JPH0427532A - Preparation of composite molded product - Google Patents

Abstract

PURPOSE:To obtain a composite molded product by relatively simple operation by foaming foamable particles in a mold by raising temp. to generate the volumetric expansion of the particle aggregate and effectively utilizing this volumetric expansion force at its max. to perform composite molding. CONSTITUTION:A thermosetting resin or a precursor thereof is fluidized through a separation layer while the separation layer is pressed to the inner surface of a mold by volumetric expansion to be allowed to be present between the separation layer and the mold and between foamable particles. Subsequently, the thermosetting resin or the precursor thereof is cured and perfectly solidified to form a surface layer and a core part and, thereafter, the obtained composite molded product is taken out of the mold. The concrete molded product has thin skins of an epoxy resin formed to both outer surfaces thereof and glass fiber fabrics are present directly under the skins in the form pressed to the inner foamed core and (a) is a foamed core layer formed by the solidification of a mixed slurry, (b) is separating layers also used as fiber reinforced layers composed of two glass fiber fabrics and (c) is cured resin layers constituting both surfaces.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for manufacturing a composite molded article. More specifically, (i) a surface layer portion made of a thermosetting resin phase containing a fibrous reinforcing material; (11) a core portion made of the resin phase containing cellular particles (foam-containing particles); The present invention relates to a method for efficiently producing an integrated composite molded article comprising a separation layer existing between a core and a core.

<Conventional technology> Composite molded products with a foam core and a surface layer made of fiber-reinforced resin are lightweight and strong, and have been put into practical use in a variety of fields. Further improved molded articles and manufacturing methods have been proposed.

As a method for manufacturing a composite molded product having the above-described structure, for example, the foam core of the core is molded in advance, this molded product is wrapped with a woven fabric as a reinforcing material, and then inserted into a mold. A method is to inject liquid molding resin into the mold to form the surface layer, and then take out the composite molded product from the mold.Alternatively, the material that will become the surface layer is pre-molded and foamed urethane resin, etc. is injected into the void in the center. However, a method of obtaining a composite molded article by forming a foamed core within the void is known.

For example, JP-A-63-162207 describes a method called thermal expansion transfer molding. That is, the method described in this publication involves preforming a thermoelastic rigid foam into a predetermined shape, wrapping the preformed foam with a woven fabric, and forming a structure in which the internal constraint surface forms the outer shape of the final member and A specific part of the molded foam core is placed in a heatable mold, a thermosetting liquid molding resin is injected, the foam core is expanded by heating, and the expansion force presses the woven fabric surrounding the foam core against the internal constraint surface of the mold. This is a method of curing resin to obtain molded products. This method has the advantage of producing an unprecedentedly lightweight and strong composite molded product, but (a) it is necessary to preform a form core with a shape as close as possible to the shape of the mold; (b) ) It is necessary to select a material for the form core that has an appropriate thermal expansion behavior, and (
C) There are restrictions such as the need to use a foam core with closed cells to prevent the thermosetting resin from penetrating.

Furthermore, Japanese Utility Model Publication No. 62-24521 discloses a core layer made of an unsaturated polyester resin containing a large number of foamed polyolefin resin particles or pulverized particles thereof, between two surface layers made of a fiber-containing unsaturated polyester resin. A lightweight molded article made of fiber-reinforced unsaturated polyester resin is described.

This lightweight molded product is produced by placing glass fiber in a mold, coating it with an unsaturated polyester resin stock solution to form a surface layer, and then adding foamed polyolefin resin particles and an unsaturated polyester resin stock solution to the glass fiber. Pour the mixture (
The core layer) is coated with a glass fiber-containing unsaturated polyester resin (surface layer), and is then molded and cured.

Since this method uses particles that have already been foamed, it is difficult to apply pressure uniformly throughout the molding process. Therefore, it is not easy to stably obtain a homogeneous composite molded product using this method. Furthermore, this method is suitable for obtaining a board-shaped molded article in which an unsaturated polyester resin containing expanded particles exists as a core between the upper and lower surface layers, but it is not suitable for obtaining a molded article with a curved surface. is not appropriate.

The conventionally known techniques as described above have the disadvantages that (i) the steps for obtaining a composite molded product are diverse and the operations are complicated, resulting in low production efficiency and high cost of the molded product; (11) The strength and appearance of the resulting composite molded product are unsatisfactory, and (iii) the shape and size of the composite molded product are limited.

<Problems to be Solved by the Invention> Therefore, the first object of the present invention is to improve the surface layer portion and the foamed particles (
The object of the present invention is to provide a method that allows a composite molded article substantially formed from a core portion containing (cell-containing particles) to be obtained by a relatively simple operation.

A second object of the present invention is to provide a method that allows a composite molded article having the above structure to be obtained substantially in one step, without requiring complicated operations or complicated conditions. It is in.

Another object of the present invention is to provide a method with excellent production efficiency, in particular a high production rate of composite molded articles per molding machine.

Still another object of the present invention is to provide a method for manufacturing a composite molded article that is lightweight, has high physical strength, and has a structure with excellent appearance.

Still another object of the present invention is to provide a method for manufacturing a composite molded article whose shape and size can be arbitrarily selected.

Still other objects of the present invention will become clearer from the following description.

According to the research conducted by the present inventors, the objects of the present invention are as follows: (i) a surface layer portion made of a thermosetting resin phase containing a fibrous reinforcing material; (11) foaming; A method for producing an integrated composite molded article comprising a core made of the resin phase containing particles (cell-containing particles), and (iiD) a separation layer existing between the surface layer and the core, ,
Next steps (a) to (h) (a) A thermosetting resin or its precursor that has fluidity during molding, although the expandable particles do not substantially pass through the substantially closed mold. (b) providing the thermosetting resin or its precursor in the mold; (e) integrating the separation layer between the separation layer and the mold in the mold; (d) further providing an aggregate of expandable particles in the mold at a position opposite to the inner surface of the mold of the separation layer; (e) increasing the temperature to foaming the expandable particles to cause volumetric expansion of the aggregate, (f) pressing the separation layer toward the inner surface of the mold due to the volumetric expansion in (e), while applying the thermosetting resin or its precursor; (g) allowing the thermosetting resin or its precursor to flow through the separating layer, thus causing the presence of the thermosetting resin or its precursor between the separating layer and the mold and between the expanded particles; (g) then curing the thermosetting resin or its precursor to cause solidification; The present invention has been found to be achieved by a method for manufacturing a composite molded product, which is characterized in that the method for manufacturing a composite molded product is characterized by: (h) removing the composite molded product thus obtained from the mold. It was done.

The above-mentioned method of the present invention causes foaming of expandable particles in a mold by raising the temperature, thereby causing volumetric expansion of an aggregate of these particles, and maximally and effectively utilizing the force of this volumetric expansion. It is characterized by the fact that it molds composite molded products.

In other words, the force due to the volume expansion of the particle aggregate is the force that presses the separation layer surrounding the aggregate toward the inner surface of the mold, and the force created by the gaps (voids) between the foamed particles inside the separation layer. It acts directly to form a homogeneous core part.

Further, due to the volumetric expansion of the aggregate of particles, the fluid thermosetting resin or its precursor present in the mold moves through the separation layer and penetrates into the fibrous reinforcement material.
Alternatively, sufficient penetration into the foamed particle aggregate is achieved, and formation of a dense surface layer and gap core is achieved.

A composite molded article having the following characteristics is thus obtained.

(i) A surface layer made of a synthetic resin phase containing a fibrous reinforcing material is formed homogeneously and uniformly over the entire surface of the molded article. There are virtually no foamed particles in this surface layer.

(11) Since there are substantially no foamed particles in the surface layer, the formed surface layer has a dense structure, and the resulting molded product has high physical strength and an excellent appearance. are doing.

(ii1+ Inside the separation layer, a core portion is formed in which the expanded particles and the synthetic resin are packed together without any gaps.

('IV) The surface layer portion and the core portion are formed by flowing the fluid thermosetting resin or its precursor through the separation layer in the sealed mold, so that the surface layer portion and the core portion are form a strongly integrated structure through communication of the same resin.

Next, the molding process in the method of the present invention will be explained in more detail.

The molding process of the present invention is carried out in a virtually closed mold in a virtually closed mold. The mold used in this case may be one that can be substantially sealed during molding and can withstand the molding pressure and temperature, and is usually a hand-lay method.

RTM method (Resin Transfer Moldi)
ng method> or RIM method (Reaction Infe
A mold used in a molding method such as cation molding method) can be used. The material of the mold may be a metal mold, a wooden mold, or a resin mold.

As mentioned above, the advantage of the method of the present invention is that the foaming of the expandable particles causes volume expansion of the aggregate of these particles;
This is achieved by maximally and effectively exerting the force of volumetric expansion by using a separation layer.

Therefore, the use of a separation layer is essential to achieving the objectives of the present invention.

Thus, in the present invention, the separation layer must be able to pass through the fluid thermosetting resin or its precursor during molding, although it does not substantially pass through the expandable particles.

Furthermore, a desired performance of the separation layer is that it be able to withstand the pressure caused by the volume expansion of the particle aggregate. As a result of the volumetric expansion, if the separation layer is torn or holes are formed and the foamed particles pass through the separation layer, it becomes difficult to obtain the desired composite molded product.

To achieve the above performance, the aperture, strength or pore size of the separation layer should be selected based on the size and shape of the expandable particles used.

On the other hand, if a separation layer through which expandable particles can pass is used, the surface layer will contain bubble-containing particles, and as a result, the resulting composite molded product may not have satisfactory strength or Moreover, the appearance becomes inferior and the commercial value decreases.

Specifically, the material for the separation layer is a woven fabric or a knitted fabric.

Examples include non-woven fabrics, webs, paper, wire mesh or porous membranes. Among these, preferred are woven or knitted fabrics, nonwoven fabrics, or webs, and these materials may be synthetic fibers, natural fibers, or inorganic fibers.

It is desired that the separation layer has a structure that substantially prevents the passage of expandable particles. That is, the structure of the separation layer is determined depending on the structure of the mold used for molding and the shape of the intended composite molded product. Generally, it is a bag structure or a planar structure, and a bag-like structure is particularly preferable. The bag structure or planar structure does not need to be entirely a separation layer, and a part thereof may be made of other material that does not allow the resin to pass through, as long as the resin does not pass therethrough and the expandable particles do not pass therethrough. For example, it may be composed of a film, membrane, microporous membrane, or the like.

In the method of the invention, the separation layer can be a structural material integrated with the fibrous reinforcement forming the surface layer. The use of this integral structural material is one of the preferred embodiments of the method of the invention. A typical integrated structural material is a fibrous reinforcement material that has at least a surface portion thereof that functions as the separation layer described above.

The fibrous reinforcing material that forms the surface layer will be explained in detail later, but when a woven fabric, a non-woven fabric, or a web is used as this reinforcing material, the inner surface of the reinforcing material comes into contact with the aggregate of expandable particles. If the reinforcing material does not substantially pass through these particles, the reinforcing material itself has a function as a separating layer and can also serve as a separating layer. When using such a fibrous reinforcing material, there is no need to take the trouble to provide a separate separation layer.

However, the separation layer and the fibrous reinforcing material can be used separately in conjunction with each other, or they can be stacked and used in an integrated manner.

The fibrous reinforcing material forming the surface layer of the composite molded article of the present invention is a fibrous material generally used for reinforcing plastics. The fibrous reinforcement materials include glass fiber, carbon fiber, silicon carbide fiber, metal fiber, and aramid fiber.

Polyarylate fibers, polyolefin fibers, and mixed fibers of two or more of these are preferred. In addition to these fibers,
polyester fiber, polyamide fiber.

Viscose fibers, natural fibers or asbestos can also be used. These fibers may be short fibers, long l/M fibers, or whiskers, but long fibers, particularly continuous fibers, are preferred.

These fibrous reinforcements are generally preferably used as fibrous structures. In other words, this reinforcing material is a woven fabric (plain weave, sudare weave, twill weave, etc.).

Advantageously, it is a knitted fabric, a non-woven fabric, a UD yarn (unidirectional filament) or a web. These forms are not limited to flat ones, but may also be three-dimensional fabrics, three-dimensional knitted fabrics,
Alternatively, it may be something like a braided tube.

Short fibers or whiskers (e.g., silicon carbide whiskers, carbon whiskers, silicon oxide whiskers, etc.) are not suitable for use as reinforcing materials in the surface layer by themselves, but they can be used as some materials for webs and nonwoven fabrics. 52 and ``kiru''.

In the composite molded product that is the object of the present invention, the expanded particles (cell-containing particles) contained in the core are made to exist in the resin and heated during molding of the composite molded product. It is formed by foaming or expanding a material.

As the expandable particles, those that can expand in volume by heating during molding and substantially contain air bubbles in the particles after foaming are used.

The expandable particles used are those whose volume increases by at least about 10%, preferably at least about 20%, when heated. Currently available expandable particles are typically about 20
% to about 70 times. Here, the volume expansion ratio indicates the volume expansion ratio when expandable particles are foamed at molding temperature and normal pressure, and does not necessarily mean the expansion ratio in the composite molded product obtained by molding. It's not something you do.

The size of the expandable particles used is approximately 1μ in average diameter.
m to about 5 mm, preferably about 10 μm to about 1 stone,
is suitable. The polymer forming the expandable particles is one that foams and expands in volume when heated during molding, substantially contains air bubbles, and does not flow due to the heating temperature during molding. - Expandable particles suitable for boat fishing are formed from polyvinylidene chloride copolymer, polystyrene or polystyrene copolymer, polyolefin, polyphenylene oxide copolymer, or a mixture of polyphenylene oxide and polystyrene, etc., in which foam is formed. It contains sexual gas.

In particular, polyvinylidene chloride polymer particles containing low-boiling hydrocarbons that expand in volume as a gas when heated.
This expands several times to several tens of times in the atmosphere). Such particles are manufactured by Norpel's
"Expancel", "Matsumoto Microspheres" by Matsumoto Yushi Pharmaceutical Co., Ltd., and "Eslen Beads" by Sekisui Plastics Co., Ltd. are commercially available, and these can be used as they are.

However, in the production of foamed beads such as polyolefin and polystyrene, it is also possible to use beads that stop foaming midway and allow further foaming when heated (these expand by 10% to several tens of percent when heated later). be.

The aggregate of expandable particles can be used by mixing non-expandable expanded particles that do not substantially expand in volume upon heating or the like. The non-expandable expanded particles must also not substantially pass through the separation layer. When these non-expandable foamed particles are mixed into the gas mixture of the particles and used,
The molding operation becomes easier, and the resulting composite molded product has even better toughness and rigidity.

The non-expandable expanded particles may be either inorganic expanded particles or organic expanded particles, but inorganic expanded particles are generally preferred. As non-expandable inorganic foam particles,
Examples include glass balloons, silica balloons, and glass balloons, which have an average particle size of about 1 μm to about 1 μm.
lTllTl, preferably from about 5 μm to about 0.5 mm. The mixing ratio of the above-mentioned expandable particles and the non-expandable expanded particles is preferably in the range of 10:1 to 1:5, preferably 9:1 to 1:3 by weight.

In the production of the composite molded article of the present invention, the thermosetting resin used for the surface layer and core is often used as a precursor or prepolymer thereof. Any of these resins may be used as long as they exhibit fluidity during molding and are generally used as molding resins. The thermosetting resin or its precursor is one that hardens through a polymerization reaction and/or crosslinking reaction upon molding to give a solid resin, and is generally advantageous to be liquid at room temperature. Precursors shall mean monomers and prepolymers. Examples of thermosetting resins include epoxy resins, polyurethane resins, unsaturated polyester resins, polyvinyl ester resins, polyimide resins, and polyamide resins, and among these, epoxy resins, polyurethane resins, unsaturated polyester resins, and polyvinyl ester resins are preferred. . In some cases, curable polycycloolefin resin (e.g. dicyclopentadiene resin)
can also be used.

Thermosetting resins are commonly used in which a curing agent and/or
The present invention can also be used in combination with promoters and the like, and it is advantageous to use these in combination.

As these thermosetting resins or their precursors, those that are solid at room temperature and exhibit fluidity when heated can also be used, and this may be preferable depending on the case.

In carrying out molding according to the method of the present invention, first, a mold is prepared which has a vent hole for discharging excess resin, etc. to the outside of the mold, and which can substantially seal the inside of the mold during molding. A fibrous reinforcing material is placed along the line, and a separation layer is placed inside the fibrous reinforcing material.

When the separation layer and the fibrous reinforcement are integrated, typically when using a fibrous reinforcement that has the function of a separation layer, the integrated colored material is attached to the inner surface of the mold to function as the separation layer. The surface with is on the inside (center side)! It is preferable to arrange it almost over the entire surface so that the

How to place the separation layer and fibrous reinforcement
The shape and size of the desired composite molded product.

It is determined depending on physical properties and usage.

As mentioned above, the method of the present invention effectively utilizes the volumetric expansion of the expandable particle aggregate during the molding process, so that the volumetric expansion of the particle aggregate causes the separation layer to fit onto the inner surface of the mold, causing the entire mold to expand. The separating layer and the fibrous reinforcement should be placed so that they are pressed against each other.

Also, it goes without saying that the separation layer should be arranged according to the shape of the mold so that air bubble-containing particles do not enter the surface layer of the composite molded article. Even if the separation layer has the ability to substantially prevent expandable particles from passing through, these particles may flow from a part of the periphery during molding due to imperfect placement of the separation layer in the mold. Migration to the surface layer is undesirable and should be avoided.

For example, when manufacturing a rod-shaped or cylindrical molded product, the separation layer and the fibrous reinforcing material may be arranged on the inner surface of the mold in the shape of a hollow cylinder to match the shape of the molded product. . This type of arrangement is schematically illustrated in the attached FIGS. 2 and 3. Furthermore, when manufacturing a flat plate molded product, a separation layer and a fibrous reinforcing material may be placed on the inner surface of the mold so as to be adhered to the entire surface. The separating layer can then be a bag structure. An example of the arrangement of the separating layer and the fibrous reinforcement in the mold when manufacturing this flat plate is shown in FIG.

Further, in the case of a flat plate or a planar molded product with front and back surfaces, the separation layer can be provided only on one side of the inner surface of the mold. On the side of this case, there may be an example in which no separation layer is provided, or an example in which a material such as a film that does not allow even liquid molding resin to pass through is provided in place of the separation layer, but it may be selected depending on the purpose.

For example, in the case of motorcycle cowlings, by installing a printed film on the front side and using a separation layer of glass fiber fabric on the back side, it is possible to simplify the work of painting the front side after molding and applying decals. When molding a flat plate as a structural material that requires high rigidity, separation layers may be provided on both sides, and a fibrous reinforcing material may be placed between each separation layer and the inner surface of the mold.

As described above, after placing the separation layer and the fibrous reinforcement in the mold, the expandable particles are provided in a position opposite the mold surface of the separation layer, i.e., in such a way that the expandable particles can be surrounded by the separation layer. be done. If the separation layer is a bag structure, it is provided inside the bag structure. In particular, when the separation layer is a bag structure, expandable particles and, if necessary, non-expandable expanded particles may be placed inside the bag structure beforehand outside the mold.

Since the aggregate of expandable particles is an aggregate of small particles as described above, it itself has a fluid, and it is also possible to supply it into the mold through the flow pipe after the mold is closed. . However, care must be taken to feed the particle aggregate into the mold through a narrow flow tube in a stable manner. Therefore, it is usually desirable to place the expandable particles and non-expandable expandable particles into the mold before closing the mold.

In the composite molded article that is the object of the present invention, there are several methods for arranging or supplying the thermosetting resin or its precursor (hereinafter collectively referred to as "resin component") into the mold. be.

Broadly speaking, there are the following methods.

(a) A method of mixing or impregnating a resin component (liquid or solid at room temperature) with the separation layer and the fibrous reinforcing material. (b) A method of mixing or impregnating a resin component (liquid or solid at room temperature) with foamable particles. A method of mixing or impregnating the aggregate with the aggregate (c) A method of injecting the resin component (in liquid form) into the mold after closing the mold These (8) methods can be used alone or in combination.
It can be any combination of two or more.

Which of the above (a) to (c) to adopt depends mainly on the type of thermosetting resin, especially whether it is in a liquid or solid state during use.

When the thermosetting resin or its precursor is liquid at room temperature, the above (b) or (c) or a combination thereof with (a) is practical. In this case, a part of the thermosetting resin or its precursor passes from the core through the separation layer and is impregnated into the fibrous reinforcement material as the expandable particles undergo thermal expansion (foaming), and the entire mold is covered with resin. The ingredients will be distributed.

On the other hand, if the thermosetting resin or its precursor is solid at room temperature and can be fluidized at the temperature during molding, the combination of (b) or <4) + II)) above is adopted. . Specifically, one method is to mix a solid powder of a thermosetting resin or its precursor with expandable particles in advance and place the obtained solid phase mixture at a predetermined position in a mold. This is a method of molding.

In this method, the resin component is fluidized by heating the mold, and as the particle aggregate expands in volume, a core is formed and a portion of it flows into the fiber reinforcement material through the separation membrane, forming a surface layer.

Another improvement of this method is to prepare a solid intermediate stopper (intermediate material) that contains expandable particles dispersed in advance outside the mold and has the resin component as a matrix, and then mixes the expandable particles and This method uses the resin as a mixture. This - suspended solid material (e.g. sheet-like)
Place the mixture in the designated position in the mold! When the mold is closed and heated, the matrix resin component in the solid mixture becomes fluidized, a core is formed as the expandable particles expand, and a portion of the resin component passes through the separation membrane and flows into the fiber reinforcement material. A surface layer portion is formed.

In any of the above methods, it is preferable from the viewpoint of workability that the expandable particles or the mixture of expandable particles and the resin component are housed in a bag-like material and then put into a mold and subjected to molding.

As mentioned above, it is preferable to use the separation layer as a bag structure and to put expandable particles or a mixture containing them therein, but if the viscosity of the resin component is low, the resin component may leak out of the bag through the separation layer. In such cases, it is preferable to separately make a bag-like product from a film that can be torn by the internal pressure caused by foaming during molding, and to use the mixture by placing the mixture in the bag-like product made of the film.

Separation layer, fibrous reinforcement present in the mold.

The amount and ratio of resin component 5 expandable particles and other components will vary depending on the properties and use of the intended composite molded product.
It can be changed in various ways. However, what is necessary is that the amounts of each of the above-mentioned components in the mold are such that no voids are present after the expandable particle aggregate expands in volume during molding.

In particular, a separation layer, a fibrous reinforcing material, and a resin component are used so that the composite molded article of the present invention has the following compositions (a) to (e+).

It is desirable to select and use expandable particles.

(a) In the substantial portion of the composite molded article where the core is present, the core is about 30% to about 95% by volume, preferably about 4% by volume.
(b) the specific gravity at the core is about 0.05 to 0.8 g/ml, preferably about 0.1 to 0.6 g/ml; (C) (a) The proportion of the resin component in the core is about 15 to 70% by volume, preferably about 20 to 50% by volume; (a) The proportion of the fibrous reinforcement and separation layer in the surface layer is about 30 to 80% by volume, preferably (e) substantially no foamed particles or lightweight elastic particles are present in the surface layer;

In addition, in the method of the present invention, reinforcing short fibers, whiskers, and other additives can be contained in the core.
In that case, it is preferable to mix it into the expandable particle aggregate.

In the method of the present invention, as described above, each component is placed in a mold,
The temperature inside the mold is increased by heating the mold from the outside, or by the heat generated by curing heat, or both, to first cause the expandable particles to foam (thermal expansion). Causes volumetric expansion of a collection of particles. In the case of using an intermediate integral stopper of a synthetic resin matrix containing these particles dispersed therein, the matrix component is first fluidized by heating or the like to cause volume expansion of the aggregate of these particles.

At this time, it is necessary that at least the resin component maintains fluidity while the volume expansion of the aggregate of these particles occurs. In this way, the separation layer is pressed toward the inner surface of the mold due to the volume expansion of the aggregate of particles, and the resin component flows from the inside (core) to the outside (toward the surface layer of the molded product) through the separation layer. .

In this way, a dense surface layer is formed, a core made of expanded particles and hardened resin is formed, and the surface layer and core are connected and firmly integrated by the same resin via a separation layer, resulting in composite molding. Goods can be obtained.

On the other hand, during molding, the synthetic resin is cured after the excess resin component is collected in a reservoir part of the mold or removed from a vent. Next, the mold is opened, and the formed composite molded article is taken out from the mold according to a conventional method and can be finished as required to form a product.

Furthermore, the obtained composite molded article can be post-cured in an oven.

Furthermore, by placing a film or thin sheet on the innermost surface of the mold during molding, it is also possible to obtain a product with a structure in which the film or sheet is attached to the outside of the surface layer of the composite molded product. In this way, even if a mold with an unpolished inner surface is used, a molded product with a beautiful surface can be obtained, and the film or sheet can be colored.

By adding a pattern or the like, a molded product with excellent design can be obtained.

Thus, according to the present invention, a lightweight and strong composite molded article can be obtained in virtually a single process.

<Effects of the Invention> According to the present invention as described above, it is not necessary to form a foam core in advance, and a lightweight and strong integrally molded sandwich foam core composite molded product can be manufactured with high productivity and at low cost in a process. be able to.

Furthermore, there is also the advantage that thin composite molded products and composite molded products with curved surfaces, which were extremely difficult to manufacture using conventional methods, can be easily manufactured.

The resulting composite molded product is, for example, a canoe paddle.

Masts, rudders, windsurfing stabilization fins (skeg), one-man hydrofoils, skis (boards, balls), hockey sticks, baseball bats, wheels without spokes, bicycle frames, skateboards and other sporting goods, automobiles. Spoilers for cars, buses, trucks, etc.
Vehicle fields such as drive shafts, interior and exterior parts, train doors and structural members, heat exchanger head plates, air conditioner/compressor blades, stirring blades, electrical insulation support beams.

Industrial fields such as fittings, medical equipment fields such as wheelchairs ()\idrims, side panels), X-ray projection tables, prosthetic arms and legs, and propellers and seats.

It can be effectively used in a wide range of applications such as furniture, control surfaces, secondary structural materials, and satellite broadcasting antenna glue lifters.

<Example> Next, the method of the present invention will be explained in more detail with reference to Examples.

In addition, "r parts" in steel means parts by weight unless otherwise specified.

Example 1 This example is an example of manufacturing a flat plate-shaped composite Santoi-Noti foam core molded product by the method of the present invention.

A transparent acrylic resin "mold" (having a vent at the top and a liquid injection port at the bottom) for a flat plate measuring 160 mm vertically, 60 mm horizontally, and 3 mm thick was prepared. Next, vertical 160mm
Prepare 2 sets of 2 pieces of glass fiber fabric with small openings (Nittobo WE-181-100BV) cut to 60 mm horizontally, place each on the inner side of the mold, tighten both sides of the mold together, and then press the mold. Using a syringe from the lower injection port of
[Matsumoto Microsphere-F-] manufactured by Matsumoto Yushi Pharmaceutical ■
30D J) and "Epicor) 828, +/'' Epomate J manufactured by Shell Epoxy Co., Ltd.
Weight ratio of YL11006: 100. A slurry of 20/80 weight ratio of 20/31 mixture) was injected under pressure between two sets of glass fiber fabrics from the bottom of the mold to a height of 50IlIITl. At this time, the upper vent of the mold was left open.

When the entire mold was immersed in a 90°C water bath, the temperature was approx.
After 20 minutes, the volume of the slurry began to expand, and after 20 minutes, a small amount was blown out from the vent, and the expansion ended.

After 50 minutes, the mold was removed from the hot water bath, and after cooling with water, the cured molded product was released from the mold.

A thin epoxy resin skin is formed on both sides of the molded product, and the glass fiber fabric exists just below the skin and is pressed against the inner foam core along the skin, creating a cross-sectional structure as shown in Figure 1. It was confirmed that a composite sandwich core molded product having the following properties was obtained. The specific gravity of this molded product is 0.80
．． Bending strength: 11.7kg Z-en 22 modulus of elasticity: 1335kg/
+tm2.

In FIG. 1, a is a foamed core layer in which the mixed slurry is solidified, b is a separation layer/fiber reinforcing layer each made of two glass fiber fabrics, and C is a cured resin layer constituting the surface.

Separately, ``When Matsumoto Microspheres-F-30D J were foamed alone and suspended in water and filtered through the glass fiber fabric, a small amount of particles were observed to pass through, but most of the particles were I remained with Murakami.

Example 2 This example is an example in which a tabular composite sandwich foam core molded product is manufactured using a combination of expandable particles and inorganic hollow particles.

Using the same mold as in Example 1, the length is 160 mm and the width is 60 mm.
Glass fiber fabric cut into mm (Nittobo WE-181-
100BV) Prepare 2 sets of 2 sheets and fill each set with epoxy resin (Ebiko) 828 J/r.
They were immersed in a mixture of YLHOO6J (weight ratio: 100/31) to allow the resin to penetrate sufficiently, and each was pasted on both sides of the mold. Next, apply Example 1 to the concave side of the mold.
Expandable microparticles (“Matsumoto Microspheres”) used in
A paste made by mixing F-30D J), an inorganic hollow sphere (Silica Balloon JQ-CEL) manufactured by Asahi Glass Co., Ltd., and an epoxy resin with the above composition in a weight ratio of 14:17:69 was scooped out with a spoon and placed on the balloon. Both sides of the mold were tightened together and stood vertically.The paste-like material flowed and descended, filling the mold to 65M from the bottom.

When the upper vent of the mold was opened and the entire mold was immersed in a 90°C water bath, after about 18 minutes, the paste-like substance started to expand in the mold, and at 25 minutes, a small amount of liquid resin was released from the vent. A speech bubble appears and the expansion is complete.

After 50 minutes, the mold was taken out, and after cooling with water, the molded product was released from the mold to obtain the desired molded product. This thing has a specific gravity of 0.72. Bending strength 10.1kg/ITW112. Elastic modulus 887kg/r
It was 111TI2.

Example 3 This example shows an example in which a round bar whose core material is a foamed core whose outer periphery is reinforced with carbon fiber blades is manufactured by the method of the present invention.

FIGS. 2 and 3 are diagrams for explaining this embodiment, and FIG. 2 is a cross-sectional view showing the metal mold 1 for a round bar in an open state. Here, the outer diameter of the carbon fiber is 20ITIITl with a polyester nonwoven fabric 2 with an opening of 10 μm arranged on the inner lining.
The blade 3 was installed and the mold 1 was closed. Next, as shown in the vertical cross-sectional view of FIG. 2, Example 1 containing a low-boiling hydrocarbon that can be foamed and microcapsulated by applying heat of 80° C. or higher from the bottom of the vertical mold is heated with a pump. Expandable fine particles 4 and 70 of vinylidene chloride copolymer similar to
A paste mixture of epoxy resin 5, which begins to harden at ~80°C, was pushed into the inside of the plate until it reached about 1/3 of the total length (height).Then, the mold was heated to 80°C. C
After a while, gas with bubbles started coming out from the vent 6 at the top of the mold, and soon the epoxy resin started to blow out in liquid form.

After 2 hours, the mold was cooled to form a composite molded article.

The thus obtained molded product was opened and taken out from the mold. Example 4 This example is an example in which a round bar is manufactured using both expandable resin particles and inorganic hollow particles.

FIG. 4 is a diagram illustrating another example using the same mold for a round bar as in Example 2.3. In this example, instead of the paste mixture of expandable resin particles and epoxy resin in Example 3, "Shirasu balloons" with a particle size of 30 μm and a specific gravity of 0.1 were used.
and vinylidene chloride copolymer particles (particle size: 20 μm, specific gravity after foaming: 0.02) containing a low-boiling hydrocarbon that foams and microcapsulates when heated to 80°C or more in a weight ratio of 10:1. After thoroughly mixing the mixture in a uniform ratio, the upper part 11 of the mold was opened and the mixture was poured into the mold until it was full.

After charging, the opening was closed and a vent 13 was provided inside with a nonwoven fabric 12 to prevent the foamed particles from flying out of the mold. After that, inject the epoxy resin from the resin injection port 14 at the bottom.

When the temperature of the mold was raised to 80° C., gas with bubbles began to come out from the vent 13 at the top of the mold after a while, and soon the epoxy resin that had passed through the nonwoven fabric 12 began to blow out in liquid form. After 2 hours, the mold was cooled and a round bar-shaped composite molded product having a foam core was taken out from the mold.

Example 5 This example is an example in which a flat composite sandwich foam core molded article is manufactured by the method of the present invention using particles of a polyimide precursor as the expandable resin fine particles.

A stainless steel mold for a flat plate with a length of 150 W+, a width of 110 nm, and a thickness of 10 mm (having a vent at the top and a resin liquid injection port at the bottom) was prepared. Next, two pieces of glass fiber fabric with small openings (Nittobo WE-181-100B) cut into pieces of length 150 x width 110 mm were prepared and placed on the inner surface of the mold.

As foamable resin particles, methanol and isopropanol ring-opened product of benzophenone tetracarboxylic acid anhydride and mixed diamine of 4,4'-diaminodiphenylmethane and hexamethylene diamine were mixed in isopropanol and a surfactant was added. In addition, remove excess alcohol under reduced pressure to prepare solidified and pulverized polyimide precursor particles.

The weight ratio of the polyimide precursor particles and the epoxy resin (Epicoat)/' [Rikazid MT-500J (manufactured by Shin Nippon Rika, catalyst triethanolamine 1% by weight) is 40.
．． 140 g of the '60 mixture was placed between two sets of glass fiber fabrics in the mold.

When the mold was closed except for the vent and the entire mold was immersed in an oil bath at 160°C, the polyimide precursor powder expanded and the liquid leaked out from the vent after about 10 minutes. When 5 g came out, the vent was closed and the solution was left standing at the same temperature for 10 hours.

After cooling, the cured foam core molded product was released from the mold using a mold, and the molded product had the shape exactly as the mold, and the epoxy resin formed a skin on the glass fibers on the outer surface.

A mixed solution was prepared by mixing the polyimide precursor powder after foaming with "Epicote" and was filtered using the glass fiber fabric used in this example as a furnace cloth, but the furnace solution was mostly "Epicote" liquid. there were.

Example 6 This example is an example of manufacturing a flat sandwich foam core composite molded product using ABS particle powder as the expandable resin fine particles.

Two sets of polyester nonwoven fabric and carbon fiber fabric with apertures of 10 μm were cut into lengths of 150 mm and width of 110 mm. Then, the non-woven fabrics and textiles are coated with epoxy resin using "Epicoat"/[Rikasi-Ndo MT-500].
J, immersed in catalytic triethanolamine (2% by weight);
I drained the liquid.

The nonwoven fabric and woven fabric were placed in the mold used in Example 4 in the following order: carbon fiber fabric/nonwoven fabric/nonwoven fabric/carbon fiber fabric. ABS resin (containing blowing agent p, p'-oxybis<benzenesulfonyl hydrazide)) was used as the foamable resin, and particles of the ABS resin, the epoxy resin, and inorganic hollow spheres (Silica Balloon J Q-CEC manufactured by Asahi Glass Co., Ltd.) were used.
) was mixed in a weight ratio of 20:20:60 and 140g of a paste was inserted between the nonwoven fabrics in the mold.

When the entire mold is immersed in an oil bath at 150°C, the temperature is approximately 8
After a few minutes, liquid came out from the vent, so the vent was closed and the mixture was heated for 8 hours.

After cooling, the molded product was taken out of the mold, and a molded product was obtained in which both surfaces were made of carbon fiber fabric and polyester nonwoven fabric integrated with epoxy resin. The internal core cross section of this molded article was a brown homogeneous foamed resin.

Example 7 This example is an example in which a flat composite sandwich foam core molded article is manufactured using expanded polypropylene particles as expandable particles.

(Production of foamed polypropylene particles) Polypropylene and a foaming agent such as freon are mixed under pressure and discharged under normal pressure. The obtained pre-expanded particles are aged at normal pressure, then placed in a pressure vessel and heated at 160°C. 6kg at external temperature
Compression was carried out at a pressure of /ci-G for 1 hour. After returning to room temperature, the pressure was returned to normal pressure to obtain expanded polypropylene particles. The expanded particles have a particle size of 1 to 2 mm, and immediately expand in volume by 20% when heated to 100°C. Even when this is returned to room temperature, no volumetric contraction is observed.

(Manufacture of composite molded product) A stainless steel mold for a flat plate with a length of 150 mm, a width of 110 nm, and a thickness of 10 mm (having a vent at the top and a resin liquid injection port at the bottom) was prepared, and then a mold of 150 mm in length was prepared.

Two pieces of glass fiber fabric with small openings cut to 110 mm in width were prepared, and one was placed on both inner surfaces of the mold. Between this glass fiber fabric, the polypropylene foam particles 100c
c and glass balloon (Asahi Glass 1M-cel,
Diameter 60-80um > 100cc and vinyl ester resin manufactured by Dainippon Ink, UE-5101L, Catalyst Parriki Dox 16 (manufactured by Kako Nouri, IPHR added)
20g of the mixture was mixed well.

The mold was closed by removing the vent, and then the vinyl ester resin solution was injected through the lower liquid injection port until it overflowed from the vent. The entire mold was then immersed in an oil bath at 100°C, and after about 5 minutes, resin liquid was observed to flow out from the vent.

After cooling at the same temperature for 30 minutes, the solidified molded product was released from the mold.

The molded product had the same shape as the mold, and was a sandwich core composite molded product with a foam core layer in the center and a vinyl ester resin outer skin formed on glass fibers on the surface.

This molded product had a density of 0.33 gjcr&, which was lightweight and resistant to bending.

Example 8 This example is an example of manufacturing a flat composite sandwich foam core molded product using polyethylene foam particles.

(Manufacture of polyethylene foam particles) Polyethylene, a crosslinking agent, and a foaming agent such as Freon are mixed under pressure, and the resulting pre-expanded particles are aged under normal pressure and then placed in a pressure vessel again. It was compressed for 1 hour at an external temperature of 120°C and a pressure of 7 kg/'-.G. After returning to room temperature, the pressure was returned to normal pressure to obtain expanded polyethylene particles. The expanded particles have a particle size of 3 to 4 mm, and when heated to 100° C., the expanded particles immediately expand in volume by 20%. Even when this is returned to room temperature, no volumetric contraction is observed.

(Manufacture of composite molded product) Prepare a stainless steel mold for a flat plate (with a vent at the top and a liquid injection port at the bottom) with a length of 150 mm, a width of 110 mm, and a thickness of 10 mm.
Two pieces of glass fiber fabric cut to 0 m were prepared and placed on both inner surfaces of the mold. Separately, 100 cc of the polyethylene foam particles and a glass balloon (manufactured by Asahi Glass Co., Ltd., M-e
el, diameter 60-80 μm > 100 cc unsaturated polyester resin (“Yupica 4007J” manufactured by Nippon Upica).

Mix well with 20g of Catalyst Parryoku Dox 16 (1PHR added) and place it in a bag made of non-woven fabric (openings of 10 μm or less) whose main component is polyethylene terephthalate fiber (size: 150nwn vertically, 110nwn horizontally), and place it inside the mold. Placed between glass fibers.

Remove the vent and close the mold, then inject the unsaturated polyester resin liquid from the lower liquid injection port until it overflows from the upper vent. The entire mold was then immersed in an oil bath at 100°C, and after about 5 minutes, resin liquid was observed to flow out from the vent. After cooling at the same temperature for 30 minutes, the cured molded product was released from the mold.

This molded product had the shape exactly as the mold, and the surface was a sandwich core molded product with an outer skin made of unsaturated polyester resin on glass fibers. The density of this molded product is 38g.
It was light in weight and resistant to bending.

Example 9 This example is an example of manufacturing a composite molded article in which the outer side of the surface layer (fiber-reinforced resin layer) of the composite molded article is formed with a polyester film using the method of the present invention.

A stainless steel mold for a flat plate measuring 150 mm in length, 110 mm in width, and 10R11 in thickness (having a vent at the top and a liquid injection port at the bottom) was prepared. Next, a glass fiber fabric with small openings (Nittobo WE-181-100B
V) 2 sets of 2 sheets, and polyethylene terephthalate films of the same size that have been treated with corona discharge on one side (the corona discharge treated side should be on the inside side), and the inside (closer to the core)
Do not install glass fiber fabric in the area.

Also, install two layers of the above glass fiber fabric in the upper vent of the mold. After tightening both sides of the mold, use a syringe from the injection port at the bottom of the mold,
Heat-expandable microcapsules “Matsumoto Microspheres-F-30-DJ” and epoxy resin “Epicote”
/ “Ebome)” lo.

/31 mixture 'S) in a weight ratio of 20/80 was injected under pressure into the space between two sets of layers consisting of polyethylene terephthalate film and glass fiber fabric from the bottom of the mold. The injection amount was approximately 100g, and at this time,
The upper vent of the mold was left open.

Next, when the entire mold was immersed in an oil bath at 95° C., volumetric expansion started after about 10 minutes and a liquid mainly consisting of epoxy resin flowed out from the vent hole. Outflow amount is approximately 2
It was 0g. After the spill, I closed the vent.

After 1 hour, the mold was taken out of the oil bath, and after cooling with water, the mold was opened to release the cured molded product.

The molded product was a composite molded product in the form of a sandwich core, with a foam core in the center, a polyethylene terephthalate film skin on the outside, and a glass fiber-reinforced resin reservoir formed along the skin just inside the skin.

The overall molded product is the same size (inner dimension) as the mold,
Even if the stainless steel inner surface of the mold was not particularly polished, a molded product with a film on the surface and a smooth surface was obtained.

Example 10 This example is an example in which a composite molded article similar to Example 1 was manufactured in which the outer surface of the molded article was made of a polyimide film.

Using the same two-part mold as in Example 9, the height was 150.
Two pieces of glass fiber fabric (Nittobo WE-181-100BV) cut in the order of myn and width 110 and a polyimide film (25 μm, one side corona discharge treated) were prepared.

On one side of the mold, place a glass fiber fabric and a polyester nonwoven fabric with small openings on top of the polyimide film (discharge-treated side facing inside), and then add epoxy resin (Epicoat/Rikagid MT-500J).
(manufactured by Shin Nihon Rika) 100/70 mixture (containing 2 wt% of catalyst triethanolamine) and a mixture of expandable microcapsules of acrylonitrile polymer (Matsumoto Microspheres-F-80SDJ) (weight ratio 70/30)
An operation was performed in which 90 g was placed.

Next, the other side of the mold in which the polyimide film, glass fiber woven fabric, and nonwoven fabric were laminated was brought together and tightened in the same manner.

The lower inlet is closed in advance, and the upper vent is equipped with two layers of glass fiber fabric! did. 160'C
When the entire mold was immersed in an oil bath of
After a few minutes, liquid began to flow out from the vent, and after approximately 20 g of fluid flowed out, the vent was closed and the mixture was heated at 160'C for 10 hours. After cooling, do not release the cured molded product.

The molded product has the shape exactly as the mold, and is an integrated composite molded product with a foam core in the center, a reddish-brown polyamide film on the outer skin, and a glass fiber woven reinforced resin layer firmly attached to it. Met.

When I cut this molded product and examined its interior, I found that the interior was brown, homogeneous, and had no whiskers.

Example 11 This example uses an unsaturated polyester resin as the thermosetting resin.

The mold used in Example 9 was prepared.

Two pieces of glass fiber fabric with small openings similar to those in Example 9 and two pieces of polyethylene terephthalate film (one side corona discharge treated) were prepared and placed in a mold in the same manner as in Example 1.

In addition, the above glass fiber fabric was attached to the upper vent of the mold.
Keep them stacked up.

Inside the glass fiber fabric in the mold, an unsaturated polyester resin solution (50 wt% diluted with styrene, containing 1 wt% of initiator dicumyl peroxide) and a thermally foamable microcapsule ("Matsumoto Microfair F-30D J") were added in a weight ratio. 140g of the 65/35 mixture was added.Then, only the vent provided at the top of the mold was opened, the rest was closed, and the entire mold was immersed in an oil bath at 110°C.After about 5 minutes, the liquid was released from the vent. When about 20 g of water began to come out, the vent was closed and heating was continued for 2 hours.

After heating, the molded product was released from the mold.

The overall molded product had the same size as the mold, and a composite molded product with a smooth film surface was obtained.

Moreover, the cross section of the molded article is homogeneous, and the glass fiber reinforced resin layer is pressed against the film and is present on the outer surface.

Example 12 This example is an example in which a flat composite sandwich foam core molded article is manufactured by the method of the present invention using a urethane foam sheet as a separation layer.

A stainless steel mold for flat plate molding with a length of 160 mm, a width of 60 strokes, and a thickness of 10 mm (having a vent at the top) was prepared. Next, as a reinforcing material, unidirectionally arranged glass fibers were made with a length of 160 mm and a width of 60 mm, and a length of 60 nm and a width of 160 mm.
Cut two pieces into mm pieces and stack one piece on top of the other so that the glass fiber arrangement is perpendicular to each other, and the length is 420 mm.
, a felt made of glass fiber cut into strips with a width of 10 ynyn and a thickness of 3ITw11 was prepared. Separately, a stretchable sheet-like urethane foam with continuous holes is used as a separate layer, measuring 150 mm vertically, 55 mm horizontally, and 7 mm thick.
Inside the bag-shaped bag are polystyrene expandable particles ("Eslen Beads JHE type" manufactured by Tanemizu Kaseihin Co., Ltd.) and epoxy resin ("Epicoat 828" manufactured by Yuka Shell Epoxy Co., Ltd.).
Prepare a bag containing 20g of a mixture of J/r Epomate YLOO6Jloo/31 mixture at a weight ratio of 50150 and sealing the top with adhesive tape.

Place a set of reinforcing materials on the inner surface of the cavity side of the mold, surround it with felt, and apply epoxy resin of the above composition to the installed reinforcing materials using a brush. The above-mentioned bag was placed on top of this, and epoxy resin was applied thereon with a brush, and then a set of reinforcing materials was placed on top of the bag, and the mold was closed.

The mold is set up and the vent is opened to the atmosphere at 110°.
When the entire mold was immersed in the oil bath C, a small amount of liquid began to blow out from the vent after about 5 minutes. 100
After a few minutes, the mold was removed, cooled with water, and then opened to release the molded product.

The molded product has a thin epoxy resin skin formed on both sides, and the glass fiber reinforcement and sheet-like urethane foam are present just below the skin and pressed against the inner porous foam core along the skin. It was confirmed that a composite sandwich core molded product having a cross-sectional structure similar to that shown in the figure was obtained.

Example 13 This example is an example of manufacturing an L-shaped composite sandwich foam core molded product by the method of the present invention.

A stainless steel mold (with a vent at the top) was prepared so that a molded product could be obtained by bending a flat plate measuring 200 mm vertically, 60 mm horizontally, and 10 mm thick into an L shape at a position of 150 mm vertically. .

Next, a glass fiber fabric cut into 450 mm in length and 60 mm in width was prepared as a reinforcing material. Separately, stretchable spandex fiber fabric (opening 5μ) is used as a separate layer.
m), press the part that corresponds to the bent part of the L-shaped corner with an iron to eliminate the opening part, and then fuse the four circumferences and the neighboring parts with an iron to make a length of 170 + nm and a width of 50 mm.
It was made into a bag with a thickness of 8M.

Average particle size of 10 to 20 μm that expands when heat is applied to it.
Hollow particles of polyacrylonitrile polymer (Matsumoto Microsphere-F80DJ, manufactured by Matsumoto Yushi Pharmaceutical Co., Ltd.) and glass/mild fiber, manufactured by Nittobo Co., Ltd., with an average fiber length of 1
00 to 300 μm> and epoxy resin "Epicoat" manufactured by Shell Epoxy Co., Ltd./'"Epomate J 100"
A bag was prepared in which 70 g of a mixture of 40:45:15 (mixture 31/31) was placed and the upper part of the bag was sealed with adhesive tape.

The reinforcing material is placed on the inner surface of the mold cavity side so that it forms a surface that covers the entire molded product when it is completed. The above-mentioned bag was placed on top of this, and the bag was further wrapped in reinforcing material and the mold was closed.

Stand the mold upright and open the vent to the atmosphere at 160°.
When the entire mold was immersed in the oil bath C, a small amount of liquid began to blow out from the vent after about 5 minutes. After 60 minutes, take out the mold, cool it with water, open the mold and release the molded product to obtain the desired molded product. Although part of the separation layer did not allow the liquid resin to pass through, a surface layer made of the liquid resin was formed over the entire surface of the molded product.

Example 16 This example is a method in which an intermediate material is first manufactured and then used for molding in carrying out the method of the present invention.

I obtained Matsumoto Microspheres F-80SDJ, thermally expandable foam beads manufactured by Matsumoto Yushi ■.These foam beads begin to expand at temperatures above 140°C and have the property of expanding up to about 70 times. It is abbreviated as -803D.

On the other hand, the epoxy resin and curing agent made by Shell, i.e.
70 parts of Epicote 100IJ (this resin itself is solid at room temperature and exhibits thermoplastic behavior), 30 parts of Epicote 348, 30 parts of phthalic anhydride, 1 part of Evomate YLH185J, melted at 80°C. This was referred to as resin composition A.

Mix 100 parts of the above F-80SD and 100 parts of resin composition A at 80°C. This was poured into a mold preheated to 80°C and immediately cooled. Thereafter, the mold was opened to obtain a thin plate with a thickness of about 31 mTl. The obtained thin plate is referred to as intermediate material B.

A mold was made with a Teflon frame sandwiched between two aluminum plates, and nozzles were installed at the top and bottom ends. Prepare Nittobo glass fiber cloth WF-181-100BV,
The above mold-cup glass cloth and 10 strips of glass cloth whose length matches the mold and whose width is sized to cover the nozzle.
A sheet was made, and using a large glass cloth, it was placed in a mold in the order of glass cloth/intermediate material B/glass cloth. Fill the position covering the nozzle, that is, the upper and lower ends of the mold, with small layers of glass cloth to prevent F-80SDi swelling particles from entering this area. Make a vacuum inside the mold by drawing air using both nozzles. Next, the mold was placed in a silicone oil bath at 145°C and heated. Allow a small amount of liquefied resin and gas to overflow from the nozzle, then close the nozzle one after another. 1
After a period of time, the mold was removed from the silicone oil bath, cooled, and the molded article was taken out from the mold. Thus, the surface is a glass fiber reinforced epoxy resin and the inner layer is a hardened epoxy resin 71~
A good lightweight sandwich structure was obtained consisting of a foam in which non-foaming F-80SD was dispersed in the matrix. In the obtained molded product, the foamed F-80SD was evenly distributed except for the area where the small glass cloth was inserted, and the density was 0.54/am3.

Example 15 In this example, as in Example 14, an intermediate material is manufactured and then molded to create a snake-shaped model.

F-80SD, resin composition A,
Intermediate material B was prepared.

Maximum width 120 mm, fl, large length 350 mm,
Prepare a set of two molds to make a serpentine model with a thickness of 14 mm.

Nozzles were provided at the top and bottom of the mold. Prepare 4 sheets of glass cloth and 2 sheets of carbon cloth that match this mold.

The glass cloth is a glass fiber cloth WF-180-100BV made by Nittobo Co., Ltd. with a small opening, and the carbon cloth is a carbon fiber fabric C06304 made by Toshi Co., Ltd. On the other hand, the polyester nonwoven fabric “Unicell BT-04” manufactured by Unicell ■
04J was made into a bag according to the mold.

Intermediate material B was cut into a slightly smaller size 1" to roughly match the inner shape of the mold, placed in the above-mentioned "Unicell" bag, sandwiched between glass cloth and carbon cloth, and placed in the mold.

The inside of the mold was evacuated and after fS, the mold was placed in a hot bath of silicone oil at 145°C. Make sure that liquefied resin and gas come out of each nozzle before closing the nozzles.

After holding for 1 hour, remove the mold from the hot bath, cool and remove the molded product. A good snake-shaped model with a specific gravity of 0.8 was obtained.

Example 16 This example is an example of using polypropylene foam particles in a method via an intermediate material.

Prepare a mold with a cross section of 20 mm x 20 mm and a length of 500 mm, with nozzles on both ends.

Polypropylene and a blowing agent such as freon are mixed under pressure and discharged under normal pressure, and the obtained pre-expanded particles are aged at normal pressure, then put into a pressure vessel and packed at an external temperature of 160°C to produce 6 kg.
/aa pressure for 1 hour. After returning to room temperature, the pressure was returned to normal pressure to obtain expanded polypropylene particles. These foamed particles have a particle size of 1 to 2 pus, and have the property that when heated to 100° C., the volume immediately expands by 20%, but no volume contraction is observed even when the foamed particles are returned to room temperature.

A thin plate was made in the same manner from these polypropylene particles and the same resin composition A as in Example 14, and this was cut into a rod shape. This is called intermediate material C.

A tube with a circumference of 80 mm was made using a polyester nonwoven fabric (Unicell BT-0404J) and the above intermediate material C was placed therein.

A cylinder made from "Unicell" containing this intermediate material C was covered with two layers of carbon fiber braid and one layer of glass fiber braid. The blade used was a carbon fiber blade made of "Trading Card".
J T-3964, T-3484, the glass fiber blade is "Adkins &Pierce"#9273, each blade is T-3484, #9273, T-39
Stacked in the order of 64.

This was placed in the mold described above, and the mold was closed. The mold was placed horizontally, and then the pressure was reduced using a vacuum pump to create a nearly vacuum. Then, in substantially the same manner as in Examples 14 and 15, the resin was cured by placing it in a hot bath at 110° C. while removing excess resin and gas. The mold was removed from the hot bath after 1 hour, cooled, and the molded article was removed from the mold.

In this way, a lightweight square timber was obtained whose surface was made of carbon/glass fiber reinforced epoxy resin and whose inner layer was a foam of epoxy resin and polypropylene. The specific gravity of the square timber including the FRP layer on the surface was 9.50 g/cm3.

Example 17 This example shows that a suitable separation membrane can be used by changing the foamed beads used, and also shows an example in which a woven fabric is used as the separation membrane.

Thermal expandable foam beads "Matsumoto Microsphere-F-50D J" manufactured by Matsumoto Yushi Seiyaku ■, Nopel Co., Ltd. (No.
bel Industries)'s "Expancel 4"
61" was prepared. Both are fine particles that expand at 100 to 110°C'''C.Hereafter, they will be referred to as F-50D and E, respectively.
It is abbreviated as xpancel-461.

100% of Shell's epoxy resin "Epicote 807"
31 parts of a curing agent [Epicure YLHOO6J] were mixed. This is called resin A.

100 parts of Resin A and 100 parts of F-50D were mixed.

This mixture will be referred to as mixture B. On the other hand, 100 parts of Resin A and 100 parts of Expancel-461 were mixed. This mixture is referred to as Mixed ZC.

A mold was made with a Teflon frame sandwiched between two aluminum plates. Nozzles were provided at the top and bottom ends. Non-woven fabrics "Unicel BTO404J and nylon taffeta fabric Shirasaki Kogyo 5D2510) were prepared. Bags were made using these to fit the molds. Mixture B and Mixture C were placed in these bags, respectively. Unicel/Mixture B intermediate material (1), nylon taffeta/mixture B as intermediate material (2),
Unicell/mixture C is used as an intermediate material (3), and nylon taffeta/mixture C is used as an intermediate material (4).

Glass fiber cloth MS253E-1040-2NT-10FS manufactured by Asahi Fiberglass and having a relatively large opening was prepared. Mold - Make 2 pieces of cup glass cloth and 10 strips of glass cloth whose length matches the mold and whose width is sized to cover the nozzle, then use the large glass cloth to make glass cloth/intermediate material +1 ) (2! ((3) or (4)/Put it into a mold with a glass cloth base.

The positions that covered the nozzle, that is, the top and bottom ends, were filled with small layers of glass cloth.

Create a vacuum inside the mold using both nozzles.

The mold was then placed in a 110°C silicone oil bath and heated. Apply a small amount of resin and gas to the nozzle! was allowed to overflow, and the nozzles were shut down at about the same time. After 1 hour, remove the mold from the hot bath, cool, and remove the mold from the mold. By using intermediate materials (1), (2), and (4), a good sand german material was obtained in which the surface was made of glass fiber-reinforced epoxy resin and the inner layer was made of epoxy resin with foamed beads dispersed therein. When F-50D was used, foamed beads appeared on the surface and the appearance was poor.
61, the unicell does not function as a separation layer;
It shows what nylon taffeta can do.

The specific gravity of the one using intermediate material (1) is 0.63. Bending test strength: 9.7 kg/lngn2. Elastic modulus 883 kg
/ (Foundation) 2, the one using (2) has a specific gravity of 0.74. Strength of bending test: 9.6 kg/mm2. Elastic modulus 886 ki
The specific gravity of the one using r/mm2 (4) is 0.80. Bending test strength 12.5kg/mm2 Modulus of elasticity 886k
g/mm2.

Example 18 This example is an example of making a fin (skeg) for a sailing board.

A mold for molding the fins was made in advance from resin. A drain was provided at both ends of this mold. The mold was made into two parts. Maximum width 120mm, maximum length 350mm, maximum thickness 14m
It is m. Nozzles were installed at the top and bottom.

100% of Shell's epoxy resin "Epicote 807"
31 parts of the curing agent "Ebomate" were mixed.

This is called resin A.

Microsphere F-30D J manufactured by Matsumoto Yushi Pharmaceutical
and 10 parts of Inorganic Balloon 28 manufactured by Asahi Glass were mixed. This and about 1/3 of Resin A were mixed. The obtained mixture is referred to as mixture B.

One piece of plain weave mixed fabric of carbon fiber cloth T-400 manufactured by Toshi and large-scale aramid fiber "Technora", two pieces of glass fiber cloth WF-181-100BV manufactured by Nittobo, and polyester non-woven fabric manufactured by Unicell. [Unicel T-4
Cut out one piece of 0404 according to the inner shape of the mold and stack it. The two sets were connected and the mixed 'SB was put inside. This was placed in a mold for molding, and after the mold was tightened, the remaining resin A was injected into the fiber layer inside the mold while expelling air. Injected until overflow.

Close one vent (liquid drain) and open vent 1.
-<Liquid drained) side up, placed in a hot bath at 80°C and heated. After 1 hour, the molded product was removed from the hot bath, cooled, and removed from the mold. The surface is epoxy resin, the explant is carbon fiber/
A beautiful, fashionable, lightweight, and good-characteristic fin made of aramid fiber/glass fiber-reinforced epoxy resin and a core made of inorganic beads and microsphere foam was obtained.

Example 1 A mold with a cross section of 20 nm x 20 mm and a length of 5 QOmm was made, and nozzles were provided at both ends. Mix 100 parts of the epoxy resin "Epicote 807" manufactured by Shell and 31 parts of the curing agent [Evomate YLHOO6J]. This is called resin A.

Commercially available foam beads "Microsphere F-30D J" manufactured by Matsumoto Yushi Seiyaku were obtained. 20 parts of these beads were mixed with 10 parts of [Inorganic Balloon! 1!-28J manufactured by Asahi Glass Co., Ltd.].

``Make a tube with a circumference of 80 mm using Unicell BTO404J and fill it with 1/2 of the mixed beads above.The Unicell tube filled with beads was covered with two layers of carbon fiber braid and one layer of glass fiber braid. The blades used were "Trading Card T-3964J" and "Trading Card T-3484J, and the glass fiber blade was [Adkins and Pierce 192
It is 734. These are T-3484, #9273, T
Stacked in the order of -3964.

Place this in the mold mentioned above, push in the rest of the mixed beads, and close the "unicell" cylinder and mold.

The mold was leveled, and then the upper nozzle was used to reduce the pressure with a vacuum pump until it was almost a vacuum, and then liquid resin A was injected from the lower nozzle, making sure that the resin overflowed from the upper nozzle. I stopped the injection.

Next, it was placed in a 70°C hot bath and cured while removing the resin. After 1 hour, remove from the hot bath, cool and remove the mold from the mold. In this way, a lightweight square material was obtained whose surface was made of carbon/glass fiber reinforced epoxy resin and whose inner layer was a foam made of epoxy resin and inorganic hollow bodies/microspheres. The specific gravity including the epidermis was 0.62 kg/alN.

Examples 20 to 22 and Comparative Examples 1 to 6 This example is an integrally molded product with a resin in which reinforcing fibers are omnipresent just below the surface and foamed particles are unevenly distributed in the other parts, and foamed particles are formed directly under the surface of the resin. Differences between a molded product in which reinforcing fibers and resin are unevenly distributed in the center of the hollow, and a molded product in which reinforcing fibers are unevenly distributed just below the surface, but foam particles are also present therein. The purpose of this study is to compare and examine the differences between the two cases in which the reinforcing fibers are eliminated.

100% of Shell's epoxy resin "Epicote 807"
33 parts of a curing agent "Evomate YLHOO6J" were mixed. This is referred to as resin A.

"Microsphere F-50D J2 manufactured by Matsumoto Yushi Pharmaceutical
Mix 0 parts with 40 parts of the above resin A. This is called mixture B.

A two-piece mold was made in advance, consisting of two flat aluminum plates and a Teflon spacer, and drains were provided at both ends. The thickness of the spacer was 3 mm.

Asahi Fiberglass MS253E-1040-2
8T-10FS (flat ¥a) was cut to fit the mold.

This was cut into the same size and layered with a Unicell nonwoven fabric [Unicell BTO404J]. Resin A was applied thinly to one of the two molds, and the glass cloth/nonwoven fabric described above was placed in the mold with the glass cloth outside. Eight pieces of the above-mentioned glass cloth were cut into a width of 20 own and placed in the upper and lower nozzle positions, and Mixture B was added thereto. Resin A is applied to the other mold, and a sheet having the same structure is similarly pasted with the glass cloth layer removed to form mixture B.
It was placed upside down on the side of the mold that had been placed. Close the mold, remove excess resin and air, and place in a 110°C hot bath.
Heated. It was cured while expelling excess resin and air. After 1 hour, the molded product was taken out from the hot bath, cooled, and taken out from the mold. The obtained sample had a thickness of 3 mm,
Glass cloth is placed just below the surface with a density of 0.76 g/-.
This is an epoxy resin integrally molded product with foamed particles present in other parts. This molded product is referred to as sample (a).

Similarly, an integrally molded product was obtained in the same manner except for the nonwoven fabric "UNICEL BTO404J. Foamed particles were observed on the surface of the molded product. This is referred to as sample (b).

Asahi fiberglass glass cloth MS253E-10
Instead of 40-2NT-10FS, use Nittobo's glass fiber cloth WF-181-100BV with a small opening.
(Satin weave) was cut to fit the mold. A sheet of nonwoven fabric "Unicell BTO404" cut in the same manner was overlapped to obtain a molded product in the same manner as sample fa). This will be referred to as sample (C). This was a molded product with an appearance similar to that of sample (a).

In the same way as sample (C) was molded, except that ``Obtain the sample without using Unicell BTO404J.''

This will be referred to as sample (d). This molded product also had the same appearance as the sample (al).

Asahi fiberglass glass cloth MS253E-10
40-2NT-10FS was cut to fit the mold. “I cut Unicell BTO404J to the same size and layered it on top of this.

Mixture B was applied to one side of the mold, this glass cloth and Unicel BTO404J were placed on top of this, and mixture B was placed on top of this. Mixture B was applied in the same way to the other mold, and It was placed upside down on the mold.The two were placed together, the mold was closed, and the mixture was heated to 110°C while expelling excess resin and air.
I put it in a hot bath and heated it.

After 1 hour, the molded product was taken out from the hot bath, cooled, and taken out from the mold. A lightweight molded plate was obtained whose surface was made of epoxy resin/expanded particles and whose inside was made of glass fiber-reinforced epoxy resin. This is referred to as sample (e).

Furthermore, except for the above “unicell”, sample (e)
I made a sample in the same way. This is a sample (f
).

Asahi fiberglass glass cloth M8253E-10
A composite molded product was produced in the same manner as sample (e) except that Nittobo's glass fiber cloth WF-181-100BV was used instead of 40-2NT-10FS. This is called the sasiple (g).

Sample (h) is a similar composite molded product made in the same manner as N (except for Unicell B'TO40b).

Next, [UNICELL BTO404J was cut out to fit the mold. This was then placed in one of the two divided molds coated with resin A. Mixture %B was placed on top of this. Resin A was similarly applied to the other mold, and Unicell BT0404 J was pasted on it, and the mold was placed upside down.The mold was closed, and the excess resin and air were expelled, then placed in a 110°C hot bath and heated. I did.1
After that time, remove from the hot bath, cool and remove the mold from the mold. A lightweight molded plate was obtained whose surface was made of Unicell/epoxy resin and whose inside was made of foamed balloon/epoxy resin. The obtained molded product is referred to as sample +i).

A bending test was performed on each of the obtained samples using an Instron testing machine. The results are shown in the table below.

In these Examples and Comparative Examples, glass fiber cloth WF-181-100BV manufactured by Nittobo with a small opening was used.
In the case of <satin weave>, the separation layer specified in the present invention also serves as reinforcing fibers, and the reinforcing fibers serve as the separation layer and prevent the foamed particles from migrating to the surface layer. . Example 22 (sample (d)) is a case in which the separation layer and the reinforcing material are the same, and Example 21 (sample (C)) is an example for confirming this effect. Asahi fiberglass glass cloth MS253E-1040-2NT-10F
In the case of S (plain weave), the opening is large and the expandable particles cannot be blocked, so a separate nonwoven fabric [Unicell B] is used as a separation layer.
This is an example in which TO404J is used and reinforcing fibers are used separately. Example 20 Sample (a)) is an example of this,
Comparative Example 1 (sample (b)) confirms this. Furthermore, in Comparative Examples 2 to 5 (samples (e) to (h)),
Reinforcing fibers are located directly under the epidermis, and foam particles are unevenly distributed in other areas.
This shows that separation from each other is important for the physical properties of the molded product, and Comparative Example 6 (sample (i)) shows that the contribution of the nonwoven fabric "Unicell BTO404, J" used as a separation layer as a reinforcing material can be ignored. ing.

Example 23 This example is an example in which a mixture of expandable resin particles and a thermosetting resin is packed into a tube made of a film that breaks during molding.

Epoxy resin and curing agent manufactured by Shell, “Ebiko”
100 parts of 807 J and 31 parts of "Evomate" were mixed. This is called liquid resin A.

100 parts of this liquid resin A, 44 parts of Matsumoto Yushi Seiyaku's foamable resin particles "Microspheres F-30D J" and 22 parts of hollow glass beads were mixed. This is referred to as a foamable mixture B.

On the other hand, a tube made of a film of polyvinylidene chloride/vinyl chloride copolymer with a diameter of 10 mm was made, foamable mixture B was loaded onto it, both ends and the middle were tied with a 50 mm gap, and the mixture was stored in a bag-like material. We made a continuous intestine-shaped molding material.

Next, Adkins & Pierce
& Pearce) carbon fiber braided tube (
Three layers of a tubular knitted fabric were hand-combined and placed on the surface of the above-mentioned continuous intestine-shaped molding material, and the intestine-shaped molding material was connected in a ring so that the braided tube covered the entirety of the above-mentioned molding material.

On the other hand, create a ring-shaped "mold" out of resin. This mold was equipped with gas and liquid vents and was split into two halves, top and bottom.

The annular molding material covered with the above-mentioned braided tube is placed into one mold whose inner surface has been coated with liquid resin A according to its shape, and then liquid resin A is added on top of the mold.
was applied. The other mold was placed upside down on top of this.

After tightening the mold, the mold was evacuated through the nozzle with the gas/liquid vent facing upward, and the inside of the mold was evacuated. After the nozzle was closed, the mold was placed in a 100° C. oil bath and heated. After leaving it for a while, open the gas/liquid drain nozzle and check that gas and liquid come out, then close it again. After 1 hour, the molded product was removed from the oil bath, cooled, and removed from the mold. In this way, a light and good ring was obtained, the surface of which was made of epoxy resin, the explant made of carbon fiber-reinforced epoxy resin, and the inner layer made of epoxy resin foam.

[Brief explanation of the drawing]

Fig. 1 is a partial cross-sectional view showing an example of a composite molded product obtained by the method of the present invention, Fig. 2 is a cross-sectional view showing the metal mold implementing the present invention in an open state, and Fig. 3 is a closed mold. FIG. 4 is a vertical cross-sectional view showing a state in which hollow expandable resin particles and liquid molding resin are filled into the separation layer, and FIG. 4 is a vertical cross-sectional view showing another embodiment.

Claims (16)

[Claims] (1) A surface layer made of a thermosetting resin phase containing a fibrous reinforcing material, a core made of the resin phase containing expanded particles, and a separation layer existing between the surface layer and the core. A method for producing an integrated composite molded article comprising: (a) a thermosetting material that substantially does not pass through a substantially closed molding mold, but has fluidity during molding; (b) providing the thermosetting resin or its precursor in a mold; (c) providing a separation layer through which the thermosetting resin or its precursor can pass; (c) providing a separation layer between the separation layer and the mold in the mold; (d) further providing an aggregate of expandable particles in the mold at a position opposite the inner surface of the mold of said separating layer; (e) foaming the expandable particles by raising the temperature to cause volumetric expansion of the aggregate; (f) pressing the separation layer toward the inner surface of the mold due to the volumetric expansion of (e); (g) flowing the resin or its precursor through the separation layer so that the thermosetting resin or its precursor is present between the separation layer and the mold and between the foamed particles; A method for manufacturing a composite molded product, comprising the steps of: hardening the body to complete solidification to form the surface layer and core; and (h) taking out the composite molded product thus obtained from the mold. . (2) The manufacturing method according to claim (1), wherein the separation layer is a structural material integrated with a fibrous reinforcing material. (3) The manufacturing method according to any one of claims (1) and (2), wherein the separation layer is a woven fabric, knitted fabric, nonwoven fabric, paper, wire mesh, or porous membrane that does not substantially allow the expandable particles to pass through. (4) Claims (1) to (3) wherein the fibrous reinforcing material is a woven fabric, a knitted fabric, a nonwoven fabric, a unidirectionally aligned filament, or a web.
). (5) The material of the fibrous reinforcing material is glass fiber, carbon fiber,
Claim (1) The fiber is at least one type of fiber selected from the group consisting of silicon carbide fiber, metal fiber, aramid fiber, polyarylate fiber, and polyolefin fiber.
The manufacturing method according to any one of -(4). (6) The manufacturing method according to any one of claims (1) to (5), wherein the expandable particles can expand in volume by heating and substantially contain air bubbles after foaming. (7) The manufacturing method according to claim (6), wherein the expandable particles have an average particle size of about 1 μm to about 5 mm. (8) The manufacturing method according to claim (6) or (7), wherein the expandable particles are capable of expanding in volume by at least 10% upon heating. (9) Any one of claims (6) to (8), wherein the expandable particles are formed of polyvinylidene chloride copolymer, polystyrene or polystyrene copolymer, polyolefin or polyphenylene oxide copolymer. Manufacturing method described. (10) The thermosetting resin or its precursor is a polyurethane resin, an epoxy resin, an unsaturated polyester resin, a polyvinyl ester resin, or a polycycloolefin resin, which has fluidity at least at the molding temperature. Production method. (11) The manufacturing method according to any one of claims (1) to (10), wherein the expandable particle aggregate further contains non-expandable expanded particles. (12) Claim (12) wherein the ratio of the expandable particles to the non-expandable expanded particles is within the range of 10:1 to 1:2 by weight.
) manufacturing method. (13) The manufacturing method according to claim (11) or (12), wherein the non-expandable expanded particles are inorganic expanded particles. (14) The manufacturing method according to claim (1), wherein the expandable particle aggregate is housed in a bag-like material. (15) Claim (1) wherein the separation layer is in the form of a bag-like structure.
) to (3). (16) The manufacturing method according to any one of claims (14) to (15), wherein the separation layer is a bag-like structure and contains at least an expandable particle aggregate in the bag-like structure.