KR102053326B1 - Composite sheet having an excellent thermal and electric conductivity and manugacturing method there of - Google Patents

Abstract

materials; A primer layer formed on at least one surface of the substrate and including a copolymer of an epoxy compound and an amino alkoxysilane; And a conductive sheet formed on the primer layer, the conductive layer including a carbon-based compound and a polymer binder, and having an average density of 1.0 to 5.0 g / cc, having excellent thermal conductivity and electrical conductivity.

Description

COMPOSITE SHEET HAVING AN EXCELLENT THERMAL AND ELECTRIC CONDUCTIVITY AND MANUGACTURING METHOD THERE OF}

The present invention is used as a heat dissipating material for various electrical and electronic processing equipment, including semiconductor processing equipment, and relates to a composite sheet excellent in thermal conductivity and electrical conductivity, and a manufacturing method thereof.

Semiconductor manufacturing process equipment using plasma, such as vacuum deposition and dry etching, suffers from severe thermal problems and various electromagnetics due to high plasma density and driving power during process operation. (electro-magnetic) problems arise. Due to these thermal and electromagnetic problems, the process yield of the silicon wafer is greatly affected, and in particular, it is a big problem to solve the thermal problem of the upper and lower electrode portions applying high voltage.

As a means to solve the thermal problem of the electrode part of semiconductor process equipment and the electromagnetic instability related to plasma, the material of high thermal conductivity and electric conductivity is attached to the electrode part of the process equipment to enable fast heat transfer and local heat concentration problem. I am using a method to solve the problem. In particular, at this time, since the thermal conductivity and the electrical conductivity of the heat dissipation material used in the inside of the electrode portion has a great influence on the process yield, research has been made to develop a material of the heat generating material excellent in thermal conductivity and electrical conductivity.

Meanwhile, conventionally, as a heat dissipating material for semiconductor processing equipment, a composite material in which conductive carbon materials are coated on both sides of metal foils such as Al and Cu is widely used, but the metal foil is continuously exposed in an extreme plasma environment. There is a problem that the conductive carbon material and the separation (delamination). This acts as a factor affecting the process yield as the semiconductor process time passes, and an attempt has been made to find a solution to solve this problem.

The present invention is to provide a composite sheet excellent in durability and excellent thermal conductivity and electrical conductivity due to high density because the peeling phenomenon does not occur even after prolonged exposure at high temperature, and a method of manufacturing the same.

According to one embodiment of the invention, the substrate; A primer layer formed on at least one surface of the substrate and including a copolymer of an epoxy compound and an amino alkoxysilane; And a conductive layer formed on the primer layer, the conductive layer including a carbon-based compound and a polymer binder, and having an average density of 1.0 to 5.0 g / cc, a composite sheet having excellent thermal conductivity and electrical conductivity.

In addition, according to another embodiment of the present invention by applying and curing the primer composition on at least one side of the substrate, to form a primer layer comprising a copolymer of an epoxy compound and an aminoalkoxysilane; Coating and curing the conductive coating liquid composition on the primer layer to form a conductive layer including a carbon-based compound and a polymer binder; And compressing the laminate including the substrate, the primer layer, and the conductive layer. A composite sheet manufacturing method having excellent thermal conductivity and electrical conductivity may be provided.

Hereinafter, a composite sheet having excellent thermal conductivity and electrical conductivity according to a specific embodiment of the present invention will be described in detail.

The composite sheet having excellent thermal conductivity and electrical conductivity according to the embodiment includes a substrate, a primer layer formed on at least one surface of the substrate, and a conductive layer formed on the primer layer, and has an average density of 1.0 to 5.0 g / cc. to be.

In addition, the composite sheet having excellent thermal conductivity and electrical conductivity may be used as a heat dissipation material for electric and electronic process equipment, and may be used as a gasket included in a semiconductor vacuum plasma equipment (especially a dry etching process equipment). have.

On the other hand, the heat dissipation material for semiconductor processing equipment has a great influence on the process yield of the semiconductor manufacturing process according to the thermal conductivity and electrical conductivity. Accordingly, the inventors of the present invention to produce a composite sheet having a mean density of 1.0 to 5.0 g / cc by pressing a laminate comprising a substrate, a primer layer, and a conductive layer in sequence and applying it as a heat radiation material for semiconductor process equipment In this case, the high density of the composite sheet is excellent in thermal conductivity and electrical conductivity, thereby confirming through experiments that the process yield of the semiconductor manufacturing process can be excellent through experiments and completed the invention.

More specifically, the thermal conductivity and the electrical conductivity of the composite sheet can be improved by increasing the density of the composite sheet. In particular, according to Equation 1, since the density has a relationship proportional to the thermal conductivity, the density of the composite sheet is increased. It can be seen that the higher the value significantly affects the improvement of thermal conductivity.

[Equation 1]

λ = α Ⅹ Cp Ⅹ ρ

In Equation 1,

λ is thermal conductivity (W / mK), α is thermal diffusivity (mm ² / sec), Cp is specific heat (J / gK), and ρ is density (g / cc).

The average density of the composite sheet affecting the thermal and electrical conductivity of the composite sheet may be 1.0 to 5.0 g / cc, 1.2 to 4.0 g / cc, or 1.5 to 3.0 g / cc. When the average density of the composite sheet is less than 1.0 g / cc, thermal conductivity and electrical conductivity may be lowered. When the average density of the composite sheet is greater than 5.0 g / cc, adhesion characteristics and coating film strength to the substrate may be reduced.

The higher the density of the composite sheet, the lower the content of pores contained in the composite sheet. For example, the porosity of the composite sheet may be 5% or less, 0.1 to 4%, 0.2 to 3%, or 0.5 to 2%. When the porosity of the composite sheet exceeds 5%, thermal conductivity and electrical conductivity may decrease.

In addition, the composite sheet may have a thickness of 50 to 500㎛. If the thickness of the composite sheet is less than 50㎛ may worsen the thermal conductivity and coating workability, if the thickness of more than 500㎛ may include a substrate of too thick thickness, the flexibility is also lowered and the thermal conductivity and coating workability may be worse.

The composite sheet may be in a state in which the substrate, the primer layer, and the conductive layer are sequentially stacked and compressed, and thus, the density of the composite sheet may be increased, thereby improving thermal conductivity and electrical conductivity. For example, the composite sheet may have a thermal conductivity of 1.0 W / mK or more, 2.0 to 6.0 W / mK, or 3.5 to 4.5 W / mK. On the other hand, the composite sheet may have a resistance of less than 100 kPa, 10 to 100 kPa, or 40 to 90 kPa.

The base material included in the composite sheet according to the embodiment is a layer for supporting the composite sheet, for example, may be a metal thin film, plastic, paper, non-woven fabric, glass-fiber, or metal mesh have. When the substrate is a metal thin film, aluminum (Al), gold (Au), silver (Ag), copper (Cu), nickel (Ni), tin (Sn), zinc (Zn), tungsten (W) and iron ( It may be one or two or more alloys selected from the group consisting of Fe), and among them, may be composed of aluminum or an aluminum alloy which is advantageous in terms of weight and price.

The plastic that can be used as the substrate is not particularly limited and may be selected from materials that can be used as a known plastic substrate. For example, with cellulose acetate, polyimide, polycarbonate, polyester, polystyrene, polyolefin, polymethylmethacrylate, polysulfone, polyethersulfone, polyetherketone, polyetherimide, polyoxyethylene and polyethylethylketone It may be one or more selected from the group consisting of.

The thickness of the substrate included in the composite sheet of the embodiment is not particularly limited, but may be 10 to 800 μm, 10 to 250 μm, or 10 to 100 μm. If the thickness of the substrate is less than 10㎛ may degrade the physical properties and coating workability of the entire composite sheet, if it exceeds 300㎛ may include a substrate of too thick thickness to reduce the flexibility and also worsen thermal conductivity and coating workability have.

A primer layer is formed on at least one surface of the substrate, and the primer layer includes a copolymer of an epoxy compound and an aminoalkoxysilane. The copolymer of the epoxy compound and the aminoalkoxysilane has many crosslinking points due to the three-dimensional network structure of the epoxy functional group and may have a high reactivity with the hydroxyl group (-OH) present on the surface of the coating substrate by the aminoalkoxy group. Accordingly, the primer layer has a high adhesion to the coating substrate and has a high cross-liking density, so that the primer layer itself and the composite sheet including the same have a long-term reliability at high temperature. This can be excellent. Therefore, the composite sheet of the embodiment including the primer layer may have a property that the peeling phenomenon does not occur even after prolonged exposure at a high temperature, the durability is remarkably excellent.

The copolymer included in the primer layer is a copolymer of the epoxy compound and the aminoalkoxysilane, and the weight ratio of the epoxy compound and the aminoalkoxysilane is 1: 0.2 to 30, 1: 0.5 to 15, or 1: 1 to 2 Can be. When the weight ratio of the epoxy compound and the aminoalkoxysilane is less than 1: 0.2, the adhesion to the coating substrate may be deteriorated, and when the weight ratio is greater than 1:30, the cross-liking density may be lowered to reduce long-term reliability at high temperatures. .

The copolymer is produced by polymerization of the epoxy compound and aminoalkoxysilane, and the weight average molecular weight (Mw) of the copolymer is 10,000 to 900,000 g / mol, 30,000 to 700,000 g / mol, or 100,000 to 500,000 g / mol Can be. If the weight average molecular weight is less than 10,000g / mol has a low cross-linking point (cross-linking point), the cross-linking density (low), the reaction site of the amino alkoxy group is small, the adhesion to the coating substrate may also be lowered If it exceeds 900,000 g / mol, the cross-linking point is too high, resulting in a hardened coating sheet, and high viscosity, making it difficult to compound.

In addition, the copolymer of the epoxy compound and the aminoalkoxysilane may have a viscosity of 10 to 300,000cps, 20 to 30,000cps, or 30 to 3,000cps. If the viscosity is less than 10 cps, the primer layer may be brittle, so that the punching process may be difficult. If the viscosity exceeds 300,000 cps, the coating workability may be deteriorated due to a high compound viscosity.

Although the kind of the said epoxy compound is not specifically limited by this, For example, a polyglycidyl ether compound, a polyglycidyl amine epoxy compound, a bisphenol-A type epoxy compound, a bisphenol-F type epoxy compound, a resorcinol type It may be at least one selected from the group consisting of an epoxy compound, a tetrahydroxybisphenyl-F type epoxy compound, a cresol-novolak type epoxy compound, a phenol-novolak type epoxy compound and a cycloaliphatic epoxy compound.

On the other hand, the aminoalkoxysilane is an amino group substituted with an alkoxysilane (Alkoxysilane) having a structure of the formula (1), the kind is not particularly limited thereto, for example, aminopropyltrimethoxysilane, aminopropyltri At least one selected from the group consisting of ethoxysilane, aminopropyltriisopropoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane.

[Formula 1]

R _4-m Si (OR ') _n

R and R 'are alkyl groups, n is 1-3.

In addition to the copolymer of the epoxy compound and the aminoalkoxysilane, the primer layer may further include at least one selected from the group consisting of metals, organic acid metal salts, organopolysiloxanes, retarders, and surfactants.

The metal is nickel (Ni), bismuth (Bi), tin (Sn), titanium (Ti), lead (Pb), palladium (Pd), chromium (Cr), cobalt (Co), germanium (Ge), zinc ( Zn), molybdenum (Mo), tantalum (Ta), niobium (Nb), tungsten (W), and vanadium (V) may be one kind of metal or two or more kinds of alloys, but is not necessarily limited thereto. no. The metal may be in the form of a powder, but the size of the metal powder is not particularly limited, but in order to prevent the thickness of the primer layer from being excessively thick and to make the thickness of the primer layer uniform, the particle diameter of the metal powder is 70 nm or less, Or 1 to 45 nm.

The metal salt of the organic acid metal salt is nickel (Ni), bismuth (Bi), tin (Sn), titanium (Ti), lead (Pb), palladium (Pd), chromium (Cr), cobalt (Co), germanium (Ge) , Zinc (Zn), molybdenum (Mo), tantalum (Ta), niobium (Nb), tungsten (W), and vanadium (V) may include at least one metal salt selected from the organic acid of the organic acid metal salt Silver acetic acid, butyric acid, valeric acid, acrylic acid, pivalic acid, n-hexanoic acid, t-octanoic acid, isobutyl acid, benzoic acid, propionic acid, 2-ethyl-hexanoic acid, neodecanoic acid, lauric acid, stearic acid, oleic acid It may include one or more selected from naphthenic acid, dodecanoic acid, and liron acid. The primer layer may exhibit conductivity by including a metal and / or an organic acid metal salt.

On the other hand, the organopolysiloxane is not limited thereto, but for example, polymethylvinylsiloxane, methylvinylsiloxane-dimethylsiloxane copolymer, dimethylvinylsiloxy-terminal dimethylsiloxane, dimethylvinylsiloxy-terminal dimethylsiloxane-methylphenyl Siloxane copolymer, trimethylsiloxy-terminal dimethylsiloxane-methylvinylsiloxane copolymer, trimethylsiloxy-terminal dimethylsiloxane-methylphenylsiloxane-methylvinylsiloxane, or a mixture of two or more.

The retardant may be ethylcyclohexanol, and the surfactant was added for the purpose of smoothly coating the substrate when the primer composition was applied on the substrate, and may be omitted if unnecessary. When the surfactant is added, conventional leveling agents, such as silicone-based or polyether-based surfactants can be used.

The primer layer included in the composite sheet of one embodiment may have an average density of 0.9 to 2.0 g / cc. When the average density of the primer layer is less than 0.9 g / cc, thermal conductivity and electrical conductivity may be lowered, but substrate adhesion and substrate bonding strength with the carbon coating layer may be increased, and when the average density of the primer layer exceeds 2.0 g / cc, thermal conductivity and electrical conductivity may be increased. Although it may be raised, the substrate adhesion and substrate bonding strength with the carbon coating layer may be lowered.

The higher the density of the primer layer, the lower the content of pores contained in the primer layer. For example, the porosity may be 5.0% or less. When the porosity is greater than 5.0%, the coating film strength may decrease, and thermal conductivity and electrical conductivity may decrease.

Meanwhile, the thickness of the primer layer may be 10 nm to 25 μm, 50 nm to 15 μm, or 1 to 5 μm. When the thickness of the primer layer is less than 10 nm, the support force of the composite sheet may be lowered or peeling may occur due to the inclusion of an excessively thin primer layer. Thermal and electrical conductivity of the sheet may be lowered.

In the composite sheet of the embodiment, a conductive layer is formed on the primer layer, and the conductive layer includes a carbon-based compound and a polymer binder. The carbon-based compound is a material having thermal conductivity and electrical conductivity, and the polymer binder is a material which promotes bonding strength between the carbon-based compound and between the conductive layer and the primer layer.

Since the composite sheet includes a carbon-based compound having thermal conductivity and electrical conductivity, the composite sheet has excellent thermal conductivity and electrical conductivity, and when the composite sheet is used as a heat dissipating material for various electrical and electronic processing equipment including semiconductor processing equipment, Local heat concentration can be solved by enabling heat transfer, and electromagnetic instability, such as charging by plasma, can be prevented.

The conductive layer may include a carbon-based compound and a polymer binder, and the weight ratio of the carbon-based compound and the polymer binder may be 1: 0.2 to 30, 1: 0.5 to 15, or 1: 1 to 2. When the weight ratio of the carbon-based compound and the polymer binder is less than 1: 0.2, the adhesive force between the polymer binder and the primer layer may be reduced to cause delamination, and the filler may not be held by the binder. It may be buried, and if the content exceeds 1:30, the polymer binder content may be too high, resulting in low thermal and electrical conductivity.

The maximum particle diameter of the carbonaceous compound is not particularly limited, but in order to prevent the thickness of the conductive layer from becoming too thick and to make the thickness of the conductive layer uniform, the maximum particle diameter of the carbonaceous compound is 0.01 to 100 μm, 0.1 to 70 micrometers, or 0.5-50 micrometers can be used.

The carbon-based compound included in the conductive layer may include at least one selected from the group consisting of carbon black, graphite, carbon nanotubes (CNT), graphene, graphene oxide, carbon fiber, and fullerene. It may include. As the carbon-based compound is included, the conductive layer may exhibit high conductivity in the horizontal direction as well as the vertical direction on one side of the conductive layer. Preferably, the carbon-based compound included in the conductive layer may include graphite. Individual particles of such graphite may have a flake form, have a maximum diameter of 0.01 to 100 μm, and a density of 1.5 to 3.0 g / cm 3.

The polymer binder is preferably used a material having excellent conductivity and shock absorbing properties. Specific examples of the material that can be used as the polymer binder include at least one selected from the group consisting of a thermosetting silicone rubber compound, a one-component thermosetting silicone binder, a two-component thermosetting silicone binder, an acrylic resin, an epoxy resin, a urethane resin, and a urea resin. These materials can be used, because of their excellent adhesive force does not need to have a separate adhesive layer, etc. can simplify the work fixing and reduce the production cost of the final product.

The conductive layer included in the composite sheet of the embodiment may have an average density of 1.0 to 3.0 g / cc. When the average density of the conductive layer is less than 1.0 g / cc, the thermal conductivity and the electrical conductivity may be lowered. When the average density of the conductive layer is greater than 3.0 g / cc, the coating film strength may be lowered and the flexibility of the composite sheet may be lowered.

The higher the density of the conductive layer, the lower the content of pores contained in the conductive layer. For example, the porosity of the conductive layer may be 5.0% or less. When the porosity of the conductive layer is greater than 5.0%, the coating film strength, thermal conductivity, and electrical conductivity may decrease.

On the other hand, the conductive layer thickness may be 5 to 400㎛, 10 to 300㎛, or 80 to 150㎛. When the thickness of the primer layer is less than 5 μm, the supporting force of the composite sheet may decrease due to the excessively thin conductive layer. When the thickness exceeds 400 µm, the composite sheet may have a low thickness and may have low flexibility and thermal conductivity and electrical conductivity.

According to another embodiment of the present invention, a method of manufacturing a composite sheet having excellent thermal conductivity and electrical conductivity may include applying and curing a primer composition on at least one surface of a substrate to form a primer layer including a copolymer of an epoxy compound and an aminoalkoxysilane. step; Coating and curing the conductive coating liquid composition on the primer layer to form a conductive layer including a carbon-based compound and a polymer binder; And compressing the laminate including the substrate, the primer layer, and the conductive layer. The method of manufacturing a composite sheet having excellent thermal conductivity and electrical conductivity may be included.

First, in the composite sheet manufacturing method, a primer composition may be coated and cured on at least one surface of a substrate to form a primer layer including a copolymer of an epoxy compound and an aminoalkoxysilane.

The primer composition applied to the substrate may include a copolymer of an epoxy compound and an aminoalkoxysilane, and may further include a solvent, a metal, an organic acid metal salt, an organopolysiloxane, a retardant, a surfactant, and the like. The applied primer composition may be volatilized through a curing process to form a primer layer including a copolymer of an epoxy compound and an aminoalkoxysilane.

Meanwhile, the primer composition may include an epoxy compound, an aminoalkoxysilane, and an initiator. After applying the primer composition to the substrate and thermally cured and / or photocured, crosslinking of the epoxy compound and the aminoalkoxysilane is performed, and volatile components such as a solvent may be volatilized. For this reason, a copolymer of an epoxy compound and an aminoalkoxysilane may be included in the primer layer formed on the substrate after the coating and curing process.

Kinds of the above epoxy compound, aminoalkoxysilane, metal, organic acid metal salt, organopolysiloxane, retardant, surfactant; Weight ratio of epoxy compound to aminoalkoxysilane; Weight average molecular weight of the polymer; And the viscosity of the polymer is as mentioned above.

After forming the primer layer, the conductive coating liquid composition may be applied and cured on the primer layer to form a conductive layer including a carbon-based compound and a polymer binder. In this case, the type and weight ratio of the carbon-based compound and the polymer binder are as mentioned above.

On the other hand, the coating method of the primer layer and the conductive layer may use a coating method known in the art. For example, Gravure Coating, Micro Gravure Coating, Kis Gravure Coating, Comma Knife Coating, Roll Coating, Spray Coating, Meyer Bar Bar coating, Slot Die coating, Reverse coating, Flexo method or offset method can be coated.

In the composite sheet manufacturing method according to an embodiment of the present invention, a composite sheet having a high density may be obtained by pressing a laminate including the substrate, the primer layer, and the conductive layer sequentially. Since the composite sheet is compressed to have high density, it exhibits excellent thermal conductivity and electrical conductivity. When the composite sheet is used as a heat dissipating material for semiconductor process equipment, the process yield of semiconductor manufacturing process is high due to high thermal conductivity and electrical conductivity. This can be high.

Meanwhile, the crimping process may be applied without limitation as long as it can increase the density of the composite sheet. For example, various processes such as a pressure press process, a vacuum press process, a roll press process, a stamp press process, and a press injection process may be used. Can be applied.

In the composite sheet manufacturing method according to an embodiment of the present invention, the pressing may be made through a pressing press process, and specifically, the pressing press process may include pressing the laminate with a press to press. ; Cooling the thermocompression laminated body while maintaining a press pressure; And removing press pressure from the cooled laminate.

In the pressure press process, first, the laminate may be thermocompressed while applying pressure to the laminate. In this case, the pressure applied to the laminate may be 10 to 100kgf / cm ² or 20 to 60kgf / cm ² . If the pressure can be lowered in thermal conductivity and electric conductivity of 10kgf / cm ² is less than if the effect of increasing the density mimihayeo composite sheet, more than 100kgf / cm ² binder and filler, by reducing the bonding force between the filler and the filler, the film coating strength May deteriorate.

In addition, the pressure press process is preferably carried out at a temperature of 20 to 200 ℃, when heat is applied during the pressure press process, further crosslinking of the uncrosslinked epoxy compound and amino alkoxysilane is further promoted to improve the material / chemical properties of the composite sheet You can.

After pressing the laminate by pressing with pressure by pressing, cooling is performed while maintaining the press pressure. When the pressure is immediately removed at a high temperature except for a cooling process, the density of the composite sheet is increased by a spring back phenomenon. This is to prevent this because it falls again.

On the other hand, when the pressure press process is carried out in a vacuum condition, it is possible to promote the volatilization of the non-volatile components included in the laminate can be effective to further increase the density of the composite sheet.

In the composite sheet manufacturing method according to an embodiment of the present invention, the pressing may be made through a roll press process.

The pressure applied to the laminate by the roll may be 10 to 100 kgf / cm ² or 20 to 60 kgf / cm ² . The pressure is when is 10kgf / cm ² under the effect of increasing the density mimihayeo can lower the thermal conductivity and the electric conductivity of the composite sheet, more than 100kgf / cm ² the bonding force between the binder and the filler, the filler and the filler is reduced, the film coating strength May deteriorate.

The roll may have a temperature of 20 to 200 ° C., and heat of the roll may be transferred to the laminate to further crosslink the uncrosslinked epoxy compound and aminoalkoxysilane, thereby improving physical / chemical properties of the composite sheet.

The composite sheet having excellent thermal conductivity and electrical conductivity manufactured by the manufacturing method may be used as a heat dissipation material included in an electric and electronic process facility, and may be used as a gasket included in, for example, a semiconductor vacuum plasma facility (especially a dry etching process facility). Can be.

According to the present invention, even after long-term exposure at high temperature does not occur peeling phenomenon is excellent in durability, due to the high density can be provided a composite sheet excellent in thermal conductivity and electrical conductivity.

1 is a view schematically showing a pressure press step.
It is a figure which shows typically a roll press process.
3 is a photograph taken with a scanning electron microscope (SEM) of the cross section of the composite sheet of Example 3.
4 is a photograph taken with a scanning electron microscope of a cross section of the composite sheet of Comparative Example 3.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Example 1

1) Preparation of a laminate comprising a base material, a primer layer and a conductive layer

A primer composition comprising a copolymer of a bisphenol-A type epoxy compound and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and ethylcyclohexa (delay agent) was prepared, and graphite having a maximum diameter of 15 nm was prepared. A conductive coating liquid composition including 10 parts by weight and 90 parts by weight of urea resin was prepared. Subsequently, a primer composition is applied and dried on both sides of an aluminum thin plate having a thickness of 40 μm to form a primer layer of 10 μm, and the conductive coating composition is applied and dried on both sides of the conductive layer having a thickness of 150 μm. It formed and manufactured the laminated body. At this time, it controlled so that the weight ratio of the bisphenol-A type epoxy compound and N- (2-aminoethyl) -3-aminopropyl trimethoxysilane contained in the said primer layer might be 1: 1.

2) Composite sheet manufacturing by compressing laminate

FIG. 1 schematically shows a pressure press process. Thus, a release film, an aluminum foil, and an aluminum plate are laminated on both surfaces of the laminate, and heated at 150 ° C. for 30 minutes by applying a pressure of ²⁰ kgf / cm ² . Squeezed. Then, the composite sheet was manufactured by cooling to room temperature (25 ° C.) while maintaining the pressure applied to the laminate, and removing the press pressure and the release film, the aluminum foil, and the aluminum plate from the cooled laminate.

Example 2

1) Preparation of a laminate comprising a base material, a primer layer and a conductive layer

Except for the weight ratio of the bisphenol-A type epoxy compound and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane contained in the primer layer is 1: 0.2, in the same manner as in Example 1 The laminate was produced.

2) Composite sheet manufacturing by compressing laminate

A composite sheet was produced in the same manner as in Example 1, except that the pressure applied to the laminate was 40 kgf / cm ² .

Example 3

1) Preparation of a laminate comprising a base material, a primer layer and a conductive layer

Except for the weight ratio of the bisphenol-A type epoxy compound and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane contained in the primer layer is 1:20, in the same manner as in Example 1 The laminate was produced.

2) Composite sheet manufacturing by compressing laminate

Fig. 2 schematically shows a roll press step. Thus, the laminated body was introduced into a roll press device composed of a plurality of rolls and pressed to produce a composite sheet. At this time, the surface temperature of the roll was 150 degreeC, the moving speed of the laminated body was 0.2 m / min, and the pressure applied to the laminated body was 10 kgf / cm <^2> . In addition, the cross section of the composite sheet was photographed with a scanning electron microscope and shown in FIG. 3.

Example 4

1) Preparation of a laminate comprising a base material, a primer layer and a conductive layer

Except for the weight ratio of the bisphenol-A type epoxy compound and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane contained in the primer layer is 1:30, in the same manner as in Example 1 The laminate was produced.

2) Composite sheet manufacturing by compressing laminate

A composite sheet was manufactured by pressing the laminate in the same manner as in Example 3, except that the pressure applied to the laminate was 20 kgf / cm ² .

Comparative Example 1

The laminate which was not crimped in Example 1 was prepared as a composite sheet.

Comparative Example 2

The laminate which was not crimped in Example 2 was prepared as a composite sheet.

Comparative Example 3

The laminate which was not crimped in Example 3 was prepared as a composite sheet. In addition, the cross section of the composite sheet was photographed with a scanning electron microscope and shown in FIG. 4.

Comparative Example 4

The laminate which was not crimped in Example 4 was prepared as a composite sheet.

1. Adhesion Test

For Examples 1 to 4 and Comparative Examples 1 to 4 were measured based on the Cross Hatch Cut Adhesion Test (ASTM D 3359) and are shown in Table 1 below. However, the standing time was 30 minutes at room temperature.

2. Thermal conductivity test

The thermal conductivity of the Examples 1 to 4 and Comparative Examples 1 to 4 by the laser flash method is shown in Table 1 below.

3. Conductivity test

The wire resistance of the Examples 1 to 4 and Comparative Examples 1 to 4 by the multi-tester at the same thickness and the same distance are shown in Table 1 below.

4. Density Measurement

For Examples 1 to 4 and Comparative Examples 1 to 4 based on the ASTM D792 standard, the density of the film was measured using an electronic specific gravity meter that can be measured up to 0.1 mg using the Archimedes principle, and the results are shown in Table 1 below. .

5. Thickness Measurement

The thickness of the film was measured using a micrometer that can measure up to 0.0025 mm based on ASTM D374 standard for Examples 1 to 4 and Comparative Examples 1 to 4, and the results are shown in Table 1 below.

Adhesive force (B) Thermal Conductivity (W / mK) Electrical resistance Density (g / cc) Thickness (㎛) Example 1 5B 3.85 60 1.8978 150 Example 2 5B 4.12 50 2.0628 151 Example 3 4B 3.56 80 1.8263 152 Example 4 4B 3.74 70 1.8798 150 Comparative Example 1 3B 2.74 110 1.7172 168 Comparative Example 2 3B 2.72 110 1.7161 172 Comparative Example 3 3B 2.74 110 1.7186 164 Comparative Example 4 3B 2.74 110 1.7179 167

According to the said Table 1, it confirmed that the composite sheets of Examples 1-4 are higher in density than the composite sheets (laminated body) of the comparative examples 1-4 which are not crimped, and therefore high thermal and electrical conductivity. 3 and 4 confirmed that the composite sheet of Example 3 was thinner than Comparative Example 3, which was not crimped.

Claims (25)

materials;
A primer layer formed on at least one surface of the substrate and including a copolymer of an epoxy compound and an amino alkoxysilane; And
It is formed on the primer layer, and includes a conductive layer containing a carbon-based compound and a polymer binder,
Average density is 1.0 to 5.0 g / cc,
The copolymer of the epoxy compound and aminoalkoxysilane has a weight average molecular weight (Mw) of 10,000 to 900,000g / mol, a composite sheet excellent in thermal conductivity and electrical conductivity.
The composite sheet of claim 1, wherein the composite sheet has a porosity of 5% or less.
The composite sheet of claim 1, wherein the composite sheet has a thickness of 50 to 500 μm.
The composite sheet of claim 1, wherein the substrate, the primer layer, and the conductive layer are sequentially laminated and compressed to have a high thermal conductivity and electrical conductivity.
The method of claim 1, wherein the epoxy compound is a polyglycidyl ether compound, polyglycidylamine epoxy compound, bisphenol-A type epoxy compound, bisphenol-F type epoxy compound, resorcinol type epoxy compound, tetrahydroxybis A composite sheet having excellent thermal conductivity and electrical conductivity, which is at least one selected from the group consisting of a phenyl-F type epoxy compound, a cresol-novolak type epoxy compound, a phenol-novolak type epoxy compound, and a cycloaliphatic epoxy compound.
The method of claim 1, wherein the aminoalkoxysilane is aminopropyltrimethoxysilane, aminopropyltriethoxysilane, aminopropyltriisopropoxysilane and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane One or more selected from the group consisting of a composite sheet having excellent thermal conductivity and electrical conductivity.
The composite sheet of claim 1, wherein the primer layer has an average density of 0.9 to 2.0 g / cc.
The composite sheet of claim 1, wherein the primer layer has a porosity of 5% or less.
The composite sheet of claim 1, wherein the primer layer has a thickness of 10 nm to 25 μm.
The method of claim 1, wherein the carbon-based compound is carbon black, graphite (graphite), carbon nanotubes (CNT), graphene (Graphene), graphene oxide, carbon fiber and at least one selected from the group consisting of fullerene (Fullerene) Comprising a composite sheet having excellent thermal conductivity and electrical conductivity.
The method of claim 1, wherein the polymer binder is one or more selected from the group consisting of a thermosetting silicone rubber compound, a one-component thermosetting silicone binder, a two-component thermosetting silicone binder, an acrylic resin, an epoxy resin, a urethane resin, and a urea resin. Composite sheet with excellent electrical conductivity.
The composite sheet of claim 1, wherein the conductive layer has an average density of 1.0 to 5.0 g / cc.
The composite sheet of claim 1, wherein the conductive layer has a porosity of 5% or less.
The composite sheet of claim 1, wherein the conductive layer has a thickness of 5 to 400 μm.
The composite sheet of claim 1, wherein the composite sheet is a heat dissipating material included in an electrical and electronic process facility.
The composite sheet of claim 15, wherein the electrical and electronic processing equipment is a semiconductor vacuum plasma equipment.
The composite sheet according to claim 1, wherein the composite sheet has excellent thermal conductivity and electrical conductivity, having a thermal conductivity of 1.0 W / mK or more and a resistance of 100 kPa or less.
Coating and curing the primer composition on at least one side of the substrate to form a primer layer comprising a copolymer of an epoxy compound and an aminoalkoxysilane;
Coating and curing the conductive coating liquid composition on the primer layer to form a conductive layer including a carbon-based compound and a polymer binder; And
And compressing the laminate including the substrate, the primer layer, and the conductive layer.
The copolymer of the epoxy compound and aminoalkoxysilane has a weight average molecular weight (Mw) of 10,000 to 900,000 g / mol,
Composite sheet manufacturing method with excellent thermal and electrical conductivity.
19. The method of claim 18, wherein the primer composition comprises a copolymer of an epoxy compound and an aminoalkoxysilane.
The method of claim 18, wherein the primer composition comprises an epoxy compound, an aminoalkoxysilane, and an initiator.
The composite sheet manufacturing method of claim 18, wherein the pressing is performed through a pressure press process.
The method of claim 21, wherein the pressure press process,
Thermally compressing the laminate with a press;
Cooling the thermocompression laminated body while maintaining press pressure; And
Comprising the step of removing the press pressure in the cooled laminate, a composite sheet manufacturing method excellent in thermal and electrical conductivity.
The method of claim 22, wherein in the thermocompression step,
The pressure applied to the laminate is 10 to 100kgf / cm ² , the temperature is 20 to 200 ℃, the composite sheet manufacturing method excellent thermal conductivity and electrical conductivity.
The composite sheet manufacturing method of claim 18, wherein the pressing is performed through a roll press process.
The composite sheet manufacturing method of claim 24, wherein the pressure applied to the laminate by the roll is 10 to 100 kgf / cm ² , and the temperature of the roll is 20 to 200 ° C. 25.

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