TW201125901A - Thermosetting heat conductive material and preparation method thereof - Google Patents

Abstract

This invention provides a preparation method for a thermosetting heat conductive material. This preparation method includes steps of reacting the hydroxyl group (-OH) of an epoxy resin with a silane coupling agent having an isocyanto group (-NCO) to obtain a modified epoxy resin. By physically adsorbing or chemically bonding a titanium based coupling agent or a germanium based coupling agent to a ceramic powder, a modified ceramic powder is obtained. Under the condition of taking trifluoroboronethylamine as a catalyst, an anhydrous sol-gel reaction is performed for the modified epoxy resin and the modified ceramic powder to prepare the thermosetting heat conductive material of this invention. In the prepared thermosetting heat conductive material according to this invention, the ceramic powder and epoxy resin therein have very good compatibility so as to have better thermal conductivity and electric insulation.

Description

201125901 • Sixth, the invention description: 'The technical field of the invention belongs to the present invention relates to a thermal conductive material and a preparation method thereof, in particular to a thermosetting thermal conductive material prepared by an anhydrous sol-gel method and a preparation method thereof . [Prior Art] Engineers have long hoped to find new materials that can effectively derivate the heat generated by electron transport because the heat generated when the components operate can exceed the temperature that can withstand the damage, especially in the light. The effect of temperature on the light-emitting diode (LED) is more obvious. When the temperature is increased, the life of the LED is also significantly reduced. Therefore, it is very important to effectively transfer the generated heat energy away from the component so that the component can be operated at room temperature. For example, a heat sink or a fan may be added to the CPU of the computer, or some heat conductive material may be filled between the CPU and the heat sink, and the purpose is to improve the heat dissipation efficiency and increase the heat conduction area of the component. Therefore, in recent years, in the literature of thermal conductive composite materials, materials are generally developed in the direction of high thermal conductivity, low dielectric constant, and low expansion coefficient, and how to effectively disperse the thermally conductive filler between the polymers. It can be applied to substrate bonding, semiconductor wafer bonding, heat-dissipating adhesives, wafer encapsulant, surface mount technology or electronic packaging. The thermal conductive filler is generally suitable for thermal conductivity of various resins and rubbers. It has chemical stability, high fluidity, thermal conductivity, high lubricity, electrical insulation, and low mold wear. And easy to disperse and mix. It can be used for heat sink gaskets, thermal grease (glue), heat transfer film and thermal tape, etc., and can finally meet the application needs of markets such as automotive electronics, display devices, radiators, power supplies, electric motors and military supplies. . Generally speaking, the polymer itself is a thermal insulator. Its thermal conductivity (TC) is usually between 0.14 and 0.6 W/mK, and the thermal conductive filler is often several times or even hundreds of times higher than the polymer. Inorganic materials such as metal powder, glass powder, carbon black, graphite, calcium, copper, aluminum, and magnesium oxides are selected, and suitable filling is selected according to the application range. For example, in an electronic package, it is necessary to select a filler having a high thermal conductivity, a low dielectric constant, and a high volume resistance, such as boron nitride (BN), aluminum nitride (A1N), or sputum (8 丨〇). The dispersion of the thermally conductive filler material is good or not, which deeply affects various properties of the polymer material after blending. Among the backing materials, epoxy resin is currently the most widely used thermosetting resin in the industry. Epoxy resin has many characteristics superior to other thermosetting resins', such as: high bonding strength, high mechanical properties, low shrinkage, strong hydrolysis resistance and crack resistance, easy to add I, etc. It is very extensive, and the industries such as adhesives, earth building materials, etc. are all in their materials. More because of epoxy resin, composite materials industry, two = various electronic information products and the rapid development of optoelectronic components, epoxy ί = 201125901 battle 'especially in the light, high hardness, high resistance characteristics of the function == change: The addition of epoxy resin to improve epoxy resin has become a very important issue in this industry. The m-two gel process synthesizes a nano-sized y, yt or polyoxyalkylene inorganic material with a nano-sized structure, which is then introduced and disturbed by the seven-mesh", epoxy: grease or hard: two composite materials. Party: Mesh::Open:::=: Machine mixed into nanometer r using aqueous phase sol-gel method in the ring rice, into the structure, the resulting mixed hardened material with the cerium oxide =: the rigidity in the south temperature is improved, In the high temperature mechanical properties are also obtained. The second body of the carcass-inorganic polymer mixture = selection, dissolution _, the change of the cause is quite a lot, the second = difficult to reverse the second degree:, affecting the 'making method of organic sinless silk _ From the eye-to-gel-hydrolysis condensation, the _solvent, the organism containing water in the system (for example, the epoxy resin and the alcohol are incompatible with each other. At the same time, because of the use of inorganic acid or no: :: Machine inorganic miscible acid or inorganic base residue often affects the final ring: Second, the electrical properties and reliability of the inorganic structure. '丨知夕氧烧混成[Inventive content] 201125901 Thermal materials and their preparation ί: Ming: Solution η::------------------------------------------------------------------------------------------------------------------------------------------------------------------ According to the purpose of the present invention, it is proposed that the thermosetting conductive material is made of a mixture of an epoxy resin and an isocyanate group, which is an isocyanate group and a ring. Oxygenated titanium oxide car l:: should be 'to obtain a modified epoxy resin. The ceramic powder anthraquinone coupling agent or wrong coupling agent mixed reaction, so that titanium = ^ coupling agent physical adsorption or The chemical bond is on the ceramic powder: the second modification is obtained: the body is used. In the case of boron trifluoride ethylamine as a catalyst, the prepared modified epoxy resin is modified into a sol-gel. In response to the object of the present invention, "a thermosetting heat-conducting material is proposed", which is prepared by the above-mentioned preparation method, and includes a modified epoxy tree raft for the purpose of having a uniform Disperse "Chinese method, =::= thermal conductive material and its preparation phase is not possible? Square = material ' is a non-aqueous amine catalyst he μ 〇 type, in the trifluoride butyl structure, the epoxy resin ^ Oxygen-fired organic-inorganic hybrid junction insulation, can be applied to light-emitting diodes to improve the light-emitting diode: 201125901 . (2) The thermosetting heat conductive material of the present invention is prepared by using a thermally conductive powder surface modification technique and a novel modified resin, and is bonded by an anhydrous sol-gel method, and can be applied as a new type of LED for development. The ultra-thin, high thermal conductivity dielectric material of the metal core substrate can be combined with the dispersion and coating technology to complete the formulation of the material formulation and processing process to benefit the future heat dissipation design of high-power and high-brightness LEDs. The invention focuses on the establishment of a thermal interface between the thermal conductive powder and the resin, and the resin and the thermal conductive powder are modified, and the technology is independent, which is advantageous for cost control. [Embodiment] The following description will be made with reference to the related drawings. A thermosetting heat conductive material of a preferred embodiment and a method of preparing the same. Please refer to Fig. 1, which is a flow chart of the steps of the method for preparing the thermosetting heat conductive material of the present invention. The step may include: in step S11, mixing an epoxy resin with a decane coupling agent having an isocyanato group (-NCO) to react an isocyanate group with a hydroxyl group (-OH) of the epoxy resin. To obtain a modified epoxy resin. Step S12, mixing the ceramic powder with the titanium coupling agent or the lanthanide coupling agent, and physically or chemically bonding the titanium coupling agent or the lanthanum coupling agent to the ceramic powder to obtain a modified ceramic powder, and the steps S13, in the case of 201125901 gel with boron trifluoride monoethylamine (BF3.MEA, BF3.C2H5NH2) as a catalyst, 'I-gel reaction of modified epoxy resin with modified ceramic powder, In order to prepare the thermosetting heat conductive material of the present invention, the ceramic powder has a weight of 1 to 70 wt% relative to the thermosetting heat conductive material. Ceramic powders include alumina (Al2〇I is preferred)

Wt°/〇 Better (A1N), aluminum powder (A1), zinc oxide (Zn0) powder. The weight of the titanium-based three-coupled aluminum nitride-based coupling agent relative to the ceramic powder is preferably 0.05-0.2 wt% of the 〇 〇 Ui mixture or 锗 系. The titanium coupling agent or the lanthanide couple Wt%, the powder mixture is diluted with an organic solvent, and the titanium coupling couple = the ratio of the ceramic mixture to the organic solvent is 1: 5 to 1: 20. The weight of the tri tomy or the dynamylamine relative to the modified epoxy resin is preferably 1-2% by weight of the oxime ethyl group. Further, the above anhydrous sol-gel reaction well further comprises a hardener for adding an epoxy resin, and the curing agent is subjected to a hardening reaction to form a three-dimensional crosslinked network structure. The following description is a preferred embodiment of the invention, but is not limited thereto. In this embodiment, the epoxy resin is diglycidyl ether of bisphenol A (DGEBA type), such as the trade name NPEL-128E (Taiwan South Asia Company), and has isocyanic acid. The decane coupling agent of the group (-NC0) was carried out as 3-isocyanatopropyltriethoxysilane (iptS). The selected ceramic powder is an alumina powder having a particle diameter of about 2 μm, and a titanium coupling agent such as trade name CA-108 (Taiwan Zengge) or a lanthanide coupling agent such as the trade name CA-288 is used. As a modifier for this powder. Please refer to Fig. 2, which is a schematic diagram of the chemical reaction of the modified epoxy resin of the present invention. In order to improve the compatibility between the epoxy resin and the inorganic phase, it is necessary to modify the epoxy resin. Therefore, in the present invention, the isocyanate group (-NCO) which is contained in the Shixia Hyun coupling agent is selected. Reacts with the oxygen functional group (-OH) of DGEBA type epoxy resin to produce urethane bond, so that the DGEBA type epoxy resin has appropriate functional groups on the main chain for anhydrous sol-gel reaction. In order to establish a bond of a covalent bond between the organic phase and the inorganic phase. In the figure, the preparation process of the modified epoxy resin is as follows. In the l〇g DGEBA type epoxy resin solution, an IPTS (which has an NCO equivalent of 247 g) of 5-15 wt% 'preferably about 1 〇wt0/〇 (ie, lg) Φ is slowly added. The -NCO functional group on IPTS is reacted with the hydroxyl group (-OH) on the epoxy resin, and dibutyltin dilaurate (DBTDL) is added as a catalyst to assist the reaction. The magnet was stirred at 60 ° C, uniformly mixed and refluxed, and the concentration was kept constant, and the reaction of the functional group was monitored by Fourier transform infrared spectroscopy (FTIR), and the reaction was completed in about 20 to 24 hours to form IPTS-Epoxy. Solution. Wherein the 3-isocyanopropyltriethoxydecane is from 5 to 15% by weight based on the weight of the epoxy resin. • Refer to Figure 3 for the FTIR spectrum of the epoxy resin and coupling agent IPTS reaction of the present invention. In order to understand the reaction between the epoxy resin and the decane coupling agent IPTS, the change of the -NCO functional group was monitored by FTIR. Among them, the infrared line used in the FT1R analysis was a solution casting using a solution casting method. The epoxy resin and the coupling agent IPTS are uniformly mixed in a tetrahydrofuran (THF) solvent, and the sample is coated with potassium bromide (KBr) salt at each fixed time under the action of a promoter. On-chip, FTIR was used for measurement to observe changes in the functional groups. It can be seen from the figure that the -NCO functional group 201125901 2270 cm_1 changes with time, and the NCO functional group 2270 cm-1 completely disappears from the start of the reaction to the reaction time of 4 hours. This phenomenon indicates that the epoxy resin has been reacted with the decane coupling agent IPTS. reaction. Preparation of modified ceramic powder: 500g of alumina powder is added to the powder high-speed mixer, and 0.5g of titanium coupling agent solution is prepared, which is obtained by diluting titanium coupling agent with 5g acetone (1:10 ratio dilution coupling agent) When the alumina powder is agitated in a high-speed mixer, the diluted coupling agent is slowly added to the powder by a sprayer, and the coupling agent is adhered to the powder, and then dried to be used. Figure 5 is a FTIR spectrum of the alumina powder of the present invention reacted with the titanium coupling agent CA-108 and the lanthanide coupling agent CA-228, respectively. The OH group and the coupling agent on the surface of the oxidized surface have physical adsorption. Or the ability of chemical bonding, so after the spray modification and drying treatment, the characteristic functional groups of the coupling agent can be found on the modified powder. As shown in Fig. 4, after the modification by the titanium coupling agent CA108, oxidation is performed. In addition to its own functional groups, aluminum also has isopropyl octyl butylpyrophosphatotitante-related functional functional groups, which represent modified functional groups and alumina powders. Bonding The same phenomenon is also observed, as shown in Fig. 5. Preparation of thermosetting heat conductive material: the modified epoxy nucleate and the modified ceramic powder obtained above are added to 1 wt% (relative to the total weight of the epoxy resin) Boron fluoride ethylamine is subjected to anhydrous sol-gel reaction, and a hardener is added, and after stirring to form a uniform transparent liquid, the following thermal hardening behavior is discussed. 201125901 - Please refer to Fig. 6, which is a difference of the present invention. The DSC exotherm of the thermosetting thermal conductive material prepared by the alumina powder is used to investigate the effect of the amount of alumina added on the maximum exothermic temperature. The measurement method is to place the sample in a daily weighing of about 4 mg in aluminum. In the sample tray (A1 Sample Pan), the heat release rate was observed at a heating rate of 1 〇 min / min in a nitrogen-passing environment. As can be seen from the data in the figure, the increase in the amount of alumina added would raise the epoxy resin. The maximum exothermic temperature of the heat hardening. When the content of the modified powder is increased from 〇wt% to 6〇~〇/0, the maximum heat hardening temperature

• The degree is increased from 167 ° C to 173 ° C, which may be related to the chemical reaction of the surface of the alumina surface. A. See Fig. 7, which is a comparison chart of the exothermic curves of the heat-hardening of the modified epoxy resin of the present invention and the unmodified epoxy resin. As shown in the figure, using the epoxy resin NPEL-128E plus hardener to compare the exothermic curve of the modified and unmodified epoxy resin, it can be found that the modified % oxygen resin has a higher maximum exothermic temperature. The pendant grafted functional groups will affect the hardening reaction itself; #167°C is raised to 169. Hey. .凊 Refer to Section 8 ’, which is the exothermic curve of the epoxy resin at the 17 〇 C temperature. In the figure, it can be found that at this temperature, the thermal hardening reaction of the epoxy resin is completed within 10 minutes, and it is possible to: find the optimum processing conditions. = 参(四)9图' is an exothermic graph of 30 wt% and 50 wt% of the modified epoxy resin after modification of the present invention. As shown in the figure, after the modified epoxy resin is added, the oxidation peak is 1203) 3G wt% and 5〇201125901. The graph can be found along with the modified thermal conductive ceramic powder. σ: The maximum exothermic temperature of the modified & epoxy resin is determined by Η. . . Raised to 175C, the functional group and powder-modified functional groups on the side of the modified epoxy resin have been shown to affect their own hardening reaction. - month refers to Fig. 10, which is a dynamic viscosity change diagram of the thermosetting thermal conductive material containing different oxidation contents at different temperatures. This drawing is to investigate the effect of coating on a substrate of a thermosetting heat-conductive material prepared by the present invention. The coating process is as follows: using a screen printing platform, the mesh number is 150 mesh, 70 degree hardness of the offset printing, # will be configured to brush! On the s substrate, the printed _ sheet and the slab are pre-baked in an oven at 120 ° C for 30 minutes, and the copper foil is placed on top for hot pressing. When 30, 50, and 60 wt% of alumina powder was added, it was found that the viscosity increased as the amount of addition increased, and the same phenomenon was observed regardless of the treatment. When the powder was added to 70 wt%, the printing could not be performed. The film thickness is controlled at 70~90μπι, about 3.5mil' is thinner than the film which is generally available in the market, and the tolerance is 2 (^m or less). The substrate can be printed by the screen printing method. The epoxy resin is used for simulating the aluminum substrate and the copper foil. Thermal paste (i e. even if the paste made of the thermosetting heat conductive material of the present invention) is adhesively bonded at different temperatures. The present invention uses a late_and_piate dynamic viscosity meter (Model: MC-100) to measure thermal conductivity. The dynamic viscosity of the epoxy resin paste of the powder is measured under the condition that the shear rate is 〇.5 Ι/s, and the thermal conductivity paste containing less than 60 wt% is measured, and the viscosity change is as shown in the first As shown in the figure, it can be found that the viscosity of the epoxy resin paste begins to change drastically after the temperature exceeds 18 ,, which represents the generation of the resin hardening reaction, and the viscosity of the thermal paste before the temperature reaches 180 degrees. All are in 12 201125901 . 6000 Pa · s beat changes, even before the supplier recommends 150 ° C baking, baking temperature, the viscosity of the thermal paste is below 2000 Pa. s, the instrument is not easy to accurately measure, can be judged in general processing process In the case of heat treatment of at least 150 ° C, the material has a basic supporting viscosity for lamination processing. Thermal conductivity test: measured by thermal measurement (model: Longwin, LW-9091IR) The thermal resistance and thermal conductivity of the thermosetting thermal conductive material prepared by the present invention, and the results thereof are shown in Table 1. As shown in Table 1, it was found that the epoxy resin modified by the decane coupling agent IPIS, plus the surface of the titanium ruthenium The coupling agent CA-108 modified alumina powder has a lower thermal resistance value at different powder ratios than the resin without IPIS modification and the powder modified without CA-108. The resin can lower the resistance, but it will not continue to decrease as the amount of powder added increases. The resin that has not been modified will increase the thermal resistance value with the addition of powder, but the addition amount will increase the viscosity is too high. Coating. Convert the thermal resistance value into thermal conductivity for comparison. As shown in Table 1, the modified resin and powder can increase the thermal conductivity by 2 to 3 times as long as 30 wt% is loaded. Powder cost The cost of the resin is much higher, and the resin is obviously economical after being treated. Table 1 Comparison of the thermal resistance values of the modified epoxy resin and powder with the unmodified epoxy resin and powder and the thermal conductivity comparison epoxy Resin loaded with IPIS modified ceramic powder (wt%) Modified by CA-108 Thermal resistance value R (C/W) Thermal conductivity k (W/mK) NPEL-128E is X 0 0.320 1.191 NPEL-128E is A1203 30 Is 0.096 1.410 13 201125901 NPEL-128E Al2〇3 50 is 0.081 1.150 NPEL-128E is A]2〇3 60 is 0.119 1.915 NPEL-128E No X 0 0.438 0.382 NPEL-128E No AI2O3 30 No 0.472 0.197 NPEL-128E No AI2O3 50 No 0.214 0.043 The following Table 2 shows that the epoxy resin or powder is modified by a coupling agent, and the powder modified by the coupling agent and the powder modified without the coupling agent are compared under the solid content ratio of different powders. The change in thermal resistance value can also be found that the addition of 30 wt% alumina powder can significantly reduce the thermal resistance value, but as the addition amount of the powder increases, the thermal resistance value decreases. By comparing the thermal resistance value to the thermal conductivity coefficient, when the powder is loaded at 30 wt%, the modified powder has a heat transfer value that is 3 times higher than that of the powder without the modified powder. Table 2 Comparison of Thermal Resistance of Epoxy Resin or Powder Modified by Coupling Agent and Comparison of Thermal Conductivity Comparison of Epoxy Resin Loaded by IPIS Modified Ceramic Powder (wt%) Modified by CA-108 Thermal Resistance R (C/ W) Thermal conductivity k (W/mK) NPEL-128E is X 0 0.320 1.191 NPEL-128E is AI2O3 30 No 0.096 1.410 NPEL-128E is AI2O3 50 No 0.081 1.150 NPEL-128E is AI2O3 60 No 0.119 1.915 NPEL-128E No X 0 0.438 0.382 NPEL-128E No ai2o3 30 Yes 0.472 0.197 NPEL-128E No AI2O3 50 is 0.214 0.043

The epoxy resin is modified by a coupling agent and the epoxy resin is not modified, and the powder modified by the coupling agent is added, and the difference in the thermal resistance value is exhibited. 14 201125901 • The resin has no surface treatment of the coupling agent. If the proportion of the powder to be added is above 50 wt%, the thermal resistance value will be significantly reduced. Comparing the thermal resistance values into the thermal conductivity coefficients, when the powder is loaded at 30% by weight, the heat-reducing value of the resin which has not been subjected to the coupling agent treatment is significantly lower than that of the resin which has been treated with the coupling agent. It is observed from the results that the optimum formulation is that the resin and the powder are treated by the coupling agent, which can significantly increase the heat conduction effect. Table 3 below shows the comparison of the thermal resistance values of the resins using E-2200L single-liquid resin (Yunde) and epoxy resin NPEL-128E (South Asia). The single-liquid type resin is added with 60 wt% of the alumina modified by the coupling agent, such as alumina, nitrogen oxide, aluminum powder and zinc oxide. The experimental results show that the effect of alumina on the thermal conductivity is most obvious, which is significantly different from the thermal conductivity of the raw material. It can be seen that the surface treatment has obviously changed the physical properties of the raw materials. It is speculated that the reason may be that the coupling agent selected in this experiment has a significant improvement on the surface bonding of alumina. Other powders may not be able to appear due to their different surface characteristics. More advantageous features. Table 3 Comparison of thermal resistance values of E-2200L single-liquid resin and different powders modified by coupling agent and thermal conductivity comparison Epoxy resin loaded with IP IS modified ceramic powder (wt%) modified by CA-108 Thermal resistance value R (C/W) Thermal conductivity k (W/mK) E-2200L No X 0.326 0.547 E-2200L No Al2〇3 60 Yes 0.035 1.188 E-2200L No A1N 60 Yes 0.175 1.702 E-2200L No A1 60 Is 0.074 1.426 E-2200L No ZnO 60 is 0.103 1.410 NPEL-128E is Al2〇3 60 is 0.043 6.118 15 201125901 Table 4 below shows epoxy resin NPEL-128E (South Asia Company) and alumina powder modified by coupling agent and Compared with Bergquist TCP-1000, it was found that the thermal resistance of NPEL-128E and alumina powder modified by the coupling agent of the present invention is significantly better than other, and the thermal conductivity is significantly higher than that of Bergquist TCP-1000. coefficient. Table 4 Thermosetting thermal conductive material of the present invention and thermal insulation material of the industry ¥ 1 · Thermal resistance ratio 4 Biting and thermal conductivity comparison Epoxy resin loaded by IPIS modified ceramic powder (wt%) Modified by CA-108 Resistance R (C/W) Thermal Conductivity k (W/mK) NPEL-128E is Al2〇3 60 is 0.043 6.118 E-2200L No A1203 60 is 0.035 1.188 Bergquist 0.111 2.081 Power Test: Use a voltage tester ( Withstanding voltage tester, model: Chen Hwa, CWV-902) measuring the thermal resistance value and thermal conductivity of the thermosetting thermal conductive material prepared by the present invention, the result of which is shown in Fig. 11, which is the thermosetting thermal conductive material of the present invention. The resistance to voltage changes. In the figure, it can be found that the thermosetting heat conductive material of the present invention (indicated by "modified Epoxy/modified powder" in the figure) is treated with a coupling agent, and the withstand voltage is at a different powder ratio. Wt% tensile test: using a ring-shaped tree t modified with a decane coupling agent and a surface-modified alumina with a coupling agent added at 30 wt%, 5 () 9 60 wt%, and a different ratio of the plate. Cut the wide handle of the inch, about 10 cm long, and use a force gauge to fix the board and the copper cymbal to show the force needed to tear off the surface copper foil. As shown in Figure 12, the change in the tensile strength of this &% 'modified epoxy resin (NPEL-128E) and alumina powder is 4,225,901. The data shows that the single modified resin or powder When the peel strength decreases with the addition of the powder, and the modified resin and the powder are not treated at the same time, the peel strength increases as the added powder pulls, but the tensile strength increases to 60 wt%. The intensity drops rapidly. Temperature resistance test: using an epoxy resin modified with a decane coupling agent, and the surface modification of the coupling agent with addition of a coupling agent is stirred at a ratio of 30 wt%, 50 wt%, 60 wt%, and then passed through a triaxial roller. Coated on aluminum plate • Hot pressed. Press the plate, cut a 1 inch wide board, about 10 cm long, set it to 280 °C using a high temperature tin furnace, place the board in tin liquid, remove it after 10 seconds, cool it, and then peel the surface copper. The foil confirms whether it can be torn. As can be seen from the data in Tables 5 and 6 below, when the resin or powder is treated alone, the high temperature resistance of the substrate is not good, and if the resin or powder is simultaneously coupled, the temperature resistance effect is significantly improved. In the data, it is obvious that the addition of alumina powder to the resin can significantly improve the financial effect of the rubber.

Table 5 NPEL-128E resin modification and Al2〇3 powder modification 280 °C / l〇s and substrate bonding

Epoxy resin loaded by IPIS modified ceramic powder (wt%) Modified by CA-108 280〇C /10s NPEL-128E is XX NG NPEL-128E is A1203 30 is OK NPEL-128E is Al2〇3 50 is OK NPEL-128E is A1203 60 is OK NPEL-128E no X NG 17 201125901

NPEL-128E No Al2〇3 30 No OK NPEL-128E No Al2〇3 50 No OK Table 6 Single NPEL-128E resin modification or Al2〇3 powder modification 280°C /10 s and substrate bonding

Epoxy resin loaded by IPIS modified ceramic powder (wt%) Modified by CA-108 280〇C /10s NPEL-128E is Abo 30 No NG NPEL-128E is A1203 50 No NG NPEL-128E is A1203 60 No NG NPEL-128E No A1203 30 Yes NG NPEL-128E No A1203 50 is NG coated surface microscopic observation: Please refer to Figure 13 for NPEL-128E epoxy resin via coupling agent (a) modification and (b) Without modification, a comparison chart of surface conditions was observed under an optical microscope, and it was found that the surface which was not modified by the coupling agent was not smooth and flat, and the modified surface was flat. Please refer to Figure 14 for a comparison of the surface condition of the NPEL-128E epoxy resin via the coupling agent (a) and (b) without modification, under the electron microscope, and found that it has not been modified by the coupling agent. The surface has a lot of fine pores, and the display of the modifier modification is like a dendritic interlacing, indicating that the modified bonding method has been significantly changed. Please refer to Figure 15 for (a) NPEL-128E epoxy resin and 30 wt% of alumina powder modified with a coupling agent on the surface, and (b) conditions in which both the resin and the powder are not modified. Observed under the optical microscope 201125901 Please refer to the figure l6, which is (4) npel_12se and the surface of the alumina powder modified by the coupling agent 30 wt% ^ 曰 resin and powder are not modified conditions 'in the electron microscope A comparison of the conditions of the bottom surface. In the figure, the coupler can be found

There are many pores on the surface, such as the branches (four) are interlaced, and there is no (four) modification. The situation obviously has many fracture points. It is speculated that although the local area is combined with the complete 'but the range of the pores is larger to block the heat transfer path, because the second Previous thermal test values were significantly lower than half of the modified ones. According to the above analysis results, it is known that the thermosetting heat conductive material prepared by the present invention has excellent thermal conductivity, withstand voltage, high temperature resistance and electrical insulation. In addition, the thermosetting heat conductive material of the present invention can effectively improve the thermal conductivity by only carrying 50 wt% of the alumina powder. Compared with the heat transfer powder which needs to be added in the general literature, the formula has a large difference. Production and Lu' has considerable advantages. Therefore, the thermosetting heat conductive material prepared by the present invention can be applied to, for example, a light-emitting diode, thereby effectively improving the service life of the light-emitting diode. The above is intended to be illustrative only and not limiting. Any equivalent modifications or changes to the spirit and scope of the present invention are intended to be included in the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the steps of a method for preparing a thermosetting heat conductive material of the present invention; ^ Fig. 2 is a diagram showing the chemical reaction of a modified epoxy resin according to the present invention; " Figure 3 is the FTIR spectrum of the epoxy resin and coupling agent IPTS reaction of the present invention; 4th and 5th series, the oxidized powder of the present invention and the titanium coupling agent CA-108 and the lanthanide series respectively The coupling agent ca_228 reacts with the ftir ancient. And the Fig. 6 is the DSC exothermic curve of the thermosetting thermal conductive material prepared under the different alumina powder contents of the invention; Fig. 7 is a modification of the invention A comparison chart of the heat-curing curves of the epoxy resin and the unmodified epoxy resin; Figure 8 is an exothermic curve of the modified epoxy resin of the present invention at a constant temperature; The modified epoxy resin is modified and oxidized to reflect the exothermic curve of 3〇wt〇/〇 and 50wt%; the 10th figure is the dynamic viscosity change of the thermosetting thermal conductive material with different alumina contents at different temperatures according to the present invention. Figure 11 is a thermosetting heat transfer of the present invention The change of the withstand voltage of the material; Fig. 12 is the change of the tensile strength of the modified epoxy resin and the alumina powder of the present invention under various conditions; 201125901. The first and the 14th drawings are NPEL-128E epoxy resin Comparison of the surface conditions observed under the optical microscope and electron microscope, respectively, via the coupling agent (a) and (b) without modification; and Figures 15 and 16 are (a) NPEL-128E epoxy resin and The surface of the alumina powder modified by the coupling agent was 30 wt%, and (b) the resin and the powder were not modified. The comparison of the surface conditions was observed under the optical microscope and the electron microscope, respectively. [Main component symbol description] S11-S13: Process step.

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Claims (1)

201125901 VII. Patent application scope: A method for preparing a thermosetting heat conductive material, comprising the steps of: mixing an epoxy resin with a compound having a mixture to react the isocyanate group with the epoxy (::):: group (·〇Η) To obtain - change the epoxy resin; Mixing a ceramic powder with a titanium coupling agent or a combination of 'the titanium coupling agent or the lanthanide coupling agent=bonding to the auditory body to obtain - changing the f (four) powder; one muscle..., 〇丞In the case of making a horse catalyst, the modified epoxy resin and the modified ceramic listener are subjected to an anhydrous sol-gel to prepare a thermosetting heat conductive material. 〆 2· ” Patent _ i the thermosetting thermal conductive material preparation method ‘wherein the decane coupling agent includes 3-isocyanopropyl ethoxy decane. 3. The method of claim 2, wherein the 3-isocyanpropyltriethoxy group has a weight of 5-15 wt0/〇 relative to the epoxy resin. 4. The method for preparing a thermosetting thermally conductive material according to claim 1, wherein the ceramic powder comprises a powder of alumina, aluminum nitride, slag powder, and zinc oxide. 5. The method for preparing a thermosetting thermally conductive material according to claim 1, wherein the titanium coupling agent or the lanthanide coupling agent has a weight of 〇〇Mwt% relative to 22 201125901. The thermosetting heat conductive material according to item 5 has a (four) coupling agent or the wrong coupling agent diluted, and the ratio of the titanium coupling agent or the lanthanide coupling agent to the organic granule is 1: 5~ 1 : 20. The method for producing a thermosetting thermally conductive material according to claim 1, wherein the potter body has a weight of from 1 to 70% by weight relative to the thermosetting weight. The method of preparing a thermosetting heat conductive material according to the scope of the invention, wherein the two chaotic boron ethylamines are 0.5 to 5 wt% based on the weight of the modified epoxy resin. The method for preparing a thermosetting heat conductive material according to claim 1, wherein the anhydrous sol-gel reaction step further comprises adding a hardener for an epoxy resin, and the modified epoxy resin is The hardener undergoes a hardening reaction to form a three-dimensional crosslinked network structure. A thermosetting heat conductive material obtained by the method for producing a thermosetting heat conductive material according to any one of claims 1 to 10. twenty three