KR101261261B1 - Manufacturing method for thin film with expanded graphite - Google Patents

Abstract

PURPOSE: A manufacturing method of a super-thin thermal diffusion film using expansion graphite is provided to manufacture the super-thin thermal diffusion film having the uniform surface and constant thickness by improving slip property and adhesiveness when rolling the expanded graphite, to improve thermal conductivity, electric conductivity, and electron shielding, and to continuously manufacture the film without tearing when coiling. CONSTITUTION: A manufacturing method of a super-thin thermal diffusion film comprises the following steps: a step of manufacturing an expended graphite/coupling agent compound by coating a titanate coupling agent between layers of expanded graphite sheet structures(S1); and a multi-stage continuous rolling step of manufacturing the super-thin thermal diffusion film by rolling the manufactured expanded graphite/coupling agent compound(S2). In the expanded graphite/coupling agent compound manufacturing step, expanded graphite is inserted into a supermix before mixing at a speed of 900-1100rpm, and the titanate coupling agent is dissolved in isopropyl alcohol before being sprayed to manufacture the expanded graphite/coupling agent compound. [Reference numerals] (S1) Expanded graphite/coupling agent compound manufacturing step; (S2) Multi-stage continuous rolling step

Description

Manufacturing Method of Ultra-thin Thermal Diffusion Film Using Expanded Graphite {MANUFACTURING METHOD FOR THIN FILM WITH EXPANDED GRAPHITE}

The present invention relates to a method for producing an ultra-thin thermal diffusion film using expanded graphite, specifically, to prepare an expanded graphite / coupling agent compound by coating a titaniumate-based coupling agent between the interlaminar plate-like structure of the expanded graphite, the prepared expansion It relates to a method for producing an ultra-thin thermal diffusion film using expanded graphite, characterized in that the ultra-thin thermal diffusion film is produced by applying a multi-stage rolling continuous process to the compound / coupling agent compound.

Recently, as the performance of electronic devices has been developed due to the development of electronic and semiconductor technologies, miniaturization and high performance of electronic products have been rapidly progressed. Accordingly, it is becoming an important issue to secure the performance and lifespan of electronic devices by emitting heat generated from the electronic devices to the outside.

Meanwhile, in the related art, although the cooling fan performs the heat absorption function as described above, it has not exceeded the limit of the thickness. Accordingly, studies on the application of graphite having a laminated structure as a new type of heat absorption means have been actively conducted. Graphite film having flexibility has been widely applied as a good conductor of electricity and heat.

In particular, expanded graphite has been widely used in the electronics industry, the mechanical industry, and the chemical device industry, as it has excellent elasticity, an impermeability of a flexible gas or a liquid, together with heat resistance and a good conductor of electricity and heat.

Specifically, the expanded graphite is oxidized crystalline graphite with concentrated sulfuric acid and hydrogen peroxide solution, washed with water, and then put into an expansion furnace maintained at high temperature, the graphite expands between layers of graphite, that is, in the c-axis direction of the graphite crystals. That is, it is expanded to 100% to 700% in the initial volume. Such expanded graphite is used in materials of heat-resistant equipment in chemical processes, casting molds in steel castings, caps for heating ingots, electrodes in steel mills, high elastic refractory materials for furniture and mattresses, and the like.

Recently, it is being actively used as a heat dissipation material, heat conductive sheet, flame retardant, conductive filler, semiconductor component, display (LED), and field emission material of electronic devices. The performance of the

As related related arts, Patent Documents 1 and 2 disclose a technique of manufacturing expanded graphite in a film form using a polymer binder and using the same as a heat dissipation member. In the case of the rolling, as the surface and thickness of the film is nonuniform, not only thermal conductivity, electrical conductivity and electromagnetic shielding properties are insufficient, but also there is a problem of easy tearing.

In addition, as the interlayer adhesion of the expanded graphite is insufficient, it is not possible to manufacture continuously and thus the productivity is low and the price is high. As it is not manufactured in the form of ultra thin film, there is a problem that it cannot be applied to an ultra-small electronic device or a slim mobile phone. .

: Republic of Korea Patent Publication No. 10-2010-0017842 "Graphite film and graphite composite film" : Republic of Korea Patent Publication No. 10-2011-0059716 "Manufacturing method of carbonaceous film, and the graphite film obtained by this"

The present invention is to solve the above problems, by coating a titaniumate-based coupling agent between the interlaminar plate-like layer structure of the expanded graphite to prepare the expanded graphite / coupling agent compound and apply it to the ultra-thin thermal diffusion film, rolling the expanded graphite During the process, the slippage and adhesiveness are improved to make the surface of the film uniform and the thickness uniform, which not only improves thermal conductivity, electrical conductivity and electron shielding property, but also expands to allow continuous manufacture without tearing the film. An object of the present invention is to provide a method for producing an ultra-thin thermal diffusion film using graphite.

In addition, by applying a continuous multi-stage rolling process to the expanded graphite / coupling agent compound as described above, it is possible to manufacture an ultra-thin thermal diffusion film having a thickness of 0.03mm or less, thereby providing excellent productivity and price competitiveness, as well as microelectronic devices Another object is to provide a method for manufacturing an ultra-thin thermal diffusion film using expanded graphite, which can be easily applied to a slim mobile phone.

The present invention provides a method for producing an ultra-thin thermal diffusion film using expanded graphite,

An expanded graphite / coupling agent compound manufacturing step (S1) of preparing a expanded graphite / coupling agent compound by coating a titaniumate-based coupling agent between interlaminar plate-like structure layers; And

Solving the problem of the manufacturing method of the ultra-thin thermal diffusion film using expanded graphite comprising a multi-stage continuous rolling step (S2) to produce the ultra-thin thermal diffusion film by rolling the prepared expanded graphite / coupling agent compounder By means.

Here, in the expanded graphite / coupling agent compound manufacturing step (S1), the expanded graphite is introduced into a super mixer and mixed at 900 to 1100 rpm, while spraying a titaniumate-based coupling agent dissolved in isopropyl alcohol. After preparing the expanded graphite / coupling agent compound, it is preferred to volatilize isopropyl alcohol as a solvent by heating the mixture at 90 to 110 rpm for 30 minutes to 1 hour.

In addition, in the multi-stage continuous rolling step (S2), the expanded graphite / coupling agent compound is preferably thinly rolled over three times using a plurality of rolling rolls to produce an ultra-thin thermal diffusion film.

In addition, the titanate-based coupling agent is added to 3 to 5 parts by weight based on 100 parts by weight of expanded graphite (G), 3 to 5 parts by weight based on 100 parts by weight of isopropyl alcohol as a solvent. It is preferable to be.

The present invention is to prepare a expanded graphite / coupling agent compound by coating a titaniumate-based coupling agent between the interlaminar plate-like layer structure of the expanded graphite and apply it to the ultra-thin thermal diffusion film, thereby improving the slip properties and adhesion during rolling of the expanded graphite film The surface of the film is uniform and its thickness is constant, which not only improves thermal conductivity, electrical conductivity and electromagnetic shielding property, but also enables continuous production without tearing the film during winding. In addition, the expanded graphite / coupling agent as described above By applying the multi-stage rolling continuous process to the compound, it is possible to manufacture ultra-thin thermal diffusion film having a thickness of 0.03mm or less, which is excellent in productivity and price competitiveness, and can be easily applied to small electronic devices or slim mobile phones. It is effective.

1 is a flow chart showing a method of manufacturing an ultra-thin thermal diffusion film using expanded graphite according to an embodiment of the present invention.
FIG. 2 is a schematic view showing a supermix in which the spray injector of FIG. 1 is installed
3 is a schematic view showing the vibrator and the rolling roll of FIG.
Figure 4 is a photograph showing the thickness of the ultra-thin thermal diffusion film according to the Examples and Comparative Examples of the present invention
Figure 5 is a photograph showing the surface of the ultra-thin thermal diffusion film according to the Examples and Comparative Examples of the present invention

The present invention for achieving the above effect relates to a method for producing an ultra-thin thermal diffusion film using expanded graphite, only the parts necessary for understanding the technical configuration of the present invention will be described, the description of the other parts are the gist of the present invention. Note that it will be omitted so as not to scatter.

Hereinafter, the manufacturing method of the ultra-thin thermal diffusion film using expanded graphite according to the present invention will be described in detail.

As shown in FIG. 1, the method for manufacturing an ultra-thin thermal diffusion film using expanded graphite according to the present invention includes an expanded graphite / coupling agent compound manufacturing step (S1) and a multi-stage continuous rolling step (S2).

In the expanded graphite / coupling agent compound manufacturing step (S1), the expanded graphite / coupling agent compound is prepared by coating a titaniumate-based coupling agent between the lamellar structure layers of the expanded graphite, and applying the same to an ultra-thin thermal diffusion film. When rolling, the slip and adhesiveness are improved, so that the surface of the film is uniform and the thickness is constant, which not only improves thermal conductivity, electrical conductivity and electron shielding property, but also enables continuous production without tearing when the film is wound. It's a step.

Specifically, as shown in FIG. 2, expanded graphite (G) is added to a super mixer 10 in which a spray injector 10a is installed, and mixed at 900 to 1100 rpm, and mixed with isopropyl alcohol as a solvent. After dissolving the titanium titanate coupling agent through the spray injector (10a) to produce an expanded graphite / coupling agent compound, while mixing the prepared expanded graphite / coupling agent compound at a super mixer at 90 ~ 110rpm Heated at 50-70 ° C. for 30 minutes to 1 hour to volatilize the solvent isopropyl alcohol to prepare expanded graphite / coupling agent compound.

At this time, if the conditions for each process of the expanded graphite / coupling agent compound manufacturing step (S1) is out of the above range, there is a fear that the titaniumate-based coupling agent is not coated between the interlaminar plate-like structure or thickness control This may not be easy.

In the expanded graphite used in the present invention, crystalline graphite having excellent heat dissipation characteristics is oxidized in a solution of chromic acid and dilute sulfuric acid, and water is deposited between layers of graphite and expanded to 100 to 700% of the initial volume by heating. As the graphite, one having a thermal conductivity of 400 W / mk or more is used.

In addition, the titaniumate-based coupling agent used in the present invention, isopropyl triisostearoyl titanate, isopropyltris (N-aminoethyl-aminoethyl) titanate (isopropyltris (N- aminoethyl-aminoethyl) titanate), tetraisopropyl bis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, Tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioxyl Pyrophosphite) oxyacetate titanate (bis (dioctylpyrophosphate) oxyacetate titanate), isopropyl tridodecylbenzene sulfonyl titanate, isopropyl di (dioxylsilpyropas) Fight) Titanate (isopropyl di (dioctylphosphite) titanate) or isopropyl tris (dioctylpyrophosphate) titanate (isopropyl tris (dioctyl pyrophosphate) titanate) can be selected singly or in combination. 3 to 5 parts by weight based on 100 parts by weight of expanded graphite, and 3 to 5 parts by weight based on 100 parts by weight of isopropyl alcohol as a solvent are added.

At this time, when the mixing amount of the titanate-based coupling agent is less than 3 parts by weight, when the third rolling and winding of the multi-stage continuous rolling step (S2) to be described later, there is a fear that the film is broken due to the lack of slip and adhesiveness, 5 When it exceeds the weight part, there is a risk that the thickness control is difficult due to excessive slip properties during tertiary rolling and winding.

In the multi-stage continuous rolling step (S2), by applying a multi-stage rolling continuous process to the expanded graphite / coupling agent compound as described above, it is possible to manufacture an ultra-thin thermal diffusion film having a thickness of 0.03mm or less, thereby productivity and cost competitiveness This is not only excellent but also easy to apply to ultra-small electronic devices or slim mobile phones.

Specifically, as shown in FIG. 3, the expanded graphite / coupling agent compound manufactured in the expanded graphite / coupling agent compound manufacturing step S1 is transferred to the primary rolling roll 21 through the vibrator 20. First rolling to a thickness of 0.2 mm to 1.0 m under conditions of a temperature of 30 to 40 ° C. and a speed of 1 to 3 m / min, and then transferred to a secondary rolling roll 22 to a temperature of 30 to 40 ° C. and a speed of 1 to After the second rolling so that the thickness is 0.04mm ~ 0.1mm at the conditions of 3m / min, and transferred to the third rolling roll 23, the thickness is 0.01 ~ 0.03mm at the temperature of 20 ~ 30 ℃, speed 1 ~ 3m / min Rolled three times to make an ultra-thin thermal diffusion film.

At this time, if the conditions for each process of the multi-stage continuous rolling step (S2) is out of the range, there is a fear that ultra-thin film of 0.03mm or less may not be manufactured.

Hereinafter, the present invention will be described in more detail with reference to the following examples, which are not intended to limit the present invention.

1. Preparation of Ultra Thin Thermal Diffusion Film

(Example 1)

In the expanded graphite / coupling agent compound manufacturing step (S1), the expanded graphite is introduced into a supermix equipped with a spray injector and mixed at 1000 rpm, while the titanium injector coupling agent dissolved in a solvent of isopropyl alcohol is added to the spray injector. After spraying through to produce an expanded graphite / coupling compound, the expanded graphite / coupling agent compound is heated at 60 ° C. for 40 minutes while mixing the prepared expanded graphite / coupling agent compound at 100 rpm in a super mixer to volatilize isopropyl alcohol as a solvent. / Coupling agent compound is prepared, and in the multi-stage continuous rolling step (S2), the prepared expanded graphite / coupling agent compound is transferred to the primary rolling roll through a vibrator at a temperature of 35 ℃, speed 2m / min After the primary rolling to a thickness of 1.0m, and then to the secondary rolling rolls and then secondary rolled to a thickness of 0.1mm under the conditions of the temperature 35 ℃, speed 2m / min, the third pressure Transferred to a soft roll and rolled 3 times so that it may become thickness 0.03mm on the conditions of 25 degreeC and the speed of 2 m / min, and manufactured the ultra-thin thermal-diffusion film.

Here, the titanate-based coupling agent is added to 3 parts by weight with respect to 100 parts by weight of expanded graphite (G), but added to 3 parts by weight with respect to 100 parts by weight of isopropyl alcohol as a solvent, the titaniumate As the system coupling agent, isopropyl triisostearoyl titanate was used.

(Example 2)

In the expanded graphite / coupling agent compound manufacturing step (S1), the expanded graphite is introduced into a supermix equipped with a spray injector and mixed at 1000 rpm, while the titanium injector coupling agent dissolved in a solvent of isopropyl alcohol is added to the spray injector. After spraying through to produce an expanded graphite / coupling compound, the expanded graphite / coupling agent compound is heated at 60 ° C. for 40 minutes while mixing the prepared expanded graphite / coupling agent compound at 100 rpm in a super mixer to volatilize isopropyl alcohol as a solvent. / Coupling agent compound is prepared, and in the multi-stage continuous rolling step (S2), the prepared expanded graphite / coupling agent compound is transferred to the primary rolling roll through a vibrator at a temperature of 35 ℃, speed 2m / min After the primary rolling to a thickness of 1.0m, and then to the secondary rolling rolls and then secondary rolled to a thickness of 0.1mm under the conditions of the temperature 35 ℃, speed 2m / min, the third pressure Transferred to a soft roll and rolled 3 times so that it may become thickness 0.03mm on the conditions of 25 degreeC and the speed of 2 m / min, and manufactured the ultra-thin thermal-diffusion film.

Here, the titaniumate-based coupling agent is added to 4 parts by weight with respect to 100 parts by weight of expanded graphite (G), 4 parts by weight with respect to 100 parts by weight of isopropyl alcohol as a solvent, is added to the state of titanium acetate Tetraisopropyl bis (dioctylphosphite) titanate was used as the system coupling agent.

(Example 3)

In the expanded graphite / coupling agent compound manufacturing step (S1), the expanded graphite is introduced into a supermix equipped with a spray injector and mixed at 1000 rpm, while the titanium injector coupling agent dissolved in a solvent of isopropyl alcohol is added to the spray injector. After spraying through to produce an expanded graphite / coupling compound, the expanded graphite / coupling agent compound is heated at 60 ° C. for 40 minutes while mixing the prepared expanded graphite / coupling agent compound at 100 rpm in a super mixer to volatilize isopropyl alcohol as a solvent. / Coupling agent compound is prepared, and in the multi-stage continuous rolling step (S2), the prepared expanded graphite / coupling agent compound is transferred to the primary rolling roll through a vibrator at a temperature of 35 ℃, speed 2m / min After the primary rolling to a thickness of 1.0m, and then to the secondary rolling rolls and then secondary rolled to a thickness of 0.1mm under the conditions of the temperature 35 ℃, speed 2m / min, the third pressure Transferred to a soft roll and rolled 3 times so that it may become thickness 0.03mm on the conditions of 25 degreeC and the speed of 2 m / min, and manufactured the ultra-thin thermal-diffusion film.

Here, the titaniumate-based coupling agent is added to 5 parts by weight based on 100 parts by weight of expanded graphite (G), but 5 parts by weight based on 100 parts by weight of isopropyl alcohol as a solvent, was added to the titaniumate As the system coupling agent, isopropyltris (N-aminoethyl-aminoethyl) titanate was used.

(Comparative Example 1)

A 0.03 mm ultra thin dediffusion film manufactured and sold in China was used.

2. Evaluation of Ultra Thin Thermal Diffusion Film

Examples 1 to 3 and the ultra-thin film thermal diffusion sheet according to Comparative Example 1 were measured in the same manner as in [Table 1] below, and the results are shown in [Table 1], FIGS. 4 and 5 below.

Test Items How to measure Example 1 Example 2 Example 3 Comparative Example 1 Face direction
Thermal conductivity
(W / mk) ASTM D 5470 400 500 600 350 Surface resistance
(ohm / sq) ASTM D 573 5 × 10 ^-4 5 × 10 ^-4 5 × 10 ^-4 5 × 10 ^-3 Electronic shielding
(db) KS C0305
(500.3 MHz) 60 or more 60 or more 60 or more 60 or more

As shown in Figures 4 and 5, the ultra-thin thermal diffusion film according to Examples 1 to 3 of the present invention has a uniform surface and uniform thickness, as shown in Table 1, the performance of thermal conductivity, etc. On the other hand, in the case of Comparative Example 1, the surface is uneven and the thickness is not constant, it can be seen that the performance, such as thermal conductivity is inferior to Examples 1-3.

As described above, the method for producing an ultra-thin thermal diffusion film using expanded graphite according to the present invention has been described through the above-described preferred embodiments, and the superiority thereof has been confirmed, but those skilled in the art will appreciate the present invention described in the following claims. It will be understood that various modifications and changes can be made in the present invention without departing from the spirit and scope of the invention.

G: Expanded Graphite 10: Super Mix
10a: spray injector 20: vibrator
21: 1st rolling roll 22: 2nd rolling roll
23: 3rd rolling roll

Claims (5)

In the manufacturing method of ultra-thin thermal diffusion film using expanded graphite,
An expanded graphite / coupling agent compound manufacturing step (S1) of preparing a expanded graphite / coupling agent compound by coating a titaniumate-based coupling agent between interlaminar plate-like structure layers; And
It comprises a; multi-stage continuous rolling step (S2) to manufacture the ultra-thin thermal diffusion film by rolling the prepared expanded graphite / coupling agent compounder,
The expanded graphite / coupling agent compounding step (S1),
After adding expanded graphite into a super mixer and mixing at a speed of 900 to 1100 rpm, a titanate-based coupling agent dissolved in isopropyl alcohol was sprayed to prepare an expanded graphite / coupling compound, and then 90 to 90 Method for producing an ultra-thin thermal diffusion film using expanded graphite characterized in that the solvent isopropyl alcohol is volatilized by heating at 50 ~ 70 ℃ for 30 minutes to 1 hour while mixing at 110rpm
delete The method of claim 1,
The multi-stage continuous rolling step (S2),
Method for producing an ultra-thin thermal diffusion film using expanded graphite to produce an ultra-thin thermal diffusion film by rolling the expanded graphite / coupling agent compound thinly sequentially over three times using a plurality of rolling rolls.
The method of claim 1,
The titaniumate-based coupling agent,
3 to 5 parts by weight based on 100 parts by weight of expanded graphite (G),
A method for producing an ultra-thin thermal diffusion film using expanded graphite, wherein 3 to 5 parts by weight is added to 100 parts by weight of isopropyl alcohol as a solvent. delete

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