TWI586722B - Composite graphite substrate with porous surface and method of producing thereof - Google Patents
Composite graphite substrate with porous surface and method of producing thereof Download PDFInfo
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本發明是有關於一種複合石墨基材及其製造方法，且特別是有關於具有多孔表面之複合石墨基材及其製造方法，所述之複合石墨基材具有粗糙且不平整的表面，以增加其與銅箔之間的附著性。 The present invention relates to a composite graphite substrate and a method of manufacturing the same, and more particularly to a composite graphite substrate having a porous surface having a rough and uneven surface to increase Its adhesion to the copper foil.
發光二極體(Light-Emitted Diode；LED)因具有體積小、能耗低、效率高及污染少等優點，目前以備廣泛使用於各式照明設備中。然而，LED容易發熱，一般而言，多數的LED之輸入功率約有80%至85%被轉換為熱能。因此，若所產生的熱能無法順利排出，將導致LED的介面溫度過高，進而影響其發光效率和使用壽命。 Light-Emitted Diode (LED) is widely used in various lighting equipment due to its small size, low energy consumption, high efficiency and low pollution. However, LEDs are prone to heat. In general, about 80% to 85% of the input power of most LEDs is converted into heat. Therefore, if the generated thermal energy cannot be discharged smoothly, the interface temperature of the LED will be too high, which will affect its luminous efficiency and service life.
為使LED可順利排出所產生的熱量，發展出各種與LED連接之散熱基板。一般而言，常見的散熱基板可為金屬(例如：鋁或銅)、陶瓷(例如：氧化鋁或氧化硼)或石墨。其中石墨具有高的熱傳導係數(約為50W/mK至 150W/mK)，且其密度及熱膨脹係數皆小於金屬，具有輕量化和不易因熱膨脹而與LED介面產生剝離的優點。再者，石墨也具有良好的加工性，因此十分適合作為LED之散熱基板。 In order to enable the LED to smoothly discharge the generated heat, various heat-dissipating substrates connected to the LED are developed. In general, common heat sink substrates can be metals (eg, aluminum or copper), ceramics (eg, aluminum oxide or boron oxide), or graphite. Among them, graphite has a high heat transfer coefficient (about 50W/mK to 150W/mK), and its density and thermal expansion coefficient are smaller than that of metal, which has the advantages of being lightweight and not easily peeling off from the LED interface due to thermal expansion. Furthermore, graphite also has good processability, so it is very suitable as a heat sink substrate for LEDs.
LED通常安裝於銅箔上，再藉由黏接用的樹脂使銅箔和散熱基板貼合，其中銅箔可用以設置LED所需的電路結構，而樹脂可提供絕緣性。然而，使用石墨製的散熱基板時，由於石墨為二維片狀結構，具有良好的自潤滑性和離型性，使得石墨難以藉由黏接用的樹脂與銅箔貼合，造成石墨製的散熱基板易與LED之銅箔剝離。此外，接著不良也會使得介面熱阻增加，降低整體LED光源的散熱能力。 The LED is usually mounted on a copper foil, and the copper foil and the heat dissipation substrate are bonded together by a resin for bonding, wherein the copper foil can be used to provide a circuit structure required for the LED, and the resin can provide insulation. However, when a graphite heat-dissipating substrate is used, since graphite is a two-dimensional sheet-like structure, it has good self-lubricity and release property, making it difficult for graphite to adhere to copper foil by bonding resin, resulting in graphite. The heat dissipation substrate is easily peeled off from the copper foil of the LED. In addition, the subsequent failure will also increase the interface thermal resistance and reduce the heat dissipation capability of the overall LED light source.
為了克服樹脂對LED與散熱基板之間接合不佳的問題，習知技術以導電膠取代上述樹脂。前述導電膠雖可增加散熱性，但石墨的自潤滑性，使得導電膠不易與石墨黏接，且導電膠的連結力與耐久性皆不佳。 In order to overcome the problem of poor bonding between the LED and the heat-dissipating substrate by the resin, the prior art replaces the above resin with a conductive paste. Although the conductive paste can increase heat dissipation, the self-lubricity of the graphite makes the conductive adhesive difficult to adhere to the graphite, and the bonding strength and durability of the conductive adhesive are not good.
因此，目前亟需提出一種用於石墨基材之接合材料，以改善習知LED與散熱基板之間接合不佳的問題。 Therefore, there is a need to propose a bonding material for a graphite substrate to improve the problem of poor bonding between a conventional LED and a heat-dissipating substrate.
因此，本發明之一態樣是在提供一種具有多孔表面的複合石墨基材的製造方法，其係利用包含高殘碳率之碳質材料以及低殘碳率之樹脂之含碳塗佈組成物，經高溫的碳化步驟後，以於石墨基材的表面形成多孔層。 Accordingly, an aspect of the present invention provides a method for producing a composite graphite substrate having a porous surface, which utilizes a carbonaceous coating composition comprising a carbonaceous material having a high residual carbon ratio and a resin having a low residual carbon ratio. After the high temperature carbonization step, a porous layer is formed on the surface of the graphite substrate.
本發明之另一態樣是在提供一種具有多孔表面 的複合石墨基材，其可藉由多孔表面而增加複合石墨基材與銅箔之間的附著性。 Another aspect of the present invention is to provide a porous surface The composite graphite substrate can increase the adhesion between the composite graphite substrate and the copper foil by the porous surface.
根據本發明之上述態樣，提出一種具有多孔表面的複合石墨基材的製造方法。在一實施例中，上述方法首先於石墨基材的表面上形成第一薄膜，以形成塗佈基材。上述之第一薄膜可由含碳塗佈組成物所形成，其包含碳質材料、樹脂、增黏劑和溶劑，其中碳質材料可具有在600℃至1300℃之第一溫度下，至少50%以上之第一殘碳率，而樹脂於前述第一溫度下可具有低於50%之第二殘碳率。基於樹脂之使用量為100重量份，碳質材料之使用量為100重量份至200重量份、增黏劑之使用量為2.5重量份至15重量份，以及溶劑之使用量為375重量份至625重量份。接下來，對上述塗佈基材進行碳化步驟，以使第一薄膜形成第二薄膜，且碳化步驟係於惰性氣氛及前述之第一溫度下進行。之後，對第二薄膜進行氣體吹拂步驟，去除第二薄膜上的片狀剝離物，以製得具有多孔表面的複合石墨基材，其中第二薄膜具有多孔表面。 According to the above aspect of the invention, a method of producing a composite graphite substrate having a porous surface is proposed. In one embodiment, the above method first forms a first film on the surface of the graphite substrate to form a coated substrate. The first film described above may be formed of a carbon-containing coating composition comprising a carbonaceous material, a resin, a tackifier, and a solvent, wherein the carbonaceous material may have a first temperature of 600 ° C to 1300 ° C, at least 50% The first residual carbon ratio above, and the resin may have a second residual carbon ratio of less than 50% at the first temperature. The amount of the carbonaceous material used is 100 parts by weight to 200 parts by weight, the amount of the tackifier used is 2.5 parts by weight to 15 parts by weight, and the solvent is used in an amount of 375 parts by weight based on 100 parts by weight of the resin. 625 parts by weight. Next, the coating substrate is subjected to a carbonization step to form the first film into a second film, and the carbonization step is performed under an inert atmosphere and the aforementioned first temperature. Thereafter, the second film is subjected to a gas blowing step to remove the sheet-like exfoliate on the second film to obtain a composite graphite substrate having a porous surface, wherein the second film has a porous surface.
依據本發明之一實施例，前述之石墨基材可由碳質粉體經加壓成型步驟以及熱處理步驟而形成。 According to an embodiment of the present invention, the graphite substrate described above may be formed from a carbonaceous powder by a press molding step and a heat treatment step.
依據本發明之一實施例，上述加壓成型步驟之壓力可為20MPa至300MPa。 According to an embodiment of the present invention, the pressure of the press molding step may be 20 MPa to 300 MPa.
依據本發明之一實施例，上述熱處理步驟可於2000℃至3300℃之第二溫度下進行。 According to an embodiment of the present invention, the heat treatment step may be performed at a second temperature of 2000 ° C to 3300 ° C.
依據本發明之一實施例，前述之碳質材料可包 含瀝青、介相碳微球、碳黑、煤焦油、煤炭、石油焦或上述之任意組合。 According to an embodiment of the invention, the aforementioned carbonaceous material can be packaged Bituminous, mesocarbon microspheres, carbon black, coal tar, coal, petroleum coke or any combination of the above.
依據本發明之一實施例，前述之樹脂可包含苯乙烯-丁二烯橡膠、聚氨酯樹脂、壓克力樹脂或上述之任意組合。 According to an embodiment of the present invention, the aforementioned resin may comprise styrene-butadiene rubber, urethane resin, acrylic resin or any combination thereof.
依據本發明之一實施例，前述之含碳塗佈組成物之黏度可介於300cps至5000cps之間。 According to an embodiment of the present invention, the viscosity of the carbon-containing coating composition may be between 300 cps and 5000 cps.
依據本發明之一實施例，於石墨基材之表面上形成第一薄膜的步驟與碳化步驟之間更包含進行乾燥步驟。 According to an embodiment of the invention, the step of forming the first film on the surface of the graphite substrate and the step of carbonizing further comprises performing a drying step.
依據本發明之一實施例，乾燥後的第一薄膜可具有100μm至300μm之厚度。 According to an embodiment of the present invention, the dried first film may have a thickness of from 100 μm to 300 μm.
依據本發明之一實施例，前述之於石墨基材之表面上形成第一薄膜的步驟，可包含以刮刀塗佈步驟、狹縫塗佈步驟或浸漬塗佈步驟進行。 According to an embodiment of the present invention, the step of forming the first film on the surface of the graphite substrate may include performing a blade coating step, a slit coating step, or a dip coating step.
依據本發明之一實施例，第二薄膜可至少包含碳質材料以及片狀剝離物，且片狀剝離物係由樹脂經碳化步驟所形成。 According to an embodiment of the present invention, the second film may include at least a carbonaceous material and a sheet-like release, and the sheet-like release is formed by a carbonization step of the resin.
根據本發明之上述態樣，提出一種具有多孔表面的複合石墨基材。在一實施例中，上述具有多孔表面的複合石墨基材可藉由前述之具有多孔表面的複合石墨基材的製造方法所製得，且具有多孔表面的複合石墨基材可包含石墨基材以及多孔層，其中多孔層可設於石墨基材的表面上，多孔層至少包含碳質材料，且於600℃至1300℃之第一溫度下，碳質材料之殘碳率可為至少50%。 According to the above aspect of the invention, a composite graphite substrate having a porous surface is proposed. In one embodiment, the composite graphite substrate having a porous surface can be produced by the above-described method for producing a composite graphite substrate having a porous surface, and the composite graphite substrate having a porous surface can comprise a graphite substrate and The porous layer, wherein the porous layer may be disposed on a surface of the graphite substrate, the porous layer contains at least a carbonaceous material, and the residual carbon ratio of the carbonaceous material may be at least 50% at a first temperature of 600 ° C to 1300 ° C.
應用本發明之具有多孔表面之複合石墨基材及其製造方法，藉由將含碳塗佈組成物(包含於600℃至1300℃之溫度下具有不同殘碳率之碳質材料和樹脂)形成於石墨基材的表面，並經過碳化步驟及氣體吹拂步驟，可使所製得之複合石墨基材具有粗糙且不平整的表面，進而可增加複合石墨基材具有與銅箔之間的附著性。 The composite graphite substrate having a porous surface of the present invention and a method for producing the same are formed by forming a carbon-containing coating composition (carbonaceous material and resin having different residual carbon ratios at a temperature of 600 ° C to 1300 ° C) On the surface of the graphite substrate, and through the carbonization step and the gas blowing step, the prepared composite graphite substrate can have a rough and uneven surface, thereby increasing the adhesion between the composite graphite substrate and the copper foil. .
100‧‧‧方法 100‧‧‧ method
110‧‧‧於石墨基材之表面上形成第一薄膜，以形成塗佈基材 110‧‧‧ Forming a first film on the surface of the graphite substrate to form a coated substrate
120‧‧‧對塗佈基材進行碳化步驟，以使第一薄膜形成第二薄膜 120‧‧‧Carriding the coated substrate to form the first film into a second film
130‧‧‧對第二薄膜進行氣體吹拂步驟，去除第二薄膜之片狀剝離物，以製得具有多孔表面的複合石墨基材 130‧‧‧ gas-blowing step of the second film to remove the sheet-like exfoliate of the second film to obtain a composite graphite substrate having a porous surface
200A‧‧‧塗佈基材 200A‧‧‧ coated substrate
200D‧‧‧複合石墨基材 200D‧‧‧Composite graphite substrate
210‧‧‧石墨基材 210‧‧‧Graphite substrate
210a‧‧‧表面 210a‧‧‧ surface
220A‧‧‧第一薄膜 220A‧‧‧First film
220B‧‧‧分層 220B‧‧‧ layering
220C‧‧‧第二薄膜 220C‧‧‧Second film
221a‧‧‧碳質材料 221a‧‧‧Carbon materials
221b‧‧‧連續狀薄層 221b‧‧‧Continuous thin layer
223a‧‧‧樹脂 223a‧‧‧Resin
223b‧‧‧樹脂層 223b‧‧‧ resin layer
223c‧‧‧片狀剝離物 223c‧‧‧Sheet strips
225‧‧‧表面 225‧‧‧ surface
301、401、402‧‧‧圓圈 301, 401, 402‧‧ ‧ circles
501、503、505‧‧‧曲線 501, 503, 505‧‧‧ curves
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂，所附圖式之詳細說明如下：[圖1]係繪示根據本發明之一實施例所述之具有多孔表面的複合石墨基材的製造方法之部分流程圖；[圖2A]至[圖2D]係繪示上述製造方法之中間製程的示意圖；[圖3]係繪示本發明之實施例1之具有多孔表面之複合石墨基材的表面(連續狀薄層之一側)的光學顯微鏡圖，其中以200μm為比例尺；[圖4A]係繪示比較例1之表面粗糙化之石墨基材的表面(以砂紙研磨並粗糙化的一側)之光學顯微鏡圖，其中以200μm為比例尺；[圖4B]係繪示比較例3之複合石墨基材的表面(連續狀薄層之一側)之光學顯微鏡圖，其中以200μm為比例尺；以及[圖5]係繪示本發明之實施例1至2以及比較例1進行剝 離強度測試之結果。 The above and other objects, features, advantages and embodiments of the present invention will become more <RTIgt; A partial flow chart of a method for manufacturing a surface composite graphite substrate; [Fig. 2A] to [Fig. 2D] are schematic views showing an intermediate process of the above manufacturing method; [Fig. 3] shows a first embodiment of the present invention An optical micrograph of the surface of the composite graphite substrate of the porous surface (on one side of the continuous thin layer), with a scale of 200 μm; [Fig. 4A] shows the surface of the surface roughened graphite substrate of Comparative Example 1 ( An optical microscope image of a side polished and roughened with sandpaper, with a scale of 200 μm; [Fig. 4B] shows an optical microscope of the surface of the composite graphite substrate of Comparative Example 3 (one side of the continuous thin layer) The figure is in the range of 200 μm; and [Fig. 5] shows the peeling of Examples 1 to 2 of the present invention and Comparative Example 1 The result of the strength test.
本發明之一態樣是提供一種具有多孔表面的複合石墨基材的製造方法。藉由將含碳塗佈組成物形成於石墨基材的表面，以形成包含第一薄膜的塗佈基材。之後，經過碳化步驟及氣體吹拂步驟，可使所製得之複合石墨基材具有粗糙且不平整的表面，進而可增加複合石墨基材與銅箔之間的附著性。以下將詳細說明含碳塗佈組成物以及上述製造方法的具體步驟。 One aspect of the present invention provides a method of producing a composite graphite substrate having a porous surface. A coated substrate comprising the first film is formed by forming a carbon-containing coating composition on the surface of the graphite substrate. Thereafter, through the carbonization step and the gas blowing step, the obtained composite graphite substrate can have a rough and uneven surface, thereby further increasing the adhesion between the composite graphite substrate and the copper foil. Specific steps of the carbon-containing coating composition and the above production method will be described in detail below.
本發明此處所述之將含碳塗佈組成物形成於石墨基材的表面的步驟，可使用塗佈步驟進行。在一例子中，上述之塗佈步驟可例如為刮刀塗佈步驟、狹縫塗佈步驟或浸漬塗佈步驟。 The step of forming the carbon-containing coating composition on the surface of the graphite substrate described herein can be carried out using a coating step. In one example, the coating step described above can be, for example, a knife coating step, a slit coating step, or a dip coating step.
本發明此處所稱之碳化步驟係於600℃至1300℃之溫度以及惰性氣氛下進行，其中惰性氣氛可例如為氦氣、氬氣、氮氣或上述之任意組合。較佳地，上述溫度可為900℃至1300℃。特別說明的是，本發明之碳化步驟的主要目的是使含碳塗佈組成物中的碳質材料熔融並形成連續狀薄層，並使樹脂碳化，以於上述連續狀薄層上形成片狀剝離物。上述現象只要碳化步驟達到預定溫度範圍即會發生，因此本發明之碳化步驟可進行任意時間，然較佳以60秒內，以節省時間和製造成本。此外，經碳化步驟後第一薄膜係形成第二薄膜，其係由上述連續狀薄層、片狀剝離物以及未燒 毀之多孔表面組成物的其他成分所形成。 The carbonization step referred to herein is carried out at a temperature of from 600 ° C to 1300 ° C under an inert atmosphere, which may be, for example, helium, argon, nitrogen or any combination of the above. Preferably, the above temperature may be from 900 ° C to 1300 ° C. In particular, the main purpose of the carbonization step of the present invention is to melt the carbonaceous material in the carbon-containing coating composition and form a continuous thin layer, and carbonize the resin to form a sheet on the continuous thin layer. Stripping. The above phenomenon occurs as long as the carbonization step reaches a predetermined temperature range, so the carbonization step of the present invention can be carried out for any time, but preferably within 60 seconds, to save time and manufacturing cost. In addition, after the carbonization step, the first film forms a second film which is composed of the continuous thin layer, the sheet-like peeling material, and the unfired Formed by other components of the ruined porous surface composition.
本發明此處所稱之氣體吹拂步驟係以高壓氣體吹拂上述第二薄膜，以去除片狀剝離物，藉此可製得具有多孔表面之複合石墨基材，其中第二薄膜具有多孔表面。 The gas blowing step referred to herein is a step of blowing the second film with a high pressure gas to remove the sheet-like exfoliate, whereby a composite graphite substrate having a porous surface, wherein the second film has a porous surface, can be obtained.
本發明之含碳塗佈組成物可包含碳質材料、樹脂、增黏劑以及溶劑。此外，含碳塗佈組成物可具有300cps至5000cps之黏度。以下分別說明含碳塗佈組成物之各個成分。 The carbon-containing coating composition of the present invention may comprise a carbonaceous material, a resin, a tackifier, and a solvent. Further, the carbon-containing coating composition may have a viscosity of from 300 cps to 5000 cps. The respective components of the carbon-containing coating composition are separately described below.
承前所述，在經過高溫的碳化步驟後，本發明之碳質材料會熔融而形成連續狀薄層，進而可貼覆於石墨基材的表面。所形成之連續狀薄層與樹脂係因密度大小不同，因而形成連續狀薄層位於樹脂下方之分層之現象，後述將詳細說明。此外，連續狀薄層會因不均勻分散的樹脂而有不平整之表面，藉此形成多孔表面。 As described above, after the high-temperature carbonization step, the carbonaceous material of the present invention is melted to form a continuous thin layer which can be attached to the surface of the graphite substrate. Since the formed continuous thin layer and the resin are different in density, a layered phenomenon in which a continuous thin layer is located under the resin is formed, which will be described in detail later. Further, the continuous thin layer may have an uneven surface due to the unevenly dispersed resin, thereby forming a porous surface.
因此，本發明之碳質材料可為在600℃至1300℃之溫度下，殘碳率至少為50%之材料。具體而言，上述碳質材料可包括但不限於瀝青、介相碳微球、碳黑、煤焦油、煤炭、石油焦或上述之任意組合。基於後述之樹脂之使用量為100重量份，碳質材料的使用量可為100重量份至200重量份。 Therefore, the carbonaceous material of the present invention may be a material having a residual carbon ratio of at least 50% at a temperature of from 600 ° C to 1300 ° C. Specifically, the above carbonaceous materials may include, but are not limited to, asphalt, mesocarbon microspheres, carbon black, coal tar, coal, petroleum coke, or any combination thereof. The carbonaceous material may be used in an amount of from 100 parts by weight to 200 parts by weight based on 100 parts by weight of the resin to be described later.
若上述碳質材料的殘碳率低於50%，則碳質材 料容易在高溫中(例如進型碳化步驟時)被燒毀，而無法於石墨基材上形成連續狀薄層(或稱多孔表面)。 If the residual carbon ratio of the above carbonaceous material is less than 50%, the carbonaceous material The material is easily burned at high temperatures (for example, during the carbonization step), and a continuous thin layer (or porous surface) cannot be formed on the graphite substrate.
此外，上述碳質材料的使用量過少會使得其不足以形成連續狀薄層，進而無法製得預定的多孔表面。另一方面，若上述碳質材料的使用量過多，碳質材料不易貼覆於石墨基材的表面，容易在製程中脫落，造成所形成之連續狀薄層過薄。 Further, the use of the above-mentioned carbonaceous material is too small to make it insufficient to form a continuous thin layer, and thus it is impossible to obtain a predetermined porous surface. On the other hand, if the amount of the carbonaceous material used is too large, the carbonaceous material is less likely to adhere to the surface of the graphite substrate, and is liable to fall off during the process, resulting in the formation of a continuous thin layer which is too thin.
特別說明的是，本發明之碳質材料不可為平面結構或已經過高溫處理(例如：大於2000℃)的碳質材料，例如：石墨烯或石墨粉。由於石墨烯為平面片狀結構，即使經過後述之碳化步驟，也無法熔融而貼覆於石墨基材之表面，更無法強化複合石墨基材與銅箔之間的附著性。此外，由於石墨粉在製造過程中已經過高溫處理(或稱石墨化處理)，因此若使用石墨粉作為本發明之碳質材料，即使對其進行碳化步驟，也無法使之形成連續狀薄層，故無法藉以製得預定的多孔表面。 In particular, the carbonaceous material of the present invention may not be a planar structure or a carbonaceous material that has been subjected to high temperature treatment (for example, greater than 2000 ° C), such as graphene or graphite powder. Since graphene has a planar sheet-like structure, it cannot be melted and adhered to the surface of the graphite substrate even after the carbonization step described later, and the adhesion between the composite graphite substrate and the copper foil cannot be enhanced. In addition, since the graphite powder has been subjected to high temperature treatment (or graphitization treatment) in the manufacturing process, if graphite powder is used as the carbonaceous material of the present invention, even if it is subjected to a carbonization step, it cannot be formed into a continuous thin layer. Therefore, it is impossible to produce a predetermined porous surface.
在高溫的碳化步驟中，本發明之樹脂首先會因較高的黏度而無法均勻分布於前述連續狀薄層上，進而提供連續狀薄層之不平整表面。然後，樹脂會因高溫燒毀而形成片狀剝離物，覆於前述的連續狀薄層上。 In the high temperature carbonization step, the resin of the present invention is firstly unable to be uniformly distributed on the continuous thin layer due to the high viscosity, thereby providing an uneven surface of the continuous thin layer. Then, the resin is burned at a high temperature to form a sheet-like release material, which is applied to the above-mentioned continuous thin layer.
為使樹脂形成上述的片狀剝離物，樹脂於600℃至1300℃之溫度下可具有低於50%之殘碳率。本發明此 處所稱之樹脂並無特別限制，僅以利於含碳塗佈組成物於石墨基材的表面上成膜為宜。具體而言，上述樹脂可包含苯乙烯-丁二烯橡膠、聚氨酯樹脂、壓克力樹脂或上述之任意組合。 In order to form the above-mentioned sheet-like release product, the resin may have a residual carbon ratio of less than 50% at a temperature of from 600 ° C to 1300 ° C. The present invention The resin referred to in the space is not particularly limited, and it is preferred to form a film on the surface of the graphite substrate only for the carbon-containing coating composition. Specifically, the above resin may comprise styrene-butadiene rubber, urethane resin, acrylic resin or any combination of the above.
若上述樹脂之殘碳率不低於50%，樹脂無法藉由碳化步驟，形成易於去除的片狀剝離物，因此無法使連續狀薄層具有多孔表面，進而無法改善所製得之複合石墨基材與銅箔之間的附著性。 If the residual carbon ratio of the above resin is not less than 50%, the resin cannot be formed into a sheet-like exfoliate which is easy to remove by the carbonization step, so that the continuous thin layer cannot have a porous surface, and the composite graphite base obtained cannot be improved. Adhesion between the material and the copper foil.
本發明之含碳塗佈組成物可包含增黏劑，其主要係用以調整含碳塗佈組成物之黏度，以使其黏度可介於300cps至5000cps之間。 The carbon-containing coating composition of the present invention may comprise a tackifier which is mainly used to adjust the viscosity of the carbon-containing coating composition so that its viscosity may be between 300 cps and 5000 cps.
在一實施例中，上述增黏劑可例如為無機增黏劑、纖維素類增黏劑、聚丙烯酸酯增黏劑、締合型聚氨酯增黏劑或上述之任意組合。 In one embodiment, the tackifier may be, for example, an inorganic tackifier, a cellulosic tackifier, a polyacrylate tackifier, an associative polyurethane tackifier, or any combination thereof.
在一具體例中，上述無機增黏劑可例如為膨潤土、凹凸棒土(或稱水合鎂鋁矽酸鹽)、矽酸鋁或上述之任意組合等。 In one embodiment, the inorganic tackifier may be, for example, bentonite, attapulgite (or hydrated magnesium aluminum silicate), aluminum ruthenate, or any combination thereof.
在一具體例中，上述纖維素類增黏劑可例如為甲基纖維素、羧甲基纖維素、羥乙基纖維素、羥丙基甲基纖維素或上述之任意組合等。 In a specific example, the cellulose-based tackifier may be, for example, methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose, or any combination thereof.
在一具體例中，上述聚丙烯酸酯增黏劑可例如為水溶性的聚丙烯酸鹽、丙烯酸和甲基丙烯酸所形成的均聚 物或共聚物乳液增黏劑或上述之任意組合等。 In one embodiment, the polyacrylate tackifier may be, for example, a homopolymer formed from a water-soluble polyacrylate, acrylic acid, and methacrylic acid. Or a copolymer emulsion tackifier or any combination of the above.
基於上述樹脂之使用量為100重量份，增黏劑之使用量可為2.5重量份至15重量份。 The tackifier may be used in an amount of from 2.5 parts by weight to 15 parts by weight based on 100 parts by weight of the above-mentioned resin.
若上述增黏劑的添加量少於2.5重量份，致使含碳塗佈組成物之黏度小於300cps，則不易於石墨基材的表面上形成第一薄膜，而無法進行後續之步驟。另一方面，若上述增黏劑的添加量多於15重量份，致使含碳塗佈組成物的黏度大於5000cps，則會使多孔表面組成物不易均勻塗佈於石墨基材上。 If the amount of the tackifier added is less than 2.5 parts by weight, so that the viscosity of the carbon-containing coating composition is less than 300 cps, it is not easy to form the first film on the surface of the graphite substrate, and the subsequent steps cannot be performed. On the other hand, if the amount of the tackifier added is more than 15 parts by weight, the viscosity of the carbon-containing coating composition is more than 5,000 cps, so that the porous surface composition is not easily uniformly applied to the graphite substrate.
本發明此處所稱之溶劑主要的目的係為使樹脂可溶於其中，並使碳質材料和增黏劑可均勻分散，因此只要可達到上述目的，溶劑之種類並無特別限制。 The main purpose of the solvent referred to in the present invention is to dissolve the resin therein and to uniformly disperse the carbonaceous material and the tackifier. Therefore, the kind of the solvent is not particularly limited as long as the above object can be attained.
在一實施例中，上述溶劑可包含但不限於水、乳酸乙酯(Ethyl Lactate；EL)、環己酮、乳酸乙酯、乙二醇單甲基醚、乙二醇單甲基醚乙酸酯、丙二醇甲基醚乙酸酯、3-乙氧基丙酸乙酯、甲基乙二醇或上述之任意組合等。 In one embodiment, the solvent may include, but is not limited to, water, ethyl lactate (Ethyl Lactate; EL), cyclohexanone, ethyl lactate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate Ester, propylene glycol methyl ether acetate, ethyl 3-ethoxypropionate, methyl glycol or any combination of the above.
基於上述樹脂的使用量為100重量份，溶劑的使用量可為375重量份至625重量份。 The solvent may be used in an amount of from 375 parts by weight to 625 parts by weight based on 100 parts by weight of the above resin.
本發明之含碳塗佈組成物係根據前述所揭露的使用量，首先將樹脂溶於溶劑中，再將碳質材料加入後，進 行黏度的測量。接著，依照預定之黏度添加適量的增黏劑，以製備具有300cps至5000cps之黏度的含碳塗佈組成物。 The carbon-containing coating composition of the present invention is first dissolved in a solvent according to the amount of use disclosed above, and then the carbonaceous material is added. Measurement of line viscosity. Next, an appropriate amount of tackifier is added in accordance with a predetermined viscosity to prepare a carbon-containing coating composition having a viscosity of 300 cps to 5000 cps.
接下來請參考圖1和圖2A至圖2D，其中圖1係繪示根據本發明之一實施例所述之具有多孔表面的複合石墨基材的製造方法之部分流程圖，以及圖2A至圖2D係繪示上述製造方法之中間製程的示意圖。 1 and 2A to 2D, wherein FIG. 1 is a partial flow chart showing a method of manufacturing a composite graphite substrate having a porous surface according to an embodiment of the present invention, and FIG. 2A to FIG. 2D is a schematic diagram showing the intermediate process of the above manufacturing method.
如圖1之步驟110與圖2A所示，上述製造方法首先將含碳塗佈組成物形成於石墨基材210之表面210a上，以形成塗佈基材200A。具體的形成方法悉如前述，此處不另說明。 As shown in step 110 of FIG. 1 and FIG. 2A, the above manufacturing method first forms a carbon-containing coating composition on the surface 210a of the graphite substrate 210 to form a coated substrate 200A. The specific formation method is as described above and will not be described here.
如圖2A所示，塗佈基材200A包含石墨基材210和第一薄膜220A，其中第一薄膜220A係由含碳塗佈組成物所形成，且含碳塗佈組成物包含碳質材料221a、樹脂223a、增黏劑和溶劑(未繪示)。在步驟110中，碳質材料221a和樹脂223a係均勻分布於含碳塗佈組成物中。在一實施例中，可對塗佈基材進行乾燥步驟，以揮發部份溶劑，藉以降低含碳塗佈組成物的流動性。上述乾燥步驟的溫度以90℃至130℃為宜。經乾燥後的第一薄膜220A之厚度以100μm至300μm為佳。 As shown in FIG. 2A, the coated substrate 200A comprises a graphite substrate 210 and a first film 220A, wherein the first film 220A is formed of a carbon-containing coating composition, and the carbon-containing coating composition comprises a carbonaceous material 221a. , resin 223a, tackifier and solvent (not shown). In step 110, the carbonaceous material 221a and the resin 223a are uniformly distributed in the carbon-containing coating composition. In one embodiment, the coating substrate can be subjected to a drying step to volatilize a portion of the solvent to reduce the fluidity of the carbon-containing coating composition. The temperature of the above drying step is preferably from 90 ° C to 130 ° C. The thickness of the dried first film 220A is preferably from 100 μm to 300 μm.
若上述厚度大於300μm，會使得所形成的連續狀薄層厚度增加，進而增加熱阻而影響散熱基板之效率。若上述厚度小於100μm，所形成之多孔表面的粗糙度不足， 無法有效改善複合石墨基材與銅箔之間的附著性。 If the thickness is more than 300 μm, the thickness of the continuous thin layer formed is increased, thereby increasing the thermal resistance and affecting the efficiency of the heat dissipation substrate. If the thickness is less than 100 μm, the roughness of the formed porous surface is insufficient. The adhesion between the composite graphite substrate and the copper foil cannot be effectively improved.
接下來，如圖1之步驟120、圖2B以及圖2C所示，對塗佈基材200A進行碳化步驟，以使第一薄膜220A形成如圖2C所示之第二薄膜220C。關於碳化步驟的具體進行方式和條件悉如前述，此處不另贅述。如圖2B所示，碳質材料221a在高溫的碳化步驟中，熔融而形成連續狀薄層221b，同時由於連續狀薄層221b之密度較高，因此會下沉而貼覆於石墨基材210之表面210a。另一方面，樹脂223a在高溫的碳化步驟中，會形成樹脂層223b。由於樹脂層223b的密度較低，因而會分佈於前述之連續狀薄層221b上，進而產生如圖2B所示之分層220B。然而，由於樹脂層223b具有一定黏度，因此並非均勻分散於連續狀薄層221b上，藉此使連續狀薄層221b可具有不平整之表面225。 Next, as shown in step 120 of FIG. 1, FIG. 2B and FIG. 2C, the coating substrate 200A is subjected to a carbonization step such that the first film 220A forms the second film 220C as shown in FIG. 2C. The specific manner and conditions for the carbonization step are as described above and will not be further described herein. As shown in FIG. 2B, the carbonaceous material 221a is melted to form a continuous thin layer 221b in the high-temperature carbonization step, and at the same time, because the continuous thin layer 221b has a high density, it sinks and adheres to the graphite substrate 210. Surface 210a. On the other hand, in the high temperature carbonization step of the resin 223a, the resin layer 223b is formed. Since the density of the resin layer 223b is low, it is distributed on the aforementioned continuous thin layer 221b, thereby producing a layer 220B as shown in Fig. 2B. However, since the resin layer 223b has a certain viscosity, it is not uniformly dispersed on the continuous thin layer 221b, whereby the continuous thin layer 221b may have an uneven surface 225.
之後，如圖2C所示，樹脂層223b因暴露於外層並持續處於高溫中而被燒毀，且因樹脂層223b於600℃至1300℃間的殘碳率較低，因而形成片狀剝離物223c，覆蓋於連續狀薄層221b之表面225上。在圖2C中，第二薄膜220C係包含連續狀薄層221b、片狀剝離物223c以及含碳塗佈組成物未燒毀之成分(未繪示)，且第二薄膜220C之連續狀薄層221b即為後述之多孔表面。 Thereafter, as shown in FIG. 2C, the resin layer 223b is burned by exposure to the outer layer and continues to be at a high temperature, and since the residual carbon ratio of the resin layer 223b between 600 ° C and 1300 ° C is low, the sheet-like peeling material 223 c is formed. Covering the surface 225 of the continuous thin layer 221b. In FIG. 2C, the second film 220C comprises a continuous thin layer 221b, a sheet-like release 223c, and a non-burned component of the carbon-containing coating composition (not shown), and the continuous thin layer 221b of the second film 220C. This is a porous surface to be described later.
然後，如圖1之步驟130和圖2D所示，對第二薄膜220C進行氣體吹拂步驟，清除第二薄膜220C之片狀剝離物223c，以製得具有多孔表面的複合石墨基材200D。氣體吹拂步驟的具體進行方式悉如前述，此處不另贅述。如圖 2D所示，具有多孔表面的複合石墨基材200D包含石墨基材210和連續狀薄層221b。具體而言，本發明係藉由氣體吹拂步驟以清除如圖2C所示之片狀剝離物223c，僅留下貼覆於石墨基材210之表面的連續狀薄層221b，其具有不平整之表面225。 Then, as shown in step 130 of FIG. 1 and FIG. 2D, the second film 220C is subjected to a gas blowing step to remove the sheet-like exfoliate 223c of the second film 220C to obtain a composite graphite substrate 200D having a porous surface. The specific implementation of the gas blowing step is as described above and will not be further described herein. As shown As shown in Fig. 2D, the composite graphite substrate 200D having a porous surface comprises a graphite substrate 210 and a continuous thin layer 221b. Specifically, the present invention employs a gas blowing step to remove the sheet-like exfoliate 223c as shown in FIG. 2C, leaving only a continuous thin layer 221b attached to the surface of the graphite substrate 210, which has unevenness. Surface 225.
在一實施例中，上述石墨基材210可由碳質粉體經加壓成型步驟以及熱處理步驟而形成。所述碳質粉體可例如為焦炭、蘭炭(或稱焦粉)、石油焦、木炭、碳素或上述之組合。 In one embodiment, the graphite substrate 210 may be formed of a carbonaceous powder by a pressure forming step and a heat treatment step. The carbonaceous powder may be, for example, coke, blue carbon (or coke breeze), petroleum coke, charcoal, carbon, or a combination thereof.
在一例子中，上述加壓成型步驟可於20MPa至300MPa之壓力進行。舉例而言，加壓成型步驟可為冷均壓。在另一例子中，上述之熱處理步驟2000℃至3300℃之溫度下進行。具體而言，上述石墨基材210係將碳質粉體經加壓成型步驟形成胚體後，可先於約1000℃下進行碳化處理，再於2000℃至3300℃下進行熱處理，以形成石墨基材210。 In one example, the press molding step described above can be carried out at a pressure of from 20 MPa to 300 MPa. For example, the press forming step can be cold equalizing. In another example, the heat treatment step described above is carried out at a temperature of from 2000 ° C to 3300 ° C. Specifically, the graphite substrate 210 is formed by subjecting the carbonaceous powder to the embryo body by a pressure molding step, and then performing carbonization treatment at about 1000 ° C, and then heat treatment at 2000 ° C to 3300 ° C to form graphite. Substrate 210.
經由上述之製造方法，可製得具有多孔表面的複合石墨基材。如圖2D所示，上述複合石墨基材200D包含石墨基材210和連續狀薄層221b，其中連續狀薄層221b的表面225為不平整表面，因此複合石墨基材之表面具有相當的粗糙度。藉由上述粗糙且不平整之表面，可使複合石墨基材在後續應用時，與銅箔有良好的附著性。以下將提供數個 實施例具體說明本發明之具有多孔表面的複合石墨基材及其製造方法。 A composite graphite substrate having a porous surface can be obtained by the above-described production method. As shown in FIG. 2D, the composite graphite substrate 200D comprises a graphite substrate 210 and a continuous thin layer 221b, wherein the surface 225 of the continuous thin layer 221b is an uneven surface, so that the surface of the composite graphite substrate has a considerable roughness. . By the above rough and uneven surface, the composite graphite substrate can be well adhered to the copper foil in subsequent applications. Several will be provided below EXAMPLES A composite graphite substrate having a porous surface of the present invention and a method for producing the same will be specifically described.
製備例1係先製造後述實施例所需之石墨基材。將介相碳微球(中鋼碳素公司製之BCP產品)進行壓力為120MPa之冷均壓(Cold Isostatic Press)成形後，先以1000℃進行碳化處理，再經過約3000℃之石墨化處理後，可製得石墨胚體。接著，將上述石墨胚體裁切為110mm×50mm×20mm，並以1400號之砂紙拋光後，可製得下述實施例所需的石墨基材。 Preparation Example 1 is a graphite substrate required for the production of the examples described later. The carbon microspheres (BCP products made by Sinosteel Carbon Co., Ltd.) were formed by cold Isostatic Press at a pressure of 120 MPa, then carbonized at 1000 ° C, and then graphitized at about 3000 ° C. Thereafter, a graphite embryo body can be obtained. Next, the graphite blank body was cut into 110 mm × 50 mm × 20 mm, and polished with a 1400-grit sandpaper to obtain a graphite substrate required for the following examples.
首先，將100重量份之水溶性聚氨酯樹脂(型號為HUD-7012N，於600℃至1300℃的殘碳率為10%；展宇化工製；B-1)溶於625重量份之水(D-1)中，並將200重量份之黏結瀝青(型號為HSP-260，軟化點為約260℃，研磨為平均粒徑11μm之細粉，於600℃至1300℃的殘碳率為89%；中鋼碳素公司製；A-1)和15重量份之增黏劑(型號為HUD-400；展宇化工製；C-1)加入且均勻分散，以形成實施例1之含碳塗佈組成物。 First, 100 parts by weight of a water-soluble polyurethane resin (model: HUD-7012N, residual carbon ratio at 600 ° C to 1300 ° C; 10%; manufactured by Zhanyu Chemical Industry; B-1) is dissolved in 625 parts by weight of water (D -1), and 200 parts by weight of cemented asphalt (model HSP-260, softening point of about 260 ° C, ground to a fine powder with an average particle diameter of 11 μm, the residual carbon ratio at 600 ° C to 1300 ° C is 89% ; China Steel Corporation; A-1) and 15 parts by weight of tackifier (model HUD-400; manufactured by Zhanyu Chemical; C-1) were added and uniformly dispersed to form the carbon-coated coating of Example 1. Cloth composition.
接下來，將上述含碳塗佈組成物以狹縫式刮刀(狹縫高度為550μm)，塗佈於製備例1之石墨基材的表面上，並於95℃下先乾燥1小時。之後，將塗佈有含碳塗佈組 成物之石墨基材於1000℃之氮氣氣氛中進行碳化步驟達60秒。然後，以高壓氮氣吹拂上述石墨基材的表面，以製得實施例1之複合石墨基材。 Next, the carbon-containing coating composition was applied onto the surface of the graphite substrate of Preparation Example 1 by a slit blade (slit height: 550 μm), and dried at 95 ° C for 1 hour. After that, it will be coated with a carbon-coated coating group. The graphite substrate of the product was subjected to a carbonization step in a nitrogen atmosphere at 1000 ° C for 60 seconds. Then, the surface of the above graphite substrate was blown with high pressure nitrogen gas to obtain a composite graphite substrate of Example 1.
實施例2及比較例2至3係以與實施例1相同之技術手段進行，不同的是，實施例2及比較例2至3係改變含碳塗佈組成物的成分種類、使用量或其他製程條件，具體的製程條件以及評價結果係記載於表1，故此處不另贅述。 Example 2 and Comparative Examples 2 to 3 were carried out in the same manner as in Example 1, except that Example 2 and Comparative Examples 2 to 3 were used to change the type, amount or other component of the carbon-containing coating composition. The process conditions, specific process conditions, and evaluation results are described in Table 1, and therefore are not described here.
比較例1係使用製備例1之石墨基材，並以80號之砂紙研磨上述石墨基材的表面，以製得表面粗糙化的石墨基材。 In Comparative Example 1, the graphite substrate of Preparation Example 1 was used, and the surface of the above graphite substrate was ground with a No. 80 sandpaper to obtain a surface roughened graphite substrate.
1.表面結構觀察1. Surface structure observation
本發明此處所稱之表面結構觀察係以光學顯微鏡觀察實施例和比較例所製得之石墨基材的表面，藉以得知所述石墨基材表面的粗糙度。在此評價方式中，粗糙度越高越佳。 The surface structure observation referred to herein is an observation of the surface of the graphite substrate obtained in the examples and the comparative examples by an optical microscope, whereby the roughness of the surface of the graphite substrate was known. In this evaluation method, the higher the roughness, the better.
2.剝離強度2. Peel strength
本發明此處所稱之剝離強度代表石墨基材與銅箔之間的附著性，其係以福田金屬製之鍍鎳銅箔 NIMT-CF-35進行。將上述銅箔裁切成長條狀(寬度為2.5公分，長度大於10公分)，並以環氧樹脂(LORD® 304 epoxy)貼合上述銅箔和實施例或比較例之石墨基材，其中貼合面為連續狀薄層或粗糙化表面之一側。之後，對貼合後的石墨基材進行退火處理，以使環氧樹脂固化。然後，將石墨基材的一端固定，並利用拉力試驗機(MTS Criterion Model-43)對石墨基材上的銅箔進行剝離強度的測試，其中剝離角度為180度。在此評價方式中，剝離強度越大越佳。 The peel strength referred to in the present invention represents the adhesion between the graphite substrate and the copper foil, and is carried out by nickel-plated copper foil NIMT-CF-35 made of Fukuda Metal. The copper foil is cut into strips (width: 2.5 cm, length greater than 10 cm), and the copper foil and the graphite substrate of the embodiment or the comparative example are bonded with epoxy resin (LORD ® 304 epoxy), wherein The face is a continuous thin layer or one side of the roughened surface. Thereafter, the bonded graphite substrate is annealed to cure the epoxy resin. Then, one end of the graphite substrate was fixed, and the peeling strength of the copper foil on the graphite substrate was measured by a tensile tester (MTS Criterion Model-43), wherein the peeling angle was 180 degrees. In this evaluation method, the greater the peel strength, the better.
首先請先參考圖3，其中圖3係繪示本發明之實施例1之具有多孔表面之複合石墨基材的表面(連續狀薄層之一側)的光學顯微鏡圖。首先，如圖3所示，本發明實施例1之複合石墨基材的表面具有許多孔洞。此外，圖3亦顯示本發明實施例1之複合石墨基材的表面還產生如圓圈301所圈示之明顯的島狀結構，其代表實施例1之複合石墨基材的表面具有大面積不平整之高低落差。此外，實施例2之複合石墨基材亦與實施例1類似，具有不平整之表面。 First, please refer to FIG. 3, wherein FIG. 3 is an optical micrograph showing the surface (one side of the continuous thin layer) of the composite graphite substrate having the porous surface of Example 1 of the present invention. First, as shown in Fig. 3, the surface of the composite graphite substrate of Example 1 of the present invention has a plurality of pores. In addition, FIG. 3 also shows that the surface of the composite graphite substrate of Example 1 of the present invention also produces a distinct island-like structure as circled by circle 301, which represents the surface of the composite graphite substrate of Example 1 having a large area unevenness. The difference between the heights. Further, the composite graphite substrate of Example 2 was similar to that of Example 1, and had an uneven surface.
請參考圖4A，其係繪示比較例1之表面粗糙化之石墨基材的表面(以砂紙研磨並粗糙化的一側)之光學顯微鏡圖。如圖4之圓圈401所圈示，比較例1之石墨基材的表面僅有研磨之刻槽，且上述刻槽的痕跡並不明顯，顯示刻槽深度過淺而無法提供足夠的粗糙度。 Referring to FIG. 4A, an optical micrograph of the surface of the surface roughened graphite substrate of Comparative Example 1 (the side polished and roughened by sandpaper) is shown. As circled by circle 401 of Fig. 4, the surface of the graphite substrate of Comparative Example 1 has only a groove for grinding, and the trace of the above groove is not obvious, indicating that the depth of the groove is too shallow to provide sufficient roughness.
此外，根據圖4B之圓圈402所圈示的地方可看出，比較例3雖然使用大量的碳質材料，但反而可清楚觀察到石墨基材上的切割痕跡。上述現象證實若使用過多的碳質 材料，過厚的連續狀薄層反而不易貼覆於石墨基材的表面，因而在經過氣體吹拂步驟之後，大部分的碳質材料會從石墨基材上脫落。 Further, as can be seen from the circled circle 402 of Fig. 4B, although Comparative Example 3 uses a large amount of carbonaceous material, the cutting marks on the graphite substrate can be clearly observed. The above phenomenon confirms that if too much carbon is used The material, the thick, continuous thin layer is not easily attached to the surface of the graphite substrate, so most of the carbonaceous material will fall off the graphite substrate after the gas blowing step.
接下來，請參考圖5和表1，其中圖5係繪示本發明之實施例1至2以及比較例1進行剝離強度測試之結果。在圖5中，曲線501代表實施例1、曲線503代表實施例2，且曲線505代表比較例1。根據圖5可知，在產生相同剝離量之情況下，本發明之實施例1至2之複合石墨基材需施以較大的拉力。相反地，比較例1僅以較小的拉力就可以產生剝離。因此，從圖5可得知本發明之複合石墨基材與銅箔之間的附著性較佳。 Next, please refer to FIG. 5 and Table 1, wherein FIG. 5 shows the results of the peel strength test performed in Examples 1 to 2 and Comparative Example 1 of the present invention. In FIG. 5, a curve 501 represents Embodiment 1, a curve 503 represents Embodiment 2, and a curve 505 represents Comparative Example 1. As can be seen from Fig. 5, in the case where the same amount of peeling was produced, the composite graphite substrates of Examples 1 to 2 of the present invention were subjected to a large pulling force. On the contrary, Comparative Example 1 was able to cause peeling with only a small pulling force. Therefore, it can be seen from Fig. 5 that the adhesion between the composite graphite substrate of the present invention and the copper foil is preferred.
此外，根據表1所示之剝離強度平均值也可了解，本發明實施例1至2之複合石墨基材的平均剝離強度分別為7.2牛頓/公分(N/cm)以及7.0N/cm，然而，比較例1之平均剝離強度僅4.9N/cm。本發明之實施例1至2需施以較大的拉力方可產生剝離，因此從平均剝離強度也可得知本發明之實施例1至2之複合石墨基材與銅箔之間的附著性較佳。 Further, it is also understood from the average peel strength shown in Table 1, that the average peel strength of the composite graphite substrates of Examples 1 to 2 of the present invention is 7.2 Newtons/cm (N/cm) and 7.0 N/cm, respectively. The average peel strength of Comparative Example 1 was only 4.9 N/cm. In the first to second embodiments of the present invention, a large tensile force is required to cause peeling, and therefore the adhesion between the composite graphite substrate of Examples 1 to 2 of the present invention and the copper foil is also known from the average peel strength. Preferably.
補充說明的是，表1之比較例2因為含碳塗佈組成物之黏度過低、流動性過高，因此無法有效於石墨基材之表面上形成第一薄膜，故並未進行後續碳化處理之測試。從比較例2可得知，本發明之含碳塗佈組成物的各成分需落於本發明所主張的範圍內，才得以進行後續之應用。 In addition, in Comparative Example 2 of Table 1, since the viscosity of the carbon-containing coating composition is too low and the fluidity is too high, the first film cannot be effectively formed on the surface of the graphite substrate, so that subsequent carbonization is not performed. Test. As is understood from Comparative Example 2, the components of the carbon-containing coating composition of the present invention are required to fall within the scope of the present invention for subsequent application.
應用本發明之具有多孔表面的複合石墨基材及 其製造方法，藉由包含不同殘碳率之碳質材料和樹脂的含碳塗佈組成物，配合碳化步驟之特定溫度，可製得具有粗糙且不平整的表面之複合石墨基材，因此可有效提升複合石墨基材與銅箔之間的附著性。 Application of the composite graphite substrate with porous surface of the invention The manufacturing method comprises a composite graphite substrate having a rough and uneven surface by a carbonaceous coating composition comprising a carbonaceous material having different carbon residue ratios and a resin, and a specific temperature of the carbonization step. Effectively improve the adhesion between the composite graphite substrate and the copper foil.
雖然本發明已以數個實施例揭露如上，然其並非用以限定本發明，在本發明所屬技術領域中任何具有通常知識者，在不脫離本發明之精神和範圍內，當可作各種之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。 While the invention has been described above in terms of several embodiments, it is not intended to limit the scope of the invention, and the invention may be practiced in various embodiments without departing from the spirit and scope of the invention. The scope of protection of the present invention is defined by the scope of the appended claims.
100‧‧‧方法 100‧‧‧ method
110‧‧‧於石墨基材之表面上形成第一薄膜，以形成塗佈基材 110‧‧‧ Forming a first film on the surface of the graphite substrate to form a coated substrate
120‧‧‧對塗佈基材進行碳化步驟，以使第一薄膜形成第二薄膜 120‧‧‧Carriding the coated substrate to form the first film into a second film
130‧‧‧對第二薄膜進行氣體吹拂步驟，去除第二薄膜之片狀剝離物，以製得具有多孔表面的複合石墨基材 130‧‧‧ gas-blowing step of the second film to remove the sheet-like exfoliate of the second film to obtain a composite graphite substrate having a porous surface
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| US6849338B2 (en) * | 2000-11-29 | 2005-02-01 | Pacific Northwest Coatings | Coating system for a porous substrate using an asphalt-containing thermosetting basecoat composition and a thermoplastic top coat composition |
| US20070013094A1 (en) * | 2003-05-16 | 2007-01-18 | Norman Bischofsberger | Method for the preparation of porous, carbon-based material |
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| US20070013094A1 (en) * | 2003-05-16 | 2007-01-18 | Norman Bischofsberger | Method for the preparation of porous, carbon-based material |
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