CN103756252B

CN103756252B - A kind of thermosetting resin base heat-conductive composite material and its preparation method and application

Info

Publication number: CN103756252B
Application number: CN201310636293.8A
Authority: CN
Inventors: 林湖彬; 杜崇铭; 李华军
Original assignee: HUIZHOU CHANGYI NEW MATERIAL Co Ltd
Current assignee: Huizhou Moreware Industrial Co., Ltd.
Priority date: 2013-12-03
Filing date: 2013-12-03
Publication date: 2016-09-28
Anticipated expiration: 2033-12-03
Also published as: CN103756252A

Abstract

Open a kind of thermosetting resin base heat-conductive composite material of the present invention and its preparation method and application, this heat-conductive composite material contains matrix and the filler being filled in matrix, described matrix is thermosetting resin, described filler is modified hollow glass micro-ball, and described modified hollow glass micro-ball is the hollow glass micro-ball of the Surface coating heat conduction powder formed after surface is modified processing by conduction powder.Thermosetting resin used by the present invention can disperse conduction powder well, it is ensured that drawing abillity；Hollow glass micro-ball, the reasonably combined of conduction powder make material have the advantage such as lighting, corrosion-resistant, heat conductivility is excellent, mechanical property is good, pollution-free, low cost, precision height, life-span length, can be used as the heat radiation product of electronic product, the fin of light fixture and other are for the higher environment of cooling requirements.

Description

A kind of thermosetting resin base heat-conductive composite material and its preparation method and application

Technical field

Invention relates to thermal-conductive polymer matrix composites technical field, particularly relate to thermosetting polymer base heat-conductive composite material, be specifically related to a kind of thermosetting resin thing base heat-conductive composite material filled by the hollow glass micro-ball of conduction powder surface modification and its preparation method and application.

Background technology

Heat Conduction Material is widely used in the fields such as heat exchange engineering, heating engineering, electronic information.

Traditional Heat Conduction Material mostly is the preferable metal material of heat conductivity, but owing to the corrosion resistance of metal material is poor, electric conductivity high, density is big, it is high to manufacture energy consumption, limits its application in the field such as chemical industry, electronics.

Most polymers material has the advantages such as excellent decay resistance, light weight, good insulating, low cost of manufacture, but they are the non-conductor of heat mostly, heat conductivity is little, therefore to expand its application in heat conduction and heat radiation field, and it is crucial for improving heat conductivility.

Metal or the Inorganic Fillers Filled polymeric material of currently used high-termal conductivity are the more commonly used methods, the easy machine-shaping of Heat Conduction Material so obtained, and can apply to the most special field through suitable PROCESS FOR TREATMENT or formula adjustment.

Thermal-conductive polymer matrix composites refers to polymeric material as matrix, with heat conductivity material as filler, is combined through blended dispersion and obtains, have the heterogeneous compound system of certain heat conduction function.Thermal-conductive polymer matrix composites had both had heat conduction function, had again many excellent specific properties of complex polymer composites, interior can regulate the conduction of material, heat conduction and mechanical performance, thus be with a wide range of applications.

But, the polymeric matrix major part used at present is thermoplastic, and with the blended employing mechanical blending of inorganic functional fillers, the compatibility is poor, and the requirement for heat conduction network is higher.As patent of invention 201110169387.X discloses a kind of thermoplastic polymer based thermal conductive composite, having higher heat conductivity, but its heat conduction functional stuffing still up to 30% to 40% could form preferable heat conduction network, and technique is complex, ratio is great.

Summary of the invention

Present invention aims to the deficiencies in the prior art, it is provided that a kind of with thermosetting resin as matrix, there is the thermosetting resin thing base heat-conductive composite material of high heat conduction, cost degradation and lighting feature.

It is a further object to provide the preparation method of above-mentioned thermosetting resin base heat-conductive composite material.

It is a further object to provide the application of above-mentioned thermosetting resin base heat-conductive composite material.

The above-mentioned purpose of the present invention is achieved by following scheme:

A kind of thermosetting resin thing base heat-conductive composite material, this heat-conductive composite material contains matrix and the filler being filled in matrix, described matrix is thermosetting resin, described filler is modified hollow glass micro-ball, and described modified hollow glass micro-ball is the hollow glass micro-ball of the Surface coating heat conduction powder formed after surface is modified processing by conduction powder.

In above-mentioned heat-conductive composite material, thermosetting resin may refer to epoxy resin, unsaturated-resin or polyurethane resin or other other kinds of resins that can solidify.

In above-mentioned heat-conductive composite material, hollow glass micro-ball uses particle diameter to be 40 μm～the hollow glass micro-ball of 50 μm, in order to more preferable and fiber, graphite and other conduction powder build heat conduction network jointly；Described hollow glass micro-ball uses commercially available prod.

In above-mentioned heat-conductive composite material, conduction powder is micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide, micron-sized heat conduction carbon dust and the mixture of micron-sized conductive graphite powder composition, the specific descriptions of each component in this mixture, and the consumption (parts by weight) that this component is in the mixture is as follows:

Described micron-sized nitride refers to that particle diameter is 1 μm～the aluminium nitride of 2 μm, and consumption is 10-50 part；

Described micron-sized carbide refers to that particle diameter is 1 μm～the carborundum of 2 μm, and consumption is 5-25 part；

Described micron-sized heat-conducting metal oxide refers to particle diameter 30 μm～the aluminium sesquioxide of 100 μm, consumption 10-40 part；

Described micron-sized heat conduction carbon dust refers to the heat conduction carbon dust that particle diameter is 30 μm～100 μm, consumption 5-30 part；

Described micron-sized conductive graphite powder refers to the conductive graphite powder that particle diameter is 30 μm～100 μm, and consumption is 5-30 part；

Above-mentioned aluminium nitride, carborundum, aluminium sesquioxide, heat conduction carbon dust and conductive graphite powder are commercially available prod, use the heat filling of different-grain diameter and different structure can preferably build heat conduction network.

In above-mentioned heat-conductive composite material, the present inventor is by finding after research, again hollow glass micro-ball is carried out surface process after conduction powder is carried out pretreatment, more preferable result can be realized, its conduction powder pretreatment is: after the irradiated activation of mixture form micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder, uniform through acetone ultrasonic disperse；So process and follow-up heat filling and resin matrix can be made preferably to build heat conduction network, improve the surface compatability of itself and resin；Described micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide, micron-sized heat conduction carbon dust and the mixture of micron-sized conductive graphite powder composition are 1:1 with the mass ratio of acetone.

In above-mentioned heat-conductive composite material, it is necessary to containing the conduction powder being filled in Medium Culture and hollow glass and substrate gap.Its effect of the conduction powder of the present invention is divided into two parts, a part is to use micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide, micron-sized heat conduction carbon dust and the mixture of micron-sized conductive graphite powder composition as previously mentioned, and its effect is by Hollow Glass Microballoon Surface Improving is coated on hollow glass micro-ball surface；Another part is to use micro-sized nitride, any one or two or more combination in micron-sized carbide, micron-sized heat-conducting metal oxide, micron-sized heat conduction carbon dust or micron-sized conductive graphite powder, its effect is to be filled in the gap between substrate and filler, increases goods heat conductivility further.Hollow glass micro-ball is because be filled in substrate, so defining mutually having a common boundary of spherome surface, being coated on the conduction powder on hollow glass micro-ball surface and being then forced formation and be connected with each other passage of heat.

In above-mentioned heat-conductive composite material, hollow glass micro-ball accounts for the 10%～40% of thermosetting resin thing base heat-conductive composite material gross weight, thermosetting resin accounts for the 40%～75% of thermosetting resin thing base heat-conductive composite material gross weight, and conduction powder (conduction powder that described conduction powder includes modified hollow glass micro-ball and the conduction powder being filled in the gap between substrate and filler) accounts for the 5%～30% of thermosetting resin thing base heat-conductive composite material gross weight；In aforementioned conduction powder, the conduction powder consumption for surface modification hollow glass micro-ball accounts for the 15%～25% of conduction powder gross weight, and remaining conduction powder is all with filling substrate and the modified glass microballoon gap crossed for follow-up addition.

The present invention also provides for the preparation method of above-mentioned a kind of thermosetting resin base heat-conductive composite material, and this preparation method comprises the steps:

Step 1.

By micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder respectively with plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 DEG C) carry out more than irradiation activation 1h after, take again after the conduction powder of surface modification hollow glass micro-ball mixes, uniform through acetone ultrasonic disperse, obtain mixed liquor；Described for the conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone be 1:1；

Hollow glass micro-ball is put into after the sodium hydroxide solution that concentration is 0.1mol/L impregnates 1 hour and take out, silane coupler or potassium titanate coupling agent are sprayed directly on the bead surface processed through sodium hydroxide solution after air-drying by room temperature, obtaining the hollow glass micro-ball of surface irregularity, the glass microballoon so obtained preferably can be covered by conduction powder in ensuing process step；The consumption of described silane coupler or potassium titanate coupling agent is the 3% of hollow glass micro-ball quality；

Step 2.

The hollow glass micro-ball of surface irregularity step 1 prepared is put in conduction powder mixed liquor prepared by step 1, ultrasonic disperse more than 1 hour is until being uniformly dispersed together, allowing solvent obtain modified hollow glass micro-ball after volatilizing in atmosphere, namely the hollow glass micro-ball of conduction powder has been wrapped up on surface；

Step 3.

Conduction powder in the gap being used for being filled between substrate and filler of irradiation activation and firming agent prepared by the modified hollow glass micro-ball that thermosetting resin, step 2 prepared, step 1 solidify after physical blending, a kind of thermosetting resin base heat-conductive composite material needed for preparing the present invention.

In above-mentioned steps 1, the effect of acetone ultrasonic disperse can evenly disperse heat filling, in order to surface processes glass microballoon further below.

In above-mentioned steps 3, described firming agent is to use the firming agent corresponding with thermosetting resin used.

In above-mentioned steps 3, by thermosetting resin, the modified hollow glass micro-ball that step 2 prepares, the conduction powder in the gap being filled between substrate and filler through irradiation activation and the firming agent of step 1 preparation solidify after physical blending, described curing operation is specifically divided into two steps to be carried out: first by thermosetting resin, modified hollow glass micro-ball that step 2 prepares and the conduction powder in the gap being filled between substrate and filler through irradiation activation of step 1 preparation, and the firming agent corresponding to thermosetting resin used solidifies certain time at 25 DEG C, then at 80 DEG C, solidify certain time；Inventor is found by research, and solidification is divided into two steps to walk as described above, can control molding shrinkage, it is ensured that the physical property of goods goodly:

A kind of thermosetting resin base heat-conductive composite material that above-mentioned preparation method obtains, it not only has good heat conductivility, and mechanical property is the most excellent, can be used as the heat radiation product of electronic product, the fin of light fixture and other are for the higher environment of cooling requirements.

Compared with prior art, there is advantages that

1. the present invention uses thermosetting resin to be matrix, carries out synthesis is blended with glass hollow microsphere and other functional heat fillings, finally obtains polymer base heat-conducting article；

2. the dispersion conduction powder that the thermosetting resin such as epoxy resin used by the present invention, unsaturated-resin, polyurethane can be good, it is ensured that drawing abillity；Hollow glass micro-ball can preferably be wrapped up by conduction powder etc. after surface processes, and its addition greatly reduces the consumption of conduction powder；Simultaneously because the filling of hollow glass micro-ball so that material lighting；These conduction powder cover at tiny balloon surface and gap portion, entrance polymeric matrix is forced to formation and is connected with each other passage of heat, and the heat conduction network formed is due to the hollow parts without tiny balloon, directly leads away from conduction powder, and therefore heat transfer efficiency is higher；

3. heat filling is disperseed in the base by the mode of the plastic matrix material synthesis used by the present invention, therefore highly efficient with the heat conduction network that functional stuffing is formed, and can be led away as early as possible by the heat produced, improve thermostability and operating temperature during materials'use；

4. present invention employs the way adding greater particle size hollow glass micro-ball, make other function Heat Conduction Material consumptions the most less, ensure that material has the advantage such as lighting, corrosion-resistant, pollution-free, low cost, precision height, life-span length, can be used for the many aspects of industrial circle.

Detailed description of the invention

Below in conjunction with specific embodiment, the present invention is further described, but the present invention is not done any restriction by specific embodiment.

Embodiment 1

A kind of thermosetting resin base heat-conductive composite material of the present embodiment, its preparation method comprises the steps:

Step 1.

Pretreatment for the conduction powder of surface modification hollow glass micro-ball: by micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder respectively with plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 DEG C) carry out more than irradiation activation 1h after, remix formation mixture, uniform through acetone ultrasonic disperse, obtain mixed liquor；The specific descriptions of each component in described mixture, and the consumption (parts by weight) that this component is in the mixture is as follows:

Described micron-sized nitride be particle diameter be 1 μm～the aluminium nitride of 2 μm, consumption is 30 parts；

Described micron-sized carbide be particle diameter be 1 μm～the carborundum of 2 μm, consumption is 24 parts；

Described micron-sized heat-conducting metal oxide is particle diameter 30 μm～the aluminium sesquioxide of 100 μm, and consumption is 18 parts；

Described micron-sized heat conduction carbon dust be particle diameter be the heat conduction carbon dust of 30 μm～100 μm, consumption is 18 parts；

Described micron-sized conductive graphite powder be particle diameter be the conductive graphite powder of 30 μm～100 μm, consumption is 10 parts；

Described for the conduction powder mixture of surface modification hollow glass micro-ball and the mass ratio of acetone be 1:1.

The pretreatment of the conduction powder in the gap being filled between substrate and filler: the aluminium nitride plasma activation instrument (1.01MPa, 30 DEG C) under common plasma treatment pattern that particle diameter is 1 μm～2 μm is carried out more than irradiation activation 1h.

The pretreatment of hollow glass micro-ball: the hollow glass micro-ball that particle diameter is 40 μm～50 μm is put into after the sodium hydroxide solution that concentration is 0.1mol/L impregnates 1 hour and take out, Silane coupling agent KH550, silane coupler KH570 and potassium titanate coupling agent are sprayed directly on the bead surface processed through sodium hydroxide solution after air-drying by room temperature, obtaining the hollow glass micro-ball of surface irregularity, the glass microballoon so obtained preferably can be covered by conduction powder in ensuing process step；Total consumption is hollow glass micro-ball quality the 3% of described Silane coupling agent KH550, silane coupler KH570 and potassium titanate coupling agent；

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 80gE-44 epoxy resin, 10g step 2 prepared and 10g step 1, then ultrasonic disperse 15min, add firming agent 650 polyamide of 80g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 1h, then at 80 DEG C, solidify 3h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Relevant heat conductivility, mechanical property, extrudate density and the dimensional stability of the present embodiment thermosetting resin base heat-conductive composite material are shown in Table 1.

Embodiment 2

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 70gE-44 epoxy resin, 10g step 2 prepared and 20g step 1, then ultrasonic disperse 15min, add firming agent 650 polyamide of 70g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 1h, then at 80 DEG C, solidify 3h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 3

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 60gE-44 epoxy resin, 10g step 2 prepared and 30g step 1, then ultrasonic disperse 15min, add firming agent 650 polyamide of 60g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 1h, then at 80 DEG C, solidify 3h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 4

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 50gE-44 epoxy resin, 10g step 2 prepared and 40g step 1, then ultrasonic disperse 15min, add firming agent 650 polyamide of 60g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 1h, then at 80 DEG C, solidify 3h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 5

Step 1.

Pretreatment for the conduction powder of surface modification hollow glass micro-ball: by micron-sized nitride, micron-sized carbide, micron-sized heat conduction carbon dust and micron-sized conductive graphite powder respectively with plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 DEG C) carry out more than irradiation activation 1h after, remix formation mixture, uniform through acetone ultrasonic disperse, obtain mixed liquor；The specific descriptions of each component in described mixture, and the consumption (parts by weight) that this component is in the mixture is as follows:

Described micron-sized carbide be particle diameter be 1 μm～the carborundum of 2 μm, consumption is 40 parts；

Described micron-sized heat conduction carbon dust be particle diameter be the heat conduction carbon dust of 30 μm～100 μm, consumption is 20 parts；

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 40gE-44 epoxy resin, 10g step 2 prepared and 50g step 1, then ultrasonic disperse 15min, add firming agent 650 polyamide of 60g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 1h, then at 80 DEG C, solidify 3h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 6

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 70gE-44 epoxy resin, 20g step 2 prepared and 10g step 1, then ultrasonic disperse 15min, add firming agent 650 polyamide of 70g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 1h, then at 80 DEG C, solidify 3h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 7

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 60gE-44 epoxy resin, 30g step 2 prepared and 10g step 1, then ultrasonic disperse 15min, add firming agent 650 polyamide of 70g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 1h, then at 80 DEG C, solidify 3h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 8

Step 1.

Described micron-sized heat-conducting metal oxide is particle diameter 30 μm～the aluminium sesquioxide of 100 μm, and consumption is 20 parts；

Step 2.

Step 3.

The modified hollow glass micro-ball high speed dispersion homogenizer 5min that 70gE-44 epoxy resin and 30g step 2 are prepared, then ultrasonic disperse 15min, add firming agent 650 polyamide of 70g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 1h, at 80 DEG C, then solidify 3h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 9

Step 1.

Pretreatment for the conduction powder of surface modification hollow glass micro-ball: by micron-sized nitride, micron-sized carbide, heat-conducting metal oxide and micron-sized conductive graphite powder respectively with plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 DEG C) carry out more than irradiation activation 1h after, remix formation mixture, uniform through acetone ultrasonic disperse, obtain mixed liquor；The specific descriptions of each component in described mixture, and the consumption (parts by weight) that this component is in the mixture is as follows:

The pretreatment of the conduction powder in the gap being filled between substrate and filler: the aluminium sesquioxide plasma activation instrument of particle diameter 30 μm～100 μm (1.01MPa, 30 DEG C) under common plasma treatment pattern is carried out more than irradiation activation 1h.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 80g unsaturated polyester resin resin, 10g step 2 prepared and 10g step 1, then ultrasonic disperse 15min, add the firming agent cobalt naphthenate of 1g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 3h, then at 80 DEG C, solidify 2h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 10

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 70g unsaturated polyester resin resin, 10g step 2 prepared and 10g step 1, then ultrasonic disperse 15min, add the firming agent cobalt naphthenate of 1g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 3h, then at 80 DEG C, solidify 2h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 11

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 60g unsaturated polyester resin resin, 10g step 2 prepared and 30g step 1, then ultrasonic disperse 15min, add the firming agent cobalt naphthenate of 1g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 3h, then at 80 DEG C, solidify 2h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 12

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 50g unsaturated polyester resin resin, 10g step 2 prepared and 40g step 1, then ultrasonic disperse 15min, add the firming agent cobalt naphthenate of 1g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 3h, then at 80 DEG C, solidify 2h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 13

Step 1.

Pretreatment for the conduction powder of surface modification hollow glass micro-ball: by micron-sized nitride, micron-sized carbide, heat-conducting metal oxide and micron-sized heat conduction carbon dust respectively with plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 DEG C) carry out more than irradiation activation 1h after, remix formation mixture, uniform through acetone ultrasonic disperse, obtain mixed liquor；The specific descriptions of each component in described mixture, and the consumption (parts by weight) that this component is in the mixture is as follows:

Described micron-sized heat conduction carbon dust be particle diameter be the heat conduction carbon dust of 30 μm～100 μm, consumption is 10 parts；

The pretreatment of the conduction powder in the gap being filled between substrate and filler: the heat conduction carbon dust plasma activation instrument (1.01MPa, 30 DEG C) under common plasma treatment pattern that particle diameter is 30 μm～100 μm is carried out more than irradiation activation 1h.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 70g unsaturated polyester resin resin, 20g step 2 prepared and 10g step 1, then ultrasonic disperse 15min, add the firming agent cobalt naphthenate of 1g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 3h, then at 80 DEG C, solidify 2h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 14

Step 1.

Step 2.

Step 3.

Conduction powder high speed dispersion homogenizer 5min in the gap being used for being filled between substrate and filler prepared by modified hollow glass micro-ball 60g unsaturated polyester resin resin, 30g step 2 prepared and 10g step 1, then ultrasonic disperse 15min, add the firming agent cobalt naphthenate of 1g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 3h, then at 80 DEG C, solidify 2h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 15

Step 1.

Step 2.

Step 3.

100gEP, 200g have been dissolved the TCM solvent of 20gPC, conduction powder high speed dispersion homogenizer 5min in modified hollow glass micro-ball that 20g step 2 prepares and the gap being used for being filled between substrate and filler prepared by 20g step 1, then ultrasonic disperse 15min, add the firming agent TEPA of 15g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 6h, then at 80 DEG C, solidify 6h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 16

Step 1.

Step 2.

Step 3.

100gEP, 200g have been dissolved the TCM solvent of 20gPC, conduction powder high speed dispersion homogenizer 5min in modified hollow glass micro-ball that 10g step 2 prepares and the gap being used for being filled between substrate and filler prepared by 20g step 1, then ultrasonic disperse 15min, add the firming agent TEPA of 15g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 6h, then at 80 DEG C, solidify 6h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 17

Step 1.

Pretreatment for the conduction powder of surface modification hollow glass micro-ball: by micron-sized carbide, heat-conducting metal oxide, micron-sized heat conduction carbon dust and conductive graphite powder respectively with plasma activation instrument (1.01MPa under common plasma treatment pattern, 30 DEG C) carry out more than irradiation activation 1h after, remix formation mixture, uniform through acetone ultrasonic disperse, obtain mixed liquor；The specific descriptions of each component in described mixture, and the consumption (parts by weight) that this component is in the mixture is as follows:

Described micron-sized carbide be particle diameter be 1 μm～the carborundum of 2 μm, consumption is 30 parts；

Described micron-sized heat-conducting metal oxide is particle diameter 30 μm～the aluminium sesquioxide of 100 μm, and consumption is 40 parts；

The pretreatment of the conduction powder in the gap being filled between substrate and filler: the conductive graphite powder plasma activation instrument (1.01MPa, 30 DEG C) under common plasma treatment pattern that particle diameter is 30 μm～100 μm is carried out more than irradiation activation 1h.

Step 2.

Step 3.

80gEP, 200g have been dissolved the TCM solvent of 20gPC, conduction powder high speed dispersion homogenizer 5min in modified hollow glass micro-ball that 20g step 2 prepares and the gap being used for being filled between substrate and filler prepared by 20g step 1, then ultrasonic disperse 15min, add the firming agent TEPA of 15g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 6h, then at 80 DEG C, solidify 6h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 18

Step 1.

Step 2.

Step 3.

80gEP, 200g are dissolved the TCM solvent of 20gPC and modified hollow glass micro-ball high speed dispersion homogenizer 5min that 40g step 2 prepares, then ultrasonic disperse 15min, add the firming agent TEPA of 15g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 6h, at 80 DEG C, then solidify 6h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 19

Step 1.

Step 2.

Step 3.

80gEP, 200g are dissolved the TCM solvent of 20gPC and conduction powder high speed dispersion homogenizer 5min in prepared by 40g step 1 gap being used for being filled between substrate and filler, then ultrasonic disperse 15min, add the firming agent TEPA of 15g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 6h, at 80 DEG C, then solidify 6h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 20

Step 1.

Step 2.

Step 3.

70gEP, 200g are dissolved the TCM solvent of 30gPC and modified hollow glass micro-ball high speed dispersion homogenizer 5min that 40g step 2 prepares, then ultrasonic disperse 15min, add the firming agent TEPA of 15g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 6h, at 80 DEG C, then solidify 6h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 21

Step 1.

Step 2.

Step 3.

60gEP, 200g are dissolved the TCM solvent of 40gPC and modified hollow glass micro-ball high speed dispersion homogenizer 5min that 40g step 2 prepares, then ultrasonic disperse 15min, add the firming agent TEPA of 15g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 6h, at 80 DEG C, then solidify 6h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

Embodiment 22

Step 1.

Step 2.

Step 3.

50gEP, 200g are dissolved the TCM solvent of 50gPC and modified hollow glass micro-ball high speed dispersion homogenizer 5min that 40g step 2 prepares, then ultrasonic disperse 15min, add the firming agent TEPA of 15g afterwards and stir at short notice, within working life, it is poured in mould, at 25 DEG C, first solidify 6h, at 80 DEG C, then solidify 6h, prepare thermosetting resin base heat-conductive composite material needed for the present embodiment.

The performance test results of the thermosetting resin base heat-conductive composite material of table 1 embodiment 1～22 preparation

Table 1 is the performance data of the material of several preferable embodiment chosen in patent of the present invention, it appeared that, increase along with the consumption of hollow glass micropearl, the proportion of product declines, heat conductivity also can decline, and therefore selects the hollow glass micropearl of appropriate ratio and heat filling and thermosetting resin can ensure the mechanical property of material and the stable molding performance of product simultaneously.This product can use in the occasion that required precision is higher, and as the heat radiation product of electric equipment products, and the cooling base of light fixture or heat-dissipating casing use, and have obvious practical value.

Claims

1. a thermosetting resin thing base heat-conductive composite material, it is characterised in that this heat-conductive composite material contains matrix and filling Filler in matrix, described matrix is thermosetting resin, and described filler is modified hollow glass micro-ball, the hollow glass of described modification Glass microsphere is the hollow glass micro-ball of the Surface coating heat conduction powder formed after surface is modified processing by conduction powder, institute Stating thermosetting resin is epoxy resin, unsaturated-resin or polyurethane resin, and described hollow glass micro-ball uses particle diameter to be 40 μm ～50 hollow glass micro-balls of μm, described conduction powder is micron-sized nitride, micron-sized carbide, micron-sized leads Thermometal oxide, micron-sized heat conduction carbon dust and the mixture of micron-sized conductive graphite powder composition, described conduction powder is wanted First carrying out pretreatment, described pretreatment is by uniform through acetone ultrasonic disperse again after conduction powder first irradiated activation, described sky Heart glass microsphere accounts for the 10%～40% of thermosetting resin thing base heat-conductive composite material gross weight, and thermosetting resin accounts for thermosetting resin The 40%～75% of thing base heat-conductive composite material gross weight.

2. according to a kind of thermosetting resin thing base heat-conductive composite material described in claim 1, it is characterised in that described thermosetting Resin object base heat-conductive composite material is possibly together with the conduction powder being filled in Medium Culture and hollow glass and substrate gap.

3. the preparation method of thermosetting resin thing base heat-conductive composite material described in a claim 2, it is characterised in that this is prepared Method comprises the steps:

Step 1.

By micron-sized nitride, micron-sized carbide, micron-sized heat-conducting metal oxide, micron-sized heat conduction carbon dust and Micron-sized conductive graphite powder carries out more than irradiation activation 1h with plasma activation instrument respectively under common plasma treatment pattern After, then take after the conduction powder of surface modification hollow glass micro-ball mixes, and uniform through acetone ultrasonic disperse, mixed Liquid；Hollow glass micro-ball is put into after the sodium hydroxide solution that concentration is 0.1mol/L impregnates 1 hour and take out, after room temperature air-dries Silane coupler or potassium titanate coupling agent are sprayed directly on the bead surface processed through sodium hydroxide solution, obtain surface Rough hollow glass micro-ball；

Step 2.

The hollow glass micro-ball of surface irregularity step 1 prepared is put in conduction powder mixed liquor prepared by step 1, Ultrasonic disperse allows solvent obtain modified hollow glass micro-ball after volatilizing in atmosphere until being uniformly dispersed in more than 1 hour together, Namely the hollow glass micro-ball of conduction powder has been wrapped up on surface；

Step 3.

Modified hollow glass micro-ball that thermosetting resin, step 2 are prepared, step 1 prepare through irradiation activation Conduction powder and firming agent in the gap being filled between substrate and filler solidify after physical blending, prepare power Profit requires a kind of thermosetting resin base heat-conductive composite material described in 2.

4. according to the preparation method of thermosetting resin thing base heat-conductive composite material a kind of described in claim 3, it is characterised in that institute State in step 3, modified hollow glass micro-ball that thermosetting resin, step 2 are prepared, step 1 prepare through irradiation The conduction powder in the gap being filled between substrate and filler of activation and firming agent are first cured at 25 DEG C After cured at 80 DEG C again.

5. described in claim 2, a kind of thermosetting resin thing base heat-conductive composite material is preparing electronic product radiating product or lamp Application in tool fin.