JP2013075447A - Composite laminated plate, integrated molded article using composite laminated plate, and method of manufacturing these items - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a composite laminated plate capable of preventing the deterioration of radio communication performance while maintaining, in particular, electromagnetic wave interception performance, achieving excellent design performance and partially having a radio wave transmission region, and an integrated molded article using the composite laminated plate.SOLUTION: The integrally-molded composite laminated plate (1C) is formed by laminating a first reinforced base material (2a) which is paper having a sheet shape and having a conductive discontinuous reinforcement fiber and a second base material (2b) different from the first base material to make the base materials adjacent to each other, laminating a matrix resin sheet (2c) mainly formed of thermoplastic resin at least on a surface layer in the thickness direction so as to sandwich the base materials (2a) (2b), impregnating the matrix resin sheet by hot melt press and then cooling the matrix resin sheet in a mold for shaping. The integrated molded article having the composite laminated plate is formed by performing injection molding using thermoplastic resin (1D) so as to surround at least part of the outer periphery of the composite laminated plate (1C).

Description

  The present invention relates to a composite laminate, an integrally molded product using the composite laminate, and a method for producing the same, and in particular, the wireless communication performance is not deteriorated while maintaining electromagnetic shielding properties, and a partial design excellent in design. The present invention relates to a composite laminate having a radio wave transmission region, an integrally molded product using the composite laminate, and a method for manufacturing the same.

  In recent years, products with built-in wireless communication functions typified by notebook computers and mobile phones have become more sophisticated, and have rapidly spread to offices and homes. Many of these products are equipped with antennas for wireless communication, but from the viewpoint of portability and design, most cases have antennas arranged inside the housing.

  An electromagnetic shielding performance (EMI) is a characteristic required for a general electronic device casing. This is used as an index for preventing radio waves emitted by the operation of a certain device from affecting the operation of other devices and the human body. If no measures are taken, electronic devices may cause troubles such as functional degradation, malfunction, stoppage, loss of records, etc. due to the effects of electromagnetic radiation, lightning, and solar activity from other nearby devices. It has also been generally discussed that electromagnetic waves emitted by electronic devices themselves may adversely affect the operation of other devices and the health of nearby humans. For this reason, conductive plastics and metals with high electromagnetic shielding performance are used as housing materials for electronic devices. However, especially for case materials for small electronic devices such as laptop computers and mobile phones that are easy to carry. In many cases, carbon fiber reinforced plastics or magnesium alloys that are excellent in robustness and light weight in addition to electromagnetic shielding performance are selected.

  When a material with high electromagnetic shielding performance, such as a metal such as carbon fiber reinforced plastic or magnesium alloy, is selected for the entire casing of such an electronic device casing, the average antenna gain decreases and the biased radio wave directivity develops. As a result, a functional problem that wireless communication performance deteriorates has occurred.

  In Patent Document 1, an insulating base material, which is a separate molding base material, is fitted into a part of a casing having an electromagnetic wave shielding effect, and hot press molding is performed at a temperature higher than the melting temperature of the thermoplastic resin contained in the base material. An integrated manufacturing method has been disclosed, and it has become possible to produce a casing having a radio wave transmission region by using an insulating base material in part. A manufacturing process was added, and problems remained in terms of mass productivity.

  In Patent Document 2, a fiber-reinforced thermosetting resin material having an electromagnetic wave shielding effect is placed in a mold, and then an insulator member is injection-molded to have a strong bonding strength and secure mass productivity. Outsert injection molding joining technology is disclosed, and molding technology that secures joint strength and mass productivity has been established, but insulating material used in the radio wave transmission region to obtain wireless communication performance is generally Since the molding shrinkage rate is large, there remains a problem that if the radio wave transmission region is large, the casing is likely to be warped or deformed from the difference in molding shrinkage rate after injection molding. For such technical problems, there is no document that clearly describes the material design guidelines for insulating members.

  In this way, in the conventional technology, thermoplastic resin is used for the top surface base material of the housing that has an electromagnetic wave shielding effect and the insulating material, and it effectively prevents warping and deformation, has excellent design properties, and is mass-produced. Development of a method of manufacturing an electronic device casing using a composite laminate plate that secures high performance has been desired.

JP 2011-93213 A JP 2008-34823 A

  In light of the background of the prior art, the present invention effectively prevents warping and deformation, has excellent design properties, and ensures mass productivity, and an integrally molded product using the composite laminate and a method for manufacturing the same The purpose is to provide.

As a result of intensive studies to achieve the above-mentioned object, the present inventors can achieve the above-mentioned problem, and a method for manufacturing a composite laminate having a partially radio wave transmission region and an integrally molded product using the same. I found.
(1) A composite base material in which a first reinforcing base (2a) that is a sheet-like paper having conductive discontinuous reinforcing fibers and a second base (2b) different from the first base are butt-joined At least a part of the layers of the substrate laminate, and a matrix resin sheet (2c) mainly composed of a thermoplastic resin is interposed between the laminates before molding, and the laminate before molding is formed. A method for producing a composite laminate (1C), in which a molding die placed inside is impregnated with a matrix resin by a hot melt press into the composite base material and then cooled in the molding die to be integrally molded.
(2) The method for producing a composite laminate (1C) according to (1), wherein the laminates are laminated so that a part of the boundary portion between the adjacent composite base materials overlaps.
(3) In the heating and melting press, the pressure is maintained during cooling until the temperature of the laminated body before molding is equal to or higher than the melting point and then cooling to a solidification temperature or lower (1) or The manufacturing method of the composite laminated sheet (1C) as described in (2).
(4) A material in which the electromagnetic wave shielding property measured by the KEC method of the molding material (1A), which is an electromagnetic wave shielding region impregnated with the matrix resin in the first reinforced substrate (2a), is 10 to 80 dB in the frequency 1 GHz band. The method for producing a composite laminate (1C) according to any one of (1) to (3), wherein:
(5) A material whose electromagnetic wave shielding property measured by the KEC method of the molding material (1B), which is a radio wave transmission region in which the second base material (2b) is impregnated with a matrix resin, is 0 to 10 dB in the frequency band of 1 GHz. A method for producing a composite laminate (1C) according to any one of (1) to (4), wherein the method is used.
(6) The composite laminate according to any one of (1) to (5), wherein a fiber weight content (Wf) of the molding material (1A) serving as the electromagnetic wave shielding region is 5% to 80%. Manufacturing method of board (1C).
(7) The molding material (1B) serving as the radio wave transmitting region can include reinforcing fibers, and the reinforcing fibers are at least one selected from glass fibers, aramid fibers, chemical fibers, and reinforcing fillers, which are non-conductive fibers. A method for producing a composite laminate (1C) according to any one of (1) to (6).
(8) The range of the fiber weight content (Wf) of the molding material (1B) serving as the radio wave transmission region is from 0% to 80%, according to any one of (1) to (7) A method for producing a composite laminate (1C).
(9) After providing the slope shape which becomes a junction part in at least one part of the peripheral part of the said composite laminated board (1C) in any one of (1) to (3), at least one part of the said peripheral part is used. A method for producing an integrally molded product, wherein the thermoplastic resin (1D) is injection-molded and integrated so as to cover.
(10) One or more types selected from resin films, sheets, and foams are laminated as the core layer (11E) between the layers of the composite laminate (1C) according to any one of (1) to (9). A method for producing an integrally molded product,
(11) The method for producing an integrally molded product according to (9) or (10), wherein the method is used for any one of an electrical / electronic device housing and a home appliance housing.
(12) A composite base material in which a first reinforcing base (2a), which is a sheet-like paper having conductive discontinuous reinforcing fibers, and a second base (2b) different from the first base are butt-joined Is impregnated with a matrix resin by a hot melt press into a laminate before molding in which a matrix resin sheet (2c) containing a thermoplastic resin as a main component is sandwiched between at least a part of the layers of the substrate laminate. A composite laminate (1C) obtained by cooling and integrally molding the matrix resin.
(13) The composite laminate (1C) according to (12), wherein a part of the laminate before molding is bent to form part of a standing wall.
(14) A joint having a slope shape is provided on at least a part of the peripheral part of the composite laminate (1C) according to any one of (12) and (13), and at least a part of the peripheral part is covered. Thus, an integrally molded product characterized by integrating the thermoplastic resin (1D) by injection molding.
(15) The integrally molded product according to (14), wherein the insulating material of the separately molded small part (14F) is integrally molded together with the thermoplastic resin (1D).

  The manufacturing method of the composite laminate and the integrally molded product of the present invention does not deteriorate the wireless communication performance while maintaining the electromagnetic wave shielding property, effectively prevents warping and deformation, and ensures mass productivity while being excellent in design. It can be manufactured in a shorter time than the prior art.

(A) The perspective view which shows an example of the integrally molded product using the manufacturing method of the composite laminated board in this invention, the fragmentary sectional view of the junction part, (b) The enlarged view of a part of fragmentary cross section. It is process drawing explaining one form of the manufacturing method of the composite laminated board in this invention, (a) Lamination process, (b) Press molding process, (c) Schematic sectional drawing of the obtained composite laminated board, respectively. . (A) The lamination | stacking method in the boundary part of the 2nd base material (3b) different from the 1st reinforcement base material (3a) and the 1st base material which are sheet-like papermaking which has an electroconductive discontinuous reinforcement fiber is shown. It is a schematic cross-sectional view, and (b) is a front view showing a state of butting in the same plane. (A) The lamination | stacking method in the boundary part of the 2nd base material (4b) different from a 1st reinforcement base material (4a) and a 1st base material which is a sheet-like papermaking which has an electroconductive discontinuous reinforcement fiber is shown. And (b) is a front view in which a part (4L) is superimposed. (A) It is the figure which showed the temperature history at the time of press molding, took the temperature on the vertical axis, took time on the horizontal axis, and showed each process, and (b) the schematic diagram which shows the measuring method of a temperature history. (A) Perspective view of a composite laminate having distortion when laminated so as to surround the molding material (6B) serving as a radio wave transmission region by the molding material (6A) serving as an electromagnetic wave shielding region, (b) It is a schematic diagram of the composite laminated board by which the internal strain was open | released by cut | disconnecting a part. In outsert injection molding, it is the figure which showed one form of the slope process so that the junction part shape with outsert resin might be provided in the outer peripheral edge part of a composite laminated board. (A) The composite laminate plate (8C) and the small component (8F) insulating material are simultaneously molded so as to surround at least part of the outer periphery of the composite laminate plate and the small component of the molded product having the composite laminate plate in the present invention Sectional drawing which represented typically the process for explaining an example which inserts in and encloses at least one part of these outer periphery, and performs an outsert molding using a thermoplastic resin (8D), and (b) It is a partial cross section perspective view of the molded product obtained at this process. It is the schematic for demonstrating the measuring method of electric field shielding property (KEC method). (A) The perspective view of the obtained composite laminated board, (b) The schematic for demonstrating the measuring method of the level | step difference of a junction part, (c) It is an example of the roughness curve figure measured. (A) The perspective view which cut a part of the composite laminated board which concerns on another aspect of this invention, (b) In the laminated structure of a composite laminated board (11C), when the resin film is selected as a core layer (11E) It is the expanded sectional view which showed the lamination example. (A) To explain an example in which outsert molding is performed using a thermoplastic resin (12D) so as to enclose at least a part of the outer periphery of a composite laminate in which a part of a casing-shaped standing wall is integrally molded simultaneously. FIG. 4 is a cross-sectional view schematically showing the step (b), (b) a perspective view of the molded product obtained in this step, and (c) a partial cross-sectional perspective view of the molded product obtained in this step. (A) A perspective view of a molded product that is outsert molded using a thermoplastic resin (13D) so as to surround at least a part of the outer periphery of a composite laminate in which a part of a casing-shaped standing wall is integrally molded simultaneously; (B) It is the perspective view which cut a part of molded article. The insulating material of the small component (14F) that has been molded separately from the composite laminate is inserted into the mold at the same time, and injection molding is performed using the thermoplastic resin (14D) so as to surround at least a part of the outer periphery thereof. It is a perspective view which shows an example of the integrally molded article which has a composite laminated board characterized by being obtained by doing.

  Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. In addition, this invention is not limited to the structure described in drawing.

  As shown in FIG. 1 and FIG. 2, the composite laminate 1C used in the present invention includes at least a first reinforcing substrate 2a and a first substrate which are sheet-like papermaking having conductive discontinuous reinforcing fibers. And a matrix resin sheet 2c mainly composed of a thermoplastic resin. In the following, the manufacturing method of the present invention will be described in detail with respect to these components and preferred embodiments.

  First, components according to the manufacturing method of the present invention will be described in detail.

  The first reinforcing substrate 2a, which is a sheet-like paper having conductive discontinuous reinforcing fibers, is, for example, throwing reinforcing fiber bundles into a dispersion medium, dispersing the reinforcing fibers in the dispersion medium, and then removing the dispersion medium Thus, it is obtained by a process of aligning the reinforcing fibers into a sheet shape. The composite laminated board impregnated with the first reinforcing substrate 2a, which is a sheet-like paper having conductive discontinuous reinforcing fibers, and the matrix resin sheet 2c mainly composed of a thermoplastic resin, which will be described later, is dimensionally stabilized by the fiber reinforcing effect. The first reinforcing substrate 2a, which is a sheet-shaped paper having a conductive discontinuous reinforcing fiber, functions as an electromagnetic wave shielding material by using conductive fibers as well as excellent properties and rigidity, and will be described later. The region formed by the matrix resin sheet 2c containing the thermoplastic resin as a main component is an electromagnetic wave shielding region having high radio wave shielding performance.

The basis weight of the sheet paper according to the present invention is not particularly limited, but is preferably a sheet paper of 30 to 300 g / m ² , and the thickness at this basis weight is 15 to 170 μm. More preferably, the paper is 75 to 200 g / m ² , the thickness is 40 to 120 μm, more preferably 100 to 150 g / m ² , and the thickness is 55 to 90 μm. If the basis weight of the papermaking is too small, fine adjustment can be made in order to obtain the target fiber weight content (Wf), but a large number of papermaking is required for lamination, and the handling at the time of molding is reduced. On the other hand, if the basis weight of the papermaking is large, it becomes possible to form with a small number of laminated sheets in order to achieve the target fiber weight content (Wf). However, since the papermaking is thick, it is difficult to impregnate the molten resin at the time of molding. Become. Based on this, it is possible to exemplify that the basis weight is 100 to 150 g / m ² from the balance of the handleability at the time of molding.

  The second base material 2b different from the first base material functions as a radio wave transmitting material by using insulating fibers or using only a resin, and a second base material different from the first base material. Since the area | region formed with the matrix resin sheet 2c which has 2b and the thermoplastic resin mentioned later as a main component has low radio wave shielding performance, it becomes a radio wave transmission area | region.

  Examples of the conductive fiber used as the reinforcing fiber in the first reinforcing substrate 2a that is a sheet-like paper having conductive discontinuous reinforcing fibers include metal fibers such as aluminum fibers, brass fibers, and stainless fibers, and polyacrylonitrile. Examples thereof include carbon fiber of rayon type, rayon type, lignin type and pitch type (including graphite fiber). These fibers may be subjected to a surface treatment such as a treatment with a coupling agent, a treatment with a sizing agent, or an adhesion treatment of an additive. Moreover, these conductive fibers may be used individually by 1 type, and may use 2 or more types together. Among these conductive fibers, it is preferable to use carbon fibers that can efficiently increase the lightness and rigidity of the housing.

  Examples of the insulating fiber used as the reinforcing fiber in the second base material 2b different from the first base material include glass fiber, organic fiber such as aramid, PBO, polyphenylene sulfide, polyester, acrylic, nylon, and polyethylene, Examples thereof include inorganic fibers such as silicon carbide and silicon nitride. These fibers may be subjected to a surface treatment such as a treatment with a coupling agent, a treatment with a sizing agent, or an adhesion treatment of an additive. Moreover, these insulating fibers may be used individually by 1 type, and may use 2 or more types together. Among these conductive fibers, it is particularly preferable to use glass fibers from the viewpoint of radio wave transmission, specific rigidity, and cost.

  The main component is a thermoplastic resin used as a matrix resin by impregnating the first reinforced substrate 2a, which is a sheet-like paper having conductive discontinuous reinforcing fibers, and the second substrate 2b different from the first substrate. The thermoplastic resin that is the matrix resin sheet 2c is not particularly limited, and specific examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), Polyester such as liquid crystal polyester, polyolefin such as polyethylene (PE), polypropylene (PP), polybutylene, styrene resin, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), polymethylene methacrylate (PMMA), poly salt Vinyl (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), polysulfone (PSU), modified PSU, polyethersulfone ( PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR), polyethernitrile (PEN), phenolic resin, phenoxy resin Fluorine resins such as polytetrafluoroethylene, thermoplastic elastomers such as polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, and fluorine These copolymers, modification products, and may be a two or more blended resins. As the thermoplastic resin component, PPS is preferable from the viewpoint of heat resistance and chemical resistance, polycarbonate and styrene resin are preferable from the viewpoint of molded product appearance and dimensional stability, and polyamide is preferable from the viewpoint of the strength and impact resistance of the molded product. Used. The matrix may contain other elastomers such as rubber components to improve impact resistance in addition to the thermoplastic resin, depending on the application etc., and other fillings to give various functions You may contain a material and an additive. Examples of such fillers and additives include inorganic fillers, flame retardants, conductivity-imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, and coloring prevention. Agents, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, coupling agents and the like.

  Further, the thickness of the matrix resin sheet 2c mainly composed of a thermoplastic resin is not particularly limited, but is preferably a sheet thickness of 30 to 1000 μm, more preferably 50 to 600 μm, and still more preferably 100 to 100 μm. It is a matrix resin sheet having a thickness of 300 μm.

The preferred thickness of the resin sheet is also determined for the same reason as in papermaking. If the thickness is too thin, fine adjustment and impregnation are improved in order to achieve the target fiber weight content (Wf), but a large number of matrix resin sheets are required for lamination, and handling during molding is easy. Decreases. On the other hand, if the thickness is thick, the target fiber weight content (Wf) can be formed with a small number of laminated sheets, but the resin-rich layer that has not been completely impregnated into the papermaking is impregnated. It becomes difficult to do. Based on this, it is possible to exemplify that the basis weight is 100 to 150 g / m ² from the balance of the handleability at the time of molding.

  A preferable production method used for the composite laminate of the present invention is a first reinforcing substrate 2a which is a sheet-like paper having conductive discontinuous reinforcing fibers, and a second substrate 2b which is different from the first substrate. And forming a laminated body before molding in which a matrix resin sheet 2c containing a thermoplastic resin as a main component is laminated on at least a part of layers between at least a plurality of laminated substrates. The pre-molding laminate is placed in the mold, and pressure is applied while the mold is heated and melted with a press, so that the matrix resin that has been in the form of a sheet is impregnated into the pre-molding laminate and then cooled in the mold. Then, it is a method of obtaining the composite laminate 2C by integrally forming by shaping.

  FIG. 1 shows an example of a method for producing a composite laminate obtained by the present invention. The composite laminate 2C obtained according to the present invention is an electromagnetic shielding material in which a matrix resin sheet 2c mainly composed of a thermoplastic resin is impregnated in a first reinforcing substrate 2a which is a sheet-like paper having conductive discontinuous reinforcing fibers. A molding material 1A serving as a region and a molding material 1B serving as a radio wave transmission region in which a matrix resin sheet 2c mainly composed of a thermoplastic resin is impregnated in a second base material 2b different from the first base material, A joint 1AB is formed between the molding material 1A serving as the shielding region and the molding material 1B serving as the radio wave transmission region.

  The composite base material obtained by butt-joining the first reinforced base material 2a and the second base material 2b different from the first base material can obtain sufficient strength even if the base materials are butt-joined in the in-plane direction. . As shown in FIG. 2, the composite base material is laminated as shown in FIG. 4 as a more preferable form in order to align the butt-joined portions in the thickness direction and to further improve the smoothness of the surface appearance. In this way, it is preferable that the joint portions 1AB are alternately stacked. By alternately superimposing, the depth of the groove formed in the joint after molding becomes shallow, and the surface state can be kept smoother.

  As shown in FIG. 4, when the overlapped region length is an overlap length of 4L, the upper limit of the overlap length is not particularly limited, but the overlap length 4L is changed according to the size of the molded product to be manufactured. It is preferable. The length is preferably 1% to 10%, more preferably 1% to 5%, with respect to the length of the molded product in the overlapping direction. If it is less than 1%, a large base material may not be a problem. However, in the case of a case size of a notebook personal computer like the present invention, the overlap length is too short when overlapping, It becomes difficult to match. In addition, when the size exceeds 10%, when considering the case size, the appearance may be deteriorated because the overlap region is formed over a wide range within the top surface of the case. Due to the overlap, the groove depth becomes shallow and the surface state tends to be kept smoother, and a stronger joint can be formed. Further, it can be exemplified as 10% or less from the balance of surface smoothness, bonding strength, and productivity.

  Further, the arrangement method of the second base material 3b is not particularly limited. However, as shown in FIG. 3 or FIG. 4, the first base material 3b is different from the first base material 3b in the second base material 3b. The state arrange | positioned so that at least one part of outer periphery may be covered is preferable. For example, when the second base material 3b different from the first base material is only a resin, or the reinforcing fibers of the second base material 3b different from the first base material are compared with the first reinforcing base material 3a. When a fiber having a large fiber diameter is selected, or when the fiber weight content (Wf) is low, the second base material 3b different from the first base material may flow due to the molding pressure, and the shape may be greatly collapsed. This is to prevent this.

  Such a substrate laminate is not limited to the above-described lamination method, and may be laminated as long as the other substrates other than the composite substrate are not impaired. Similarly, the position and area size of the molding material 1B to be a radio wave transmission area are not limited, and the position may be changed as necessary, or divided into two or more locations, or the size may be changed. Also good. Further, a layer without the molding material 1B serving as the radio wave transmission region (only the molding material 1A serving as the electromagnetic wave shielding region) may be provided.

  In addition, the method of laminating the matrix resin sheet 3c mainly composed of a thermoplastic resin in the thickness direction is different from the first reinforcing substrate 3a and the first substrate at least on the surface layer in the thickness direction as described above. 2 base material 3b or a base material laminate composed of a composite base material, and more preferably, the first reinforcing base material 3a and the second base material different from the first base material. A matrix resin sheet 3c mainly composed of a thermoplastic resin is sandwiched and laminated between any layers of the material 3b and the composite base material to form a laminate before molding. If the target is to have the same volume content with no unevenness in the thickness direction, the first reinforced substrate is divided by dividing the matrix resin impregnation position into several locations in the thickness direction of the substrate molded body. 3a, the second substrate 3b different from the first substrate, or the matrix resin sheet 3c composed mainly of a thermoplastic resin between the layers of the composite substrate is impregnated in the thickness direction with high flow resistance. Since the distance is shortened, it is effective in making it easier to impregnate each matrix with the molten matrix resin. More preferably, when the matrix resin sheet 3c containing a thermoplastic resin as a main component is arranged between the layers of the base material laminate at substantially equal intervals in the thickness direction, the composite molded plate 2C as a whole has a uniform volume content. Can be molded.

  In addition, as an application example of the laminating method, a plurality of resins having different fluidity are prepared as the matrix resin sheet 3c containing a thermoplastic resin as a main component, and a resin having good fluidity is used for the surface layer. Even the standing wall shape can be formed at a time. Further, by using a decorative film or the like as the outermost layer, a composite laminate having a good appearance can be formed. In this way, the composite laminate can be applied in various ways by changing the lamination method.

  Next, the laminate before molding obtained as described above is subjected to hot press molding at a temperature equal to or higher than the melting point of the matrix resin sheet 2c mainly composed of the thermoplastic resin, and then the matrix resin mainly composed of the thermoplastic resin. The composite laminate 2C is formed by holding the pressure at a temperature lower than the melting temperature of the thermoplastic resin of the sheet 2c until the pressure becomes equal to or lower than the solidification temperature, and performing cooling press molding.

Here, press molding is a method of obtaining a molded body by applying deformation such as bending, shearing, compression, etc. to various materials exemplified by metals, plastic materials, ceramic materials, etc. using a processing machine, a mold, a tool and the like. is there. In the present invention, from the viewpoint of the design properties of the product obtained, the thermoplastic resin is preliminarily heated to a temperature higher than the melting temperature of the thermoplastic resin of the matrix resin sheet 2c mainly composed of the thermoplastic resin. The so-called cold press method is selected, in which after being melted and softened, press molding is performed at a temperature lower than the melting temperature of the thermoplastic resin. Specifically, when the thermoplastic resin of the matrix resin sheet 2c containing a thermoplastic resin as a main component is a crystalline resin, when the melting point is Tm, it is molded to Tm or more, preferably in the range of Tm + 5 ° C. to Tm + 65 ° C. The pre-laminate is heated. Here, the crystalline resin means a resin having substantially a crystallization peak measured by a scanning scanning calorimeter (DSC). When there are a plurality of crystallization peaks, the highest one is selected as Tm. When the thermoplastic resin of the matrix resin sheet 2c composed mainly of thermoplastic resin is a noncrystalline resin, when the melting point of the matrix resin sheet 2c mainly containing thermoplastic resin was _{T g, T g + 120 ℃} ~ The pre-molding laminate is heated to T _g + 170 ° C., preferably in the range of T _g + 120 ° C. to T _g + 150 ° C. Here, the non-crystalline resin means a resin in which a crystallization peak measured by a scanning scanning calorimeter (DSC) does not substantially exist. If the glass transition point there are a plurality is selected as the most high T _g.

  The laminated body before molding is placed on the lower mold which is the lower surface of the molding die, heated to melt and impregnate the thermoplastic resin of the matrix resin sheet 2c mainly composed of the thermoplastic resin, and the thermoplastic resin is melted. In the softened state, the upper mold is then closed and the mold is clamped, and then pressurized, and cooled until the temperature is equal to or lower than the solidification temperature of the thermoplastic resin contained in the matrix resin sheet 2c containing the thermoplastic resin as a main component. . Thereby, the composite laminated board of the design surface with uniform surface roughness can be manufactured.

  The composite laminate produced by the above method may be distorted as shown in FIG. 6 due to a difference in shrinkage ratio or a difference in plate rigidity. In this case, by cutting so that a part of the molding material 6B that becomes a radio wave transmission region different from the first base material in the composite laminate remains, due to a difference in shrinkage rate of the molding material 6B that becomes the radio wave transmission region. It is possible to release the distortion deformation generated in the composite laminate.

However, in each fiber and resin combination, there is a fiber weight content (Wf) value that does not cause distortion. This is not the case when an appropriate Wf is selected for molding and no distortion occurs. At this time, the calculation of the fiber weight content (Wf) is determined by the following equation using w _f : fiber weight and w _re : resin weight.
Wf = w _f / (w _re + w _f ) × 100 (%)

  The composite laminate 1C obtained as described above may be used as an electronic device casing as it is. However, the molded composite laminate is inserted into an injection mold, and then clamped to provide at least one outer periphery of the composite laminate. By subjecting the thermoplastic resin 1D to outsert injection molding so as to cover the part and integrating it, a part having a detailed shape such as a casing-shaped boss or rib can be provided.

  Further, in order to effectively improve the bonding strength, it is preferable to process the outer peripheral end portion of the composite laminated plate so as to provide a bonding portion shape before outsert injection molding. A preferred slope shape is shown in FIG.

  FIG. 7 is a longitudinal sectional perspective view of a slope processing example of a composite laminate.

  An injection molded product IMA7 shown in FIG. 7 is composed of one thermoplastic resin member 7A (corresponding to 1A of the present invention) and the other thermoplastic resin member 7B (corresponding to 1B of the present invention).

  The injection-molded product IMA7 is obtained by injection-molding a resin that forms the thermoplastic resin member 7A on one side end surface SEA in the longitudinal direction of the thermoplastic resin member 7B, so that the thermoplastic resin member 7A has a thermoplastic resin. This is an injection molded product in which the member 7B is joined and both members are integrated. The side end face SEB and the side end face SEA on one side in the longitudinal direction of the thermoplastic resin member 7A are joined together to form a joined face JAB.

  The joint line JL7 drawn by the intersection of the longitudinal section LCS7 of the injection molded product IMA7 and the joint surface JAB is a first joint line segment 7a extending inward from the surface FS7 of the injection molded product and having an end on the inside. A second joint line 7b extending inward from the back surface BS7 and having an end on the inside, and a third joint line connecting the end of the first joint line 7a and the end of the second joint line 7b It is formed from the minute 7ab. In the injection molded product, the third joint line segment 7ab is inclined with respect to the direction of the normal line of the front surface FS7 or the direction of the normal line of the back surface BS7.

  In the injection molded product IMA7, the direction of the first bonding line segment 7a is inclined with respect to the normal line of the front surface FS7, and the direction of the second bonding line segment 7b is inclined with respect to the normal line of the back surface BS7. Yes.

  The first joint line segment 7a, the second joint line segment 7b, and the third joint line segment 7ab are preferably straight lines. It may be gently bent in the thickness direction, that is, in the normal direction. Further, the third joint line segment 7ab may be formed of a combination of a plurality of sub line segments having different angles with respect to the normal line. In this case, the angle with respect to the normal line of the joint line segment 7ab is an average value of the angles with respect to the normal lines of the sub-line segments.

  In the injection molded product IMA7, the normal direction of the front surface FS7 and the normal direction of the back surface BS7 may be the same or different. In the injection molded product, the direction of the first joint line segment 7a is substantially parallel to the normal line of the surface FS7, and the direction of the second joint line segment 7b is inclined with respect to the normal line of the back surface BS7. Alternatively, the direction of the first bonding line segment 7a is inclined with respect to the normal line of the front surface FS7, and the direction of the second bonding line segment 7b is substantially parallel to the normal line of the back surface BS7. May be.

  When the direction of the first joint line segment 7a is substantially parallel to the normal line of the surface FS7 and the direction of the second joint line segment 7b is inclined with respect to the normal line of the back surface BS7, the second The inclination angle of the joining line segment 7b is selected to be different from the inclination angle of the third joining line segment 7ab. As a result, three types of bonding surfaces having different angles with respect to the normal line are formed on the bonding surface JAB. That is, the joint surface JAB is formed by two types of slope surfaces having different angles and an upright surface.

  When the direction of the second bonding line segment 7b is substantially parallel to the normal line of the back surface BS7 and the direction of the first bonding line segment 7a is inclined with respect to the normal line of the surface FS7, the first The inclination angle of the joining line segment 7a is selected to be different from the inclination angle of the third joining line segment 7ab. As a result, three types of bonding surfaces having different angles with respect to the normal line are formed on the bonding surface JAB. That is, the joint surface JAB is formed by two types of slope surfaces having different angles and an upright surface.

  The direction of the first bonding line segment 7a is inclined with respect to the normal line of the front surface FS7, the direction of the second bonding line segment 7b is inclined with respect to the normal line of the back surface BS7, and the inclination angles thereof are different. If so, these inclination angles are selected so as to be different from the inclination angle of the third joint line segment 7ab. As a result, three types of bonding surfaces having different angles with respect to the normal line are formed on the bonding surface JAB. That is, the joint surface JAB is formed by three types of slope surfaces having different angles.

  The direction of the first bonding line segment 7a is inclined with respect to the normal line of the front surface FS7, the direction of the second bonding line segment 7b is inclined with respect to the normal line of the back surface BS7, and these inclination angles are the same. In this case, these inclination angles are selected so as to be different from the inclination angle of the third joint line segment 7ab. Thereby, two types of joint surfaces having different angles with respect to the normal line are formed on the joint surface JAB. That is, the joint surface JAB is formed by two slope surfaces having the same angle and one slope surface having a different angle.

  A width direction joint line WJL7 formed by joining the joint surface JAB to the front surface FS7 or the back surface BS7 is drawn as a straight line in the injection molded product IMA7. However, the width direction joining line WJL7 may draw a curve.

  In this injection-molded product, it is preferable that one thermoplastic resin member 7A and the other thermoplastic resin member 7B have regions that do not overlap with each other in the normal direction. FIG. 7 shows regions 7A1 and 7B1 that do not overlap each other. Since there are regions that do not overlap each other, the characteristics of the respective resin members are maximized in the regions that do not overlap each other. Thereby, the thickness of the injection molded product can be further reduced. When there is no region that does not overlap each other, that is, when one of the thermoplastic resin member 7A and the other thermoplastic resin member 7B is biased to either the front or back of the injection molded product, one thermoplastic resin member Due to the difference in molding shrinkage between 7A and the other thermoplastic resin member 7B, the warpage of the injection molded product may increase.

  In this injection molded product, the thickness 7t0 of the injection molded product in the vertical cross section where the angle (slope angle) that forms an acute angle with respect to the direction perpendicular to the normal to the third joining line segment is maximum is 0.5 to 3. It is preferably 0 mm.

In this injection molded product, in the longitudinal section where the slope angle is maximum, the thickness of the injection molded product at the joint surface where the first joint line segment is located is 7t1, and the injection molding at the joint surface where the third joint line segment is located. When the thickness of the product is 7t2, the thickness of the injection-molded product at the joint surface where the second joint line is located is 7t3, and the length when the third joint line is projected in the normal direction is L7, It is preferable to satisfy the formulas (1) to (4) shown in FIG.
0.7> 7t1 / 7t0> 0.1 (1)
0.8> 7t2 / 7t0 ≧ 0 (2)
0.7> 7t3 / 7t0> 0.1 (3)
1.0> 7t2 / L7 ≧ 0 (4)

  Note that the value of 7t2 is equal to the value of (7t0-7t1-7t3).

  When each value of (7t1 / 7t0) and (7t3 / 7t0) exceeds 0.7, the length of the first joining line segment and the second joining line segment becomes too long, and a thermoplastic resin member is formed. When resin is injection-molded, stress concentration based on injection pressure is likely to occur, and bonding strength may be reduced.

  When each value of (7t1 / 7t0) and (7t3 / 7t0) is less than 0.1 or (7t2 / 7t0) is greater than 0.8, the intersection of the joint surface of both members and the mold surface is sharp. Since it becomes an edge and the injection pressure is concentrated on the tip of the edge, burrs are likely to occur during injection molding.

  If the value of (7t2 / 7t0) is less than 0.1, the inclination of the third joining line segment is substantially eliminated and the area of the joining surface cannot be increased, so that the joining strength may be lowered.

  It is more preferable that the relationship of 0.8> 7t2 / 7t0> 0.1 is satisfied. Further, by satisfying the relationship of 1.0> 7t2 / L7 ≧ 0, it is possible to reduce the resin shortage (drop) and maintain the bonding strength.

  Avoid sharp edges formed by these boundary portions at the boundary portion between the first joint line segment and the third joint line segment and at the boundary portion between the second joint line segment and the third joint line segment. For this reason, it is preferable that a curved surface portion is appropriately provided for reinforcing the strength of the joint portion. The radius R of the curved surface portion is preferably 0.1 to 1.5 mm.

  Convex portions such as ribs and protrusions, or concave portions such as holes and grooves may be provided on the joint surface as long as they do not impair the injection moldability.

  In the present injection-molded product, it is preferable that the front surface or the back surface including a portion protruding from the one thermoplastic resin member 7A on the other thermoplastic resin member 7B side through the bonding surface is a design surface. A slope consisting of the third joint line segment of the thermoplastic resin member that is preliminarily placed in the mold projects over to the design surface side, and the thermoplastic resin member that is subsequently injection-molded is placed on the surface opposite to the design surface As a result, the thermoplastic resin member arranged in advance in the mold is integrated with the resin injected later while being pressed against the design surface forming surface of the mold by the injection pressure of the resin injected later. Since it shape | molds, the surface position of each member by the side of a design surface aligns, and the width direction joining line between each member which appears on a design surface, and its vicinity part become smoother.

  In this injection molded product, the angle formed by the normal line between the first joint line segment 7a and the surface FS7 of the thermoplastic resin member 7A is R1, and the second joint line segment 7b and the normal line of the back surface BS7 of the thermoplastic resin member 7B. It is preferable that the relationship of 10 ° <R1 ≦ 90 ° and 10 ° <R2 ≦ 90 ° is simultaneously satisfied when the angle formed by R2 is R2. More preferably, the relationships of 20 ° <R1 <40 ° and 20 ° <R2 <40 ° are simultaneously satisfied.

  When the angle R1 and the angle R2 exceed 90 °, burrs are generated in the width direction joining line on the front surface or the back surface and in the vicinity thereof. When the angle R1 and the angle R2 are 10 ° or less, the flow of the resin is hindered, so that a short shot occurs, the smoothness of the front or back surface is impaired, and the strength may be lowered.

  The thermoplastic resin 1D for outsert injection molding preferably contains the same thermoplastic resin as that of the matrix resin sheet 2c containing the thermoplastic resin as a main component. As a preferable form, 3 to 100% of the same thermoplastic resin is contained. The thermoplastic resin 1D is more preferably the same as the matrix resin sheet 2c whose main component is a thermoplastic resin. By making it the same as the matrix resin sheet 2c which has a thermoplastic resin as a main component, the bonding strength of the molding material 1A serving as an electromagnetic wave shielding region and the molding material 1B serving as a radio wave transmission region and the thermoplastic resin 1D is improved. Because it can. There is no restriction | limiting in particular about a reinforcement, A reinforcement fiber resin can also be used only with a thermoplastic resin. The reinforcing fiber used for the thermoplastic resin 1D may be the conductive fiber or the insulating fiber. The fiber content is 5 to 80% by weight, preferably 10 to 60% by weight, more preferably 15 to 50% by weight. Generally, if the reinforcing fiber is less than 5% by weight, the effect of improving the mechanical properties of the molded product is small, and if it exceeds 70% by weight, the fluidity may be lowered during molding such as injection molding.

  Specifically, as shown in FIG. 8, the outsert injection molding of the present invention comprises a composite laminate made of fiber reinforced plastic partially molded with the above-described manufacturing method and having a radio wave transmission region, and an injection mold cavity. After being placed on the side, the mold is clamped, the thermoplastic resin 8D is injected from the injection molding machine with a screw, and is injection molded onto the outer periphery of the composite laminate via a sprue and a runner. The parts molded with the thermoplastic resin 8D are integrated to form an integrally molded product.

  Further, the standing wall of the present invention is an outer frame portion formed so that an angle with respect to the composite laminated plate serving as the casing top surface in the casing-shaped molded product of FIG. 1 is 90 degrees. In the present invention, the formation by outsert molding on the outer edge of the composite laminate with the thermoplastic resin 1D and the simultaneous molding when the composite laminate is press-molded are exemplified.

  The thickness of the standing wall is preferably 0.5 to 3.0 mm. More preferably, it is 1-2 mm. If the thickness is too thin, the strength may be insufficient, or the resin may not reach the thinnest part during injection molding, which may cause molding defects such as short shots and gas accumulation. The thickness may be appropriately changed in terms of the size of the molded product and the moldability strength.

  Moreover, it is desirable that the thickness of the standing wall be approximately the same as the thickness of the composite laminate that forms the top surface of the housing. The thickness may be different at one end portion on the top surface side and the other end portion. The length of the standing wall is preferably 5 to 10 mm. Moreover, each four sides may have different lengths.

  The electromagnetic wave shielding property of the composite laminate of the present invention molded as described above is such that the molding material 1A serving as the electromagnetic wave shielding region has good electromagnetic wave shielding performance, and specifically, an electric field shield measured by the KEC method. The characteristic is 10 to 80 dB in the frequency band of 1 GHz. In addition, the molding material 1B serving as the radio wave transmission region has good radio wave transmission performance, and specifically, the electric field shielding property measured by the KEC method is 0 to 10 dB in the frequency 1 GHz band. In the integrally molded product having the composite laminate, the electric field shielding property of the electromagnetic wave shielding region and the electric field shielding property at each part of the radio wave transmission region are the molding material 1A that becomes the electromagnetic wave shielding region that forms each part and the molding that becomes the radio wave transmission region. It is measured by a reference molded body using a single material 1B. Specifically, an integral molded product having a composite laminate is formed by forming a molding precursor using a single molding material base by laminating the same number of laminates as in the case of producing an integrally molded product having a composite laminate. Is molded under the same molding process conditions as in the case of manufacturing, and the electric field shielding property is measured for a reference molded body having the same thickness as the molded product. The same equivalent thickness here is the target thickness ± 0.05 mm. If the material thickness is within this range, there is often no clear difference in electromagnetic shielding properties. FIG. 9 shows an electric field shielding measuring device.

  The preferred form of the fiber weight content (Wf) of the conductive fibers in the molding material 1A to be an electromagnetic wave shielding region is preferably 5 to 80% by weight, more preferably 10 to 70% by weight, and still more preferably 15% per weight. It is contained at a ratio of ˜60% by mass. If the amount is less than 5% by weight, the resulting product may have insufficient rigidity and may be easily deformed. If the amount exceeds 80% by weight, the fluidity of the thermoplastic resin may be significantly reduced and press molding may be difficult.

  A preferable form of the fiber weight content Wf of the insulating fiber in the molding material 1B to be the radio wave transmission region is preferably 0 to 80% by weight, more preferably 5 to 70% by weight, and further preferably 10 to 60% by weight. It is contained in the ratio of the mass%.

  Furthermore, the weight average fiber length of the reinforcing fibers contained in the molding material 1A serving as an electromagnetic wave shielding region and the molding material 1B serving as a radio wave transmission region is preferably 1 to 15 mm, more preferably 1.5 to 10 mm, and even more preferably 2 ˜6.5 mm. If the weight average fiber length of the reinforcing fiber is less than 1 mm, the resulting product may have insufficient rigidity and may be easily deformed. If the weight average fiber length of the reinforcing fiber is more than 15 mm, the appearance after pressing, such as fiber floating Defects are likely to occur.

  The composite laminate 1C of the present invention includes a molding material 1A serving as an electromagnetic wave shielding region, a molding material 1B serving as a radio wave transmission region, a matrix resin sheet 2c mainly composed of a thermoplastic resin, and a core as shown in FIG. It can also have a layer 11E. In the present invention, the core layer is at least one selected from a film, a sheet, and a foam.

  In terms of material mechanics, the bending rigidity of the laminated member on the surface layer side is much larger than the rigidity of the core layer, so that the surface layer is a molding material 1A layer serving as an electromagnetic shielding region and a molding material 1B serving as an electromagnetic wave transmission region. By configuring the core layer 11E with a core member layer such as a foam material or a lightweight resin sheet, the laminated member can be reduced in weight and rigidity can be ensured.

  The film, sheet, and foam used as the core layer are not particularly limited as long as the adhesive force with the molding material on the surface layer side is ensured. For example, a thermoplastic resin, a thermosetting resin, or a metal is used. Can do. Further, a film or sheet containing reinforcing fibers in the core layer may be used.

  The thermoplastic resin constituting the core layer is not particularly limited, and specific examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), liquid crystal polyester. Polyester such as polyethylene, polyolefin such as polyethylene (PE), polypropylene (PP), polybutylene, styrene resin, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), polymethylene methacrylate (PMMA) ), Polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyetherimide (PEI), poly Luhon (PSU), modified PSU, polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR), poly Fluorine resins such as ether nitrile (PEN), phenolic resin, phenoxy resin, polytetrafluoroethylene, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, fluorine, etc. It may be a thermoplastic elastomer or the like, a copolymer, a modified body thereof, or a resin blended with two or more. As the thermoplastic resin component, PPS is preferable from the viewpoint of heat resistance and chemical resistance, polycarbonate and styrene resin are preferable from the viewpoint of molded product appearance and dimensional stability, and polyamide is preferable from the viewpoint of the strength and impact resistance of the molded product. Used.

  Examples of the thermosetting resin constituting the core layer include unsaturated polyesters, vinyl esters, epoxies, phenols (resol type), urea melamines, polyimides, copolymers thereof, modified products, and at least of these. A resin in which two kinds are blended can be used. Further, in order to improve impact resistance, a resin obtained by adding a thermoplastic resin or other elastomer or rubber component to the thermosetting resin may be used. The thermoplastic resin and the thermosetting resin constituting the core layer may contain other elastomers such as a rubber component in order to improve impact resistance, in addition to the resin, depending on the application. In order to provide various functions, other fillers and additives may be contained. Examples of such fillers and additives include inorganic fillers, flame retardants, conductivity-imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, and coloring prevention. Agents, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, coupling agents and the like.

  Examples of the reinforcing fibers contained in the matrix constituting the core layer include metal fibers such as aluminum fibers, brass fibers and stainless fibers, polyacrylonitrile-based, rayon-based, lignin-based, pitch-based carbon fibers, graphite fibers, and glass fibers. , Inorganic fibers such as silicon carbide fiber and silicon nitride fiber, organic fibers such as aramid fiber, polyparaphenylene benzobisoxazole (PBO) fiber, polyphenylene sulfide fiber, polyester fiber, acrylic fiber, nylon fiber, polyethylene fiber, etc. Can be used. These reinforcing fibers may be used alone or in combination of two or more. The reinforcing fibers do not necessarily have to be continuous throughout the core layer, and there is no particular problem even if they are divided in the middle.

  Alternatively, the molded product produced by the production method of the present invention can take an applied form. The application forms are shown in FIGS. 12, 13 and 14. FIG. In FIG. 12, after impregnating with a hot-melt press, when cooling and shaping in a mold, a part of the casing-shaped standing wall is simultaneously molded so as to surround at least a part of the outer periphery of the composite laminate. (1D) An integrally molded product having a composite laminate 1C obtained by injection molding using a thermoplastic resin is formed separately from the integrally formed composite laminate 14A in FIG. A composite laminate obtained by inserting the insulating material of the small component 14F into the mold at the same time and injection-molding it using the thermoplastic resin 1D so as to surround at least a part of the outer periphery thereof. The form of an integrally molded product having 1C was shown.

  A composite laminate in which a part of the casing-shaped standing wall is integrally formed at the same time can be obtained by adding an application in which a part of the plate is bent and formed. When bending is performed, a molding pressure can be effectively applied to the standing wall portion by providing a gradient to the mold portion that shapes the standing wall.

  The method for molding the insulating material of the small component 14F is not particularly limited, and specific examples include injection molding, press molding, pultrusion molding, RTM molding, autoclave molding, and hand layup molding that are generally used in industry. Machining and forming such as lathe processing and milling. Among these, the injection molding method is preferable from the viewpoint of productivity.

  There is no restriction | limiting in particular in the insulating material of the small components 14F, For example, a thermoplastic resin, a thermosetting resin, or a metal can be used. Furthermore, you may use a reinforced fiber for the insulating material of the small components 14F.

  The thermoplastic resin constituting the insulating material of the small component 14F is not particularly limited, and specific examples include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), and polyethylene naphthalate (PEN). ), Polyesters such as liquid crystal polyester, polyolefins such as polyethylene (PE), polypropylene (PP) and polybutylene, styrene resins, polyoxymethylene (POM), polyamide (PA), polycarbonate (PC), poly Methylene methacrylate (PMMA), polyvinyl chloride (PVC), polyphenylene sulfide (PPS), polyphenylene ether (PPE), modified PPE, polyimide (PI), polyamideimide (PAI), polyetherimide PEI), polysulfone (PSU), modified PSU, polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyarylate (PAR) ), Polyether nitrile (PEN), phenolic resin, phenoxy resin, polytetrafluoroethylene, and other fluorine resins, polystyrene, polyolefin, polyurethane, polyester, polyamide, polybutadiene, polyisoprene, fluorine It may be a thermoplastic elastomer such as a system, a copolymer, a modified body thereof, or a resin blended with two or more kinds. As the thermoplastic resin component, PPS is preferable from the viewpoint of heat resistance and chemical resistance, polycarbonate and styrene resin are preferable from the viewpoint of molded product appearance and dimensional stability, and polyamide is preferable from the viewpoint of the strength and impact resistance of the molded product. Used.

  Examples of the thermosetting resin constituting the insulating material of the small component 14F include unsaturated polyester, vinyl ester, epoxy, phenol (resole type), urea melamine, polyimide, and their copolymers, modified products, and the like. A resin in which at least two of these are blended can be used. Further, in order to improve impact resistance, a resin obtained by adding a thermoplastic resin or other elastomer or rubber component to the thermosetting resin may be used. The thermoplastic resin and the thermosetting resin constituting the core layer may contain other elastomers such as a rubber component in order to improve impact resistance, in addition to the resin, depending on the application. In order to provide various functions, other fillers and additives may be contained. Examples of such fillers and additives include inorganic fillers, flame retardants, conductivity-imparting agents, crystal nucleating agents, ultraviolet absorbers, antioxidants, vibration damping agents, antibacterial agents, insect repellents, deodorants, and coloring prevention. Agents, heat stabilizers, mold release agents, antistatic agents, plasticizers, lubricants, colorants, pigments, dyes, foaming agents, antifoaming agents, coupling agents and the like.

  Examples of the reinforcing fibers contained in the matrix constituting the insulating material of the small component 14F include inorganic fibers such as polyacrylonitrile, rayon, lignin, glass fiber, silicon carbide fiber, silicon nitride fiber, aramid fiber, Organic fibers such as polyparaphenylene benzobisoxazole (PBO) fiber, polyphenylene sulfide fiber, polyester fiber, acrylic fiber, nylon fiber, and polyethylene fiber can be used. These reinforcing fibers may be used alone or in combination of two or more.

  Hereinafter, the present invention will be described in more detail with reference to examples. EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, the following Example does not restrict | limit this invention.

[Measurement method of electric field shielding properties (KEC method)]
FIG. 9 is a schematic longitudinal sectional view of an electric field shielding measuring apparatus. In FIG. 9, the electric field shielding measuring device 9b is composed of a measuring casing made of a metal tube 9f. The internal space of the metal tube 9f is shielded from the outside. A signal transmission antenna 9c and a signal reception antenna 9e are provided in the internal space of the metal tube 9f. In the metal tube 9f, a measurement sample 9a can be inserted between both antennas from the outside. The measurement sample 9a has a measurement sample thickness 9d.

A measurement sample 9a is inserted between the signal transmitting antenna 9c and the signal receiving antenna 9e in the space shielded by the metal tube 9f, and the strength of the electric field due to the presence or absence of the sample is measured.
The measuring device 9b measures the strength of the electric field depending on the presence or absence of the measurement sample 9a. The shielding effect is obtained by the following equation, where E ₀ [V / m] is the electric field strength in the space when there is no measurement sample, and E _X [V / m] is the electric field strength in the space when the measurement sample is present. The sign of the measured value is the direction in which the positive direction has a shielding effect.
Field shielding (shield _{effect) = - 20log 10 E 0 /} E X [dB]

[Step difference of joint in fiber reinforced plastic molding]
At the joint portion of the fiber reinforced plastic molded body in which a plurality of molding material base materials are joined, the surface roughness meter measuring head 10a is scanned across the joint portion by using a surface roughness measuring device, and the surface of the molded body The roughness curve of Y direction displacement (unit: μm) -measurement stroke (unit: mm) is measured by the method as illustrated in FIG. 10e is obtained. As measurement conditions, a measurement stroke is 20 mm, a measurement speed is 0.3 mm / s, a cutoff value is 0.3 mm, a filter type is Gaussian, and no tilt correction is selected. The joint is set at a 10 mm portion which is the midpoint of the measurement stroke. Here, the step 10f of the joint portion refers to a difference between the maximum Y-direction displacement of the peak and the minimum Y-direction displacement of the bottom of the obtained roughness curve. In this example, Surfcom 480A manufactured by Tokyo Seimitsu Co., Ltd. was used as the surface roughness measuring instrument, and the surface roughness meter measuring head 10a was scanned so as to cross the joint vertically.

(Reference Example 1)
A carbon fiber continuous bundle of “Torayca (registered trademark)” T700S-24K manufactured by Toray Industries, Inc. was cut with a cartridge cutter to obtain a chopped yarn having a fiber length of 6.4 mm. A surfactant was added thereto and stirred, then poured into a paper machine, dehydrated by suction, and then dried to obtain a non-woven material composed of carbon fibers. Next, this non-woven material was cut into a size outside the product, and then three non-woven materials, polyamide 6 resin (“Amilan” (registered trademark) CM1001 manufactured by Toray Industries, Inc., melting point: 225 ° C., glass transition temperature) A resin material 4A made of 47 ° C., a crystalline resin) was sandwiched, pressed at a temperature of 260 ° C. and a pressure of 5 MPa, and then cooled to obtain a molding material 1A serving as an electromagnetic wave shielding region having a thickness of 1.0 mm. The content of the carbon fiber in the molding material 1A serving as the electromagnetic shielding region was 35% by weight, and the obtained reference molded product had an electric field shielding property in the KEC method of 35 dB in the 1 GHz band.

(Reference Example 2)
Except for changing the carbon fiber continuous bundle to a glass chopped strand CS13C-897 made by Nittobo, a molding material 1B that becomes a radio wave transmission region having a thickness of 1.0 mm was obtained by the same method as in Reference Example 1. The obtained reference molded product had an electric field shielding property in the KEC method of 2 dB in the 1 GHz band.

(Reference Example 3)
A non-woven material made of carbon fiber and a non-woven material made of glass fiber are laminated so as to have the same weight fiber content Wf, and the resin film 4 layers are sandwiched, and the temperature is 260 ° C., pressure After pressing at 5 MPa, cooling was performed to obtain a composite laminate 1C composed of a molding material 1A serving as an electromagnetic wave shielding region having a thickness of 1.0 mm and a molding material 1B serving as a radio wave transmission region.

  When the level difference of the joint portion between the molding material 1A serving as an electromagnetic wave shielding region and the molding material 1B serving as a radio wave transmission region of the obtained composite laminate 1C was measured with a surface roughness measuring instrument, the level difference was 10 μm.

Example 1
A carbon fiber continuous bundle of “Torayca (registered trademark)” T700S-24K manufactured by Toray Industries, Inc. was cut with a cartridge cutter to obtain a chopped yarn having a fiber length of 6.4 mm. A surfactant was added thereto and stirred, then poured into a paper machine, dehydrated by suction, and then dried to obtain a non-woven material composed of carbon fibers.

  A surfactant was added to a glass chopped strand CS13C-897 manufactured by Nittobo Co., Ltd. and stirred, then poured into a paper machine, dehydrated by suction, and then dried to obtain a nonwoven material composed of glass chopped strands.

  Next, after these non-woven materials are cut to the outer size of the product, non-woven materials made of carbon fibers and non-woven materials made of glass fibers are laminated so that the non-woven materials made of carbon fibers are Polyamide 6 resin (manufactured by Toray Industries, Inc., “Amilan” (registered trademark) CM1001 (melting point: 225 ° C.), so that the non-woven material made of glass fiber has a fiber content Wf of 25% and a weight fiber content Wf of 30%. A resin film made of a glass transition temperature of 47 ° C. and a crystalline resin) was sandwiched in a sandwich shape to obtain a laminate before molding.

  After melt impregnation with a heating press (temperature 260 ° C., pressure 5 MPa), a composite laminate 1C having a thickness of 1.45 mm was obtained by cooling press (temperature 100 ° C., pressure 5 MPa).

  Next, the obtained composite laminate was cut into the shape of the top surface of the casing with an NC processing machine MDX-540 manufactured by Roland. At this time, the composite laminate was processed so as to have a slope shape with the outsert resin at the outer peripheral end portion.

  The composite laminate obtained as described above is placed on the injection mold cavity side and clamped, and the thermoplastic resin 1D is injection-molded on the outer periphery of the composite laminate, and the composite laminate 1C is obtained. And the site | part shape | molded with the thermoplastic resin 1D was integrated, and it was set as the integrally molded product.

  The joint bending strength was cut out from the molded integrally molded product and subjected to a bending test, and the warpage of the casing ridge line was measured by applying a ruler to the molded product placed on a surface plate. The characteristic evaluation results are collectively shown in Table 1.

(Example 2)
The non-woven material made of carbon fiber and the non-woven material made of glass fiber in the pre-molded laminate were laminated so as to be adjacent to each other, except that they were laminated so that the joints overlap each other by 5 mm. Then, the composite laminate 1C and the part molded with the thermoplastic resin 1D were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Example 3)
The non-woven material made of carbon fiber and the non-woven material made of glass fiber in the pre-molded laminate were laminated so as to be adjacent to each other, except that they were laminated so that the joints overlap each other by 10 mm. Then, the composite laminate 1C and the part molded with the thermoplastic resin 1D were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

Example 4
The composite laminate 1C and the thermoplastic resin 1D are obtained in the same manner as in Example 1 except that the nonwoven material made of glass fiber is laminated so that the weight fiber content Wf is 50% when the laminate before molding is obtained. The parts molded in step 1 were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Example 5)
The composite laminate 1C and the thermoplastic resin 1D are obtained in the same manner as in Example 1 except that the non-woven material made of glass fiber is laminated so that the weight fiber content Wf is 80% when the laminate before molding is obtained. The parts molded in step 1 were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Example 6)
The composite laminate 1C and the thermoplastic resin 1D are obtained in the same manner as in Example 1 except that the non-woven material made of carbon fibers is laminated so that the weight fiber content Wf is 7% when the laminate before molding is obtained. The parts molded in step 1 were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Example 7)
The composite laminate 1C and the thermoplastic resin 1D are obtained in the same manner as in Example 1 except that the non-woven material made of carbon fiber is laminated so that the weight fiber content Wf is 60% when obtaining the laminate before molding. The parts molded in step 1 were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Example 8)
In the same manner as in Example 1 except that a resin film is used instead of the non-woven material made of glass fiber that becomes the molding material 1B that becomes the radio wave transmission region when obtaining the laminate before molding, the composite laminate 1C, The parts molded with the thermoplastic resin 1D were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

Example 9
A composite laminate 1C and a thermoplastic resin 1D are obtained in the same manner as in Example 1 except that a resin film N66 sheet (thickness t = 0.5 mm) serving as a core layer is laminated at the center when obtaining a laminate before molding. The parts molded in step 1 were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Comparative Example 1)
A carbon fiber continuous bundle of “Torayca (registered trademark)” T700S-24K manufactured by Toray Industries, Inc. was cut with a cartridge cutter to obtain a chopped yarn having a fiber length of 6.4 mm. A surfactant was added thereto and stirred, then poured into a paper machine, dehydrated by suction, and then dried to obtain a non-woven material composed of carbon fibers. Next, the nonwoven material is cut into an outer size of the product, and then the polyamide 6 resin (“Amilan” (manufactured by Toray Industries, Inc.) is used so that the nonwoven material made of carbon fiber has a weight fiber content Wf of 25%. 4 layers of resin films made of registered trademark CM1001 (melting point: 225 ° C., glass transition temperature 47 ° C., crystalline resin) are sandwiched, pressed at a temperature of 260 ° C. and a pressure of 5 MPa, and then cooled to a thickness of 1. A molding material 1A to be a 45 mm electromagnetic wave shielding region was obtained.

  Next, the obtained molding material is placed on the injection mold cavity side and then clamped, and the thermoplastic resin 1D is injection-molded on the outer periphery of the composite laminate 1C, so that the molding material 1A and the heat are heated. The parts molded with the plastic resin 1D were integrated into an integrally molded product.

  Further, a surfactant was added to Nittobo Co., Ltd. glass chopped strand CS13C-897 and stirred, then poured into a paper machine, dehydrated by suction, and then dried to obtain a nonwoven material composed of glass chopped strands. Next, the nonwoven material is cut into an outer size of the product, and then the polyamide 6 resin (“Amilan” (manufactured by Toray Industries, Inc.) is used so that the nonwoven material made of carbon fiber has a weight fiber content Wf of 50%. 4 layers of resin films made of registered trademark CM1001 (melting point: 225 ° C., glass transition temperature 47 ° C., crystalline resin) are sandwiched, pressed at a temperature of 260 ° C. and a pressure of 5 MPa, and then cooled to a thickness of 1. A molding material 1B to be a 45 mm radio wave transmission region was obtained.

  Next, a part of the integrally molded product was cut out with an NC processing machine, and the molding material 1B was fitted into the cut-out portion of the integrally molded product to obtain a pre-molding precursor.

  Thereafter, the molding precursor is heated in an oven equipped with a far-infrared heater until the surface temperature reaches 235 ° C. The surface temperature of a molding die having a male die as a lower die and a female die as an upper die is adjusted to 85 ° C., the die is opened, a heated molding precursor is set, and the thickness of the cavity is 1. The mold was clamped to 45 mm and press-molded to obtain a molded product. The characteristic evaluation results are collectively shown in Table 1.

(Comparative Example 2)
When obtaining a laminate before molding, a nonwoven material made of glass fibers is laminated so as to have a weight fiber content Wf of 50%, and a liquid thermosetting epoxy resin is used as the impregnating resin, and a heating press (temperature 160). A composite laminate 1C having a thickness of 1.45 mm was obtained in the same manner as in Example 1 except that it was thermally cured at 0 ° C. and a pressure of 2 MPa.

  Next, the obtained composite laminate was cut into the shape of the top surface of the casing with an NC processing machine MDX-540 manufactured by Roland. At this time, the composite laminate was processed so as to have a slope shape with the outsert resin at the outer peripheral end portion.

  The composite laminate obtained as described above is placed on the injection mold cavity side, and then clamped, and the thermoplastic resin 1D is injection-molded on the outer periphery of the composite laminate 1C. The part molded with 1C and the thermoplastic resin 1D was integrated into an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Comparative Example 3)
The composite laminate 1C and the thermoplastic resin 1D are obtained in the same manner as in Example 1 except that the non-woven material made of carbon fibers is laminated so that the weight fiber content Wf is 90% when the laminate before molding is obtained. The parts molded in step 1 were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Comparative Example 4)
The composite laminate 1C and the thermoplastic resin 1D are obtained in the same manner as in Example 1 except that the nonwoven material made of glass fiber is laminated so that the weight fiber content Wf is 90% when the laminate before molding is obtained. The parts molded in step 1 were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

(Comparative Example 5)
In the same manner as in Example 1 except that the resin film made of Prime Polypro J105G resin made by Prime Polymer Co., Ltd. is used to obtain the laminate before molding, the composite laminate 1C and the thermoplastic resin 1D are used. The molded parts were integrated to obtain an integrally molded product. The characteristic evaluation results are collectively shown in Table 1.

  The above characteristic evaluation results are collectively shown in Tables 1 and 2.

  According to the present invention, an electronic device housing having both radio wave blocking performance and wireless communication performance and excellent surface design can be manufactured. Therefore, the electronic device housing can be used without limitation in the field where the functional compatibility is required. It can also be used as a single component constituting a built-in component, but it can be suitably used especially for manufacturing a case for a small electronic device such as a notebook computer or a mobile phone. The integrally molded product of the present invention is extremely useful for various parts and members such as electrical / electronic equipment, OA equipment, home appliances, or automobile parts, internal members, and housings.

DESCRIPTION OF SYMBOLS 1A Molding material 1B used as an electromagnetic wave shielding region Molding material 1C used as a radio wave transmission region 1C Composite laminate 1D Thermoplastic resin 1AB Joining portion 2a of base materials A and B First sheet-shaped paper having conductive discontinuous reinforcing fibers Reinforced base material 2b Second base material 2c different from the first base material 2c Matrix resin sheet 2d containing thermoplastic resin as a main component Press surface plate 2A Molding material 2B serving as an electromagnetic wave shielding region 2C Molding material 2C serving as an electromagnetic wave transmission region Composite laminated board 3a First reinforced base material 3b which is a sheet-like paper having conductive discontinuous reinforcing fibers Second base material 3c different from the first base material Matrix resin sheet 4a mainly composed of a thermoplastic resin First reinforcing substrate 4b which is a sheet-like paper having conductive discontinuous reinforcing fibers Second substrate 4c which is different from the first substrate Matrix resin sheet 4L comprising a thermoplastic resin as a main component -Burr length 5a Heating step 5b Impregnation step 5c Cooling step 5d Temperature history curve 5e Temperature data collection device 5f Reinforced base material composite material 5g Press molding machine 5t Time axis 5t1 Melting temperature 5t2 Solidification temperature 5T Temperature axis 6A Molding material to be an electromagnetic shielding region 6B Molding material IMA7 serving as a radio wave transmission region 7A Injection molded product 7A One thermoplastic resin member 7B The other thermoplastic resin member 7a First joint line segment 7b Second joint line segment 7ab Third joint line segment L7 Third Length JL7 when projected in the normal direction The joint line WJL7 drawn by the intersection of the longitudinal section LCS7 and the joint surface JAB 7 in the width direction joint line 7A1 Both members 7A7B on the one thermoplastic resin member 7A side are Region 7B1 that does not overlap each other Region 7t0 where both members 7A7B on the other thermoplastic resin member 7B side do not overlap each other Molded product thickness 7t1 Injection molded product thickness 7t2 at the joint surface where the first joint line segment is located Injection molding product thickness 7t3 at the joint surface where the third joint line segment is located The second joint line segment is located Thickness R1 of injection-molded product on the joint surface Angle R2 formed by the first joint line segment 7a and the normal line of the surface FS7 of the thermoplastic resin member A Method of the second joint line segment 7b and the back surface BS7 of the thermoplastic resin member 7B Angle SEA formed by one side Side end surface SEB on one side JAB side end surface JAB Joint surface LCS7 Longitudinal section FS7 Surface of injection molded product BS7 Back surface of injection molded product 8A Molding material 8B serving as electromagnetic wave shielding region Molding material serving as radio wave transmission region 8C Composite laminated plate 8D Thermoplastic resin 8F Small part 8a Injection molding machine die 8b Injection molding machine nozzle 9a Measurement sample 9b Electric field shielding measuring device 9c Signal transmission antenna 9d Measurement sample Thickness 9e Signal receiving antenna 9f Metal tube 10A Molding material 10B serving as an electromagnetic wave shielding region Molding material 10a serving as a radio wave transmission region Surface roughness meter measuring head 10b Measurement start point 10c Measurement end point 10d Scanning direction 10e Roughness curve 10f Step 10L Measurement stroke 10XL X-direction stroke axis 10YL Y-direction displacement axis 11A Molding material 11B serving as an electromagnetic wave shielding region Molding material 11C serving as a radio wave transmission region Composite laminate 11D Thermoplastic resin 11E Core layer 11AB Joining portion 12A between base materials A and B Electromagnetic wave Molding material 12B serving as shielding region Molding material 12D serving as radio wave transmission region 12D Thermoplastic resin 12AB Joining portion 13A of base materials A and B Molding material 13B serving as electromagnetic wave shielding region 13D Molding material 13D serving as radio wave transmission region Thermoplastic resin 13AB Base material A and B joint 14A Molding material 14B which becomes electromagnetic wave shielding region 14B Radio wave transmission Joint 14F small part of the joint 14DF substrate D and F of the molding material 14D thermoplastic resin 14DB substrate D and B to be the frequency

Claims (15)

A composite base material obtained by butt-joining a first base material (2a) which is a sheet-like paper having conductive discontinuous reinforcing fibers and a second base material (2b) different from the first base material, A pre-molding laminate is formed in which a matrix resin sheet (2c) mainly composed of a thermoplastic resin is sandwiched between at least a part of the layers of the laminated substrate laminate, and the pre-molding laminate is disposed inside. A method for producing a composite laminate (1C) in which a molded resin is impregnated with a matrix resin by a hot melt press and then integrally molded by cooling in the mold. The method for producing a composite laminate (1C) according to claim 1, wherein the laminates are laminated so that a part of the boundary portion between the adjacent composite substrates overlaps. 3. The heat-melt press, wherein the pressure is maintained during cooling until the temperature of the laminated body before molding is equal to or higher than the melting point and then cooled to a solidification temperature or lower. A method for producing a composite laminate (1C). A material having an electromagnetic wave shielding property measured by the KEC method of 10 to 80 dB in the frequency 1 GHz band of the molding material (1A) to be an electromagnetic wave shielding region impregnated with the matrix resin in the first reinforced substrate (2a) is used. The manufacturing method of the composite laminated sheet (1C) in any one of Claim 1 to 3 characterized by the above-mentioned. Use a material in which the electromagnetic wave shielding property measured by the KEC method of the molding material (1B) which becomes the radio wave transmission region in which the matrix resin is impregnated in the second base material (2b) is 0 to 10 dB in the frequency 1 GHz band. The manufacturing method of the composite laminated sheet (1C) in any one of Claim 1 to 4 characterized by these. The composite laminate (1C) according to any one of claims 1 to 5, wherein a fiber weight content (Wf) of the molding material (1A) serving as the electromagnetic wave shielding region is 5% to 80%. Production method. The molding material (1B) to be the radio wave transmission region can include reinforcing fibers, and the reinforcing fibers include at least one selected from glass fibers, aramid fibers, chemical fibers, and reinforcing fillers that are non-conductive fibers. Item 7. A method for producing a composite laminate (1C) according to any one of Items 1 to 6. The composite laminate (1C) according to any one of claims 1 to 7, wherein a range of fiber weight content (Wf) of the molding material (1B) serving as the radio wave transmission region is 0% to 80%. ) Manufacturing method. Thermoplastic so as to cover at least a part of the peripheral part after providing a slope shape as a joint part on at least a part of the peripheral part of the composite laminate (1C) according to any one of claims 1 to 3. A method for producing an integrally molded product, wherein the resin (1D) is integrated by injection molding. One or more types selected from a resin film, a sheet, and a foam are laminated as a core layer (11E) between the layers of the composite laminate (1C) according to any one of claims 1 to 9. A method for manufacturing an integrally molded product. The method for producing an integrally molded product according to claim 9 or 10, wherein the method is used for any one of an electrical / electronic device housing and a household electrical appliance housing. A composite base material obtained by butt-joining a first base material (2a) which is a sheet-like paper having conductive discontinuous reinforcing fibers and a second base material (2b) different from the first base material, A laminate body before molding in which a matrix resin sheet (2c) mainly composed of a thermoplastic resin is sandwiched between at least a part of the layers of a plurality of laminated substrate laminates is impregnated with a matrix resin by a hot melt press, A composite laminate (1C) in which matrix resin is cooled and integrally molded. The composite laminate (1C) according to claim 12, wherein a part of the laminate before molding is bent to form part of a standing wall. A thermoplastic resin is provided so as to provide at least a part of the peripheral part of the composite laminate plate (1C) according to any one of claims 12 and 13 with a joining part having a slope shape and to cover at least a part of the peripheral part. (1D) is integrally molded by injection molding. 15. The integrally molded product according to claim 14, wherein the insulating material of the separately molded small part (14F) is integrally molded together with the thermoplastic resin (1D).

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