WO2018041007A1 - Macromolecular material and metal composite material and preparation method therefor - Google Patents

Macromolecular material and metal composite material and preparation method therefor Download PDF

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Publication number
WO2018041007A1
WO2018041007A1 PCT/CN2017/098919 CN2017098919W WO2018041007A1 WO 2018041007 A1 WO2018041007 A1 WO 2018041007A1 CN 2017098919 W CN2017098919 W CN 2017098919W WO 2018041007 A1 WO2018041007 A1 WO 2018041007A1
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Prior art keywords
metal
polymer material
porous metal
rubber
composite
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PCT/CN2017/098919
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French (fr)
Chinese (zh)
Inventor
韩辉升
丁阳
张红梅
陆婷
施捷
孙强
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南通万德科技有限公司
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Priority to DE112017003833.2T priority Critical patent/DE112017003833B4/en
Publication of WO2018041007A1 publication Critical patent/WO2018041007A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/04—Co-operating contacts of different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2705/00—Use of metals, their alloys or their compounds, for preformed parts, e.g. for inserts

Definitions

  • This invention relates to the field of composite materials, and more particularly to a polymeric material and a metal composite conductive material that can be used to make electrical contacts in conductive plates and buttons.
  • the various rubbers themselves are electrically insulating. To date, all conductive rubbers are not intrinsic. Although conductive plastics are intrinsic, the intrinsic conductive plastics have high production costs, are difficult to produce, and are generally inferior in electrical conductivity and stability to metal conductors, and have not been produced and used in large quantities.
  • the widely used conductive polymer materials are generally composite polymer materials, which are compounded by polymer materials (such as rubber and plastic) and conductive fillers.
  • An antistatic polymer material and a conductive polymer material can be prepared by adding conductive carbon black to the polymer substrate. By adding a metal powder, in particular, a silver powder or a silver-plated powder, to a polymer substrate, a conductive polymer material having better conductivity can be obtained.
  • conductive fibers are added to a polymer material to prepare a conductive polymer material.
  • the conductive fibers used are metallized glass fibers (as described in US Patent No. 4332853 "Conductive plastic with metalized glass fibers retained in partial clumps"), carbon fibers or carbon nanotubes (for example, Chinese Patent Application No. 201210011604.7) Conductive rubber and its preparation method”) and the like. Since the conductive carbon black, the metal powder and the conductive fiber are dispersedly distributed in the conductive rubber, the conductive polymer material prepared from these fillers has a larger volume resistivity and surface resistivity than the common metal conductive material, and the conduction is larger. The ability of current does not appear to be sufficient in some situations.
  • the conductive plastic disclosed in the patent document "A conductive plastic and its processing method and processing device" of the application No. 200510086201.9 comprises 0.1-45 v% of conductive fibers, 55-99 v% of thermoplastics and 0-3 v% of processing aids.
  • the conductive fibers are arranged in a three-dimensional network in the thermoplastic;
  • the plastic fiber is evenly dispersed, the overlap between the fibers is high, and the conductivity is high, so that the shielding performance is improved significantly, the SE value can reach 40-99 dB, and the antistatic and electromagnetic shielding effects are good.
  • the patent document "A Highly Efficient Conductive Material” of the application No. 201110448918.9 discloses an efficient conductive material which can be used as an antenna for satellites, ground radars, directional antennas for broadcasting communication, electromagnetic interference shielding elements for cables, aviation and automobiles,
  • the structure comprises at least one layer of metal fiber non-woven mat which can conduct electricity, heat and electromagnetic at high speed, preferably aluminum fiber non-woven mat; the base body is various plastics, preferably glass fiber reinforced plastic.
  • 201010592410.1 discloses a composite conductive sheet composed of a polymer matrix and a metal foil compounded therein.
  • the metal foil here refers to a nickel foil, a copper foil, an aluminum foil, a stainless steel foil, a gold foil, a silver foil or a woven mesh containing pores
  • the polymer matrix refers to a silicone rubber, a nitrile rubber, an ethylene propylene rubber, a natural rubber, a rubber plastic material. , thermoplastics, thermosets or fiber reinforced plastics.
  • a conductive rubber is prepared by molding a rubber and a metal fiber sintered felt (or a metal nonwoven fabric) by molding or injection, and the metal fiber sintered felt has pores. The pores are at least partially filled with rubber.
  • U.S. Patent 6,475,933, "Highly conductive elastomeric sheet” discloses a highly conductive rubber sheet composed of an electrically conductive mesh and an elastomeric substrate filled with electrically conductive particles, wherein the electrically conductive particles are submicron sized carbonaceous materials.
  • the coefficient of thermal expansion of the polymer material is usually much larger than that of a common metal material, sometimes even as high as ten times or more (for example, the coefficient of thermal expansion of the silicone rubber is approximately It is 15 times that of pure nickel.
  • the polymer material in these composite materials will protrude from the surface of the composite due to the large coefficient of thermal expansion, making the surface contact resistance of the electrical contacts larger, and maybe even The electrical contacts become rendered non-conductive and completely fail.
  • a button containing such an electrical contact if used in a car, may create a safety problem.
  • OBJECT OF THE INVENTION To provide a composite material of a polymer material and a porous metal, and a preparation method thereof, the composite material having a protruding metal material at least on one surface, which is suitable for preparing a conductive function under elevated temperature conditions. Electrical contacts that do not fail.
  • Electrical contacts are a key component of the button and are typically used in conjunction with contact switches on printed circuit boards (PCBs). It must have a low contact resistance. If the contact resistance is too large, the key switch function will be invalid and misjudged.
  • the rubber When used as an electrical contact on a rubber button, the rubber swells and bulges when it is raised from room temperature to 80 °C. Due to the phenomenon of the surface of the electrical contact, the conduction is affected, and the contact resistance is raised from 0.4 ⁇ to more than 2 ⁇ , and is even non-conductive. As shown in Figure 1.
  • the reason for the rubber bulging is due to the large coefficient of thermal expansion of the rubber. For example, the coefficient of thermal expansion of silicone rubber is about 15 times that of metallic nickel.
  • the present invention discloses a composite material and a preparation process thereof: by combining a polymer material containing an extractable substance and a porous metal, the composite method includes thermosetting molding, thermal vulcanization molding, radiation curing molding, thermoplastic molding, and the like. , producing a polymer material containing an extractable substance and porous A molded article of a metal, in particular, a molded article in which a polymer material having an extractable substance and a metal material are simultaneously exposed on at least one surface. The pores in the porous metal in the molded body are partially or completely filled in the composite material during the composite molding, and then the extractables in the molded product are extracted by a solvent, thereby causing the molded body to be in the molded body.
  • the volume shrinkage of the polymer material and the surface of the polymer material in the molded body collapse, thereby producing a composite material of a polymer material and a porous metal in which the porous metal protrudes from at least one surface.
  • the composite material can be a sheet, a bar, a tube or a profile.
  • the porous metal in the present invention refers to a metal material or a metal material having pores and holes, and includes a metal sheet having a plurality of uniformly distributed or randomly distributed pores, a metal mesh, a sintered metal mesh, and a metal plate. Net, metal foam or metal fiber sintered felt, etc., or a multilayer metal structure containing them.
  • the metal mesh and the sintered metal mesh may be a single layer or a plurality of layers, and the metal mesh and the metal mesh are formed into a porous metal by a specific vacuum sintering process.
  • the pores in the porous metal are independent or interconnected, and at least a portion of the pores are exposed on the surface of the porous metal so that the polymer material can penetrate into the pores.
  • the holes may be of a regular cylindrical shape, for example, all holes in the metal mesh may have a diameter of 0.25 mm or may be irregular. The diameter of the cross-sectional area of the hole may be in the range of 1 ⁇ m to 3.0 mm.
  • the porous metal may be a metal mesh having a uniformly distributed pores, a pore diameter of 50 ⁇ m to 1.0 mm, a pore spacing of 25 ⁇ m to 1.0 mm, and a circular shape, a regular polygon or other geometric shape.
  • the material of the porous metal can be varied.
  • the porous metal may be composed of aluminum, iron, cobalt, nickel, copper, zinc, tin, manganese, tungsten, silver, gold or alloys thereof.
  • the alloys include Hastelloy, Monel, Inconel, and the like.
  • Stainless steel, nickel or a nickel alloy is preferred. This is because stainless steel, nickel or nickel alloys have relatively stable chemical properties at room temperature and are inexpensive and readily available.
  • the porous metal is composed of a homogeneous or non-homogeneous metal material; further, the outer surface of the porous metal and the pores thereof may be coated with a metal, and the metal plating may be partially or partially covered with a porous layer.
  • Gold plating or silver plating is preferred.
  • Gold and silver have A relatively good electrical conductivity, as a coating of the outer layer of the metal material, can improve the surface conductivity of the electrical contact, reduce the contact resistance of the electrical contact, and improve the electrical conductivity and service life of the electrical contact.
  • the porous metal is free or contains a metal plating; the metal plating completely or partially covers the surface of the porous metal and the inner surface of the porous metal hole.
  • the outer surface of the porous metal or the inner surface of the pore may be coated with an adhesion promoter, a coupling agent or a primer having an average thickness of not more than 1 ⁇ m to increase the bonding strength between the porous metal and the polymer material.
  • the adhesion promoter, coupling agent or primer to be applied should not be too thick, and the average thickness of the coating should not exceed 1 ⁇ m, otherwise the contact resistance of the porous metal may be significantly increased, thereby affecting the electrical conductivity of the electrical contact.
  • the porous metal may be various, and the selection range of the polymer material in the present invention is also broad, and the composite material of the polymer material and the metal and the preparation process thereof are characterized in that the polymer material is: It is a thermosetting rubber, thermoplastic rubber, thermoplastic, thermosetting plastic, radiation curable material, adhesive, ink or coating.
  • thermosetting rubber liquid or solid diene rubber, olefin liquid rubber, polyurethane rubber, acrylate rubber, polysulfide rubber, silicone rubber, fluororubber, fluorosilicone rubber, etc. can be used and porous metal.
  • a conductive composite is prepared.
  • liquid rubber is that the viscosity of the liquid rubber is lower than that of the solid rubber, which facilitates the compounding of the rubber and the porous metal by various methods. But this is not to say that solid rubber is not available.
  • the solid raw rubber and the porous metal can be combined together, for example, the solid raw rubber and the porous metal (such as a metal mesh) are stacked together, and then placed in a mold cavity and pressed by a flat vulcanizer. The solid rubber is infiltrated into the pores of the porous metal, and the solid rubber and the porous metal are combined and vulcanized at a high temperature.
  • the formulation of the polymer material may contain various additives such as pigments, fillers or conductive fillers.
  • the present invention differs from the formulation of a general polymer material in that an extractable substance must be added to the formulation of the polymer material.
  • the purpose of adding an extractable material to a polymer material formulation is not to allow the extractable material to remain in the polymer material after molding the polymer material, but to pass the polymer material after molding.
  • the extraction method drives the extractable material out of the polymer material to shrink the polymer matrix in the composite material of the polymer material and the porous metal, so that the polymer matrix in the pore of the porous metal in the composite material occurs. Collapse.
  • the content of the extractable material in the polymer material is from 1 to 95% by weight before being compounded with the porous metal.
  • These extractables are low molecular weight, oligomeric or uncrosslinked polymers that are compatible or partially compatible with the polymeric material.
  • the polymer material and the extractable material contained therein need to be compatible or partially compatible, so that when the extractable material is extracted from the polymer material, the volume of the polymer material shrinks instead of Holes are formed in the polymer material so that no or substantially no shrinkage occurs.
  • liquid silicone rubber or solid silicone rubber is used to prepare a composite material of a polymer material and a metal
  • various silicone oils liquid paraffin waxes, paraffin wax, chlorinated paraffin, naphthalene, tetralin, decalin, tetramethylbenzene
  • a substance such as tetramethylbenzene, hexamethylbenzene or a high-boiling solvent oil is added as an extractable substance to a liquid silicone rubber or a solid silicone rubber, and after the silicone rubber and the metal are composite-molded, some or all of these extractables are extracted.
  • the preparation method of the composite material in the present invention is also various. Can be superimposed by means of lamination, pad printing, silk screen printing, brush coating, roller brushing, blade coating, spray coating, dip coating, shower coating, and draw coating.
  • the molecular material and the porous metal are combined together, and then solidified by a thermoplastic molding process, a thermosetting molding process or a radiation curing process to obtain a composite material containing an extractable polymer material and a porous metal, and then impregnated with a volatile solvent.
  • the molding process depends on the type of polymer material.
  • the composite material can be die cut into small discs having a diameter of 1.0 to 10.0 or other geometrical pieces after pumping or extraction.
  • the composite material described in the present invention is punched into a small wafer having a diameter of 1.0 to 10.0 mm, which has good electrical conductivity and a contact resistance of less than 1 ⁇ , and can be used as an electrical contact in a rubber button.
  • the surface of the electrical contact prepared by using the composite material shrinks and collapses after the extraction of the polymer material, and the material of the porous metal protrudes from the surface of the composite material, so that the electrical contact has good dust resistance and resistance. Oil stain performance and good electrical conductivity when temperature rises.
  • the thermal expansion coefficient of polymer materials is usually larger than that of metal materials
  • the shrinkage and collapse of polymer materials in composite materials can offset the thermal expansion of polymer materials due to the large thermal expansion coefficient of polymer materials, preventing polymer materials from protruding in composites.
  • the surface of the material affects the electrical conductivity of the contacts.
  • Figure 1 is a schematic view showing the surface of a composite material prepared from a rubber and a metal mesh when the temperature is raised in the present invention; wherein, 1-rubber, 2-metal mesh;
  • FIG. 2 is a schematic view showing the shrinkage of rubber in a porous metal hole in the present invention; wherein, 3-nickel mesh, 4-rubber;
  • Figure 3 is a schematic view showing the shrinkage of the rubber in the porous metal hole in the present invention; wherein, 5-nickel mesh, 6-rubber;
  • Formulation A a mixture of methyl vinyl silicone rubber containing fumed silica (SE 4705U from Dow Corning) 100 (parts by weight, the same below), dimethyl silicone oil (selected Dow Corning's Xiameter PMX-200) , 1000cs) 50, vinyl tri-tert-butylperoxysilane (VTPS) 1, dicumyl peroxide (DCP) 0.5.
  • SE 4705U fumed silica
  • DCP dicumyl peroxide
  • Formulation B SE 4705U 100, VTPS 1, DCP 0.5.
  • the mixed film of Formulation A and Formula B was laminated with a nickel mesh (nickel purity of not less than 99.5%) having a thickness of 0.25 mm, a pore diameter of 0.5 mm, and a hole pitch of 0.25 mm, and placed on a Teflon coating.
  • the mold cavity of the layer was vulcanized and molded at a temperature of 175 ° C for 10 minutes to form a sheet having a thickness of 0.25 mm.
  • the sheet was die cut into small discs having a diameter of 3.0 mm.
  • the small discs prepared from Formulation A and Formulation B were separately extracted with ethanol as a solvent for 3 hours using a Soxhlet extractor. It is then dried at 60 ° C to a substantially constant weight.
  • the small wafer obtained by Formulation B is used as an electrical contact.
  • the contact resistance between the electrical contact and the PCB electrical contact with it is increased from no more than 0.5 ⁇ to more than 2 ⁇ . Not even conductive.
  • the surface of the small disc obtained by using the formula A due to the extraction of the silicone oil, causes the rubber in the metal hole to shrink and collapse (as shown in Fig. 2).
  • the small disc has good dust resistance and oil resistance, and can overcome the disadvantage that the thermal expansion coefficient of the silicone rubber is large and the resistance becomes large or non-conductive at high temperature. Warm The scope of application. At elevated temperatures, the contact resistance is still below 0.5.
  • One side of the nickel mesh in the first embodiment was attached with a 0.025 mm thick polyimide (PI) self-adhesive film, and then a compound of the formula A and a nickel mesh were combined to form a 0.8 mm thick composite sheet. material.
  • the PI was removed from the mucosa and punched into small discs having a diameter of 2.0-5.0 mm. Soaking with solvent gasoline, the silicone oil contained in the small round silicone rubber is extracted, and the rubber in the nickel mesh cavity shrinks (Fig. 3).
  • These small wafers act as electrical contacts and also have good electrical conductivity when the ambient temperature rises. This is because, when the temperature is raised, such as from 25 ° C to 80 ° C, the rubber in the porous metal hole does not protrude from the surface of the porous metal even if it has a lower expansion coefficient (as shown in FIG. 4 ).
  • the addition of polyvinyl butyral is to improve the adhesion of PVC to metals.
  • the materials are put into a high-speed mixer for mixing and mixing, the time is controlled at about 15 minutes, the temperature reaches 110-120 ° C, and the PVC powder absorbs the plasticizer without being sticky, and is placed in a low-speed cooling mixer while stirring. Cooling; when cooled to about 25 ° C, the material is discharged.
  • the material is applied to a multi-layer stainless steel sintering net made by a 5-layer 80-mesh AISI 304 stainless steel wire plain weave through special lamination pressing and vacuum sintering, or by a two-roll mill at 160 ° C.
  • a 1.5 mm thick sheet was placed on a multi-layer stainless steel sintered wire, placed in a Teflon-coated mold cavity at 175 ° C, and hot-pressed and formed on a flat vulcanizing machine to make a 1.5 mm thick sheet. .
  • the sheet or the small circular piece having a diameter of 2.5-10 mm which is die-cut from the sheet is extracted by a solvent gasoline soaking method of 120 or by a Soxhlet extractor for 5-120 minutes, wherein Part of low molecular weight such as trioctyl trimellitate and epoxidized soybean oil or Almost all drawn up.
  • the extraction time and other parameters can be determined according to the degree of collapse of the resin in the multi-layer stainless steel sintered mesh.
  • the composite material of the polyvinyl chloride-stainless steel sintered mesh obtained by this method the polyvinyl chloride shrinks to the inside of the material, and the stainless steel material protrudes from the surface.
  • This composite material can be used as a conductive material, a shielding material, or as an electrical contact having good high-temperature electrical conductivity.
  • the preparation of a composite material of a polymer material and a porous metal by extraction is advantageous for environmental protection because the extracted plasticizer can be recycled without being discharged to the environment.
  • This embodiment prepares a composite of a polymer material and a porous metal as in Example 1, wherein the polymer material is based on Formulation A in Example 1, and the porous material used is the surface and hole inner surface plating in Example 3.
  • a gold plating having an average thickness of 0.05-0.75 ⁇ m and a purity greater than 99.0%. Gold plating reduces the surface contact resistance of the composite and keeps the contact resistance at 0.3 ⁇ .
  • the preparation method was the same as in Example 1, and a small wafer having a diameter of 2 to 10 mm was obtained. After the small wafer was subjected to an extraction process, 0.1 ⁇ m of gold was plated by electroless plating. Compared with the embodiment 4, the composite material or the electrical contact obtained in the embodiment consumes less gold, and the surface contact resistance of the composite material or the electrical contact is substantially the same as that of the embodiment 1. The surface contact resistance of the composite or electrical contacts is the same or similar.

Abstract

Disclosed in the present invention are a macromolecular material and metal composite material and a preparation method therefor: under certain conditions, performing composite moulding of a porous metal and a macromolecular material containing extractable matter, preparing sheet material, and then performing solvent extraction on the obtained sheet material so that the extractable matter therein is extracted, and thereby preparing a composite material having shrunken or collapsed macromolecular material. In a composite material prepared using said method, the porous metal protrudes from the surface of the electrically conductive composite material, so that the composite material is suitable for use as electrical contact material.

Description

一种高分子材料和金属的复合材料及其制备工艺Composite material of polymer material and metal and preparation process thereof 技术领域Technical field
本发明涉及复合材料领域，更具体地说，本发明涉及高分子材料和金属复合的导电材料，这种复合材料可用于制作导电板和按键中的电触点。Field of the Invention This invention relates to the field of composite materials, and more particularly to a polymeric material and a metal composite conductive material that can be used to make electrical contacts in conductive plates and buttons.
背景技术Background technique
各种橡胶本身是电绝缘的。迄今为止，所有的导电橡胶都不是本征的。虽然导电塑料有本征型的，但本征型的导电塑料的生产成本高、生产工艺难度大、导电率和稳定性通常比金属导体差，尚无大量生产和应用。目前广泛应用的导电高分子材料一般都是复合型高分子材料，它们由高分子材料(例如橡胶和塑料)和导电性的填充物复合而成。在高分子基材中加入导电炭黑，可制备抗静电高分子材料和导电高分子材料。在高分子基材中加入金属粉末，特别是银粉或镀银粉末，可制得导电性能更好的导电高分子材料。也有报道，将导电纤维加入到高分子材料中制备导电高分子材料。所用的导电纤维有金属化的玻璃纤维(如美国专利4332853“Conductive plastic with metalized glass fibers retained in partial clumps”所描述)、碳纤维或碳纳米管(如申请号为201210011604.7的中国专利文献“各向异性导电橡胶及其制备方法”)等。由于导电炭黑、金属粉末和导电纤维在导电橡胶中是分散分布的，由这些填充物制得的导电高分子材料，体积电阻率和表面电阻率还是比常见金属导电材料大，导通较大电流的能力在某些场合显得不足够。The various rubbers themselves are electrically insulating. To date, all conductive rubbers are not intrinsic. Although conductive plastics are intrinsic, the intrinsic conductive plastics have high production costs, are difficult to produce, and are generally inferior in electrical conductivity and stability to metal conductors, and have not been produced and used in large quantities. The widely used conductive polymer materials are generally composite polymer materials, which are compounded by polymer materials (such as rubber and plastic) and conductive fillers. An antistatic polymer material and a conductive polymer material can be prepared by adding conductive carbon black to the polymer substrate. By adding a metal powder, in particular, a silver powder or a silver-plated powder, to a polymer substrate, a conductive polymer material having better conductivity can be obtained. It has also been reported that conductive fibers are added to a polymer material to prepare a conductive polymer material. The conductive fibers used are metallized glass fibers (as described in US Patent No. 4332853 "Conductive plastic with metalized glass fibers retained in partial clumps"), carbon fibers or carbon nanotubes (for example, Chinese Patent Application No. 201210011604.7) Conductive rubber and its preparation method") and the like. Since the conductive carbon black, the metal powder and the conductive fiber are dispersedly distributed in the conductive rubber, the conductive polymer material prepared from these fillers has a larger volume resistivity and surface resistivity than the common metal conductive material, and the conduction is larger. The ability of current does not appear to be sufficient in some situations.
申请号为200510086201.9的专利文献“一种导电塑料及其加工方法、加工装置”公开的导电塑料包含0.1-45v％的导电纤维，55-99v％的热塑性塑料和0-3v％的加工助剂，其中，导电纤维在热塑性塑料中呈三维网络状排列；导电 塑料纤维分散均匀、纤维之间搭接点多、导电性高，从而使屏蔽效能提高显著，SE值可达到40-99dB，抗静电和电磁屏蔽效果好。为了更进一步提高导电高分子材料的导电性能，技术人员制备了连续的金属材料和高分子材料的复合物，作为传统的导电高分子材料的替代品。申请号为201110448918.9的专利文献“一种高效传导材料”公开了一种可以用做卫星、地面雷达的天线，广播通讯的定向天线，电缆，航空和汽车的电磁干扰屏蔽元件的高效传导材料，其结构中至少含有一层能高速传导电、热、电磁的金属纤维无纺毡层，优选铝纤维无纺毡；基体为各种塑料，优选玻璃纤维增强塑料。申请号为201010592410.1的专利文献“复合导电片材”公开了由高分子基体和复合在其中的金属箔构成的复合导电片材。这里的金属箔是指含有孔洞的镍箔、铜箔、铝箔、不锈钢箔、金箔、银箔或者编织网，高分子基体是指硅橡胶、丁晴橡胶、乙丙橡胶、天然橡胶、橡塑材料、热塑性塑料、热固性塑料或者纤维增强塑料等。申请号为201010609386.8的专利文献“一种导电橡胶及其应用”公开了以模压或注射方式将橡胶与金属纤维烧结毡(或金属无纺布)复合制得导电橡胶，该金属纤维烧结毡具有孔隙，该孔隙至少部分被橡胶填充。美国专利6475933“Highly conductive elastomeric sheet”公开了一种由导电的丝网和填充有导电微粒的弹性体基材组成的高导电橡胶片材，其中的导电微粒是亚微米尺寸的碳质材料。中国专利申请号200680015484.0“导电接触部及其制造方法”和美国专利号7964810“Electrically conducting contact and method for production thereof”的文献，公开了由至少部分地被弹性体材料渗透的金属海绵制成的电触点。美国专利申请20040242095“Composites reinforced by wire net or mesh for lightweight,strength and stiffness”公开了一种以一个或多个网络、丝网或筛网结构来增强的聚合物基的或金属基的复合材料。 The conductive plastic disclosed in the patent document "A conductive plastic and its processing method and processing device" of the application No. 200510086201.9 comprises 0.1-45 v% of conductive fibers, 55-99 v% of thermoplastics and 0-3 v% of processing aids. Wherein, the conductive fibers are arranged in a three-dimensional network in the thermoplastic; The plastic fiber is evenly dispersed, the overlap between the fibers is high, and the conductivity is high, so that the shielding performance is improved significantly, the SE value can reach 40-99 dB, and the antistatic and electromagnetic shielding effects are good. In order to further improve the electrical conductivity of the conductive polymer material, the skilled person prepares a composite of a continuous metal material and a polymer material as a substitute for the conventional conductive polymer material. The patent document "A Highly Efficient Conductive Material" of the application No. 201110448918.9 discloses an efficient conductive material which can be used as an antenna for satellites, ground radars, directional antennas for broadcasting communication, electromagnetic interference shielding elements for cables, aviation and automobiles, The structure comprises at least one layer of metal fiber non-woven mat which can conduct electricity, heat and electromagnetic at high speed, preferably aluminum fiber non-woven mat; the base body is various plastics, preferably glass fiber reinforced plastic. The patent document "Composite Conductive Sheet" of Application No. 201010592410.1 discloses a composite conductive sheet composed of a polymer matrix and a metal foil compounded therein. The metal foil here refers to a nickel foil, a copper foil, an aluminum foil, a stainless steel foil, a gold foil, a silver foil or a woven mesh containing pores, and the polymer matrix refers to a silicone rubber, a nitrile rubber, an ethylene propylene rubber, a natural rubber, a rubber plastic material. , thermoplastics, thermosets or fiber reinforced plastics. The patent document "A conductive rubber and its application" of the application No. 201010609386.8 discloses that a conductive rubber is prepared by molding a rubber and a metal fiber sintered felt (or a metal nonwoven fabric) by molding or injection, and the metal fiber sintered felt has pores. The pores are at least partially filled with rubber. U.S. Patent 6,475,933, "Highly conductive elastomeric sheet" discloses a highly conductive rubber sheet composed of an electrically conductive mesh and an elastomeric substrate filled with electrically conductive particles, wherein the electrically conductive particles are submicron sized carbonaceous materials. Chinese Patent Application No. 200680015484.0 "Electroconductive Contact and Method of Making Same" and U.S. Patent No. 7,964,810, "Electrically conducting contact and method for production thereof", discloses an electric made of a metal sponge at least partially infiltrated by an elastomer material. Contact. US Patent Application No. 20040242095 "Composites reinforced by wire net or mesh for lightweight, strength and stiffness" discloses a polymer-based or metal-based composite material reinforced with one or more network, mesh or mesh structures.
将由连续的金属材料和高分子材料制备的复合材料作为电触点时，由于高分子材料的热膨胀系数通常比常见金属材料大得多，有时甚至高达十倍以上(例如，硅橡胶的热膨胀系数大约是纯镍的15倍)，在温度升高的时候，这些复合材料中的高分子材料将因较大的热膨胀系数而突出于复合材料表面，使得电触点的表面接触电阻变大，甚至可能使得电触点变得不导通而完全失效。事实上，含有这样的电触点的按键如用到汽车上，可能会产生安全问题。When a composite material made of a continuous metal material and a polymer material is used as an electrical contact, the coefficient of thermal expansion of the polymer material is usually much larger than that of a common metal material, sometimes even as high as ten times or more (for example, the coefficient of thermal expansion of the silicone rubber is approximately It is 15 times that of pure nickel. When the temperature rises, the polymer material in these composite materials will protrude from the surface of the composite due to the large coefficient of thermal expansion, making the surface contact resistance of the electrical contacts larger, and maybe even The electrical contacts become rendered non-conductive and completely fail. In fact, a button containing such an electrical contact, if used in a car, may create a safety problem.
因此，有效地解决由高分子材料和连续的金属材料的复合材料制备的电触点在高温下失效的问题的方法，是生产行业所急需的。Therefore, a method for effectively solving the problem of failure of an electrical contact prepared from a composite material of a polymer material and a continuous metal material at a high temperature is urgently required in the production industry.
发明内容Summary of the invention
发明目的：提供一种高分子材料和多孔金属的复合材料及其制备方法，这种复合材料至少在有一个表面上有凸出的金属材质，适合于制备在升高温度的条件下导电功能也不失效的电触点。OBJECT OF THE INVENTION: To provide a composite material of a polymer material and a porous metal, and a preparation method thereof, the composite material having a protruding metal material at least on one surface, which is suitable for preparing a conductive function under elevated temperature conditions. Electrical contacts that do not fail.
电触点是按键中的关键组成部分，它通常用来与印刷电路板(PCB)的触点开关配对使用。它必须有低的接触电阻。如果接触电阻过大，就会造成按键开关功能失效、误判。Electrical contacts are a key component of the button and are typically used in conjunction with contact switches on printed circuit boards (PCBs). It must have a low contact resistance. If the contact resistance is too large, the key switch function will be invalid and misjudged.
以下是一个电触点导通功能失效的例子：橡胶和金属板网制备的复合材料，作为橡胶按键上的电触点时，在由室温升高至80℃时，出现橡胶胀大而凸出于电触点表面的现象，从而影响导通，使接触电阻由0.4Ω升高至2Ω以上，甚至不导电。如图1所示。橡胶凸出的原因是由于橡胶有较大的热膨胀系数。比如，在硅橡胶的热膨胀系数，约为金属镍的15倍。The following is an example of a failure of the electrical contact conduction function: a composite material prepared from rubber and metal mesh. When used as an electrical contact on a rubber button, the rubber swells and bulges when it is raised from room temperature to 80 °C. Due to the phenomenon of the surface of the electrical contact, the conduction is affected, and the contact resistance is raised from 0.4 Ω to more than 2 Ω, and is even non-conductive. As shown in Figure 1. The reason for the rubber bulging is due to the large coefficient of thermal expansion of the rubber. For example, the coefficient of thermal expansion of silicone rubber is about 15 times that of metallic nickel.
技术方案：本发明公开一种复合材料及其制备工艺：通过将含有可抽提物质的高分子材料和多孔金属进行复合，复合的方式包括热固性成型、热硫化成型、辐射固化成型和热塑性成型等，制得含有可抽提物质的高分子材料和多孔 金属的成型物，特别是制得一种有可抽提物质的高分子材料和金属两种材质同时外露于至少一个表面的成型物。所述的成型物中的多孔金属中的孔洞为所述的高分子材料在复合成型时所部分或全部填充，然后用溶剂把成型物中的可抽提物抽提出来，从而使得成型物中的高分子材料的体积收缩、成型物中的高分子材料表面塌陷，从而制得一种多孔金属突出于至少一个表面的高分子材料和多孔金属的复合材料。所述复合材料可以是片材、棒材、管材或异型材。Technical Solution: The present invention discloses a composite material and a preparation process thereof: by combining a polymer material containing an extractable substance and a porous metal, the composite method includes thermosetting molding, thermal vulcanization molding, radiation curing molding, thermoplastic molding, and the like. , producing a polymer material containing an extractable substance and porous A molded article of a metal, in particular, a molded article in which a polymer material having an extractable substance and a metal material are simultaneously exposed on at least one surface. The pores in the porous metal in the molded body are partially or completely filled in the composite material during the composite molding, and then the extractables in the molded product are extracted by a solvent, thereby causing the molded body to be in the molded body. The volume shrinkage of the polymer material and the surface of the polymer material in the molded body collapse, thereby producing a composite material of a polymer material and a porous metal in which the porous metal protrudes from at least one surface. The composite material can be a sheet, a bar, a tube or a profile.
本发明中的多孔金属，指的是有孔隙、孔洞的金属材料或金属材料制成品，包括有多个均匀分布的或随机分布的孔洞的金属片材、金属网、烧结金属网、金属板网、金属泡沫或金属纤维烧结毡等，或者含有它们的多层金属结构。金属网和烧结金属网可以是单层或多层的，金属网和金属板网经特定的真空烧结工艺制成一种多孔金属。多孔金属中的孔洞是独立的或相互连通的，孔洞至少有部分外露于多孔金属的表面，以便高分子材料能渗入到孔洞中。孔洞可以是规则的圆柱体型的，例如金属板网中所有孔洞的直径是0.25mm，也可以是不规则的。孔洞的横截面积的直径可以在1μm-3.0mm的范围内取值。The porous metal in the present invention refers to a metal material or a metal material having pores and holes, and includes a metal sheet having a plurality of uniformly distributed or randomly distributed pores, a metal mesh, a sintered metal mesh, and a metal plate. Net, metal foam or metal fiber sintered felt, etc., or a multilayer metal structure containing them. The metal mesh and the sintered metal mesh may be a single layer or a plurality of layers, and the metal mesh and the metal mesh are formed into a porous metal by a specific vacuum sintering process. The pores in the porous metal are independent or interconnected, and at least a portion of the pores are exposed on the surface of the porous metal so that the polymer material can penetrate into the pores. The holes may be of a regular cylindrical shape, for example, all holes in the metal mesh may have a diameter of 0.25 mm or may be irregular. The diameter of the cross-sectional area of the hole may be in the range of 1 μm to 3.0 mm.
举例来说，所述的多孔金属可以为孔洞均匀分布的、孔径为50μm-1.0mm、孔间距为25μm-1.0mm的、孔型为圆形、正多边形或其它几何形状的金属板网。For example, the porous metal may be a metal mesh having a uniformly distributed pores, a pore diameter of 50 μm to 1.0 mm, a pore spacing of 25 μm to 1.0 mm, and a circular shape, a regular polygon or other geometric shape.
多孔金属的材质可以是多种多样的。多孔金属可以由铝、铁、钴、镍、铜、锌、锡、锰、钨、银、金或它们的合金构成的。所述的合金包括哈氏合金、蒙乃尔合金、英科乃尔等。优选不锈钢、镍或镍合金。这是因为不锈钢、镍或镍合金在室温条件下，化学性能比较稳定，并且价廉易得。The material of the porous metal can be varied. The porous metal may be composed of aluminum, iron, cobalt, nickel, copper, zinc, tin, manganese, tungsten, silver, gold or alloys thereof. The alloys include Hastelloy, Monel, Inconel, and the like. Stainless steel, nickel or a nickel alloy is preferred. This is because stainless steel, nickel or nickel alloys have relatively stable chemical properties at room temperature and are inexpensive and readily available.
多孔金属是由均质的或非均质的金属材料构成的；进一步地说，所述的多孔金属及其孔洞的外表面是可以有金属镀层的，金属镀层可以全部地或部分的覆盖着多孔金属的表面和多孔金属孔洞的内表面。优选镀金或镀银。金和银有 比较良好的导电率，作为金属材料外层的镀层，可以提高电触点的表面导电率，降低电触点的接触电阻，提高电触点的电导通能力和使用寿命。多孔金属是不含或含有金属镀层的；金属镀层全部地或部分地覆盖着多孔金属的表面和多孔金属孔洞的内表面。The porous metal is composed of a homogeneous or non-homogeneous metal material; further, the outer surface of the porous metal and the pores thereof may be coated with a metal, and the metal plating may be partially or partially covered with a porous layer. The surface of the metal and the inner surface of the porous metal hole. Gold plating or silver plating is preferred. Gold and silver have A relatively good electrical conductivity, as a coating of the outer layer of the metal material, can improve the surface conductivity of the electrical contact, reduce the contact resistance of the electrical contact, and improve the electrical conductivity and service life of the electrical contact. The porous metal is free or contains a metal plating; the metal plating completely or partially covers the surface of the porous metal and the inner surface of the porous metal hole.
多孔金属的外表面或孔洞的内表面，可以涂有一层平均厚度不大于1μm的的粘合增进剂、偶联剂或底涂剂，以增加多孔金属和高分子材料之间的粘合强度。所涂的粘合增进剂、偶联剂或底涂剂不能太厚，涂层的平均厚度不能超过1μm，否则或明显增加多孔金属的接触电阻，从而影响电触点的导电性能。The outer surface of the porous metal or the inner surface of the pore may be coated with an adhesion promoter, a coupling agent or a primer having an average thickness of not more than 1 μm to increase the bonding strength between the porous metal and the polymer material. The adhesion promoter, coupling agent or primer to be applied should not be too thick, and the average thickness of the coating should not exceed 1 μm, otherwise the contact resistance of the porous metal may be significantly increased, thereby affecting the electrical conductivity of the electrical contact.
不仅多孔金属可以是多种多样的，本发明中的高分子材料的选材范围也是很宽广的，可以分别高分子材料和金属的复合材料及其制备工艺，其特征在于：所述的高分子材料是热固性橡胶、热塑性橡胶、热塑性塑料、热固性塑料、辐射固化材料、粘合剂、油墨或涂料。就热固性橡胶来说，液态的或固态的二烯类橡胶、烯烃类液体橡胶、聚氨酯类橡胶、丙烯酸酯橡胶、聚硫橡胶、硅橡胶、氟橡胶、氟硅橡胶等都可以使用来和多孔金属制备导电复合材料。选用液体橡胶的原因是液体橡胶的粘度比固体生胶低，便于用各种方法使橡胶和多孔金属复合到一起。但这并不是说固体生胶是不可以使用的。用某些方法一样可以使固体生胶和多孔金属复合在一起，比如将固体生胶和多孔金属(如金属板网)叠合在一起，然后放在模具模腔中，用平板硫化机压制，使固体生胶渗入多孔金属的孔洞中，使固体生胶和多孔金属结合在一起，在高温下硫化成型。The porous metal may be various, and the selection range of the polymer material in the present invention is also broad, and the composite material of the polymer material and the metal and the preparation process thereof are characterized in that the polymer material is: It is a thermosetting rubber, thermoplastic rubber, thermoplastic, thermosetting plastic, radiation curable material, adhesive, ink or coating. For thermosetting rubber, liquid or solid diene rubber, olefin liquid rubber, polyurethane rubber, acrylate rubber, polysulfide rubber, silicone rubber, fluororubber, fluorosilicone rubber, etc. can be used and porous metal. A conductive composite is prepared. The reason for choosing liquid rubber is that the viscosity of the liquid rubber is lower than that of the solid rubber, which facilitates the compounding of the rubber and the porous metal by various methods. But this is not to say that solid rubber is not available. In some ways, the solid raw rubber and the porous metal can be combined together, for example, the solid raw rubber and the porous metal (such as a metal mesh) are stacked together, and then placed in a mold cavity and pressed by a flat vulcanizer. The solid rubber is infiltrated into the pores of the porous metal, and the solid rubber and the porous metal are combined and vulcanized at a high temperature.
在选定橡胶的种类时，应考虑这些复合材料的后续用途。如果用这些复合材料制备橡胶按键上的电触点，就应了解橡胶按键是用哪一种橡胶制备的，以使得在热硫化成型或辐射固化成型时，电触点和按键基体之间有良好的粘合。例如，由液体或固体丁腈橡胶和烧结镍丝网制备的复合材料所制得的电触点， 适用于制备丁腈橡胶按键，由液体或固体硅橡胶和不锈钢板网制备的复合材料所制得的电触点，适用于制备硅橡胶按键，由液体或固体氟橡胶和镍纤维烧结毡制备的复合材料所制得的电触点，适用于制备氟橡胶按键。The subsequent use of these composites should be considered when selecting the type of rubber. If these composite materials are used to make electrical contacts on the rubber keys, it should be understood which rubber is used to make the rubber keys have a good relationship between the electrical contacts and the key substrate during hot vulcanization or radiation curing. Bonding. For example, an electrical contact made of a composite material prepared from a liquid or solid nitrile rubber and a sintered nickel mesh, Applicable to the preparation of nitrile rubber buttons, electrical contacts made of composite materials prepared from liquid or solid silicone rubber and stainless steel mesh, suitable for the preparation of silicone rubber buttons, prepared from liquid or solid fluororubber and nickel fiber sintered felt The electrical contacts made of composite materials are suitable for the preparation of fluororubber buttons.
高分子材料的配方中可含有各种助剂，如颜料、填料或导电填料等。本发明与一般高分子材料的配方不同的是，在高分子材料的配方中必须加入可抽提物。在高分子材料配方中加入可抽提物的目的，不是为了让可抽提物在高分子材料成型后还留在高分子材料中起某种作用，而是为了在高分子材料成型后，通过抽提的方法把这些可抽提物从高分子材料中驱赶出来，使高分子材料和多孔金属的复合材料中的高分子基体发生收缩，使得复合材料中多孔金属的孔洞中的高分子基体发生塌陷。The formulation of the polymer material may contain various additives such as pigments, fillers or conductive fillers. The present invention differs from the formulation of a general polymer material in that an extractable substance must be added to the formulation of the polymer material. The purpose of adding an extractable material to a polymer material formulation is not to allow the extractable material to remain in the polymer material after molding the polymer material, but to pass the polymer material after molding. The extraction method drives the extractable material out of the polymer material to shrink the polymer matrix in the composite material of the polymer material and the porous metal, so that the polymer matrix in the pore of the porous metal in the composite material occurs. Collapse.
在与多孔金属复合前，高分子材料中的可抽提物的含量为1-95w％。这些可抽提物是与高分子材料相容的或部分相容的低分子化合物、低聚物或未交联的聚合物。The content of the extractable material in the polymer material is from 1 to 95% by weight before being compounded with the porous metal. These extractables are low molecular weight, oligomeric or uncrosslinked polymers that are compatible or partially compatible with the polymeric material.
高分子材料和其所包含的可抽提物需是相容的或部分相容的，以使得可抽提物从高分子材料中被抽提出去时，高分子材料的体积收缩，而不是在高分子材料中形成孔洞以致不发生或基本不发生收缩。The polymer material and the extractable material contained therein need to be compatible or partially compatible, so that when the extractable material is extracted from the polymer material, the volume of the polymer material shrinks instead of Holes are formed in the polymer material so that no or substantially no shrinkage occurs.
当使用液体硅橡胶或固体硅橡胶来制备高分子材料和金属的复合材料时，可将各种硅油、液体石蜡、固体石蜡、氯化石蜡、萘、四氢化萘、十氢化萘、四甲苯、四甲苯、六甲苯或高沸点溶剂油等物质作为可抽提物加入到液体硅橡胶或固体硅橡胶中，硅橡胶和金属复合成型后，将这些可抽提物部分或全部抽提出来。When liquid silicone rubber or solid silicone rubber is used to prepare a composite material of a polymer material and a metal, various silicone oils, liquid paraffin waxes, paraffin wax, chlorinated paraffin, naphthalene, tetralin, decalin, tetramethylbenzene, A substance such as tetramethylbenzene, hexamethylbenzene or a high-boiling solvent oil is added as an extractable substance to a liquid silicone rubber or a solid silicone rubber, and after the silicone rubber and the metal are composite-molded, some or all of these extractables are extracted.
本发明中复合材料的制备方法也是多种多样的。可通过叠合、移印、丝印、刷涂、辊刷涂、刮涂、喷涂、浸涂、淋涂、抽涂的方式，使含有可抽提物的高 分子材料和多孔金属组合在一起，然后通过热塑性成型工艺、热固性成型工艺或辐射固化工艺固化成型，制得含有可抽提物的高分子材料和多孔金属的复合材料，然后用挥发性溶剂浸渍抽提法、用水蒸气或溶剂蒸汽抽提法、或者用超临界CO2萃取法将所得到的复合材料中的可抽提物部分或全部抽提出来，从而使得复合材料中的高分子材料的体积收缩，而复合材料中的多孔金属的形状或体积基本保持不变，从而使得多孔金属突出于复合材料的表面。成型工艺取决于高分子材料的类别。在抽提前或抽提后，所述的复合材料可冲切成直径为1.0-10.0的小圆片或其它几何形状的小片。The preparation method of the composite material in the present invention is also various. Can be superimposed by means of lamination, pad printing, silk screen printing, brush coating, roller brushing, blade coating, spray coating, dip coating, shower coating, and draw coating. The molecular material and the porous metal are combined together, and then solidified by a thermoplastic molding process, a thermosetting molding process or a radiation curing process to obtain a composite material containing an extractable polymer material and a porous metal, and then impregnated with a volatile solvent. Extraction, steam or solvent vapor extraction, or extraction of part or all of the extractable material in the obtained composite by supercritical CO2 extraction, thereby causing volume shrinkage of the polymer material in the composite And the shape or volume of the porous metal in the composite remains substantially unchanged such that the porous metal protrudes from the surface of the composite. The molding process depends on the type of polymer material. The composite material can be die cut into small discs having a diameter of 1.0 to 10.0 or other geometrical pieces after pumping or extraction.
有益效果：本发明所描述的复合材料冲切成直径为1.0-10.0mm的小圆片的导电性良好，接触电阻可小于1Ω，可以作为橡胶按键中的电触点。使用该复合材料制备的电触点的表面由于高分子材料在抽提后发生收缩和塌陷，多孔金属的材质因而突出于复合材料的表面，使得这种电触点有良好的抗尘性、耐油污性能，并且在温度升高时有良好的电导通能力。虽然高分子材料的热膨胀系数通常比金属材料大，但由于复合材料中高分子材料收缩和塌陷，可以抵消高分子材料由于较大的热膨胀系数而造成高分子材料的热膨胀，防止高分子材料突出于复合材料的表面对触点导电性能造成影响。Advantageous Effects: The composite material described in the present invention is punched into a small wafer having a diameter of 1.0 to 10.0 mm, which has good electrical conductivity and a contact resistance of less than 1 Ω, and can be used as an electrical contact in a rubber button. The surface of the electrical contact prepared by using the composite material shrinks and collapses after the extraction of the polymer material, and the material of the porous metal protrudes from the surface of the composite material, so that the electrical contact has good dust resistance and resistance. Oil stain performance and good electrical conductivity when temperature rises. Although the thermal expansion coefficient of polymer materials is usually larger than that of metal materials, the shrinkage and collapse of polymer materials in composite materials can offset the thermal expansion of polymer materials due to the large thermal expansion coefficient of polymer materials, preventing polymer materials from protruding in composites. The surface of the material affects the electrical conductivity of the contacts.
附图说明DRAWINGS
图1为本发明中当升高温度时，橡胶凸出于由橡胶和金属板网制备的复合材料的表面示意图；其中，1-橡胶，2-金属板网；Figure 1 is a schematic view showing the surface of a composite material prepared from a rubber and a metal mesh when the temperature is raised in the present invention; wherein, 1-rubber, 2-metal mesh;
图2为本发明中抽提使多孔金属孔洞中的橡胶收缩示意图；其中，3-镍板网，4-橡胶；2 is a schematic view showing the shrinkage of rubber in a porous metal hole in the present invention; wherein, 3-nickel mesh, 4-rubber;
图3为本发明中抽提使多孔金属孔洞中的橡胶收缩示意图；其中，5-镍板网，6-橡胶； Figure 3 is a schematic view showing the shrinkage of the rubber in the porous metal hole in the present invention; wherein, 5-nickel mesh, 6-rubber;
图4.升高温度时，多孔金属孔洞中的橡胶不会凸出于多孔金属的表面示意图，虚线表示在温度升高前多孔金属孔洞中橡胶表面的位置；其中，7-镍板网，8-橡胶。Figure 4. When the temperature is raised, the rubber in the porous metal hole does not protrude from the surface of the porous metal. The broken line indicates the position of the rubber surface in the porous metal hole before the temperature rises; wherein, the 7-nickel mesh, 8 -rubber.
具体实施方式detailed description
下面结合具体实施例对本发明作进一步说明。The invention will now be further described in conjunction with specific embodiments.
实施例1Example 1
配方A：含有气相法白炭黑的甲基乙烯基硅橡胶的混炼胶(选用道康宁公司的SE 4705U)100(重量份，下同)，二甲基硅油(选用道康宁公司的Xiameter PMX-200，1000cs)50，乙烯基三叔丁基过氧硅烷(VTPS)1，过氧化二异丙苯(DCP)0.5。Formulation A: a mixture of methyl vinyl silicone rubber containing fumed silica (SE 4705U from Dow Corning) 100 (parts by weight, the same below), dimethyl silicone oil (selected Dow Corning's Xiameter PMX-200) , 1000cs) 50, vinyl tri-tert-butylperoxysilane (VTPS) 1, dicumyl peroxide (DCP) 0.5.
配方B：SE 4705U 100，VTPS 1，DCP 0.5。Formulation B: SE 4705U 100, VTPS 1, DCP 0.5.
将配方A和配方B的混炼胶片，分别和厚度为0.25mm、孔径0.5mm、孔间距0.25mm的镍板网(镍的纯度不低于99.5％)叠合，放在有特氟龙涂层的模具模腔中，在175℃温度条件下，压合10分钟硫化成型，制成厚度为0.25mm的薄片。将此薄片冲切成直径为3.0mm的小圆片。以乙醇为溶剂，用索氏提取器分别将由配方A和配方B制得的小圆片抽提3小时。然后在60℃下烘干至基本恒重。The mixed film of Formulation A and Formula B was laminated with a nickel mesh (nickel purity of not less than 99.5%) having a thickness of 0.25 mm, a pore diameter of 0.5 mm, and a hole pitch of 0.25 mm, and placed on a Teflon coating. The mold cavity of the layer was vulcanized and molded at a temperature of 175 ° C for 10 minutes to form a sheet having a thickness of 0.25 mm. The sheet was die cut into small discs having a diameter of 3.0 mm. The small discs prepared from Formulation A and Formulation B were separately extracted with ethanol as a solvent for 3 hours using a Soxhlet extractor. It is then dried at 60 ° C to a substantially constant weight.
配方B所得的小圆片用作电触点，在温度升高的情况下，电触点和其配匹的PCB电触点之间的接触电阻会由不大于0.5Ω升高至2Ω以上，甚至不导通。和使用配方B所得的小圆片比较起来，由使用配方A所得的小圆片的表面，由于硅油在被抽提掉，引起金属孔洞中的橡胶收缩和塌陷(如图2所示)，这种小圆片作为电触点，具有良好的有良好的抗尘性、耐油污性能，并且可以克服硅橡胶的热膨胀系数大而引起在高温下电阻变大或不导通的缺点，具有良好的温 度适用范围。在升高温度的时候，其接触电阻仍在0.5以下。The small wafer obtained by Formulation B is used as an electrical contact. When the temperature rises, the contact resistance between the electrical contact and the PCB electrical contact with it is increased from no more than 0.5 Ω to more than 2 Ω. Not even conductive. Compared with the small disc obtained by using the formula B, the surface of the small disc obtained by using the formula A, due to the extraction of the silicone oil, causes the rubber in the metal hole to shrink and collapse (as shown in Fig. 2). As a kind of electrical contact, the small disc has good dust resistance and oil resistance, and can overcome the disadvantage that the thermal expansion coefficient of the silicone rubber is large and the resistance becomes large or non-conductive at high temperature. Warm The scope of application. At elevated temperatures, the contact resistance is still below 0.5.
实施例2Example 2
将实施例一中的镍板网的一面，贴以一0.025mm厚的聚酰亚胺(PI)自粘膜，然后用配方A的混炼胶和镍板网复合制成0.8mm厚的复合片材。除去PI自粘膜，冲切成直径为2.0-5.0mm的小圆片。用溶剂汽油浸泡，抽提掉小圆片硅橡胶中所含的硅油，镍板网孔洞中的橡胶发生收缩(图3)。One side of the nickel mesh in the first embodiment was attached with a 0.025 mm thick polyimide (PI) self-adhesive film, and then a compound of the formula A and a nickel mesh were combined to form a 0.8 mm thick composite sheet. material. The PI was removed from the mucosa and punched into small discs having a diameter of 2.0-5.0 mm. Soaking with solvent gasoline, the silicone oil contained in the small round silicone rubber is extracted, and the rubber in the nickel mesh cavity shrinks (Fig. 3).
这些小圆片用作电触点，在环境温度升高时也有良好导电能力。这是因为在温度升高时，比如由25℃升高至80℃，多孔金属孔洞中橡胶即使有较低的膨胀系数，也不会凸出于多孔金属的表面(如图4所示)。These small wafers act as electrical contacts and also have good electrical conductivity when the ambient temperature rises. This is because, when the temperature is raised, such as from 25 ° C to 80 ° C, the rubber in the porous metal hole does not protrude from the surface of the porous metal even if it has a lower expansion coefficient (as shown in FIG. 4 ).
实施例3Example 3
配方C：PVC(P＝500)100，乙烯-醋酸乙烯-一氧化碳共聚物(选用杜邦公司的Elvaloy 741)45，二月桂酸二辛基锡2，环氧大豆油3.5，聚乙烯蜡0.3，单硬脂酸甘油酯3，偏苯三酸三辛酯65、聚乙烯醇缩丁醛(分子量20000)5。聚乙烯醇缩丁醛的加入，是为了提高PVC对金属的附着力。Formulation C: PVC (P=500) 100, ethylene-vinyl acetate-carbon monoxide copolymer (using Elvaloy 741 from DuPont) 45, dioctyltin dilaurate 2, epoxidized soybean oil 3.5, polyethylene wax 0.3, mono-hard fat Acid glyceride 3, trioctyl trimellitate 65, polyvinyl butyral (molecular weight 20000) 5. The addition of polyvinyl butyral is to improve the adhesion of PVC to metals.
按配方C将各物料投入高速混合机混合搅拌，时间控制在15分钟左右，温度达110-120℃，让PVC粉料吸收增塑剂而又不发粘，放入低速冷却搅拌机中边搅拌边冷却；冷却到25℃左右时，放出物料。将此物料施加在由5层80目的AISI 304不锈钢丝平纹网经过特殊叠层压制与真空烧结等工艺制造而成的多层不锈钢烧结网上，或者由双辊开炼机在160℃下塑炼成1.5mm厚的薄片，将薄片放在多层不锈钢烧结网上，放入175℃的有特氟龙涂层的模具模腔中，在平板硫化机上热压复合成型，制成1.5mm厚的片材。将此片材或有此片材冲切而成的直径为2.5-10mm的的小圆片，用120号溶剂汽油浸泡法抽提或用索氏抽提器抽提5-120分钟，使得其中的偏苯三酸三辛酯和环氧大豆油等低分子物质部分或 几乎全部抽提出来。可根据所需要的多层不锈钢烧结网中树脂的塌陷程度，来决定抽提时间等参数。由这种方法制得的聚氯乙烯-不锈钢烧结网的复合材料，聚氯乙烯向材料内部收缩，而不锈钢材质突出于表面上。这种复合材料，可用作导电材料、屏蔽材料，或者用作具有良好高温电导通性能的电触点。According to the formula C, the materials are put into a high-speed mixer for mixing and mixing, the time is controlled at about 15 minutes, the temperature reaches 110-120 ° C, and the PVC powder absorbs the plasticizer without being sticky, and is placed in a low-speed cooling mixer while stirring. Cooling; when cooled to about 25 ° C, the material is discharged. The material is applied to a multi-layer stainless steel sintering net made by a 5-layer 80-mesh AISI 304 stainless steel wire plain weave through special lamination pressing and vacuum sintering, or by a two-roll mill at 160 ° C. A 1.5 mm thick sheet was placed on a multi-layer stainless steel sintered wire, placed in a Teflon-coated mold cavity at 175 ° C, and hot-pressed and formed on a flat vulcanizing machine to make a 1.5 mm thick sheet. . The sheet or the small circular piece having a diameter of 2.5-10 mm which is die-cut from the sheet is extracted by a solvent gasoline soaking method of 120 or by a Soxhlet extractor for 5-120 minutes, wherein Part of low molecular weight such as trioctyl trimellitate and epoxidized soybean oil or Almost all drawn up. The extraction time and other parameters can be determined according to the degree of collapse of the resin in the multi-layer stainless steel sintered mesh. The composite material of the polyvinyl chloride-stainless steel sintered mesh obtained by this method, the polyvinyl chloride shrinks to the inside of the material, and the stainless steel material protrudes from the surface. This composite material can be used as a conductive material, a shielding material, or as an electrical contact having good high-temperature electrical conductivity.
以抽提法制备高分子材料和多孔金属的复合材料，有利于环境保护，这是因为被抽提出来的增塑剂可以循环利用而不外排至环境中。The preparation of a composite material of a polymer material and a porous metal by extraction is advantageous for environmental protection because the extracted plasticizer can be recycled without being discharged to the environment.
实施例4：Example 4:
此实施例制备高分子材料和多孔金属的复合物如实施例1，其中高分子材料是基于实施例1中的配方A，而所使用的多孔材料是实施例3中的表面和孔洞内表面镀有平均厚度0.05-0.75μm厚的纯度大于99.0％的金镀层。镀金可降低复合材料的表面接触电阻，使接触电阻保持在0.3Ω。This embodiment prepares a composite of a polymer material and a porous metal as in Example 1, wherein the polymer material is based on Formulation A in Example 1, and the porous material used is the surface and hole inner surface plating in Example 3. A gold plating having an average thickness of 0.05-0.75 μm and a purity greater than 99.0%. Gold plating reduces the surface contact resistance of the composite and keeps the contact resistance at 0.3 Ω.
实施例5：Example 5:
制备方法与实施例1相同，制得直径为2-10mm的小圆片，在小圆片经过抽提工艺之后，以化学镀的方法在镀上0.1μm的金。本实施例同实施例4相比，本实施例中制得的复合材料或电触点所耗用的金减少，而复合材料或电触点的表面接触电阻基本上与实施例1制得的复合材料或电触点的表面接触电阻相同或相近。The preparation method was the same as in Example 1, and a small wafer having a diameter of 2 to 10 mm was obtained. After the small wafer was subjected to an extraction process, 0.1 μm of gold was plated by electroless plating. Compared with the embodiment 4, the composite material or the electrical contact obtained in the embodiment consumes less gold, and the surface contact resistance of the composite material or the electrical contact is substantially the same as that of the embodiment 1. The surface contact resistance of the composite or electrical contacts is the same or similar.
本发明不局限于上述最佳实施方式，任何人在本发明的启示下都可得出其他各种形式的产品，但不论在其形状或结构上作任何变化，凡是具有与本申请相同或相近似的技术方案，均落在本发明的保护范围之内。 The present invention is not limited to the above-described preferred embodiments, and any other form of product can be derived by anyone of the present invention, but without any change in shape or structure, it is the same as or equivalent to the present application. Approximate technical solutions are all within the scope of the present invention.

Claims (10)

  1. 一种高分子材料和金属的复合材料，其特征在于：所述的复合材料是由高分子材料和多孔金属复合的片材、棒材、管材或异型材；将含有可抽提物质的高分子材料和多孔金属通过热固性成型、热硫化成型、辐射固化成型或热塑性成型的方式进行复合成型，制得一种含有可抽提物质的高分子材料和多孔金属的复合材料，其中高分子材料和金属两种材质同时外露于复合材料的至少一个表面，且多孔金属中的孔洞或孔隙被含有可抽提物质的高分子材料所部分或全部填充，然后用溶剂把成型物中的可抽提物抽提出来，使得成型物中的高分子材料的体积收缩、成型物中的高分子材料表面塌陷，从而制得一种多孔金属突出于至少一个表面的高分子材料和多孔金属的复合材料。A composite material of a polymer material and a metal, characterized in that the composite material is a sheet, a rod, a tube or a profile material which is composed of a polymer material and a porous metal; a polymer containing an extractable substance The material and the porous metal are composite-molded by thermosetting molding, hot vulcanization molding, radiation curing molding or thermoplastic molding to obtain a composite material containing a polymer material and a porous metal containing an extractable substance, wherein the polymer material and the metal The two materials are simultaneously exposed on at least one surface of the composite material, and the pores or pores in the porous metal are partially or completely filled with the polymer material containing the extractable substance, and then the extractable substance in the molded product is pumped with a solvent. It is proposed that the volume of the polymer material in the molded body shrinks and the surface of the polymer material in the molded body collapses, thereby producing a composite material of a polymer material and a porous metal in which the porous metal protrudes from at least one surface.
  2. 根据权利要求1所述的一种高分子材料和金属的复合材料，其特征在于：所述的多孔金属是有多个均匀分布的或随机分布的孔洞的金属片材、金属网、烧结金属网、金属板网、金属泡沫或金属纤维烧结毡，或者是它们的层状复合物；所述的孔洞是独立的或相互连通的；所述的孔洞中至少有部分孔洞外露于多孔金属的表面；所述的孔洞的直径为1μm-3.0mm。The composite material of a polymer material and a metal according to claim 1, wherein the porous metal is a metal sheet having a plurality of uniformly distributed or randomly distributed pores, a metal mesh, and a sintered metal mesh. a metal mesh, a metal foam or a metal fiber sintered felt, or a layered composite thereof; the holes are independent or interconnected; at least some of the holes are exposed on the surface of the porous metal; The pores have a diameter of from 1 μm to 3.0 mm.
  3. 根据权利要求1所述的一种高分子材料和金属的复合材料，其特征在于：所述的多孔金属为孔洞均匀分布的、孔径为50μm-1.0mm、孔间距为25μm-1.0mm的、孔型为圆形、正多边形或其它几何形状的金属板网。The composite material of a polymer material and a metal according to claim 1, wherein the porous metal is a hole having a uniform pore size, a pore diameter of 50 μm to 1.0 mm, and a pore spacing of 25 μm to 1.0 mm. A metal mesh of a circle, regular polygon or other geometric shape.
  4. 根据权利要求1或2所述的一种高分子材料和金属的复合材料，其特征在于：所述的多孔金属是由铝、铁、钴、镍、铜、锌、锡、锰、钨、银、金或它们的合金构成的；所述的多孔金属是由均质的或非均质的金属材料构成的；所述的多孔金属是不含或含有金属镀层的；所述的金属镀层是全部或部分覆盖着多孔金属的外表面和多孔金属孔洞的内表面。The composite material of a polymer material and a metal according to claim 1 or 2, wherein the porous metal is made of aluminum, iron, cobalt, nickel, copper, zinc, tin, manganese, tungsten, silver. Made of gold or an alloy thereof; the porous metal is composed of a homogeneous or non-homogeneous metal material; the porous metal is free or contains a metal plating; the metal plating is all Or partially covering the outer surface of the porous metal and the inner surface of the porous metal hole.
  5. 根据权利要求1所述的一种高分子材料和金属的复合材料，其特征在于： 所述的多孔金属的外表面或孔洞的内表面，涂有一层平均厚度不大于1μ的的粘合增进剂、偶联剂或底涂剂。A composite material of a polymer material and a metal according to claim 1, wherein: The outer surface of the porous metal or the inner surface of the pore is coated with an adhesion promoter, a coupling agent or a primer having an average thickness of not more than 1 μ.
  6. 根据权利要求1所述的一种高分子材料和金属的复合材料，其特征在于：所述的高分子材料是热固性橡胶、热塑性橡胶、热塑性塑料、热固性塑料、辐射固化材料、粘合剂、油墨或涂料。The composite material of a polymer material and a metal according to claim 1, wherein the polymer material is a thermosetting rubber, a thermoplastic rubber, a thermoplastic, a thermosetting plastic, a radiation curing material, a binder, and an ink. Or paint.
  7. 根据权利要求6所述的一种高分子材料和金属的复合材料，其特征在于：所述的高分子材料是由二烯类液体橡胶、链烯烃类液体橡胶、聚氨酯类液体橡胶、丙烯酸酯液体橡胶、液体聚硫橡胶、硅系液体橡胶、氟系液体橡胶或者相应的固体生胶制备而成。The composite material of a polymer material and a metal according to claim 6, wherein the polymer material is a diene liquid rubber, an olefin liquid rubber, a polyurethane liquid rubber, or an acrylate liquid. It is prepared from rubber, liquid polysulfide rubber, silicon-based liquid rubber, fluorine-based liquid rubber or corresponding solid rubber.
  8. 根据权利要求1所述的一种高分子材料和金属的复合材料，其特征在于：所述的可抽提物是与高分子材料相容的或部分相容的低分子化合物、低聚物或未交联的聚合物，或它们的混合物；可抽提物在与多孔金属复合前的高分子材料中的含量为1-95％。The composite material of a polymer material and a metal according to claim 1, wherein the extractable material is a low molecular compound or oligomer which is compatible or partially compatible with the polymer material or The uncrosslinked polymer, or a mixture thereof; the extractables are present in the polymer material before the composite with the porous metal in an amount of from 1 to 95%.
  9. 根据权利要求1所述的一种高分子材料和金属的复合材料，其特征在于：所述的高分子材料是由液体硅橡胶或固体硅橡胶制备的；所述的可抽提物是硅油、液体石蜡、固体石蜡、氯化石蜡、萘、四氢化萘、十氢化萘、四甲苯、六甲苯或高沸点溶剂油。The composite material of a polymer material and a metal according to claim 1, wherein the polymer material is prepared from liquid silicone rubber or solid silicone rubber; and the extractable material is silicone oil. Liquid paraffin, paraffin wax, chlorinated paraffin, naphthalene, tetralin, decalin, tetramethylbenzene, hexamethylbenzene or high boiling solvent oil.
  10. 根据权利要求1所述的一种高分子材料和金属的复合材料的制备工艺，其特征在于：所述的复合材料的制备方法是：通过叠合、移印、丝印、刷涂、辊刷涂、刮涂、喷涂、浸涂、淋涂、抽涂的方式，使含有可抽提物的高分子材料和多孔金属组合在一起，加以压合或热压合，或者通过热塑性成型工艺、热固性成型工艺或辐射固化工艺固化成型，制得含有可抽提物的高分子材料和多孔金属的成型物，然后用挥发性溶剂浸渍抽提法、用水蒸气或溶剂蒸汽抽提法、或者用超临界CO2萃取法将所得到的成型物中的可抽提物部分或全部抽提出来，从而使得复合材料中的高分子材料的体积收缩，使得多孔金属突出于复合材料的表面；在抽提前或抽提后，所述的复合材料冲切成直径为1.0-10.0mm的小圆片 或其它几何形状的小片。 The process for preparing a composite material of a polymer material and a metal according to claim 1, wherein the composite material is prepared by laminating, pad printing, silk screen printing, brush coating, and roller coating. , scraping, spraying, dip coating, shower coating, drawing, so that the polymer material containing the extractable material and the porous metal are combined, pressed or thermocompression, or through thermoplastic molding process, thermosetting molding The process or radiation curing process is solidified and molded to obtain a polymer material containing an extractable material and a porous metal molding, and then subjected to extraction by a volatile solvent extraction method, steam or solvent vapor extraction, or supercritical CO. 2 extraction method extracts part or all of the extractable material in the obtained molded body, so that the volume of the polymer material in the composite material shrinks, so that the porous metal protrudes from the surface of the composite material; Thereafter, the composite is die cut into small discs of 1.0-10.0 mm in diameter or other geometrical pieces.
PCT/CN2017/098919 2016-08-30 2017-08-24 Macromolecular material and metal composite material and preparation method therefor WO2018041007A1 (en)

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