TWM441988U - Combined heat conductive copper clad laminate - Google Patents

Description

M441988 V. New description: [New technical field] This creation is about the flexible substrate on the heat dissipation products such as led, especially a composite thermal conductive copper foil substrate with high heat dissipation efficiency. [Prior Art] With the awareness of Wang Qiu's environmental protection rising, energy saving has become a trend today. The LED industry is the most watched industry in recent years...to date, LED products have the advantages of energy saving, power saving, high efficiency, fast response time, long life cycle and environmental benefits without mercury. However, usually only about 2% of the power of the high-power products can be converted into light, and the remaining 80% of the energy is converted into heat. In general, if the thermal energy generated by LED illumination cannot be remitted, the LED junction φ temperature will be too high, which will affect the product life cycle, efficiency and stability. X " Traditional heat-dissipating materials need to consider the insulation properties, the thickness of the glue used to bond the copper #羯 layer needs to be 6〇 to 12〇um to achieve the insulation. Therefore, the total thickness of the product will be reported, and the heat dissipation effect will not be ideal. If a thermoplastic polyimine (such as a heat dissipation model of τρ; 〇, which is used to reduce the thickness of the product) is used, it can meet the requirements of insulation properties, but it requires high temperature operation when processing τρι (operating temperature is greater than 35). (rc), so the cost is too high to be effectively mass-produced. Therefore, there is still a need to provide a thermally conductive copper foil substrate that can simplify processing conditions while still maintaining high heat dissipation efficiency and insulation properties. [New content] 3 M441988 To compensate for the above deficiencies, the present invention provides a composite thermally conductive copper foil substrate having a product thickness, high heat dissipation efficiency, and high breakdown voltage, etc. In order to solve the technical problems, the present invention provides a composite thermal conductive copper foil substrate. Provided is a composite thermally conductive copper foil substrate comprising a copper foil layer; an insulating polymer layer; and a thermally conductive adhesive layer, wherein the thermally conductive adhesive layer comprises a polyimide and a heat dissipating heat dispersed in the polyimide adhesive a powder, and the insulating polymer layer is fixedly sandwiched between the copper foil layer and the thermally conductive adhesive layer. As a further improvement of the present invention, The heat dissipating powder accounts for 10 to 90% of the solid content of the thermally conductive adhesive layer. In one embodiment, the heat dissipating powder of the present invention may be selected from the group consisting of niobium carbide, boron nitride, aluminum oxide, and nitriding. At least one of the groups consisting of aluminum. As a further improvement of the present invention, the heat dissipating powder has an average particle diameter of 〇丨 to 5 μm. The copper foil layer of the present invention can be used for one of electrolytic copper foil and rolled steel box. The copper beryllium layer can form a high heat dissipation circuit layer on the composite thermally conductive copper drop substrate. Generally, the thickness of the copper foil layer is 12.5 to 70 micrometers, preferably 35 micrometers. The material can be polyimine, so the composite thermal conductive copper substrate formed by using the insulating polymer layer has obvious improvement in electrical breakdown resistance and mechanical strength. As a further improvement of the present invention, the thickness of the insulating polymer layer is improved. It is 3 to 15 micrometers. As a further improvement of the present invention, the polyimine adhesive in the thermally conductive adhesive layer of the present invention may be selected from the group consisting of a polyamine imide adhesive composed of a diamine monomer and a dianhydride monomer. M441988 As a further improvement of the creation, the thickness of the thermally conductive adhesive layer is from ι to 25 μm. / The composite thermal conductivity (4) substrate can be composed of a metal layer having a thickness of 0.3 to 3 mm to make the thermal adhesive layer sandwich. The metal layer may be disposed between the insulating polymer layer and the metal layer. The metal layer may be a metal substrate such as a substrate, a copper substrate or an iron substrate. The characteristics of the heat conduction copper box substrate can be effectively applied to heat dissipation products such as LEDs, and the thickness of the heat conductive adhesive layer formed by the invention is preferably from 1 to 25 μm, and the thickness of the insulating polymer layer is preferably 3 The method for fabricating the composite thermally conductive copper foil substrate comprises the steps of: coating an insulating compound on the surface of the copper box layer, and drying the insulating polymer to form an insulating polymer layer, Obtaining a single-sided copper foil substrate; forming a thermally conductive adhesive layer on the surface of the insulating polymer layer by coating or transfer method, so that the insulating polymer layer is sandwiched between the thermally conductive adhesive layer and the copper foil layer 'And Thermally conductive adhesive layer in a semi-polymeric semi-hardened state; and curing the thermally conductive adhesive layer to form a composite thermally conductive copper foil substrate. In the method for fabricating the composite thermally conductive copper box substrate of the present invention, before curing the β-thermally conductive adhesive layer, the step of bonding the metal layer to the outer surface of the thermally conductive adhesive layer may be performed to sandwich the thermally conductive adhesive layer Between the insulating polymer layer and the metal layer. The creator of the case found that the composite thermal conductive copper foil substrate of the present invention has high heat transfer efficiency and high breakdown voltage by adjusting the thickness of the insulating polymer layer and the thickness of the 5 M441988 thermal conductive adhesive layer. [Embodiment] Fig. 1 is a view showing a first specific example of the structure of the composite thermally conductive copper foil substrate of the present invention. In this specific example, the composite thermally conductive copper foil substrate comprises: a copper foil layer 11, an insulating polymer layer 12, and a thermally conductive adhesive layer 13, wherein the thermally conductive adhesive layer comprises a polyimide adhesive and is dispersed in the polyfluorene A heat dissipating powder in the imide adhesive, the insulating polymer layer 12 is fixedly sandwiched between the copper foil layer 11 and the thermally conductive adhesive layer 13. The copper foil used in the present copper foil layer 11 may be one of an electrolytic copper foil (ED copper foil) and a rolled copper foil (RA copper foil). Generally, the copper foil layer 11 has a thickness of 12.5 to 70 micrometers. And preferably 35 microns. The insulating polymer layer 12 may be made of a polyimide, and is preferably a halogen-free thermosetting polyimide material, more preferably a self-adhesive and halogen-free thermosetting polyimide material. The heat-conductive adhesive layer 13 formed on the surface of the insulating polymer layer 12 contains a heat-dissipating powder, and the heat-dissipating powder can improve the heat-dissipating effect. Therefore, the composite heat-conductive copper foil substrate of the present invention has a good heat-dissipating effect. In general, the heat-dissipating powder used in the present invention has an average particle diameter of 0.1 to 5 μm in order to maintain good adhesion of the thermally conductive adhesive layer 13. The heat dissipating powder may be at least one selected from the group consisting of niobium carbide, boron nitride, aluminum oxide, and aluminum nitride. In the heat conductive adhesive layer 13, the heat dissipating powder accounts for 10 to 90% of the solid content of the thermally conductive adhesive layer 13. In one embodiment, the thermally conductive adhesive layer 13 has a thickness of 10 to 25 M441988 microns. Further, the thermally conductive adhesive layer 13 may further include a curing agent, a nanofiller, a dye, an additive, and the like in addition to the polyimine adhesive and the thermal powder. In the present invention, the polyimide adhesive of the thermally conductive adhesive layer has the following formula (I)

Wherein ΑΓι and AiV are independently selected from the group consisting of: ch3 〇

Ch3 cf3 __ ο CF3 —c— or Αγ2 is selected from the following groups

7 M441988

or

;as well as

In addition, X of the formula (I) is introduced into the group by a 2,6-diaminopyridine (DAP), which is a functional group containing a nitrogen heterocycle. Forming a charge-transfer complex with copper or other metals enhances the bond strength between it and copper or other metals. The molar ratio of the polyimine adhesive before polymerization to the additive DAP is between 1:0.02 and 1:0.48. Fig. 2 is a view showing a second concrete example of the structure of the composite thermally conductive copper foil substrate of the present invention. In this embodiment, the composite thermally conductive copper foil substrate comprises: a copper foil layer 21, an insulating polymer layer 22, a thermally conductive adhesive layer 23, and a metal layer 24, wherein the thermally conductive adhesive layer 23 comprises a polyimide and an adhesive. a heat dissipating powder in the polyimine adhesive, the insulating polymer layer 22 is fixedly sandwiched between the copper foil layer 21 and the thermally conductive adhesive layer 23, and the thermally conductive adhesive layer 23 is sandwiched between the insulating polymerization Between the object layer 22 and the metal layer 24. The copper foil used for the copper foil layer 21 may be an electrolytic copper foil (ED copper foil) or M441988 calendered _ (RA_). In general, the copper material 21 has a thickness of 12.5 to 70 μm, and preferably 35 μm. For a specific application, the material of the insulating polymer layer 22 is a polyimide. Further, the material f of the primary layer 22 may be a halogen-free thermosetting polyimine material or a self-purifying and self-containing thermosetting material. Since the lead-in layer 23 contains a heat-dissipating powder which can enhance the heat-dissipating effect, the composite heat-conductive copper box substrate of the present invention has a good effect. In general, the heat dissipating powder has an average particle diameter of 〇1 to 5 μm and the heat conductive adhesive layer 23 has a thickness of 1 〇 to 25 μm. The heat dissipating powder may be selected from at least one of the group consisting of carbon carbide, nitriding, oxidizing, and nitriding. The heat dissipating powder accounts for 1 to 9% of the solid content of the thermally conductive adhesive layer 23 in the heat conductive adhesive layer. The thermally conductive adhesive layer 23 can be applied to various metals or other substrates. In this embodiment, the metal layer 24 may be bonded to the outer surface of the thermally conductive adhesive layer 23 for thermal curing. The metal layer may be a metal substrate such as a chain substrate, a copper substrate or an iron substrate. In order to maintain the characteristics of the composite thermally conductive copper foil substrate of the present application, application = LED electrical purity, and to effectively control the cost, the thickness of the conductive adhesive layer and the insulating polymer layer can be adjusted as needed. Preferably, the thermally conductive adhesive layer has a thickness of 10 to 25 microns and the insulating polymer layer has a thickness of 3 microns. > The method for fabricating the composite thermal conductive copper foil substrate comprises the following steps: 9 M441988 coating an insulating polymer on the surface of the copper beryllium layer and drying it to form an insulating polymer layer to obtain a single-sided copper foil substrate; Forming a thermally conductive adhesive layer on the surface of the insulating polymer layer using a coating or transfer method such that the insulating polymer layer is sandwiched between the thermally conductive adhesive layer and the copper foil layer 'and the thermally conductive adhesive layer In a semi-polymeric semi-hardened state; and curing the thermally conductive adhesive layer' to form a composite thermally conductive copper foil substrate. In another embodiment, the method for fabricating the composite thermally conductive copper foil substrate of the present invention includes laminating a metal layer to the outer surface of the thermally conductive adhesive layer to completely heat the thermally conductive adhesive layer. An adhesive layer is interposed between the insulating polymer layer and the metal layer to form a composite thermally conductive copper foil substrate. The polyimine adhesive of the thermal conductive adhesive layer in the present invention is mainly composed of diamine monomer 1,3-bis(3-aminophenoxy)benzene (i,3-Bis(3-aminophenoxy)benzene, 0.2kmol of APB-133) was dissolved in dimercaptoacetamide (DMAc) and stirred for half an hour; then added to a solution of 0.035 mol of 2,6-diaminopyridinium (DAP) dissolved in DMAc to continue stirring. After one hour of reaction, the O.lkmol and 4,4丨-diphenyl ether dianhydride of the dianhydride monomer 3,3',4,4'-dibenzophenone tetraphthalic acid dianhydride (BTDA) were continuously added. DPA) O.lkmol stirred reaction for eight hours to 'copolymerize polyimine adhesive; then add heat-dissipating powder aluminum nitride A1N (5%) and boron nitride BN (5%) and continue to stir for two hours, and A thermally conductive adhesive layer was obtained in the same manner as described above. M441988 Examples 2 to 7 Polyimine adhesives were prepared in the same manner as in Example 1 except that the proportion of the heat-dissipating powder added was adjusted as shown in Table 1. Test Example Thermal Conduction Analysis Test The heat conduction analysis test of the composite thermally conductive copper foil substrate: thermal conduction analysis test using a hot disk instrument (Hot Disk), covering the upper and lower sides of the sensor # two fully cured copper foil layer composite thermal copper A sample of the foil substrate was placed on the outer side of the two composite thermally conductive copper foil substrates with the two steel plates sandwiching the sample and the sensor, and the thermal conductivity of the sample was measured by the sensor. The test of the sample of the creation was taken as an experimental group. The thermal conductivity of the adhesive layer of a general heat-conductive substrate was tested in the same manner as a comparative example, and the measured results of the heat transfer coefficient were recorded in Table 1. Use a pressure analyzer (Model: 19057-20); remove the copper foil from the composite thermal conductive copper foil • substrate; then cut into a size of 3cm×3cm; then measure the film thickness; then rinse with pure water for 10 minutes; The sheet was allowed to dry for half an hour in an oven U 〇 ° C; finally, the test piece was placed in a financial analyzer to test the breakdown voltage of the test piece. The combustion test equipment (model: UL-94X) was used; the composite thermal conductive copper foil substrate was etched to remove the copper foil, and then the test piece was cut. According to the 94-UL test method, the number of combustion seconds was determined to be V-0. 11 M441988 Table 1 Insulation polymer layer thickness (um) Thermal adhesive layer thickness (um) Thermal powder content (%) Thermal conductivity coefficient of insulation (W/mk) Breakdown voltage (KV) UL 94 Combustion performance test example 1 3 22 A1N (5%) / BN (5%) 0.58 4.6 V-0 Example 2 5 20 A1N (4%) / BN (8%) 0.7 4.4 • V-0 Example 3 8 17 A1N (10%) / BN (10%) 0.85 4.3 V-0 Example 4 15 10 A1N (5%) / BN (5%) 0.4 6.5 V-0 Example 5 3 22 Al2O3 (60%) 0.75 2 V-0 Example 6 5 20 Al2〇3 (70%) 1.06 4.3 ν_ο· Example 7 8 17 Al2〇3 (75%) 1.3 4.2 V-0 Comparative Example 1 LX07022016RA —— 22 —— 0.8 4 V-0 Comparative Example 2 LX03517016RA —— 17 —— 0.8 2.5 V-0 12 M441988 t As can be seen from Table 1, the composite thermally conductive copper foil substrate of the present invention is designed to have a thickness of 1 〇 to 25 μm by thermal conductive adhesive layer; The insulating polymer layer has a thickness of 3 to 15 microns and has a high heat transfer coefficient or breakdown voltage. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing the structure of a composite thermally conductive copper foil substrate according to a first specific example of the present invention; and Fig. 2 is a cross-sectional view showing the structure of a composite thermally conductive copper foil substrate according to a second specific example of the present invention. [Main component symbol description] 11, 21 copper foil layer 12, 22 insulating polymer layer 13, 23 thermal conductive adhesive layer 24 metal layer 13

Claims (1)

M441988 VI. Patent Application Range: 1. A composite thermally conductive copper foil substrate comprising: a copper fl layer; an insulating polymer layer; and a thermally conductive adhesive layer comprising a polyimide adhesive and dispersed in the polyimide. a heat dissipating powder in the agent, and the insulating polymer layer is fixedly sandwiched between the copper foil layer and the heat conductive adhesive layer, wherein the polyimine adhesive has the following formula (I) Ar2 is selected from the following groups or M441988 2. The composite thermally conductive copper foil substrate according to claim 1, wherein the heat dissipating powder in the thermally conductive adhesive layer accounts for 10 to 90% of the solid content of the thermally conductive adhesive layer. 3. The composite thermally conductive copper foil substrate according to claim 1 or 2, wherein the heat dissipating powder has an average particle diameter of 0.1 to 5 μm, and the heat dissipating powder is selected from the group consisting of niobium carbide and nitriding. At least one of the group consisting of boron, aluminum oxide, and aluminum nitride. 4. The composite thermally conductive copper foil substrate according to claim 1, wherein the copper foil layer is an electrolytic copper foil or a rolled copper foil. 5. The composite thermally conductive copper foil substrate according to claim 1, wherein the copper foil layer has a thickness of 12.5 to 70 micrometers, the insulating polymer layer has a thickness of 3 to 15 micrometers, and the heat conductive adhesive layer The thickness of the layer is 15 M441988 10 to 25 microns. 6. The composite thermally conductive copper foil substrate according to claim 1, wherein the insulating polymer layer is made of polyimide. 7. The composite thermally conductive copper foil substrate of claim 1, further comprising a metal layer of 0.3 to 3 mm thick to sandwich the thermally conductive adhesive layer between the insulating polymer layer and the metal layer .