JP2006175375A - Composite structure of resin and brittle material and production method used for it, and electronic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite composition enabling a brittle material layer to be stably formed on a resin material, and also to provide a production method used for it. <P>SOLUTION: The composite composition of the resin material and the brittle material has a base layer comprising an adhesive material adhered to the surface of a resin substrate and a polycrystalline brittle material layer on a part or a whole of the base layer. In the production method of the composite composition of the resin material and the brittle material, fine particles of the brittle material harder than the adhesive material are made to bite into the surface of the adhesive material adhered to the surface of the resin material to form the basic layer. The fine particles of the brittle material are made to collide with the base layer at high speed and are deformed or crushed by the impact of the collision. The polycrystalline brittle material layer is formed on the base layer by recombining the fine particles through an active newly prepared surface caused by the deformation or the crush. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a composite structure including a resin base material and a brittle material such as ceramics or a semimetal, a method for manufacturing the composite structure, and an electronic apparatus to which the composite structure is attached.

  As a method for forming a film of metal or ceramic on the surface of the substrate, a sol-gel method, a vapor deposition method such as PVD or CVD, or a thermal spraying method is known.

  Recently, as a new film formation method, the gas deposition method (Seiichiro Kashu: metal, January 1989 issue) and electrostatic fine particle coating method (Igawa et al .: Preprint of the academic conference of the Japan Society for Precision Machinery Fall 1977 )It has been known. In the former, ultrafine particles such as metals and ceramics are aerosolized by gas agitation and accelerated through a minute nozzle. When they collide with a substrate, part of the kinetic energy is converted into thermal energy, and between particles or between the particles and the substrate. The latter is based on the basic principle. The latter is charged with fine particles and accelerated using an electric field gradient. After that, similar to the gas deposition method, the latter is sintered using thermal energy generated at the time of collision. The basic principle is to do.

Further, as prior arts improved from the above-described gas deposition method or electrostatic fine particle coating method, JP-A-8-81774, JP-A-10-202171, JP-A-11-21777, JP-A-11-330577 are disclosed. And those disclosed in Japanese Patent Application Laid-Open No. 2000-212766. Japanese Patent Application Laid-Open No. 2002-097177 or Japanese Patent Application Laid-Open No. 2002-097176 is known as a prior art using magnetic particles as a raw material.
JP-A-8-81774 JP-A-10-202171 Japanese Patent Laid-Open No. 11-21677 JP 11-330577 A JP 2000-212766 A JP 2002-097177 A JP 2002-097176 A Gas Deposition Method (Seiichiro Kashu: Metal, January 1989 issue) Electrostatic fine particle coating method (Ikawa et al .: Preprint of the academic conference of the Japan Society for Precision Mechanics Fall 1982)

Many of the above-described prior arts are not suitable for forming a brittle material structure on the surface of a resin substrate because the film formation involves heating to such an extent that the resin is melted or gasified. Among the above-described prior arts, some of the improved gas deposition methods form a film without a heating step. However, when the brittle material fine particles directly collide with the resin substrate, the resin substrate In general, it is rich in elasticity compared to brittle materials typified by inorganic materials, and since it is soft, the following two problems may occur.
(1) When it is rich in elasticity, such as unsaturated polyester, nylon, rubber, fluororesin, etc., brittle material fine particles are rebounded, making it impossible to form a film well.
(2) If the resin material is relatively hard and poor in plasticity, such as an acrylic resin or an epoxy resin, the resin substrate will be scraped if it is strongly collided. Also, it is difficult to form a film on polycarbonate or polypropylene.

  Therefore, an international application (PCT JP00 / 07076) has been filed by a part of the present inventors for forming a brittle material structure on the surface of a resin substrate. This invention was made based on the following findings. That is, when a mechanical impact force is applied to a brittle material (ceramics) that does not have spreadability, the crystal lattice shifts along the cleaved surface such as the interface between crystallites or is crushed. When these phenomena occur, a new surface is formed on the slipping surface or fracture surface, in which atoms originally present inside and bonded to other atoms are exposed. The part of the atomic layer on the new surface is exposed to an unstable surface state by an external force from a stable atomic bond state, and the surface energy is high. The active surface joins the adjacent brittle material surface, the newly formed brittle material surface, or the substrate surface, and shifts to a stable state.

  The addition of a continuous mechanical impact force from the outside continuously generates this phenomenon, and the joining is progressed and densified by repeated deformation and crushing of fine particles, thereby forming a brittle material structure. Further, an embodiment of the present invention in which the above-described mechanical impact is caused to cause the brittle material to collide with the substrate with the carrier gas is hereinafter referred to as a fine particle beam deposition method. This method is also called an aerosol deposition method.

  When the cross section of the brittle material structure prepared by the fine particle beam deposition method was observed, there was an anchor part where the injected fine particles or crushed fine fragment particles pierced the base material, and the brittleness that was crushed and deformed on it It was found that the material fine particles had a structure formed by closely bonding without firing. That is, whether or not a brittle material structure is successfully formed by the fine particle beam deposition method depends largely on whether or not the anchor portion exists on the surface of the substrate. Once the thin anchor portion is formed, A brittle material structure is formed on it relatively easily.

  The anchor portion generally has a high elastic modulus, and when an attempt is made to directly form a brittle material structure on a resin base material that is relatively hard and poor in plasticity, the brittle material fine particles are formed on the resin base material. The resin base material is scraped by the brittle material fine particles, and the resin base material is scraped off.

  The above-described problem is a resin characterized in that a base layer made of an adhesive material that adheres closely to the surface of the resin base material is formed, and a polycrystalline brittle material layer is formed on all or part of the base layer. Solved by composite structures with brittle materials.

  In addition, the above-described problem is that a brittle material fine particle having a hardness higher than that of the pressure-sensitive adhesive material is bitten into the surface of the pressure-sensitive adhesive material that is in close contact with the surface of the resin base material, and then the brittle material fine particle is applied to the ground layer. By colliding at high speed, the brittle material fine particles are deformed or crushed by the impact of the collision, and the fine particles are recombined through the active new surface generated by the deformation or crushing, so that many particles are formed on the base layer. This is solved by a method for producing a composite structure of a resin and a brittle material, characterized by forming a brittle material layer of crystals.

  In addition, the above-described problems include a resin and a brittle material in which a base layer made of an adhesive material that is in close contact with the resin base material surface is formed, and a polycrystalline brittle material layer is formed on all or part of the base layer. This is solved by an electronic device characterized in that the composite structure is attached to the inner peripheral surface and / or the upper and lower inner wall surfaces of the housing.

  Furthermore, the above problem is that an underlying electronic layer made of an adhesive material that adheres to the surface of the resin substrate is formed on the internal electronic component, and a polycrystalline brittle material layer is formed on all or part of the underlying layer. This is solved by an electronic device characterized in that a composite structure of a resin and a brittle material is attached.

  More specifically, in order to overcome the above-mentioned drawbacks, a part of the inventor has issued a patent for forming a base layer on a resin base material and forming a brittle material thereon. It was. As a result of intensive studies by the present inventors, it has been found that there are brittle materials (for example, magnetic particles such as ferrite) that are difficult to generate even by the formation method of the prior patent application. In order to overcome this drawback, when a base layer made of an adhesive material having appropriate adhesion to such a resin base is formed, the brittle material film can be easily formed without the brittle material rebounding on the base layer. The present invention has been made by obtaining the knowledge that the

  That is, in the composite structure of the resin and the brittle material belonging to the first aspect of the present invention, a base layer made of a hard material partially digging into the resin base material surface is formed, and the polycrystalline layer is formed on the base layer. The brittle material structure is formed. The thickness of the underlayer is preferably 1 μm or more.

  In order to fabricate the composite structure described above, particles having a hardness higher than that of the resin base material are formed on the surface of the adhesive material on the resin base material to form a base layer, and then brittle material fine particles are applied to the base layer at high speed. The brittle material fine particles are deformed or crushed by the impact of the collision, and the fine particles are recombined with each other through the active new surface generated by the deformation or crushing. A brittle material layer is formed.

  As a means for forming the base layer, it is formed on the resin substrate by an appropriate coating method (gravure coating, brush coating, spray coating, transfer method, etc.).

  The temperature of the brittle material layer forming step is preferably set to be equal to or lower than the glass transition temperature (Tg) of the adhesive resin.

  In the above-described method for manufacturing a composite structure of a resin and a brittle material, an adhesive layer may be further applied on the first brittle material, and a second brittle material may be further formed thereon.

  In the above-described method for manufacturing a composite structure of resin and brittle material, the adhesive layer and the brittle material layer are alternately stacked in the same manner as the second and subsequent layers, and a multilayer structure of n layers (n ≧ 2) is also a feature. Good.

  In the above method for manufacturing a composite structure of a resin and a brittle material, the adhesive layer may be applied to one side or both sides of a support such as a resin or a base material.

On the other hand, when the adhesive material is made of a curable resin, the precursor of the curable resin is semi-cured by an appropriate curing method such as heat or UV until it becomes a semi-cured state. The brittle material layer is formed by causing the hard material particles to penetrate the surface of the adhesive material in the semi-cured state. It is not necessary to further cure the adhesive curable resin in a semi-cured state after the brittle material forming step by heating, UV irradiation, or the like. Note that the brittle material layer is formed at room temperature or in a heated state.

  In the present invention, a brittle material is formed on all or part of the adhesive material on the resin base material. When brittle materials such as ferrite are applied as electromagnetic wave absorbing materials to housings and circuits of video cameras and digital still cameras, etc., when brittle materials are directly formed on all or part of the adhesive material on the resin substrate For example, when a brittle material is formed in a part of the adhesive tape and the periphery is surrounded by a portion where the brittle material is not formed, the adhesive tape is formed with a brittle material having electromagnetic wave absorption characteristics. This tape can be attached to the noise generation source of the circuit board with the brittle material formation side down, and the brittle material formation process and the application process can be separated, so that the brittle material that has not solidified in unnecessary parts of the circuit board Can be prevented, and there is a great merit in terms of process.

Here, the interpretation of the words that are important for understanding the present invention will be described below.
(Underlayer) A thin layer with an adhesive material formed on the outermost surface of the resin base material. While maintaining adhesion to the base material, a brittle material structure or brittle material layer is formed on it by a fine particle beam deposition method. In this case, the layer is firmly bonded to the structure. In addition, it is desirable that the joint with the brittle material structure is partly cut into the anchor portion when the brittle material structure particles collide. A material that satisfies these conditions is an adhesive material, and can be used by adjusting the adhesiveness of an acrylic adhesive material, a rubber adhesive material, a silicone adhesive material, or the like.
(Polycrystalline) In this case, it refers to a structure in which crystallites are joined and accumulated. The crystallite is essentially one crystal, and its diameter is usually 5 nm or more. However, the case where the fine particles are taken into the structure without being crushed rarely occurs, but is substantially polycrystalline.
(Crystallinity) In this case, the degree of pulverization of raw material particles is qualitatively compared based on how the characteristic peak of the raw material powder crystal is broadened by powder X-ray diffraction in a polycrystalline structure.

  According to the present invention, a brittle material layer on the surface of a soft resin substrate, which has been difficult in the past, can be reliably formed by interposing an adhesive base layer.

  Hereinafter, embodiments and examples of the present invention will be described with reference to the accompanying drawings. In addition, this invention is not limited to these, A various deformation | transformation is possible based on the technical idea.

  The composite structure shown in FIG. 1 is a case where an adhesive material layer exists as a base layer on a base material, and a brittle material layer as a brittle material structure is formed thereon. In this case, after forming an adhesive material layer on a resin base material in advance, certain fine particles of brittle material are implanted by a fine particle beam deposition method. There are cases where the adhesive layer does not require curing and cases where it is semi-cured. That is, in FIG. 1, an adhesive material layer or an adhesive layer 2 is formed on a resin substrate 1, and a brittle material layer 3 is formed thereon.

Examples of the resin substrate material shown in this embodiment include ABS, acetal resin, methacrylic resin, cellulose acetate, chlorinated polyether, ethylene-vinyl acetate copolymer, fluororesin, ionomer, methylpentene polymer, nylon, polycarbonate, polyethylene, polyethylene terephthalate, polybutylene terephthalate, polyimide, polyphenylene oxide, polyphenylene sulfide, polyacrylate, polypropylene, polystyrene, polysulfone, vinyl acetate resin, vinylidene chloride resin, aS resin, vinyl chloride resin, as a brittle material, Al ₂ O ₃ , NiO, TiO ₂ , CuO, ZnO, ZrO ₂ , SnO ₂ , MgO, oxides such as ferrite, metals such as Fe and Cu, carbonization such as WC, diamond, SiC, and B ₄ C Materials, brittle materials such as nitrides such as AlN and Si ₃ N ₄ , fluorides such as Ca ₂ F and ZrF, etc., and carrier gases for transport include dry air, nitrogen, helium, argon, oxygen, Hydrogen, a mixed gas whose oxygen partial pressure is controlled, or the like can be used.

  FIG. 2 shows an example of a multilayer structure in the case of n = 2. Furthermore, an adhesive layer and a brittle material layer may be alternately stacked to form an n layer (n ≧ 3). In FIG. 2, the parts corresponding to those in FIG. That is, the second adhesive layer 4 is formed on the first brittle material layer 3, and the second brittle material layer 5 is further formed thereon.

  Next, a structure forming apparatus according to an embodiment of the present invention will be described with reference to FIG. As described above, the fine particle beam deposition method is applied to this apparatus. A heating plate 11 is disposed in the structure forming chamber 8 and a thermosetting resin substrate 17 is placed thereon. A thermometer 12 is installed to measure the temperature of the substrate 17. The output of the thermometer 12 is supplied to the temperature controller 13. The control signal of the temperature controller 13 is supplied to the heating plate 11. A raw material tank 14 containing fine particle powder, which is a brittle material, is connected to a connecting pipe 16 via a valve 20, to which a carrier gas storage layer 15 for storing helium gas is connected.

  Further, an injection pipe 18 is connected to the raw material tank 14 via a valve 21, and a tip portion thereof is in the structure forming chamber 8 and is connected to an injection nozzle 19. The spray nozzle 19 faces the resin base material 17. An air cooling nozzle 23 for forcibly cooling the resin base material 17 on which the base layer is formed by air cooling is disposed obliquely with respect to the resin base material 17 as shown in the figure. The raw material tank 14 has a mechanism for vibrating and stirring the brittle material fine particles, not shown.

  The operation is performed by setting the kneaded thermosetting resin base material 17 formed on the thermoplastic base material at the tip of the injection port of the injection pipe 19 and using the temperature controller 13 for controlling the base material temperature. Is set at a temperature that is 10 ° C. lower than the substrate curing temperature and not higher than the curing temperature. The temperature of the substrate surface is measured by a thermometer 12 installed on the substrate and controlled by a temperature controller 13. When the temperature of the base material 17 reaches a predetermined temperature, the valve 20 of the carrier gas storage tank 15 is opened, the carrier gas in the carrier gas storage tank 15 is flowed, and the brittle material fine particles in the raw material tank 14 are transferred to the carrier gas. At the same time, it is ejected from the ejection port of the ejection nozzle 19 through the ejection pipe 18 and collides with the surface of the base material 17 controlled to a predetermined temperature.

  At this time, since the temperature of the substrate surface is controlled to be equal to or lower than the temperature at which the resin material is cured, the brittle material fine particles ejected from the ejection port are based on a soft state in which curing is not completely achieved. The base layer is easily formed on the surface of the base material by piercing the surface of the material.

  After passing through this step, the brittle material fine particles are again sprayed from the spray nozzle 19 toward the underlayer at a high speed, and then the brittle material fine particles collide with the underlayer to cause deformation or crushing. A brittle material structure is formed such that the particles and crushed fragment particles having an active surface re-join and grow from the underlayer. In the above-described method for producing a brittle material structure on a resin base material, the process from the base layer formation process to the brittle material structure formation process is performed continuously. The brittle material structure can be formed on the resin base material even by an intermittent manufacturing method in which the forming step is performed after the resin base material is sufficiently cooled.

  As the thermosetting resin material shown in this embodiment, acrylic ester resin, alkyd resin, allyl resin, amino resin, melamine resin, epoxy resin, urea resin, phenol resin, unsaturated polyester resin, silicone resin, Polyurethane or the like is used. The same material as that of the above-described embodiment can be applied to the material of the underlayer and the material of the brittle material structure.

An example of actually trying to form a structure on a plastic material using the fine particle beam deposition method will be described below.
(Reference Example) In the reference example, a ferrite fine particle having a purity of 99% or more is sprayed on a plastic substrate by a fine particle beam deposition method to try to form a structure. ABS, polyimide, and epoxy resin ARALDITE XD911 (trademark) were used as the base material. The structure forming apparatus conforms to FIG. 3 and does not heat the substrate. A nozzle for injecting fine particles, which is an injection tube, has an opening of 17 mm and 0.4 mm, and an aerosol in which ferrite fine particles are mixed with nitrogen gas is sprayed at a flow rate of 7 L / min. The chamber for forming the structure was adjusted to 1 kPa or less with a vacuum pump. Formation was performed with an area of 17 mm / 5 mm, and the time was 10 minutes. Table 1 shows whether or not a structure is formed and the film thickness when it is formed. The film thickness was measured using a stylus type surface shape measuring device Dektak 3030 manufactured by Nippon Vacuum Technology Co., Ltd. The film was formed with ABS and polyimide, but the film was not formed with the epoxy resin, and the surface was found to have unevenness of about several microns on the surface.

Example 1
Next, an example in which a base layer is formed on an ABS substrate using an adhesive and a structure is formed thereon will be described. An epoxy adhesive layer having a thickness of 25 μm was coated on an epoxy resin substrate by a transfer method, and a structure was formed on the adhesive layer by a fine particle beam deposition method for 30 minutes under the same film forming conditions as in the reference example. . As a result, a 20 μm structure film was formed on the underlayer. It can be seen that the structure was formed through the adhesive layer as compared with the reference example.

(Example 2)
Next, an example in which an epoxy resin ARALDITE XD911 (trademark) is semi-cured as a thermosetting resin and a structure is formed thereon will be described.

  First, an uncured epoxy resin is poured onto an ABS base material to flatten the surface, and then a slurry in which ferrite is dispersed in ethanol is dropped, followed by drying at room temperature to form a fine particle adhesion layer on the substrate. Thereafter, a curing treatment at 120 ° C. for 1 hour which is a curing temperature of the resin was performed, and the adhesion layer was fixed on the ABS substrate as a base layer.

  Thereafter, the substrate was subjected to ultrasonic cleaning to remove fine particles that were not immobilized. Next, a structure was formed by a fine particle beam deposition method in the same manner as in the reference example. As a result, although it was a thin film with a film thickness of about 1 μm, it was found that the substrate was not scraped as in the reference example, and a structure was formed.

  As a result of performing X-ray diffraction of the ferrite structures formed in Example 1 and Example 2, it is qualitative that a characteristic peak is detected at the same position as the raw material ferrite and a ferrite structure is formed. I understood.

Example 3 Flow Rate Dependence of Film Formation Rate, Film Dependence on Film Formation Time Helium is used as a carrier gas on one side of an adhesive surface of a double-sided adhesive tape having a thickness of 0.2 mm, and ferrite particles are used as raw materials by a fine particle beam deposition method. Structure formation was performed in the same manner as in the reference example. Table 2 shows the film thickness in the case where the film was formed for 30 minutes when the flow rate of helium gas was changed. It can be seen that the film formation is easier than the case where the film is formed directly on the resin substrate of Table 1. Table 3 shows the change in film thickness when the flow rate of helium gas is 7 liters per minute. Unlike the resin substrate, it can be seen that the film thickness increases with the film formation time.

(Example 4) When a film formation surface is partly shown FIG. 4 shows an example in which a film formation surface is partly part of the adhesive surface. For example, as shown in FIG. 4, a part of the double-sided adhesive tape is formed with a fine particle beam deposition method using ferrite particles, and the adhesive surface that is not formed is attached to the inside of the housing. Take measures to absorb electromagnetic waves.

  That is, in FIG. 4, 30 is the surface of the adhesive material, and a region 31 in which ferrite is formed is formed in the approximate center. Alternatively, only a part of the film is formed on the adhesive surface of the single-sided adhesive tape as shown in FIG. 4 and the film-formed surface is attached to an IC package, IC chip, flexible wiring board, etc., and electromagnetic absorption countermeasures are taken.

  For both double-sided and single-sided adhesive tapes, film formation is performed for each piece of adhesive tape cut to an appropriate size as shown in FIG. 4, or continuously on a part of a large adhesive surface as shown in FIG. After film formation, the film may be cut into an appropriate size. Alternatively, as shown in FIG. 6, the film may be continuously formed by a role to role method and cut into an appropriate size.

  That is, in FIG. 5, reference numeral 40 represents the surface of the adhesive, and is partitioned as shown by the boundary line 42. A region where fine particles of ferrite are formed is formed in each of the sections. In this case, nine adhesive plates are formed along the boundary line 42. FIG. 6 shows the above-described role to role method. The pair of rollers 50a and 50b has shafts 54a and 54b, and one shaft 50b is a drive shaft and is driven and controlled by a drive control unit.

  An adhesive tape 54 is wound around these rollers, and the adhesive tape as shown in FIG. 5 formed at predetermined intervals in the length direction of the tape is cut by an upper cutter 52. The drive controller repeatedly drives and stops at regular intervals, and eventually forms an adhesive tape as shown in FIG. When a nozzle is used instead of the cutter 52, an adhesive region is continuously formed with a predetermined width on the tape 54, or film forming regions are formed at regular intervals as described above.

(Example 5) In the case of adhesive spray When the adhesive is spray-applied to the entire inner surface of the housing (made of resin) as shown in FIG. When the ferrite particles can be formed by the fine particle beam deposition method, the ferrite can be formed even on the curved surface portion of the corner which is difficult to form unless an adhesive is applied.

  FIG. 7 shows a casing 60 made of a thermoplastic resin, and a spray gun 62 is provided above the casing 60, and after forming an adhesive layer, ferrite fine particles are formed on the entire bottom surface and inner peripheral surface. Is.

This is a simplified representation of an outer case of an electronic device such as a video camera or a mobile phone, which functions to absorb external electromagnetic waves. In particular, if the system shown in FIG. 7 is used, an adhesive material film can be easily formed on the curved surface 60a by the operation of the spray gun 62 without leakage.

  For example, a brittle material layer made of ferrite is formed on the bottom surface and the inner peripheral surface of the nozzle gun by ejecting ferrite fine particles, for example, by appropriately operating the nozzle gun in the X, Y, and Z directions. The internal parts are protected from external electromagnetic waves.

(Example 6) Radio wave absorption effect Fig. 8 shows an example of an electromagnetic wave absorption effect using Ni-Zn ferrite. The measuring method is as follows. Using a network analyzer, a signal is incident on the microstrip line, S11 characteristics (reflection characteristics) and S21 characteristics (transmission characteristics) are measured, and a sample (for example, FIG. 4) is obtained from the measurement results of the signal characteristics with and without the sample. The shape of the transmission signal filter (shielding) effect is evaluated.

  The characteristic impedance of the microstrip line is designed to be about 50Ω. The loss amount is calculated as an amount obtained by subtracting the S11 amount and the S21 amount from the incident signal energy amount. In FIG. 8, the electromagnetic wave absorption effect obtained by changing the flow rate of helium to 3 L / min, 5 L / min, and 7 L / min and depositing the ferrite on the adhesive tape for 30 minutes is the same as that of the adhesive tape at 3 L / min. However, it can be seen that there is a difference between 5 L / min and 7 L / min.

  FIG. 9 shows the electromagnetic wave absorption effect obtained by forming a Ni—Zn ferrite film on an adhesive tape by changing the film formation time to 10 minutes, 30 minutes, and 60 minutes at a helium flow rate of 7 L / min. Both have an electromagnetic wave absorption effect as compared with the adhesive tape alone, but it can be seen that there is no difference even when the film formation time is changed and the film thickness is increased.

  The electromagnetic absorption effect is not limited to this Ni—Zn-based ferrite, and it is possible to cope with radio wave absorption in all frequency bands by using magnetic particles having a composition corresponding to the frequency band of the radio wave to be absorbed.

  Even a brittle material such as ferrite can be used to stably form a composite on a resin substrate.

It is sectional drawing of the composite structure of a brittle material and resin by embodiment of this invention. It is sectional drawing of the composite structure of the brittle material and resin by other embodiment of this invention. It is a general | schematic piping system diagram of the apparatus for producing the composite structure by this invention. 1 is a plan view of a first embodiment of a composite structure according to the present invention. It is a top view of 2nd Example of the composite structure by this invention. It is a front view of the apparatus for manufacturing the composite structure of 1st Example. (A) is a perspective view which produces the 3rd Example of the composite structure by this invention, (B) is the top view. 6 is a graph showing frequency-loss (Loss) characteristics indicating the radio wave absorption effect when the flow rate of helium is changed in manufacturing the composite structure of the present invention. 4 is a graph showing frequency-loss characteristics indicating the electromagnetic wave absorption effect when the film formation time is changed while the flow rate of helium is kept constant in producing the composite structure of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Resin substrate, 2 ... Adhesive material, 3 ... Brittle material layer, 8 ... Structure formation chamber, 14 ... Raw material layer, 15 ... Carrier gas storage layer, 17 ... -Resin base material, 18 ... injection pipe, 19 ... injection nozzle.

Claims (30)

  A composite of a resin and a brittle material, characterized in that a base layer made of an adhesive material adhering to the surface of the resin substrate is formed, and a polycrystalline brittle material layer is formed on all or part of the base layer. Structure.   The composite structure of a resin and a brittle material according to claim 1, wherein the base layer made of the adhesive material is formed on the resin base material by coating. The composite structure of a resin and a brittle material according to claim 2, wherein the coating method is any one of gravure coating, brush coating, spray coating, and transfer method.   The resin and brittle material according to any one of claims 1 to 3, wherein the adhesive material is any one of an acrylic adhesive, a rubber adhesive, a silicone adhesive, and the like. And composite structure. The resin base material is ABS, acetal resin, methacrylic resin, cellulose acetate, chlorinated polyether, ethylene-vinyl acetate copolymer, fluororesin, ionomer, methylpentene polymer, nylon, polycarbonate, polyethylene, polyethylene terephthalate, polybutylene. The terephthalate, polyimide, polyphenylene oxide, polyphenylene sulfide, polyacrylate, polypropylene, polystyrene, polysulfone, vinyl acetate resin, vinylidene chloride resin, AS resin, vinyl chloride resin, or the like. A composite structure of the resin according to 1 and a brittle material. The brittle material includes Al ₂ O ₃ , NiO, TiO ₂ , CuO, ZnO, ZrO ₂ , SnO ₂ , MgO, ferrite or similar oxide, Fe, Cu or similar metal, WC, diamond, SiC, B _4. C, or any of its similar carbides, AlN, Si ₃ N ₄ or any of its similar nitrides, Ca ₂ F, ZrF or any of its similar fluorides. A composite structure of the resin according to 1 and a brittle material.   The composite structure of a resin and a brittle material according to claim 2 or 3, wherein the underlayer is not subjected to the post-coating curing treatment.   4. The composite structure of a resin and a brittle material according to claim 2, wherein the underlayer is subjected to a curing treatment after application of a curable low molecular weight compound in order to exhibit appropriate tackiness.   The composite structure of a resin and a brittle material according to claim 8, wherein the curing process is any one of a thermosetting process, a UV curing process, and an electron beam curing process.   The composite structure of a resin and a brittle material according to any one of claims 1 to 3, wherein the underlayer has a thickness of 1 µm or more. The brittle material layer and the base layer are joined by generating a new surface by crushing or deforming the brittle material on the adhesive material constituting the base layer by collision of particles constituting the brittle material layer. A composite structure of the resin according to any one of claims 1 to 3 and a brittle material. 4. The composite structure of a resin and a brittle material according to claim 1, wherein a part of the brittle material layer bites into the base layer to form an anchor portion. 5. The composite structure of a resin and a brittle material according to claim 1, wherein an adhesive layer is further coated on the first brittle material, and a second brittle material is further formed thereon. . The composite structure of the resin and the brittle material according to claim 13, wherein the adhesive layer and the brittle material layer are alternately stacked in the same manner from the second layer onward, and has a multilayer structure of n layers (n ≧ 2). A brittle material fine particle having a hardness higher than that of the pressure-sensitive adhesive material is caused to penetrate into the surface of the pressure-sensitive adhesive material that adheres to the surface of the resin base material, and then the brittle material fine particle collides with the ground layer at a high speed. The brittle material fine particles are deformed or crushed by the impact of the material, and the fine brittle material layer is formed on the underlayer by recombining the fine particles with each other through the active new surface generated by the deformation or crushing. A method for manufacturing a composite structure of a resin and a brittle material. The resin base material is ABS, acetal resin, methacrylic resin, cellulose acetate, chlorinated polyether, ethylene-vinyl acetate copolymer, fluororesin, ionomer, methylpentene polymer, nylon, polycarbonate, polyethylene, polyethylene terephthalate, polybutylene. The terephthalate, polyimide, polyphenylene oxide, polyphenylene sulfide, polyacrylate, polypropylene, polystyrene, polysulfone, vinyl acetate resin, vinylidene chloride resin, AS resin, vinyl chloride resin, or the like. A method for producing a composite structure of the resin according to 15 and a brittle material. The brittle material includes Al ₂ O ₃ , NiO, TiO ₂ , CuO, ZnO, ZrO ₂ , SnO ₂ , MgO, ferrite or similar oxide, Fe, Cu or similar metal, WC, diamond, SiC, B _4. C, or any of its similar carbides, AlN, Si ₃ N ₄ or any of its similar nitrides, Ca ₂ F, ZrF or any of its similar fluorides. A method for producing a composite structure of the resin according to 15 and a brittle material. 16. The carrier gas for transporting the brittle material fine particles to the surface of the adhesive material is any one of dry air, nitrogen, helium, argon, oxygen, hydrogen, and a mixed gas whose oxygen partial pressure is controlled. A method for producing a composite structure of a resin and a brittle material as described in 1. The underlayer is formed by impact caused by collision of hard fine particles of a brittle material, and the collision speed of the hard particles toward the base material is 50 m / s or less. A method for manufacturing a composite structure with a brittle material. The pressure-sensitive adhesive material is made of an acrylic, rubber-based, or silicone-based pressure-sensitive resin or the like, and the glass transition temperature (Tg) of the pressure-sensitive adhesive material is normal temperature or lower. A method for producing a composite structure of the resin according to 16 and a brittle material. The method for producing a composite structure of a resin and a brittle material according to claim 17, wherein the temperature of the brittle material layer forming step is set to a glass transition temperature (Tg) or more of the adhesive material. The composite structure of a resin and a brittle material according to claim 15, wherein an adhesive layer is further applied on the first brittle material, and a second brittle material is further formed thereon. Manufacturing method. The adhesive layer and the brittle material layer are alternately stacked in the same manner from the second layer onward, and a multilayer structure of n layers (n ≧ 2) is provided. Manufacturing method. The method for producing a composite structure of a resin and a brittle material according to claim 15, wherein the adhesive layer is applied to one side or both sides of the resin base material. A base structure made of an adhesive material that adheres to the surface of a resin base material is formed, and a composite structure of resin and a brittle material in which a polycrystalline brittle material layer is formed on all or part of the base layer is a housing The electronic device is attached to the inner peripheral surface and / or the upper and lower inner wall surfaces.   26. The electronic apparatus according to claim 25, wherein the brittle material is a magnetic material. 27. The electronic apparatus according to claim 26, wherein the magnetic material is ferrite. An internal electronic component is formed with a base layer made of an adhesive material that adheres closely to the surface of the resin substrate, and a polycrystalline brittle material layer is formed on all or part of the base layer. An electronic device having a composite structure attached thereto. The electronic device according to claim 28, wherein the brittle material is a magnetic material. 30. The electronic apparatus according to claim 29, wherein the magnetic material is ferrite.