JPH08187738A - Manufacture of composite molded form and molding material used therefor - Google Patents

Abstract

PURPOSE: To obtain a composite molded form having a light weight and tough foam core sandwich structure by removing bubbles while impregnating liquid molding resin in resin composition to upper and lower reinforcing fibrous sheets by pressurizing and relaxing specific laminate, and pressurizing or heating. CONSTITUTION: Two separate films 1, 4, reinforcing fibrous sheets 2, 5 and flexible films 3, 6 are supplied, particle-containing resin composition containing curable liquid molding resin and rigid light-weight filling particles having mean particle size of 0.01 to 2mm as main bodies is supplied from a supply unit 10 between the films 1 and 4 to form a laminate, and which is supplied to a resin impregnated part 11. A pair of rollers are provided at an inlet and an outlet of the part 11, fed on many guide rollers to repeatedly pressurize and relax the laminate, the liquid molding resin in the composition is impregnated in the upper and lower sheets 2 and 5, and bubbles are smoothly removed. Then, the liquid molded resin is cured in a curing furnace 13 to form a composite molded form 7.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a fiber reinforced resin (FR
A method for continuously producing a composite molded article having a porous resin core between two surface layers (skins) made of P) and integrally forming the whole, and a molding material therefor. is there. More specifically, fiber reinforced resin (FR
P), two dense surface layer parts (skins) are integrally molded so as to sandwich a core part made of a porous resin layer containing innumerable small bubbles uniformly, and is lightweight and The present invention relates to a method for continuously and efficiently manufacturing a tough composite molded article having a foam core / sandwich structure at low cost, and a molding material used in the manufacturing method.

[0002]

2. Description of the Related Art A lightweight foam core / sandwich composite molded product having a fiber reinforced resin (FRP) surface layer and a porous core has excellent lightness and toughness.
It has a wide range of applications such as transportation equipment for railway vehicles, automobiles, ships, various structural materials, interior / exterior members, medical equipment, telecommunications equipment, sports equipment, and panels for containers.

As a method of manufacturing such a composite molded article, for example, (a) a resin foam such as polyurethane, polystyrene, polypropylene, etc., which has been molded in advance as a core material, is used,
A method of laminating and adhering fiber reinforced resin (FRP) plates and the like on the upper and lower sides, (b) Wrapping the resin foam with a woven fabric as a reinforcing material, inserting it again into the mold, and injecting the liquid molding resin into the mold To form an outer shell, or (c) to form FRP of the outer shell in advance and inject a foamable polyurethane resin or the like into the void in the center thereof to foam in the void. It has been known.

However, in these methods, the steps for obtaining a composite molded article are various and the operation is complicated,
Therefore, it has a drawback that the production efficiency is low and the cost is high.

The following method is known as a method for producing a syntactic foam core / sandwich composite molded article.

For example, in Japanese Patent Publication No. 58-21579, an uncured liquid thermosetting resin has an average particle size of 30 to 50.
A resin composition obtained by blending 10 to 60% by volume of a 0 micron hollow sphere filler is applied to a fiber reinforcing material to allow the resin component in the resin composition to permeate into the fiber reinforcing material and the resin composition. For forming a composite laminate in which a syntactic foam layer and a fiber-reinforced plastics layer containing no fine hollow sphere filler are alternately laminated, characterized in that the resin is pressure-cured while remaining on the surface of the fiber reinforcement. , Are listed. In this method, the fine hollow sphere filler easily enters the surface of the fiber-reinforced plastics layer, and in order not to include the filler, the openings of the fiber reinforcement and the fine hollow sphere filler are It is necessary to appropriately select and combine the sizes, and it is not possible to arbitrarily select both.
Further, in this method, it is impossible to efficiently remove the air contained in the resin or the air bubbles generated by the partial damage of the fine hollow sphere filler, and it is possible to avoid the air or air bubbles remaining as pinholes or voids. Absent. Further, in this method, it is difficult to uniformly control the thickness of the fiber reinforced plastics layer formed by mixing a part of the micro hollow sphere filler into the fiber reinforced plastics layer, and therefore the physical properties are There is a problem that a uniform product cannot be stably obtained, and a composite molded product having a small specific gravity is difficult to obtain.

Further, in Japanese Utility Model Publication No. 62-24521, an unsaturated material containing 20 to 80% by volume of polyolefin resin expanded particles or a pulverized product thereof is provided between two surface layers of a fiber-containing unsaturated polyester resin. There is described a fiber-reinforced unsaturated polyester resin lightweight molded article characterized by integrally forming a core layer made of a polyester resin. This molded body uses expanded polyolefin resin particles, and therefore the particles are relatively large. In the "Example" described in the publication, particles having a diameter of 6 mm are used, and a composite molded body having an overall thickness of 5.8 mm. Is getting
Since this molded body has large particles, it does not have a core layer having a fine and uniform structure, and the polyolefin resin particles do not have sufficient adhesiveness with the unsaturated polyester resin and do not use inorganic particles. Therefore, the physical strength of the obtained molded product is not sufficient.

As a method for improving such a drawback, a foamed resin particle and a liquid molding resin are used to form a porous core portion and a surface layer portion (skin) made of fiber reinforced resin (FRP). A method for producing a composite molded article has been proposed (see, for example, US Pat. No. 5,242,637). In this method, a reinforcing fibrous sheet and a separation membrane are installed in a molding die, and a mixture of expandable resin particles and a liquid molding resin is supplied in a layered form on the reinforcing fibrous sheet, and a separation membrane is further formed thereon. And cover with a reinforcing fibrous sheet, after closing the mold,
The expandable resin particles are expanded by heating the inside of the mold, and the pressure (internal pressure) generated thereby is used to permeate the liquid molding resin into the upper and lower reinforcing fibrous sheets,
This is a method of molding a composite molded article having a foam core / sandwich structure by curing in a mold. According to this method, fine particles foamed between minute surface layers of fiber reinforced resin (FRP) are included. A lightweight and tough composite molded article having a syntactic foam core portion made of a porous resin layer and integrally formed as a whole is efficiently manufactured.

The method of molding using the expandable resin particles has the advantage that a composite molded article having a foam core / sandwich structure can be molded in one step, but the expandable resin particles used in this method are Since it is relatively expensive, there is a problem that the cost of the molded product also increases. Further, when the expandable resin particles expand, gas may leak out from some of the particles, which is one of the factors that cause voids inside or on the surface of the molded product. Further, when some of the particles leak out from the separation membrane, the re-heating of the expandable resin particles easily causes gas generation, which may cause pinholes in a coating process or the like. Further, depending on the type of the liquid molding resin, the skin of the expandable resin particles may be attacked and gas leakage from the particles may easily occur, and it may be difficult to obtain a molded article having excellent surface properties.

Further, in the above-mentioned molding method, it is important to adjust the timing of the foaming of the expandable resin particles and the curing reaction of the liquid molding resin, and complicated process control is required to control the temperature.

The above-mentioned US Patent also describes a mode in which compressed lightweight particles are used in place of the expandable particles and the expanded particles are expanded at the time of molding. However, the method of using the compressed lightweight particles is as follows. It requires a separate special step to compact the particles.

In any of the above-mentioned molding methods, since the particles are expanded and expanded in the mold, continuous molding is difficult.

[0013]

Therefore, the first aspect of the present invention
It is an object of the invention to provide a method for continuously producing a composite molded article having a foam core / sandwich structure by the above-mentioned conventional method having no problem.

A second object of the present invention is to use a variety of liquid resins without using expandable resin particles, and to have a wide selection range of molding conditions such as molding temperature, so that complicated process control is possible. An object is to provide a continuous molding method that is unnecessary.

A third object of the present invention is to provide a method for producing the above-mentioned composite molded article having no voids or pinholes.

Another object of the present invention is to provide a method for producing the above-mentioned composite molded article having excellent physical strength.

Still another object of the present invention is to provide a low cost and industrially advantageous method for molding the composite molded article.

[0018]

The above objects of the present invention are achieved by the following continuous molding method using rigid lightweight filling particles.

That is, the continuous molding method of the present invention is used for producing a composite molded article in which the core portion made of the porous resin layer is present between the surface layer portions made of the fiber reinforced resin and the whole is integrated. Each of the following steps (a) A curable liquid molding resin and an average particle size of 0.01 to
A resin composition preparing step for preparing a particle-containing resin composition mainly composed of rigid and lightweight filling particles of 2 mm, (b) two separation membranes are located inside, and a reinforcing fibrous sheet is provided outside each separation membrane. The two separation membranes and the two reinforcing fibrous sheets are continuously fed so that they are positioned, and the resin composition in the step (a) is continuously fed between the two separation membranes to strengthen the fibers. A laminate preparation step of continuously preparing a laminate comprising a fibrous sheet / separation membrane / resin composition layer / separation membrane / reinforcing fibrous sheet, (c) subsequent to the step (b), The laminated body is continuously subjected to pressure and relaxation from the upper and lower directions at least once, respectively, so that the liquid molding resin in the layer of the resin composition permeates into the upper and lower reinforcing fibrous sheets through the separation membrane. While removing the bubbles other than the bubbles in the particles from the laminate. An impregnation step of removing bubbles, and (d) a step of (preliminary) curing of the resulting impregnated laminate to be a (preliminary) composite molded article by curing by heating with or without pressure (preliminary) It is a method for producing a composite molded article, which is characterized by being carried out.

The continuous method for producing the composite molded article of the present invention will be described in more detail below. First, the main molding materials used in the method of the present invention, namely, the reinforcing fibrous sheet, the separation membrane, and the rigidity and light weight. The filling particles, the liquid molding resin, and each material used as an auxiliary when necessary will be described.

As the reinforcing fibrous sheet used as one of the main molding materials in the method of the present invention, a sheet-like fiber structure made of reinforcing fibers is used. As the reinforcing fiber, for example, glass fiber, carbon fiber, silicon carbide fiber, metal fiber, aramid fiber, polyarylate fiber, high-strength polyolefin fiber and a mixed fiber of two or more thereof are used. In addition to these fibers, polyester fibers, polyamide fibers, polyvinyl alcohol (vinylon) fibers, rayon fibers, acetate fibers, natural fibers and the like can be used. Among these, high strength and high modulus fibers such as glass fiber, carbon fiber and para-aramid fiber are preferable.

As the form of the reinforcing fibrous sheet, each of the above fibers is woven (plain weave, woven weave, twill weave, etc.), knitted fabric,
A sheet-shaped structure such as non-woven fabric, mat, paper, or roving that is aligned in one direction and collected in layers is used. These may be used alone or in combination of two or more. The fibrous sheet can also be supplied as a prepreg impregnated with a liquid molding resin described later in advance. The type of the reinforcing fibrous sheet is appropriately selected according to the form of the composite molded product, the use or performance required for the molded product, the surface appearance of the molded product, and the like.

In the method of the present invention, as will be described later, particles containing a liquid molding resin present in a portion to be a porous core and light weight filling particles mainly composed of rigid particles due to pressurization and relaxation during molding. The liquid molding resin is squeezed out of the resin composition (mixture) and evenly penetrates into the upper and lower fibrous sheets, and a part of it reaches the vicinity of the surface. At this time, the light weight filling particles enter into the reinforcing fibrous sheet. The surface layer that is dense to prevent it (that is, the upper and lower fiber-reinforced resin layers)
It is necessary for forming.

Therefore, in the method of the present invention, the light weight filler particles are not substantially passed through the surface (core side) where the mixed composition of the light weight filler particles and the liquid molding resin is in contact with each other in the upper and lower reinforcing fibrous sheets. However, a membrane (separation membrane) having a separating function that allows the liquid molding resin to pass through is arranged. That is, in the method of the present invention, it is important to interpose the separation membrane between each reinforcing fibrous sheet and the layer of the particle-containing resin composition.

As the separation membrane capable of exhibiting such a separation function, a fiber sheet and / or a porous sheet having a small opening is used. Examples of the fiber sheet for the separation layer include, for example, woven fabrics, knitted fabrics, braids, non-woven fabrics, papers, and the like made of various natural fibers, synthetic fibers, inorganic fibers,
The porous sheet is a sheet or film having continuous air holes, and a foam sheet such as polyurethane, polystyrene or polypropylene, or a porous membrane such as polyethylene, polypropylene or polysulfone produced by a stretching, extraction or coagulation method is used. These openings are appropriately selected depending on the size of the lightweight filling particles. Further, as the material of the separation membrane, a material having elasticity can be selected so that it can be easily matched with the shape of the molded product.

The separation membrane may be made of a material, a part of which is impermeable to the liquid molding resin. For example, a part made of a material having a separating function and a material different from the material used in the part are joined together, and a part of the sheet having a separating function is pre-sealed with a resin or the like. If the fibrous sheet can be fused by heat treatment such as polypropylene fiber sheet, some of the openings have been crushed by the fusion treatment, or a non-porous film attached to a part of the material having a separating function. And so on.

As the separation membrane, a fiber sheet having a small opening such as glass fiber, carbon fiber or aramid fiber, which itself has a function as a reinforcing material, can be used. In this case, this fiber sheet is used. The reinforcing fibrous sheet and the separation membrane can be used together.

However, if the reinforcing fibrous sheet and the separation membrane are provided separately, the openings of the reinforcing fibrous sheet can be freely selected. For example, a unidirectional fiber array prepreg or a three-dimensional woven or knitted fabric can be used. The preform of (1) and the like can be used, and a material can be arbitrarily selected according to the appearance and characteristics required for the surface of the molded product, which is preferable.

In the research conducted by the present inventors, for example, a long-fiber non-woven fabric with a small opening, which is commercially available under the trade name of "UNICEL", is excellent in many aspects such as separation function and handleability. It was confirmed to be suitable.

In the method of the present invention, rigid particles having a low specific gravity or mixed particles in which a small amount (for example, less than 5% by volume) of other lightweight particles are mixed are used as the rigid lightweight filler particles. All of these rigid lightweight filling particles are particles that do not substantially expand under curing and molding conditions, and are lightweight (low specific gravity) hollow particles containing bubbles inside.

The rigid lightweight filling particles have an average particle size of 0.01 to
Those having a range of 2 mm, preferably 0.03 to 1 mm are used. Since fine particles having an average particle diameter (diameter) of less than 0.01 mm easily pass through the separation membrane and easily leak to the surface layer portion, the density of the surface layer portion is lowered and the strength of the molded product is lowered. become. On the other hand, when the average particle size exceeds 2 mm, it becomes difficult to form a uniform mixture when mixed with the liquid molding resin, the handling property is deteriorated, and an uneven pattern is likely to be formed on the surface of the molded product, which is a cause of deteriorating the surface property. Become.

The specific gravity of the particles is preferably 0.02 to 0.8. A low specific gravity is advantageous in terms of light weight, but a too low specific gravity is fragile and easily breaks when mixed with a liquid molding resin. Also, if the specific gravity is larger than this, the effect of weight reduction is not sufficient and the commercial value of the molded product is reduced.
A particularly preferable specific gravity of the rigid lightweight filling particles is 0.05 to 0.
7 Here, the specific gravity means the substantial volume (c
It means the weight (g) with respect to m ³ ) and is expressed in the unit of g / cm ³ .

The rigid particles that make up the rigid lightweight filler particles are:
It has a rigidity such that its shape is not substantially deformed in a series of steps of the method for producing a composite molded article of the present invention.
Usually, inorganic hollow particles are suitable as such rigid particles. Specific examples of the rigid particles include inorganic hollow particles called glass balloons, silica balloons, and shirasu balloons (silica hollow particles).

On the other hand, the liquid molding resin mixed with the rigid lightweight filling particles is a thermosetting resin composition, for example, epoxy resin, polyurethane resin, unsaturated polyester resin, polyvinyl ester resin, polyimide resin,
Phenol resin, polydicyclopentadiene resin, etc. are used. Of these, epoxy resins, unsaturated polyester resins and phenol resins are preferable, and these are usually used together with necessary curing agents, curing accelerators, diluents and the like.

In the method of the present invention, since the resin particles are not foamed in the molding step, the type of liquid molding resin can be widely selected regardless of the type of particles. The liquid molding resin is preferably liquid at room temperature, but may be solid (powder) or semi-solid (paste) at room temperature as long as it becomes liquid at the molding temperature.

The mixing ratio of the rigid lightweight filling particles and the liquid molding resin is preferably such that the volume of the lightweight filling particles in the entire core portion after molding is in the range of 50 to 80% by volume.

In the method of the present invention, carbon, aramid, silicon carbide, potassium titanate, as a material that can be supplementarily used together with the rigid lightweight filling particles and the liquid molding resin for the purpose of improving the mechanical properties of the molded product. Short fibers such as boron and fibers shorter than 6 mm such as whiskers can be added to the particle-containing resin composition. In addition, for the purpose of imparting functions such as electromagnetic shielding effect, or for absorbing reaction heat generated when the liquid molding resin system is cured and suppressing a rapid temperature rise to prevent the generation of local high temperature parts. , Carbon, graphite, silicon carbide whiskers, milled glass, mica, iron powder, calcium carbonate, silica sand, pigments, etc. can be added.
Furthermore, it is also possible to add a crushed product of the used recovered product of the composite molded product to the resin composition. In any case, it is preferable to mix the components so that the specific gravity of the core after molding is 0.8 or less.

Further, a flexible film is arranged along the surface not in contact with the separation membrane (that is, the outside of the molded product) in both or one of the upper and lower reinforcing fibrous sheets to perform pressure / relaxation. By molding, the steps of impregnation and defoaming can be performed more stably, the moldability can be improved, and the surface property of the molded product can be improved.

These flexible films can form a good film surface of a lightweight foam core / sandwich composite molded article by selecting a type that firmly adheres to the upper and lower reinforcing fibrous sheets. Yes, again
By selecting a type that can be easily peeled from the surface of the reinforcing fibrous sheet after molding and removing the film after molding, the moldability and surface property can be improved.

As the flexible film used here, various flexible films or sheets made of an organic polymer,
Specifically, polyester film, polycarbonate film, nylon film, polypropylene film, polyethylene film, polyvinyl chloride film,
Polyvinylidene chloride film, fluororesin film,
Polyimide film, polyarylate film, cellophane, triacetate film, etc., and copolymers or coextruded films of these, and / or metal foils of aluminum, copper, iron, etc., paper, non-woven fabric etc. that prevent liquid permeation by resin processing etc. Is mentioned.

Further, for the purpose of improving the appearance and surface function of the composite molded article, for example, a woven fabric for surface modification, a non-woven fabric, a film, artificial leather and the like can be used as the outermost layer forming material.

Further, in the method of the present invention, for the purpose of improving the mechanical properties of the composite molded article, in particular, the flexure against bending load, the reinforcing material is reinforced at the upper and lower ends of the porous core locally. It may be installed so as to reach the surface layer (skin) including the fiber sheet, and it is often preferable depending on the form and application of the composite molded article. Examples of such a reinforcing material to be locally incorporated include braids, ropes, blades, rods, corrugated materials, and honeycombs, and the materials thereof are glass, aramid,
Polyester, polyamide, cellulose and the like can be preferably used. Particularly, glass braids are preferable, but the braids are not limited thereto.

The size (thickness or thickness) of the reinforcing material to be incorporated in the core portion must be such that the upper and lower sides of the core portion are in contact with at least the upper and lower surface layer portions of the core portion. The larger one is not particularly limited, but a too large one leads to an increase in weight. Therefore, it is economical that the thickness or thickness is 1.2 to 50 times the thickness of the surface layer (skin). . The number of such core reinforcements may be one or more.

According to the method of the present invention, each of the above materials is prepared, and as described above, each of the following steps (a) to (d):
Carrying out (a) a resin composition preparing step for preparing a particle-containing resin composition, (b) a laminate preparing step, (c) an impregnating step, and (d) a curing step (or a preliminary curing step) in this order. Thus, a desired foam core / sandwich composite molded article (or preliminary composite molded article) can be obtained.

At that time, it is important to use only the rigid particles or the mixed particles composed mainly of the rigid particles as the lightweight filling particles, and to form the laminate in which the separation membranes are arranged above and below the particle-containing resin composition layer. And applying and relaxing the laminate at least once. By this pressurization and relaxation, a layer of the particle-containing resin composition composed of the light weight filling particles and the curable liquid molding resin is effectively and uniformly formed, and bubbles other than the particles (for example, air or a part of the particles are crushed). Gas) is released from the laminate or is in a state of being easily released.

That is, a homogeneous and dense porous core (syntactic foam core layer) is formed by pressurization and relaxation, and at the same time, the curable liquid resin is reinforced through the separation layer. By penetrating into the fibrous sheet layer, a strong surface layer portion having excellent surface characteristics is formed.

The molding method of the present invention comprises the above (a) to (d).
The steps (1) and (2) are carried out in this order, and they are carried out by a continuous system in which each step is continuously operated to obtain a long molded product.

[0048]

BEST MODE FOR CARRYING OUT THE INVENTION Main embodiments of the continuous system according to the present invention will be described below with reference to the drawings.

FIGS. 1 and 2 are side plan views showing two modes of the continuous system. In FIG. 1, in order to apply pressure to and relax the laminate in the impregnation process, the laminate has an arcuate convex shape. A plurality of guide rollers are arranged so as to take the traveling route of, and the rollers are traveling while being in contact with each roller. In FIG. 2, traveling in a zigzag manner between the plurality of rollers installed by shifting the positions in the upper and lower two stages. I try to make it meander. In both cases, the laminate is pressed when it comes into contact with the rollers and is relaxed between the rollers.

Due to such a combination of the effects of pressurization and relaxation, the curable liquid molding resin in the particle-containing mixture layer impregnates the upper and lower reinforcing fibrous sheets through the separation membrane, and the bubbles are out of the system. Is discharged to. However, the lightweight packing particles mainly composed of rigid particles are prevented from moving by the separation membrane and remain in the region sandwiched between the separation membranes.

In the example of FIG. 1, in the curing step, the laminated body is heated and cured while being conveyed between a plurality of upper and lower support rolls provided in the curing furnace via a steel belt. In the example, shaping and curing are performed by running the laminated body through the slit-shaped voids of a plurality of molding dies provided in the curing furnace.

Here, when a die having a linear slit-like void as shown in FIG. 3 is used as a molding die, a flat plate-shaped composite molded article is obtained, and a product having a corrugated slit-like void as shown in FIG. 4 is used. Then, a corrugated plate-shaped composite molded product is obtained.

The molded product thus continuously cured is cut into an appropriate size to obtain a product. The impregnation step of FIG. 1 and the curing step of FIG. 2 may be combined, and conversely, the impregnation step of FIG. 2 and the curing step of FIG. 1 may be combined.

Next, the case where the molding is continuously performed by the molding apparatus shown in FIGS. 1 and 2 will be described more specifically.

In FIG. 1, two separation membranes (1, 4),
Two reinforcing fibrous sheets (2, 5) and two flexible films (3, 6) are each continuously fed.
Then, the particle-containing resin composition is continuously supplied from the supply part (10) between the upper and lower separation membranes. Thus, reinforcing fibrous sheet / separation membrane / particle-containing resin composition layer /
A laminate composed of the separation membrane / reinforcing fibrous sheet is formed and continuously supplied to the resin impregnation section (11) which is the impregnation zone. The impregnated portion (11) has a structure in which the laminated body travels on a large number of guide rollers while drawing a convex gentle arc. As shown in FIG. 1, a pair of rollers is provided at both ends of the inlet and the outlet of the impregnated portion (11), whereby tension is applied to the laminate in the flow direction. Thus, in the impregnated portion (11), pressure and relaxation are repeatedly applied to the laminate from above and below.

As shown in FIG. 1, the upper film of the two flexible films is the impregnated portion (11).
It may be supplied from (6) on the front side (upstream side) or from (6 ') on the rear (downstream side) end of the impregnating portion (11). In this impregnated portion (11), the liquid molding resin has upper and lower reinforcing fibrous sheets (2,
5) Penetration into and smooth removal of bubbles.

In FIG. 1, the impregnated laminate having passed through the impregnation section (11) is sent to a curing furnace (13) which is a heating / curing zone. This curing furnace (13) has a pair of steel belts (1
2) has a structure in which the impregnated laminate is conveyed by being sandwiched between two steel belts (by combining two upper and lower endless belts), and the impregnated laminate is introduced into the curing furnace (13) thereof. Is equipped with a large number of support rolls (14). In this curing furnace (heating / curing zone),
The liquid molding resin is cured to form a composite molded product.

In the continuous molding apparatus of FIG. 1, a sheet (panel) -shaped long (continuous length) composite molded product is continuously obtained. This molded product is taken by a take-up device (16) through a trimming cutter (15) so as to have an appropriate width,
It is cut by a cutting machine (17) to a desired length.

In the continuous molding apparatus shown in FIG. 2, the laminate is formed by the same means as the apparatus shown in FIG. In the apparatus shown in FIG. 2, the impregnation zone is sandwiched by a pair of endless belts (20), and a large number of pressure rollers (21) are arranged vertically so that the laminate meanders in a zigzag path. The laminate moves up and down between the plurality of pressure roller groups, and the laminate is repeatedly pressed and relaxed in the vertical direction during the movement. In the apparatus of FIG. 2 as well, the upper film of the laminate is (6) before the impregnation step (upstream side).
Can be supplied from, and also after the impregnation zone (downstream)
It may be supplied from (6 ').

In the example of FIG. 2, the impregnated laminate passing through the impregnation zone is sent to the curing furnace (22) which is a heating / curing zone. In this curing oven (22), the upper die (2
The impregnated laminate passes between 3) and the lower die for forming (24), and is cured and shaped (molded). The shape of the void slit formed between the upper die for forming (23) and the lower die for forming (24) regulates the shape of the composite molded product. Specific examples thereof are shown in FIGS.
As shown in FIG. 3, the molding die shown in FIG. 3 is for manufacturing a flat plate-shaped composite molded product, and the molding die of FIG. 4 is for manufacturing a corrugated plate-shaped composite molded product. . The composite body cured through the curing furnace (22) is the trimming cutter (15) and the take-up device (1) as in FIG. 1.
After 6), it is cut into a desired size by a cutting machine (17).

In the method of the present invention, at least one of the reinforcing fibrous sheets (2, 5) may be previously impregnated with the curable liquid resin, and the lower film (3) may be preliminarily impregnated with the curable liquid resin. It may be supplied after coating.

In this continuous method, in the curing step (d), the impregnated laminate is preliminarily cured by pressurizing it or heating it without pressurizing to partially cure it to obtain a precomposite molded article having shape retention. Which is also included in the present invention. In this case, a pre-cured intermediate composite molded article is obtained. This corresponds to a B-stage molded product such as an epoxy resin molded product. This intermediate composite molded article has shape retention at room temperature and can be deformed at room temperature or under heating. This intermediate composite molded article can be further heated to shape and cure it to give a final molded article, if necessary.

In a preferred embodiment of the continuous system of the present invention, the resin composition is applied onto the surface of the separation membrane of the three-layer sheet while moving the three-layer sheet consisting of the separation membrane / the reinforcing fibrous sheet / flexible film. Layer of the composition is continuously formed, and a separation membrane and a reinforcing fibrous sheet are laminated in this order on the surface of the layer of the composition, and further, a flexible film is laminated if necessary, A laminated body composed of a reinforcing fibrous sheet / separation membrane / resin composition layer / separation membrane / reinforcing fibrous sheet / (flexible film as required) is formed, and the laminated body is formed in at least an upper and lower pair. Achieved by passing between rollers, repeating pressure and relaxation from above and below, carrying out the impregnation process while transferring while maintaining a flat surface, and then preferably transferring while applying surface pressure, and carrying out the curing process. Be done

This continuous system comprises (b) a laminated body preparing step,
It is a method for producing a (preliminary) composite molded article by continuously operating (c) the impregnation step and (d) the curing step (or the preliminary curing step). Therefore, in the continuous method, a composite molded article is obtained by successively successively passing through the laminate forming zone, the impregnation zone and the heating / curing zone.

In this continuous system, two layers of the reinforcing fibrous sheets are continuously run side by side in the vertical direction and supplied to the laminate forming zone. At this time, the upper and lower reinforcing fibrous sheets face each other. Separation membranes are respectively arranged along the surface (the surface located inside), and the resin composition containing the light weight filling particles and the liquid molding resin is supplied to the inside thereof (the portion to be the core) so as to form a layer. Then, at least from the reinforcing fiber sheet / separating film / layer of the resin composition / separating film / reinforcing fiber sheet, the layer is sandwiched between the laminated body of the reinforcing fiber sheet and the separating film. Is formed.

To carry out the method industrially, in the laminate forming zone, first, the separating film for the lower layer is laminated on the reinforcing fibrous sheet for the lower layer which is continuously supplied, and the above composition is formed thereon. The object is formed into a substantially uniform layer with a predetermined thickness. The mixture may be preheated and then layered. And
The separation membrane for the upper layer and the reinforcing fibrous sheet, which are continuously supplied thereto, are sequentially stacked so as to sandwich the layer of the resin composition. At this time, after forming a layer of the resin composition as necessary, both ends (ears) of the upper and lower separation membranes are fused, adhered or sewn to each other to form a tubular shape. The layer may be enclosed between the cylindrical upper and lower separation membranes.

When gas (air bubbles) is contained in the resin composition of the liquid molding resin and the lightweight filling particles to be supplied, voids are likely to occur on the surface of the molded product, the fiber reinforced resin layer, etc. It is preferable to make sure that the composition at that time does not contain non-aggregating gas such as air or nitrogen, or defoam by vacuum treatment in advance.

Further, when molding a composite molded article having a small deflection, it is preferable to dispose the reinforcing material locally in the core portion, as described above. In this case, the reinforcing material is It is necessary that at least the upper and lower ends thereof be connected to the upper and lower surface layer portions (skin layers), respectively. Further, as a method of arranging the reinforcing material in the core portion in the plane direction, in continuous molding, it is suitable to dispose continuously at intervals of 30 mm to 150 mm along the length direction (with respect to the machine flow direction). . If the interval is too wide, the effect of the reinforcing material decreases, and if it is too narrow, it is necessary to supply a large amount of the reinforcing material, which leads to high cost and increased weight.

In this continuous system, next, in the impregnation step, the laminate is subjected to pressure and relaxation from the upper and lower sides at least once in succession. By this pressurization and relaxation, air bubbles contained in the laminate are released,
The liquid molding resin penetrates the upper and lower reinforcing fibrous sheets through the separation membrane and wets the sheets sufficiently, and a part thereof reaches the vicinity of the surface to form a dense surface layer portion. At this time, the movement of the lightweight filling particles is blocked by the separation membrane, and together with the resin in which the particles remain, a syntactic foam core in which the particles are uniformly and densely packed is formed between the separation membranes.

Further, as shown in FIG. 2, the pressure and relaxation of the laminated body are performed by passing the laminated body between at least one pair of upper and lower rollers arranged so that the laminated body forms a corrugated shape and moves in a zigzag shape. You can do it while.

The pressing and relaxation of the laminate are preferably carried out continuously by at least one pair of rollers. And at the same time or following this pressurization,
The layered product is introduced into a heating / curing zone, where appropriate surface pressure is applied to heat the resin to a temperature not lower than the curing temperature of the liquid molding resin while maintaining a flat (smooth) plane.

As the surface pressure imparting mechanism in the heating / curing zone, for example, a plurality of pairs of upper and lower roller groups having a certain clearance is installed along the path of the laminate to be a molded article, or the laminate is provided. A pair of upper and lower belt conveyors, wire mesh conveyors, etc. that sandwich and convey the material are used. The heating means of the heating / curing zone can be arbitrarily selected. For example, the roller group or the conveyors constituting the surface pressure imparting mechanism of the molding part may be heated, far infrared heating, high frequency heating, dielectric heating, induction heating. May be adopted. Further, not only external heating but also reaction heat generated by curing the resin may be used.

At this time, if a flexible film or a metal plate is arranged on or above (upper or lower (outside) of the reinforcing fibrous sheet, and molded, the surface pressure can be applied to the laminate more uniformly and effectively. Thus, not only the moldability is improved, but also the laminate can be conveyed smoothly and the stress at the time of driving can be compensated.

Further, in order to prevent the resin composition from protruding from both end faces when applying a surface pressure to the laminate from above and below, a string, a rope or the like may be arranged at both ends (both sides).

Further, by molding in a state where a liquid molding resin containing a reinforcing material and / or a filler is locally arranged on at least one surface of the laminate, a composite molded article having ribs as shown in FIG. A composite molded article having a boss can also be used.

Thus, dense fiber reinforced resin (FRP)
A composite molding with a tough and lightweight sandwich structure that has a uniform and dense syntactic foam core layer that is made of a cured resin that tightly contains a large number of lightweight filling particles between the surface layers consisting of Continuously drawn from.

Since the composite molded product obtained by such continuous molding is in the form of a long (continuous length) panel, the desired composite molded product is manufactured by cutting it into a predetermined size if necessary. be able to.

According to the conventional knowledge of the present inventors, when a composite molded article is produced by forming a syntactic layer using only rigid and lightweight particles, the composition of the particles and the liquid molding resin is It is difficult to release bubbles easily,
Further, it was not easy to form a fine porous layer having a high packing rate of particles by a stable operation. In particular, when rigid and lightweight particles are used by the batch method, it is extremely difficult to obtain a composite molded product having excellent quality without voids or pinholes. The reason for this is not clear, but probably due to the non-deformability of the rigid lightweight particles, no pressure builds up in the mould, or no pressure is maintained in the mould, so bubbles do not release smoothly and the packing of the particles It is speculated that this is because the molding shrinkage of the core portion becomes large because the porous layer having a high rate is not formed.

However, according to the continuous method of the present invention, surprisingly, a composite molded article having a homogeneous and dense porous core layer free from voids and pinholes can be obtained even when rigid lightweight particles are used. found. It is considered that the above-mentioned (c) impregnation step is a process suitable for smooth release of bubbles and formation of a porous material having a high particle packing rate even when rigid particles are used.

In this continuous method, in the curing step (d) described above, the impregnated laminate is heated with or without being pressed to partially cure it, and a preliminary composite molded article having a shape-retaining property in a partially cured state is obtained. It may be a pre-curing step, which is also included in the present invention. In this case, a partially cured preliminary composite molded article is obtained. This preform is
A desired molded article can be obtained by heating and curing in a desired mold.

The composite molded article produced by the continuous method of the present invention is a porous layer containing lightweight filler particles in a uniform and high filling ratio between the surface layer portion (skin layer) formed of the fiber reinforced resin. It is a molded product in which the (core layer) is integrated, and has a lightweight and tough foam core sandwich structure as a whole. Moreover, it is substantially free of voids and pinholes, has excellent surface characteristics, and has excellent quality.

Thus, the composite molded article according to the method of the present invention is a panel (plate) -shaped lightweight molded article having an average thickness of 1
-100 mm, preferably 1.5-50 mm. The surface layer has a three-layer structure in which there are two layers above and below and a porous layer (syntactic foam core layer) exists between them. When observing a cross section of the composite molded article cut at right angles, the surface layer is And the porous layer are characterized in that they have a clear boundary surface through the separation membrane. The ratio of the thickness of the surface layer portion (total of two layers) / the thickness of the porous layer is 2: 1 to
The range of 1:50, preferably the range of 2: 1 to 1:30 is desirable, but the ratio and the thickness are not necessarily required to be uniform as a whole of the composite molded article, and even if they are partially changed. Good.

The porous layer in the composite molded article according to the method of the present invention has a relatively high filling rate of the light weight filling particles, and therefore the proportion (volume ratio) of the light weight filling particles in the porous layer is high. The volume ratio is preferably 50 to 85%, particularly 60 to 85%.
80% is preferable.

The composite molded article produced by the method of the present invention is lightweight, and its average specific gravity is in the range of 0.2 to 1.2, preferably 0.25 to 1.0, and particularly preferably 0.3 to 0.
The range is 8.

The composite molded article according to the method of the present invention has a panel (plate) shape, but the thickness does not need to be uniform as a whole, and even if the thickness partially changes. Well, in that case, the thick layer may have a thicker porous layer, or may have the thicker surface layer portion. Further, even if the average thickness is substantially the same, the plate shape may not be flat, and may be formed in, for example, a wavy shape or an uneven shape.

Further, the composite molded article may be locally provided with ribs or bosses as shown in FIG. 5 if necessary.

Thus, the composite molded article according to the method of the present invention is
Since it is excellent in lightness and toughness and has a good surface appearance, it can be effectively used for various transportation equipment, structural materials, interior / exterior members, medical equipment, telecommunications equipment, sports equipment and the like.

[0088]

EXAMPLES Hereinafter, specific examples of the present invention will be described, but the present invention is not limited thereto.
In addition, unless otherwise indicated, the part in an example means a weight part.

Example 1 This example shows an example of a continuous molding method using the molding apparatus shown in FIG.

As a flexible film, a polyethylene terephthalate film ("Tetron" film "Type S-31" manufactured by Teijin Ltd .: thickness 25 μm) is shown in FIGS.
Glass fiber chopped strand mat as a reinforcing fibrous sheet ("CM305 manufactured by Asahi Fiber Glass Co., Ltd."
-300 ": A basis weight of 300 g / m ² is shown in Figures 2 and 5 as a separation membrane, and a polyester nonwoven fabric (Teijin Unicell Co., Ltd.)
"UNICEL BT0708W" manufactured by Mitsui Co., Ltd., having a basis weight of 40 g / m ² ) was arranged at 1 and 4 in the figure, respectively.

On the other hand, as a curable liquid molding resin, 100 parts of unsaturated polyester resin (“Polylite FC104N” manufactured by Dainippon Ink and Chemicals, Inc.) and 2 parts of a curing agent (“Permec N” manufactured by NOF Corporation) Glass hollow particles (“Glass Bubbles K-1” manufactured by Sumitomo 3M Ltd.) with a specific gravity of 0.1.
11) of 25) was added and mixed to prepare a particle-containing resin composition.

This particle-containing resin composition is set in the resin composition supply section (10) of FIG. 2 and continuously transferred by the take-up device (16): film / fibrous sheet for reinforcement / separation membrane. A uniform thickness was applied to the laminated body of, and then the separation membrane / the reinforcing fibrous sheet / film were sequentially laminated on the laminated body to form a laminated body.

The laminate thus obtained is supplied to the impregnation / degassing section, and a plurality of sets of pressure roller groups (21) and pressure and relaxation are repeatedly applied by the tension of the film, so that the curable liquid molding resin is separated. It was squeezed out through and was permeated into the upper and lower reinforcing fibrous sheets (glass mats) so that a part of it was allowed to reach the vicinity of the surface and air bubbles in the laminate were discharged. The thickness of the laminate was adjusted to 5 mm with a pair of upper and lower rollers installed at the final part of the impregnation / degassing section, and then the laminate was conveyed to the heating / curing section.

The heating / curing section is composed of a curing furnace (22), an upper die for forming (23) and a lower die for controlling the thickness of the laminate (24), and the introduced laminate is covered with a film. While adjusting the thickness in this state, it was cured by heating at 130 ° C. to form a composite molded article. Further, the molded product that has exited the heating / curing part was cut at both ends by a trimming cutter (15) and then cut to a desired length by a movable cutting machine (17).

The obtained composite molded article is a lightweight molded article having a sandwich structure in which the core portion is a homogeneous syntactic foam and the upper and lower surface layer portions are dense fiber reinforced resin layers.
Its specific gravity was 0.77 (the specific gravity of the core was 0.6
2). The bending strength of this composite molded product is 7.9 kgf.
/ Mm ² , the flexural modulus is 610 kgf / mm ² ,
It was found to have good mechanical properties.

[Embodiment 2] This embodiment is a continuous molding comprising a resin impregnated portion by pressing a film as shown in FIG. 1 and a heating / curing portion whose upper and lower sides are fixed by a steel belt in a state of being continuously conveyed. Here is an example.

Epoxy resin (“Epiclon 85” manufactured by Dainippon Ink and Chemicals, Inc. as a curable liquid molding resin)
0 ") and 2 parts of a curing agent (" Epicure T "manufactured by Yuka Shell Co., Ltd.) are mixed, and the same rigid particles as those of Example 1 (manufactured by Sumitomo 3M Ltd.) are used as lightweight filling particles. 15 parts of glass bubbles K-1 "(specific gravity 0.125) were added and mixed to prepare a particle-containing resin composition.

The mixing ratio of the curable liquid molding resin and the rigid particles in this particle-containing resin composition is 46: by volume.
It was 54.

As shown in FIG. 1, the same polyethylene terephthalate film (3, 6) as in Example 1 was used as a flexible film, and a glass mat (“CM455” manufactured by Asahi Fiber Glass Co., Ltd.) as a reinforcing fibrous sheet: Basis weight 4
50 g / m ² ) (2, 5) was used as the separation membrane, and the same polyester-based nonwoven fabric (1, 4) as in Example 1 was arranged.

The particle-containing resin composition was continuously supplied from the composition supply section (10) of FIG. 1 so as to have a uniform thickness, and in the same manner as in Example 1, the film / fibrous sheet for reinforcement / A laminate comprising a separation membrane / a resin composition containing particles / a separation membrane / a fibrous sheet for reinforcement / a film is formed, and is passed through a plurality of rolls arranged in a convex arc shape at the resin impregnation section (11). On the other hand, the film was pressed and relaxed, and the curable liquid molding resin was permeated into the reinforcing fibrous sheet layer on the surface side through the separation membrane. Then, the thickness of the laminate was adjusted with the last roll of the impregnating section, and introduced into the heating / curing section.

The heating / curing section comprises a steel belt (12) and a curing furnace (13) which are continuously sandwiched from above and below (in this embodiment, the temperature is adjusted to 140 ° C.), a support roller for fixing the laminate and the steel belt. The laminated body composed of (14) was cured by heating while being sandwiched between steel belts and having its thickness adjusted, to obtain a molded product.

The molded product exiting the heating / curing part was cut into a desired size by a trimming cutter (15) and a movable cutting machine (17).

The sandwich type molded article having the syntactic foam core thus obtained has a specific gravity of 0.77.
It was confirmed that a lightweight composite molded article was obtained.

[Example 3] 100 parts of unsaturated polyester resin ("Polylite PS281" manufactured by Dainippon Ink and Chemicals, Inc.) as a curable liquid molding resin, and 1.0 part of BPO (benzoyl peroxide) as a curing agent. Department, CH
0.4 part of P (cumene hydroperoxide) and 0.1 part of DMA (dimethylaniline) as a curing accelerator.
4 parts were mixed, and 70 parts of rigid particles (“Glass Bubbles K-20” manufactured by Sumitomo 3M Ltd .: specific gravity 0.20) were added to and mixed with this resin liquid, and the particle-containing resin composition was added. The thing was prepared.

The mixing ratio of the curable liquid molding resin and the lightweight filling particles in the particle-containing resin composition is 2 by volume.
It was 0:80.

In the continuous molding apparatus shown in FIG. 2, the lower film (3) and the separation membrane (1) are unwound, and the particles containing particles are fed from the resin composition supply section (10) onto the separation membrane (1). The resin composition is supplied and spread in a sheet shape, and the upper separation membrane (4) and the film (6) are further laid on this,
A laminate composed of film / separation film / particle-containing resin composition / separation film / film was formed. (The reinforcing fibrous sheet was not included in the laminate.)

By introducing the laminate into a resin-impregnated part consisting of a plurality of pressure roller groups (21) and repeatedly applying pressure and relaxation, unnecessary air bubbles in the laminate are removed. The curable liquid molding resin in the particle-containing resin composition was permeated into the upper and lower separation membranes to be integrated, and the thickness of the laminate was adjusted to 5 mm through a roll whose thickness could be regulated.

Then, while pressing the laminated body with the film on the upper and lower sides, the curable liquid-forming resin is in a non-cured state of the film / separation film / particle-containing resin through the slits of the upper and lower mold dies which are not heated. Composition / separation membrane /
A laminate composed of a film, that is, a molding material for producing a composite molded article was obtained. The molding material was cut into a desired size by using a trimming cutter (15) and a movable cutting machine (17).

The molding material was stored while being covered with a film on the upper and lower sides, preferably in a non-breathable film bag in order to prevent the styrene crosslinking agent from scattering.

Next, a lightweight composite molded article was molded using the molding material.

That is, 210 mm × 300 mm × 6 m
Glass fiber chopped strand mat (“CM-305” manufactured by Asahi Fiber Glass Co., Ltd.) as a reinforcing fibrous sheet on a flat mold of mt (thickness is controlled by a spacer):
(Basis weight 300 g / m ² ), and 20 parts of the above resin liquid (curable liquid molding resin + curing agent + curing accelerator) is placed thereon, and then the above-mentioned laminate stored in a bag is placed in a predetermined area. The film was cut into a size, the film was peeled off, and the film was laminated. Furthermore, the same chopped strand mat and resin liquid (20 parts) as described above are supplied thereon, the mold is closed and pressurized, and the curable liquid molding resin is uniformly impregnated into the reinforcing fibrous sheet in the mold. Let

In this way, the temperature of the mold was raised to 110 ° C. and held for 10 minutes to complete the curing. The specific gravity of the obtained sandwich-type composite molded product (6 mm thick) having the syntactic foam core was as light as 0.60,
The surface property was also good.

The spacer of the mold was replaced, and the mold set to have a thickness of 11 mm was used.
A sandwich type composite molded article having a syntactic foam core having a thickness of 11 mm was obtained by the same operation except that two plies of the laminate (molding material) for molding the plate were stacked. The specific gravity of this molded product was as light as 0.51.

[Example 4] 100 parts of an epoxy resin ("Epiclon 850" manufactured by Dainippon Ink and Chemicals, Inc.) and 22 parts of a curing agent ("Epicure Z" manufactured by Yuka Shell Co., Ltd.) were mixed and mixed. 30 parts of rigid particles (“Glass Bubbles K-1” manufactured by Sumitomo 3M Ltd .: specific gravity 0.125) were added and mixed to prepare a particle-containing resin composition.

In this particle-containing resin composition, the mixing ratio of the curable liquid molding resin and the rigid particles is 30: by volume.
It was 70.

In the continuous molding apparatus shown in FIG. 2, the films (3, 6) and the reinforcing fibrous sheet (unit weight:
300 g / m ² ) (2, 5) and separation membrane (Basis weight: 40
g / m ² ) (1, 4) was set, and a laminate was formed by the same operation as in Example 1.

Then, pressure and relaxation are repeated through the pressure roller group (21) of FIG. 2 to remove unnecessary air bubbles and to separate a part of the curable liquid molding resin in the particle-containing resin composition. The reinforcing fibrous sheet was permeated and impregnated through the membrane.

At the final stage of the impregnation step, the thickness of the laminate was regulated by a pressure roller, and the laminate was guided to the curing furnace (22).
The temperature of the curing furnace in this example is set to 50 ° C., and in this zone the curable resin changes to a partially cured state,
A so-called preliminary composite molded product was obtained. This preliminary composite molded article can be stored in a cool and dark place, and after storage, it is cut into a desired size, and curing is completed by molding using a normal mold to obtain a composite molded article having a syntactic foam core. I was able to get it.

[0119]

As described above, according to the method of the present invention, a composite molded article having a sandwich structure having a porous core is continuously and efficiently produced at low cost without using expandable resin particles. It becomes possible to do. Moreover, the obtained composite molded article contains substantially no voids or pinholes,
The quality is extremely good.

[Brief description of drawings]

FIG. 1 is a simplified sectional view of a continuous molding apparatus showing an embodiment of the present invention.

FIG. 2 is a simplified sectional view of a continuous molding apparatus showing another embodiment of the present invention.

FIG. 3 is a front view showing an example of the die for molding shown in FIG.

FIG. 4 is a front view showing another example of a die.

FIG. 5 is a sketch drawing showing an example of a composite molded product with ribs.

[Explanation of symbols]

 1: Lower separation membrane 2: Lower reinforcing fibrous sheet 3: Lower film 4: Upper separating membrane 5: Upper reinforcing fibrous sheet 6,6 ': Upper film 7: Molded product (flat plate, corrugated sheet) 10: Resin Composition supply part 11: Resin impregnation part 12: Steel belt 13: Curing furnace 14: Support roller 15: Trimming cutter 16: Take-off device 17: Movable cutting machine 20: Belt 21: Pressure roller group 22: Curing furnace 23 : Upper mold dies 24: Lower mold dies

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Claims (18)

[Claims] 1. When producing a composite molded article in which a core made of a porous resin layer is present between surface layers made of fiber reinforced resin and the whole is integrated, the following steps (a) curable liquid Molding resin and average particle size 0.01-
A resin composition preparing step for preparing a particle-containing resin composition mainly composed of rigid and lightweight filling particles of 2 mm, (b) two separation membranes are located inside, and a reinforcing fibrous sheet is provided outside each separation membrane. The two separation membranes and the two reinforcing fibrous sheets are continuously supplied so that they are positioned, and the resin composition in the step (a) is continuously supplied between the two separation membranes to enhance the strength. A laminate preparation step of continuously preparing a laminate comprising a fibrous sheet / separation membrane / resin composition layer / separation membrane / reinforcing fibrous sheet, (c) following the step (b), The laminated body is continuously subjected to pressure and relaxation from the upper and lower directions at least once, respectively, and the liquid molding resin in the resin composition layer is permeated into the upper and lower reinforcing fibrous sheets through the separation membrane. While removing the bubbles other than the bubbles in the particles from the laminate. It is characterized in that an impregnation step of removing bubbles, and (d) a step of hardening the obtained impregnated laminate by heating or by heating without applying pressure to obtain a composite molded article are sequentially carried out. Manufacturing method of composite molded article. 2. When producing a composite molded article in which a core made of a porous resin layer is present between surface layers made of fiber reinforced resin and the whole is integrated, the following steps (a) curable liquid Molding resin and average particle size 0.01-
A resin composition preparing step for preparing a particle-containing resin composition mainly composed of rigid and lightweight filling particles of 2 mm, (b) two separation membranes are located inside, and a reinforcing fibrous sheet is provided outside each separation membrane. The two separation membranes and the two reinforcing fibrous sheets are continuously fed so that they are positioned, and the resin composition in the step (a) is continuously fed between the two separation membranes to strengthen the fibers. A laminate preparation step of continuously preparing a laminate comprising a fibrous sheet / separation membrane / resin composition layer / separation membrane / reinforcing fibrous sheet, (c) subsequent to the step (b), The laminated body is continuously subjected to pressure and relaxation from the upper and lower directions at least once, respectively, so that the liquid molding resin in the layer of the resin composition permeates into the upper and lower reinforcing fibrous sheets through the separation membrane. While removing the bubbles other than the bubbles in the particles from the laminate. An impregnation step for removing bubbles, (d) a pre-curing step for obtaining a pre-composite molded article having shape-retaining property by subjecting the obtained impregnated laminate to heating with or without heating to partially cure, (E) A method for producing a composite molded article, which comprises sequentially performing a curing step of heating and curing the preliminary composite molded article under shaping conditions. 3. The method for producing a composite molded article according to claim 1, wherein the rigid lightweight filling particles are inorganic hollow particles which do not substantially expand under curing conditions. 4. The rigid lightweight filling particles have an average particle size of 0.03.
The method for producing a composite molded article according to claim 1, claim 2 or claim 3, wherein the particles are particles having a size of ˜1 mm. 5. The rigid lightweight packing particles have a specific gravity of 0.02 to 0.02.
The method for producing a composite molded article according to any one of claims 1 to 4, wherein the particles are 0.8 particles. 6. The composite molding according to claim 1 or 2, wherein the separation membrane is a fibrous sheet or a porous membrane having openings that pass through the curable liquid resin but prevent passage of the rigid lightweight filling particles. Method of manufacturing goods. 7. The two separation membranes facing each other are joined to each other to form a bag-like or tubular shape, and a curable liquid resin and a composition mainly composed of rigid lightweight filling particles are enclosed therein. Item 1. A method for producing a composite molded article according to Item 1 or 2. 8. A flexible film is arranged below or above and below a laminate composed of a reinforcing fibrous sheet / separation membrane / resin composition layer / separation membrane / reinforcing fibrous sheet to apply pressure and relaxation. After carrying out, the method for producing a composite molded article according to claim 1 or 2, which is cured by heating. 9. The composite according to claim 1 or 2, wherein the step (b) for preparing a laminate, the step (c) for impregnation and the step (d) for curing (or pre-curing) are carried out in a continuous series of steps. Molded article manufacturing method. 10. The method according to claim 1, wherein (c) the impregnation step is carried out while passing the laminate between at least a pair of upper and lower rollers and repeating pressure and relaxation from the upper and lower sides while maintaining a flat flat surface. The method for manufacturing the composite molded article according to claim 2. 11. (d) In the curing (or pre-curing) step, surface pressure is applied from the top and bottom of the laminated body, and a constant pressure is applied while the laminated body is continuously conveyed in a mechanism capable of holding a flat plane. The method for producing a composite molded article according to claim 1, which is carried out in a state. 12. A layer of a particle-containing resin composition is continuously formed on the surface of a separation membrane of the three-layer sheet while moving the three-layer sheet in which the separation membrane / reinforcing fibrous sheet / flexible film is laminated. A flexible film / reinforcing fibrous sheet is formed by laminating a separation film and a reinforcing fibrous sheet in this order on the surface of the resin composition layer, and further laminating a flexible film if necessary. / Separation membrane / Layer of resin composition / Reinforcing fibrous sheet / (Flexible film) is formed, and the laminate is passed between at least one pair of upper and lower rollers, and pressure is applied from above and below. The method for producing a composite molded article according to claim 1 or 2, wherein the impregnation step is carried out by repeating the above-mentioned relaxation and relaxation, and then the hardening (or pre-curing) step is carried out by heating while transferring while maintaining a flat surface. . 13. The impregnating step of carrying out the impregnation step while passing the laminate between a plurality of pairs of rollers arranged so that the laminate moves up and down in a zigzag path. A method for producing the described composite molded article. 14. The method for producing a composite molded article according to claim 1, wherein a reinforcing material is arranged in the layer of the resin composition. 15. A composite molded article having ribs or bosses, which is formed by locally disposing a composition containing a liquid molding resin and a reinforcing material on at least one surface of the laminate, and molding the composition.
Alternatively, the method for manufacturing the composite molded article according to claim 2. 16. A molding material for use in the manufacture of a composite molded article, wherein a core portion made of a porous resin layer is present between surface layer portions made of fiber reinforced resin, and the whole is integrated, which is curable. A molding material for producing a composite molded article, comprising a particle-containing resin composition mainly composed of a liquid resin and rigid lightweight filling particles, wherein the composition is formed into a slurry, cake or sheet. 17. The molding material for producing a composite molded article according to claim 16, wherein the particle-containing resin composition is in the form of a sheet, and the upper and lower sides of which are covered with a separation film. 18. A reinforcing fiber material, wherein the particle-containing resin composition is in the form of a sheet, the upper and lower sides thereof are covered with a separation membrane, and the upper and lower sides thereof are impregnated with or without a liquid molding resin. The molding material for producing a composite molded article according to claim 16, which is covered with a sheet, and each layer is substantially integrated.