KR102079371B1 - Method for preparation of heat-sink compound - Google Patents

Abstract

The present invention comprises i) treating the surface of the yarn made from inorganic long fiber yarn with reactive silane, ii) treating the surface of the silane treated yarn with transition metal ions to activate it, and iii) preparing it in the form of slurry, A method of preparing a polymer-based heat dissipating compound, which is coated with a metal on the surface of the yarn, and is then surface treated with a reactive silane and blended with the polymer substrate, and a polymer-based heat dissipating compound having increased strength and / or thermal conductivity prepared accordingly. It is about.

Description

Method for preparation of heat-sink compound

The present invention comprises i) treating the surface of the yarn prepared from inorganic long fiber yarn with reactive silane, ii) treating the surface of the silane treated yarn with precious metal ion, and then iii) preparing it in the form of slurry, A method for preparing a polymer-based heat dissipating compound, which is coated with a metal on a surface, and iv) surface treated with a reactive silane, and blended with a polymer substrate, and a polymer-based heat dissipating compound having an increased strength and / or thermal conductivity prepared accordingly. will be.

Recently, various portable digital electronic devices such as smartphones and tablet PCs are becoming necessities around our daily lives. Furthermore, there are many cases where various functions are integrated into one device called device convergence. The development of such electronic devices basically depends on the high integration technology of semiconductors, but this high integration technology inevitably generates heat that is the main cause of deterioration, lifespan, and failure of electronic devices. Heat-sink technology, which can effectively emit heat, has become a big issue. In particular, the future of electronic devices are expected to become more light and thin, multifunctional, the need and importance of the development of heat dissipation technology and the material to achieve this will be gradually expanded.

This heat dissipation material is used in automobiles, LEDs as well as electronic devices. In the case of automobiles, due to the globalization of automobile bodies, the demand for electronic devices and power usage in the automobiles are rapidly increasing. Furthermore, the electronic components used therein are further required for small, light and reliable functions. Due to the high integration of electric devices for automobiles and the increase in power consumption, development of high-performance information technology-automotive high heat-dissipating material parts is in progress.

The heat dissipation material widely used throughout the industry is a composite material mixed with a high thermal conductivity filler and a polymer material. These composite materials can obtain excellent thermal conductivity and easy processability at the same time, but the limit of processability and physical properties of the polymer may decrease as the amount of the inorganic filler added to obtain high thermal conductivity increases. There is.

On the other hand, the general conductivity of the polymer material is 0.2 W / mK level, because most of the vibration mode (phonon) due to various defects present in the polymer is scattered and do not propagate. Therefore, in order to implement a polymer composite having high thermal conductivity, it is expected that theoretically equivalent to thermal conductivity can be achieved when polymer chains composed of strong covalent bonds are continuously connected continuously over a thermal conductive path. . To this end, various thermally conductive polymer composite materials have been developed, but there are still fundamental limitations such as requiring significantly lower thermal conductivity or higher production cost than using inorganic fillers.

Accordingly, various composite materials including inorganic fillers have been developed. For example, International Application WO2008 / 126829 discloses a high thermal conductivity containing 85 to 97% by weight of inorganic powder filler of metal oxide or metal powder, 2 to 15% by weight of base oil and 0.001 to 10% by weight of polyester resin. Compounds, Japanese Patent No. 4796704, a crosslinked grease heat dissipating agent in which a thermally conductive filler is dispersed in a crosslinked silicone gel, and International Patent WO2013 / 146478 discloses a C _1-9 alkylene having a C _1-18 alkyl group on the side chain thereof. Soluble processability, flowability, flexibility with low melt viscosity at low melting point where phenylene units or naphthylene units in which alkylene and 2 to 4 phenylene groups are directly or via a linker are crosslinked by ether bonding via epoxy; , Korean Patent No. 10-1220209 discloses a polyol, expanded graphite, water, and a catalyst by mixing an epoxy resin having excellent adhesion and thermal conductivity into a mixer, followed by stirring. Polyol / expanded graphite mixture

Preparing a; Preparing a polyurethane / expanded graphite master batch by injecting a polyol / expanded graphite mixture and an isocyanate into the reactor by an In Situ reaction; Grinding the polyurethane / expanded graphite master batch to produce a polyurethane / expanded graphite master batch powder; And manufacturing an engineering synthetic resin, expanded graphite and polyurethane / expanded graphite master batch powder, and an antioxidant and a coupling agent to an extruder to form a master batch pellet. The method, Korean Patent No. 10-0885653 discloses a high thermal conductivity composite resin composition in which a hybrid filler mixed with a fibrous filler and a particulate filler is dispersed throughout the volume of the polymer matrix including polyetheretherketone. It is starting.

However, since many polymers have low thermal conductivity, they may require a high content of high thermal conductivity inorganic fillers, which may make it difficult to maintain the physical properties of the polymer or may be detrimental to weight, and most inorganic fillers have poor compatibility with the polymer. It may be difficult to exhibit high and stable thermal conductivity because it is not evenly dispersed in the polymer resin.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly researched in order to discover the method of improving the miscibility with a polymeric base material by modifying the surface of an inorganic filler in manufacturing the heat dissipation compound containing a high thermal conductivity inorganic filler in a polymeric base material, After coating a metal on the surface of the inorganic filler and then modifying it by treating with a reactive silane group, it is confirmed that the dispersibility in the polymer substrate is improved, and furthermore, the strength and / or thermal conductivity are significantly increased, thereby completing the present invention. It was.

The first aspect of the invention

A first step of manufacturing a yarn from an inorganic long fiber yarn;

A second step of treating the surface of the yarn with the first reactive silane by injecting the yarn obtained from the first step into a reactor containing an aqueous solution of the first reactive silane compound;

A third step of activating the surface of the silane-treated yarn by treating with an aqueous solution containing an activator, a metal salt reducing agent, and an acid to provide transition metal ions;

A fourth step of preparing a surface-activated yarn slurry by injecting and stirring the surface-activated yarn and water into a reactor;

After adding a metal salt, a complexing agent, a stabilizer, and a reducing agent to water sequentially, the mixed solution was added to the surface-activated yarn slurry solution prepared in step 4, and then the pH was adjusted to 4 to 14 by adding a pH adjusting agent. A fifth step of coating a metal on the surface of the activated yarn by reacting at 30 to 95 ° C. with stirring;

A sixth step of treating the surface of the metal-coated yarn with the second reactive silane by adding a metal-coated yarn to the surface obtained from the fifth step in an aqueous solution of the second reactive silane compound and reacting at 20 to 30 ° C; And

A seventh step of injecting and blending a metal-coated yarn with a surface treatment with a polymer resin or a polymer elastomer and a second reactive silane obtained from the sixth step;

It includes, provides a method for producing a polymer-based heat dissipating compound.

In the manufacturing method of the present invention, the yarn can be prepared using a chipping machine equipped with a series of cutters arranged at predetermined intervals. At this time, the interval of the cutter is a factor for determining the size of the yarn. Therefore, in the manufacturing method of the present invention, the first step may be performed using a chipping machine equipped with a series of cutters arranged at 0.5 to 6 mm intervals, preferably at 0.5 to 3 mm intervals. For example, when the spacing of the cutter is less than 0.5 mm, cutting workability is inferior, and when it is more than 6 mm, the blendability of the polymer substrate on which the final heat dissipating compound is based may be low.

For example, the first step,

Step 1-1 to apply a polymer resin sizing agent on the inorganic long fiber yarn;

A first step of drying the wet long-fiber yarn in which the sizing agent is applied to the surface obtained in step 1-1 by cutting with a chucking machine, and then putting the wet long fiber yarn into a hot air drying furnace maintained at 150 to 250 ° C .; And

This can be done through steps 1-3 of removing the sizing agent.

In the production method of the present invention, a sizing agent can be used in order to impart processability to the inorganic long fiber yarn when manufacturing the warp yarn from the inorganic long fiber yarn. By applying the sizing agent to the surface as described above and cutting it, it can be prevented from being broken in any form, and can be prepared into a yarn of a desired constant size.

The inorganic long fiber yarn usable in the heat dissipating compound of the present invention may be made of filament made of carbon, glass, alumina, ceramic or aramid material. In addition, the long fiber yarn may be a fiber yarn composed of a filament diameter of 1 to 40 μm, the number of filaments 50 to 3,000, but is not limited thereto. For example, when the filament diameter is less than 1 μm, reinforcement due to the cut yarns may be degraded, and when the filament diameter is greater than 40 μm, the blendability with the polymer that is the basis of the final heat dissipating compound may be poor. On the other hand, when the number of filaments is less than 50, the economic efficiency is low, and if the 3,000 is more disadvantageous for cutting, and in severe cases may damage the cutting blade may reduce workability.

The sizing agent may be a cross-linkable resin or a water-soluble polymer resin such as epoxy, urethane, acrylic, and polyvinyl alcohol, but is not limited thereto, and any material commonly used as a sizing agent in the art is not limited thereto. Can be used

Steps 1-3 may be achieved by heat treatment and carbonization for 1 to 10 hours in a heating furnace maintained at 300 to 700 ° C. when using a conventional hydrocarbon polymer such as a curable resin as a sizing agent, and the sizing agent is water-soluble. In the case of a polymer resin, it can be achieved by simply washing with water. When the sizing agent is removed by carbonization by the heat treatment, when the heat treatment temperature is less than 300 ° C., the polymer resin used as the sizing agent may be incompletely carbonized and remain on some yarns. Thermal decomposition of the dust itself may be involved.

The second step may be performed using a reactor equipped with a stirrer and a temperature controller. Specifically, after a series of reactants are added to the reactor, it can be performed for 10 to 120 minutes at 20 to 30 ℃ while stirring at a rate of 100 to 1,000 RPM. In this case, 300 to 600 parts by weight of water (for example, distilled water) and 0.4 to 1 part by weight of the first reactive silane compound may be used based on 100 parts by weight of yarn used. Furthermore, after the reaction is completed, the step of filtering and washing the obtained product may be further performed, but is not limited thereto. The washing may use 100 to 300 parts by weight of water based on 100 parts by weight of the used yarn, but is not limited thereto.

For example, as the first reactive silane compound, gamma-ureidopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, 3-aminopropyltrimethoxysilane (3 -aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-glycidoxypropyltriethoxysilane Compounds selected from the group consisting of these may be used alone or in combination of two or more compounds, but the kind of reactive silane compounds that can be used is not limited thereto. Treatment with the first reactive silane compound allows subsequent surface activation to be carried out more efficiently. In this case, when the amount of the first reactive silane compound is less than 0.4 part by weight, the surface adhesion between the yarn and the metal may be low when the metal is coated later, and when used in excess of 1 part by weight, the economical efficiency is low.

The third step is to activate the surface of the yarn treated with the first reactive silane to more easily adhere the metal during subsequent metal coating, platinum chlorine (platinum chloride), palladium chloride ( palladium chloride) or gold chloride may be used, but is not limited thereto. In this case, the activating agent may be used in 0.1 to 5 parts by weight based on 100 parts by weight of yarn used, but is not limited thereto. For example, when the amount of the activator is less than 0.1 part by weight, the adhesion to the metal may still be low because the desired level of surface activation may not be achieved, and when it is more than 5 parts by weight, the economic efficiency may be low.

The surface activation may be performed in the presence of a metal salt reducing agent and an acid, and as the metal salt reducing agent, tin chloride containing tin, which is a metal having a higher ionization tendency than a transition metal ion included in the activating agent, may be used. However, the present invention is not limited thereto. In addition, hydrochloric acid or sulfuric acid may be used as the acid, but is not limited thereto. The metal salt reducing agent and acid may be used in an amount of 5 to 20 parts by weight and 30 to 100 parts by weight, respectively, based on 100 parts by weight of the yarn used, but is not limited thereto.

For example, activation of the surface of the transition metal on the surface of the yarn to induce reduction of the transition metal contained in the activator by treating the yarn with a metal salt reducing agent together with the activator, and then act as a seed when introducing the metal coating layer. It may be a process of forming microparticles.

For example, the third step may be performed for 10 to 60 minutes while stirring at a rate of 300 to 700 RPM in the reactor, but the reaction method and conditions are not limited thereto, as long as the surface of the yarn used can be evenly activated. .

Meanwhile, the third step may further include filtering and washing after the reaction with the activator, but is not limited thereto. The washing may be performed again with water after washing with diluted acid solution, but is not limited thereto.

The surface-activated filament may form a metal coating layer on the surface by using a metal salt solution. In this case, the reaction of coating with the metal may be performed on the yarn in the slurry state. Thus, surface activated yarns can be prepared in slurry form by mixing with water prior to metal coating. Specifically, the slurry may be prepared by mixing the surface-activated yarn with water of 5 to 20 times its weight and stirring at a rate of 150 to 500 RPM, but is not limited thereto. The metal salt is a material providing a metal precursor to be coated, and the metal may be copper, nickel, gold, or silver.

Metal salts that can be used in the production method of the present invention may be a sulfate, acetate, carbonate, chloride, cyanide or nitrate of the metal, the ratio thereof Restrictive examples include copper sulfate, copper acetate, copper carbonate, nickel sulfate, nickel chloride, gold cyanide, gold chloride And silver nitrate. Non-limiting examples of complexing agents that can be used in the preparation method of the present invention are citric acid, sodium citrate, sodium phosphate, succinic acid, propionic acid, glycolic acid (glycolic acid), sodium acetate, ethylenediaminetetraacetate, ethylenediaminetetraacetate disodium, pyridine-3-sulfonyl chloride, potassium tartarate Potassium tartrate, potassium citrate, potassium borate, sodium borate, ammonia, methylamine and ammonium chloride may be included. Non-limiting examples of stabilizers that can be used in the production process of the present invention are lead acetate, thallium nitrate, vanadium oxide, citric acetate, sodium cyanide , Thiourea, triethanolamine, thioglycolic acid, acetylacetone and urea. Non-limiting examples of reducing agents that can be used in the preparation method of the present invention are sodium hypophosphite, sodium borohydride, formate, formaldehyde, diethylamine borane ), Dimethylamine borane, hydrazine, hydrazine sulfate, hydrazine sulfate, potassium borohydride, and potassium cyanoborohydride.

Furthermore, ammonium hydroxide, ammonia water, sulfuric acid, sulfuric acid, phosphoric acid, hydrochloric acid, sodium hydroxide and potassium hydroxide may be used as the pH adjusting agent. However, the present invention is not limited thereto.

The coating with the metal was sequentially added to each of the above-mentioned components in the surface-activated sand slurry, stirred, and then adjusted to a desired pH by adding a pH adjuster, at an increased temperature of 30 to 60 ° C., at 300 to 700 RPM. It may be performed for 10 to 60 minutes while stirring at a rate of, but is not limited thereto.

In the production method of the present invention, metal salts, complexing agents, stabilizers, and reducing agents and pH adjusting agents, which are components used in the fifth step of coating the metal, may be organically selected from each other. For example, if the metal salt is first determined according to the type of metal to be coated, a suitable combination of complexing agents, stabilizers, reducing agents and pH adjusting agents can be selected accordingly. As a specific example, in the embodiment of the present invention, in order to introduce a copper coating layer, copper sulfate was selected as the metal salt. Thus, sodium phosphate as a complexing agent, lead acetate as a stabilizer, and sodium hypophosphite as a reducing agent were used. The pH of the mixture was adjusted to 10 by adding ammonium hydroxide as a pH adjusting agent. As another example, in order to introduce a nickel coating layer, nickel sulfate was selected as the metal salt, ethylenediaminetetraacetate as the complexing agent, citric acid acetate as the stabilizer, and sodium hypophosphite as the reducing agent were used. PH was adjusted to 9 by adding ammonia water as a pH adjuster. In another example, in order to introduce a silver coating layer, silver nitrate was selected as a metal salt, and thus ethylenediaminetetraacetate disodium was used as a complexing agent, thallium nitrate as a stabilizer, and sodium borohydride as a reducing agent. The pH was adjusted to 10 by adding sodium hydroxide as a pH adjuster to the solution. However, these are merely examples of combinations of metal salts, complexing agents, stabilizers, reducing agents and pH adjusting agents, and the scope of the present invention is not limited thereto.

The metal-coated filament obtained through the above process may improve the interfacial adhesive force when blending with the polymer substrate through the sixth step of surface treatment with the second reactive silane.

For example, the second reactive silane compound may include triazinethiol propenyl dimethylpolysiloxane, triazinethiol butenyl dimethylpolysiloxane, gamma-ureidopropyltrimethoxysilane, and gamma-ureido. Selected from the group consisting of propyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane and gamma-glycidoxypropyltriethoxysilane Compounds to be used may be used alone or in combination of two or more, but is not limited thereto. In this case, the second reactive silane compound may be used as a solution of 0.05 to 0.3% by weight, or 0.4 to 1 part by weight based on 100 parts by weight of the metal-coated yarn, but the surface is in contact with the metal-coated yarn to be modified evenly. As long as it can be modified, it is not limited to this.

The polymer resin which is the basis of the heat dissipating compound of the present invention may be a polyolefin resin such as polyethylene, polypropylene, or ethylene copolymer; Polyester resins such as polyethylene terephthalate or polybutylene terephthalate; Nylon resins such as nylon 6, nylon 66 or nylon 12; Or a fluororesin.

Alternatively, the polymeric elastomer that is the basis of the heat dissipating compound of the present invention may be natural rubber, ethylene propylene (diene monomer) rubber (EPR or EPDM rubber), silicone rubber, nitrile butadiene rubber ( nitrile butadiene rubber (NBR) or chloroprene rubber.

In addition, the heat dissipating compound of the present invention, in addition to the metal-coated inorganic yarns treated with the second reactive silane prepared according to the first step to the sixth step on the base polymer substrate, metal oxides, inorganic heat dissipating agents, auxiliary heat dissipating agents and / or It may be prepared by further including a pore aid. For example, these components may be further added to the seventh step of combining the metal coated inorganic yarns treated with the second reactive silane with the polymeric substrate. The seventh step of combining the metal-coated inorganic yarn and the polymer substrate treated with the second reactive silane and the above-described component (s) optionally added is kneader, banbury, intensive, roll mill -mill) may be used using a mixing mixer, but is not limited thereto.

The metal oxide is added to impart flame retardancy and / or durability, and magnesium oxide, aluminum oxide, beryllium oxide, zirconium oxide, or hafnium oxide ) May be used, and the amount thereof may be 1 to 1000 parts by weight based on 100 parts by weight of yarn, but is not limited thereto. For example, when the content of the metal oxide is less than 1 part by weight, it may be difficult to achieve desired flame retardancy and / or durability, and when the content of the metal oxide is more than 1000 parts by weight, the physical properties of the heat dissipating compound itself may be reduced.

The inorganic heat radiating agent may include silicon carbide, aluminum nitride, boron nitride, or the like, but is not limited thereto. At this time, the inorganic heat radiation agent may be added in an amount of 1 to 100 parts by weight based on 100 parts by weight of yarn, but is not limited thereto. For example, when the inorganic heat dissipant content is less than 1 part by weight, it may be difficult to achieve a desired heat dissipation property, and when it is more than 100 parts by weight, the physical properties of the heat dissipating compound itself may be reduced.

As the auxiliary heat radiator, carbon black, carbon nanotubes, graphite, graphene, or the like may be used. At this time, the auxiliary heat radiation agent may be added in 0.05 to 10 parts by weight based on 100 parts by weight of yarn, but is not limited thereto. For example, when the auxiliary heat dissipating agent content is less than 0.05 parts by weight, it may be difficult to achieve the desired heat dissipation characteristics, and when it is more than 10 parts by weight, the physical properties of the heat dissipating compound itself may decrease.

Examples of the processing aid include hardening agents such as 2,4-dichlorobenzoyl peroxide; Lubricants such as calcium stearate; Antioxidants such as 2,6-di-tert-butyl-4-methylphenol (2,6-di-tert-butyl-4-methylphenol); Or a combination of two or more selected from them, but is not limited thereto. In this case, the total amount of the processing aid may be 0.1 to 10 parts by weight based on 100 parts by weight of yarn, but is not limited thereto.

A second aspect of the present invention includes an inorganic fiber yarn cut with a chipping machine equipped with a series of cutters arranged at intervals of 0.5 to 6 mm coated with a metal resin or polymer elastomer and evenly distributed reactive silanes. To provide polymer-based heat dissipating compounds.

For example, the polymer-based heat dissipating compound of the present invention can be prepared by the method described above.

The polymer-based heat dissipating compound thus prepared may contain metal coated inorganic fiber yarns surface-treated with 3 to 10 parts by weight of reactive silane relative to 100 parts by weight of polymer resin or polymer elastomer.

Specifically, the polymer-based heat dissipating compound of the present invention has an increased tensile strength of 8 to 35% compared to the polymer-based heat dissipating compound prepared by the same method, including the surface-untreated metal coated inorganic fiber yarn of the same kind, size and content. May have strength.

In addition, the polymer-based heat dissipating compound of the present invention exhibits an increased thermal conductivity of 15-25% compared to the polymer-based heat dissipating compound prepared by the same method, including the surface untreated metal coated inorganic fiber yarn of the same kind, size and content. Can have.

As described above, in the polymer-based heat dissipating compound of the present invention, the metal-coated inorganic fiber yarns can be evenly dispersed in the polymer without being aggregated based on the increased miscibility with the polymer by surface treatment with the reactive silane. It can exhibit better strength and / or thermal conductivity properties, and may further contain a higher content.

The polymer-based heat dissipating compound manufacturing method according to the present invention is a polymer substrate based on increased miscibility by treating the inorganic fiber yarn with a reactive silane, then coated with a metal, and then treated with a reactive silane to modify the surface to disperse in the polymer substrate. Since it can be distributed evenly within, it is possible to provide a heat dissipating compound that is lighter and has increased strength and / or thermal conductivity compared to the case of including a metal coated inorganic fiber yarn with no surface modification.

1 is a view showing the dispersibility of a metal coated inorganic yarn modified with an untreated or reactive silane inserted therein through a cross-sectional image of a heat dissipating compound prepared according to a specific embodiment of the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by these examples.

Example  1: Gamma With ureidopropyltrimethoxysilane Surface treatment  Copper coated carbon fiber Articles  Polyethylene Based Heat Resistant Compound  Produce

Step 1: weapon From long fiber yarn Articles  Manufacturing steps

The urethane resin, which is a sizing agent, was applied to the carbon fiber having a filament diameter of 20 μm and the number of filaments by 500 by impregnation, cut using a chipping machine equipped with a cutter with a cutting blade spacing of 1 mm, and then heated to 150 ° C. Continuously charged and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Reactivity To silane  Surface Treatment Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, and the mixture was stirred and mixed at 300 RPM. 100 g of desized carbon fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated carbon fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3 g obtained in step 2 above. Carbon fiber yarns treated with -aminopropyltrimethoxysilane were sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated carbon fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated carbon fiber yarn obtained in step 3 was added and dispersed with stirring at a speed of 300 RPM, thereby dispersing the surface-activated carbon fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 30 g of copper sulfate, 10 g of sodium phosphate, 1 g of lead acetate, and 10 g of tea were placed in a reactor equipped with a stirrer and a thermostat. After sequentially adding sodium hypophosphite, a surface-activated carbon fiber yarn slurry prepared in advance was added thereto, stirred at a speed of 500 RPM for 10 minutes, and 20 g of ammonium hydroxide was added to adjust the pH. The temperature was adjusted to 10 and the temperature was raised to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and the copper surface was coated with copper, and then filtered to separate from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain a copper coated carbon fiber yarn.

Step 5: Reactivity To silane  Surface Treatment Step-2

500 g of distilled water and 0.6 g of gamma-ureidopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a thermostat. Copper coated carbon fiber yarns were added, further stirred at 20 ° C. for 20 minutes, filtered, washed by spraying 200 g of water and coated with a gamma-ureidopropyltrimethoxysilane. Carbon fiber yarns were prepared.

Step 6: heat dissipation Compound  Manufacturing steps

1,000 g polyethylene resin in a 5 L kneader, copper coated carbon fiber yarns surface treated with 50 g gamma-ureidopropyltrimethoxysilane prepared from step 5, 200 g aluminum oxide ), 50 g of boron nitride, 1 g of carbon black, and 1 g of processing aid (antioxidant, 0.5 g of 2,6-di-tert-butyl-4-methylphenol (2 0.5 g of calcium stearate) were sequentially added with, 6-di-tert-butyl-4-methylphenol) and lubricant, melted and kneaded at 165 ° C. for 15 minutes, and then in the form of a lump dough. The polyethylene resin-based heat dissipating compound was prepared in a pellet form having a size of 2 to 3 mm through a melt extrusion process using a twin extruder made of a composition.

Example  2: gamma With ureidopropyltrimethoxysilane Surface treatment  Silicone rubber based heat dissipation containing copper coated carbon fiber yarn Compound  Produce

Step 1: preparing the yarn from the inorganic long fiber yarn

The urethane resin, which is a sizing agent, was applied to the carbon fiber having a filament diameter of 20 μm and the number of filaments by 500 by impregnation, cut using a chipping machine equipped with a cutter having a cutting blade spacing of 1 mm, and then heated to 150 ° C. Continuously charged and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat-treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, and the mixture was stirred and mixed at 300 RPM. 100 g of desized carbon fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated carbon fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3-aminopropyltrimethoxysilane obtained in step 2 were used. The treated carbon fiber filament was sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated carbon fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated carbon fiber yarn obtained in step 3 was added and dispersed with stirring at a speed of 300 RPM, thereby dispersing the surface-activated carbon fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 30 g of copper sulfate, 10 g of sodium phosphate, 1 g of lead acetate, and 10 g of sodium hypophosphite were sequentially added to a reactor equipped with a stirrer and a thermostat, and then the surface prepared in advance. Activated carbon fiber yarn slurry was added and stirred at a rate of 500 RPM for 10 minutes, 20 g of ammonium hydroxide was added to adjust the pH to 10 and the temperature was raised to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and the copper surface was coated with copper, and then filtered to separate from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain a copper coated carbon fiber yarn.

Step 5: Surface Treatment with Reactive Silane Step-2

500 g of distilled water and 0.6 g of gamma-ureidopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a thermostat, followed by stirring at a rate of 100 RPM. After adding a fiber yarn, the mixture was further stirred at 20 ° C. for 20 minutes, filtered, and washed by spraying 200 g of water to obtain a copper coated carbon fiber yarn coated with gamma-ureidopropyltrimethoxysilane. Prepared.

Step 6: heat dissipation compound manufacturing steps

1,000 g of silicon rubber was introduced into a 1 m roll mill to form a sheet on the surface of the roll mill, and 50 g of gamma-ureidopropyltrimethoxy prepared from step 5 was used. Copper coated carbon fiber yarns surface-treated with silane, 200 g aluminum oxide, 50 g boron nitride, 0.1 g carbon black, and 1 g processing aid (2,4-dichlorobenzoylfur as hardening agent) Oxide (2,4-dichlorobenzoyl peroxide) was sequentially added and kneaded at room temperature of 15 to 25 ° C. for 60 minutes to prepare a sheet-shaped silicone rubber-based heat dissipating compound.

Example  3: gamma With glycidoxypropyltrimethoxysilane Surface treatment  Silicone rubber based heat dissipation containing nickel coated carbon fiber yarn Compound  Produce

Step 1: preparing the yarn from the inorganic long fiber yarn

The urethane resin, which is a sizing agent, was applied to the carbon fiber having a filament diameter of 20 μm and the number of filaments by 500 by impregnation, and cut using a chipping machine equipped with a cutter with a cutting blade spacing of 1 mm. Continuously charged and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, followed by mixing at 300 RPM. 100 g of desized carbon fiber yarn obtained in step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated carbon fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3-aminopropyltrimethoxysilane obtained in step 2 were used. The treated carbon fiber filament was sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated carbon fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated carbon fiber yarn obtained in step 3 was added and dispersed with stirring at a speed of 300 RPM, thereby dispersing the surface-activated carbon fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 50 g of nickel sulfate, 10 g of ethylenediaminetetraacetate, 1 g of citric acetate, and 10 were placed in a reactor equipped with a stirrer and a thermostat. g of sodium hypophosphite was added sequentially, and then prepared surface-activated carbon fiber yarn slurry was added and stirred at a speed of 500 RPM for 10 minutes, and 20 g of ammonia water (50% ammonia water = 10 g ammonia and 10 g Distilled water) was added to adjust the pH to 9 and raise the temperature to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and then nickel was coated on the surface of the yarn, followed by filtration to separate it from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain nickel coated carbon fiber yarns.

Step 5: Surface Treatment with Reactive Silane Step-2

500 g of distilled water and 0.6 g of gamma-glycidoxypropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, followed by stirring at a rate of 100 RPM. g of nickel-coated carbon fiber yarn was added, further stirred at 20 ° C. for 20 minutes, filtered, washed by spraying 200 g of water and surface treated with gamma-glycidoxypropyltrimethoxysilane. Nickel coated carbon fiber yarns were prepared.

Step 6: heat dissipation compound manufacturing steps

1,000 g of silicon rubber was introduced into a 1 m roll mill to form a sheet shape on the surface of the roll mill, and 50 g of gamma-glycidoxypropyltrime prepared from step 5 was used. Nickel coated carbon fiber yarns surface-treated with oxysilane, 200 g aluminum oxide, 50 g boron nitride, 1 g carbon black, and 1 g processing aid (2,4-dichlorobenzoyl peroxide as hardener) After sequentially feeding and kneading at room temperature of 15 to 25 ℃ for 60 minutes, a sheet-like silicone rubber-based heat dissipating compound was prepared.

Example  4: Gamma With glycidoxypropyltrimethoxysilane Surface treatment  Nylon 6 Based Heat Resistant with Nickel Coated Fiberglass Yarn Compound  Produce

Step 1: weapon From long fiber yarn Articles  Manufacturing steps

Apply the sizing epoxy resin by impregnation method on glass fiber with filament diameter of 25 μm and number of filaments 1,000, cut it with a chipping machine equipped with a cutter with a cutting blade spacing of 2 mm, and then heat it to 150 ℃. Continuously added and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, followed by mixing at 300 RPM. 100 g of desized glass fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated glass fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3-aminopropyltrimethoxysilane obtained in step 2 were used. The treated glass fiber yarns were sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated glass fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated glass fiber yarns obtained in step 3 were added and dispersed with stirring at a speed of 300 RPM to prepare a surface-activated glass fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 50 g of nickel sulfate, 10 g of ethylenediaminetetraacetate, 1 g of citric acetate, and 10 were placed in a reactor equipped with a stirrer and a thermostat. g of sodium hypophosphite was sequentially added, and then, a surface-activated glass fiber yarn slurry prepared in advance was added thereto, stirred for 10 minutes at a speed of 500 RPM, and 20 g of ammonia water (50% ammonia water) was added to adjust the pH to 9. And the temperature was raised to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and then nickel was coated on the surface of the yarn, followed by filtration to separate it from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain nickel coated glass fiber yarns.

Step 5: Reactivity To silane  Surface Treatment Step-2

500 g of distilled water and 0.6 g of gamma-glycidoxypropyltrimethoxysilane were added to a reactor equipped with a stirrer and a thermostat, followed by stirring at a rate of 100 RPM. Nickel-coated glass fiber surface-treated with gamma-glycidoxypropyltrimethoxysilane by adding glass fiber yarn, further stirring at 20 ° C. for 20 minutes, then filtration and washing by spraying 200 g of water. The yarn was manufactured.

Step 6: heat dissipation Compound  Manufacturing steps

In a 5 L kneader, 1,000 g of Nilo 6 resin, nickel coated glass fiber yarns surface-treated with 50 g of gamma-ureidopropyltrimethoxysilane prepared from step 5, 200 g of aluminum oxide, 50 g of Boron nitride, 1 g of carbon black, and 1 g of a processing aid (0.5 g of 2,6-di-tert-butyl-4-methylphenol as antioxidant and 0.5 g of calcium stearate as lubricant) were added sequentially After melting and kneading at 255 ° C. for 20 minutes, a nylon 6 resin-based heat dissipating compound was prepared in a pellet form having a size of 2 to 3 mm through a melt extrusion molding process using a twin screw extruder.

Example  5: Gamma With ureidopropyltrimethoxysilane Surface treatment  Polybutylene terephthalate based heat dissipation containing silver coated ceramic fiber yarn Compound  Produce

Step 1: weapon From long fiber yarn Articles  Manufacturing steps

Apply urethane resin, a sizing agent, by impregnation method on ceramic fiber with filament diameter of 10 μm and filament number 500, cut it using a chipping machine equipped with a cutter with a cutting blade spacing of 1 mm, and then to a heating furnace maintained at 150 ° C. Continuously added and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of gamma-glycidoxypropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, and the mixture was stirred and mixed at 300 RPM. 100 g of desized ceramic fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with a spray of 200 g of water to gamma-glycidoxypropyltrimethoxy. Ceramic fiber yarns treated with silane were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.7 g of palladium chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of gamma-glycidoxy obtained in step 2 above. The ceramic fiber yarns treated with propyltrimethoxysilane were added sequentially, and the surface was activated while stirring at a rate of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated ceramic fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated ceramic fiber yarns obtained in step 3 were added and dispersed with stirring at a speed of 300 RPM to prepare a surface-activated ceramic fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 50 g of silver nitrate, 10 g of diisodium ethylenediaminetetraacetate, 1 g of thallium nitrate, and a reactor equipped with a stirrer and a thermostat were used. After 10 g of sodium borohydride was added sequentially, a surface-activated ceramic fiber yarn slurry prepared in advance was added thereto, stirred at a speed of 500 RPM for 10 minutes, and 20 g of sodium hydroxide was added to adjust the pH. Adjust to 10 and raise the temperature to 50 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and the silver surface was coated with silver, and then filtered to separate from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain a silver coated ceramic fiber yarn.

Step 5: Surface Treatment with Reactive Silane Step-2

500 g of distilled water and 0.6 g of gamma-ureidopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a thermostat, and 100 g of silver-coated carbon obtained from step 4 was stirred at a rate of 100 RPM. After adding a fiber yarn, the mixture was further stirred at 20 ° C. for 20 minutes, filtered, and washed by spraying 200 g of water to obtain a silver coated ceramic fiber yarn surface-treated with gamma-ureidopropyltrimethoxysilane. Prepared.

Step 6: heat dissipation Compound  Manufacturing steps

1,000 g of polybutylene terephthalate in a 5 L kneader, silver coated ceramic fiber yarn coated with 50 g of gamma-ureidopropyltrimethoxysilane prepared from step 5, 200 g of oxidation Aluminum, 50 g boron nitride, 1 g carbon black, and 1 g processing aid (0.5 g 2,6-di-tert-butyl-4-methylphenol as antioxidant and 0.5 g calcium stearate with lubricant) Were added sequentially and melted and kneaded at 275 ° C. for 15 minutes, and then made into a composition in the form of a lump dough to form a polybutylene terephthalate in pellet form having a size of 2 to 3 mm through a melt extrusion molding process using a twin screw extruder. Based heat dissipating compound was prepared.

Example  6: Gamma With glycidoxypropyltrimethoxysilane Surface treatment  Ethylenepropylene rubber based heat dissipation containing nickel coated carbon fiber yarn Compound  Produce

Step 1: preparing the yarn from the inorganic long fiber yarn

The urethane resin, which is a sizing agent, was applied to the carbon fiber having a filament diameter of 20 μm and the number of filaments by 500 by impregnation, cut using a chipping machine equipped with a cutter with a cutting blade spacing of 1 mm, and then heated to 150 ° C. Continuously charged and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, followed by mixing at 300 RPM. 100 g of desized carbon fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated carbon fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3-aminopropyltrimethoxysilane obtained in step 2 were used. The treated carbon fiber filament was sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated carbon fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated carbon fiber yarn obtained in step 3 was added and dispersed with stirring at a speed of 300 RPM, thereby dispersing the surface-activated carbon fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 50 g of nickel sulfate, 10 g of ethylenediaminetetraacetate, 1 g of citric acid acetate, and 10 g of sodium hypophosphite were sequentially added to a reactor equipped with a stirrer and a thermostat. The prepared surface-activated carbon fiber yarn slurry was added and stirred at a speed of 500 RPM for 10 minutes, 20 g of ammonia water (50% ammonia water) was added to adjust the pH to 9 and the temperature was raised to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and then nickel was coated on the surface of the yarn, followed by filtration to separate it from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain nickel coated carbon fiber yarns.

Step 5: Surface Treatment with Reactive Silane Step-2

500 g of distilled water and 0.6 g of gamma-glycidoxypropyltrimethoxysilane were added to a reactor equipped with a stirrer and a thermostat, followed by stirring at a rate of 100 RPM. Nickel-coated carbon fiber surface-treated with gamma-glycidoxypropyltrimethoxysilane by addition of carbon fiber yarn, further stirred at 20 ° C. for 20 minutes, then filtered, washed by spraying 200 g of water The yarn was manufactured.

Step 6: heat dissipation compound manufacturing steps

Nickel coated carbon fiber surface treated with 1,000 g ethylene propylene rubber in a 10 L banbury mixer, 50 g gamma-glycidoxypropyltrimethoxysilane prepared from step 5 above. After dipping, 200 g of aluminum oxide, 50 g of boron nitride, and 0.01 g of carbon black were sequentially added and kneaded at 150 ° C. for 30 minutes, 1 g of a processing aid (dicumyl peroxide as a hardener) was used. (dicumyl peroxide)) was mixed for 15 minutes to prepare a sheet-like ethylene propylene rubber based heat dissipating compound.

Example  7: Triazinethiol Propenyl With dimethylpolysiloxane Surface treatment  Preparation of Polyethylene-based Heat Dissipating Compounds Containing Nickel Coated Carbon Fiber Yarn

Step 1: preparing the yarn from the inorganic long fiber yarn

The urethane resin, which is a sizing agent, was applied to the carbon fiber having a filament diameter of 20 μm and the number of filaments by 500 by impregnation, cut using a chipping machine equipped with a cutter with a cutting blade spacing of 1 mm, and then heated to 150 ° C. Continuously charged and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, followed by mixing at 300 RPM. 100 g of desized carbon fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated carbon fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3-aminopropyltrimethoxysilane obtained in step 2 were used. The treated carbon fiber filament was sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated carbon fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated carbon fiber yarn obtained in step 3 was added and dispersed with stirring at a speed of 300 RPM, thereby dispersing the surface-activated carbon fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 50 g of nickel sulfate, 10 g of ethylenediaminetetraacetate, 1 g of citric acid acetate, and 10 g of sodium hypophosphite were sequentially added to a reactor equipped with a stirrer and a thermostat. The prepared surface-activated carbon fiber yarn slurry was added and stirred at a speed of 500 RPM for 10 minutes, 20 g of ammonia water (50% ammonia water) was added to adjust the pH to 9 and the temperature was raised to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and then nickel was coated on the surface of the yarn, followed by filtration to separate it from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain nickel coated carbon fiber yarns.

Step 5: Surface Treatment with Reactive Silane Step-2

500 g of distilled water and 0.6 g of triazinethiol propenyl dimethylpolysiloxane were added to a reactor equipped with a stirrer and a temperature controller, and 100 g of nickel obtained from step 4 was stirred at a rate of 100 RPM. Nickel coated carbon fiber yarn coated with triazinethiol propenyl dimethylpolysiloxane by addition of coated carbon fiber yarn, further stirring at 20 ° C. for 20 minutes, followed by filtration and washing by spraying with 200 g of water. Was prepared.

Step 6: heat dissipation compound manufacturing steps

1000 g of silicone rubber was charged into a 1 m roll mill and molded into a sheet shape on the surface of the roll mill, and 200 g of nickel-coated carbon fiber yarn treated with 50 g of triazinethiol propenyl dimethylpolysiloxane prepared from step 5 above. Aluminum oxide, 50 g of boron nitride, 1 g of carbon black, and 1 g of a processing aid (2,4-dichlorobenzoyl peroxide as a hardener) were sequentially added and kneaded at room temperature of 15 to 25 ° C. for 60 minutes. After that, a sheet-shaped silicone rubber-based heat dissipating compound was prepared.

Example  8: Gamma With ureidopropyltrimethoxysilane Surface treatment  Nickel Coated Carbon Fiber Articles  Silicone Rubber Based Heat Resistant Compound  Produce

Step 1: preparing the yarn from the inorganic long fiber yarn

The urethane resin, which is a sizing agent, was applied to the carbon fiber having a filament diameter of 20 μm and the number of filaments by 500 by impregnation, cut using a chipping machine equipped with a cutter with a cutting blade spacing of 1 mm, and then heated to 150 ° C. Continuously charged and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, followed by mixing at 300 RPM. 100 g of desized carbon fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated carbon fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3-aminopropyltrimethoxysilane obtained in step 2 were used. The treated carbon fiber filament was sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated carbon fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated carbon fiber yarn obtained in step 3 was added and dispersed with stirring at a speed of 300 RPM, thereby dispersing the surface-activated carbon fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 50 g of nickel sulfate, 10 g of ethylenediaminetetraacetate, 1 g of citric acid acetate, and 10 g of sodium hypophosphite were sequentially added to a reactor equipped with a stirrer and a thermostat. The prepared surface-activated carbon fiber yarn slurry was prepared and stirred at a speed of 500 RPM for 10 minutes, 20 g of ammonia water (50% ammonia water) was added to adjust the pH to 9 and the temperature was raised to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and then nickel was coated on the surface of the yarn, followed by filtration to separate it from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain nickel coated carbon fiber yarns.

Step 5: Surface Treatment with Reactive Silane Step-2

500 g of distilled water and 0.6 g of gamma-ureidopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a thermostat, followed by stirring at a rate of 100 RPM. After adding a fiber yarn, the mixture was further stirred at 20 ° C. for 20 minutes, filtered, and washed by spraying 200 g of water to obtain a nickel coated carbon fiber yarn surface-treated with gamma-ureidopropyltrimethoxysilane. Prepared.

Step 6: heat dissipation compound manufacturing steps

1 g roll mill was charged with 1,000 g of silicone rubber and molded into a sheet shape on the surface of the roll mill, and a nickel coated carbon fiber yarn treated with 50 g of gamma-ureidopropyltrimethoxysilane prepared in Step 5; 200 g of aluminum oxide, 50 g of boron nitride, 1 g of carbon black, and 1 g of a processing aid (2,4-dichlorobenzoyl peroxide as a hardener) were sequentially added, followed by 60 minutes at a temperature of 15 to 25 ° C. After kneading, a sheet-shaped silicone rubber based heat dissipating compound was prepared.

Example 9: 3 - With aminopropyltrimethoxysilane Surface treatment  Nickel coating Carbon fiber Articles  Silicone Rubber Based Heat Resistant Compound  Produce

Step 1: preparing the yarn from the inorganic long fiber yarn

The urethane resin, which is a sizing agent, was applied to the carbon fiber having a filament diameter of 20 μm and the number of filaments by 500 by impregnation, cut using a chipping machine equipped with a cutter with a cutting blade spacing of 1 mm, and then heated to 150 ° C. Continuously charged and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, followed by mixing at 300 RPM. 100 g of desized carbon fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated carbon fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3-aminopropyltrimethoxysilane obtained in step 2 were used. The treated carbon fiber filament was sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated carbon fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated carbon fiber yarn obtained in step 3 was added and dispersed with stirring at a speed of 300 RPM, thereby dispersing the surface-activated carbon fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 50 g of nickel sulfate, 10 g of ethylenediaminetetraacetate, 1 g of citric acid acetate, and 10 g of sodium hypophosphite were sequentially added to a reactor equipped with a stirrer and a thermostat. The prepared surface-activated carbon fiber yarn slurry was added and stirred at a speed of 500 RPM for 10 minutes, 20 g of ammonia water (50% ammonia water) was added to adjust the pH to 9 and the temperature was raised to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and then nickel was coated on the surface of the yarn, followed by filtration to separate it from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain nickel coated carbon fiber yarns.

Step 5: Surface Treatment with Reactive Silane Step-2

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, and 100 g of nickel-coated carbon fiber obtained from step 4 was stirred at a rate of 100 RPM. Coated yarn was added, further stirred at 20 ° C. for 20 minutes, filtered, washed by spraying 200 g of water to prepare a nickel coated carbon fiber yarn coated with 3-aminopropyltrimethoxysilane. .

Step 6: heat dissipation compound manufacturing steps

1,000 g of silicone rubber was introduced into a 1 m roll mill and molded into a sheet shape on the surface of the roll mill, and the nickel-coated carbon fiber filament coated with 50 g of 3-aminopropyltrimethoxysilane prepared in Step 5, 200 g of aluminum oxide, 50 g of boron nitride, 1 g of carbon black, and 1 g of a processing aid (2,4-dichlorobenzoyl peroxide as a hardening agent) were sequentially added, and the mixture was kept at a temperature of 15 to 25 ° C. for 60 minutes. After kneading, a sheet-shaped silicone rubber based heat dissipating compound was prepared.

Comparative example  1: surface Unprocessed  Nickel coating Carbon fiber Articles  Silicone Rubber Based Heat Resistant Compound  Produce

Step 1: preparing the yarn from the inorganic long fiber yarn

The urethane resin, which is a sizing agent, was applied to the carbon fiber having a filament diameter of 20 μm and the number of filaments by 500 by impregnation, cut using a chipping machine equipped with a cutter with a cutting blade spacing of 1 mm, and then heated to 150 ° C. Continuously charged and dried to prepare a sized carbon fiber yarns. The sized carbon fiber yarns were heat treated in a heating furnace maintained at 500 ° C. for 6 hours to obtain desized carbon fiber yarns from which the sizing agent was removed.

Step 2: Surface Treatment with Reactive Silane Step-1

500 g of distilled water and 0.6 g of 3-aminopropyltrimethoxysilane were added to a reactor equipped with a stirrer and a temperature controller, followed by mixing at 300 RPM. 100 g of desized carbon fiber yarn obtained from step 1 was added to the solution, stirred at 20 ° C. for 20 minutes, filtered, and washed with spraying 200 g of water to 3-aminopropyltrimethoxysilane. Treated carbon fiber yarns were prepared.

Step 3: Surface Activation to Transition Metal

In a reactor equipped with a stirrer and a thermostat, 1,000 g of distilled water, 0.6 g of platinum chloride, 10 g of tin chloride, 60 g of hydrochloric acid, and 100 g of 3-aminopropyltrimethoxysilane obtained in step 2 were used. The treated carbon fiber filament was sequentially added, and the surface was activated while stirring at a speed of 500 RPM for 20 minutes and filtered. The filtered surface activated carbon fiber yarns were washed with 200 g of 10% by weight aqueous hydrochloric acid solution (180 g distilled water, 20 g hydrochloric acid) and washed again with 500 g distilled water to obtain surface activated carbon fiber yarns.

Step 4: coating the metal

Into a reactor equipped with a stirrer and a temperature controller containing 1,000 g of distilled water, 100 g of surface-activated carbon fiber yarn obtained in step 3 was added and dispersed with stirring at a speed of 300 RPM, thereby dispersing the surface-activated carbon fiber yarn slurry. Prepared.

Subsequently, 1,000 g of distilled water, 50 g of nickel sulfate, 10 g of ethylenediaminetetraacetate, 1 g of citric acetate, and 10 were placed in a reactor equipped with a stirrer and a thermostat. g of sodium hypophosphite was added sequentially, and then prepared surface-activated carbon fiber yarn slurry was added and stirred at a speed of 500 RPM for 10 minutes, and 20 g of ammonia water (50% ammonia water = 10 g ammonia and 10 g Distilled water) was added to adjust the pH to 9 and raise the temperature to 45 ° C. The reaction was continued for 20 minutes while continuing to stir at a rate of 500 RPM, and then nickel was coated on the surface of the yarn, followed by filtration to separate it from the reaction solution. The separated product was washed by spraying 1,000 g of water, and then dried at 80 ° C. to obtain nickel coated carbon fiber yarns.

Step 5: heat dissipation Compound  Manufacturing steps

1,000 g of silicon rubber was added to a 1 m roll mill and molded into a sheet shape on the surface of the roll mill, and 50 g of nickel coated carbon fiber yarn obtained from step 4, 200 g of aluminum oxide, 50 g of boron nitride, 1 g of carbon black, and 1 g of a processing aid (2,4-dichlorobenzoyl peroxide as a hardener) were sequentially added and kneaded at room temperature of 15 to 25 ° C. for 60 minutes, and then the sheet Shaped silicone rubber based heat dissipating compound was prepared.

Experimental Example  1: reactivity With silane Surface treatment  Metal Coated Inorganic Fiber Articles  Polymer based heat dissipation Compound  Characterization

The cross sections of the representative specimens of Examples 3, 7, 8, and 9 and Comparative Example 1 among the specimens prepared according to the above Examples and Comparative Examples were confirmed by enlarging 200 times by using a video microscope, and the results were confirmed. 1 is shown. As shown in FIG. 1, the dispersibility of the inorganic fiber yarns is significantly improved in the polymer-based heat dissipating compound containing the metal-coated inorganic fiber yarns surface-treated with the series of reactive silanes according to the present invention. No entanglement, which appeared in polymer-based heat dissipating compounds containing metal-coated inorganic fiber yarns, was not found.

In addition, the strength of the specimens were prepared in the dumbbell (bell) specimen of the IEC 68011-1-1 standard and measured the strength at a speed of 200 mm / min with a universal testing machine. In addition, using a laser flash analyzer (LFA), the thermal conductivity was measured for a disk-shaped specimen of 25.4 mm in diameter, 0.1 to 0.4 mm in thickness. Dispersibility, tensile strength and thermal conductivity for the specimens of the present invention are shown in Table 1 below.

Psalter Dispersibility Tensile Strength (MPa) Thermal Conductivity (W / mK) Example 3 Great 6.7 3.6 Example 7 Great 6.9 3.7 Example 8 Great 7.3 3.6 Example 9 Great 6.1 3.5 Comparative Example 1 Bad 5.6 3.0

Claims (26)

A first step of preparing a yarn from an inorganic long fiber yarn;
A second step of treating the surface of the yarn with the first reactive silane by introducing the yarn obtained from the first step into a reactor containing an aqueous solution of the first reactive silane compound;
A third step of activating the surface of the silane treated yarn by treating with an aqueous solution containing an activator, a metal salt reducing agent, and an acid to provide transition metal ions;
A fourth step of preparing the surface-activated yarn slurry by injecting and stirring the surface-activated yarn and water into the reactor;
After adding a metal salt, a complexing agent, a stabilizer, and a reducing agent to water, the mixed solution was added to the surface-activated yarn slurry solution prepared from the fourth step, and then the pH was adjusted to 4 to 14 by adding a pH regulator, followed by stirring. A fifth step of coating a metal on the surface of the activated yarn by reacting at 30 to 95 ° C;
A sixth step of treating the surface of the metal-coated yarn with the second reactive silane by adding a metal-coated yarn to the surface obtained from the fifth step in an aqueous solution of the second reactive silane compound and reacting at 20 to 30 ° C; And
And a seventh step of injecting and blending a metal-coated yarn coated with a polymer resin or a polymer elastomer and a second reactive silane obtained from the sixth step into a mixing mixer.
The method of claim 1,
The first step,
Step 1-1 to apply a polymer resin sizing agent on the inorganic long fiber yarn;
A first step of drying the wet long-fiber yarn in which the sizing agent is applied to the surface obtained from step 1-1 by cutting with a chucking machine, and then putting the same into a hot air drying furnace maintained at 150 to 250 ° C .; And
It is composed of the 1-3 steps to remove the sizing agent, the manufacturing method.
The method of claim 1,
The inorganic long fiber yarn is a carbon, glass, alumina, ceramic or aramid (aramid) material, manufacturing method.
The method of claim 2,
The sizing agent is an epoxy, urethane, acrylic or polyvinyl alcohol, manufacturing method.
The method of claim 2,
Step 1-3 is achieved by carbonizing by heat treatment for 1 to 10 hours in a heating furnace maintained at 300 to 700 ℃, or by washing with water.
The method of claim 1,
The first reactive silane compound may be gamma-ureidopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane (gamma-glycidoxypropyltrimethoxysilane) and gamma-glycidoxypropyltriethoxysilane (gamma-glycidoxypropyltriethoxysilane) It is selected, manufacturing method.
The method of claim 1,
The activator is selected from the group consisting of platinum chloride, platinum chloride (palladium chloride) and gold chloride (gold chloride).
The method of claim 1,
The metal salt reducing agent is tin chloride (tin chloride), manufacturing method.
The method of claim 1,
The acid is hydrochloric acid or sulfuric acid, the production method.
The method of claim 1,
The metal salt may be copper sulfate, copper acetate, copper carbonate, copper sulfate, nickel sulfate, nickel chloride, gold cyanide, gold chloride and The production method is selected from the group consisting of silver nitrate.
The method of claim 1,
The complexing agent may be citric acid, sodium citrate, sodium phosphate, succinic acid, propionic acid, glycolic acid, glycolic acid, sodium acetate, Ethylenediaminetetraacetate, ethylenediaminetetraacetate disodium ethylenediaminetetraacetate, pyridine-3-sulfonyl chloride, potassium tartrate, potassium citrate, boric acid Sodium (sodium borate), ammonia (ammonia), methylamine (methylamine) and ammonium chloride (ammonium chloride) is selected from the group consisting of.
The method of claim 1,
The stabilizer is lead acetate, thallium nitrate, vanadium oxide, vanadium oxide, citric acetate, sodium cyanide, thiourea, triethanolamine , Thioglycolic acid (thioglycolic acid), acetylacetone (acetylacetone) and urea (urea) is selected from the group consisting of.
The method of claim 1,
The reducing agent is sodium hypophosphite, sodium borohydride, formate, formaldehyde, formaldehyde, diethylamine borane, dimethylamine borane, hydrazine ( hydrazine), hydrazine sulfate, potassium borohydride and potassium cyanoborohydride.
The method of claim 1,
The pH adjusting agent is selected from the group consisting of ammonium hydroxide, aqueous ammonia, sulfuric acid, sulfuric acid, phosphoric acid, hydrochloric acid, sodium hydroxide and potassium hydroxide. That, the manufacturing method.
The method of claim 1,
The second reactive silane compound is triazinethiol propenyl dimethylpolysiloxane, triazinethiol butenyl dimethylpolysiloxane, gamma-ureidopropyltrimethoxysilane, gamma-ureidopropyltrier Group consisting of oxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, and gamma-glycidoxypropyltriethoxysilane It is selected from.
The method of claim 1,
The polymer resin is selected from the group consisting of polyolefin resin, polyester resin, nylon resin and fluorine resin.
The method of claim 1,
The polymer elastomer may include natural rubber, ethylene propylene (diene monomer) rubber (EPR or EPDM rubber), silicone rubber, nitrile butadiene rubber (NBR) and chloroprene rubber ( chloroprene rubber) is selected from the group consisting of, manufacturing method.
The method of claim 1,
In the seventh step, a metal oxide selected from the group consisting of magnesium oxide, aluminum oxide, aluminum oxide, beryllium oxide, zirconium oxide, and hafnium oxide is further added. the compounding and will, method.
The method of claim 1,
Of the first SiC (silicone carbide), aluminum nitride (nitride aluminium) and boron nitride (boron nitride) may be added and blended with the inorganic heat claim selected from the group consisting in the step 7, the method of manufacturing.
The method of claim 1,
In the seventh step, the carbon black, carbon nanotubes (carbon nanotube), graphite (graphite) and graphene (graphite), further comprising an auxiliary heat radiation agent selected from the group consisting of graphene (graphene).
The method of claim 1,
Wherein the formulation further combination of two or more of the processing aid in the step 7 that the curing agent, a lubricant, an antioxidant, or selected from these and will, method.
Inorganic fiber yarns cut with a chipping machine equipped with a series of cutters arranged at intervals of 0.5 to 6 mm coated with a metal-coated surface coated with a polymer resin or polymer elastomer and evenly distributed reactive silanes,
A polymer based heat dissipating compound prepared by the method of any one of claims 1 to 21.
delete The method of claim 22,
A polymer-based heat dissipating compound comprising a metal coated inorganic fiber yarn surface-treated with 3 to 10 parts by weight of reactive silane relative to 100 parts by weight of polymer resin or polymer elastomer.
The method of claim 22,
A polymer based heat dissipating compound having a tensile strength increased by 8 to 35% compared to a polymer based heat dissipating compound made by the same method, including a surface untreated metal coated inorganic fiber yarn of the same kind, size and content.
The method of claim 22,
A polymer based heat dissipating compound, wherein the polymer based heat dissipating compound has a 15 to 25% increased thermal conductivity compared to a polymer based heat dissipating compound prepared by the same method, including a surface untreated metal coated inorganic fiber yarn of the same kind, size and content.

Images