KR102170476B1 - Composite for rediation of heat and printed circuit board using the same - Google Patents

Abstract

The heat dissipation composition according to an embodiment of the present invention includes 0.01 to 750 parts by weight of an inorganic filler based on 100 parts by weight of the binder composition, and the binder composition includes 50 to 500 parts by weight of an alkoxy silane based on 100 parts by weight of an alumina sol. Include.

Description

Heat dissipation composition and printed circuit board using the same {COMPOSITE FOR REDIATION OF HEAT AND PRINTED CIRCUIT BOARD USING THE SAME}

The present invention relates to a heat radiation composition and a heat radiation layer using the same.

Electronic components included in electronic devices, automobiles, and electric vehicles may be heating elements. The heat emitted by the heating element can degrade the performance of electronic components.

As electronic components become highly integrated and have higher capacity, interest in heat dissipation of electronic components is increasing.

For heat dissipation of electronic components, a heat dissipation composition having high heat dissipation and high heat resistance properties has been developed. Examples of the heat dissipation composition include organic resins such as silicone resins, epoxy resins, acrylic resins, urethane resins, organic compositions including inorganic fillers and inorganic pigments, silane hydrolyzates, organic resins, organic-inorganic composites including inorganic fillers and inorganic pigments. Composition, colloidal silica, inorganic fillers and inorganic compositions including inorganic pigments.

In general, organic resins have lower thermal conductivity than metal or inorganic resins. Therefore, the heat dissipation property of the inorganic composition is superior to that of the organic composition or the organic-inorganic composite composition. As the level of heat dissipation required for high integration and high capacity of electronic components is increasing, there is a need for a new inorganic composition that satisfies this.

The technical problem to be achieved by the present invention is to provide a heat radiation composition and a heat radiation layer using the same.

The heat dissipation composition according to an embodiment of the present invention includes 0.01 to 750 parts by weight of an inorganic filler based on 100 parts by weight of the binder composition, and the binder composition includes 50 to 500 parts by weight of an alkoxy silane based on 100 parts by weight of an alumina sol. Include.

The alkoxy silane is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, n-propyltriethoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, tetraethylosilicate, and a mixture selected from these may be included.

It further includes a solvent and additives, and may include 50 to 1000 parts by weight of a solvent and 0.01 to 10 parts by weight of an additive based on 100 parts by weight of the alumina sol.

The additive may include at least one of an inorganic acid, an organic acid, an anti-settling agent, and a leveling agent.

It may include 0.01 to 2 parts by weight of the anti-settling agent based on 100 parts by weight of the inorganic filler.

The inorganic filler may include at least one selected from carbon nanotubes, graphene, and graphite.

A printed circuit board according to an embodiment of the present invention includes a metal plate, an insulating layer formed on the metal plate, and a circuit pattern formed on the insulating layer, wherein the insulating layer is based on 100 parts by weight of the binder composition. It includes 0.01 to 750 parts by weight of an inorganic filler, and the binder composition includes alumina sol.

According to an embodiment of the present invention, a heat dissipating composition having high heat dissipation, high radiation, and high heat resistance properties can be obtained. In addition, by applying such a heat radiation composition, an electronic component with improved heat radiation performance can be obtained.

1 is a cross-sectional view of a printed circuit board according to an embodiment of the present invention.
2 is a perspective view of a heat sink according to an embodiment of the present invention, and FIG. 3 is a light source disposed on an upper surface of the heat sink according to an embodiment of the present invention.
4 is a cross-sectional view of a solar cell according to an embodiment of the present invention.
5 is an apparatus for measuring heat radiation performance of a heat radiation composition according to an embodiment of the present invention.

The present invention is intended to illustrate and describe specific embodiments in the drawings, as various changes may be made and various embodiments may be provided. However, this is not intended to limit the present invention to a specific embodiment, it is to be understood to include all changes, equivalents, and substitutes included in the spirit and scope of the present invention.

Terms including ordinal numbers, such as second and first, may be used to describe various elements, but the elements are not limited by the terms. These terms are used only for the purpose of distinguishing one component from another component. For example, without departing from the scope of the present invention, a second component may be referred to as a first component, and similarly, a first component may be referred to as a second component. The term and/or includes a combination of a plurality of related listed items or any of a plurality of related listed items.

The terms used in the present application are only used to describe specific embodiments, and are not intended to limit the present invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present application, terms such as "comprise" or "have" are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, but one or more other features. It is to be understood that the presence or addition of elements or numbers, steps, actions, components, parts, or combinations thereof, does not preclude in advance.

Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs. Terms as defined in a commonly used dictionary should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and should not be interpreted as an ideal or excessively formal meaning unless explicitly defined in this application. Does not.

When a part of a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where the other part is "directly above", but also the case where there is another part in the middle. Conversely, when one part is "directly above" another part, it means that there is no other part in the middle.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings, but the same reference numerals are assigned to the same or corresponding components regardless of the reference numerals, and redundant descriptions thereof will be omitted.

In the present specification, wt% may be replaced by parts by weight.

According to an embodiment of the present invention, a binder composition and an inorganic filler are included, wherein the binder composition provides a heat dissipation composition including alumina sol and alkoxy silane.

The heat dissipation composition according to an embodiment of the present invention includes 0.01 to 750 parts by weight of an inorganic filler based on 100 parts by weight of the binder composition. The alumina sol included in the binder composition may be mixed with colloidal alumina, and refers to a state in which alumina hydrate (AlOOH) is dispersed in water in a colloidal form. Alumina sol has excellent film-forming properties, good adhesive bonding, and excellent heat resistance. The alumina sol may use water or an organic solvent as a dispersion medium. The alumina sol may contain, for example, 10 to 30 wt% of solids and 70 to 90 wt% of water.

The alkoxy silane can be represented by R _n Si(OR') _4-n . Here, R is an alkyl group having 1 to 6 carbon atoms, and R'may be an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms. Alkoxy silanes are, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, and n-propyltriethoxysilane. It may be one of silane, phenyltrimethoxysilane, phenyltriethoxysilane, tetraethylorthosilicate, and a mixture selected from these.

The alkoxy silane reacts with water of the alumina sol to form a silanol group, and a dehydration condensation reaction occurs at room temperature or under a heated condition to form a coating film. Accordingly, adhesion, hardness, thermal conductivity, insulation performance, and the like of the paint can be improved. In this case, 50 to 500 parts by weight of alkoxy silane may be included based on 100 parts by weight of the alumina sol. If less than 50 parts by weight of alkoxy silane is contained with respect to 100 parts by weight of the alumina sol, it is not easy to form a coating film and storage properties may be poor. In addition, when the alkoxy silane is contained in an amount exceeding 500 parts by weight based on 100 parts by weight of the alumina sol, self-condensation of excess silane occurs, resulting in lower binder performance.

The binder composition according to an embodiment of the present invention may further include a solvent and an additive. The solvent can be water or an organic solvent. In this case, 50 to 1000 parts by weight of the solvent may be included based on 100 parts by weight of the alumina sol. The organic solvent may be one of a lower aliphatic alcohol, a higher aliphatic alcohol, a ketone solvent, an aromatic solvent, and a mixture selected from these. The lower aliphatic alcohol may be, for example, one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and mixtures selected therefrom. When a lower aliphatic alcohol or a higher aliphatic alcohol is used as the organic solvent, if the organic solvent is contained less than 50 parts by weight based on 100 parts by weight of the alumina sol, the painted surface is poor and the pot life is reduced. And, when the organic solvent is contained higher than 1000 parts by weight per 100 parts by weight of the alumina sol, the polymerization reaction continuously occurs due to the strong hydrogen bonding force of the alcohol, the pot life is reduced, and the thermal conductivity and insulation performance are lowered.

The solvent may vary depending on the type of the object to be coated with the heat dissipation composition according to an embodiment of the present invention, for example, metal, non-metal, glass, plastic, and the like.

The additive may include at least one of an inorganic or organic acid, an anti-settling agent, and a leveling agent. In this case, 0.01 to 10 parts by weight of an additive may be included based on 100 parts by weight of the alumina sol. If 0.01 to 10 parts by weight of the additive is included with respect to 100 parts by weight of the alumina sol, the pH of the heat dissipating composition can be adjusted, and a sedimentation preventing effect can be obtained.

The inorganic or organic acid may be one of phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, formic acid, and mixtures selected from these. The inorganic acid or organic acid hydrolyzes the alkoxy silane and the alumina sol, and the pH of the binder composition can be adjusted to 2 to 5. When the pH of the binder composition is 2 or less, storage properties after preparation are poor, and when the pH is 5 or more, stability is poor and adhesive bondability is poor.

The anti-settling agent prevents the precipitation of inorganic fillers. The ceramic-based inorganic filler has a high specific gravity, and there is a problem that it precipitates as time passes after manufacture. Therefore, it is intended to prevent precipitation of the inorganic filler by adding an anti-settling agent to the heat dissipation composition. The anti-settling agent may be, for example, a clay-based anti-settling agent or a silica-based anti-settling agent. The anti-settling agent may be contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the inorganic filler. If the anti-settling agent is contained less than 0.01 parts by weight based on 100 parts by weight of the inorganic filler, the effect of preventing settling cannot be obtained. When the anti-settling agent is contained more than 2 parts by weight based on 100 parts by weight of the inorganic filler, adhesive bonding and heat dissipation properties are deteriorated.

The leveling agent improves the workability by improving the flowability of the paint. The leveling agent may be one of a mixed solvent of an aromatic or aliphatic hydrocarbon compound, for example, xylene, toluene, ethylenic glycol monobutyl ether, methyl ethyl ketone, and a mixture selected from these.

The heat dissipation composition according to an embodiment of the present invention includes 0.01 to 750 parts by weight of an inorganic filler based on 100 parts by weight of the binder composition. When the inorganic filler is included in an amount of 0.01 to 750 parts by weight based on 100 parts by weight of the binder composition, hardness, durability, insulation, thermal conductivity, and heat resistance of the heat dissipating composition may be improved. The thermal conductivity and heat resistance are better as the amount of the inorganic filler added increases, but does not improve according to the volume fraction, and improves drastically from a specific added amount. However, if the inorganic filler is contained in an amount greater than 0.01 to 750 parts by weight based on 100 parts by weight of the binder composition, the viscosity increases and the moldability is weakened.

According to an embodiment of the present invention, the inorganic filler may be one of carbon nanotubes (CNT), graphene, graphite, and a mixture selected from these. In addition, the inorganic filler is, for example, cordierite, germanium, iron oxide, mica, manganese dioxide, silicon carbide, macsumstone, carbon, copper oxide, cobalt oxide, nickel oxide, tin oxide, chromium oxide, silica, magnesium oxide, and zinc oxide. , Silica, alumina, barium titanate, aluminum nitride, alumina whisker, titania, zirconia, and may further include one of a mixture selected from these.

In the heat dissipation composition according to an embodiment of the present invention, the weight ratio of the solid content of the alumina sol and the inorganic filler (alumina sol/inorganic filler) may be 50/50 to 97/3, preferably 70/30 to 95/5. When the weight ratio of the solid content of the alumina sol and the inorganic filler is lower than 50/50, when the inorganic filler contains more than the alumina sol, the adhesive bond between the coating film and the material is poor, making it difficult to apply to electronic parts. And, when the weight ratio of the solid content of the alumina sol and the inorganic filler is greater than 97/3, the adhesive bond between the coating film and the material is increased, but the heat dissipation performance is lowered.

The heat dissipation composition according to an embodiment of the present invention may further include an inorganic pigment. The inorganic pigment may be a rutile type inorganic pigment having an average particle diameter of 0.1 nm to 20 μm or a non-toxic pearl pigment such as mica-titanium oxide.

The heat dissipation composition according to an embodiment of the present invention may be obtained by mixing an alkoxy silane, an alumina sol, and an additive to hydrolyze, adding a solvent and an inorganic filler, and stirring in a disperser. The disperser may be, for example, a ball mill, a sand mill, a ring mill, a basket mill, a dyno mill, a jet mill, and the like, and may be stirred at room temperature and pressure for 2 to 24 hours. Such a heat dissipation composition may be coated on an object such as metal, non-metal, glass, or plastic.

The heat dissipation composition according to an embodiment of the present invention may be applied to a printed circuit board. 1 is a cross-sectional view of a printed circuit board according to an embodiment of the present invention.

Referring to FIG. 1, the printed circuit board 100 includes a metal plate 110, an insulating layer 120, and a circuit pattern 130.

The metal plate 110 may be made of copper, aluminum, nickel, gold, platinum, and an alloy selected from these.

An insulating layer 120 made of a heat dissipating composition according to an embodiment of the present invention is formed on the metal plate 110. After the metal plate 110 is preheated, an insulating layer may be formed by applying and curing the heat dissipation composition according to an embodiment of the present invention on the surface of the metal plate 110.

A circuit pattern 130 is formed on the insulating layer 120. The circuit pattern 130 may be made of a metal such as copper or nickel.

The insulating layer 120 insulates between the metal plate 110 and the circuit pattern 130.

By curing the heat dissipation composition according to an embodiment of the present invention and using it as an insulating layer, a printed circuit board having excellent heat dissipation performance can be obtained.

The heat dissipation composition according to an embodiment of the present invention may also be applied to a heatsink of lighting. 2 is a perspective view of a heat sink according to an embodiment of the present invention, and FIG. 3 is a light source disposed on an upper surface of the heat sink according to an embodiment of the present invention.

2 and 3, the heat sink 200 is embedded in the lighting device, and the light source 300 of the lighting device may be disposed on the upper surface of the heat sink 200. The light source 300 may include, for example, at least one LED (Light Emitting Diode) package. Heat generated from the light source 300 is transferred to the heat sink 200 and is discharged to the outside. In order to increase the contact area between the heat sink 200 and air, the surface of the heat sink 200 may have an uneven shape 210.

The heat sink 200 may include a heat dissipation composition according to an embodiment of the present invention. Accordingly, it is possible to obtain a heat sink excellent in heat dissipation performance.

The heat dissipation composition according to an embodiment of the present invention may be applied to a solar cell or a battery of an electric vehicle. 4 is a cross-sectional view of a solar cell according to an embodiment of the present invention.

Referring to FIG. 4, a solar cell 400 includes a support substrate 410, a rear electrode layer 420, a light absorption layer 430, a buffer layer 440, and an upper electrode layer 450.

The support substrate 410 has a plate shape and supports the rear electrode layer 420, the light absorption layer 430, the buffer layer 440, and the upper electrode layer 450. The support substrate 410 may be an insulator.

The rear electrode layer 420 is formed on the support substrate 410 and is a conductive layer.

The light absorption layer 430 is formed on the rear electrode layer 420 and may include a group I-III-VI compound.

The buffer layer 440 is formed on the light absorbing layer 430 and may include a plurality of buffer layers having different energy band gaps.

The front electrode layer 450 is formed on the buffer layer 440 and is a conductive layer.

In addition, the solar cell 400 may further include a heat dissipation layer 460. Although it is shown that the heat dissipation layer 460 is formed under the support substrate 410, it is not limited thereto. The heat dissipation layer 460 is between the support substrate 410 and the rear electrode layer 420, between the rear electrode layer 420 and the light absorption layer 430, between the light absorption layer 430 and the buffer layer 440, the buffer layer 440 and the upper surface. It may be formed between the electrode layers 450 or on the upper electrode side 450.

The heat dissipation layer 460 may include a heat dissipation composition according to an embodiment of the present invention. Accordingly, a battery having excellent heat dissipation performance can be obtained. Hereinafter, it will be described in more detail with reference to Examples and Comparative Examples.

<Example 1>

To 300 parts by weight of the solvent, 100 parts by weight of methylmethoxysilane, 100 parts by weight of alumina sol, and 1 part by weight of an additive were added, and 2 parts by weight of graphite were further added and stirred to obtain the heat dissipating composition of Example 1.

<Comparative Example 1>

Methylmethoxysilane, 100 parts by weight of silica sol, and 1 part by weight of an additive were added to 300 parts by weight of the solvent, and 2 parts by weight of graphite were further added and stirred to obtain a heat dissipating composition of Comparative Example 1.

<Example 2>

Methylmethoxysilane, 100 parts by weight of alumina sol and 1 part by weight of an additive were added to 300 parts by weight of the solvent, and 2 parts by weight of carbon nanotubes were further added and stirred to obtain a heat dissipating composition of Example 2.

<Comparative Example 2>

Methylmethoxysilane, 100 parts by weight of silica sol and 1 part by weight of an additive were added to 300 parts by weight of the solvent, and 2 parts by weight of carbon nanotubes were further added and stirred to obtain a heat dissipating composition of Comparative Example 2.

<Example 3>

Methylmethoxysilane, 100 parts by weight of alumina sol, and 1 part by weight of an additive were added to 300 parts by weight of the solvent, and 1 part by weight of graphite and 1 part by weight of carbon nanotubes were further added and stirred to obtain the heat dissipation composition of Example 3.

<Comparative Example 3>

Methylmethoxysilane, 100 parts by weight of silica sol, and 1 part by weight of an additive were added to 300 parts by weight of the solvent, and 1 part by weight of graphite and 1 part by weight of carbon nanotubes were further added and stirred to obtain a heat dissipating composition of Comparative Example 3.

The heat dissipating compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were coated on an aluminum specimen having a thickness of 0.6 mm and a size of 5 cm×5 cm, followed by drying and curing. In addition, after heating each of the unpainted aluminum specimens and the aluminum specimens coated with the heat dissipating compositions of Examples 1 to 3 and Comparative Examples 1 to 3, the temperature at a predetermined position was measured. 5 is a device for measuring the heat radiation performance of the heat radiation composition according to an embodiment of the present invention. Table 1 shows the results.

No. P1(℃) P2(℃) P3(℃) △P1(℃) △P2(℃) △P3(℃) Reference 105.3 94.9 95.5 - - - Comparative Example 1 91.6 80.1 79.7 -13.7 -14.8 -15.8 Example 1 87.6 77.9 78.2 -17.7 -17.0 -17.3 Comparative Example 2 90.2 78.4 83.1 -15.0 -16.5 -12.3 Example 2 88.7 78.0 78.1 -16.6 -16.9 -17.4 Comparative Example 3 90.5 80.7 81.7 -14.7 -14.2 -13.7 Example 3 87.6 78.3 79.4 -17.7 -16.6 -16.1

In Table 1, P1, P2, and P3 represent the temperatures (℃) measured in P1, P2 and P3 of FIG. 2, respectively, and △P1, △P2 and △P3 are the temperatures with the unpainted aluminum specimen (reference), respectively. Indicate the car.

In P1, the temperature difference between the unpainted aluminum specimen and the aluminum specimen coated with the composition of Comparative Example 1 is 13.7 °C, whereas the temperature difference between the unpainted aluminum specimen and the aluminum specimen coated with the composition of Example 1 is 17.7 °C.

In P2, the temperature difference between the unpainted aluminum specimen and the aluminum specimen coated with the composition of Comparative Example 1 is 14.8°C, whereas the temperature difference between the unpainted aluminum specimen and the aluminum specimen coated with the composition of Example 1 is 17.0°C.

In P3, the temperature difference between the unpainted aluminum specimen and the aluminum specimen coated with the composition of Comparative Example 1 is 15.8°C, whereas the temperature difference between the unpainted aluminum specimen and the aluminum specimen coated with the composition of Example 1 is 17.3°C.

The comparison between Example 2 and Comparative Example 2 and Example 3 and Comparative Example 3 is similar.

As described above, it is considered that the temperature difference between the unpainted aluminum specimen and the aluminum specimen coated with the composition containing the alumina sol is greater than the temperature difference between the unpainted aluminum specimen and the aluminum specimen coated with the composition containing the silica sol, It can be seen that the heat dissipation performance of the composition containing the alumina sol is superior to the heat dissipation performance of the composition containing the silica sol.

On the other hand, the already commercially available heat dissipation composition was coated on an aluminum specimen having a thickness of 0.6 mm and a size of 5 cm×5 cm, dried and cured, and then the temperature was measured in the same manner as in Table 1. Table 2 shows the results.

No. P1(℃) P2(℃) P3(℃) △P1(℃) △P2(℃) △P3(℃) Reference 105.3 94.9 95.5 - - - Composition 1 (Company M) 91.0 81.0 82.6 -14.3 -13.9 -12.9 Composition 2 (Company F) 90.9 82.5 83.0 -14.4 -12.4 -12.5 Composition 3 (Company I, white) 89.6 83.2 82.2 -15.7 -11.7 -13.3 Composition 4 (Company I, Black) 90.5 82.2 82.6 -14.8 -12.7 -12.9

In Table 2, Composition 1 is a heat radiation composition containing an epoxy resin and an acrylic resin, Composition 2 is a heat radiation composition containing a ceramic resin, and Compositions 3 and 4 are a heat radiation composition containing an acrylic resin.

P1, P2, and P3 represent the temperatures (°C) measured in P1, P2, and P3 of FIG. 2, respectively, and ΔP1, ΔP2, and ΔP3 each represent the temperature difference with the unpainted aluminum specimen (reference).

In all examples of Table 1, the temperature difference between the unpainted aluminum specimen and the coated aluminum specimen is 16°C or higher, whereas in all the compositions of Table 2, the temperature difference between the unpainted aluminum specimen and the coated aluminum specimen is 15°C or less.

From this, it can be seen that the heat dissipation composition according to the embodiment of the present invention has superior heat dissipation performance compared to other commercially available heat dissipation compositions.

Although the above has been described with reference to preferred embodiments of the present invention, those skilled in the art will variously modify and change the present invention within the scope not departing from the spirit and scope of the present invention described in the following claims. You will understand that you can do it.

Claims (7)

Including 0.01 to 750 parts by weight of an inorganic filler based on 100 parts by weight of the binder composition,
The binder composition includes 50 to 500 parts by weight of an alkoxy silane based on 100 parts by weight of an alumina sol,
The inorganic filler includes at least one selected from carbon nanotubes, graphene, and graphite,
The inorganic filler is the same as the alumina sol or the heat dissipation composition contained in a less weight than the alumina sol. The method of claim 1,
The alkoxy silane is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, n-propyltriethoxysilane, phenyl A heat dissipation composition comprising one of trimethoxysilane, phenyltriethoxysilane, tetraethylososilicate, and a mixture selected from these. The method of claim 2,
Further comprising a solvent and additives,
A heat radiation composition comprising 50 to 1000 parts by weight of a solvent and 0.01 to 10 parts by weight of an additive based on 100 parts by weight of the alumina sol. The method of claim 3,
The additive is a heat radiation composition comprising at least one of an inorganic acid, an organic acid, an anti-settling agent and a leveling agent. The method of claim 4,
A heat radiation composition comprising 0.01 to 2 parts by weight of the anti-settling agent based on 100 parts by weight of the inorganic filler. delete Metal plate,
An insulating layer formed on the metal plate, and
It includes a circuit pattern formed on the insulating layer,
The insulating layer includes 0.01 to 750 parts by weight of an inorganic filler based on 100 parts by weight of the binder composition, and the binder composition includes 50 to 500 parts by weight of an alkoxy silane based on 100 parts by weight of an alumina sol,
The inorganic filler includes at least one selected from carbon nanotubes, graphene, and graphite,
The inorganic filler is the same as the alumina sol or the printed circuit board contained in a weight less than the alumina sol.

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