KR101757229B1 - Composite multi-layer sheet with EMI shield and heat radiation and Manufacturing method thereof - Google Patents

Abstract

The present invention relates to a multilayer composite sheet with electromagnetic shielding and heat dissipating function, and a method of manufacturing the same, which comprises introducing a graphite sheet provided with a through hole and introducing a heat insulating adhesive having a proper composition and composition ratio, An electromagnetic wave shielding and heat dissipation function integrated multi-layer composite sheet having excellent electromagnetic wave shielding property and heat shock resistance, and a method of manufacturing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to an integrated multi-layer composite sheet for electromagnetic shielding and heat dissipation, and a manufacturing method thereof.

The present invention relates to a heat-radiating composite sheet, and more particularly, to an integrated multi-layer composite sheet having a thin electromagnetic wave shielding and heat dissipating function which is excellent in horizontal thermal conductivity, durability against thermal shock, and electromagnetic shielding property and a method for manufacturing the same.

As a result of the high performance and light weight and short life of electric and electronic devices, there is a steadily increasing demand for a heat-radiating sheet capable of effectively dissipating heat generated from heat sources such as semiconductor components and light emitting parts built therein, .

Generally, a heat-radiating sheet uses copper foil, a copper foil / graphite laminate, and a graphite sheet. The copper foil has both heat dissipation properties and electromagnetic shielding characteristics. However, when the thickness is thick, flexibility is insufficient. It is insignificant and has a high density, which limits its weight. If the thickness exceeds about 50 탆, flexibility is insufficient, and thus there is a limit to the application as a heat radiation sheet having a complicated shape.

In addition, although a commercial product made of various materials is widely used as an electromagnetic wave shielding sheet for shielding electromagnetic waves, a conventional electromagnetic wave shielding sheet has a low thermal conductivity and can not sufficiently obtain a heat radiation effect, Is being developed. For example, Korean Patent No. 10-1457914 discloses a thermal diffusion sheet having an electromagnetic wave absorbing layer in which an electromagnetic wave absorbing layer is laminated on one surface or both surfaces of a thermal diffusion sheet composed of a metal foil layer and a graphite layer. It is disadvantageous in that it is thinned. Therefore, there are technical limitations in application to a portable electronic device such as a smart phone, which is a small electronic device, and there is a problem that flexibility is greatly reduced.

2. Description of the Related Art In recent years, portable electronic devices have been required to be flexible and thin. As a result, the heat radiation sheet and the electromagnetic wave shielding sheet which are essential parts used therefor have been increasingly demanded for flexibility and thinness.

U.S. Published Patent Application No. 2007-0246208 (published on October 25, 2007)

SUMMARY OF THE INVENTION The present invention has been conceived to solve the problems as described above, and it is an object of the present invention to provide a method of manufacturing a semiconductor device, which comprises introducing an adhesive layer and a metal sheet having specific compositions and composition ratios, introducing a graphite layer having a specific- And a functionally integrated multi-layer composite sheet which secures flexibility and thinness while ensuring electromagnetic wave shielding function, and a method of manufacturing the same.

According to an aspect of the present invention, there is provided an electromagnetic wave shielding and heat dissipating multi-layer composite sheet comprising a first electromagnetic wave shielding layer, a first adhesive layer, a graphite layer having a plurality of through holes, a second adhesive layer, Are stacked in this order.

As a preferred embodiment of the present invention, the passivation film may not be provided on the upper and lower portions of the graphite layer.

In one preferred embodiment of the present invention, the multilayer composite sheet of the present invention may further include a metal sheet layer on top of the second electromagnetic wave shielding layer.

As a preferred embodiment of the present invention, the graphite layer may have a thickness satisfying the following equation (1).

[Equation 1]

 (d2 + d3)? d1? 4 (d2 + d3)

D1 is the average thickness of the graphite layer, d2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer

As a preferred embodiment of the present invention, the first adhesive layer and the second adhesive layer can satisfy the following equation (2).

[Equation 2]

d2? d3

D2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer.

In one preferred embodiment of the present invention, the inside of the through hole of the graphite layer is filled with an adhesive derived from the first adhesive layer and / or the second adhesive layer.

In one preferred embodiment of the present invention, the first electromagnetic wave shielding layer may be a copper foil, an aluminum foil or a metal sheet.

In one preferred embodiment of the present invention, the second electromagnetic wave shielding layer may be a copper foil or an aluminum foil.

In a preferred embodiment of the present invention, the graphite layer may be a graphite sheet containing at least one of pyrolytic graphite and graphitized polyimide.

In a preferred embodiment of the present invention, the first adhesive layer and / or the second adhesive layer may each be a heat dissipation adhesive layer.

In one preferred embodiment of the present invention, each of the first adhesive layer and the second adhesive layer may include a thermosetting resin, a rubber binder, a silane coupling agent, a fluorine surfactant, a curing agent, and a curing accelerator.

In one preferred embodiment of the present invention, each of the first adhesive layer and / or the second adhesive layer comprises 25 to 100 parts by weight of a rubber binder, 1 to 10 parts by weight of a silane coupling agent, 0.01 to 2 parts by weight of a surfactant, 5 to 20 parts by weight of a curing agent, and 1 to 5 parts by weight of a curing accelerator.

In a preferred embodiment of the present invention, each of the first adhesive layer and the second adhesive layer further comprises at least one selected from the group consisting of 30 to 60 parts by weight of a flame retardant, 0.5 to 10 parts by weight of a moisture-proofing agent, and a thermally conductive filler .

As a preferred embodiment of the present invention, the thermally conductive filler may be a graphite powder, a carbon nanotube (CNT), a carbon black powder, a carbon fiber, a ceramic powder, and a metal And may include at least one selected from metal powder.

As a preferred embodiment of the present invention, the metal sheet of the metal sheet layer and / or the first electromagnetic wave shielding layer includes a thermosetting epoxy resin, a rubber binder, a silane coupling agent, a fluorine surfactant, a soft magnetic powder, Or a mixture thereof.

In one preferred embodiment of the present invention, the mixed resin used for forming the metal sheet of the metal sheet layer and / or the first electromagnetic wave shielding layer includes 160 to 350 parts by weight of a rubber binder, 100 parts by weight of a silane couple 4 to 25 parts by weight of a ring agent, 0.5 to 5 parts by weight of a fluorinated surfactant, 700 to 1,500 parts by weight of a soft magnetic powder, 2 to 30 parts by weight of a curing agent and 1 to 25 parts by weight of a moisture resistant agent.

In one preferred embodiment of the present invention, the soft magnetic powder is selected from the group consisting of Fe-Si-Al alloys, Fe-Si-Cr alloys, Fe-Si-B alloys, highflux, permalloy alloys , A Ni-Zn ferrite alloy, and a Mn-Zn ferrite alloy.

In a preferred embodiment of the present invention, the through hole area of the graphite layer may be 2% to 30% of the total area of the upper or lower surface of the graphite layer.

In a preferred embodiment of the present invention, the through hole area of the graphite layer may be 5% to 20% of the total area of the upper or lower surface of the graphite layer.

In a preferred embodiment of the present invention, each of the first adhesive layer and the second adhesive layer has an average thickness of 2 탆 to 20 탆, and the graphite layer may have a thickness of 8 탆 to 50 탆.

As a preferred embodiment of the present invention, each of the through holes of the graphite layer may have a peel strength of 50 to 1,200 gf / hole when the peel strength is measured.

As a preferred embodiment of the present invention, the through holes of the graphite layer may have a cross-sectional shape having a profile of the following formula (3).

[Equation 3]

0.500 ≤

In the above-mentioned eccentricity 3, the mold-outline is (inner width of the shape / circumference length of the shape) ^1/2 .

In one preferred embodiment of the present invention, the cross-sectional shape of the through-hole may include at least one selected from the group consisting of a circle, an ellipse, a + type, a X type, a ┝ type, a ┏ type, an I type and a linear type.

In a preferred embodiment of the present invention, when the cross-sectional shape of the through-hole is circular, the diameter of the ellipse is 1: 2 to 10, and the + The diameter ratio of the circumscribed circle may be 1: 2 ~ 10.

As a preferred embodiment of the present invention, in the electromagnetic wave shielding and heat dissipating function integrated multi-layer composite sheet of the present invention, the peel strength between the graphite layer and the second electromagnetic wave shielding layer is 300 gf / cm < cm ² to 720 gf / cm ² Lt; / RTI >

As a preferred embodiment of the present invention, the electromagnetic shielding and heat-dissipating integrated multi-layer composite sheet of the present invention may have a horizontal thermal conductivity of 300 to 1000 W / m · k and a vertical thermal conductivity of 1 to 15 W / m · k.

Another object of the present invention is to provide a method of manufacturing an integrated multi-layer composite sheet of the present invention in various forms as described above, including a first electromagnetic wave shielding layer, a first adhesive layer, a graphite layer having a plurality of through holes, A shielding layer and a methyl sheet layer, into a hot press equipment at 60 ° C to 80 ° C; Two steps of heating and pressing the laminate under a pressure of 145 to 160 DEG C and 45 to 60 kgf / cm < 2 > for 50 to 70 minutes; And a third step of cooling the hot press and then separating the composite sheet integrated from the hot press.

As a preferred embodiment of the present invention, the heating in the second step may be carried out by heating a hot press at 10 ° C to 35 ° C at a rate of 3 ° C / minute to 5 ° C / minute to 145 ° C to 160 ° C.

As a preferred embodiment of the present invention, the cooling in the above three stages may be performed by cooling a hot press at 145 ° C to 160 ° C at a rate of 3 ° C / min to 5 ° C / min to 60 ° C to 80 ° C.

As a preferred embodiment of the present invention, the first adhesive layer, the graphite layer and the second heat-dissipative adhesive layer of the integrated sheet of three stages may have a thickness satisfying the following equation (1).

[Equation 1]

 (d2 + d3)? d1? 4 (d2 + d3)

In the above Equation 1, d1 is the average thickness of the graphite layer, d2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer.

As a preferred embodiment of the present invention, the first adhesive layer and the second adhesive layer of the three-stage composite sheet can satisfy the following equation (2).

[Equation 2]

d2? d3

In the above equation (2), d2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer.

Another object of the present invention is to provide a coverlay film and / or a flexible circuit board comprising the above-described various types of the integral multi-layer composite sheet of the present invention.

It is also intended to provide an electronic apparatus, preferably a portable electronic apparatus, comprising the integral multi-layer composite sheet of the present invention.

In a preferred embodiment of the present invention, the electronic device may be a flexible electronic device.

The integrated multi-layer composite sheet of the present invention introduces a graphite sheet having a plurality of through holes satisfying specific conditions, thereby maximizing the horizontal thermal conductivity while minimizing the vertical thermal conductivity, and has an excellent electromagnetic wave shielding effect. Further, the integrated composite sheet of the present invention can provide a composite sheet having flexibility while being capable of being thinned, excellent in peel strength between the second electromagnetic wave shielding layer and the graphite layer and excellent in interlaminar peeling strength of the graphite layer itself, can do.

1 is a schematic cross-sectional view of an electromagnetic shielding and heat-dissipating function integrated composite sheet according to a preferred embodiment of the present invention.
FIG. 2 is a schematic view of a preferred embodiment of a graphite layer having a plurality of through holes constituting the electromagnetic shielding and heat-dissipating function integrated composite sheet of the present invention.
Figs. 3 (a) and 3 (b) are schematic views of a form in which an adhesive component derived from the first adhesive layer and / or the second adhesive layer is filled in the through hole of the graphite layer.
FIG. 4 is a schematic view of a digitizer module incorporating the electromagnetic shielding and heat dissipation function integrated composite sheet 100 of the present invention.

Hereinafter, the present invention will be described in more detail.

Conventionally, the heat-radiating sheet and / or the composite sheet use a copper foil, a copper foil / graphite laminate, a graphite sheet or the like as a heat dissipating material. The copper foil has both heat dissipation characteristics and electromagnetic wave shielding characteristics. However, , The thermal conductivity in the horizontal direction is inferior to the graphite in the horizontal thermal conductivity, and the density is high, so there is a limit in weight reduction. In addition, if the thickness exceeds about 50 탆, flexibility is insufficient, and thus there is a limit to apply to a flexible heat radiation sheet having a complicated shape. Further, the adhesiveness between the copper foil and the graphite laminate is low, and the graphite has a problem that delamination occurs in the graphite itself.

1, the present invention includes a graphite layer 10 having a first electromagnetic wave shielding layer 30, a first adhesive layer 20, a plurality of through holes 1, 2, 3, 4, (Hereinafter referred to as "composite sheet") having a structure in which a first adhesive layer 20 ', a second adhesive layer 20' and a second electromagnetic wave shielding layer 30 'are laminated in order. Generally, a graphite sheet having a passivation film on both sides or one side thereof is used for producing a heat radiation film using a graphite sheet. However, the graphite layer (10) of the composite sheet of the present invention has passivation films And the through hole of the graphite layer may be filled with an adhesive component derived from the first adhesive layer 20 and / or the second adhesive layer 20 '.

Since the planar size of the graphite layer is smaller than the planar size of the first electromagnetic wave shielding layer 30 and the second electromagnetic wave shielding layer 30 ', when seen in the planar direction of the electromagnetic wave shielding layer, And the second electromagnetic wave shielding layer, and in the case where no adhesive component originating from the first adhesive layer 20 and / or the second adhesive layer 20 'is present, as viewed from the side of the integral composite sheet, There is a space between the outside of the graphite layer and the first electromagnetic wave shielding layer and the second electromagnetic wave shielding layer due to the thickness of the graphite layer.

Referring to a schematic plan view of FIGS. 2 (a) and 2 (b), the graphite layer 10 has a plurality of through holes 1, 2, 3, 4 provided therein, The first electromagnetic wave shielding layer 30 and the second electromagnetic wave shielding layer are filled with the adhesive component originating from the first adhesive layer and / or the second adhesive layer in the spacing space between the first electromagnetic wave shielding layer and the second electromagnetic wave shielding layer, (30 ') are combined and integrated. More specifically, the first adhesive layer and / or the second adhesive layer are semi-cured. When layers are stacked, pressure is applied by a press, or heat and pressure are applied by a hot press, a part of the adhesive component in the first adhesive layer and / or the second adhesive layer is melted and filled in the through- (25, 25 ') (see Figs. 3 (a) to 3 (b)).

Each layer constituting the integral composite sheet 100 of the present invention will be described more specifically.

The first electromagnetic wave shielding layer and / or the second electromagnetic wave shielding layer is a material having heat radiation and electromagnetic wave shielding function, and may be a general metal foil used in the related art. Preferable examples thereof include a copper foil, an aluminum foil or a metal sheet Can be used. The first electromagnetic wave shielding layer and / or the second electromagnetic wave shielding layer may use metal foils of the same material or metal foils or metal sheets of different materials. For example, both of the first electromagnetic shielding layer and the second electromagnetic shielding layer may be a copper foil, the first electromagnetic shielding layer may be a metal sheet, and the second electromagnetic shielding layer may be a copper foil.

The first electromagnetic wave shielding layer 40 preferably has an average thickness of 5 to 70 탆, preferably 8 to 40 탆, more preferably 8 to 35 탆. At this time, the average thickness of the first electromagnetic wave shielding layer If it is less than 5 mu m, there may be a problem that an appearance problem occurs and a tear phenomenon occurs. If it exceeds 70 mu m, it may be difficult to form a thin film and a product flexibility may be lowered.

[Adhesive layer]

Next, the first adhesive layer 20 and / or the second adhesive layer 20 'will be described.

The first adhesive layer and the second adhesive layer serve to bond the first electromagnetic wave shielding layer, the graphite layer, and the second electromagnetic wave shielding layer to each other. The first electromagnetic wave shielding layer 30 and / or the second electromagnetic wave shielding layer It is preferable to use a heat-resistant high heat-resistant adhesive capable of allowing heat transfer to the graphite layer 10 to be well performed. The adhesive layer (or the heat-dissipating adhesive) may be a thermosetting resin, a rubber binder, a silane coupling agent, a fluorine-containing surfactant , A curing agent, and a curing accelerator, and may further include at least one selected from a flame retardant, a moisture-proofing agent and a thermally conductive filler, if necessary.

Among the components of the first adhesive layer and / or the second adhesive layer (hereinafter referred to as "adhesive layer"), the thermosetting resin is a thermosetting epoxy resin, a thermosetting phenoxy resin, a thermosetting amino resin, a thermosetting polyester resin and a thermosetting polyurethane resin One or more selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novaleak epoxy resin, and a halogen-containing epoxy resin, etc. may be used. Or more species.

When two or more kinds of thermosetting epoxy resins are used in combination, it is preferable to mix the bisphenol A epoxy resin and the novolak epoxy resin at a weight ratio of 1: 0.15 to 0.4, preferably 1: 0.18 to 0.35, It is advantageous in terms of improvement in melting point and improvement in adhesion.

The rubber binder among the components of the adhesive layer may play a role in imparting bending resistance and may include one or more of acryl rubber, silicone rubber, carboxylated nitrile elastomer and phenoxy, Preferably one or two or more of acrylic rubber and silicone rubber. Carboxylic elastomer may be used, and it is preferable to use a carboxylnitrile elastomer. The carboxyl-series elastomer preferably has a weight-average molecular weight of 180,000 to 350,000, preferably a weight-average molecular weight of 210,000 to 280,000, more preferably a weight-average molecular weight of 215,000 to 255,000, And the heat resistance of the adhesive layer. The rubber binder may be used in an amount of 25 to 100 parts by weight, preferably 35 to 80 parts by weight, based on 100 parts by weight of the thermosetting resin. When the rubber binder is used in an amount of less than 25 parts by weight, When the composite sheet is bent, the first electromagnetic wave shielding layer and the graphite layer are partially peeled off. If the composite sheet is used in an amount exceeding 100 parts by weight, the amount of other components in the adhesive layer is decreased, There is a problem that the adhesiveness of the adhesive layer may be reduced.

Among the components of the adhesive layer, the silane coupling agent plays a role of dispersing the particles and can be a conventional silane coupling agent used in the art, preferably glycidoxy (C2 to C5 alkyl) trialkoxysilane (Glycidoxy (C2 C5 alkyl) trialkoxysilane, vinyltri (C2-C5 alkoxy) silane, and aminoethylaminopropylsilane triol, and more preferably at least one selected from glycidoxyethyl At least one member selected from the group consisting of trimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, and aminoethylaminopropylsilane triol The amount of the silane coupling agent to be used is 1 to 10 parts by weight based on 100 parts by weight of the thermosetting resin, When the silane coupling agent is used in an amount of less than 1 part by weight, the amount of the silane coupling agent used is too small to exhibit the effect of dispersing the particles. When the silane coupling agent is used in an amount exceeding 10 parts by weight, There is a problem that particle aggregation occurs, so it is preferable to use it within the above range.

Among the components of the adhesive layer, the fluorine-based surfactant plays a role of improving the coating property by lowering the surface tension. The fluorine-based surfactant generally used in the art can be used, and preferably a fluoroaliphatic polymeric ester Specific examples thereof include FC4430 of 3M, Novec 4300 of Du Pont, DuPont Capstone of DuPont, and the like. The amount of the fluorinated surfactant to be used may be 0.01 to 2 parts by weight, preferably 0.02 to 1.2 parts by weight, based on 100 parts by weight of the thermosetting resin. When the fluorinated surfactant is used in an amount of less than 0.01 part by weight, It may not be effective to improve the coating property. If it is used in excess of 2 parts by weight, there may be a problem that the adhesive strength is lowered.

Among the components of the adhesive layer, at least one of an amine type hardener, an anhydride type hardener and a phenol type hardener may be used as the curing agent, preferably an amine type curing agent an amine type hardener, and an anhydride type hardener. Specific examples thereof include 4,4'-diaminodiphenlysulfone (4,4'-diaminodiphenlysulfone) as a curing agent . The curing agent may be used in an amount of 5 to 20 parts by weight, preferably 8 to 17 parts by weight, based on 100 parts by weight of the thermosetting resin. If the amount of the curing agent is less than 5 parts by weight, durability may be reduced. If it is used in an amount exceeding 20 parts by weight, there may arise a problem that the heat insulation adhesive strength is lowered.

Among the components of the adhesive layer, the curing accelerator may include at least one of an aromatic amine, an aliphatic amine, and an aromatic tertiary amine, and may preferably include at least one of an aromatic amine and an aromatic tertiary amine. The curing accelerator may be used in an amount of 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight based on 100 parts by weight of the thermosetting resin. If the curing accelerator is used in an amount of less than 1 part by weight, the curing speed of the heat- If it is used in an amount exceeding 5 parts by weight, the adhesive layer may be cured too quickly, and the heat-curing layer may be completely cured before hot pressing.

Among the components of the adhesive layer, the flame retardant is one for obtaining a flame retardant effect of the product, and may be a general one used in the art. Preferably, the flame retardant is one or two or more selected from phosphorus flame retardants, inorganic flame retardants, For example, Clariant EXOLIT OP 935, H42M of Showa Denko Corp., H32 of Showa Denko KK and H43M of Showa Denko KK can be used. The flame retardant may be used in an amount of 30 to 60 parts by weight, preferably 35 to 55 parts by weight, based on 100 parts by weight of the thermosetting resin. When the amount of the flame retardant is less than 30 parts by weight, If it is used in an amount exceeding 60 parts by weight, there is a problem that the adhesive strength of the product may be lowered due to the excessive use of the flame retardant component.

Among the components of the adhesive layer, the moisture absorbing agent is used for controlling the water content in the adhesive layer and for controlling the viscosity of the heat-dissipating adhesive, and may be selected from those generally used in the art, and examples thereof include aluminum sulfate, latex, silicone emulsion, Siloxane), a hydrophobic polymer emulsion, and a silicone-based moisture-proofing agent, or a mixture of two or more thereof. The amount of the humectant to be used may be 0.5 to 10 parts by weight, preferably 1.5 to 8 parts by weight, based on 100 parts by weight of the thermosetting resin. If the amount of the humectant is less than 0.5 parts by weight, If it is used in excess of 10 parts by weight, it may be difficult to control the proper amount of water in the adhesive layer due to overuse.

On the other hand, the adhesive layer of the present invention may be further provided with a thermally conductive filler and / or a dispersing agent to impart a heat-radiating adhesive function. The thermally conductive filler may be one or two of graphite powder, carbon nanotube (CNT), carbon black, carbon fiber, ceramic and metal powder. Or a mixture of two or more species of graphite powder, ceramics and metal powder may be preferably used. When the thermally conductive filler is further used, it may contain 45 to 1,100 parts by weight, preferably 75 to 800 parts by weight, relative to 100 parts by weight of the thermosetting resin. If the thermally conductive filler is used in excess of 1100 parts by weight, The vertical thermal conductivity of the composite sheet can be greatly increased.

The thermally conductive filler preferably has an average particle diameter of 3 to 25 占 퐉. If the average particle diameter is less than 3 占 퐉, it may be difficult to disperse the particles. If the average particle diameter exceeds 25 占 퐉, It is preferable to use a thermally conductive filler having a particle size within the above range.

The dispersant may be any of those generally used in the art, and preferably an acrylic block amine dispersant may be used.

The viscosity and solid content of the adhesive can be adjusted by introducing a mixture of the above-mentioned curable resin, rubber binder, silane coupling agent, fluorine surfactant, curing agent, curing accelerator, flame retardant and humidifier into an organic solvent. And the shape of the crosspieces, the surface state of the composition for forming a heat-radiating adhesive layer is improved, and the adhesion of the substrate and the orientation of the particles can be controlled. At this time, the organic solvent may be used alone or in combination of two or more of methyl ethyl ketone, toluene, tetrahydrofuran (THF), and cyclohexanone.

The adhesive formed in such composition and composition ratio is applied (or coated) to the upper part of the first electromagnetic wave shielding layer, followed by drying and semi-hardening to form an adhesive layer. At this time, It is preferable to apply the adhesive layer so that the adhesive layer has an average thickness of 2 탆 to 25 탆, preferably an average thickness of 3 to 15 탆, more preferably an average thickness of 4 to 8 탆 based on the composite sheet. At this time, if the average thickness of the adhesive layer in the composite sheet is less than 2 mu m, the binding force (or adhesive force) between the first electromagnetic wave shielding layer and the graphite layer may be lowered. There may be a problem with poor performance.

[Graphite layer]

Next, the graphite layer 10 provided with the through holes constituting the composite sheet of the present invention will be described.

The graphite layer is composed of a graphite sheet (or film) having a through-hole formed therein. Through this through-hole, the first electromagnetic wave shielding layer and the second electromagnetic wave shielding layer disposed below and above the graphite layer and the second electromagnetic wave shielding layer It is possible to omit a separate adhesive layer between the graphite layers, thereby making it possible to reduce the thickness of the composite sheet.

Further, the graphite sheet uses a graphite sheet having through-holes so as to have a good horizontal thermal conductivity and a degree of dissociation that satisfies the following equation (3) so as to realize a high peeling strength between the second electromagnetic wave shielding layer and the graphite layer.

[Equation 3]

0.500 ≤ 1 ≤ 1.300, preferably 0.520 ≤

In the above equation (3), the mold drawing is (inner width of shape / circumference length of shape) ^1/2 .

If the degree of dissociation is less than 0.500, the overall thermal diffusibility is excellent, but the peel strength such as peel strength per through hole may be low and the peel strength between the second electromagnetic wave shielding layer and graphite layer may be low. On the other hand, But there is a problem that the vertical thermal conductivity increases.

The cross-sectional shape of the through-hole may have a cross-sectional shape satisfying the above-described separation diagram, and may have at least one selected from a circle, an ellipse, a +, a x, a ┝, a ┏, the through holes may be formed on the graphite sheet by combining various cross-sectional shapes as shown in Fig. For example, when the cross-sectional shape of the through-hole is circular, the diameter of the ellipse is 1: 2 to 10, and the diameter of the ellipse is 1: 2 to 10, The diameter ratio of the circumscribed circle may be 1: 2 ~ 10.

As a specific example, in the case of a circular through hole, the average diameter of the circular cross-sectional shape may be 0.5 mm to 8 mm, preferably 0.5 mm to 5 mm, and more preferably 1 mm to 4 mm. If the average diameter of the through holes is less than 0.5 mm There is a problem that the durability against thermal shock due to the increase in the number of the through holes provided in the graphite layer may be reduced and the filling rate of the adhesive component filled in the through holes may be reduced to reduce the durability against thermal shock When the thickness is more than 8 mm, the thermal diffusing performance in the horizontal direction of the graphite layer decreases, and the shape retention ability of each layer may be decreased during the production of the composite sheet to increase the percentage of defects. May be lowered.

The distance between the through holes may vary depending on the size of the through hole. For example, when the diameter of the through hole is less than 1 mm, the distance between the through holes is 4 mm to 16 mm in the major axis direction, Preferably a spacing distance of 6 mm to 14 mm in the major axis direction and 8 mm to 14 mm in the minor axis direction to secure a horizontal thermal conductivity of the graphite layer, It is advantageous in terms of securing adequate adhesion between the shielding layer and the graphite layer and preventing delamination of the graphite layer itself.

The through hole area of the graphite layer may be 2% to 30%, preferably 3.5% to 15%, more preferably 3.5% to 10% of the total area of the upper or lower surface of the graphite layer, If the through hole area is less than 2%, there is a problem in that the peeling strength between the second electromagnetic wave shielding layer and the graphite layer is low. If it exceeds 30%, the peeling strength is excellent, but there may be a problem that the vertical thermal conductivity increases. There is a problem that the through hole is formed so as to have the above area ratio.

The graphite sheet (or film) constituting the graphite layer may be a general graphite sheet used in the art, preferably a graphite sheet containing at least one of pyrolytic graphite and graphitized polyimide. .

The pyrolytic graphite refers to high purity graphite having high thermal conductivity and electrical conductivity, is used at high temperature, and is manufactured by vapor deposition method and can have a very well developed microstructure.

The graphitized polyimide may be prepared through the following graphitization process.

First, as a preparation step of the graphitization process, polyimide may be put into a firing furnace by being laminated on a natural graphite sheet. Such a preparation step may be carried out in order to prevent fusion of the films, in which the polyimide may have a film form.

Next, the carbonization step of the polyimide can be carried out at a temperature of 600 to 1,800 for 2 to 7 hours in the first step of the graphitization process. This carbonization step removes nitrogen and hydrogen, as well as carbon in the polyimide.

Finally, as a second step in the graphitization process, a heat treatment step at a temperature of 2,000 to 3,200 can be performed. This heat treatment step can lead to different alignments of the carbon atoms. Specifically, there may be pores between the stacks of carbon in the polyimide after the first step. By passing the rolling roll at a temperature of 2,000 ~ 3,200 ° C, pore removal and density are increased, The maximized graphitized polyimide can be produced.

In the composite sheet 100 of the present invention, it is preferable that the graphite layer 10 has a thickness satisfying the following equation (1).

[Equation 1]

 (d2 + d3) ≤ d1 ≤ 4 (d2 + d3), preferably (d2 + d3) ≤ d1 ≤ 3.5 (d2 + d3), more preferably (d2 + d3) ≤ d1 ≤ 2.5 )

D1 is the average thickness of the graphite layer, d2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer.

At this time, if d1 is smaller than (d2 + d3), the first and second adhesive layers are entirely too thick as a whole, which is disadvantageous in making the composite sheet thinner and the heat radiation effect may be lowered. If d1 is larger than 4 (d2 + d3), the first and second adhesive layers are relatively thin, so that the adhesive component can not be sufficiently filled in the holes in the graphite layer and the peel strength per hole of the graphite layer is lowered Can be.

It is preferable that the first adhesive layer and the second adhesive layer of the composite sheet satisfy the following equation (2).

[Equation 2]

d2? d3

D2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer.

It is preferable that the first adhesive layer and the second adhesive layer satisfy Equation 1 and preferably satisfy Equation 2. When the first adhesive layer d2 is thick in the heat radiation direction, If the first adhesive layer is thin, the second adhesive layer must be formed sufficiently thick to sufficiently fill the adhesive component in the holes of the graphite layer. Therefore, if the first adhesive layer and the second adhesive layer have different thicknesses It is preferable that the second adhesive layer is thicker than the first adhesive layer.

[Metal sheet layer]

In addition, the present invention may further include a metal sheet layer 40 on top of the second electromagnetic wave shielding layer 30 ', as schematically shown in FIG. More specifically, the metal sheet 40 not only shields electromagnetic waves but also absorbs electromagnetic waves, for example, a thermosetting epoxy resin, a rubber binder, a silane coupling agent, a fluorine surfactant, a soft magnetic powder , A curing agent, and a curing accelerator.

The metal sheet layer may be bonded to the second electromagnetic wave shielding layer by partially dissolving the adhesive component in the second electromagnetic wave shielding layer during the press or hot press process for producing the composite sheet. Therefore, it is advantageous for the mixed resin to have a melting point equal to or lower than the hot pressing process temperature (145 DEG C to 160 DEG C), or preferably to have a somewhat lower melting point.

Among the mixed resin components used for forming the metal sheet layer, the thermosetting epoxy resin may be used alone or in combination of two or more selected from the group consisting of bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin and Br-containing epoxy resin .

The rubber binder of the mixed resin component may be the same as or different from the rubber binder of the adhesive layer, and may include at least one of acrylic rubber, silicone rubber, carboxylated nitrile elastomer, and phenoxy And preferably one or two or more of acrylic rubber and silicone rubber may be included. At this time, the carboxylnitrile elastomer is the same as mentioned in the description of the adhesive layer. The amount of the rubber binder used in the mixed resin may be 160 to 350 parts by weight, preferably 180 to 300 parts by weight, more preferably 200 to 280 parts by weight, based on 100 parts by weight of the thermosetting epoxy resin. If the amount of the binder used is less than 160 parts by weight, the flexibility of the metal sheet may be deteriorated. In this case, there may be a problem that the bonding site between the metal sheet and the second electromagnetic wave shielding layer is partially peeled off when the composite sheet is bent. The use amount of the composition is uneconomical and relatively different, so that the electromagnetic shielding performance of the metal sheet and the adhesive strength to the second electromagnetic wave shielding layer may be deteriorated.

Among the mixed resin components, the silane coupling agent plays a role of dispersing the particles. Typical silane coupling agents used in the art can be used, and preferably glycidoxy (C2 to C5 alkyl) trialkoxysilane ( At least one selected from the group consisting of glycidoxy (C2-C5 alkyl) trialkoxysilane, vinyltri (C2-C5 alkoxy) silane and aminoethylaminopropylsilane triol, But are not limited to, singly or in combination of two or more selected from the group consisting of glycidoxypropyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, The amount of the silane coupling agent to be used may be 4 to 4 parts by weight per 100 parts by weight of the thermosetting epoxy resin. To 25 parts by weight, preferably 4 to 18 parts by weight, more preferably 4 to 12 parts by weight may be used. When the silane coupling agent is used in an amount of less than 4 parts by weight, the amount of the silane coupling agent used is too small, If it is used in an amount exceeding 25 parts by weight, there may be a problem of aggregation due to the reaction between the coupling agents.

Among the mixed resin components, the fluorine-based surfactant plays a role of improving the coating property by lowering the surface tension, and it is possible to use a general one used in the art, preferably a fluoroaliphatic polymeric ester Specific examples thereof include FC4430 of 3M, Novec 4300 of Du Pont, DuPont Capstone of DuPont, and the like. The amount of the fluorinated surfactant to be used may be 0.5 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the thermosetting resin. When the fluorinated surfactant is used in an amount of less than 0.5 parts by weight, The coating property may not be good. If it is used in an amount exceeding 5 parts by weight, there may be a problem that the adhesive strength with the second electromagnetic wave shielding layer is lowered.

Mixed Resin Component The soft magnetic powder is at least one selected from the group consisting of Fe-Si-Al alloys, Fe-Si-Cr alloys, Fe-Si-B alloys, highflux, permalloy alloys, ferrite and Mn-Zn ferrite. The Fe-Si-Al alloy, the Fe-Si-Cr alloy and the Fe-Si-B alloy May be used alone or in combination of two or more. The soft magnetic powder may be used in an amount of 700 to 1,500 parts by weight, preferably 850 to 1,350 parts by weight, more preferably 900 to 1,300 parts by weight, based on 100 parts by weight of the thermosetting epoxy resin. If the amount is less than 700 parts by weight There may be a problem that the electromagnetic wave absorbing performance due to reduction of the permeability is lowered. If it is used in excess of 1,500 parts by weight, the electromagnetic wave shielding effect is excellent, but the mechanical properties such as flexibility may be deteriorated.

The soft magnetic powder preferably has an average particle diameter of 20 to 100 mu m, preferably 30 to 70 mu m. If the average particle diameter is less than 20 mu m, there is a problem that the electromagnetic wave shielding or absorption performance is deteriorated When the average particle size exceeds 100 탆, the coating property may be deteriorated. Therefore, it is preferable to use a soft magnetic powder having a particle size within the above range.

Mixed Resin Component The curing agent may be the same or different from the curing agent used in the first adhesive layer and / or the second adhesive layer. The curing agent may be used in an amount of 2 to 30 parts by weight, preferably 3 to 20 parts by weight, more preferably 4 to 15 parts by weight, based on 100 parts by weight of the thermosetting epoxy resin. If the amount of the curing agent is less than 2 parts by weight There may be a problem that the hardening speed becomes too long and the workability is deteriorated. If it is used in excess of 30 parts by weight, the adhesive force to the second electromagnetic wave shielding layer is lowered due to the small amount of adhesive components flowing out from the metal sheet layer during the hot pressing process May occur.

Mixed Resin Component The humidity resistance agent is for controlling the moisture content and controlling the viscosity of the metal sheet and is preferably one kind selected from aluminum sulfate, latex, silicone emulsion, poly (organosiloxane), hydrophobic polymer emulsion, These may be used singly or in combination of two or more. The amount of the humectant to be used may be 1 to 25 parts by weight, preferably 5 to 20 parts by weight, based on 100 parts by weight of the thermosetting resin. If the amount of the humectant is less than 1 part by weight, If it is used in an amount exceeding 25 parts by weight, it may be difficult to control the proper amount of water of the metal sheet due to excessive use.

The mixed resin may be prepared by mixing an organic solvent with a mixture of the thermosetting epoxy resin, the rubber binder, the silane coupling agent, the fluorine surfactant, the soft magnetic particles, the curing agent and the moisture absorber described above to adjust the viscosity and the viscosity of the composition for forming the second electromagnetic wave- The solids content can be controlled. At this time, the organic solvent used may include at least one of methyl ethyl ketone, toluene, tetrahydrofuran (THF), and cyclohexanone.

The mixed resin is preferably adjusted to have a viscosity of 800 to 1,200 cps at 25 ° C and a solid content of 40 to 60% by weight, preferably a viscosity of 950 to 1,200 cps at 25 ° C and a solid content of 48 to 56% .

The metal sheet layer may have an average thickness of 30 mu m to 300 mu m, preferably 30 mu m to 200 mu m, more preferably 35 mu m to 100 mu m. At this time, if the average thickness of the metal sheet is less than 30 mu m, the increase in electromagnetic wave shielding effect may be insufficient, and if it exceeds 300 mu m, it is very disadvantageous in terms of thinning and is not economical

The composite sheet of the present invention is a laminate obtained by laminating a first electromagnetic wave shielding layer, a first adhesive layer, a graphite layer having a plurality of through holes, a second adhesive layer, and a second electromagnetic wave shielding layer in a press or hot press equipment Step one; Heating and pressing the laminate to perform a press or a hot press process; And separating the composite sheet integrated from the press or the hot press.

The composition and composition ratio of the first electromagnetic wave shielding layer, the first adhesive layer, the graphite layer, the first adhesive layer and the second electromagnetic wave shielding layer first adhesive layer in the first step are the same as those described above.

Further, in step 1, a metal sheet layer may be further laminated on the second electromagnetic wave shielding layer. The composition and composition ratio of the metal sheet layer are the same as those described above.

In the second step, the hot press process is preferably performed at a temperature of 145 to 160 ° C and a pressure of 45 to 60 kgf / cm 2. If the temperature is lower than 145 ° C, the adhesive component in the metal sheet layer is not sufficiently melted, If the temperature is higher than 160 ° C, too much adhesive component in the metal sheet layer may melt to make it difficult to maintain the shape of the metal sheet layer, and mechanical properties may be deteriorated. If the pressure is less than 45 kgf / cm < 2 > during the two-stage hot press process, the amount of the adhesive component of the first heat-radiating adhesive and / or the second heat-insulating adhesive flowing into the through hole of the graphite layer may be small, Is uneconomical.

It is preferable that the hot press process is performed by heating and pressing the laminate under the above pressure and temperature for 40 minutes to 80 minutes, preferably 50 minutes to 70 minutes. At this time, Minute, there is a problem that the amount of the first heat-radiating adhesive and / or the second heat-radiating adhesive filled into the holes of the graphite layer is small, so that the peel strength may be lowered.

The heating in the second step may be carried out by warming a hot press at 10 ° C to 35 ° C at a rate of 3 ° C / min to 5 ° C / min to 145 ° C to 160 ° C.

The three-step cooling may be performed by cooling the hot press at 145 ° C to 160 ° C at a rate of 3 ° C / minute to 5 ° C / minute to 10 ° C to 35 ° C.

The composite sheet of the present invention produced by the above-described structure, composition and composition ratio of each layer and the production method of the present invention has a horizontal thermal conductivity of 100 to 1,000 W / m · k and a vertical thermal conductivity of 1 to 15 W / m · k or less And preferably has a horizontal thermal conductivity of 200 to 1,000 W / m · k and a vertical thermal conductivity of 1 to 10 W / m · k.

In a composite sheet of the present invention is 180 ° peel test the peel strength of the graphite layers on the basis of JIS C 6741 specifications (180 ° Peel Test) to ^{300 gf / cm 2 ~ 700gf /} cm 2 as measured It is, and may preferably be ^{350 gf / cm 2 ~ 650gf /} cm 2, more ^{preferably, 400 gf / cm 2 ~ 620gf} / cm 2.

The composite sheet according to the present invention has a peel strength per hole of 50 to 1,200 gf / hole, preferably 100 to 900 gf / cm 2, as measured by a 90 ° peel test, according to JIS C 6741 standard / Hole, and more preferably 200 to 750 gf / hole.

The electromagnetic shielding and heat-dissipating function integrated composite sheet of the present invention can be used as an electromagnetic wave shielding and heat dissipation component of an electronic device, and is preferably used for a digitizer, a smart phone, a tablet personal computer portable electronic devices such as a personal computer, a personal computer, a portable multimedia player (PMP), or a wearable electronic device such as a VR (Virtual Reality) and a smart watch.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the scope of the present invention is not limited to the examples illustrated by the following examples.

[ Example ]

Preparation Example  1-1: Preparation of adhesive

Based on 100 parts by weight of a thermosetting epoxy resin containing bisphenol A epoxy resin (K Chemicals, trade name YD series resin) and novolak epoxy resin (KODO CHEMICAL, YDCN series resin) 1: 0.25 weight ratio, (3M, trade name: FC series surfactant), 0.15 part by weight of a silane coupling agent (Dow Corning, trade name Z6106), 4,4'-diamino di A mixture of 15 parts by weight of phenylsulfone, 3.2 parts by weight of a curing accelerator (manufactured by Shikoku), 5.2 parts by weight of a moisture-proofing agent (Japan S Company, KP series) and 42 parts by weight of a flame retardant (OP series of Swiss C Company) Ethyl ketone and stirred to prepare a heat-resistant adhesive.

Preparation Example  1-2 to 1-3 and Example of comparison preparation  1-1-2

Adhesives having the compositions shown in Table 1 below were prepared in the same manner as in Preparation Example 1-1 and were used to prepare Preparative Examples 1-2 to 1-3 and Comparative Preparations 1-1 to 1-2 Respectively.

division
(Parts by weight) Preparation Example 1-1 Preparation Example 1-2 Preparation Example 1-3 Comparative Preparation Example 1-1 Comparative Preparation Example 1-2 Thermosetting resin Bisphenol A epoxy resin and
Novolac epoxy resin
Mixed resin 1: 0.25
Weight ratio 1: 0.25
Weight ratio Bisphenol A epoxy resin
Exclusive 1: 0.25
Weight ratio 1: 0.25
Weight ratio Total (parts by weight) 100 100 100 100 100 Rubber binder 65 78 65 10 120 Silane coupling agent 1.7 3.9 1.7 1.7 1.7 Fluoric surfactant 0.15 0.35 0.15 0.15 0.15 Hardener 15 9 15 15 15 Hardening accelerator 3.2 1.6 3.2 3.2 3.2 Flame retardant 42 38 42 42 42 Humidifier 5.2 2.7 5.2 5.2 5.2

Preparation Example  2-1: Through hole  Equipped Graphite  Manufacture of sheet

A plurality of circular through holes 11 were formed in a graphite sheet (T company, TGS17) having an average thickness of 17 mu m (see a schematic view of Fig. 4A).

The perforated hole 1 had an average diameter of 3 mm. The major axis distance between the centers of the through holes was 10 mm. The minor axis distance was 12 mm. The total area of the through holes was the entire 3.9 to 4.1% of the area, and the deformation degree of the through hole was 1.256 based on the following equation (1).

[Equation 1]

Deformation degree = (inside width of shape / circumference length of shape) ^1/2 .

Preparation Example  2-2 ~ Preparation Example  2-9 and Example of comparison preparation  2-1 ~ Example of comparison preparation  2-2

Graphite sheets each having a through hole having a cross-sectional shape as shown in Table 3 below were prepared on the same graphite sheet as the graphite sheet of Preparation Example 2-1, and the characteristics of these graphite sheets are shown in Table 2 below.

In Table 2, the through holes are formed by adjusting the number and spacing of the through holes so as to satisfy the entire area of the through holes.

division Through hole cross-sectional shape Heterogeneity Through hole center
Interspacing
(Long axis direction) Through hole center
Interspacing
(Short axis direction) The total area of the top of the seat
Overall area of through hole Preparation Example 2-1 circle
(Diameter 3 mm) 0.866 10 mm 12 mm 4.0% Preparation Example 2-2 circle 0.866 8 mm 12 mm 5.1% Preparation Example 2-3 circle 0.866 6 mm 12 mm 7.5% Preparation Example 2-4 circle 0.866 6 mm 10.5 mm 9.4% Preparation Example 2-5 + Type
(Width 1 mm) 0.678 13 mm 13 mm 5.2% Preparation Example 2-6 + Type
(Width 1 mm) 0.678 11 mm 13 mm 6.5% Preparation Example 2-7 + Type
(Width 1.5 mm) 0.812 13 mm 13 mm 7.4% Preparation Example 2-8 + Type
(Width 1.5 mm) 0.812 11 mm 13 mm 9.3% Preparation Example 2-9 ┏ type
(Width 1 mm) 0.678 13 13 5.2% Preparation Example 2-10 ┏ type
(Width 1 mm) 0.678 11 13 6.5% Preparation Example 2-11 ┏ type
(Width 1.5 mm) 0.812 13 13 7.4% Preparation Example 2-12 ┏ type
(Width 1.5 mm) 0.812 11 11 9.3% Comparative Preparation Example 2-1 circle
(Diameter 9mm) 1.500 10 mm 12 mm 14.8% Comparative Preparation Example 2-2 circle
(Diameter 0.94 mm) 0.485 10 mm 12 mm 3.3%

Example of comparison preparation  2-3

The graphite sheet (Taiwan T Company, TGS Series product) without the through hole of Preparation Example 2-1 itself was prepared in Comparative Preparation Example 2-3.

Preparation Example  3-1: Preparation of metal sheet

265.2 parts by weight of a carboxylate nitrile elastomer (weight average molecular weight: 235,500 to 236,500) as a polymeric binder, 100 parts by weight of a silane coupling agent (manufactured by US D Co., Ltd.) per 100 parts by weight of bisphenol A epoxy resin as a thermosetting epoxy resin 2.05 parts by weight of a fluorine surfactant (trade name of FC series surfactant manufactured by M Company, USA), 978 parts by weight of an Fe-Si-Al sandstock powder having an average particle diameter of 42 to 44 μm, , 9.7 parts by weight of 4,4'-diaminodiphenlysulfone (4,4'-diaminodiphenlysulfone), and 10.5 parts by weight of a moisture-proofing agent (Japan S, KP 392) were added to methyl ethyl ketone as an organic solvent Next, the viscosity was adjusted to 1,050 to 1,080 cps and the solid content was adjusted to 53% by weight, and the resulting mixture was applied to a mold release substrate and then aged at 60 DEG C for 24 hours to prepare a semi-cured metal sheet.

Preparation Example  3-2 ~ Preparation Example  3-3

A metal sheet as a second electromagnetic wave shielding layer was prepared in the same manner as in Preparation Example 3-1, except that a metal sheet having the composition shown in Table 3 was prepared.

division
(Parts by weight) Preparation Example
3-1 Preparation Example
3-2 Preparation Example
3-3 Thermosetting epoxy resin 100 100 100 Rubber binder 265.2 300 200 Silane coupling agent 8.5 6.0 8.5 Fluorine
Surfactants 2.05 1.87 1.98 Soft magnetic powder 978 978 1,290 Hardener 9.7 9.7 8.6 Humidifier 10.5 10.5 13.0

Example  1: Manufacture of integrated multilayer composite sheet

The adhesive prepared in Preparation Example 1-1 was coated on one surface of a copper foil (first electromagnetic wave shielding layer) having an average thickness of 9 탆 and then semi-cured to form a first adhesive layer.

Separately, the adhesive prepared in Preparation Example 1-1 was coated on one side of a copper foil (second electromagnetic wave shielding layer) having an average thickness of 12 μm, and then semi-cured to form a second adhesive layer.

Next, the first electromagnetic wave shielding layer was bonded and laminated, and then the graphite sheet of Preparation Example 2-1 was laminated on the adhesive layer. At this time, the graphite sheet is not formed with a passivation film.

Next, the second electromagnetic wave shielding layer was laminated on the top of the graphite sheet so that the second adhesive layer and the graphite sheet were laminated.

Next, hot-press equipment was put into a sheet laminated with the first electromagnetic wave shielding layer-first adhesive layer-graphite layer-second adhesive layer-second electromagnetic wave shielding layer.

Next, the hot press was heated from 70 ° C to 150 ° C at a rate of 4 ° C / minute, and thermocompression was performed for 60 minutes under the conditions of 150 and 50 kgf / cm 2 pressure.

Next, the sheet was cooled to 60 deg. C at a rate of 4.5 deg. C / minute, and then the thermally compressed sheet was taken out from the hot press to form a first adhesive layer and a second adhesive layer in the through holes of the graphite layer as shown in Fig. And the filled electromagnetic wave shielding and heat dissipating function integral multi-layer composite sheet were produced.

The total thickness of the manufactured integrated multi-layer composite sheet 100 was 48 m, the average thickness of the first electromagnetic wave shielding layer 40 was 9 m, the average thickness of the adhesive layer 30 was 5 m, the average thickness of the graphite layer 10 The average thickness of the second heat dissipative adhesive layer was 5 m, and the average thickness of the second electromagnetic wave shielding layer 30 was 12 m.

Example  2 ~ Example  13

In the same manner as in Example 1, the composite multi-layer composite sheets as shown in the following Table 4 were produced and Examples 2 to 13 were respectively conducted.

Example  14: The metal sheet layer  The formed multi-layer composite sheet

Layered composite sheet was produced in the same manner as in Example 1 except that the first electromagnetic wave shielding layer-first adhesive layer-graphite layer-second adhesive layer-second electromagnetic wave shielding layer of the sheet laminated with hot- The metal sheet prepared in Preparative Example 3-1 was laminated on the electromagnetic wave shielding layer and then put in a hot press machine to perform a hot press process in the same manner as in Example 1. [

The total thickness of the manufactured integral multi-layer composite sheet 100 was 98 m, the average thickness of the first electromagnetic wave shielding layer 40 was 9 m, the average thickness of the adhesive layer 30 was 5 m, the average thickness of the graphite layer 10 The average thickness of the second heat-radiation adhesive layer was 5 mu m, the average thickness of the second electromagnetic wave-shielding layer 30 was 12 mu m, and the average thickness of the metal sheet layer was 50 mu m (see Fig. 1).

Example  15 ~ Example  16

In the same manner as in Example 14, monolithic multilayer composite sheets having the combinations shown in Table 4 were prepared, and Examples 15 to 16 were respectively conducted.

Comparative Example  One

In the same manner as in Example 1, A multilayer composite sheet was produced using the graphite sheet of Comparative Preparation Example 3-1 instead of the graphite sheet of Preparation Example 2-1 to produce an integral multi-layer composite sheet with electromagnetic shielding and heat radiation function.

The total thickness of the manufactured integrated multi-layer composite sheet 100 was 48 m, the average thickness of the first electromagnetic wave shielding layer 40 was 9 m, the average thickness of the adhesive layer 30 was 5 m, the average thickness of the graphite layer 10 The average thickness of the second heat dissipative adhesive layer was 5 m, and the average thickness of the second electromagnetic wave shielding layer 30 was 12 m.

Comparative Example  2 ~ Comparative Example  6

Composite multi-layer composite sheets having the combinations as shown in Table 5 below were prepared in the same manner as in Example 1, and Comparative Examples 2 to 6 were respectively performed.

division The first and second electromagnetic waves
Shielding layer The first and second adhesive layers Graphite
Sheet layer The metal sheet layer Composite sheet
Overall Thickness Interlayer thickness ⁽¹⁾
(탆) Example 1 Copper foil Preparation Example
1-1 Preparation Example
2-1 - 48 탆 9/5/17/5/12 Example 2 Copper foil Preparation Example
1-1 Preparation Example
2-1 - 53 탆 9/3/17/5/12 Example 3 Copper foil Preparation Example
1-1 Preparation Example
2-1 - 54 탆 9/4/17/12/12 Example 4 Copper foil Preparation Example
1-1 Preparation Example
2-2 - 48 탆 9/5/17/5/12 Example 5 Copper foil Preparation Example
1-1 Preparation Example
2-3 - 48 탆 9/5/17/5/12 Example 6 Copper foil Preparation Example
1-1 Preparation Example
2-4 - 48 탆 9/5/17/5/12 Example 7 Copper foil Preparation Example
1-1 Preparation Example
2-5 - 48 탆 9/5/17/5/12 Example 8 Copper foil Preparation Example
1-1 Preparation Example
2-6 - 48 탆 9/5/17/5/12 Example 9 Copper foil Preparation Example
1-1 Preparation Example
2-7 - 48 탆 9/5/17/5/12 Example 10 Copper foil Preparation Example
1-1 Preparation Example
2-8 - 48 탆 9/5/17/5/12 Example 11 Copper foil Preparation Example
1-1 Preparation Example
2-9 - 48 탆 9/5/17/5/12 Example 12 Copper foil Preparation Example
1-2 Preparation Example
2-1 - 48 탆 9/5/17/5/12 Example 13 Copper foil Preparation Example
1-3 Preparation Example
2-1 - 48 탆 9/5/17/5/12 Example 14 Copper foil Preparation Example
1-1 Preparation Example
2-1 Preparation Example
3-1 98 탆 9/5/17/5/12/50 Example 15 Copper foil Preparation Example
1-1 Preparation Example
2-1 Preparation Example
3-2 98 탆 9/5/17/5/12/50 Example 16 Copper foil Preparation Example
1-1 Preparation Example
2-1 Preparation Example
3-3 98 탆 9/5/17/5/12/50 (1) The order of thickness between layers is the order of the first electromagnetic wave shielding layer, the first adhesive layer, the graphite sheet layer, the second adhesive layer, the second electromagnetic wave shielding layer and the metal sheet.

division The first and second electromagnetic waves
Shielding layer The first and second adhesive layers Graphite
Sheet layer The metal sheet layer Composite sheet
Overall Thickness Interlayer thickness ⁽¹⁾
(탆) Comparative Example 1 Copper foil Preparation Example
1-1 Example of comparison preparation
2-1 - 48 탆 9/5/17/5/12 Comparative Example 2 Copper foil Preparation Example
1-1 Example of comparison preparation
2-2 - 48 탆 9/5/17/5/12 Comparative Example 3 Copper foil Preparation Example
1-1 Example of comparison preparation
2-3 - 48 탆 9/5/17/5/12 Comparative Example 4 Copper foil Preparation Example
1-1 Preparation Example
2-1 - 41 탆 9 / 1.5 / 17 / 1.5 / 12 Comparative Example 5 Copper foil Preparation Example
1-1 Preparation Example
2-1 - 58 탆 9/10/17/10/12 Comparative Example 6 Copper foil Preparation Example
1-1 Preparation Example
2-1 - 48 탆 9/12/17/4/12 (1) The order of thickness between layers is the order of the first electromagnetic wave shielding layer, the first adhesive layer, the graphite sheet layer, the second adhesive layer, the second electromagnetic wave shielding layer and the metal sheet.

Experimental Example  : Peel strength and Thermal diffusivity  Measure

(One) Graphite layer  Total Peel Strength ( gf / cm ² ) And Perforated hall  Peel strength gf / Hole)

The integrated composite sheet prepared in each of the Examples and Comparative Examples was prepared in accordance with JIS C 6741, and the peel strength of the entire graphite layer was measured by a 180 ° peel test (180 ° Peel Test) Are shown in Table 6 below.

Further, the peel strength per through hole was measured by performing 90 占 peel test (90 占 Peel Test).

(2) Thermal diffusivity  Measure

The integrated composite sheet produced in each of the Examples and Comparative Examples was cut into a size of 100 mm x 10 mm (width, length), and a double-sided tape was attached to one surface of the copper foil (Cu).

Next, the prepared sample is attached onto the heating block and the temperature of the heating block is raised to 80 ° C (the temperature is raised to 80 ° C, which is the temperature of the AP chip in the Smart Phone).

Next, the heating block was sealed in a box and stabilized for 10 minutes. Then, the temperature was measured using an IR camera to determine the highest temperature (hot spot) and the lowest temperature (cold spot) of the composite sheet , And the temperature difference between these was measured to determine the thermal diffusivity of the composite sheet. At this time, the smaller the difference between the two temperatures is, the better the heat radiation performance is.

division Total peel strength
(gf / cm ²⁾ Perforated hall
Peel strength
(gf / hole) Hot spot
(° C) Cold spot
(° C) ΔT
(Hot spot - Cold spot) Example 1 562 346 78.12 57.52 20.60 Example 2 535 342 78.15 57.40 20.75 Example 3 552 349 78.24 57.35 20.89 Example 4 588 350 78.31 57.11 21.20 Example 5 602 350 78.34 56.83 21.51 Example 6 627 345 78.42 56.68 21.74 Example 7 583 353 78.29 57.06 21.23 Example 8 594 348 78.22 56.84 21.38 Example 9 605 350 78.36 56.81 21.55 Example 10 621 352 78.39 56.67 21.72 Example 11 586 345 78.27 57.13 21.17 Example 12 550 337 78.13 57.51 20.62 Example 13 555 340 78.15 57.48 20.67 Example 14 550 345 77.92 55.84 22.08 Example 15 553 352 77.97 55.86 22.11 Example 16 556 348 77.94 55.82 22.12 Comparative Example 1 1182 817 81.43 57.12 24.31 Comparative Example 2 310 123 78.10 57.63 20.47 Comparative Example 3 55 - 77.93 57.92 20.01 Comparative Example 4 385 155 78.15 57.67 20.48 Comparative Example 5 823 404 79.35 55.13 24.22 Comparative Example 6 715 368 78.09 56.49 21.60

As a result of the measurement of Table 6, in the case of Examples 1 to 16, the total peel strength was 400 gf / cm ² , The peel strength per pass hole was 320 gf / hole or higher, and the difference between the hot spot and the cold spot was less than 22.50, indicating excellent overall thermal diffusivity.

More specifically, through comparison of Examples 1 to 3, it can be confirmed that a change in the thickness of the first adhesive layer and the second adhesive layer affects the peel strength and thermal diffusibility, and when the second adhesive layer becomes thick It was confirmed that the peel strength was increased, but the thermal diffusivity tended to be somewhat lower.

In Examples 1 and 4 to 11, the tendency to affect the peel strength and the thermal diffusion performance was confirmed by the cross-sectional shape of the through holes, the spacing between the through holes, and the total area of the through holes.

In Examples 14 to 16, which are composite sheets having a metal sheet layer, the difference between the hot spot and the cold spot was relatively higher than that in Example 1, but the hot spot temperature itself was relatively lower, It is possible to secure the electromagnetic wave shielding effect according to the existence of the presence.

On the contrary, in the case of the integral composite sheet (Comparative Example 1) made of the graphite sheet of Comparative Preparation Example 2-1 equipped with through holes having the profile 1.5 and the total area of the through holes of 14.8%, the peel strength But the difference between the hot spot and the cold spot is 24.31, which shows that the thermal diffusivity is lowered.

Further, the integrated composite sheet of Comparative Example 2 in which the graphite sheet of Comparative Preparation Example 2-2 was introduced with less than 0.500 degree of release, and the composite composite sheet of Comparative Example 3 in which the graphite sheet of Comparative Preparation Example 2-3 without through hole was introduced , The thermal diffusivity was very good but the total peel strength was low.

In the case of Comparative Example 4 in which the average thickness D1 of the graphite layer exceeds 4 (thickness of the first adhesive layer (d2) + thickness of the second adhesive layer (d3)), the first and second adhesive layers are too The adhesive component is not sufficiently filled in the hole in the graphite layer and the peel strength per hole of the graphite layer is too low.

In the case of Comparative Example 5 in which the average thickness d1 of the graphite layer was smaller than the sum of the first adhesive layer thickness d2 and the second adhesive layer thickness d3, the total peel strength and peel strength per hole were excellent However, the difference between the hot spot and the cold spot was 24.22, which deteriorated the heat dissipation effect. The composite sheet was disadvantageous to flaking and the flexible sheet of the composite sheet was not good.

In the case of Comparative Example 6 in which the equation (1) was satisfied but the second adhesive layer thickness d3 was larger than the first adhesive layer thickness d2, the difference between the hotspots and the coldspots was 21.60 and the difference between the hotspots and the coldspots Is 20.76, the thermal diffusivity is rather reduced.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

1, 2, 3, 4: Through hole 10: Graphite sheet layer provided with through holes
20: a first adhesive layer or a first heat-dissipating adhesive
20 ': a second adhesive layer or a second heat-dissipating adhesive
25: first adhesive layer-derived adhesive component 25 ': second adhesive layer-derived adhesive component
30: first electromagnetic wave shielding layer 30: second electromagnetic wave shielding layer
40: metal sheet 100: electromagnetic wave shielding and heat radiation function integrated composite sheet

Claims (20)

delete A first adhesive layer, a graphite layer having a plurality of through holes, a second adhesive layer, and a second electromagnetic wave shielding layer laminated in this order,
The passivation film is not provided on the upper and lower portions of the graphite layer,
The inside of the through hole of the graphite layer is filled with an adhesive derived from the first adhesive layer and the second adhesive layer,
Wherein the thickness of the graphite layer satisfies the following equation (1)
Wherein each of the first adhesive layer and the second adhesive layer has an average thickness of 3 to 8 탆,
Wherein each of the first adhesive layer and the second adhesive layer comprises 25 to 100 parts by weight of a rubber binder, 1 to 10 parts by weight of a silane coupling agent, 0.01 to 2 parts by weight of a fluorinated surfactant, 1 to 5 parts by weight of a curing accelerator, 30 to 60 parts by weight of a flame retardant, and 0.5 to 10 parts by weight of a moisture-
Wherein the thermosetting epoxy resin comprises at least one selected from the group consisting of a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novaleak epoxy resin and a halogen-containing epoxy resin.
[Equation 1]
(d2 + d3)? d1? 3 (d2 + d3)
D1 is the average thickness of the graphite layer, d2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer.
The multilayer composite sheet according to claim 2, wherein the first adhesive layer and the second adhesive layer satisfy the following equation (2).
[Equation 2]
d2? d3
d2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer.
delete 3. The electromagnetic interference shielding and heat dissipation integrated multi-layer composite sheet according to claim 2, wherein a metal sheet layer is further laminated on the second electromagnetic wave shielding layer.
The electronic apparatus according to claim 2, wherein the first electromagnetic wave shielding layer is a copper foil, an aluminum foil or a metal sheet,
The second electromagnetic wave shielding layer is a copper foil or an aluminum foil,
Wherein the graphite layer is a graphite sheet comprising at least one of pyrolytic graphite and graphitized polyimide,
Wherein the first adhesive layer and the second adhesive layer comprise a thermosetting resin, a rubber binder, a silane coupling agent, a fluorine surfactant, a curing agent, and a curing accelerator.
6. The metal sheet according to claim 5, wherein the metal sheet comprises 160 to 350 parts by weight of a rubber binder, 4 to 25 parts by weight of a silane coupling agent, 0.5 to 5 parts by weight of a fluorinated surfactant, Wherein the curable composition is a cured product of a mixed resin comprising 1,500 parts by weight of a curing agent, 2 to 30 parts by weight of a curing agent and 1 to 25 parts by weight of a moistureproofing agent.
delete The composite multi-layer composite sheet according to claim 2, wherein one of the first adhesive layer and the second adhesive layer further comprises a thermally conductive filler.
8. The method of claim 7, wherein the soft magnetic powder is selected from the group consisting of Fe-Si-Al alloys, Fe-Si-Cr alloys, Fe-Si- B alloys, highflux, permalloy alloys, Zn ferrite alloy, and Mn-Zn ferrite alloy. The multi-layered composite sheet according to claim 1,
The composite multi-layer composite sheet according to claim 10, wherein the soft magnetic powder has an average particle diameter of 20 to 100 占 퐉.
The multi-layer composite sheet according to claim 2, wherein the through hole area of the graphite layer is 2% to 30% of the total area of the upper or lower surface of the graphite layer.
The integrated multi-layer composite sheet for electromagnetic shielding and heat dissipation according to claim 2, characterized in that it has a thickness of 50 to 1,200 gf / hole when measured for peel strength per through hole in accordance with JIS C 6741.
3. The electromagnetic shielding and heat dissipation integrated multi-layer composite sheet according to claim 2, wherein the through holes are formed in a cross-sectional shape having a profile that satisfies the following equation (3).
[Equation 3]
0.500 ≤
In the above-mentioned eccentricity 3, the mold-outline is (inner width of the shape / circumference length of the shape) ^1/2 .
delete A first step of putting a laminate obtained by sequentially laminating a first electromagnetic wave shielding layer, a first adhesive layer, a graphite layer having a plurality of through holes, a second electromagnetic wave shielding layer and a methyl sheet layer in this order into a hot press equipment;
Two steps of heating and pressing the laminate under a pressure of 145 to 160 DEG C and 45 to 60 kgf / cm < 2 > for 50 to 70 minutes; And
And cooling the hot press and then separating the composite sheet integrated from the hot press,
The inside of the through hole of the graphite layer of the three-stage composite sheet is filled with an adhesive derived from the first adhesive layer and the second adhesive layer,
The thickness of the graphite layer satisfies the following equation 1 and the through hole area of the graphite layer is 2 to 30% of the total area of the upper or lower surface of the graphite layer,
Wherein each of the first adhesive layer and the second adhesive layer has an average thickness of 3 to 8 탆,
Each of the first adhesive layer and the second adhesive layer in the first stage is composed of 25 to 100 parts by weight of a rubber binder, 1 to 10 parts by weight of a silane coupling agent, 0.01 to 2 parts by weight of a fluorinated surfactant, 5 to 20 parts by weight, 1 to 5 parts by weight of a curing accelerator, 30 to 60 parts by weight of a flame retardant, and 0.5 to 10 parts by weight of a moisture-
Wherein the thermosetting epoxy resin comprises at least one selected from a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novaleak epoxy resin and a halogen-containing epoxy resin,
Wherein the rubber binder comprises a carboxylate elastomer. ≪ RTI ID = 0.0 > 11. < / RTI >
[Equation 1]
(d2 + d3)? d1? 3 (d2 + d3)
D1 is the average thickness of the graphite layer, d2 is the average thickness of the first adhesive layer, and d3 is the average thickness of the second adhesive layer.

17. The method according to claim 16, wherein the heating in the second step is carried out by heating a hot press at 10 占 폚 to 35 占 폚 at 145 占 폚 to 160 占 폚 at a rate of 3 占 폚 / min to 5 占 폚 /
Wherein the cooling in the three stages is performed by cooling a hot press at 145 ° C to 160 ° C at a rate of 3 ° C / minute to 5 ° C / minute to 60 ° C to 80 ° C. .
A coverlay film comprising the integral multi-layer composite sheet of any one of claims 2 to 3, 5 to 7, and 9 to 14.
A flexible circuit board comprising the integral multi-layer composite sheet according to any one of claims 2 to 3, 5 to 7, and 9 to 14.
A portable electronic device comprising an integral multi-layer composite sheet according to any one of claims 2 to 3, 5 to 7, and 9 to 14.

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