JP2019199016A - Composite molding and method for producing composite molding - Google Patents

Abstract

To provide a composite molding having improved adhesion.SOLUTION: A composite molding 30 has a laminate of a first molding 10 and a second molding 20, the first molding 10 has a thermoplastic resin material 11, and the second molding 20 has a cured product of a sheet 21 containing a thermosetting resin and a fiber filler, and a thermoplastic resin material 11 with which the sheet 21 is impregnated.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composite molded body and a method for producing the composite molded body.

  Conventionally, thermoplastic resins have been widely used in various fields because of their good moldability. However, the surface hardness and heat resistance are not sufficient. On the other hand, thermosetting resins have good surface hardness, heat resistance, etc., but are not sufficient in moldability and shapeability. Therefore, in order to obtain various performances according to the purpose, composites in which molded bodies made of different resin materials are integrated have been developed.

  In Patent Document 1, a thermosetting resin layer, a specific thermoplastic elastomer layer, and a polyester polyether block copolymer containing 30 to 95% by weight of polyalkylene ether glycol are used in the thermosetting resin layer. A technique for heat-sealing is disclosed.

On the other hand, a papermaking body is generally used as a technical term indicating the state of an object obtained by using a method of spreading a fiber material. This state is described in Patent Documents 2 and 3, for example. According to the document, the papermaking product is described as a wet solid content remaining on a filter after a liquid component is dehydrated from a raw material slurry in which raw materials such as fibers and resins are dispersed in a dispersion medium. ing. The said wet state here means the hardening state before performing drying and heat processing, ie, the hardening state before post-cure.
Moreover, according to the same literature, the said papermaking body is utilized for the molded object obtained by heating and drying-molding in a shaping | molding die. That is, it is described that the papermaking body is used as a molding material.

JP-A-11-179850 Japanese Patent No. 4675276 Patent No. 5426399

  However, in the conventional technology such as Patent Document 1, the adhesion in the contact region between different materials of the composite is not sufficient.

  Therefore, the present invention has been intensively studied from the viewpoint of improving the adhesion in the contact region between different materials of the composite, and as a result, the papermaking is used as one material of the composite, and the papermaking and the other material are used. It was found that the other material was impregnated into the gap in the papermaking body by compression molding, whereby the adhesion between the two could be dramatically improved.

According to the present invention,
A composite molded body in which a first molded body and a second molded body are laminated,
The first molded body is made of a thermoplastic resin material,
The second molded body is provided with a composite molded body comprising a cured product of a papermaking containing a thermosetting resin and a fiber filler, and the thermoplastic resin composition material impregnated in the papermaking. .

Furthermore, according to the present invention,
After preparing a material slurry by dispersing a thermosetting resin and a fiber filler in a solvent, using a papermaking method, removing the solvent from the material slurry to obtain a papermaking,
Compression molding in a state where a thermoplastic resin material is in contact with the papermaking body, and impregnating the papermaking body with the thermoplastic resin material, and curing the papermaking body;
The manufacturing method of the composite molded object containing this is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness between the dissimilar materials of a composite molded object can be improved.

It is a schematic cross section which shows an example of the composite molded object which concerns on this embodiment. It is a perspective schematic diagram which shows the papermaking body which concerns on this embodiment. It is a cross-sectional schematic diagram which shows an example of the manufacturing method of the papermaking body which concerns on this embodiment. It is a cross-sectional schematic diagram which shows an example of the manufacturing method of the composite molded object which concerns on this embodiment. It is a cross-sectional schematic diagram which shows an example of the manufacturing method of the composite molded object which concerns on this embodiment. It is a cross-sectional schematic diagram which shows an example of the manufacturing method of the composite molded object which concerns on this embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

<Composite molded body>
FIG. 1 is a schematic cross-sectional view showing an example of a composite molded body 30 according to the present embodiment. The composite molded body 30 is a laminate of the first molded body 10 and the second molded body 20. In the present embodiment, the first molded body 10 is formed on the second molded body 20.

In the composite molded body 30, since a part of the thermoplastic resin material 11 of the first molded body 10 is impregnated in the second molded body 20, the two are firmly joined and integrated. Therefore, the adhesiveness can be increased, and mechanical properties such as bending strength are further improved.
In the composite molded body 30, the ratio of the thickness of the first molded body 10 and the thickness of the second molded body 20 is not particularly limited, but is preferably 0.001 to 3, more preferably 0.001 to 2. More preferably, it is 0.001-1. If the ratio of the thickness is within the above preferable range, a laminated structure of the first molded body 10 and the second molded body 20 can be easily formed.
Hereinafter, each molded body will be described in detail.

[First molded body]
The first molded body 10 is made of a thermoplastic resin material 11. The thermoplastic resin material 11 includes at least a thermoplastic resin.

  The melting point of the thermoplastic resin is preferably 160 ° C. or higher. Thereby, at the time of manufacture of the composite molded object 30, the 1st molded object 10 and the 2nd molded object 20 can be compressed, advancing the hardening reaction of the thermosetting resin mentioned later. That is, by making the melting point of the thermoplastic resin higher than the curing temperature of the thermosetting resin, the thermoplastic resin and the thermosetting resin can be integrated by heating and compression.

  As thermoplastic resins, polyamide resins such as nylon 6 and nylon 66, polyolefin resins such as polyester and polypropylene, polyphenylene sulfide resins, polyacetal resins, polyether ether imide resins, polybutylene terephthalate resins, polyether imide resins, polyamide imide resins And one or more selected from polyethersulfone resins. Among these, from the viewpoint of making the adhesion of new parts to the composite molded body 30 strong and easy and applicable to a wide range of uses, polyamide resins such as nylon 6 and nylon 66, and polyolefin resins such as polyester and polypropylene. Polyphenylene sulfide resin is preferable.

  The thermoplastic resin material 11 may contain a normal resin additive such as a filler such as a fiber filler and a plasticizer, if necessary, in addition to the above thermoplastic resin. As a fiber filler, the thing similar to the fiber filler contained in the 2nd molded object 20 mentioned later can be mentioned. When a fiber filler is contained in the 1st molded object 10, it may be the same as the fiber filler contained in the 2nd molded object 20, and may differ.

[Second molded body 20]
The second molded body 20 includes a cured product of the papermaking body 21 including the thermosetting resin A and the fiber filler B, and the thermoplastic resin composition material 11 impregnated in the papermaking body 21. That is, when the second molded body 20 includes the papermaking body 21, the papermaking body 21 is hardened while the thermoplastic resin material 11 is impregnated from the gaps of the papermaking body 21 by compression molding described later. The 2nd molded object 20 is obtained. As a result, the second molded body 20 is formed from the cured product of the papermaking body 21 and the thermosetting resin material 11. Thereby, in the composite molded body 30, the adhesion area | region of the 1st molded object 10 and the 2nd molded object 20 becomes very firm.
In the thickness direction of the 2nd molded object 20, it is preferable to have a density | concentration gradient which the impregnation rate of the thermoplastic resin contained in a thermoplastic resin material reduces as it leaves | separates from the 1st molded object 10. FIG. That is, in the manufacturing process of the composite molded body 30, the thermoplastic resin material 11 is pushed from one surface of the papermaking body 21, so that the thermoplastic resin material 11 is impregnated into the papermaking body 21. In the vicinity of the contact area between the molded body 10 and the second molded body 20, the concentration of the thermoplastic resin increases, and the inside of the second molded body 20, in other words, the bonding area with the first molded body 10 Follows the opposite direction, and the concentration of the thermoplastic resin decreases.

  The concentration gradient of the thermoplastic resin in the second molded body 20 is obtained by, for example, observing a cross section of the composite molded body 30 with an optical microscope (an incident image, an image through a polarizing filter) and EDS (Energy Dispersive X-ray Spectroscopy). For example, the area ratio between the second molded body 20 and the thermoplastic resin can be calculated.

Next, the papermaking body 21 will be described.
FIG. 2 is a schematic perspective view showing an example of the papermaking body 21 according to the present embodiment.
In FIG. 2, the enlarged schematic diagram of the area | region shown with a dotted line of a papermaking body is shown. The papermaking body 21 according to the present embodiment includes a thermosetting resin A and a fiber filler B.
The thermosetting resin A functions as a binder for binding the fiber fillers B together, and also functions as a molding material for obtaining a molded body by the papermaking body 21 by a subsequent heat treatment.

  The thermosetting resin A in the papermaking body 21 is not completely cured, for example, in a B stage state. Thereby, in the manufacturing process of the composite molded object 30 mentioned later, it can compress-mold with the 1st molded object 10 material, and it can fully harden by setting it as the curing temperature of the thermosetting resin A. FIG. In addition, since it is not completely cured, it has flexibility and can follow other materials.

The papermaking body 21 according to the present embodiment is obtained by a papermaking method described later, and has structural features 1 to 3 in the following points.
(Feature 1) In the plan view of the surface of the papermaking body 21, the fiber fillers B are randomly oriented.
(Characteristic 2) In the cross-sectional view in the thickness direction of the papermaking body 21, the orientation state of the fiber filler B is highly controlled, and the fiber filler B is oriented in a specific direction. In other words, the fiber filler B is laminated in the thickness direction of the papermaking body 21.
(Feature 3) The fiber fillers B are bound together by the thermosetting resin A.

  Since the papermaking body 21 is formed by a papermaking method, it is estimated that the fiber filler B can be uniformly dispersed in the papermaking body 21 and the entanglement between the fiber fillers B can be appropriately made. . Moreover, since the papermaking method is excellent in workability, the designability of the papermaking body 21 can also be improved. Moreover, the papermaking method has few restrictions on the combination of materials constituting the papermaking body 21. For this reason, according to the characteristic calculated | required by the composite molded object 30, other various additives can be used suitably with the thermosetting resin A and the fiber filler B. FIG.

In the present embodiment, the air permeability of the papermaking body 21 is preferably 3 cm ³ / cm ² · s or more, more preferably 4 cm ³ / cm ² · s or more, from the viewpoint of improving adhesion and reducing weight. .
On the other hand, the air permeability of the paper-making body 21 is preferably 15 cm ³ / cm ² · s or less, more preferably 12 cm ³ / cm ² · s or less, from the viewpoint of obtaining a good balance with adhesion while obtaining mechanical strength. It is.
The air permeability can be measured by a test according to the fragile method (JIS L 1913) of the general nonwoven fabric test method.

Moreover, the porosity of the papermaking body 21 is preferably 40% or more, more preferably 50% or more, from the viewpoint of improving adhesion and reducing weight.
On the other hand, the porosity of the papermaking body 21 is preferably 90% or less, more preferably 80% or less, from the viewpoint of obtaining a good balance with adhesiveness while obtaining mechanical strength.
The porosity can be determined by the following formula.
Porosity (%) = {1− (bulk density of material (g / cm ³ ) / true density of material (g / cm ³ ))} × 100

  Hereinafter, the material which forms the papermaking body 21 is demonstrated in detail.

(Thermosetting resin A)
The thermosetting resin A acts as a binder for binding the fiber filler B in the papermaking body 21.
As the thermosetting resin, for example, it is preferable to use a resin that is in a solid form at room temperature (25 ° C.) in an unheated state from the viewpoint of stably producing the papermaking body 21.

  Specific examples of the thermosetting resin include phenol resin, epoxy resin, unsaturated polyester resin, melamine resin, and polyurethane. These may be used individually by 1 type and may use 2 or more types together. Among these, the inclusion of at least one of a phenol resin and an epoxy resin is more preferable from the viewpoint of improving the mechanical properties of the composite molded body 30.

  The content of the thermosetting resin is preferably 5% by weight or more, more preferably 15% by weight or more, and most preferably 20% by weight or more based on the total amount of the papermaking product 21. Thereby, the workability and lightness of the papermaking body 21 can be improved more effectively. On the other hand, the content of the thermosetting resin is preferably 80% by weight or less, more preferably 60% by weight or less, and most preferably 40% by weight or less based on the total amount of the papermaking product 21. . Thereby, it becomes possible to improve the thermal characteristic of the hardened | cured material obtained by hardening the papermaking body 21 more effectively.

(Fiber filler B)
The fiber filler B includes, for example, metal fibers; inorganic fibers such as carbon fibers, glass fibers, and ceramic fibers; natural fibers such as wood fibers, cotton, hemp, and wool; regenerated fibers such as rayon fibers; semisynthetic fibers such as cellulose fibers; One kind selected from synthetic fibers such as polyamide fiber, aramid fiber, polyimide fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, polyparaphenylene benzoxazole fiber, polyethylene fiber, polypropylene fiber, polyacrylonitrile fiber, ethylene vinyl alcohol fiber or the like Two or more types can be included. Among these, from the viewpoint of imparting thermal conductivity to the composite molded body 30, it is preferable to include one or more of metal fibers and inorganic fibers, and includes at least one of metal fibers and carbon fibers. It is more preferable. Moreover, from the viewpoint of improving the mechanical properties of the composite molded body 30, it is more preferable to include one or more of synthetic fibers and inorganic fibers. In particular, from the viewpoint of improving the bending strength of the composite molded body 30, it is particularly preferable to include carbon fibers. In addition, from the viewpoint of improving the impact resistance of the composite molded body 30, it is particularly preferable to include an aramid fiber. From the viewpoint of improving the electromagnetic wave shielding performance of the composite molded body 30, it is more preferable to include metal fibers.

  The metal fiber may be a metal fiber composed of a single metal element or an alloy fiber composed of a plurality of metals. The metal fiber preferably contains one or more metal elements selected from the group consisting of aluminum, silver, copper, magnesium, iron, chromium, nickel, titanium, zinc, tin, molybdenum and tungsten, for example. In addition, as a metal fiber in this embodiment, for example, Nippon Seisen Co., Ltd. and Bekaert Japan Co., Ltd. stainless fiber, Niji Co., Ltd. copper fiber, aluminum fiber, brass fiber, steel fiber, titanium fiber, phosphor bronze fiber Are commercially available, but are not limited to these. These metal fibers may be used individually by 1 type, or may use 2 or more types together. Of these, one or more of copper fiber, aluminum fiber, and brass fiber is preferable from the viewpoint of thermal conductivity, and one or more of stainless fiber, copper fiber, and aluminum fiber are preferable from the viewpoint of electromagnetic shielding properties. preferable.

  Fiber filler B is surface treated with a silane coupling agent, aluminate coupling agent, titanate coupling agent, etc., depending on the required characteristics, or with a sizing agent treatment to improve the adhesion and handleability with the resin. You may use what you did.

  The fiber filler B can have various shapes according to required characteristics. In the present embodiment, for example, a chopped fiber can be used as the fiber filler B.

  The content of the fiber filler B is preferably 15% by weight or more, more preferably 30% by weight or more, and particularly preferably 45% by weight or more based on the entire papermaking product 21. Thereby, the balance of the mechanical characteristic and thermal characteristic of the composite molded object 30 can be improved more effectively. On the other hand, the content of the fiber filler B is preferably 80% by weight or less, more preferably 70% by weight or less, and particularly preferably 65% by weight or less with respect to the entire papermaking product 21. Thereby, the workability and lightness of the papermaking body 21 can be improved. Moreover, it is possible to improve the dispersibility of the fiber filler B more effectively and contribute to the improvement of the mechanical characteristics and thermal characteristics of the composite molded body 30.

  The papermaking body 21 may further include the following.

  The papermaking body 21 can contain, for example, pulp. Pulp is a fiber material having a fibril structure and can be obtained, for example, by mechanically or chemically fibrillating the fiber material. In the manufacturing method of the papermaking body 21 using the papermaking method to be described later, the thermosetting resin can be more effectively aggregated by making pulp together with the thermosetting resin A and the fiber filler B. It becomes possible to realize the stable production of the papermaking body 21.

  Examples of pulp include cellulose fibers such as linter pulp and wood pulp, natural fibers such as kenaf, jute and bamboo, para-type wholly aromatic polyamide fibers (aramid fibers) and copolymers thereof, aromatic polyester fibers, and polybenzazole. Examples include fibrillated organic fibers such as fibers, meta-type aramid fibers and copolymers thereof, acrylic fibers, acrylonitrile fibers, polyimide fibers, and polyamide fibers. The pulp can contain one or more of these. Among these, from the viewpoint of improving the mechanical properties of the papermaking body 21 and the viewpoint of improving the dispersibility of the fiber filler B, an aramid pulp composed of aramid fibers and a polyacrylonitrile pulp composed of acrylonitrile fibers are used. It is particularly preferable to include one or both of them.

  The pulp content is preferably 0.5% by weight or more, more preferably 1.5% by weight or more, and particularly preferably 2% by weight or more based on the total amount of the papermaking product 21. Thereby, aggregation of the thermosetting resin at the time of papermaking can be generated more effectively, and the more stable manufacture of the papermaking body 21 can be realized. The pulp content is preferably 15% by weight or less, more preferably 10% by weight or less, and particularly preferably 8% by weight or less based on the total amount of the papermaking product 21. Thereby, it becomes possible to improve the mechanical characteristics and thermal characteristics of the cured product obtained by curing the papermaking body 21 more effectively.

  The papermaking body 21 can contain a flocculant, for example. The flocculant has a function of aggregating the thermosetting resin and the fiber material in a flock shape in the method for producing the papermaking body 21 using the papermaking method described later. For this reason, more stable production of the resin sheet can be realized.

  The flocculant can include, for example, one or more selected from a cationic polymer flocculant, an anionic polymer flocculant, a nonionic polymer flocculant, and an amphoteric polymer flocculant. Examples of such flocculants include cationic polyacrylamide, anionic polyacrylamide, Hoffman polyacrylamide, mannic polyacrylamide, amphoteric copolymerized polyacrylamide, cationized starch, amphoteric starch, polyethylene oxide and the like. . In the flocculant, the polymer structure and molecular weight, the amount of functional groups such as hydroxyl groups and ionic groups, and the like can be adjusted without particular limitation depending on the required characteristics.

  The content of the flocculant is preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and more preferably 0.15% by weight with respect to the total amount of the constituent materials of the papermaking product 21 described above. % Or more is particularly preferable. Thereby, in the manufacture of the papermaking body 21 using the papermaking method, the yield can be improved. On the other hand, the content of the flocculant is preferably 3% by weight or less, more preferably 2% by weight or less, and more preferably 1.5% by weight with respect to the total amount of the constituent materials of the papermaking product 21 described above. The following is particularly preferable. Thereby, in manufacture of the papermaking body 21 using a papermaking method, it becomes possible to perform a dehydration process etc. more easily and stably.

  The papermaking body 21 can contain, for example, a powdery substance having ion exchange ability in addition to the above-described components. As the powdery substance having ion exchange ability, it is preferable to use one or more intercalation compounds selected from, for example, clay minerals, scaly silica fine particles, hydrotalcites, fluorine teniolite and swellable synthetic mica. Examples of the clay mineral include smectite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate. Examples of hydrotalcites include hydrotalcite and hydrotalcite-like substances. Examples of the fluorine teniolite include lithium-type fluorine teniolite and sodium-type fluorine teniolite. Examples of the swellable synthetic mica include sodium-type tetrasilicon fluorine mica and lithium-type tetrasilicon fluorine mica. These intercalation compounds may be natural products or synthesized ones. Among these, clay minerals are more preferable, and smectite is more preferable in that it exists from natural products to synthetic products and has a wide range of selection. Examples of the smectite include montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, and stevensite, and any one or more of these can be used. Montmorillonite is a hydrated silicate of aluminum, but may be bentonite containing montmorillonite as a main component and minerals such as quartz, mica, feldspar, and zeolite. Synthetic smectite with few impurities is preferable when used for applications such as coloring and impurities.

  In addition, the paper-making body 21 includes, for example, stabilizers such as antioxidants and ultraviolet absorbers for the purpose of improving characteristics, mold release agents, plasticizers, flame retardants, resin curing catalysts and curing accelerators, pigments, and dry paper strength. Paper strength improvers such as improvers, wet paper strength improvers, yield improvers, freeness improvers, size fixers, antifoaming agents, rosin sizing agents for acidic papermaking, rosin sizing agents for neutral papermaking, alkyl One or two selected from additives such as ketene dimer sizing agents, alkenyl succinic anhydride sizing agents, sizing agents such as specially modified rosin sizing agents, and coagulants such as sulfate bands, aluminum chloride, and polyaluminum chloride. More than seeds can be included for the purpose of adjusting production conditions and expressing required physical properties.

Next, the manufacturing method of the papermaking body 21 is demonstrated.
FIG. 3 is a schematic cross-sectional view showing an example of a method for manufacturing the papermaking body 21 according to the present embodiment. In FIG. 3, the symbol A is a thermosetting resin, the symbol B is a fiber material, the symbol F is an aggregate obtained by agglomerating the thermosetting resin A and the fiber filler B in a solvent in a floc form, Each is shown.

  First, as shown to Fig.3 (a), the component except a flocculent among the above-mentioned each components is added to a solvent, and it stirs and disperses. Here, the thermosetting resin, the fiber filler B, and other additives as required are added to the solvent, and are stirred and dispersed. Thereby, the material slurry (varnish-like resin composition) for forming the papermaking body 21 is prepared. A method for dispersing each component in a solvent is not particularly limited, and examples thereof include a method of stirring using a disperser.

  Although it does not specifically limit as a solvent, It is hard to volatilize in the process which disperse | distributes the constituent material of the said material slurry, It is easy to desolvate in order to suppress the residual in the papermaking body 21, and energy increases by desolvation. From the standpoint of suppressing the occurrence of such a phenomenon, those having a boiling point of 50 ° C. or higher and 200 ° C. or lower are preferable. Examples of such a solvent include water, alcohols such as ethanol, 1-propanol, 1-butanol, and ethylene glycol; ketones such as acetone, methyl ethyl ketone, 2-heptanone, and cyclohexanone; ethyl acetate, butyl acetate, Examples thereof include esters such as methyl acetoacetate and ethers such as tetrahydrofuran, isopropyl ether, dioxane and furfural. These solvents may be used alone or in combination of two or more. Among these, it is particularly preferable to use water because of its abundant supply amount, low cost, low environmental load, high safety and easy handling.

  In the present embodiment, a flocculant can be added to the material slurry obtained above. Thereby, it becomes easier to obtain the aggregate F by aggregating the thermosetting resin A and the fiber filler B in the solvent in a floc form.

Next, as shown in FIG. 3 (b), the solvent and the agglomerate F obtained above are put into a container having a bottom surface made of mesh 41, and the solvent is discharged from the mesh 41. Remove. Thereby, the aggregate F and the solvent can be separated from each other. At this time, the aggregate F remains in a sheet form on the mesh 41.
In the present embodiment, it is possible to adjust the shape of the resulting papermaking body 21 by appropriately selecting the shape of the mesh 41. For example, when a flat sheet-shaped mesh 41 is used, the papermaking body 21 having a sheet-like shape is obtained. Further, for example, when a mesh 41 having a three-dimensional shape such as a wave shape or unevenness is used, a papermaking body 21 having a three-dimensional shape is obtained. The shape of the papermaking body 21 can be appropriately selected according to the shape of the composite molded body 30, the shape of the mold, and the like.
The thickness of the papermaking body 21 can be adjusted by adjusting the amount of each material in the material slurry, or by repeating the papermaking process shown in FIG.

  In the present embodiment, the sheet-like aggregate F obtained above can be taken out, placed in a drying furnace and dried, and the solvent can be further removed. For example, in this way, the papermaking body 21 as shown in FIG. 3C is manufactured.

<Method for producing composite molded body>
Next, a method for manufacturing the composite molded body 30 will be described.
First, as described above, after thermosetting resin A and fiber filler B are dispersed in a solvent to prepare a material slurry, the solvent is removed from the material slurry using a papermaking method, and a papermaking body is obtained. Get 21. Next, compression molding is performed in a state where the thermoplastic resin material 11 is brought into contact with the papermaking body 21, and the papermaking body 21 is impregnated with the thermoplastic resin material 11 and the papermaking body 21 is cured. Hereinafter, the process after obtaining the papermaking body 21 will be described in detail.

  The composite molded body 30 can be manufactured using a mold having a desired shape. Examples of the molding method include compression molding and a method in which compression molding is combined with transfer or injection. Hereinafter, a description will be given with reference to FIGS.

  First, as shown in FIG. 4, the papermaking body 21 is placed in the lower mold 51, and the thermoplastic resin material 11 is filled from above. At this time, it is preferable to fill the lower mold 51 with the thermoplastic resin material 11 so as to leave a gap so that the thermoplastic resin material 11 can be deformed in the lower mold 51 in a later step. The thermoplastic resin material 11 may be filled in the lower mold 51 with a softened material by an injection molding method.

  Next, as shown in FIG. 5, the upper mold 52 is lowered, the thermoplastic resin material 11 is brought into contact with the papermaking body 21 so as to contact it, and the thermoplastic resin material 11 is deformed. As shown, the thermoplastic resin material 11 and the papermaking body 21 are heat-pressed. Thereby, a part of the thermoplastic resin material 11 is impregnated from the contact surface with the papermaking body 21, and the papermaking body 21 is completely cured. That is, in the lower mold 51 and the upper mold 52, the thermoplastic resin material 11 and the papermaking body 21 are integrated or after the thermosetting resin in the papermaking body 21 is cured. During or after curing, the thermoplastic resin is cooled and solidified. As a result, the first molded body 10 and the second molded body 20 are integrated, and a laminated composite molded body 30 can be obtained (FIG. 1).

The heating temperature is appropriately determined depending on the raw materials used, but it is preferable that the heating temperature be equal to or lower than the melting point of the thermoplastic resin contained in the thermoplastic resin material 11 and higher than the curing temperature of the thermosetting resin. For example, when a phenol resin is used, it is preferable to set it as 150-200 degreeC, and it is more preferable to set it as 160-180 degreeC. Thereby, the adhesiveness of the 1st molded object 10 and the 2nd molded object 20 can be improved, and the use of the composite molded object 30 can be made wide. From the viewpoint of shortening the molding time, the mold is preferably preheated, but from the viewpoint of increasing the density of the composite molded body 30, preheating may or may not be performed.
Moreover, as a pressurizing condition, the pressure is preferably 10 to 80 MPa, and more preferably 30 to 60 MPa. The pressurization time is preferably about 1 to 10 minutes.

  According to the manufacturing method of the composite molded body 30 of the present embodiment, a simple and stable method without pre-treating the first molded body 10 and the second molded body 20 or using an adhesive or the like. Therefore, both can be firmly integrated and high adhesion can be obtained.

  The composite molded body 30 of the present embodiment described above can be widely used for various applications such as building materials, various transport machines such as automobiles and aircraft, and sports equipment.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Next, examples of the present invention will be described.

<Example 1>
(Production of papermaking)
A thermosetting resin A and a fiber filler B shown below were added to water as a solvent, and stirred with a disperser at a peripheral speed of 16 m / sec for 30 minutes to obtain a slurry.
Next, 0.1% by weight of an aqueous solution of polyethylene oxide (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight 1,000,000) is added as a flocculant to the total of the above materials, and the above materials are aggregated in a flock shape I let you.
The slurry containing the agglomerate thus obtained was filtered through a 30-mesh metal net. Thereafter, the agglomerates remaining on the metal net were taken out, dehydrated and pressed, and further placed in a dryer at 50 ° C. for 5 hours to dry, thereby obtaining a sheet-like papermaking product.

The composition of the obtained papermaking product was as follows.
Material thermosetting resin A:
Resol type phenol resin (trade name PR-51723, manufactured by Sumitomo Bakelite Co., Ltd.) 60 vol%
Fiber filler B:
Aramid pulp (DuPont, para-aramid pulp) 5 vol%,
Aramid fiber (Teijin Limited, product number T32PNW) 28 vol%,
SUS fiber (Nippon Seisen Co., Ltd. Naslon CHOP 6/5 CMC) 7 vol%

(Manufacture of composite moldings)
Next, the obtained papermaking product was placed in a mold, and a nylon resin (containing 37 vol% glass fiber) was injected into the mold under the following conditions, followed by compression molding to obtain a composite molded body.
-Conditions Injection pressure: 8 MPa, Injection temperature: 180 ° C
Temperature: 150 ° C., mold clamping pressure: 44 MPa, time: 10 minutes, removal temperature: 120 ° C.

<Comparative Example 1>
After making a sheet-like papermaking body by the same method as in Example 1, a papermaking body was obtained by compression molding under the following conditions. A composite molded body was prepared by placing in a mold in the same manner as in Example 1 except that the paper molded body was used instead of the paper body of Example 1.
-Conditions Temperature: 180 ° C., Clamping pressure: 44 MPa, Time: 10 minutes, Removal temperature: 120 ° C.
The paper-molded body was made to be non-breathable by compression, so that the thermoplastic resin material could not be impregnated inside the paper-molded body when the composite molded body was formed later.

(Evaluation-1)
The following measurements were performed on the papermaking body obtained in Example 1 and the papermaking body obtained in Comparative Example 1. The results are shown in Table 1.

-Measurement of air permeability It measured based on the fragile form method (JIS L 1913) of the general nonwoven fabric test method.

-Measurement of porosity The porosity was calculated | required by the following formula.
Porosity (%) = {1− (bulk density of material (g / cm ³ ) / true density of material (g / cm ³ ))} × 100

(Evaluation-2)
The following measurements were performed on the composite molded bodies obtained in the examples and comparative examples. The results are shown in Table 1.

Bending test: measurement of bending elastic modulus (GPa) and bending strength (MPa) Based on ISO178, bending elastic modulus (GPa) and bending strength (MPa) were measured.

-Measurement of breaking strain (%) Breaking strain (%) was measured according to ISO178.

-Presence / absence of peeling In the composite molded body after the bending test, the presence or absence of interfacial peeling was confirmed using an optical microscope.

Furthermore, when the cross section of the composite molded body obtained in Example 1 was polished and observed with an optical microscope, a thermoplastic resin (nylon resin) was impregnated inside the papermaking, and in the thickness direction of the papermaking, It was confirmed that there is a concentration gradient in which the impregnation rate of the thermoplastic resin decreases as the distance from the molded body of the plastic resin decreases.
On the other hand, in the composite molded body obtained in Comparative Example 1, it could not be confirmed that the thermoplastic resin was impregnated.

DESCRIPTION OF SYMBOLS 10 1st molded object 11 Thermoplastic resin material 20 2nd molded object 21 Paper body 30 Composite molded object 41 Mesh 51 Lower mold 52 Upper mold A Thermosetting resin B Fiber filler F Aggregate

Claims (10)

A composite molded body in which a first molded body and a second molded body are laminated,
The first molded body is made of a thermoplastic resin material,
The said 2nd molded object is a composite molded object which consists of the hardened | cured material of the papermaking containing a thermosetting resin and a fiber filler, and the said thermoplastic resin composition material impregnated in the said papermaking.   The thickness direction of the said 2nd molded object has a concentration gradient which the impregnation rate of the thermoplastic resin contained in the said thermoplastic resin material reduces as it leaves | separates from the said 1st molded object. Composite molded body. The composite molded article according to claim 1 or 2, wherein the air permeability of the papermaking product is 3 cm ³ / cm ² · s or more and 15 cm ³ / cm ² · s or less.   The composite molded body according to any one of claims 1 to 3, wherein a porosity of the papermaking body is 40% or more and 90% or less.   The composite molded body according to any one of claims 1 to 4, wherein the thermoplastic resin contained in the thermoplastic resin material has a melting point of 160 ° C or higher.   The thermoplastic resin contained in the thermoplastic resin material includes polyamide resin, polyolefin resin, polyphenylene sulfide resin, polyacetal resin, polyether etherimide resin, polybutylene terephthalate resin, polyetherimide resin, polyamideimide resin, and polyethersulfone. The composite molded body according to any one of claims 1 to 5, comprising one or more selected from among resins.   The said thermosetting resin contains 1 type (s) or 2 or more types selected from the group which consists of a phenol resin, an epoxy resin, an unsaturated polyester resin, a melamine resin, and a polyurethane as described in any one of Claims 1 thru | or 6. Composite molded body.   The fiber filler is metal fiber, carbon fiber, glass fiber, ceramic fiber, polyamide fiber, aramid fiber, polyimide fiber, polyvinyl alcohol fiber, polyester fiber, acrylic fiber, polyparaphenylene benzoxazole fiber, polyethylene fiber, polypropylene fiber, poly The composite molded body according to any one of claims 1 to 7, comprising one or more selected from acrylonitrile fiber and ethylene vinyl alcohol fiber. After preparing a material slurry by dispersing a thermosetting resin and a fiber filler in a solvent, using a papermaking method, removing the solvent from the material slurry to obtain a papermaking,
Compression molding in a state where a thermoplastic resin material is in contact with the papermaking body, and impregnating the papermaking body with the thermoplastic resin material, and curing the papermaking body;
The manufacturing method of the composite molded object containing this.   The composite molded body according to claim 9, wherein in the step of curing the papermaking body, the composite molded body is heated to a temperature equal to or lower than a melting point of the thermoplastic resin contained in the thermoplastic resin material and equal to or higher than a curing temperature of the thermosetting resin. Manufacturing method.

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