TW201111436A - Composite high heat conduction epoxy resin polymer material and substrate thereof - Google Patents

Abstract

The invention relates to a composite high heat conduction epoxy resin polymer material prepared by using soft epoxy resin, thermosetting epoxy resin, a curable agent, an accelerating agent, and a chemical-modified high heat conduction filler. The composite high heat conduction epoxy resin polymer material is doped with the ball milling manner to control the uniform distribution of the filler in the epoxy resin material so as to obtain the high heat conduction function. The chemical-modified formula is silicone coupling agent that can increase the interface adhesion of organic and inorganic materials and improve the problem or defect of worse heat dissipation of the conventional epoxy resin.

Description

201111436 VI. Description of the Invention: [Technical Field] The present invention relates to a composite high thermal conductivity epoxy resin molecular material prepared by a ball-milled method, which is a composite high thermal conductivity epoxy resin polymer. The material can be applied between two copper foils with a thermal conductivity greater than 彳w/mK, up to 3_4 W/mK′ and flexibility and high temperature resistance. [Prior Art] According to the general problem that the polymer and inorganic materials often have uneven mixing, the characteristics of the composite material cannot be exerted, especially the heat conduction function, which is mainly • uneven dispersion and many interfaces (9 “plus The existence of boundary, so that the heat (ph〇n〇n) can not be effectively conducted. Therefore, 'many electronic products in the input electrical energy 2 〇 ~ 30% will be converted into light energy release, the remaining 80 ~ 75% is Turning into heat, the higher the power of electronic products, the more heat is generated, such as: LEDs, mobile computers, PDAs, mobile phones, and camera electronics. When the packaging structure of electronic products cannot be effectively produced When the heat is effectively discharged from the product, it will continuously accumulate inside the component, causing the temperature of the electronic product to rise during use, resulting in a decrease in efficiency and a shortened life, especially in the heat dissipation of the computer and the light-emitting body. Especially serious, how to solve it effectively# This kind of problem is a problem that many electronic industries need to solve now. The research on the development of composite thermal conductivity polymer materials is in 1 In 998, Ishida and Rimadusit et al. added 78.5 vol% (or 88 wt.%) boron nitride (BN) heat transfer coefficient (where k, q = -) to polybenzoxazole (po|ybenzoxazjne). k(DT/dx) 'where q is the heat flux W/m2, k is the heat transfer coefficient W/mK ' and dT/dx is the temperature gradient) up to 32.5 W/mK. The size of the diameter includes 9, 45, 75, 225 μm, and the thermal conductivity coefficient is closely related to the amount of filler added. When the boron nitride is 33 vol%, the k value is 1.5 W/mk, and 54 vol%, k The value is 8.56 W/mK. In 2002, Yu et al. studied the thermal conductivity of polystyrene/nitriding (p〇|ystyrene 201111436 /Aluminum nitride,PS/ΑΙΝ) composite polymer materials, kPS=0.15 W /mK,kA|N=160 W/mK, when 10 vol% AIN is added, the thermal conductivity of PS/AIN composite polymer material is between 0.286~0.326 W/mK, but the improvement is not very effective. In 2002 , Weidenfeller et al. (Composites) studied PP/PE polymer (polymer) and polyamide 6 to add high thermal conductivity magnetite (magnetite, ie Fe304, particle size 9~180 The μηι,k value is 9.7 W/mK). The experimental results show that the thermal conductivity of the composite polymer material increases from 0.22 to 〇_93 W/mK (adding 44% Fe3〇4 filler), and the theoretical calculation of the seepage The percolation threshold was 33%. In 2004 'the same' Weidenfeller et al. (Composites) studied the addition of standard high thermal conductivity filler materials such as magnetics, barite, talc to polypropylene (PP, PP), Copper, strontium and glass fibres, etc., the experimental results show that the thermal conductivity of composite polymer materials increased from 0.27 to 2.50 W / mK (add 30% talc filler) The jnterconnectivity is not good, so the heat transfer coefficient cannot be greatly improved. In 2005, Sim et al. studied the addition of AI2〇3 and ZnO fillers to silicone rubber (where the thermal conductivity of each component is as follows: kSR=0.18 W/mK ' kAI2O3=30 W/mK, kZnO= 60 W/mK), the addition amount is 0~1〇wt.%. The experimental results show that the thermal conductivity of the composite polymer material increases from 0.18 to 0.2598 W/mK. In 2006, Lee et al. studied epoxy resin hybrid hybrid materials, such as aluminum nitride (AIN), SiC, boron nitride (BN), AIN addition amount 0~75vol ° / 〇, heat transfer coefficient increased by 0.35 To 2.27 W/mK. When 60% AIN was added, it was treated with a titanate coupling agent, and the heat transfer coefficient was increased from 2.01 to 2_42 W/mK. When 50% BN is added, the heat transfer coefficient is 3_66 W/mK. In 2007, Zhou et al. studied the addition of BN (10~30%) to HDPE, and the heat transfer coefficient increased from 0.20 to 1.20 W/mK. They were prepared in two different ways, using powder mixing and melted mixing, and compared 201111436.

Predicted values for MaxweN-Eucken and Bruggeman models. In 2007, He et al. studied the polystyrene (Polystyrene) resin and added Si3N4 filler on the electronic package (e|ectronic packagjng). The experimental results showed that AIN added SbN4 to 40wt·% when its heat transfer coefficient was 3.00 w/ mK was also found to have a silane interfacial activity (iwt.〇/〇 in ethanol), preferably NH2-(CH2)3Si-(OC2H3)3>. In another 2-7 years, Zhou (Thermochimica acta) et al. studied the heat transfer coefficient of HDPE/ΒΝ composite polymer materials. The experimental results were found to increase from 〇·3〇 to 1.30 W/mK. From the above-mentioned technical literature, the experimental results of the composite polymer material and the interface between the organic and inorganic materials have poor adhesion, and problems or disadvantages of poor heat dissipation, and need to be improved. SUMMARY OF THE INVENTION The main object of the present invention is to provide a composite high thermal conductivity epoxy resin polymer material, which utilizes a different property, such as a soft, recyclable thermosetting epoxy resin, a hardener, and a helium oxygen. An alkane coupling agent and a highly thermally conductive filler material are prepared. The composite high thermal conductivity epoxy resin polymer material is prepared by ball milling method (ba丨丨_mj丨丨ed) to effectively control the uniform distribution of the filler material in the polymer material to achieve high heat conduction. Features. _ In order to achieve the above objectives, the technical means adopted in this case is to provide a composite high thermal conductivity epoxy resin polymer material, which comprises: a soft epoxy resin and a flexible thermosetting epoxy resin, wherein The soft epoxy resin accounts for between 彳〇% and 6% by weight of the total polymer component; a hardener which cures the thermosetting epoxy resin at a curing temperature, wherein the hardening The amount of the polymer component is between 彳% and 〇%, and a decane coupling agent, wherein the coupling agent accounts for 0.1% to 1〇〇/0 by weight of the polymer component. And a highly thermally conductive inorganic filler material uniformly dispersed in the epoxy resin high score 201111436 subcomponent 'and the weight percentage of the thermally conductive electrically insulating filler material is between 5% and 80%; The composite high thermal conductivity polymer material has a uniform sentence structure, and the thermal conductivity coefficient (k) is greater than 1 W/mK. The main object of the present invention is to provide a composite high-conductivity epoxy resin high score, which can be modified in the past, such as poor electronic products and meta-transfer substrates, low heat transfer coefficient, complicated process, and long service life. In order to achieve the above objectives, the technology adopted in this case provides a composite two-layer thermal conductive epoxy polymer substrate comprising: a first metal layer; a second metal layer; and a high thermal conductivity electrical insulation. The polymer material rides through the structure and has a thermal conductivity greater than 1 W/mK'. The high thermal conductive electrically insulating polymer material layer forms a joint between the metal layers; wherein the height is high; the thickness of the thermoelectric layer of the polymer layer is 0.]^ mm. - The implementation of the present invention has the effect of gaining in that the composite gas-conducting oxime molecular material is a uniform distribution in the fat material by ball milling to obtain a high heat-transferring enamel system. Between 1Ό~4OWmK. Furthermore, 'the chemical modification is equipped with an oxygen-fired coupling agent, which can increase the interfacial adhesion of organic and inorganic materials, and the second or second to improve the problem or defect of poor heat dissipation of the general epoxy resin' and has flexibility and resistance to the south. The temperature characteristics can be applied to many electronic parts or electronic products, and the right insulation and _ characteristics are excellent, especially the excellent heat conduction work. [Embodiment] Oxygen resin, heat _ epoxy hard, hardener, acceleration Promoter, polymer material is applied by ball milling method, and the surface of the thermal conductive filling material is used to make the surface chemical modification. The ball-milling method can be used to prepare the "releasable" sorghum. Aiming at molecular materials. The raw materials used in the present invention include: a soft ring and a highly thermally conductive filler material surface-treated with a coupling agent 201111436. The invention relates to a liquid epoxy resin (NPER-450, a product of Nanya Plastics Co., Ltd.) and a high thermal conductivity filling material which is processed by a silane coupling agent. For example, a丨2〇3 and aluminum nitride (AIN), a hardener, and a thermosetting epoxy resin (DER-732, manufactured by Dow Chemical Co., Ltd.) are stirred and homogenized, and then uniformly stirred using a ball mill. The purpose of using a ball mill is to uniformly disperse the highly thermally conductive filler material into the resin. Immediately, the three rollers in the coater were stirred to uniformly mix, and the purpose of the roller agitation was to uniformly and uniformly mix the particles which were not completely dispersed in the ball mill. • After the above-mentioned uniformly dispersed composite epoxy resin material is ready, it enters the baking line for crosslinking polymerization. After the pigment reaches the working viscosity, the metal foil plate, such as copper, is uniformly pressed by the press machine. By fitting it and cutting out the appropriate size with a cutting machine, the preparation of the composite high thermal conductivity epoxy resin polymer substrate can be completed, and the thermal transmission data (k) can be measured and analyzed. Therefore, by the foregoing description, it can be found that the present invention is prepared by a physical method such as a grinding method to make the high thermal conductive filling material uniform and uniform by applying the cutting force of the stainless steel ball. In addition, the chemical method is used to improve the problem of adding the interface of the Wei interface to improve the interface. Among them, the constituent materials are selected to be made of soft epoxy resin, thermosetting epoxy hardening, and high thermal conductivity inorganic material for the modification and processing. Depending on the application, two properties, agents, accelerators and high thermal conductivity fillers can be used _===== =. When adding a soft epoxy to turn the 'epoxy resin can be modified to process the glass-transition polymer material' from the experimental analysis of the potted process, the chemical (10), the can #, and this high thermal conductivity epoxy The thermal properties of the finished resin material and the number of surface 201111436 are all analyzed. _ The experimental example of the invention is that the composite high-index epoxy resin molecular material can be applied to each sub-part and product, such as a light-emitting body. Mobile phone, computer. The invention also finds various high thermal conductivity inorganic materials, for example

^ SiC;BeO ^ MgO ^ ΖηΟ ^ ΒΝ ^ 3Ι3Ν4.4 AIN/Al2〇3. The best ratio of SiC/;N is between 20~80/〇, and hybrid: type size H The same high thermal conductivity inorganic filler material works better. The composite guide thermal ring riding fat polymer (4) prepared by the invention is made in two metal layers, and the first one is

= The metal layer can be selected from paving, laying, and stainless steel materials. It has a high thermal conductivity and flexible substrate. Its thermal conductivity is greater than 1 W/mK' up to 3.4 W/mK. Flexibility and postal temperature characteristics, J applications have excellent insulation and dryness properties in many electronic parts or electronic products, especially for excellent heat transfer. Please refer to FIG. 1 ' in detail for exposing the preparation process of the composite high thermal conductivity epoxy resin high sub-material and the substrate thereof. Step 1: Add NPER_45 不锈钢 in a stainless steel container (liquid soft type (containing rubber) Epoxy resin, produced by Nanya Plastics Co., Ltd.), MTHPA2 (methyl tetraphenyl benzene (Methyl)

Tetra Hydrophthalic Anhydride), hardener, manufactured by Nanya Plastics Co., Ltd., AI2=3 (manufactured by Sigma-AldriCh), DER_732 (flexible epoxy resin, manufactured by D〇w Chemical Co., Ltd.), and 4ME (acceleration accelerator, Produced by Sjgma_A|drich) 'where the gossip 2〇3 is first treated with i〇/〇sj|ane-1120 (eg γ-amino-propylmethyldimethoxydecane) in ethanol, but The flexible epoxy resin contains polysilicon and has an epoxy equivalent (ep〇xy eqUjva|ent wejght) of 310 to 330 g/eq. The constituent materials were previously stirred for about 1 hour to form a preliminary dispersion. Women's good ball mills' and check the pumping motor and water level in the machine to make the ball mill work properly. Step 2: After the materials to be mixed are evenly mixed, first turn on the circulation motor, and transfer the composition 201111436 material to the ball mill for mixing, and mix at 300 rpm for about 3 hours. The purpose of step 2 is to enable the particles of the highly thermally conductive filler material to be dispersed very uniformly and to make the filler material invisible to the filler material. Among them, the ratio of the number of stainless steel balls to the composition of the ball mill is 10:1, and the rotation speed is below 300 rpm. Step 3: After the mixture was removed from the ball mill, it was stirred using a three-roller in the coater to uniformly mix it again. The purpose of using the roller to stir is to uniformly mix the filler material, and to stir all of the small particles of the ball mill which are not completely dispersed, and to mix them very uniformly. Among them, in order to achieve the purpose of uniform mixing, the pitch of the three rollers is adjusted to be less than 4 mm. Step 4: After everything is ready, adjust the distance between the coater and the copper foil substrate (or polyethylene terephthalate H (PET) film) to make it plumb and firm, and open the drying line before coating. A section of oven reaches 5〇~1〇〇〇c, and the second section is baked 100~150oC' to enter the drying line. Step 5: The composite material was uniformly poured into the coater uniformly, and the copper box substrate was slowly entered into the drying line for cross-linking polymerization. 1"20 ^ =7 : When the composite material reaches the proper viscosity, press the copper presser to make it stick & and then use a cutter to cut the appropriate size.日#,I,' will cut the sample' and then dry at least 1 small flexible compound ring grease at 15〇〇c, which means high thermal conductivity and first ====== When deleting samples, wei^ 400.00g/eq , mbber.based it 201111436 ) MTHPA2 (Methyl Tetra Hydrophthalic Anhydride) is a hardener for condensates of maleic anhydride and isoprene, South Asia Plastic △ Division), gossip 2〇3 (1〇/〇snane_ii2〇 (for example, γ-amino-propyl fluorenyl dimethoxy shixi) treated with ethanol), DER-732 (epoxy) The equivalent weight is 310-330 g/eq, a flexible epoxy resin containing polyoxymethylene, manufactured by D〇w Chemical Company, and 4ME (acceleration accelerator, manufactured by Sigma-Aldrich). The constituent materials were pre-mixed for about 1 hour to be initially dispersed. The two epoxy resins do not produce any phase separation, i.e., exhibit a single phase. The preparation of the invention is carried out by a ball mill, the number of stainless steel balls: resin = 5:1 to 1 〇: 1 between the Lu's speed of 300~500 rpm 'time 2~4 hours, operating under normal temperature and pressure to control the dispersion uniformity . Among them, adding high thermal conductivity of barium 2〇3 powder (via 1wt%

Silane-1120 surface modification completed a丨2〇3 powder addition ratio is 〇姒% to 33 wt_%' control drying temperature cross-linking polymerization drying time is 2~3 hours, the best condition is 90 minutes prepared sample, And analyzed by thermogravimetric analyzer (TGA) (Perkim ElmerPyris 7, sample: 1020 mg, 10oC/min, N2 ring, a, / /, tested the material change of this example at different weight percentages, experiment The analysis results are shown in Table 1, Figure 2 and Figure 3. It is found from the experimental results that it can withstand high temperatures up to 3〇〇〇c (Figure 2), and the maximum weight change temperature is between 380~390〇C (Figure 3). Table 1, at a temperature of 150~i6〇°c, 9〇 minutes, epoxy resin+xwt.% Al2Q3 type temperature (°C) 25〇C 0% 0 10% 0 15% 0 20% 0 25% 0 27 % 0 33% 0 100°C 0.4527 0.9398 0.8941 0.9392 1.6588 -0.8450 0.8136 25CTC 1.2571 2.797 Ί 8203 2.9254 2.5986 -0.1630 1.8174

350°C 19.028 19.7383 22.2984 17.4353 16.7731 16.5753 450°C ^5.3306^ 孑 7.9176— 72.9598 ^9.5363~ ^3.7905^ ^8.9257^ 57.4914— ^<2112 85.9759 ^¢5514-

Il〇955, ^5626 and 2937 201111436 Example 2 Material 1 (four) composite secret ring ring for the detection of fat polymer 矣 face, temporarily, ': ask thermal conductivity Ai2. 3 powder (1% by the amount of snane-1120 (four) day f The pure case is 33 (four), the lake wire temperature is 15 ° ° C, : thermogravimetric analyzer _ test in different cross-linking polymerization time ==, qualitative change test results as shown in Table 2, Figure 4 and

Temperature to 3〇〇〇C (Fig. 4) 'Maximum weight change temperature at 37CK395〇C AI2〇3 filler material for cross-linking polymerization of Ding Table I, ring latex resin + 33 wt.% Result type temperature (°C) ~~~ 25aC~~~ —1· · 100°c 250〇C 350〇CA^C\°n 2 hours 3 hours 0 ~ 0 0.8316 ^~〇8036 1.3186 1.0976 14.9288 14.6921 ^OU 57.7591 57.0152 550〇C 64.0951 Wide 63.143 Example 3 Preparation of composite high thermal conductivity epoxy resin in the sample of the material sample: 'Additional thermal conductivity Α丨 2〇3 powder (巳 modified by 矽 表面 surface) ^ 〇 addition ratio is 33, control Drying temperature 15〇〇c,

Htachitrs^ ^ (sL, ancient road ^ under the same magnification] the side structure analysis of the observed sample, analysis j... whether the supplementary material is evenly dispersed in the epoxy tree g|#. It can be seen from the figure that the ancient filling material A丨2〇3 can be evenly dispersed in the ring of the towel = fruit as shown in Figure 6 to Figure 11.

11 201111436 Example 4 In this example, a composite high-thermal conductivity epoxy resin polymer film sample was prepared according to Example 1, and a high thermal conductivity barium dioxide powder (completed by decane surface modification) was added, and the ratio was 33 wt.%; compared with the non-added high thermal conductivity α!2〇3 powder as a comparison of 'control drying temperature 150~180oC, cross-linking polymerization' drying time is 9〇 minutes to prepare the film sample, with energy dispersion X-ray spectrometer (EDX/SEM system, Hitachi) analysis of chemical composition properties 'Experimental analysis results have obvious A丨 (aluminum) element peak (mainly belongs to gossip 2〇3 filling material) as shown in Figure 12 and Figure 3 Shown. Embodiment 5 This embodiment prepares a composite high-thermal conductivity epoxy resin polymer film sample according to the embodiment 1 'adding high thermal conductivity AW3 powder (which has been completed by the surface modification of Shi Xi-sing), and the addition ratio is 〇~33 wt_ %, control drying temperature 150~180〇c, cross-link the sample prepared in dry ^ minutes, and test with dynamic mechanical part "3MA" (TA, QA_8Ga T: 2G~2(8).c 5Qc/mjn 1Hz) The physical property changes at different temperatures of 2 m materials at different temperatures, the experimental analysis results know that the storage nucleus value (E, storage modulus (storage m〇du|us)) s 1〇6~1〇 a resin polymer material E, between 1 () 9 ~ 1G12 Pa, the i (four) two of the two molecular materials ' as shown in Table 3, Table 4 and Figure 14 to Figure 16, by ta_ Table 3, at 180 ° C, 90 minutes, 顼氦斟日匕+ ν * η, 六甘余取人布衣氧树月曰+ X wt.% ΑΙ2〇3 for 乂, I Ε, (storage modulus) value result 12 201111436 E'(Pa) 0% 15% 20% 25% 27% 33% 40°C 8.90x106 2.50 x1〇7 8.32 x106 2.10 x1〇7 4.18 x1〇7 4.66 x1〇7 80°C 3.87x10® 6.40 x1〇6 3.04 x106 5.83 x106 8.37 X1 6 8.00 x1〇6 120°C 3.22x10® 6.88 x1〇6 3.15 x106 5.95 x106 8.78 x1〇6 8.12 x1〇6 160°C 4.38x10® 7.41 x1〇6 3.49x106 6.32 x106 9.58 x1〇6 8.67 x1〇6 200 °C 4.59x10® 7.97 x1〇6 4.42x10® 6.97 x106 1.05 x1〇7 9.36 x1〇6 Table IV, tantalum polymerization at a temperature of 180 ° C '90 minutes 'epoxy resin + xwt % ai2〇3 (5) Value tan(5) value 0% 15% 20% 25% 27% 33% 40°C 6.25x10·1 7.41x1 O'1 7.62x1 O'1 6.66x101 5.86x10-1 7.31 x1〇1 80° C 1.03x10'2 2.56x1 CT2 7.71 x102 5.56x102 3.61x1〇-2 4.88x1 〇*2 120°C 1.36x1 O'3 8.26x10·3 1.84x102 1.34x1〇·2 1.63X10'2 1.44x1〇" 2 160°C 2.67x1 O'3 9.31 x103 1.57X10·2 1.79X10'2 1.17x1〇-2 1.79x1 O'2 200°C 1.45X10·3 8.55x10·3 2.39x1 O'2 2.30x1 O'2 1.03X10·2 1.82X102

EXAMPLE 6 In this example, a composite high-thermal conductivity epoxy resin polymer material sample was prepared according to Example 1, and a thermal conductivity of barium oxalate 3 powder was added (the ruthenium was modified by decane surface, and the addition ratio was 33 wt.%). 'Control drying temperature wc 'crosslinking polymerization time

The sample prepared under 3 hours was measured by a dynamic mechanical analyzer (_, D, A, etc.) as shown in Table 5, Table 6 and Figure 17 to Figure 19. -13 2〇1111436 Table 5, E, ( Storage modulus) value E, (Pa) 33% for 2 hours 33% for 3 hours 40°C 2.54x107 2.50χ1〇^~ ' 80°C 7.28x106 7.06χ1〇®~~ 120°C 7.74x10 ® 7.48x10® 160°C 8.15x10® 7.83χϊ〇6 200°C 7.84x10® 7.50χ1〇® ~ Table VI, Tan(5) value _ temperature ^ 40°C 53% for 2 hours 7.55x10'1 33 % for 3 hours 瞎7.51xl〇^ ^ 80°C 4.71χΐ〇-2 4.57x10^ 120°C 1.85χ1〇-2 1.91x1^ 160°C 1.49x102 2·03χΐ5^~ ' 200°C Γ 2.07x102 1_58xl5^~ ' Example 7 In this example, a composite high-conductivity sample was prepared according to Example 1. The addition of (10)_ has been added from the table AI2〇3 to 〇~33wt·%, and the drying temperature is controlled to 18〇〇c. Prepared for 90 minutes, and (4) type 扫, PynS 7, 1〇〇C/min, N2 environment, D: 20~200〇C) Test the specific heat of the material at different weights 2: percentage ratio Changes, experimental analysis results show that the cross-linking polymerization temperature should be controlled at 150~180 C is the best, because the peak of the DSC (Peak) is between 148~1490C, that is, between 15〇~18〇〇c, and the best is between 150~200°C, because The sample of the present invention is heat resistant to 3 〇〇〇 c 'and thus 'between 150 and 280 ° C, or as shown in FIG. Embodiment 8 201111436 In this embodiment, the raw materials, materials, chemicals and additives used in the composite high thermal conductivity epoxy resin polymer material sample are subjected to mjcr〇_Raman biliary, 514 and 633 nm laser, 50X, sp 〇t Size: ιμηΊ) Micro Raman Spectroscopy = Instrument Analysis of Chemical Composition Structure Analysis to understand the composition of various materials (in accordance with the guide,,,,,,,,,,,,,,,,,,,,,,,,, The results of Raman spectroscopy experimental analysis are shown in Fig. 21 to Fig. 25. Example 9 Material T1 Preparation of High Thermal Conductivity Composite Epoxy Resin Polymer ^ tint Al2〇3 Powder (巳 via the surface modification of Shi Xiyuan) 'Addition ratio is 33 wt.%, control drying temperature 15 〇〇 c and 3 hours thief Wei He prepared (4) sample, and _ micro pull spectrum analyzer irjrrf = compound Shouting job analysis, real age analysis found that the chemical composition is the same, as shown in Figure 26. Example 10 film preparation of high thermal conductivity composite epoxy resin polymer 180oC, treatment will take the human μ%, control drying temperature Raman L II = not the same sample, and microscopic Structural analysis, experimental analysis results are shown in Fig. 2: = group formation and example 11 This example is prepared according to the preparation of the composite sample according to the embodiment 1, but the addition of thermal conductivity (10) powder theory powder 15 201111436 surface modification is completed) mixing 'Addition ratio AI2〇3 : A|N is 5 : 5, 7 : 3, 3 : 7, control drying temperature 18G ° C, cross-linking polymerization shop _ is the sample film prepared at 9Q minutes' and use Laser Flash LFA-447 Modify ASTM E1461 analyzes its

The physical properties and chemical properties, the experimental analysis results are shown in the table, the k value is between 彳61~3 37W/mK. Table 7. Heat transfer coefficient value sample name (AI2〇3 : AIN) Thickness (mm) Density (g/cm3) Cp (J/gK) Thermal diffusivity (mm2/s) Heat transfer coefficient (W/mK) 5:5 0.820 2.056 1 〇AA 0.282 7:3 1.429 1 •yPH-H 2.128 1.806 1.955 0.315 1.212 3:7 0.647 2.352 1.820 0.298 3.375 Example 12

Membrane (4) 1 Preparation of composite high-introduction ring lysate polymer, ' '], ..., Α丨 2 〇 3 powder (巳 through decane surface modification), Tim: the ratio is 0~7〇% , control drying temperature 180 〇 C, cross-linking polymerization = 90

EueT^l?"' ^" Laser Fl- 0.52~2^WmK, the actual age reduction is as shown in Table 八卿, k value in 201111436 Table VIII, thermal conductivity value (thermal conductivity) AI2O3 filling material (wt·% Thickness (mm) Density (g/cm3) Cp (J/gK) Thermal diffusivity (mm2/s) Heat transfer coefficient (W/mK) 0% 0.336 2.677 1.674 0.112 0.528 33% 0.163 4.237 1.337 0.227 1.285 50% 0.330 2.924 1.712 0.230 1.415 60% 0.559 2.640 1.638 0.359 1.554 70% 0.787 2.465 1.722 0.505 2.145 Example 13 This example was prepared according to Example 1 to prepare a composite high thermal conductivity epoxy resin polymer material sample, adding high thermal conductivity AIN powder (巳Through the surface modification of decane), the addition ratio is Owt.%~70 wt.%, the drying temperature is controlled at 180 ° C, the cross-linked polymerization drying time is 90 minutes, and the sample is prepared by Laser Flash method, LFA- 447 Modify ASTME1461 analyzes its physical properties and chemical properties. The experimental analysis results are shown in Table 9. The k value is between 0.53 and 2.37 W/mK.

Table 9. Thermal conductivity AIN (wt.%) Thickness (mm) Density (g/cm3) Cp (J/gK) Thermal diffusivity (mm2/s) Thermal conductivity (W/mK) 0% 0.336 2.677 1.764 0.112 0.528 33% 0.533 2.221 2.233 0.163 0.806 50% 0.690 2.135 2.019 0.254 1.096 65% 0.441 2.862 1.544 0.403 1.781 70% 0.844 2.323 1.947 0.524 2.369 17 201111436 The present disclosure, which is one of the preferred embodiments, is a partial Any change or modification resulting from the technical ideas of this case and easy for people who are familiar with the skill can not be inferred from the patent right of this case. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a flow chart showing the preparation of a composite high thermal conductivity epoxy resin polymer material and a foil substrate thereof. '

% _ 下' Wei Na into the heat of the reaction of the Qing dynasty, the minute of the Wei dynasty, the new accompaniment reaction = the temperature of 150. (: The next Wei reversal can be mismatched and mixed with the clock analysis (like (the temperature is 15G °C under the Wei 旨 蹄 交 卿 纽 New New Year's hot weight 250 ^ A, 2 ° 3 t ^ II ^ (SEM) ^ _崎子子Microscope_)_=====%_糊梅赖镜 immediately in ^ _式微镜_) in ====7 scale butterfly 刚 mirror just Figure 12 is epoxy resin without added _3 energy dispersion Analysis of χx spectrometer (edx) P. 201111436 Figure 13 is an analysis of the addition of 33 Å to epoxy resin. 2 3 Energy Dispersive X Spectrometer (EDX) Figure 14 is an epoxy resin addition X Wt.〇/Q Am E' (Storage modulus) value analysis diagram. Figure 2 shows the dynamic mechanical analyzer (DMA) of Figure 3 for the epoxy resin addition χ埘% Ε" (storage modulus) value analysis diagram. 2 3 dynamic mechanical analyzer ( Figure 16 of DMA) is an analysis of the epoxy resin addition x gift tan (5) value. 2 3 dynamic mechanical analyzer (DMA)

Fig. 17 is a graph showing the analysis of the addition of 33 鲥 0 / A E' (storage modulus) of the epoxy resin. . . . The dynamic mechanical analyzer (DMA) of 2ϋ3 is a 33哳〇/E” (storage modulus) value analysis diagram for epoxy resin. Figure 23 of the dynamic mechanical analyzer (DMA) of Figure 3 is added with epoxy resin. 33鲥tan(5) value analysis chart. · Figure 20 of W3 Dynamic Mechanical Analyzer (DMA) is an epoxy resin addition χ analysis chart. '.Α 2〇3 differential scanning thermal analyzer (DSC) Z is Liquid soft (with rubber) epoxy resin (nper_45_micro-Raman light pattern 22 is a microscopic Raman spectrum of A thermal conductive filling material (A|2〇3). Figure 23 is a hardener (MTHPA2) Microscopic Raman spectroscopy Figure 24 is a micromanogram of a flexible epoxy resin (DER-732) Figure 25 is a microscopic Raman spectrum of the acceleration accelerator (4ME) Figure 26 is a ring The micro-Raman spectrum of 33 wt.% A!2〇3 was added to the oxy-resin. Figure 27 is a micrograph of 0 wt·%, 10 wt·%, 25 wt.% 丨2〇3 added to the epoxy resin. Raman spectrum. [Main component symbol description] None 0 19

Claims (1)

201111436 VII. Patent application scope: 1_ A composite high thermal conductivity epoxy resin polymer material, comprising: a rubber based epoxy resin and a flexible (fiexjb|e) thermosetting epoxy resin a resin, wherein the soft epoxy resin accounts for between 10% and 60% by weight of the total polymer component; a hardener 'cures the thermosetting epoxy resin at a curing temperature, wherein The hardener accounts for 5% to 4% by volume of the polymer component; and a decane coupling agent, wherein the coupling agent accounts for 0.1% to 1% by weight of the polymer component. And φ a highly thermally conductive inorganic filler material uniformly dispersed in the epoxy resin polymer component, and the weight of the high thermal conductive electrically insulating filler material is between 1% and 80%; wherein the composite high thermal conductivity polymer material has a uniform structure 'and a thermal conductivity coefficient (k) greater than 1 w/mK. 2. The composite high thermal conductivity epoxy resin high molecular material according to claim 1, wherein the soft epoxy resin and the flexible thermosetting epoxy resin are mutually soluble. 3. If applying for a special machine _ 1 _ composite high-grade epoxy resin high molecular material 'where the curing temperature is higher than 15 〇 ~ 2 〇〇 0C. Lu 4_如巾, please specializes in the composite high-profile epoxy resin high molecular material described in Item 1, wherein the thermosetting epoxy resin contains an ultra-high molecular weight epoxy resin. Soil 5. For the composite high-conductivity epoxy resin polymer material described in Item 4, wherein the epoxidation equivalent of the ultrahigh molecular weight epoxy resin (ep〇Xy equivalent weight, g/eq.) The system is between 100~50 000. The combination of the high thermal conductivity epoxy resin according to item 1 of the eight early benefit range = material, wherein the soft epoxy resin is an uncured liquid epoxy resin, and the eighth has a polysilicon oxide (silicone) ) and / or rubber (rubber). 7_The composite high-thermality epoxy resin as described in claim 1 is high. 201114636 ==Materials The flexible heat-epoxy resin is an epoxy-containing cyclohexyl ketone. Eight ^ (four) 1 tear-shaped composite high-conductivity epoxy resin high knife 匕 枓 material, the fine epoxy resin is _ epoxy resin face garden tree 曰 曰 0 Please, special! And the soft epoxy resin and the flexible thermosetting epoxy resin may be in a single phase. ^If applying for a fine-twisted composite high-impact epoxy resin, the intermediate-type impurity-containing epoxy resin comprises a base-epoxy resin, and the composite is as described in claim 10 a high-conductivity hetero-oxygen molecular material, wherein the hydroxy-epoxy resin ether polymer __ 曰 oxide is polymerized with a bifunctional group. 12_Composite high thermal conductivity as described in the scope of claim 2 == The thermosetting epoxy resin is made of - liquid liftable epoxy" 13. The composite type as described in the cap patent Gu Diyu The high-conductive epoxy tree is a sub-material, wherein the hot IU-type resin is formed by reacting a liquid epoxy resin with a divalent acid. M_ is a composite high thermal conductivity ring according to claim 1 of the patent application scope. The oxy-resin is a sub-material, wherein the thermosetting resin is formed by reacting a liquid epoxy resin. ', 15. The composite high thermal conductivity epoxy resin according to the scope of the patent application. The high sub-material 'where the high thermal conductivity filling material is nitride, the tether is selected from the group consisting of nitriding, chaotic _, nitrogen _, nitriding ♦ _) or its mixed σ ΑΙΝ + ΑΙ 2 〇 3 (= 7:3) is the best. A Τ 、 , 16 · The composite high thermal conductivity epoxy resin described in the scope of the patent application is a sub-material, wherein the high thermal conductivity filling material is an oxide, and its system is Selected from oxidized sputum · · Τ 21 201111436 (AkO3), magnesium oxide (Mg0), zinc oxide (Zn0), titanium dioxide (Tj〇2) or a mixture thereof 7. The composite high thermal conductivity epoxy resin noble molecular material according to claim 1, wherein the high thermal conductive filler material is required to have a coupling dose of 0.1 to 30% via a decane interface coupling agent. 18. A composite high thermal conductivity epoxy resin polymer substrate comprising: a first metal layer; a second metal layer; ^ A high thermal conductivity electrically insulating polymer material layer having an interpenetrating structure and a guiding coefficient greater than 1 W/mK'. The high thermal conductive electrically insulating polymer material layer is stacked on the second metal layer and the second Forming a joint between the metal layers; wherein the thickness of the layer of the highly thermally conductive electrically insulating polymer material is 0.1 to 1 mm ° 19. If the composite high-thermal conductivity epoxy resin is still a molecular substrate, The first and second metal layers are copper boxes, (four), non-recorded steel boxes and the like. The composite high thermal conductivity epoxy resin polymer substrate according to claim 18, wherein the high thermal conductive electrically insulating polymer material layer comprises: a polymer component comprising a soft epoxy resin A flexible thermosetting epoxy resin, a hardener, and a highly thermally conductive filler material, which are uniformly dispersed in the polymer component. 21. The composite high thermal conductivity epoxy resin polymer substrate according to claim 20, wherein the soft epoxy resin comprises between 10% and 60% by weight of the polymer component. The composite high thermal conductivity epoxy resin polymer substrate according to claim 20, wherein the soft epoxy resin and the flexible thermosetting epoxy resin are mutually soluble. The composite high thermal conductivity epoxy resin two-molecular substrate according to claim 18, wherein the interface between the horse thermally conductive epoxy material layer and the first and second metal layers has a good flat joint 'And can withstand the high temperature of 15 〇 ~ 28 〇〇 c. 22 201111436 24. The composite high thermal conductivity epoxy resin polymer substrate according to claim 20, wherein the preparation of the polymer component is carried out by a ball mill, and the number of stainless steel balls: resin = 5:1 to 20:1. Between, the speed is 300~1200 rpm, the time is 1~24 hours, and the operation uniformity is controlled under normal temperature and normal pressure. twenty three