TW201331353A - Heat dissipation material, heat dissipation structure, preparation method and use thereof - Google Patents

Abstract

This invention provides an inorganic heat dissipation nano-material aqueous slurry, a heat dissipation material containing the inorganic heat dissipation nano-material aqueous slurry, a preparation method, and use thereof. The inorganic heat dissipation nano-material aqueous slurry comprises the following parts by weight of ingredients: 10-25 parts by weight of an inorganic heat dissipation nano-material; 0.5-20 parts by weight of a modifier solution; and 50-100 parts by weight of a solvent. The heat dissipation material comprises the following parts by weight of ingredients: 10-30 parts by weight of an inorganic heat dissipation nano-material aqueous slurry; 40-80 parts by weight of an aqueous polymeric resin; 20-30 parts by weight of the latex; 10-40 parts by weight of a film formation aid; 0.5-5 parts by weight of an aid; and 5-20 parts by weight of a diluent. With the use of the inorganic heat dissipation nano-material aqueous slurry, the system dispersion stability and compatibility between the inorganic heat dissipation nano-material and the polymeric material can be increased to obtain a heat dissipation material containing the inorganic heat dissipation nano-material aqueous slurry with the unique excellent heat dissipation performance.

Description

Heat dissipation material, heat dissipation structure, preparation method and use thereof

The present invention relates to a heat dissipating material, structure, process and use thereof, and more particularly to a heat dissipating material, structure, process and use thereof comprising a slurry of inorganic heat dissipating nano material.

Thermally conductive materials include Thermal Pad, Thermal Grease, Thermal Tape, etc., designed to provide the best conditions for heat transfer, usually placed on heating elements and heat sinks. Between, to fill the gap between the two, the heat is completely transmitted from the heating element to the heat sink. Can be applied to a variety of different products, such as: notebook computers, desktop computers, motherboards, memory modules DDR, motherboards, hard drives, LED modules, PDP / LCD TVs. Nowadays, the functions of electronic devices are getting stronger and stronger, but the volume is getting smaller and smaller. This makes the heat dissipation problem a prominent problem that designers have to face. The conventional heat dissipation design is just a few fans and several heat dissipation. Holes or add some heat sinks, but for today's small, heat-generating appliances is not enough, you must find another way.

At present, there are three main types of heat dissipating materials, namely: thermal grease, heat-dissipating graphite sheet, inorganic nano-particle-polymer composite heat-dissipating material. Thermally conductive resin is a polymer material with high thermal resistance. It is not conducive to heat dissipation in both horizontal and vertical directions. The heat-dissipating graphite sheet has a unique grain orientation. The layered structure can be well adapted to any surface and is uniform in horizontal and vertical directions. Thermal conductivity, low thermal resistance, can shield the heat source, but the processing properties (high temperature, high pressure setting) and applicability (graphite brittleness) of the heat dissipating graphite sheet are relatively poor, which is not conducive to application.

The inorganic nanoparticle-polymer composite heat-dissipating material is mainly composed of a polymer material and a heat-dissipating filler (mainly composed of carbon material, metal or ceramics), and the particle size and volume fraction of the heat-dissipating coating material all affect the thermal conductivity of the body. At present, the heat-dissipating filler in the heat-dissipating coating material on the market is mainly graphite, carbon nanotubes, etc.; however, the above-mentioned heat-dissipating filler has poor compatibility with the polymer material, and the nano-heat-dissipating material is easy to aggregate, which seriously affects the Thermal conductivity and stability.

The present invention overcomes the defects existing in the prior art, and provides an aqueous slurry of an inorganic heat-dissipating nanomaterial, a heat-dissipating material containing the aqueous slurry of the inorganic heat-dissipating nanomaterial, a preparation method of the above material, and a use thereof.

In order to achieve the object of the present invention, the present invention adopts the following technical solutions:

An aqueous slurry of an inorganic heat-dissipating nanomaterial, comprising the following components by weight:

Inorganic heat-dissipating nano material 10-25 parts by weight;

Modifier 0.5-20 parts by weight;

Solvent 50-100 parts by weight.

Wherein, the modifier solution is prepared by mixing a modifier and a diluent, and the amount of the modifier is preferably 1:0.1-5 (weight ratio), wherein the diluent is preferably selected from water and alcohol. Tetrahydrofuran or the like, the alcohol is preferably selected from the group consisting of methanol, ethanol and the like. When a mixture of water and alcohol is used, the relative amount of water to alcohol is preferably 1:0.5-1.

Preferably, the inorganic heat-dissipating nanomaterial is selected from one or a combination of a group consisting of a carbon-based nanomaterial, a metal nitride or an oxide nanomaterial, and a metal particle-based nanomaterial.

Preferably the inorganic nanomaterials heat BET surface area of 25-2500m ² / g, preferably of 500-2000 m ² / g, more preferably of 1000-1500 m ² / g.

The inorganic heat-dissipating nanomaterial preferably has a particle diameter ranging from 10 to 500 nm, more preferably from 50 to 200 nm, most preferably from 50 to 100 nm.

The carbon-based nanomaterial is preferably selected from the group consisting of a nanocarbon sphere, a carbon nanotube, a graphene, etc.; the metal nitride or oxide nanomaterial is preferably derived from aluminum nitride or tantalum nitride. Titanium nitride, boron nitride, aluminum oxide, zinc oxide, titanium oxide, cerium oxide, vanadium dioxide, zirconium oxide, cerium oxide, etc.; the metal particle nano material is preferably selected from copper powder and aluminum powder. , silver powder, silver copper alloy, nickel, etc.

Preferably, the outer shell of the nanocarbon sphere is a multi-layered graphite structure, the interior may be a hollow structure, or the inner hollow structure contains a filler, preferably a metal, a metal oxide, a metal nitride, a metal sulfide. , metal borides, metal alloys, etc.

Preferably, the inorganic heat-dissipating nano material is selected from 1 to 15 parts by weight of a carbon-based nano material, 1 to 15 parts by weight of a metal nitride or oxide nano material, and 1 to 15 parts by weight of a metal particle-type nanometer. A compound mixture of two or three types in a material.

Preferably, the modifier is a macromolecular modifier; the macromolecular modifier is preferably selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyether modified organodecane, polyethylene wax, polyacrylic acid, Polyacrylate, polyacrylate, polydiethoxy(dimethyl)decane, diaminopolyoxyalkylene, decane modified polyethylene glycol, poly(methylvinyl)decane, poly(1, 3-divinyl-tetraphenyl)ethoxime-b-poly(1,3-divinyl-tetraethoxy)ethenol-b-poly(dimethyl)decane, cellulose, hydroxyl a cellulose, a hydroxyl terminated linear or star polymer, etc., the polymer is preferably selected from the group consisting of polyacrylamide, polylactic acid, polycaprolactone, polytrimethylene carbonate, etc.; Preferably, the agent has a molecular weight (Mw) greater than or equal to 1000.

Preferably, the modifier contains 10 to 90% by weight of polyacrylic acid having a molecular weight (Mw) of 10,000 to 30,000 and 90 to 10% by weight of polyvinyl alcohol having a molecular weight (Mw) of 1000 to 5000 (total weight of the modifier) As a benchmark).

Preferably, the solvent is selected from one or a combination of water, alcohol, tetrahydrofuran, preferably from methanol, ethanol or propylene glycol. When a mixture of water and alcohol is used, the relative amount of water to alcohol is 1:0.5-1. Preferably, the solvent and the aforementioned diluent may be the same or different.

Preferably, the aqueous slurry of the inorganic heat-dissipating nano material is prepared as follows: under nitrogen protection, 10-25 parts by weight of the inorganic heat-dissipating nano-material is weighed in 50-100 parts by weight of the solvent, and the temperature is exceeded at room temperature. The sonic wave is 10-100min until the dispersion is uniform; then, under stirring or ultrasonic state, the pH is adjusted to 8-10 with 5% ammonia water, and then 2/3 (w/w) is added dropwise at a rate of 2-4 ml/min. The modifier (or its solution), after the addition is completed, continue to stir or supersonic for 10-20 minutes until the dispersion is uniform; then, the temperature is raised to 50-60 ° C at a temperature increase rate of 3-5 ° C / min, in the process to 2- The remaining modifier (or its solution) is added dropwise at a rate of 4 ml/min. When the temperature is raised to 50-60 ° C, the addition is completed, and the reaction is carried out at this temperature for 2-6 hours, and then the ultrahigh pressure nano homogenizer is dispersed 30-120. After minute and ultrasonic dispersion for 30-90 minutes, an aqueous slurry of inorganic heat-dissipating nanomaterial with uniform dispersion can be obtained. Wherein, the total amount of the modifier (or a solution thereof) is from 0.5 to 20 parts by weight.

The solid content of the aqueous slurry of the inorganic heat-dissipating nanomaterial is preferably from 10 to 50% by weight, further preferably from 20 to 40% by weight, most preferably from 20 to 25% by weight.

The present invention also provides a heat dissipating material comprising the aforementioned aqueous slurry of inorganic heat-dissipating nanomaterial, which comprises the following components by weight:

Inorganic heat-dissipating nano material aqueous slurry 10-30 parts by weight

Waterborne polymer resin 40-80 parts by weight

Latex 20-30 parts by weight

Film forming aid 10-40 parts by weight

Additive 0.5-5 parts by weight

Diluent 5-20 parts by weight.

The aqueous polymer resin is preferably selected from the group consisting of water-based acrylic resin, water-based polyurethane resin, water-based styrene-acrylic resin, water-based acrylic resin, water-based organic resin, high-temperature curing water-based organic resin, water-based acrylic modified polyurethane resin, and water-based. Polyurethane modified acrylic resin, etc.

The latex is preferably selected from the group consisting of acrylate latex, styrene-acrylic latex, carboxylated styrene-butadiene latex, and the like.

The coalescent is preferably selected from the group consisting of alcohol ester compounds, preferably alcohol esters twelve.

The auxiliaries are preferably selected from one or a combination of a dispersant, a colorant, a bactericide, a thickener, a leveling agent, an antifoaming agent, an antifreeze, a wetting agent.

Wherein, the leveling agent is preferably an acrylic leveling agent, such as a BYK leveling agent; the antifoaming agent is preferably an organic antifoaming agent such as JF-1148 antifoaming agent; the thickening agent is preferably Acrylic thickener, such as: PT-669 thickener.

The diluent is preferably selected from the group consisting of ethylene glycol butyl ether, diethylene glycol butyl ether and the like.

The invention also provides a preparation method of a heat dissipating material comprising the aqueous slurry of the inorganic heat-dissipating nano material, the preparation step comprising: weighing 40-80 parts by weight of the aqueous polymer resin, and sequentially adding 10-40 parts by weight. The membrane auxiliary agent and 5-20 parts by weight of the diluent are heated to 50-60 ° C, and stirred at a high speed of 5000-6000 rpm until the dispersion is uniform; then, at a speed of 0.5-2.5 ml/min, at a speed of 3000-4000 rpm. 20-30 parts by weight of latex and 10-30 parts by weight of aqueous slurry of inorganic heat-dissipating nanomaterial are added dropwise, stirring is continued for 10-90 min to homogenization, and then 0.5-5 parts by weight of auxiliary agent is added to obtain a mixed solution at 1000. - 2000 rpm low speed stirring down to room temperature to obtain a heat sink material.

The heat dissipating material of the invention can be processed on the surface of the substrate by spraying or screen printing, and the process is simple and easy. The substrate is preferably selected from the group consisting of copper foil, aluminum foil, resin matrix, and the like.

The present invention further provides a heat dissipation structure using the heat dissipation material, comprising: a first substrate; a first heat dissipation layer formed on one side of the first substrate, the first heat dissipation layer being as claimed in the patent application The heat dissipation material is composed of 6 pieces; and a glue layer is formed on the other side of the first substrate relative to the first heat dissipation layer.

Preferably, the heat dissipation structure further comprises a base paper attached to the adhesive layer.

Preferably, the heat dissipation structure further includes a second substrate and a second heat dissipation layer, the second heat dissipation layer is formed on the second substrate, and the second substrate is bonded to the second substrate through the adhesive layer. a substrate.

The invention has the advantages that the inorganic slurry of the inorganic heat-dissipating nano material added in the heat-dissipating material is surface physical or chemical modification of the inorganic heat-dissipating nano material by using a modifier, and the structure and hydrophilicity of the functional macromolecular modifier are adjusted. The length of the molecular segment allows selective physical adsorption or graft hybridization on the surface of the inorganic heat-dissipating nanomaterial (eg, the surface of the (hydrophilic) carbon nanotube) is enriched in the nano-heat-dissipating material. The surface forms an acid anhydride bond, an ester bond or a hydrogen bond to improve the interfacial properties of the inorganic heat-dissipating nanomaterial; the use of the inorganic heat-dissipating nanomaterial aqueous slurry improves the compatibility between the inorganic heat-dissipating nanomaterial and the polymer material. The stability of the system and the dispersion of the system to obtain a heat-dissipating material containing an aqueous slurry of an inorganic heat-dissipating nanomaterial having excellent heat dissipation performance.

Example 1:

Under nitrogen protection, weigh 10g of 30-40nm hollow nanocarbon spheres (HCNC) in 50g of solvent water, supersonic for 30min at room temperature until evenly dispersed; then in the ultrasonic state, adjust with 5% ammonia water The pH was adjusted to 8-10, and then 10 g of a modifier polyvinyl alcohol (Mw=2000) aqueous solution (concentration: 50 wt%) was added dropwise at a rate of 3 ml/min. After the addition was completed, the ultrasonic wave was continued for 30 minutes until the dispersion was uniform; The temperature was raised to 60 ° C at a temperature increase rate of 5 ° C / min, and the remaining 5 g of the above-mentioned modifier polyvinyl alcohol aqueous solution was added dropwise at a rate of 3 ml / minute in the process, and the addition was completed when the temperature was raised to 60 ° C. The reaction was carried out for 4 h at a temperature, and then the ultrahigh pressure nano homogenizer was dispersed for 60 minutes and ultrasonically dispersed for 60 minutes to obtain an aqueous slurry of the inorganic heat-dissipating nanomaterial which was uniformly dispersed.

Example 2

Under nitrogen protection, weigh 10g of 10-30nm carbon nanotubes (product number: IMC4, the same below) in 100g of solvent water, supersonic for 30min at room temperature until evenly dispersed; then in the ultrasonic state, use 5% ammonia water was adjusted to pH 8-10, then 10 g of modifier polyvinyl alcohol (Mw=2000) aqueous solution (concentration: 50 wt%) was added dropwise at a rate of 4 ml/min. After the addition was completed, the ultrasonic wave was continued for 30 min. To the uniform dispersion; then, the temperature was raised to 50 ° C at a temperature increase rate of 3 ° C / min, during which the remaining 5 g of the above-mentioned modifier polyvinyl alcohol aqueous solution was added dropwise at a rate of 4 ml / minute, and the temperature was raised to 50 ° C. After the addition is completed, the reaction is carried out at this temperature for 6 hours, and then the ultrahigh pressure nano homogenizer is dispersed for 60 minutes and the ultrasonic wave is dispersed for 60 minutes to obtain a uniformly dispersed inorganic heat-dissipating nano material aqueous slurry.

Example 3

Under nitrogen protection, weigh 25g of 30nm nano aluminum nitride (product number: DK331, the same below) in 75g solvent water, supersonic for 20min at room temperature until evenly dispersed; then in the ultrasonic state, use 5 The pH of the ammonia water was adjusted to 8, and then 12 g of a modifier polyacrylic acid (Mw=3000) aqueous solution (concentration: 50 wt%) was added dropwise at a rate of 2 ml/min. After the addition was completed, the ultrasonic wave was continued for 15 minutes until the dispersion was uniform; Then, the temperature was raised to 60 ° C at a temperature increase rate of 3 ° C / min, and in the process, the remaining 6 g of the above-mentioned modifier polyacrylic acid aqueous solution was added dropwise at a rate of 2 ml / minute, and the addition was completed when the temperature was raised to 60 ° C. The reaction was carried out for 3 hours at a temperature, and then the ultrahigh pressure nano homogenizer was dispersed for 120 minutes and the ultrasonic wave was dispersed for 90 minutes to obtain a uniformly dispersed inorganic heat-dissipating nano material aqueous slurry.

Example 4

25 g of 30 nm of nano aluminum nitride in the preparation method described in Example 3 was replaced with 25 g of 50 nm aluminum powder (product number: DK102, the same below), and the other steps were the same as those of Example 3.

Example 5

10 g of 10-30 nm carbon nanotubes in the preparation method described in Example 2 were replaced with a mixture of 5 g of 10-30 nm carbon nanotubes and 5 g of 30 nm of nano aluminum nitride, and other steps and examples 2 The preparation method is the same.

Example 6

Using 10 g of 30 nm zinc oxide (product number: DK404) and 5 g of 30 nm nano aluminum nitride mixture to replace 10 g of 10-30 nm carbon nanotubes in the preparation method described in Example 2, other steps and implementation The preparation method of Example 2 was the same.

Example 7

The 10 g of 10-30 nm carbon nanotubes in the preparation method described in Example 2 was replaced with a mixture of 5 g of 50 nm aluminum powder and 5 g of 30 nm nano aluminum nitride, and the other steps were the same as those of Example 2. .

Example 8

Replace 10 g of 10-30 nm carbon nanotubes in the preparation method described in Example 2 using a mixture of 2 g of 50 nm aluminum powder, 3 g of 30 nm nano aluminum nitride, and 5 g of 10-30 nm carbon nanotubes. The other steps were the same as those of Example 2.

Example 9

The modifier polyvinyl alcohol (Mw=2000) in the preparation method described in Example 2 was replaced with a mixture of 20 wt% of polyacrylic acid having a molecular weight (Mw) of 10,000 and 80 wt% of polyvinyl alcohol having a molecular weight (Mw) of 1000. The other steps were the same as those of Example 2.

Comparative example 1

The modifier polyvinyl alcohol (M _W = 2000) in the preparation method described in Example 2 was replaced with the small molecule modifier OP-10, and the other steps were the same as those in Example 2.

The particle size distribution diagrams of sample 1 (product of example 2) and sample 2 (product of comparative example 1) are shown in Fig. 1 and Fig. 2, respectively, and the comparison is shown in Fig. 3. From Fig. 3, the dispersion stability of sample 1 is significantly better than that of the sample. 2, and the average dynamic particle diameter of the sample 1 was 95 nm, and the average dynamic particle diameter of the sample 2 was 124 nm; by comparing the data, the dispersibility and stability of the aqueous slurry prepared by using the macromolecular modifier were remarkably increased. At the same time, Example 1,3-9 also had the same performance.

Example 10:

Weigh 40g of waterborne polymer resin waterborne acrylic resin (product number: DT-150), add 10g of film-forming auxiliary alcohol ester 12 and 10g of diluent ethylene glycol butyl ether, and heat up to 60 ° C. Stir at 6000 rpm until the dispersion was uniform; then, 20 g of styrene-acrylic latex and 30 g of the aqueous slurry of the inorganic heat-dissipating nanomaterial prepared in Example 2 were successively dropped at a speed of 2 ml/min under stirring at 4000 rpm, and stirring was continued for 30 minutes. Homogenization, followed by the addition of 2 g of acrylic thickener (PT-699), 2 g of acrylic leveling agent (BYK leveling agent), 1 g of polyoxyalkylene organic defoamer (JF-1148) to obtain a mixture. The heat sink material (Material 1) was obtained by dropping at 1000 rpm and stirring to room temperature.

Example 11

The aqueous slurry prepared in Comparative Example 1 was used in place of the raw material "aqueous slurry of inorganic heat-dissipating nanomaterial prepared in Example 2" in the preparation method described in Example 10, and the other steps were the same as those in Example 10 (Material 2). .

Example 12

The aqueous slurry prepared in Example 5 was used in place of the raw material "aqueous slurry of inorganic heat-dissipating nanomaterial prepared in Example 2" in the preparation method described in Example 10, and the other steps were the same as those in Example 10 (Material 3). .

Example 13

The aqueous slurry prepared in Example 8 was used in place of the raw material "aqueous slurry of inorganic heat-dissipating nanomaterial prepared in Example 2" in the preparation method described in Example 10, and the other steps were the same as those in Example 10 (Material 4). .

The heat dissipation performance of material 1, material 2, material 3 and material 4 prepared by different heat dissipation materials is tested as follows: the experimental equipment includes: thermostatic control box, power supply, temperature sensing record table (thermocouple line probe 53) And the heat source 54. Among them, the heat source is a 40X40 metal electric heating film. Part of the structure is shown in Figure 4.

The heating carrier as the control group was tinplate 52, and the test method (control group) was as follows: 1. The incubator was set at 40 degrees Celsius, and the object to be tested was placed; 2. The heat source was placed at the bottom of the heating carrier (tinplate); 3. Use the power supply to output 5W to the heat source.

As the heating carrier of the experimental group, the above materials 1-4 (heat-dissipating lacquer coating 51) were sprayed on one side of the tinplate, and the test mode (control group) was 1. The incubator was set at 40 degrees Celsius, and the object to be tested was placed; Place the heat source on the bottom of the heating carrier (single-side spray of tinplate); 3. Use the power supply to output 5W to the heat source.

The test results are shown in Table 1. It can be seen from Table 1 that the heat dissipation performance of the heat dissipating material 1 prepared by the sample 1 modified with the polyvinyl alcohol on the carbon nanotubes is superior to the heat dissipating material 2 prepared by using the OP-10 modified carbon nanotubes, such as: When heated for 90 min, the heat source temperature of material 1 and material 2 differs by about 1.5 °C, indicating that the modification effect of macromolecular modifier on carbon nanotubes is good; material 1 differs from material 3 and material 4 in that material 3 The compound of carbon nanotubes and nano-aluminum nitride is used. The material 4 is a combination of carbon nanotubes, nano-aluminum nitride and nano-aluminum powder. When heated for 90 minutes, material 3, material 4 and blank The temperature difference of the heat source reaches 8.8 °C and 9.4 °C respectively, which is better than the temperature difference of 5.3 °C between the heat source of the material 1 and the blank sample, which is better than the temperature difference of 3.8 °C between the heat source of the material 2 and the blank sample, and indicates the heat dissipation of the composite inorganic heat-dissipating nano particles. The material is significantly superior to the heat sink material containing a single type of inorganic heat sinking nanoparticle.

Embodiment 14: Heat dissipation structure (1)

Different heat dissipation structures can be made by using the aforementioned heat dissipation material. As shown in FIG. 5, the present disclosure discloses a heat dissipation structure 100 including: a first heat dissipation layer 1, a first substrate 2, a glue layer 3, and a backing paper 4, wherein the first heat dissipation layer 1 is formed. On one side of the first substrate 2, a glue layer 3 is formed on the other side of the first substrate 2 with respect to the first heat dissipation layer 1. The first heat dissipating layer 1 is composed of the above-mentioned heat dissipating material, and the parts by weight and components thereof are as described above, and will not be repeatedly described herein. The heat dissipation structure 100 described in this embodiment may be a heat dissipating tape or other specific structure for heat conduction (heat dissipation) in practical applications.

Embodiment 15: Heat dissipation structure (2)

In this embodiment, a heat dissipation structure similar to a sandwich type and having two heat dissipation layers is disclosed. As shown in FIG. 6, the heat dissipation structure 200 includes a first heat dissipation layer 1a, a second heat dissipation layer 1b, a first substrate 2a, a second substrate 2b, and a glue layer 3, wherein the first heat dissipation layer 1a is formed on one surface of the first substrate 2a, the second heat dissipation layer 1b is formed on the second substrate 2b, and the second substrate 2b is bonded to the first substrate 2a via the adhesive layer 3. The first heat dissipating layer 1a and the second heat dissipating layer 1b are composed of the above-mentioned heat dissipating material, and the parts and components included therein are as described above, and will not be repeatedly described herein. The heat dissipation structure 200 described in this embodiment may be a heat sink or other specific structure for heat conduction (heat dissipation) in practical applications.

It can be seen from the above embodiments that the heat dissipating material, the heat dissipating structure, the preparation method and the use thereof provided by the present invention have industrial use value, but the above description is only for the description of the preferred embodiment of the present invention. The skilled artisan can make various other modifications in light of the above description, but such changes are still within the spirit of the invention and the scope of the invention as defined below.

100, 200. . . Heat dissipation structure

1, 1a, 1b. . . First heat dissipation layer

2, 2a, 2b. . . First substrate

3. . . Glue layer

4. . . The end of paper

51. . . Heat sink coating

52. . . Tinplate

53. . . Thermocouple line probe

54. . . Heat source

1 is a particle size distribution diagram of Sample 1 of Example 2 of the present invention;

Figure 2 is a particle size distribution diagram of sample 2 of Comparative Example 1 of the present invention;

Figure 3 is a dispersion stability spectrum of the aqueous slurry of the inorganic heat-dissipating nanomaterial of Sample 1 and Sample 2;

Figure 4 is a schematic diagram of the structure of the heat dissipation performance test instrument.

Figure 5 is a cross-sectional view of the heat dissipation structure (1);

Figure 6 is a cross-sectional view of the heat dissipation structure (2).

Claims (44)

An aqueous slurry of inorganic heat-dissipating nano material, comprising the following components by weight: 10-25 parts by weight of inorganic heat-dissipating nano material; 0.5-20 parts by weight of modifier solution; 50-100 parts by weight of solvent; Wherein, the modifier solution is prepared by mixing a modifier with a diluent, and the weight of the two is preferably 1:0.1-5. The inorganic heat-dissipating nano material aqueous slurry according to claim 1, wherein the inorganic heat-dissipating nano material is selected from the group consisting of carbon-based nano materials, metal nitride or oxide nano materials, and metal particles. One or a combination of the groups of nanomaterials, the inorganic heat-dissipating nanomaterial has a BET surface area of 25 to 2500 m ² /g, and the inorganic heat-dissipating nanomaterial has a particle diameter of preferably 10 to 500 nm. The inorganic heat-dissipating nano material aqueous slurry according to claim 2, wherein the inorganic heat-dissipating nano material has a BET surface area of 500-2000 m ² /g, and the inorganic heat-dissipating nano material has a particle size range preferably. It is 50-200 nm. The inorganic heat-dissipating nano material aqueous slurry according to claim 2, wherein the inorganic heat-dissipating nano material has a BET surface area of 1000-1500 m ² /g, and the inorganic heat-dissipating nano material has a particle size range of preferably 50-100 nm. The inorganic heat-dissipating nano material aqueous slurry according to claim 1, wherein the inorganic heat-dissipating nano material is selected from 1 to 15 parts by weight of a carbon-based nano material, and 1 to 15 parts by weight of a metal nitride. Or a compounded mixture of two or three types of oxide type nano material and 1-15 parts by weight of metal particle type nano material. The aqueous slurry of an inorganic heat-dissipating nanomaterial according to claim 2, wherein the carbon-based nano material is selected from the group consisting of nano carbon spheres, carbon nanotubes, and graphene; and the metal nitride or oxide The nano material is selected from the group consisting of aluminum nitride, tantalum nitride, titanium nitride, boron nitride, aluminum oxide, zinc oxide, titanium oxide, cerium oxide, vanadium dioxide, zirconium oxide, cerium oxide; It is selected from copper powder, aluminum powder, silver powder, silver copper alloy, and nickel. The aqueous slurry of the inorganic heat-dissipating nanomaterial according to claim 1, wherein the modifier is a macromolecular modifier; the macromolecular modifier is preferably selected from the group consisting of polyvinyl alcohol and polyethylene glycol. Polyether modified organodecane, polyethylene wax, polyacrylic acid, polyacrylate, polyacrylate, polydiethoxy(dimethyl)decane, diaminopolyoxyalkylene, decane modified polyethylene glycol , poly(methylvinyl)decane, poly(1,3-divinyl-tetraphenyl)ethoxime-b-poly(1,3-divinyl-tetraethoxy)ethenol-b - poly(dimethyl)decane, cellulose, hydroxymethylcellulose, hydroxyl terminated linear or star polymers. The aqueous slurry of an inorganic heat-dissipating nanomaterial according to claim 1, wherein the modifier contains 10 to 90% by weight of polyacrylic acid having a molecular weight (Mw) of 10,000 to 30,000 and a molecular weight of 90 to 10% by weight (Mw). ) is a polyvinyl alcohol of 1000-5000 based on the total weight of the modifier. The aqueous slurry of the inorganic heat-dissipating nanomaterial according to claim 1, wherein the solvent is selected from one group consisting of water, alcohol, tetrahydrofuran or a combination thereof, and the alcohol is preferably methanol. Ethanol, propylene glycol. The aqueous slurry of an inorganic heat-dissipating nanomaterial according to claim 1, wherein the inorganic heat-dissipating nano material aqueous slurry has a solid content of 10 to 50% by weight. The invention relates to a method for preparing an aqueous slurry of inorganic heat-dissipating nano material, comprising the steps of: weighing 10-25 parts by weight of inorganic heat-dissipating nano material in 50-100 parts by weight of solvent under nitrogen protection, and supersonic at room temperature 10-100min to even dispersion; in agitated or ultrasonic state, adjust the pH to 8-10 with 5% ammonia water, and add 2/3 (w/w) of the total amount at 2-4ml/min. After the addition of the modifier solution, continue stirring or supersonic for 10-20 minutes until the dispersion is uniform; heat up to 50-60 ° C at a temperature increase rate of 3-5 ° C / min, at a rate of 2-4 ml / min in the process The remaining modifier solution is added dropwise, and the addition is completed when the temperature is raised to 50-60 ° C. The reaction is carried out at this temperature for 2-6 hours, dispersed by an ultrahigh pressure nano homogenizer for 30-120 minutes, and ultrasonically dispersed for 30-90 minutes. An aqueous slurry of the inorganic heat-dissipating nanomaterial which is uniformly dispersed is obtained; wherein the total amount of the modifier solution is 0.5-20 parts by weight. A heat dissipating material comprising the following components by weight: 10-30 parts by weight of an aqueous slurry of an inorganic heat-dissipating nanomaterial as described in claim 1; 40-80 parts by weight of an aqueous polymer resin; 20-30 parts by weight of the latex; 10-40 parts by weight of the film-forming auxiliary; 0.5-5 parts by weight of the auxiliary; and 5-20 parts by weight of the diluent. The heat dissipating material according to claim 12, wherein the water-based polymer resin is selected from the group consisting of water-based acrylic resin, water-based polyurethane resin, water-based styrene-acrylic resin, water-based acrylic resin, water-based organic resin, and high-temperature curing water-based organic hydrazine. One of a group consisting of a resin, an aqueous acrylic modified polyurethane resin, and an aqueous polyurethane modified acrylic resin. The heat dissipating material according to claim 12, wherein the latex is selected from the group consisting of acrylate latex, styrene-acrylic latex, and carboxylated styrene-butadiene latex. The heat dissipating material according to claim 12, wherein the film forming aid is selected from the group consisting of alcohol ester compounds. The heat dissipating material according to claim 12, wherein the auxiliary agent is selected from the group consisting of a dispersing agent, a coloring agent, a bactericide, a thickener, a leveling agent, an antifoaming agent, an antifreezing agent, and a wetting agent. One or a combination of groups. The heat dissipating material according to claim 12, wherein the inorganic heat dissipating nano material is selected from the group consisting of a carbon-based nano material, a metal nitride or oxide nano material, and a metal particle nano material. One or a combination of the groups, the inorganic heat-dissipating nanomaterial has a BET surface area of 25 to 2500 m ² /g, and the inorganic heat-dissipating nano material preferably has a particle diameter ranging from 10 to 500 nm. The heat-dissipating material according to claim 17, wherein the inorganic heat-dissipating nano material has a BET surface area of 500 to 2000 m ² /g, and the inorganic heat-dissipating nano material has a particle diameter of preferably 50 to 200 nm. The heat-dissipating material according to claim 17, wherein the inorganic heat-dissipating nano material has a BET surface area of 1000 to 1500 m ² /g, and the inorganic heat-dissipating nano material has a particle diameter of preferably 50 to 100 nm. The heat dissipating material according to claim 12, wherein the inorganic heat dissipating nano material is selected from 1 to 15 parts by weight of a carbon-based nano material, and 1 to 15 parts by weight of a metal nitride or an oxide nanometer. A compounded mixture of two or three types of materials and 1 to 15 parts by weight of metal particle-type nanomaterials. The heat dissipating material according to claim 17, wherein the carbon-based nano material is selected from the group consisting of a nano carbon sphere, a carbon nanotube, and a graphene; and the metal nitride or oxide nano material is selected from the group consisting of nitrogen Aluminum, tantalum nitride, titanium nitride, boron nitride, aluminum oxide, zinc oxide, titanium oxide, cerium oxide, vanadium dioxide, zirconium oxide, cerium oxide; the metal particle nano material is selected from copper powder, aluminum Powder, silver powder, silver copper alloy, nickel. The heat dissipating material according to claim 12, wherein the modifier is a macromolecular modifier; the macromolecular modifier is preferably selected from the group consisting of polyvinyl alcohol, polyethylene glycol, and polyether modified organic decane. , polyethylene wax, polyacrylic acid, polyacrylate, polyacrylate, polydiethoxy (dimethyl) decane, diamino polyoxyalkylene, decane modified polyethylene glycol, poly (methyl ethylene矽, decane, poly(1,3-divinyl-tetraphenyl) acetamyl ether-b-poly(1,3-divinyl-tetraethoxy) acetamyl ether-b-poly(dimethyl a decane, cellulose, hydroxymethylcellulose, hydroxyl terminated linear or star polymer. The heat dissipating material according to claim 12, wherein the modifier contains 10 to 90% by weight of polyacrylic acid having a molecular weight (Mw) of 10,000 to 30,000 and 90 to 10% by weight of a molecular weight (Mw) of 1000 to 5,000. Polyvinyl alcohol based on the total weight of the modifier. The heat dissipating material according to claim 12, wherein the solvent is selected from the group consisting of water, alcohol, tetrahydrofuran or a combination thereof, and the alcohol is preferably methanol, ethanol or propylene glycol. The heat dissipating material according to claim 12, wherein the inorganic dissolving nano material aqueous slurry has a solid content of 10 to 50% by weight. A method for preparing a heat dissipating material according to claim 12, wherein the method comprises: weighing 40-80 parts by weight of the aqueous polymer resin, sequentially adding 10-40 parts by weight of a film forming aid and 5-20 The parts by weight of the diluent are heated to 50-60 ° C, and stirred at a high speed of 5000-6000 rpm until the dispersion is uniform; then, 20-30 parts by weight are sequentially added at a speed of 0.5-2.5 ml/min under a rapid stirring at 3000-4000 rpm. The latex and 10-30 parts by weight of the aqueous slurry of the inorganic heat-dissipating nanomaterial, continue to stir for 10-90 min to the homogeneous phase, and then add 0.5-5 parts by weight of the auxiliary agent to obtain a mixed solution, and the mixture is lowered to a chamber at a low speed of 1000-2000 rpm. The heat is the material. A use of the heat dissipating material according to claim 12, which comprises processing the heat dissipating material on the surface of a substrate by spraying or screen printing. The use of claim 27, wherein the substrate is selected from the group consisting of copper foil, aluminum foil, and resin matrix. A heat dissipation structure comprising: a first substrate; a first heat dissipation layer formed on one side of the first substrate, the first heat dissipation layer being composed of a heat dissipation material as described in claim 12 And a glue layer formed on the other side of the first substrate relative to the first heat dissipation layer. The heat dissipation structure of claim 29, further comprising attaching a base paper to the adhesive layer. The heat dissipation structure of claim 29, further comprising a second substrate and a second heat dissipation layer, wherein the second heat dissipation layer is formed on the second substrate, and the second substrate is transparent The glue layer is bonded to the first substrate. The heat dissipation structure according to claim 29, wherein the aqueous polymer resin is selected from the group consisting of water-based acrylic resin, water-based polyurethane resin, water-based styrene-acrylic resin, water-based silicone resin, water-based organic resin, and high-temperature curing water-based organic hydrazine. One of a group consisting of a resin, an aqueous acrylic modified polyurethane resin, and an aqueous polyurethane modified acrylic resin. The heat dissipation structure according to claim 29, wherein the latex is selected from the group consisting of acrylate latex, styrene-acrylic latex, and carboxylated styrene-butadiene latex. The heat dissipation structure of claim 29, wherein the film forming aid is selected from the group consisting of alcohol ester compounds. The heat dissipation structure according to claim 29, wherein the auxiliary agent is selected from the group consisting of a dispersing agent, a coloring agent, a bactericide, a thickener, a leveling agent, an antifoaming agent, an antifreezing agent, and a wetting agent. One or a combination of groups. The heat dissipation structure according to claim 29, wherein the inorganic heat-dissipating nano material is selected from the group consisting of a carbon-based nano material, a metal nitride or oxide nano material, and a metal particle nano material. One or a combination of the groups, the inorganic heat-dissipating nanomaterial has a BET surface area of 25 to 2500 m ² /g, and the inorganic heat-dissipating nano material preferably has a particle diameter ranging from 10 to 500 nm. The heat-dissipating structure according to claim 36, wherein the inorganic heat-dissipating nano material has a BET surface area of 500 to 2000 m ² /g, and the inorganic heat-dissipating nano material has a particle diameter of preferably 50 to 200 nm. The heat-dissipating structure according to claim 36, wherein the inorganic heat-dissipating nano material has a BET surface area of 1000-1500 m ² /g, and the inorganic heat-dissipating nano material has a particle size range of preferably 50-100 nm. The heat dissipation structure according to claim 29, wherein the inorganic heat-dissipating nano material is selected from 1 to 15 parts by weight of a carbon-based nano material, and 1 to 15 parts by weight of a metal nitride or an oxide-based nanometer. A compounded mixture of two or three types of materials and 1 to 15 parts by weight of metal particle-type nanomaterials. The heat dissipation structure according to claim 36, wherein the carbon-based nano material is selected from the group consisting of a nano carbon sphere, a carbon nanotube, and a graphene; and the metal nitride or oxide nano material is selected from the group consisting of nitrogen Aluminum, tantalum nitride, titanium nitride, boron nitride, aluminum oxide, zinc oxide, titanium oxide, cerium oxide, vanadium dioxide, zirconium oxide, cerium oxide; the metal particle nano material is selected from copper powder, aluminum Powder, silver powder, silver copper alloy, nickel. The heat dissipation structure according to claim 29, wherein the modifier is a macromolecular modifier; the macromolecular modifier is preferably selected from the group consisting of polyvinyl alcohol, polyethylene glycol, and polyether modified organic decane. , polyethylene wax, polyacrylic acid, polyacrylate, polyacrylate, polydiethoxy (dimethyl) decane, diamino polyoxyalkylene, decane modified polyethylene glycol, poly (methyl ethylene矽, decane, poly(1,3-divinyl-tetraphenyl) acetamyl ether-b-poly(1,3-divinyl-tetraethoxy) acetamyl ether-b-poly(dimethyl a decane, cellulose, hydroxymethylcellulose, hydroxyl terminated linear or star polymer. The heat dissipation structure according to claim 29, wherein the modifier contains 10 to 90% by weight of polyacrylic acid having a molecular weight (Mw) of 10,000 to 30,000 and 90 to 10% by weight of a molecular weight (Mw) of 1000 to 5,000. Polyvinyl alcohol based on the total weight of the modifier. The heat dissipation structure according to claim 29, wherein the solvent is selected from the group consisting of water, alcohol, tetrahydrofuran or a combination thereof, and the alcohol is preferably methanol, ethanol or propylene glycol. The heat dissipation structure according to claim 29, wherein the inorganic heat-dissipating nano material aqueous slurry has a solid content of 10 to 50% by weight.