ゛ (Reference) B29L 9:00

Claims (7)

[Claims] 1. An impregnated body obtained by impregnating a foaming thermosetting resin composition into a continuous fiber bundle, which is continuously advanced, from one end of the molding die to all edges or two opposing edges of the molding die. Introduced along the inner surface of the mold, in the space formed by the impregnated body along the inner surface of the molding die, a filler and a thermosetting resin,
Alternatively, a filler containing a thermosetting resin is continuously charged, and the impregnated body, the filler and the thermosetting resin, or the filler containing the thermosetting resin are filled in the molding die. A method for producing a fiber-reinforced resin laminate, wherein the foaming thermosetting resin composition and the thermosetting resin are foamed and cured while being advanced and molded. 2. The method for producing a fiber-reinforced resin laminate according to claim 1, wherein the filler is held on a transport base material made of a porous sheet. 3. The method according to claim 1, wherein the filler containing the thermosetting resin contains the thermosetting resin in a state where the filler is held by a carrier base made of a porous sheet. The method for producing a fiber-reinforced resin laminate according to claim 1. 4. The step of allowing the filler held by the porous base sheet to contain a thermosetting resin is a step of passing the thermosetting resin through the thermosetting resin bath. A method for producing the fiber-reinforced resin laminate according to claim 3. 5. The method for producing a fiber-reinforced resin laminate according to claim 1, wherein the thermosetting resin is a polyurethane resin. 6. The method for producing a fiber-reinforced resin laminate according to claim 1, wherein the thermosetting resin of the foamable thermosetting resin composition is a polyurethane resin. 7. A fiber-reinforced resin laminate having a surface layer portion made of a thermosetting resin foam reinforced with long fibers and an inner layer portion made of a thermosetting resin containing a filler, wherein the surface layer portion is provided. The fiber-reinforced resin laminate produced by the method according to any one of claims 1 to 6, wherein a porous sheet is present at least at a part of an interface between the fiber and the inner layer.