KR102041859B1 - Composite sheet for absorbing impact - Google Patents

Abstract

The present invention is a thermally conductive layer formed by laminating one or more metal alone or mixed; An impact absorbing layer provided in direct contact with one surface or both surfaces of the thermal conductive layer; And a pressure sensitive adhesive layer (PSA) provided on one or both surfaces of the shock absorbing layer, and relates to a shock absorbing composite sheet having thermal conductivity according to Equations 1 and 2 below.
[Equation 1] λC = {1 / T * Σ (Ti * λi)} * (1 + D)
0.03 ≦ D ≦ 0.25

Description

Composite sheet for absorbing impact

The present invention relates to a shock-absorbing composite sheet, and more particularly, to a shock-absorbing composite sheet having improved heat dissipation properties for the heating element and buffering properties against external forces.

The trend toward miniaturization, slimming, and multifunction of electronic devices such as mobile phones, hard disk drives (HDDs), televisions, and liquid crystal displays has increased the integration of electronic devices, and the heat generation of electronic devices operated by electric energy has also increased. Doing. Since heat generated in the electronic device is accumulated in the electronic device to reduce the operating life of the electronic device, there is an increasing demand for heat dissipation characteristics that effectively disperse and dissipate heat generated in the electronic device.

In addition, electronic devices according to the trend of miniaturization, slimming, and multifunction may easily break down or be damaged when a physical shock is applied from the outside, and the electronic device is integrated due to the small space for mounting the electronic device, which is generated per unit volume. The amount of heat to be increased greatly. In addition, contaminants such as dust introduced from the outside may interfere with the air flow in the electronic device, causing overheating of the electronic device, thereby reducing the life of the electronic device.

Various materials have been adopted to solve the problem caused by the heat generation of the electronic device, but until now, an optimal material having a thin thickness and excellent heat dissipation performance has not been developed.

On the other hand, Korean Patent Laid-Open No. 10-2014-0029159 discloses a heat-resistant adhesive sheet in the form of foam for smartphones and tablet PCs made of a foam layer, the adhesive layer formed on the upper and lower surfaces of the foam layer. On the other hand, such an adhesive sheet has a limit in dissipating high temperature heat generated locally in a hot spot heating part of a portable terminal, and thus cannot solve the heat problem generated in recent high-performance electronic devices. In addition, there is a disadvantage that it is not suitable for electronic devices that are miniaturized, slimmed and multifunctional because additional members must be added because they do not include impact absorption capacity against external force.

Accordingly, various studies on materials with multi-functions that can effectively protect electronic devices from external forces while maintaining the volume of the miniaturized and slimmer electronic devices, as well as heat dissipation characteristics that effectively dissipate and dissipate heat generated from electronic devices Is going on.

It is an object of the present invention to provide a shock absorbing composite sheet in which the shock absorbing ability against external force is increased while effectively dissipating heat.

In addition, another object of the present invention is to provide a shock absorbing composite sheet having improved heat dissipation and impact absorption capacity without increasing unnecessary volume in a slim and miniaturized heating element.

In addition, another object of the present invention to provide a shock absorbing composite sheet that can omit unnecessary experiments by providing a design value for the heat dissipation optimized for the heat generated by the heating element.

According to an aspect of the present invention, embodiments of the present invention comprises a thermally conductive layer formed by stacking one or more metals alone or mixed; An impact absorbing layer provided in direct contact with one surface or both surfaces of the thermal conductive layer; And a pressure sensitive adhesive layer (PSA) provided on one or both surfaces of the shock absorbing layer, and relates to a shock absorbing composite sheet having thermal conductivity according to Equations 1 and 2 below.
The thermal conductivity of the composite sheet for shock absorption is 50W / mK to 200W / mK, the thermal conductive layer is a Cu layer, Ni-Cu-Ni layer, Sn-Cu-Sn layer, Co-Cu-Co layer and Al layer Either one, the thickness of the thermal conductive layer is 8㎛ to 150㎛, the ratio of the thickness of the thermal conductive layer to the total thickness of the shock absorbing composite sheet is 12% to 50%.

[Equation 1] λC = {1 / T * Σ (Ti * λi)} * (1 + D)

0.03 ≦ D ≦ 0.25

In Equation 1, λC is the thermal conductivity of the composite sheet for shock absorption (W / mK), T is the total thickness of the composite sheet for shock absorption (μm), Ti is a layer of a single or mixed metal constituting the thermal conductive layer Is the thickness of each layer (μm), λ i is the thermal conductivity (W / mK) of each layer on which the single or mixed metals constituting the heat conductive layer are laminated, and Σ (Ti * λ i) constitutes the thermal conductive layer. Is the total sum of the products of the individual or mixed metal layers laminated with the thermal conductivity. D follows Equation 2.

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The metal constituting the thermally conductive layer may be at least one of copper, aluminum, nickel, tin, cobalt, chromium, gold, and silver. Preferably, the thermal conductive layer may be any one or more of a Cu layer, a Ni—Cu—Ni layer, a Sn—Cu—Sn layer, a Co—Cu—Co layer, and an Al layer. More preferably, the thermal conductive layer may be one or both of nickel, tin and cobalt plated on one or both surfaces of the copper layer.

The ratio of the thickness of the heat conductive layer to the total thickness may be 12% to 50%.

The heat conductive layer may have a thickness of 8 μm to 150 μm.

The shock absorbing layer comprises a polymer foam, the polymer foam is an acrylic foam, polyurethane foam, polyethylene foam, polyolefin foam, polyvinyl chloride foam, polycarbonate foam, polyimide foam, polyetherimide foam, polyamide foam, poly At least one selected from the group consisting of ester foams, polyvinylidene chloride foams, polymethylmethacrylate foams, and polyisocyanate foams.

The shock absorbing layer may include a polymer foam, and the polymer foam may be a polyurethane foam or an acrylic foam.

The impact absorbing layer may have a density of 0.2 g / cm 3 to 0.8 g / cm 3.

The impact absorbing layer may have a thickness of 50 μm to 250 μm.

The pressure-sensitive adhesive layer may be any one or more of acrylic, silicone, epoxy, urethane, polyester and polyimide.

The pressure-sensitive adhesive layer may have a thickness of 5 μm to 50 μm.

A protective layer may be further provided on an outer surface of the pressure sensitive adhesive layer.

In addition, one surface of the thermal conductive layer may be sequentially provided with a shock absorbing layer, a pressure-sensitive adhesive layer and a protective layer, and the other surface of the thermal conductive layer may be provided with a TR-CPSA (Thermal Responsive Conductive Pressure Sensitive Adhesive) and a protective layer in sequence. .

According to another aspect of the present invention, a shock absorbing composite sheet according to the present invention comprises a thermally conductive layer formed by stacking one or more metals alone or mixed; An impact absorbing layer provided in direct contact with one surface or both surfaces of the thermal conductive layer; And a pressure sensitive adhesive layer (PSA) provided on one or both surfaces of the impact absorbing layer, and the thermal conductivity may follow Equations 3 to 6.
The thermal conductivity of the composite sheet for shock absorption is 50W / mK to 200W / mK, the thermal conductive layer is a Cu layer, Ni-Cu-Ni layer, Sn-Cu-Sn layer, Co-Cu-Co layer and Al layer The thickness of the heat conductive layer is any one, 8㎛ to 150㎛, in the following formulas 3 to 4, when the thermal conductive layer is a Cu layer a is 1.7 to 1.9, b is 0.09 to 0.11, the heat conductive layer is In the case of sequentially stacked Ni-Cu-Ni layers, a is 1.6 to 1.8, b is 0.09 to 0.1, and when the thermally conductive layers are sequentially stacked Sn-Cu-Sn layers, a is 1.6 to 1.8 and b is 0.09. To 0.1, when the thermally conductive layers are sequentially stacked Co-Cu-Co layers, a is 1.6 to 1.8, b is 0.08 to 0.1, and when the thermally conductive layer is an Al layer, a is 0.9 to 1.1 and b is 0.1 To 0.2.

Y = (aX + b) * (1 + D)

0.9 ≦ a ≦ 1.9

0.08 ≦ b ≦ 0.011

0.03 ≦ D ≦ 0.25

In Equation 3, Y is the thermal conductivity (W / mK) of the shock absorbing composite sheet, and X is the thickness (μm) of each layer on which a single or mixed metal constituting the heat conductive layer is laminated. a is according to equation 4, b is according to equation 5, and D is according to equation 6.

The ratio of the thickness of the heat conductive layer to the total thickness may be 12% to 50%.

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The metal constituting the thermally conductive layer may be at least one of copper, aluminum, nickel, tin, cobalt, chromium, gold, and silver.

The thermal conductive layer may be any one or more of a Cu layer, a Ni—Cu—Ni layer, a Sn—Cu—Sn layer, a Co—Cu—Co layer, and an Al layer.

The thermal conductive layer may be provided by plating one or more of nickel, tin, and cobalt on one or both surfaces of the copper layer.

A protective layer may be further provided on an outer surface of the pressure sensitive adhesive layer.

One surface of the thermal conductive layer may be sequentially provided with a shock absorbing layer, a pressure-sensitive adhesive layer and a protective layer, and the other surface of the thermal conductive layer may be sequentially provided with TR-CPSA (Thermal Responsive Conductive Pressure Sensitive Adhesive) and a protective layer.

According to another aspect of the invention, the present invention is a heating element; And an electronic device including the above-described shock absorbing composite sheet disposed on one or both surfaces of the heating element.

According to the present invention as described above, it is possible to provide a shock-absorbing composite sheet in which the shock absorbing ability to external force is increased while effectively dissipating heat.

According to the present invention, it is possible to provide a shock absorbing composite sheet having improved heat dissipation and shock absorption without increasing unnecessary volume in a slimmer and miniaturized heating element.

In addition, according to the present invention by providing a design value for the heat dissipation optimized for the heat generated by the heating element can provide a shock absorbing composite sheet that can omit unnecessary experiments.

1 is a view showing a composite sheet for shock absorption according to an embodiment of the present invention.
2 is a cross-sectional view of a shock absorbing composite sheet according to another embodiment of the present invention.
3 is a cross-sectional view of a shock absorbing composite sheet according to another embodiment of the present invention.
Figure 4 is a view schematically showing a shock absorbing composite sheet prepared according to Example 1.
5 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared according to Table 1.
FIG. 6 is a view schematically illustrating a shock absorbing composite sheet manufactured according to Example 11. FIG.
7 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared according to Table 2.
8 is a view schematically showing a shock absorbing composite sheet prepared according to Example 21.
9 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared according to Table 3.
10 is a view schematically showing a shock absorbing composite sheet prepared according to Example 31.
11 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared in accordance with Table 4.
12 is a view schematically showing a shock absorbing composite sheet prepared according to Example 41.
FIG. 13 is a graph showing measured values and calculated values of thermal conductivity of the composite sheet for shock absorption according to Table 5. FIG.
FIG. 14 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 51. FIG.
15 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared according to Table 6.
FIG. 16 is a view schematically illustrating a shock absorbing composite sheet manufactured according to Example 61. FIG.
17 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared in accordance with Table 7.
FIG. 18 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 71. FIG.
19 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared according to Table 8.
20 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 81. FIG.
21 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared according to Table 9.
FIG. 22 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 91. FIG.
23 is a graph showing the measured value and the calculated value of the thermal conductivity of the composite sheet for shock absorption prepared in accordance with Table 10.

Specific details of other embodiments are included in the detailed description and the drawings.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but may be implemented in various forms. In the following description, when a part is connected to another part, it is only directly connected. It also includes cases where other media are connected in between. In the drawings, parts irrelevant to the present invention are omitted for clarity, and like reference numerals designate like parts throughout the specification.

Hereinafter, the present invention will be described with reference to the accompanying drawings.

1 is a view showing a composite sheet for shock absorption according to an embodiment of the present invention.

Composite shock absorbing sheet 100 according to an embodiment of the present invention is a thermally conductive layer 110 formed by stacking one or more metal alone or mixed; An impact absorbing layer (120) provided in direct contact with one or both surfaces of the thermal conductive layer (110); And a pressure sensitive adhesive layer (PSA) 130 provided on one or both surfaces of the impact absorbing layer. The shock absorbing composite sheet 100 has thermal conductivity according to the following formula 1 and formula 2. In addition, in the following formula 1 and formula 2, the thermal conductivity of the composite sheet for shock absorption is 50W / mK to 200W / mK, the thermal conductive layer is a Cu layer, Ni-Cu-Ni layer, Sn-Cu-Sn layer, Co-Cu-Co layer and any one of the Al layer, the thickness of the thermal conductive layer is 8㎛ to 150㎛, the ratio of the thickness of the thermal conductive layer to the total thickness of the composite sheet for shock absorption 12% to 50%. to be.

[Equation 1] λC = {1 / T * Σ (Ti * λi)} * (1 + D)

0.03 ≦ D ≦ 0.25

In Equation 1, λC is the thermal conductivity of the composite sheet for shock absorption (W / mK), T is the total thickness of the composite sheet for shock absorption (μm), Ti is a layer of a single or mixed metal constituting the thermal conductive layer Is the thickness of each layer (μm), λ i is the thermal conductivity (W / mK) of each layer on which the single or mixed metals constituting the heat conductive layer are laminated, and Σ (Ti * λ i) constitutes the thermal conductive layer. Is the total sum of the products of the individual or mixed metal layers laminated with the thermal conductivity. D follows Equation 2.

The shock absorbing composite sheet 100 may be formed of a thermally conductive layer 110, a shock absorbing layer 120 and a pressure-sensitive adhesive layer 130 sequentially stacked, the shock absorbing layer 120 and the pressure-sensitive adhesive layer 130 May be provided on one surface or both surfaces with respect to the surface provided respectively.

In general, the shock absorbing composite sheet used in the electronic device is merely capable of absorbing shock against external force, but the shock absorbing composite sheet according to the present embodiment is provided with not only shock absorbing but also heat dissipation ability. In addition, the composite sheet for shock absorbing according to the present embodiment can provide an appropriate function as necessary by providing various heat generating elements such as electronic devices by controlling the heat dissipation ability according to the thickness and type of material.

The composite sheet for shock absorption 100 according to an embodiment of the present invention may have a thermal conductivity according to Equation 1. Equation 1 may be determined by the thickness and thermal conductivity of the single or composite metal constituting the thermal conductive layer 110 together with the overall thickness constituting the impact-absorbing composite sheet 100. For example, when a standard for thickness and heat dissipation required by a heating element is provided, the shock absorbing composite sheet 100 according to the present embodiment may provide a suitable shock absorbing composite sheet according to Equation 1 above.

The shock absorbing composite sheet 100 may have a thermal conductivity of 50 W / mK or more according to Equation 1.

When the thermal conductivity of the shock absorbing composite sheet is less than 50W / mK, when the shock absorbing composite sheet is applied to an electronic device, a heat dissipation effect may not be sufficient. Preferably the thermal conductivity of the composite sheet for shock absorption may be 50W / mK to 200W / mK.

The thermal conductive layer 110 is organically related to the shock absorbing layer 120 and the pressure-sensitive adhesive layer 130 in the shock absorbing composite sheet 100 according to the present embodiment to determine the heat dissipation ability of the shock absorbing composite sheet 100. Mainly can be provided. The thermally conductive layer 110 may be directly attached to the impact absorbing layer 120 without a separate adhesive or the like, and the total thickness of the impact absorbing composite sheet 100 may be omitted since a separate adhesive may be omitted. At the same time, heat dissipation can be more efficiently implemented.

The metal constituting the thermal conductive layer 110 may be at least one of copper, aluminum, nickel, tin, cobalt, chromium, gold, and silver. Preferably, the thermal conductive layer 110 may be any one or more of a Cu layer, a Ni—Cu—Ni layer, a Sn—Cu—Sn layer, a Co—Cu—Co layer, and an Al layer. More preferably, the thermal conductive layer 110 may be provided by plating one or more of nickel, tin, and cobalt on one or both surfaces of the copper layer.

The ratio of the thickness of the heat conductive layer 110 to the total thickness of the shock absorbing composite sheet 100 may be 12% to 50%.

In addition, the thickness of the thermal conductive layer 110 may be 8㎛ to 150㎛.

When the thickness of the thermally conductive layer is less than 8㎛, wrinkles may be generated in the thermally conductive layer during roll-to-roll operation, and workability may be degraded, and heat dissipation may be degraded, and thus application of the composite sheet may be difficult. If the thickness of the thermal conductive layer exceeds 150㎛ curl may occur during the roll-to-roll operation, the winding amount is reduced during the mass production of the composite sheet, the yield can be lowered, there is a problem in the workability during the punching process is not good . In addition, the thickness of the thermal conductive layer is too thick can be limited use of the composite sheet can be applied.

In the shock absorbing composite sheet 100 of the present embodiment, the shock absorbing layer 120 has a function of absorbing an impact on external force, and additionally includes a thermal conductive layer 110 and a pressure reduction respectively provided on one and the other surfaces of the shock absorbing layer 120. Along with the pressure-sensitive adhesive layer 130 may provide a heat dissipation capacity of the composite sheet 100 for shock absorption. The shock absorbing layer 120 is provided on the thermal conductive layer 110 may be provided directly without an additional adhesive member. For example, although the heat conductive layer 110 made of metal or the like is provided with a smooth surface, it is firmly fixed directly by the impact absorbing layer 120 without an adhesive member, thereby reducing the overall thickness of the composite sheet 100 for shock absorption. The production cost can be reduced.

The shock absorbing layer 120 comprises a polymer foam, the polymer foam is an acrylic foam, polyurethane foam, polyethylene foam, polyolefin foam, polyvinylchloride foam, polycarbonate foam, polyimide foam, polyetherimide foam, polyamide At least one selected from the group consisting of foams, polyester foams, polyvinylidene chloride foams, polymethylmethacrylate foams and polyisocyanate foams. Preferably, the shock absorbing layer 120 includes a polymer foam, and the polymer foam may be a polyurethane foam or an acrylic foam.

The impact absorbing layer 120 may have a density of about 0.2 g / cm 3 to about 0.8 g / cm 3.

When the polymer foam has a density of less than 0.2 g / cm 3, the strength of the impact absorbing layer may be easily torn off, poor reworkability after attachment, and the impact absorption may be lowered, thus preventing the substrate from being protected. When the polymer foam has a density of more than 0.8 g / cm 3, the impact absorbing layer becomes solid, which causes the foam to lose its function and thus cannot protect the substrate.

The impact absorbing layer 120 may have a thickness of 50 μm to 250 μm.

The shock absorbing layer 120 may be a polymer foam. When the thickness of the polymer foam is less than 50 μm, the impact absorption rate that the polymer foam can provide decreases to protect the substrate, and the polymer foam has a thickness of 250. When it exceeds the 占 퐉, heat dissipation performance is reduced, and the thickness of the composite sheet to which the polymer foam is applied becomes too thick to be a problem. Preferably, the impact absorbing layer may have a thickness of 80 μm to 250 μm.

The pressure-sensitive adhesive layer 130 is provided on the outer surface of the shock absorbing layer 120 may be provided by bringing the impact absorbing composite sheet 100 in close contact with an external device. As a result, the external device provided with the composite shock absorbing composite sheet 100 may effectively exhibit the heat dissipation ability and the shock absorbing ability provided by the impact absorbing composite sheet 100.

The pressure-sensitive adhesive layer 130 may include any one or more of acrylic, silicone, epoxy, urethane, and polyimide.

The pressure-sensitive adhesive layer 130 may have a thickness of 5 μm to 50 μm.

If the thickness of the pressure-sensitive adhesive layer is less than 5㎛ the adhesion properties between the thermal conductive layer and the impact absorbing layer is lowered and can not be firmly fixed between them, if the thickness is more than 50㎛ problem to reduce the heat radiation characteristics of the thermal conductive layer It matters.

2 is a cross-sectional view of a shock absorbing composite sheet according to another embodiment of the present invention.

Referring to FIG. 2, the shock absorbing composite sheet 100a according to another embodiment of the present invention may further include a protective layer 140 on an outer surface of the pressure-sensitive adhesive layer 130.

The protective layer may be a cellulose film such as a triacetyl cellulose (TAC) film, a polyester film such as polyethylene terephthalate (PET) film, a polycarbonate film, a polyethersulfone film, an acrylic film, a polyethylene film, a polypropylene film, A polyolefin film such as a polyolefin film or an ethylene-propylene copolymer film including a cyclo-based or norbornene structure may be used, but is not limited thereto.

3 is a cross-sectional view of a shock absorbing composite sheet according to another embodiment of the present invention.

Referring to FIG. 3, in the shock absorbing composite sheet 100b according to the present embodiment, one surface of the thermal conductive layer 110 is sequentially provided with a shock absorbing layer 120, a pressure-sensitive adhesive layer 130, and a protective layer 140. The other surface of the thermal conductive layer 110 may be sequentially provided with TR-CPSA (Thermal Responsive Conductive Pressure Sensitive Adhesive) 130a and the protective layer 140a. For example, the TR-CPSA may be an acrylic conductive thermosensitive adhesive sensitive to temperature at 60 ° C to 80 ° C. The TR-CPSA may be a kind of functional pressure-sensitive adhesive that can be easily detached when the adhesive force is lowered at a temperature of about 70 ° C., thereby repairing electronic devices.

The pressure-sensitive adhesive layer 130 and the TR-CPSA 130a provided on one side and the other side of the thermal conductive layer 110 may be the same materials or different materials, and one side and the other side of the thermal conductive layer 110 as well. Each of the protective layers 140 and 140a included in the material may be the same material or different materials.

Hereinafter, another embodiment of the present invention will be described. Except for the content to be described later, since it is similar to the content described in the embodiment described in Figures 1 to 3 will not be described in detail.

According to another aspect of the present invention, a shock absorbing composite sheet according to an embodiment of the present invention is a thermally conductive layer formed by stacking one or more metal alone or mixed; An impact absorbing layer provided in direct contact with one surface or both surfaces of the thermal conductive layer; And a pressure sensitive adhesive layer (PSA) provided on one or both surfaces of the impact absorbing layer.

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The thermal conductivity may be 50 W / mK or more.

When the thermal conductivity is less than 50W / mK, when the shock absorbing composite sheet is applied to an electronic device, there is a problem that the heat radiation effect is not sufficient. Preferably the thermal conductivity may be 50W / mK to 200W / mK.

The ratio of the thickness of the heat conductive layer to the total thickness may be 12% to 50%.

When the ratio of the thickness of the heat conductive layer is less than 12%, the heat dissipation effect is not sufficient, so it is difficult to apply it for electronic devices, and when it exceeds 50%, the total thickness of the shock absorbing composite sheet is unnecessarily increased.

The heat conductive layer may have a thickness of 8 μm to 150 μm.

When the thickness of the thermally conductive layer is less than 8㎛, wrinkles may be generated in the thermally conductive layer during roll-to-roll operation, and workability may be degraded, and heat dissipation may be degraded, and thus application of the composite sheet may be difficult. When the thickness of the thermal conductive layer exceeds 150㎛ curl may occur during the roll-to-roll operation, the winding amount decreases during mass production of the composite sheet, the yield may be lowered, and there is a problem in the workability during the punching process is not good. . In addition, the thickness of the heat conductive layer is too thick, the use of the composite sheet can be applied may be limited.

In addition, a protective layer may be further provided on an outer surface of the pressure-sensitive adhesive layer.

The protective layer may be a cellulose film such as a triacetyl cellulose (TAC) film, a polyester film such as polyethylene terephthalate (PET) film, a polycarbonate film, a polyethersulfone film, an acrylic film, a polyethylene film, a polypropylene film, A polyolefin film such as a polyolefin film or an ethylene-propylene copolymer film including a cyclo-based or norbornene structure may be used, but is not limited thereto.

Alternatively, one surface of the thermal conductive layer may be sequentially provided with a shock absorbing layer, a pressure-sensitive adhesive layer and a protective layer, and the other surface of the thermal conductive layer may be sequentially provided with TR-CPSA (Thermal Responsive Conductive Pressure Sensitive Adhesive) and a protective layer. have.

The metal constituting the thermally conductive layer may be at least one of copper, aluminum, nickel, tin, cobalt, chromium, gold, and silver. In addition, the thermal conductive layer may be any one or more of a Cu layer, a Ni—Cu—Ni layer, a Sn—Cu—Sn layer, a Co—Cu—Co layer, and an Al layer. More preferably, the thermal conductive layer may be provided by plating one or more of nickel, tin, and cobalt on one or both surfaces of the copper layer.

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According to another aspect of the present invention, the present invention includes an electronic device including the above-described shock absorbing composite sheet. The electronic device includes a heating element and the above-described shock absorbing composite sheet disposed on one or both surfaces of the heating element.

Hereinafter, Examples and Comparative Examples of the present invention will be described. However, the following examples are only preferred embodiments of the present invention and the scope of the present invention is not limited by the following examples.

1. Preparation of shock absorbing composite sheet

Example  One

Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time with a fixed ratio pump. And the copper foil formed in layer shape with thickness of 100 micrometers was prepared for the heat conductive layer. The mixed solution thus prepared was coated on the copper foil surface using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of an acrylic adhesive (Hanai HN-PA950), 1% by weight of a curing agent (Hanai HN-CA10), ethyl acetate (99% of trielectrochemical purity) were sequentially measured, and then, at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a coating film was formed on a PET release film (SKC SG31) with a thickness of 120 μm, and then dried in an oven at 110 ° C. for 2 minutes to transfer the adhesive layer having a thickness of about 30 μm to a polyurethane foam layer. After that, 40% by weight of TR-CPSA, 1% by weight of curing agent, 1% by weight of additive, 1% by weight of Ni powder, (the one particle size less than 20㎛) ethyl acetate (99% of trielectric chemical purity) After weighing with a mechanical stirrer was dispersed for 30 minutes at 500rpm at this time the solid content was prepared to 25% by weight crude liquid. Next, the crude liquid was removed using a 300 mesh to remove Ni powder, which was less dispersed, and then formed a coating film of 60 μm thickness on a PET release film (SKC SG31), followed by drying in an oven at 110 ° C. for 2 minutes, to about 15 μm thickness of TR-CPSA. The layer was transfer coated on the copper foil surface. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 235㎛. Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 1 was prepared to be provided with a polyurethane foam directly on the copper foil without using an adhesive or the like, the numerical value of each layer for Example 1 proceeded as described in Table 1 and measured the thermal conductivity.

Example  2 to Example  10

As shown in Table 1, only copper foil and polyurethane resin thickness were changed, and it manufactured similarly to Example 1, and measured thermal conductivity.

division Cu Foam PSA TR-CPSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 1 100 90 30 15 235 42.55 170.27 185.29 15.02 8.83 Example 2 90 100 30 15 235 38.3 153.25 170.57 17.32 11.31 Example 3 80 110 30 15 235 34.04 136.24 154.45 18.21 13.37 Example 4 70 120 30 15 235 29.79 119.22 136.46 17.24 14.46 Example 5 60 130 30 15 235 25.53 102.2 112.42 10.22 10 Example 6 50 140 30 15 235 21.28 85.19 95.54 10.35 12.16 Example 7 40 150 30 15 235 17.02 68.17 79.98 11.81 17.33 Example 8 30 160 30 15 235 12.77 51.15 54.54 3.39 6.63 Example 9 20 170 30 15 235 8.51 34.13 37.97 3.84 11.28 Example 10 10 180 30 15 235 4.26 17.12 18.83 1.71 10

4 is a view schematically showing a shock absorbing composite sheet prepared according to Example 1, Figure 5 is a graph showing the measured value and the calculated thermal conductivity of the shock absorbing composite sheet prepared in accordance with Table 1 to be.

Example  11

Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time with a fixed ratio pump. And the copper foil formed in layer shape with thickness of 100 micrometers was prepared for the heat conductive layer. The mixed solution thus prepared was coated on the copper foil surface using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of acrylic adhesive (Hanai HN-PA950), 1% by weight of the curing agent (Hanai HN-CA10), ethyl acetate (99% purity of Samgye Chemical) was measured at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a coating film was formed on a PET release film (SKC SG31) with a thickness of 120 μm, and then dried in an oven at 110 ° C. for 2 minutes to transfer the adhesive layer having a thickness of about 30 μm to a polyurethane foam layer. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 220㎛. Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 11 was prepared to be provided with a polyurethane foam directly on the copper foil without using an adhesive or the like, the numerical value of each layer for Example 11 proceeded as described in Table 2 and measured the thermal conductivity.

Example  12 to Example  20

As shown in Table 1, only copper foil and polyurethane resin thickness were changed, and it manufactured similarly to Example 11, and measured thermal conductivity.

division Cu Foam PSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 11 100 90 30 220 45.45 181.87 190.41 8.54 6.51 Example 12 90 100 30 220 40.91 163.7 174.78 11.08 8.7 Example 13 80 110 30 220 36.36 145.52 157.94 12.42 6.88 Example 14 70 120 30 220 31.82 127.34 138.78 11.44 12.82 Example 15 60 130 30 220 27.27 109.16 117.31 8.15 8.98 Example 16 50 140 30 220 22.73 90.99 99.16 8.17 7.47 Example 17 40 150 30 220 18.18 72.81 82.14 9.33 8.99 Example 18 30 160 30 220 13.64 54.63 58.38 3.75 8.54 Example 19 20 170 30 220 9.09 36.45 39.62 3.17 6.77 Example 20 10 180 30 220 4.55 18.28 19.47 1.19 4.7

FIG. 6 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 11, and FIG. 7 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet manufactured according to Table 2; to be.

Example  21

A foil made of Ni—Cu—Ni, having a thickness of 100 μm and being layered and sequentially stacked as a heat conductive layer, was prepared. Here, Ni, after each Cu thickness of Ni is immersed in 0.5㎛, 99㎛, 0.5㎛ and 100g / L of sulfuric acid for five seconds, washed with distilled water, after pickling treatment, NiSO ₄ · 6H ₂ on the surface of the copper foil on both sides O concentration of 300g / l, HBO ₃ concentration of 30g / l, temperature 30 ° C, current density 5 A / dm ² , the plated at a constant time at pH 3.5 and plated on both sides 0.5㎛ each. Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time with a fixed ratio pump. . The mixed solution thus prepared was coated on the copper foil surface using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of an acrylic adhesive (Hanai HN-PA950), 1% by weight of a curing agent (Hanai HN-CA10), ethyl acetate (99% purity of trielectrochemical) were measured sequentially, and then at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a 120 탆 thick PET film was formed on the PET release film (SKC SG31), and dried for 2 minutes in an oven at 110 ° C., and a pressure-sensitive adhesive layer having a thickness of about 30 탆 was transferred to the polyurethane foam layer. Thereafter, 40 wt% TR-CPSA, 1 wt% hardener, 1 wt% additive, 1 wt% Ni powder (products with a particle size of 20 μm or less), ethyl acetate, and (Simjeon Chemical purity 99%) After sequentially metering and dispersing for 30 minutes at 500rpm using a mechanical stirrer, the solid content was prepared to 25% by weight of crude liquid. Next, the crude liquid was removed using a 300 mesh to remove Ni powder, which was less dispersed, and formed a 60 μm thick film on a PET release film (SKC SG31), followed by drying in an oven at 110 ° C. for 2 minutes, followed by a TR-CPSA having a thickness of about 15 μm. The layer was transfer coated on the copper foil surface. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 235㎛. Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 21 was prepared so that the polyurethane foam was provided directly without using an adhesive or the like on the copper foil, the numerical value of each layer for Example 21 proceeded as described in Table 3 and measured the thermal conductivity.

Example  22 to Example  30

As shown in Table 3, only the foil made of Ni-Cu-Ni and the polyurethane resin thickness were different from each other to prepare in the same manner as in Example 21, and the thermal conductivity was measured.

division Ni-Cu-Ni Foam PSA TR-CPSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 21 100 90 30 15 235 42.55 166.53 182.51 15.98 9.61 Example 22 90 100 30 15 235 38.3 149.88 168.36 18.48 12.35 Example 23 80 110 30 15 235 34.04 133.24 154.23 20.99 15.77 Example 24 70 120 30 15 235 29.79 116.6 132.09 15.49 13.31 Example 25 60 130 30 15 235 25.53 99.96 109.95 9.99 10.01 Example 26 50 140 30 15 235 21.28 83.31 94.8 11.49 13.82 Example 27 40 150 30 15 235 17.02 66.67 77.67 11 16.52 Example 28 30 160 30 15 235 12.77 50.03 52.53 2.5 5.01 Example 29 20 170 30 15 235 8.51 33.39 36.39 3 9.01 Example 30 10 180 30 15 235 4.26 16.74 17.52 0.78 4.69

FIG. 8 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 21, and FIG. 9 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet manufactured according to Table 3; to be.

Example  31

A foil made of Ni—Cu—Ni, having a thickness of 100 μm, formed in layers and sequentially stacked as a heat conductive layer, was prepared. Here, Ni, after each Cu thickness of Ni is immersed in 0.5㎛, 99㎛, 0.5㎛ and 100g / L of sulfuric acid for five seconds, washed with distilled water, after pickling treatment, NiSO ₄ · 6H ₂ on the surface of the copper foil on both sides O concentration of 300g / l, HBO ₃ concentration of 30g / l, temperature 30 ° C, current density 5 A / dm ² , the plated at a constant time at pH 3.5 and plated on both sides 0.5㎛ each. Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time with a fixed ratio pump. . The mixed solution thus prepared was coated on the copper foil surface using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of an acrylic adhesive (Hanai HN-PA950), 1% by weight of a curing agent (Hanai HN-CA10), ethyl acetate (99% purity of trielectrochemical) were measured sequentially, and then at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a 120 탆 thick PET film was formed on the PET release film (SKC SG31), and dried for 2 minutes in an oven at 110 ° C., and a pressure-sensitive adhesive layer having a thickness of about 30 탆 was transferred to the polyurethane foam layer. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 220㎛. Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 31 was prepared such that the polyurethane foam was directly provided on the copper foil without using an adhesive or the like, and the numerical values of each layer for Example 31 proceeded as described in Table 4 and the thermal conductivity was measured.

Example  32 to Example  40

As shown in Table 4, only the foil made of Ni-Cu-Ni and the polyurethane resin thickness were different from each other to prepare in the same manner as in Example 31, and the thermal conductivity was measured.

division Ni-Cu-Ni Foam PSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 31 100 90 30 220 45.45 177.87 187.69 9.82 5.53 Example 32 90 100 30 220 40.91 160.1 171.61 11.51 7.2 Example 33 80 110 30 220 36.36 142.32 155.58 13.26 9.33 Example 34 70 120 30 220 31.82 124.54 135.41 10.87 8.74 Example 35 60 130 30 220 27.27 106.76 113.78 7.02 6.59 Example 36 50 140 30 220 22.73 88.99 96.92 7.93 8.92 Example 37 40 150 30 220 18.18 71.21 80.61 9.4 13.22 Example 38 30 160 30 220 13.64 53.43 56.65 3.22 6.05 Example 39 20 170 30 220 9.09 35.65 37.92 2.27 6.37 Example 40 10 180 30 220 4.55 17.88 19.14 1.26 7.06

FIG. 10 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 31, and FIG. 11 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet prepared according to Table 4; to be.

Example 41

A foil composed of Sn-Cu-Sn, which was formed in a layer form and was sequentially stacked, was 100 μm thick as a heat conductive layer. Here, the thicknesses of Sn and Cu Sn are 0.5 µm, 99 µm and 0.5 µm, respectively, soaked in 100 g / l sulfuric acid for 5 seconds, washed with distilled water after pickling, and then (CH ₃ SO ₃ ) ₂ Sn concentration is 100g / l, SH ₃ concentration is 3g / l, CH ₃ SO ₃ H concentration is 30g / l temperature 30 ° C, current density 10 A / dm ² , pH 3.5 Each was plated with 0.5 탆. Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time with a fixed ratio pump. . The mixed solution thus prepared was coated on the copper foil surface using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. After this, 40% by weight of acrylic adhesive ( Hana Ehwa) HN- PA950), 1% by weight of the curing agent (Hana-hwa HN-CA10), ethyl acetate (99% of Samjeon Chemical Purity) were sequentially measured and dispersed at 500 rpm for 30 minutes using a mechanical stirrer, where the solid content was 25 weights. A crude solution was prepared in%. Thereafter, a 120 탆 thick PET film was formed on the PET release film (SKC SG31), and dried for 2 minutes in an oven at 110 ° C., and a pressure-sensitive adhesive layer having a thickness of about 30 탆 was transferred to the polyurethane foam layer. Afterwards, 40% by weight of TR-CPSA, 1% by weight of hardener, 1% by weight of additives, 1% by weight of Ni powder (products with a particle size of 20 µm or less), ethyl acetate (99% purity of Samjeon Chemical) After weighing with a mechanical stirrer was dispersed for 30 minutes at 500rpm at this time the solid content of the crude liquid was prepared to 25% by weight. Next, the crude liquid was removed using a 300 mesh to remove Ni powder, which was less dispersed, and formed a 60 μm thick film on a PET release film (SKC SG31), followed by drying in an oven at 110 ° C. for 2 minutes, followed by a TR-CPSA having a thickness of about 15 μm. The layer was transfer coated on the copper foil surface. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 235㎛. Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 41 was prepared so that the polyurethane foam was provided directly without using an adhesive or the like on the copper foil, the numerical value of each layer for Example 41 proceeded as described in Table 5 and measured the thermal conductivity.

Examples 42-50

As shown in Table 5, only the foil made of Sn-Cu-Sn and the polyurethane resin thickness were different from each other to prepare in the same manner as in Example 41, and the thermal conductivity was measured.

division Sn-Cu-Sn Foam PSA TR-CPSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 41 100 90 30 15 235 42.55 166.31 184.06 17.75 10.66 Example 42 90 100 30 15 235 38.3 149.69 163.87 14.18 9.46 Example 43 80 110 30 15 235 34.04 133.07 147.67 14.6 10.96 Example 44 70 120 30 15 235 29.79 116.45 134.48 18.03 15.47 Example 45 60 130 30 15 235 25.53 99.83 111.28 11.45 11.46 Example 46 50 140 30 15 235 21.28 83.21 93.09 9.88 11.86 Example 47 40 150 30 15 235 17.02 66.59 78.65 10.3 15.46 Example 48 30 160 30 15 235 12.77 49.96 52.69 2.73 5.46 Example 49 20 170 30 15 235 8.51 33.34 36.49 3.15 9.46 Example 50 10 180 30 15 235 4.26 16.72 18.3 1.58 9.46

FIG. 12 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 41, and FIG. 13 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet prepared according to Table 5. to be.

Example 51

A foil composed of Sn-Cu-Sn, which was formed in a layer form and was sequentially stacked, was 100 μm thick as a heat conductive layer. Here, the thicknesses of Sn and Cu Sn are 0.5 µm, 99 µm and 0.5 µm, respectively, soaked in 100 g / l sulfuric acid for 5 seconds, washed with distilled water after pickling, and then (CH ₃ SO ₃ ) ₂ Sn concentration is 100g / l, SH ₃ concentration is 3g / l, CH ₃ SO ₃ H concentration is 30g / l temperature 30 ° C, current density 10 A / dm ² , pH 3.5 Each was plated with 0.5 탆. Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time with a fixed ratio pump. . The mixed solution thus prepared was coated on the copper foil surface using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of an acrylic adhesive (Hanai HN-PA950), 1% by weight of a curing agent (Hanai HN-CA10), ethyl acetate (99% purity of trielectrochemical) were measured sequentially, and then at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a 120 탆 thick PET film was formed on the PET release film (SKC SG31), and dried for 2 minutes in an oven at 110 ° C., and a pressure-sensitive adhesive layer having a thickness of about 30 탆 was transferred to the polyurethane foam layer. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 220㎛.

Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 51 was prepared such that the polyurethane foam was directly provided on the copper foil without using an adhesive or the like, and the numerical values of each layer for Example 51 proceeded as described in Table 6 and the thermal conductivity was measured.

Examples 52-60

As shown in Table 6, only the foil made of Sn-Cu-Sn and the polyurethane resin thickness were different from each other to prepare in the same manner as in Example 51, and the thermal conductivity was measured.

division Sn-Cu-Sn Foam PSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 51 100 90 30 220 45.45 177.65 188.42 10.77 6.06 Example 52 90 100 30 220 40.91 159.89 169.22 9.33 5.83 Example 53 80 110 30 220 36.36 142.14 154.94 12.8 8.99 Example 54 70 120 30 220 31.82 124.38 136.11 11.73 9.42 Example 55 60 130 30 220 27.27 106.63 113.56 6.93 6.49 Example 56 50 140 30 220 22.73 88.87 96.21 7.34 8.25 Example 57 40 150 30 220 18.18 71.12 78.65 7.53 10.57 Example 58 30 160 30 220 13.64 53.36 55.16 1.8 3.37 Example 59 20 170 30 220 9.09 35.61 37.25 1.64 4.6 Example 60 10 180 30 220 4.55 17.85 18.88 1.03 5.76

14 is a view schematically showing a shock absorbing composite sheet prepared according to Example 51, and FIG. 15 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet prepared according to Table 6 to be.

Example 61

A foil made of Co-Cu-Co, which had a thickness of 100 μm, was formed in layers, and sequentially stacked as a heat conductive layer, was prepared. Here, Co, after each thickness of the Cu Co is immersed for 0.5㎛, 99㎛, 0.5㎛ from 5 cho from 100g / l sulfuric acid, washed with distilled water, after pickling treatment, CoSO ₄ · 5H ₂ on the surface of the copper foil on both sides O concentration of 300g / l, HBO ₃ concentration of 30g / l, temperature 30 ° C, current density 5 A / dm ² , the plated at a constant time at pH 3.5 and plated on both sides 0.5㎛ each. Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time with a fixed ratio pump. . The mixed solution thus prepared was coated on the copper foil surface using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of an acrylic adhesive (Hanai HN-PA950), 1% by weight of a curing agent (Hanai HN-CA10), ethyl acetate (99% purity of trielectrochemical) were measured sequentially, and then at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a 120 탆 thick PET film was formed on the PET release film (SKC SG31), and dried for 2 minutes in an oven at 110 ° C., and a pressure-sensitive adhesive layer having a thickness of about 30 탆 was transferred to the polyurethane foam layer. Afterwards, 40% by weight of TR-CPSA, 1% by weight of hardener, 1% by weight of additives, 1% by weight of Ni powder (products with a particle size of 20 µm or less), ethyl acetate (99% purity of Samjeon Chemical) After weighing with a mechanical stirrer was dispersed for 30 minutes at 500rpm at this time the solid content of the crude liquid was prepared to 25% by weight. Next, the crude liquid was removed using a 300 mesh to remove Ni powder, which was less dispersed, and formed a 60 μm thick film on a PET release film (SKC SG31), followed by drying in an oven at 110 ° C. for 2 minutes, followed by a TR-CPSA having a thickness of about 15 μm. The layer was transfer coated on the copper foil surface. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 235㎛. Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 61 was prepared so that the polyurethane foam was provided directly without using an adhesive or the like on the copper foil, the numerical value of each layer for Example 61 proceeded as described in Table 7 and measured the thermal conductivity.

Examples 62-70

As shown in Table 7, the thickness of the foil made of Co-Cu-Co and the polyurethane resin were different from each other to prepare the same as in Example 61 to measure the thermal conductivity.

division Co-Cu-Co Foam PSA TR-CPSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 61 100 90 30 15 235 42.55 166.36 179.4 13.04 7.84 Example 62 90 100 30 15 235 38.3 149.69 162.42 12.73 8.51 Example 63 80 110 30 15 235 34.04 133.07 145.5 12.43 9.34 Example 64 70 120 30 15 235 29.79 116.45 129.58 13.13 11.28 Example 65 60 130 30 15 235 25.53 99.83 107.65 7.82 7.84 Example 66 50 140 30 15 235 21.28 83.21 93.73 10.52 12.65 Example 67 40 150 30 15 235 17.02 66.59 71.81 11.22 16.85 Example 68 30 160 30 15 235 12.77 49.96 50.87 1.91 3.84 Example 69 20 170 30 15 235 8.51 33.34 38.95 3.61 10.84 Example 70 10 180 30 15 235 4.26 16.72 17.9 1.18 7.08

FIG. 16 is a view schematically showing a shock absorbing composite sheet prepared according to Example 61, and FIG. 17 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet prepared according to Table 7 to be.

Example  71

A foil made of Co-Cu-Co, which had a thickness of 100 μm, was formed in layers, and sequentially stacked as a heat conductive layer, was prepared. Here, Co, after each thickness of the Cu Co is immersed for 0.5㎛, 99㎛, 0.5㎛ from 5 cho from 100g / l sulfuric acid, washed with distilled water, after pickling treatment, CoSO ₄ · 5H ₂ on the surface of the copper foil on both sides O concentration of 300g / l, HBO ₃ concentration of 30g / l, temperature 30 ° C, current density 5 A / dm ² , the plated at a constant time at pH 3.5 and plated on both sides 0.5㎛ each. Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time with a fixed ratio pump. . The mixed solution thus prepared was coated on the copper foil surface using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of an acrylic adhesive (Hanai HN-PA950), 1% by weight of a curing agent (Hanai HN-CA10), ethyl acetate (99% purity of trielectrochemical) were measured sequentially, and then at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a 120 탆 thick PET film was formed on the PET release film (SKC SG31), and dried for 2 minutes in an oven at 110 ° C., and a pressure-sensitive adhesive layer having a thickness of about 30 탆 was transferred to the polyurethane foam layer. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 235㎛.

Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 71 was prepared so that the polyurethane foam was provided directly without using an adhesive or the like on the copper foil, the numerical value of each layer for Example 71 proceeded as described in Table 8 and measured the thermal conductivity.

Example  72 to Example  80

As shown in Table 8, only the foil made of Co-Cu-Co and the thickness of the polyurethane resin were different, and prepared in the same manner as in Example 71, and thermal conductivity was measured.

division Co-Cu-Co Foam PSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 71 100 90 30 220 45.45 177.69 186.85 9.16 5.16 Example 72 90 100 30 220 40.91 159.89 169.92 10.03 6.27 Example 73 80 110 30 220 36.36 142.14 155.21 13.07 9.2 Example 74 70 120 30 220 31.82 124.38 135.05 10.67 8.58 Example 75 60 130 30 220 27.27 106.63 112.87 6.24 5.85 Example 76 50 140 30 220 22.73 88.87 97.3 8.43 9.49 Example 77 40 150 30 220 18.18 71.12 79.25 8.13 11.43 Example 78 30 160 30 220 13.64 53.36 55.93 2.57 4.82 Example 79 20 170 30 220 9.09 35.61 37.39 1.78 5 Example 80 10 180 30 220 4.55 17.85 18.62 0.77 4.31

FIG. 18 is a view schematically showing a shock absorbing composite sheet prepared according to Example 71, and FIG. 19 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet prepared according to Table 8; to be.

Example  81

A foil made of aluminum having a thickness of 100 μm and layered as a heat conductive layer was prepared.

Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time by injecting a fixed ratio using a fixed-quantity pump. . The mixed solution thus prepared was coated on the surface of aluminum foil using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of acrylic adhesive (Hanai HN-PA950), 1% by weight of the curing agent (Hanai HN-CA10), ethyl acetate (99% purity of Samgye Chemical) was measured at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a coating film was formed on a PET release film (SKC SG31) with a thickness of 120 μm, and then dried in an oven at 110 ° C. for 2 minutes to transfer the adhesive layer having a thickness of about 30 μm to a polyurethane foam layer. Thereafter, 40 wt% TR-CPSA, 1 wt% hardener, 1 wt% additive, 1 wt% Ni powder (products with a particle size of 20 μm or less), ethyl acetate, and (Simjeon Chemical purity 99%) After sequentially metering and dispersing for 30 minutes at 500rpm using a mechanical stirrer, the solid content was prepared to 25% by weight of crude liquid. Next, the crude liquid was removed using a 300 mesh to remove Ni powder, which was less dispersed, and then formed a coating film of 60 μm thickness on a PET release film (SKC SG31), followed by drying in an oven at 110 ° C. for 2 minutes, to about 15 μm thickness of TR-CPSA. The layer was transfer coated on the copper foil surface. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 235㎛. Here, the pressure-sensitive adhesive layer is an acrylic adhesive layer is a kind of pressure-sensitive adhesive layer using acrylic without mixing the blowing agent may be provided to bond the neighboring material, such as an acrylic foam material that is not provided with bubbles it means.

Example 81 was prepared so that the polyurethane foam was provided directly on the aluminum foil without using an adhesive or the like, the numerical value of each layer for Example 81 proceeded as described in Table 9 and measured the thermal conductivity.

Example  82 to Example  90

As shown in Table 9, only the aluminum foil and the polyurethane resin thickness were changed, and it manufactured similarly to Example 81, and measured thermal conductivity.

division Al Foam PSA TR-CPSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 81 100 90 30 15 235 42.55 96.23 102.81 6.58 6.84 Example 82 90 100 30 15 235 38.3 86.61 94.63 8.02 9.26 Example 83 80 110 30 15 235 34.04 77 85.46 8.46 10.99 Example 84 70 120 30 15 235 29.79 67.39 75.29 7.9 11.73 Example 85 60 130 30 15 235 25.53 57.78 63.13 5.35 9.26 Example 86 50 140 30 15 235 21.28 48.16 53.95 5.79 12.03 Example 87 40 150 30 15 235 17.02 38.55 41.78 3.23 8.39 Example 88 30 160 30 15 235 12.77 28.94 31.61 2.67 9.25 Example 89 20 170 30 15 235 8.51 19.33 22.45 3.12 16.15 Example 90 10 180 30 15 235 4.26 9.71 11.27 1.56 16.1

FIG. 20 is a view schematically showing a shock absorbing composite sheet manufactured according to Example 81, and FIG. 21 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet prepared according to Table 9; to be.

Example 91

As a heat conductive layer, a foil made of aluminum having a thickness of 100 μm and layered was prepared.

Polyether polyol (Kumho Petrochemical) and modified MDI isocyanate (Unichem) were used for the polyurethane layer, and a mixed solution was prepared by adjusting the density and hardness while injecting nitrogen gas at the same time by injecting a fixed ratio using a fixed-quantity pump. . The mixed solution thus prepared was coated on the surface of aluminum foil using an applicator (Yoshimitsu, YBA-5) and thermally cured at 150 ° C. to form a shock absorbing layer, which is a polyurethane foam layer having a thickness of 90 μm. Thereafter, 40% by weight of acrylic adhesive (Hanai HN-PA950), 1% by weight of the curing agent (Hanai HN-CA10), ethyl acetate (99% purity of Samgye Chemical) was measured at 500 rpm using a mechanical stirrer. The mixture was dispersed for 30 minutes at this time, to prepare a crude liquid with a solid content of 25% by weight. Thereafter, a coating film was formed on a PET release film (SKC SG31) with a thickness of 120 μm, and then dried in an oven at 110 ° C. for 2 minutes to transfer the adhesive layer having a thickness of about 30 μm to a polyurethane foam layer. The coating method was carried out using an applicator (Yoshimitsu, YBA-5), to prepare a composite sheet having a total thickness of 220㎛.

Example 91 was prepared to be provided with a polyurethane foam directly on the aluminum foil without using an adhesive or the like, the numerical value of each layer for Example 91 proceeded as described in Table 10 and measured the thermal conductivity.

Examples 92-100

As shown in Table 10, only the aluminum foil and the polyurethane resin thickness were different and manufactured in the same manner as in Example 91, and the thermal conductivity was measured.

division Al Foam PSA Total thickness Heat dissipation layer ratio Thermal conductivity calculation Thermal conductivity measurement Real-calculation Rate of change unit (Μm) (Μm) (Μm) (Μm) (%) (W / mk) (W / mk) (W / mk) (%) Example 91 100 90 30 220 45.45 102.78 107.89 5.11 4.97 Example 92 90 100 30 220 40.91 92.51 98.19 5.68 6.14 Example 93 80 110 30 220 36.36 82.25 89.87 7.62 9.26 Example 94 70 120 30 220 31.82 71.98 78.24 6.21 8.7 Example 95 60 130 30 220 27.27 61.71 65.93 4.22 6.85 Example 96 50 140 30 220 22.73 51.44 56.85 5.41 10.52 Example 97 40 150 30 220 18.18 41.17 45.3 4.13 10.03 Example 98 30 160 30 220 13.64 30.9 32.91 2.01 6.51 Example 99 20 170 30 220 9.09 20.64 23.13 2.49 12.07 Example 100 10 180 30 220 4.55 10.37 12.88 2.51 24.25

FIG. 22 is a view schematically showing a shock absorbing composite sheet prepared according to Example 91, and FIG. 23 is a graph showing measured values and calculated values of thermal conductivity of the shock absorbing composite sheet prepared according to Table 10; to be.

2. Performance Evaluation of Shock Absorbing Composite Sheet

How to measure thermal conductivity

It was evaluated by the Hot Disk method according to the ISO 22007-2 measurement standard. The measuring instrument used was a TPS 2500S (Sweden, Hot Disk).

The hot disk method prepares analytical specimens at 70 x 70 (mm), and directly contacts the sample with a 7577-type sensor with a heater.The heating power / heating power is 0.1W and the measurement time is 2 seconds. Thermal diffusion rate and thermal conductivity were calculated. At this time, a sample size of 70 x 70 (mm) 72㎛ or more (when the thickness is low, measured by overlapping the specimen) was used, was carried out in the slab mode (Slap mode).

3. Evaluation result

4 to 23 together with the above Tables 1 to 10, the shock absorbing composite sheet prepared according to the embodiment of the present invention is obtained by the above-described equation 1 and 2 as a result of measuring the thermal conductivity It was confirmed that it corresponds to the thermal conductivity. That is, the composite sheet for shock absorbing as in the present invention can be easily designed to fit the shock absorbing composite sheet using equations 1 and 2 to correspond to the desired thermal conductivity.

Those skilled in the art will appreciate that the present invention can be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive. The scope of the present invention is indicated by the scope of the following claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and the equivalent concept are included in the scope of the present invention. Should be interpreted.

100, 100a, 100b: composite sheet for shock absorption
110: thermal conductive layer
120: shock absorbing layer
130: pressure-sensitive adhesive layer

Claims (25)

In the composite sheet for shock absorption,
A thermally conductive layer formed by stacking one or more single or mixed metals;
An impact absorbing layer provided in direct contact with one surface or both surfaces of the thermal conductive layer; And
It consists of a pressure-sensitive adhesive layer (Pressure sensitive adhesive, PSA) provided on one side or both sides of the impact absorbing layer,
The thermal conductivity of the composite sheet for shock absorption according to the following formula 1 and formula 2, the thermal conductivity of the composite sheet for shock absorption in formula 1 and formula 2 is 50W / mK to 200W / mK, the thermal conductive layer is a Cu layer , Ni-Cu-Ni layer, Sn-Cu-Sn layer, Co-Cu-Co layer and any one of the Al layer, the thickness of the thermal conductive layer is 8㎛ to 150㎛, the entire shock absorbing composite sheet The ratio of the thickness of the heat conductive layer to the thickness is 12% to 50% composite sheet for shock absorption.
[Equation 1] λC = {1 / T * Σ (Ti * λi)} * (1 + D)
0.03 ≦ D ≦ 0.25
In Equation 1, λC is the thermal conductivity of the composite sheet for shock absorption (W / mK), T is the total thickness of the composite sheet for shock absorption (μm), Ti is a layer of a single or mixed metal constituting the thermal conductive layer Is the thickness of each layer (μm), λ i is the thermal conductivity (W / mK) of each layer on which the single or mixed metals constituting the heat conductive layer are laminated, and Σ (Ti * λ i) constitutes the thermal conductive layer. Is the total sum of the product of the respective layers or the thermal conductivity of the laminated or mixed metal is laminated, D according to the formula (2). delete delete delete delete delete delete The method of claim 1,
The impact absorbing layer comprises a polymer foam, the polymer foam is an acrylic foam, polyurethane foam, polyethylene foam, polyolefin foam, polyvinyl chloride foam, polycarbonate foam, polyimide foam, polyetherimide foam, polyamide foam, poly Composite sheet for shock absorption of at least one selected from the group consisting of ester foam, polyvinylidene chloride foam, polymethyl methacrylate foam and polyisocyanate foam. The method of claim 1,
The shock absorbing layer comprises a polymer foam, the polymer foam is a shock absorbing composite sheet is a polyurethane foam or acrylic foam. The method of claim 1,
The impact absorbing layer has a density of 0.2g / cm 3 to 0.8g / cm 3 Shock absorbing composite sheet. The method of claim 1,
The impact absorption layer has a thickness of 50㎛ to 250㎛ composite sheet for shock absorption. The method of claim 1,
The pressure-sensitive adhesive layer is a shock absorbing composite sheet containing any one or more of acrylic, silicone, epoxy, urethane and polyimide. The method of claim 1,
The pressure-sensitive adhesive layer has a thickness of 5㎛ 50㎛ composite sheet for shock absorption. The method of claim 1,
Composite sheet for shock absorbing is further provided with a protective layer on the outer surface of the pressure-sensitive adhesive layer. The method of claim 1,
One surface of the thermal conductive layer is provided with a shock absorbing layer, a pressure-sensitive adhesive layer and a protective layer sequentially
The other surface of the thermal conductive layer is a shock-absorbing composite sheet sequentially provided with TR-CPSA (Thermal Responsive Conductive Pressure Sensitive Adhesive) and a protective layer. delete delete delete delete delete delete delete delete delete delete

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