WO2020155846A1 - 一种石墨胶带及其制备方法 - Google Patents

一种石墨胶带及其制备方法 Download PDF

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WO2020155846A1
WO2020155846A1 PCT/CN2019/123308 CN2019123308W WO2020155846A1 WO 2020155846 A1 WO2020155846 A1 WO 2020155846A1 CN 2019123308 W CN2019123308 W CN 2019123308W WO 2020155846 A1 WO2020155846 A1 WO 2020155846A1
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graphite
layer
graphite layer
holes
tape
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PCT/CN2019/123308
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English (en)
French (fr)
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钟发平
肖进春
丁胜芳
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常德力元新材料有限责任公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/314—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive layer and/or the carrier being conductive
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/10—Presence of inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide

Definitions

  • the invention belongs to the technical field of graphite materials, and specifically relates to a graphite tape and a preparation method thereof.
  • the preparation process of traditional graphite thermal tape is usually made by using back adhesive polyethylene terephthalate (PET), polyimide (PI), polyethylene (PE) and other substrates and graphite layer to compound and make .
  • the obtained graphite thermally conductive adhesive tape has the characteristics of good thermal conductivity, and is usually used for heat dissipation of electronic products such as processors and other locations such as notebook computers and mobile phones.
  • the rubber system of the graphite conductive tape will age, causing the graphite layer to fall off, affecting the life of the graphite conductive tape and causing the entire product.
  • the uneven heat dissipation affects the product experience.
  • Another patent number CN103059761B discloses a graphite heat dissipation tape with high thermal conductivity.
  • the polyamic acid polymer is directly heat-treated, carbonized, graphitized, and then coated with a synthetic graphite tape, thereby obtaining a high thermal conductivity graphite heat dissipation material with a directional orientation structure.
  • the conversion rate of polyimide polymer in the heat treatment process is less than 95%, and the polyimide polymer contained in the obtained graphite layer has a serious impact on the heat dissipation coefficient of the graphite film, and the method has high raw material cost, high energy consumption, and process It is unstable and cannot be used on a large scale.
  • the purpose of the present invention is to overcome the defects of low bonding force, high energy consumption and unstable process in the graphite tape obtained by the existing preparation method, and to provide a graphite tape and a preparation method thereof.
  • the graphite tape is single-sided or double-sided.
  • the tenon-and-tenon structure on the surface has excellent mechanical properties and peel strength.
  • the tensile strength is greater than 200Mpa, and the peel strength is 1.5-3.0kgf/cm.
  • it has excellent thermal conductivity, and the thermal conductivity is above 151w/(mk).
  • the method is convenient to process and has high production efficiency.
  • the present invention provides a graphite tape, which comprises a graphite layer, the upper surface and/or the lower surface of the graphite layer are provided with a plurality of holes, and the polyimide covering the surface of the graphite layer and penetrating into the graphite layer.
  • the graphite tape has a single-sided or double-sided tenon-and-mortise structure.
  • the hole depth of the hole is 0.5-20 ⁇ m.
  • the hole diameter is 0.01-2 mm.
  • the holes are a row of holes evenly arranged.
  • the hole spacing of the holes is 0.3-15 mm, and the horizontal spacing and the longitudinal spacing between the holes are both 0.3-15 mm.
  • both the upper surface and the lower surface of the graphite layer are provided with a plurality of holes.
  • the holes on the upper surface and the lower surface of the graphite layer are symmetrically arranged single-layer holes.
  • the present invention also provides a preparation method of graphite adhesive tape, including the following steps:
  • the thickness of the graphite layer in step 1) is 10-30 ⁇ m.
  • the method for preparing the polyamic acid liquid film in step 1) is: under an inert atmosphere, pyromellitic dianhydride and 4,4'-diaminodiphenyl ether are mixed in N-N'-dimethyl
  • the reaction temperature is -20-10°C, and the more preferred reaction temperature is -10-10°C.
  • the mass ratio of pyromellitic dianhydride and 4,4'-diaminodiphenyl ether is 0.8-1.2:1, and both pyromellitic dianhydride and 4,4'-diaminodiphenyl ether are The mass and the mass ratio of N-N'-dimethylacetamide are 1:9-10.
  • the viscosity of the polyamic acid liquid film is 300-2000 centipoise.
  • the thickness of the polyamic acid liquid film is 0.1-5 mm.
  • the temperature of the imidization heat treatment is 200-400°C.
  • the thickness of the graphite tape is 10-50 ⁇ m.
  • the holes mentioned in this application are blind holes, that is, holes that are not opened.
  • the upper surface and/or lower surface of the graphite layer described in this application are provided with a plurality of holes, which can be punched at any position on the upper surface and/or the lower surface, and the surface of the graphite layer is coated with polyamic acid after punching.
  • the liquid film is then imidized to convert polyamide into polyimide.
  • the structure of the graphite layer of the present application makes the polyimide layer not only distributed on the surface of the graphite layer but also distributed inside the graphite layer. This structure It can improve the bonding force of graphite tape.
  • the graphite tape has a single-sided or double-sided tenon-and-mortise structure, that is, the position of the hole is a recessed part, two holes The position where there is no hole in between is the protruding part.
  • This single-sided or double-sided tenon-and-mortise structure can greatly improve the bonding force of the graphite tape.
  • the upper surface or the lower surface of the graphite layer can be processed with equally spaced holes, or one of the surfaces can be processed with equally spaced holes.
  • the preparation process of the existing thermal conductive graphite tape is usually made by using back adhesive PET, PI, PE and other substrates and graphite layer through acrylic or epoxy resin glue system. It is usually used for electronic product processors and others.
  • the adhesive system of the graphite conductive tape will age, causing the graphite layer to fall off, affecting the service life of the thermal conductive graphite tape, and causing the entire product to lose heat. Uniformity affects the product experience.
  • polyamic acid is a reversible reaction, and the side reaction produces a certain amount of moisture, which seriously affects the quality of the finished polyimide.
  • conversion rate of polyimide is less than 95% during the imidization heat treatment process.
  • the aminated polyamic acid and moisture are mixed in the graphite layer, which has a serious impact on the heat dissipation of the high graphite tape, and the energy consumption is high, the process is unstable, and it cannot be used on a large scale.
  • the polyimide film is graphitized at high temperature (2800 ⁇ 3200°C)
  • a highly oriented graphite film with a structure close to single crystal graphite can be obtained, and its thermal conductivity can reach more than 500w/m ⁇ K, exceeding the traditional non- Metal materials, but they also have shortcomings.
  • the graphite film obtained by graphitization has low strength and can be easily torn. It is easy to be damaged due to the slight movement of other materials attached. It is easy to use in electronic product processors. Break down, damage electronic products, or even explode.
  • the graphite layer in this application is obtained by laminating artificial graphite powder. Instead of polyimide carbonization and graphitization to obtain the graphite layer, holes are drilled on the upper and/or lower surface of the graphite layer, and the polyamic acid liquid The film is coated on the surface of the graphite layer. Due to the presence of micropores in the graphite layer and the loose structure between graphite layers, the liquid film will penetrate into the pores and part of the graphite layer, and then undergo imidization heat treatment to obtain a single-sided or double-sided graphite layer. A new type of graphite tape with high thermal conductivity and high bonding force of the tenon-tenon structure.
  • the polyamic acid only exists on the surface of the graphite layer, in the pores and in the limited graphite layer in contact with the polyamic acid, so the thermal conductivity of the graphite layer is not If there is too much change, there will be no problem that the non-imidized polyamide is mixed in the graphite layer and affects the heat dissipation of the graphite tape.
  • the polyimide film in this application covers the surface and inside of the graphite layer, so that the bonding force between the graphite layer and the polyimide is greatly improved, and the graphite layer caused by environmental changes can be greatly reduced during use.
  • the falling-off condition of the graphite heat dissipation layer can ensure the service life of the graphite heat dissipation layer.
  • the beneficial effects of the present invention are: 1.
  • the graphite tape of the present invention has a single-sided or double-sided tenon-and-mortise structure, and has excellent mechanical properties and peeling strength;
  • the graphite layer of the present application is obtained by laminating artificial graphite powder Yes, directly punch holes on the upper surface and/or lower surface of the graphite layer.
  • the polyamic acid liquid film will penetrate into the holes and part of the graphite layer through the existence of the holes and the loose graphite interlayer structure. It has good performance and bonding force with electronic devices, the tensile strength is greater than 200Mpa, the peel strength is 1.5-3.0kgf/cm, and it has excellent thermal conductivity, and the thermal conductivity is above 151w/(mk).
  • the preparation method of this application is convenient to process and has high production efficiency.
  • Figure 1 is a schematic diagram of the structure of graphite tape
  • the planar structure of the graphite tape obtained in this application is a tenon-and-mortise structure.
  • the upper and/or lower surfaces of the graphite layer 1 are provided with a plurality of holes 3, covering the surface of the graphite layer 1 and permeating the graphite Polyimide 2 inside layer 1.
  • the graphite tape has a single-sided or double-sided tenon-and-mortise structure.
  • the depth of the hole 3 described in this application is 0.5-20 ⁇ m.
  • the hole 3 described in this application has a diameter of 0.01-0.1 mm.
  • the holes 3 described in this application are a layer of holes evenly arranged.
  • the hole spacing of the holes 3 in this application is 0.3-50 mm.
  • Both the upper surface and the lower surface of the graphite layer 1 described in this application are provided with a plurality of holes 3.
  • the holes 3 on the upper surface and the lower surface of the graphite layer 1 described in the present application are single-layer holes arranged symmetrically.
  • the graphite layer is punched with a row of equally spaced holes on the upper surface of the graphite layer using a laser micro-hole punching machine.
  • the upper surface and the side surface are not punched.
  • the hole depth is about 1 ⁇ m, the hole diameter is 0.4mm, and the hole spacing is 1mm. ;
  • a layer of polyamic acid liquid film with a viscosity of 300 centipoise is coated on the surface of the graphite layer with a thickness of 5 ⁇ m.
  • the thickness of the graphite layer coated with the polyamic acid liquid film is about 0.1mm (this thickness is the polyamic acid liquid film After infiltration, the thickness of the polyamide film that stays on the surface of the graphite layer), stand for 0.5h, the liquid film will partially penetrate into the pores and the graphite layer to obtain a semi-finished product; the semi-finished product is subjected to imidization heat treatment at 200°C for 1 h to obtain Graphite tape with a thickness of 10-50 ⁇ m.
  • the thickness of the graphite tape obtained after imidization is much smaller than the thickness of the graphite layer and the coating polyamic acid liquid The sum of the thickness of the film.
  • a laser micro-hole punching machine to drill a row of equally spaced holes on the bottom surface of the graphite layer, and drill a row of equally spaced holes on the part where the bottom surface contacts the side surface.
  • the hole depth is about 4 ⁇ m and the hole diameter is 1.0. mm, the hole spacing is 8mm; then a layer of polyamic acid liquid film with a viscosity of 2000 centipoise is coated on the surface of the graphite layer with a thickness of 10 ⁇ m.
  • the thickness of the graphite layer coated with the polyamic acid liquid film is about 2mm, and it is allowed to stand for 5h , The liquid film will partially penetrate into the pores and the graphite layer to obtain a semi-finished product; the semi-finished product is subjected to imidization heat treatment at 400° C. for 3 hours to obtain a graphite tape with a thickness of 10-50 ⁇ m.
  • a laser micro-hole punching machine to drill multiple rows of equally spaced holes on the upper and lower surfaces of the graphite layer, and punch a row of holes on the upper and lower surfaces that contact the side surfaces.
  • the hole depth is about 4 ⁇ m
  • the pore diameter is 0.6mm
  • the hole spacing is 4mm; then a polyamic acid liquid film with a viscosity of 1000 centipoise is coated on the surface of the graphite layer with a thickness of 15 ⁇ m, and the graphite layer is coated
  • the thickness of the polyamic acid liquid film is about 1mm. Let it stand for 3 hours. The liquid film will partially penetrate into the pores and the graphite layer to obtain a semi-finished product; the semi-finished product is subjected to imidization heat treatment at 300°C for 2 hours to obtain a thickness of 10-50 ⁇ m Graphite tape.
  • the thickness of the polyamic acid liquid film coated on the graphite layer is about 1mm. After standing for 3h, the liquid film will partially penetrate the graphite.
  • a semi-finished product is obtained; the semi-finished product is subjected to imidization heat treatment at 200-400° C. for 0.5-3 h to obtain a graphite tape with a thickness of 10-50 ⁇ m.
  • the graphite layer is obtained by using the raw materials and methods in the patent application number CN201210584542.9.
  • Table 1 shows the properties of the graphite tapes and graphite layers prepared in the above 3 examples and 2 comparative examples.
  • the graphite tape has better performance and higher thermal conductivity, indicating that the present application punches holes on the surface of the graphite layer in contact with the side surface to obtain a graphite tape with a tenon-and-tenon structure Compared with perforating only the non-edge part of the graphite layer surface, this structure does not perforate the part where the surface is in contact with the side surface.
  • the obtained graphite tape has better adhesion to electronic devices.
  • the polyimide layer and the graphite layer The binding force is greater, the tensile strength and peel strength are higher.
  • Example 3 of the present application has better performance and higher thermal conductivity, indicating that the hole diameter, hole depth, and hole spacing in the present application are all controlled within the most preferred range, which can ensure the hole
  • the size does not affect the thermal conductivity of the graphite layer, and can greatly improve the bonding force between the polyimide layer and the graphite layer, and the resulting graphite tape has excellent performance.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

本发明提供了一种石墨胶带，包括石墨层，所述石墨层的上表面和/或下表面设有多个孔，覆盖在石墨层表面并渗透在石墨层内部的的聚酰亚胺。石墨胶带的制备方法为：在石墨层的上表面和/或下表面打孔，然后在石墨层的表面涂覆一层聚酰胺酸液膜，静置，得到半成品；将半成品进行亚胺化热处理，得到石墨胶带。本申请的石墨胶带具有极佳的机械性能和剥离强度，抗拉强度大于200Mpa，剥离强度为1.5-3.0kgf/cm，同时具有优异的导热性能，导热系数在151w/(m.k)以上。该方法加工方便，生产效率高。

Description

一种石墨胶带及其制备方法 技术领域
本发明属于石墨材料技术领域，具体涉及一种石墨胶带及其制备方法。
背景技术
随着电子产品要求功能越来越多，厚度越来越薄，电子产品发热问题要求也越来越高，已经成为电子产品重点需要解决的一个问题，而传统的导热硅脂、导热硅胶片、铝型材散热片等因为导热率不能满足日趋发展的电子产品散热要求。
传统的石墨导热胶带的制备工艺通常是使用背胶的聚对苯二甲酸乙二酯(PET)、聚亚酰胺(PI)、聚乙烯(PE)等基材与石墨层进行复合而制成的。所得石墨导热胶带具有导热性能好的特点，通常用于电子产品如笔记本电脑、手机等处理器及其它位置的散热。但由于使用温度对所用胶系的影响和石墨本身的疏松结构，通常一段时间后，石墨导热带的胶系会发生老化，造成石墨层的脱落，影响石墨导热带的使用寿命的同时造成整个产品散热不均匀，影响产品的使用体验。
另有专利号CN103059761B公开了高导热系数的石墨散热胶带，将聚酰胺酸高分子进行直接热处理、碳化、石墨化，进而覆膜合成石墨带，从而获得具有定向取向结构的高导热石墨散热材料，但聚亚酰胺高分子在热处理过程中转化率＜95％，所得石墨层中夹杂的聚酰亚胺高分子对石墨膜的散热系数有严重影响，且该方法原材料成本高，能耗高，工艺不稳定，不能大规模使用。
发明内容
本发明的目的是克服现有制备方法得到的石墨胶带存在的结合力不高，能耗高，工艺不稳定的缺陷，提供了一种石墨胶带及其制备方法，此石墨胶带为单面或双面的榫卯结构，具有极佳的机械性能和剥离强度，抗拉强度大于200Mpa，剥离强度为1.5-3.0kgf/cm，同时具有优异的导热性能，导热系数在151w/(m.k)以上。该方法加工方便，生产效率高。
本发明提供了一种石墨胶带，包括石墨层，所述石墨层的上表面和/或下表面设有多个孔，覆盖在石墨层表面并渗透在石墨层内部的的聚酰亚胺。
优选的，所述石墨胶带为单面或双面的榫卯结构。
优选的，所述孔的孔深为0.5-20μm。
优选的，所述孔的孔径为0.01-2mm。
优选的，所述孔是均等排布的一排孔。
优选的，所述孔的孔间距为0.3-15mm，孔之间的横向间距和纵向间距均为0.3-15mm。
优选的，所述石墨层的上表面和下表面均设有多个孔。
优选的，所述石墨层的上表面和下表面的孔为对称排布的单层孔。
本发明还提供了一种石墨胶带的制备方法，包括如下步骤：
1)在石墨层的上表面和/或下表面打孔，然后在石墨层的表面涂覆一层聚酰胺酸液膜，静置，得到半成品；
2)将半成品进行亚胺化热处理，得到石墨胶带。
优选的，步骤1)所述石墨层的厚度为10-30μm。
优选的，步骤1)所述聚酰胺酸液膜的制备方法为：在惰性气氛下，将均苯四甲酸二酐、4,4’-二氨基二苯醚在N-N’-二甲基乙酰胺溶剂中反应，反应温度为-20～10℃，更优选的反应温度为-10～10℃。
优选的，所述均苯四甲酸二酐、4,4’-二氨基二苯醚质量比为0.8-1.2：1，均苯四甲酸二酐、4,4’-二氨基二苯醚两者的质量和与N-N’-二甲基乙酰胺的质量比为1:9-10。
所述聚酰胺酸液膜的粘度为300-2000厘泊。
所述聚酰胺酸液膜的厚度为0.1-5mm。
所述亚胺化热处理的温度为200-400℃。
所述石墨胶带的厚度为10-50μm。
本申请所述孔为盲孔，即不打通的孔。
本申请中所述石墨层的上表面和/或下表面设有多个孔，可以在上表面和/或下表面的任一位置打孔，打孔后在石墨层的表面涂覆聚酰胺酸液膜，然后亚胺化处理，使得聚酰胺转换成聚酰亚胺，本申请的石墨层的结构使得聚酰亚胺层不仅分布在石墨层表面上而且在石墨层内部也有分布，该种结构能提高石墨带的结合力。
本申请最优选为在上表面和/或下表面的非边沿处设有等间距分布的多排孔，并且沿上表面和/或下表面的边沿处设置等间距分布的一排孔，即在上表面和/或下表面与侧面的交界处设有等间距分布的一排孔，此时石墨胶带具有单面或双面的榫卯结构，即孔所在的位置为凹进去部分，两个孔之间未设孔的位置为突出部分。这种具有单面或双面的榫卯结构，能大大提高石墨带的结合力。
本申请中石墨层的上表面或下表面都可加工出等间距分布的孔，也可在其中的一个表面加工出等间距分布的孔。
本申请孔的深度与石墨层的厚度有关，孔深/石墨层厚度＝0.15-0.45:1，优选为0.2-0.3:1；孔的直径0.01-2mm，优选为0.4-0.8mm，孔间距为0.3-15mm，优选为2-6mm。在此优选的孔深、孔径和孔间距的条件下，既能保证孔的大小不会影响石墨层的导热性，还能大大提高聚酰亚胺层与石墨层的结合力。
现有的导热石墨胶带的制备工艺通常是使用背胶的PET、PI、PE等基材与石墨层通过丙 烯酸或环氧树脂类胶系复合而制成的，通常用于电子产品处理器及其它位置的散热，但由于使用温度对所用胶系的影响，通常一段时间后，石墨导热带的胶系会发生老化，造成石墨层的脱落，影响导热石墨胶带的使用寿命，同时造成整个产品散热不均匀，影响产品的使用体验。因此，为了避免石墨胶带在使用过程中脱落，目前有人想到不使用胶系，而直接将聚酰胺酸液进行亚胺化热处理、碳化和石墨化，如专利申请号CN201210584542.9和CN201410500032.8中，将聚酰胺酸溶液中加入乙二醇或者三乙胺，充分搅拌后涂覆于一玻璃基材层或者有机基材层上，然后在氮气保护下反应，再经过亚胺化热处理得到聚酰亚胺薄膜，在1000℃以上的高温条件下碳化，在2000℃以上的温度下石墨化得到石墨层。但是聚酰胺酸的生成为可逆反应，副反应产生一定的水分，严重影响成品聚酰亚胺的质量，且聚酰亚胺在亚胺化热处理的过程中，转化率低于95％，未亚胺化的聚酰胺酸和水分夹杂在石墨层中，对高石墨胶带的散热性有严重的影响，并且能耗高，工艺不稳定，不能大规模使用。另外虽然聚酰亚胺膜经过高温(2800～3200℃)石墨化处理后，能获得接近于单晶石墨结构的高定向石墨薄膜，其导热率可达500w/m·K以上，超过了传统非金属材料，但是其也还存在着不足之处，其石墨化得到的石墨膜强度低，可以轻易被撕裂，易因所粘附的其他材料轻微移动而产生破损，用在电子产品处理器容易发生故障，损害电子产品，甚至发生爆炸。
本申请的石墨层是采用人工石墨粉层压得到的，不采用聚酰亚胺碳化及石墨化得到石墨层，而是在石墨层的上表面和/或下表面打孔，将聚酰胺酸液膜涂覆在石墨层表面，由于石墨层中微孔的存在和石墨层间疏松结构，液膜将渗透到孔中和部分石墨层中，然后再进行亚胺化热处理，得到具有单面或双面榫卯结构的高导热性和高结合力的新型石墨胶带。本申请制备石墨胶带的过程中，由于静置时间较短，聚酰胺酸只在石墨层表面、孔内以及与聚酰胺酸所接触的有限的石墨层内存在，因而石墨层的导热性能不会出现太大变化，不会出现未亚胺化的聚酰胺夹杂在石墨层中对石墨胶带的散热性造成影响的问题。本申请中的聚酰亚胺膜覆盖在石墨层的表面和内部，使得石墨层与聚酰亚胺之间的结合力大大提高，在使用过程中能大幅度的降低由于环境变化而造成石墨层的脱落情况，从而保证石墨散热层的使用寿命。
本发明的有益效果是：1、本发明的石墨胶带具有单面或双面的榫卯结构，具有极佳的机械性能和剥离强度；2、本申请的石墨层是采用人工石墨粉层压得到的，直接在石墨层的上表面和/或下表面打孔，聚酰胺酸液膜通过孔的存在和石墨疏松层间结构，将渗透到孔中和部分石墨层中，得到的石墨胶带的导热性和与电子器件的结合力好，抗拉强度大于200Mpa，剥离强度为1.5-3.0kgf/cm,同时具有优异的导热性能，导热系数在151w/(m.k)以上。3、本申请的制备方法加工方便，生产效率高。
附图说明
图1为石墨胶带结构示意图；
其中，1石墨层，2聚酰亚胺，3孔。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白，以下结合具体实施例，对本发明进一步详细说明。
如图1所示，本申请得到的石墨胶带的平面结构为榫卯结构，所述石墨层1的上表面和/或下表面设有多个孔3，覆盖在石墨层1表面并渗透在石墨层1内部的的聚酰亚胺2，所述石墨胶带为单面或双面的榫卯结构。
本申请所述孔3的孔深为0.5-20μm。
本申请所述孔3的孔径为0.01-0.1mm。
本申请所述孔3是均等排布的一层孔。
本申请所述孔3的孔间距为0.3-50mm。
本申请所述石墨层1的上表面和下表面均设有多个孔3。
本申请所述石墨层1的上表面和下表面的孔3为对称排布的单层孔。
实施例1
将石墨层使用激光微孔打孔机在石墨层上表面打一排等距分布的孔，上表面与侧面接触的部位不打孔，孔深约为1μm，孔径为0.4mm，孔间距为1mm；然后在厚度为5μm石墨层的表面涂覆一层黏度为300厘泊的聚酰胺酸液膜，石墨层涂覆聚酰胺酸液膜的厚度约为0.1mm(此厚度是聚酰胺酸液膜渗透以后停留在石墨层表面的聚酰胺膜的厚度)，静置0.5h，液膜将部分渗透到孔中和石墨层中，得到半成品；将半成品在200℃下进行亚胺化热处理1h，得到厚度为10-50μm的石墨胶带。因为聚酰胺酸液膜中含有大量的N-N’-二甲基乙酰胺溶剂，因此其经过亚胺化处理后得到的石墨胶带的厚度远远小于石墨层的厚度和涂覆聚酰胺酸液膜的厚度之和。
实施例2
将石墨层使用激光微孔打孔机在石墨层下表面打一排等距分布的孔，并在下表面与侧面接触的部位打一排等距分布的孔，孔深约为4μm，孔径为1.0mm，孔间距为8mm；然后在厚度为10μm石墨层的表面涂覆一层黏度为2000厘泊的聚酰胺酸液膜，石墨层涂覆聚酰胺酸液膜的厚度约为2mm，静置5h，液膜将部分渗透到孔中和石墨层中，得到半成品；将半成品在400℃下进行亚胺化热处理3h，得到厚度为10-50μm的石墨胶带。
实施例3
将石墨层使用激光微孔打孔机在石墨层上表面和下表面均打多排等距分布的孔，并在上表面和下表面与侧面接触的部位均打一排孔，孔深约为4μm，孔径为0.6mm，孔间距为4mm；然后在厚度为15μm石墨层的表面涂覆一层黏度为1000厘泊的聚酰胺酸液膜，石墨层涂覆
聚酰胺酸液膜的厚度约为1mm，静置3h，液膜将部分渗透到孔中和石墨层中，得到半成品；将半成品在300℃下进行亚胺化热处理2h，得到厚度为10-50μm的石墨胶带。
对比例1
在厚度为15μm石墨层的表面涂覆一层黏度为1000厘泊的聚酰胺酸液膜，石墨层涂覆聚酰胺酸液膜的厚度约为1mm，静置3h，液膜将部分渗透到石墨层中，得到半成品；将半成品在200-400℃下进行亚胺化热处理0.5-3h，得到厚度为10-50μm的石墨胶带。
对比例2
采用专利申请号CN201210584542.9中的原料和方法得到石墨层。
上述3个实施例和2个对比例制备得到的石墨胶带和石墨层的性能见表1所示。
表1各实施例和对比例制备的石墨胶带和石墨层的性能
样品 抗拉强度(Mpa) 剥离强度(kgf/cm) 导热系数(w/(m.k))
实施例1 220 1.5 160
实施例2 285 1.7 165
实施例3 314 2.2 182
对比例1 156 1.3 160
对比例2 80 0.2 250
从表1中的数据可知，采用本申请的方法在石墨层的上表面和/或下表面设有多个孔，与对比例1相比，本发明得到的石墨胶带抗拉强度、剥离强度和导热系数都较高，说明本申请石墨胶带的结构使得其具有极佳的机械性能和剥离强度。另外本申请的实施例2和实施例1相比，石墨胶带的性能更好，导热系数更高，说明本申请在石墨层的表面与侧面接触的部位打孔，得到具有榫卯结构的石墨胶带，此结构相对于只在石墨层的表面非边沿处打孔，而不在表面与侧面接触的部位打孔，其得到的石墨胶带与电子器件的结合性较好，聚酰亚胺层与石墨层的结合力较大，抗拉强度和剥离强度更高。本申请的实施例3和实施例1和2相比，性能更好，导热系数更高，说明本申请中的孔径、孔深和孔间距都控制在最优选的范围内，其既能保证孔的大小不会影响石墨层的导热性，还能大大提高聚酰亚胺层与石墨层的结合力，最终得到的石墨胶带的性能优异。

Claims (10)

  1. 一种石墨胶带，其特征在于，包括石墨层(1)，所述石墨层(1)的上表面和/或下表面设有多个孔(3)，覆盖在石墨层(1)表面并渗透在石墨层(1)内部的的聚酰亚胺(2)。
  2. 如权利要求1或2所述石墨胶带，其特征在于，所述石墨胶带为单面或双面的榫卯结构。
  3. 如权利要求1或2所述石墨胶带，其特征在于，所述孔(3)的孔深为0.5-20μm。
  4. 如权利要求1或2所述石墨胶带，其特征在于，所述孔(3)的孔径为0.01-2mm。
  5. 如权利要求1或2所述石墨胶带，其特征在于，所述孔(3)是均等排布的一排孔。
  6. 如权利要求5所述石墨胶带，其特征在于，所述孔(3)的孔间距为0.3-15mm。
  7. 如权利要求1或2所述石墨胶带，其特征在于，所述石墨层(1)的上表面和下表面均设有多个孔(3)。
  8. 如权利要求7所述石墨胶带，其特征在于，所述石墨层(1)的上表面和下表面的孔(3)为对称排布的单层孔。
  9. 如权利要求1或2所述石墨胶带的制备方法，其特征在于，包括如下步骤：
    1)在石墨层的上表面和/或下表面打孔，然后在石墨层的表面涂覆一层聚酰胺酸液膜，静置，得到半成品；
    2)将半成品进行亚胺化热处理，得到石墨胶带。
  10. 如权利要求9所述石墨胶带的制备方法，其特征在于，步骤1)所述石墨层的厚度为5-15μm。
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