TW201840733A - Resin compound and molded product formed by molding with the resin compound - Google Patents

Abstract

An objective of the present invention is to provide a thermally conductive resin compound having high thermal conductivity, excellent moldability and high mechanical strength, and a molded product thereof. In order to attain the objective of the present invention, a resin compound containing a thermoplastic resin and graphite is provided, the resin compound further containing carbon black having a nitrogen adsorption specific surface area of 10 to 100 m2/g and/or a DBP absorption amount of 30 to 100 ml/100 g.

Description

樹脂化合物及將樹脂化合物成型而成之成形物    Resin compound and molded product formed by molding the resin compound   

本發明係有關一種可獲得熱傳導率或電傳導率、成型時之樹脂的流動性及機械特性優異的成形物的樹脂化合物。 The present invention relates to a resin compound that can obtain a molded product that is excellent in thermal conductivity, electrical conductivity, resin fluidity and mechanical properties during molding.

電子零件中，目前正在開發以高密度、高輸出、重量減輕為目標之構成的零件。隨著電子零件的高性能化，每單位面積或單位體積的熱產量增加，因此有電子零件長期曝露在高溫環境的情況。由於該熱的影響，電子零件的動作變得不穩定，導致錯誤動作、性能降低、故障的可能性提高。為了防止這種熱的影響，有效率地將所產生的熱散熱的需求日益增加。 Among electronic components, components that are aimed at high density, high output, and weight reduction are currently being developed. With the higher performance of electronic parts, the heat output per unit area or unit volume increases. Therefore, electronic parts may be exposed to high-temperature environments for a long time. Due to the influence of this heat, the operation of the electronic parts becomes unstable, leading to the possibility of erroneous operation, reduced performance, and malfunction. In order to prevent such heat influence, there is an increasing demand for efficiently dissipating the generated heat.

因此現在係使用銅或鋁等熱傳導性良好的金屬。但是該等金屬有比重大而變得重、在製造散熱片等呈複雜形狀的零件時加工成本會增加的缺點。 Therefore, metals with good thermal conductivity such as copper or aluminum are now used. However, these metals have the disadvantage that the specific gravity becomes heavier and the processing cost increases when manufacturing parts with complex shapes such as heat sinks.

為此已開發使用石墨、碳黑、碳奈米管等碳系材料做為金屬以外的導電性填充劑之樹脂化合物(例 如參照專利文獻1)。 To this end, resin compounds using carbon-based materials such as graphite, carbon black, and carbon nanotubes as conductive fillers other than metals have been developed (for example, refer to Patent Document 1).

[先前技術文獻]     [Prior Technical Literature]     (專利文獻)     (Patent Literature)    

專利文獻1：日本特開2012-507587號公報 Patent Literature 1: Japanese Patent Laid-Open No. 2012-507587

這種樹脂化合物雖然比重低、成型成本下降，但為了得到良好的熱傳導性而捏合大量的熱傳導性填充劑，因而有樹脂的流動性(成型性)劣化、機械強度降低的缺點。 Although such a resin compound has a low specific gravity and a reduction in molding cost, a large amount of thermally conductive filler is kneaded in order to obtain good thermal conductivity, which has the disadvantages that the fluidity (moldability) of the resin deteriorates and the mechanical strength decreases.

因此，本發明的主要課題係提供一種熱傳導率及電傳導率高、成型性優異、機械強度高的熱傳導性樹脂化合物。 Therefore, the main subject of the present invention is to provide a thermally conductive resin compound having high thermal conductivity and electrical conductivity, excellent moldability, and high mechanical strength.

又，為了提高樹脂的流動性，在日本特開2013-159624號公報等中，有對於改善樹脂的流動性用的有機物添加劑進行研究。但是，樹脂和有機物添加劑的相溶性不足時，或者零件的使用溫度高時，會有這些有機物添加劑經常滲出零件表面、弄髒表面，或是當塗覆或鍍覆時塗膜或鍍層剝落的缺點。 In addition, in order to improve the fluidity of the resin, in Japanese Patent Application Laid-Open No. 2013-159624 and the like, there are studies on organic additives for improving the fluidity of the resin. However, when the compatibility of resin and organic additives is insufficient, or when the temperature of the parts is high, these organic additives often bleed out the surface of the parts, stain the surface, or the coating film or coating peels off when coating or plating .

鑑於上述缺點，本發明的第2課題係提供一種各種有機物朝零件表面的滲出少的熱傳導性樹脂化合物。 In view of the above-mentioned disadvantages, the second subject of the present invention is to provide a thermally conductive resin compound with little bleeding of various organic substances toward the surface of a part.

本發明係在熱塑性樹脂中調配石墨、特定的碳黑做為熱傳導填充劑者。亦即，本發明如以下所述。 The present invention is a blend of graphite and specific carbon black in a thermoplastic resin as a thermally conductive filler. That is, the present invention is as follows.

本發明(1)係一種樹脂化合物，係含有熱塑性樹脂和石墨，於該樹脂化合物中，更含有氮吸附比表面積為10至100m²/g的碳黑。 The present invention (1) is a resin compound containing a thermoplastic resin and graphite, and the resin compound further contains carbon black with a nitrogen adsorption specific surface area of 10 to 100 m ² / g.

本發明(2)係一種樹脂化合物，係含有熱塑性樹脂和石墨，於該樹脂化合物中，更含有DBP吸收量為30至100ml/100g的碳黑。 The present invention (2) is a resin compound containing a thermoplastic resin and graphite, and the resin compound further contains carbon black with a DBP absorption of 30 to 100 ml / 100 g.

本發明(3)係一種樹脂化合物，係含有熱塑性樹脂和石墨，於該樹脂化合物中，更含有氮吸附比表面積為10至100m²/g且DBP吸收量為30至100ml/100g的碳黑。 The present invention (3) is a resin compound containing a thermoplastic resin and graphite. The resin compound further contains carbon black having a nitrogen adsorption specific surface area of 10 to 100 m ² / g and a DBP absorption of 30 to 100 ml / 100 g.

本發明(4)係如前述發明(1)至(3)中任一項所述之樹脂化合物，其中，相對於樹脂化合物整體，含有1至30重量%之前述碳黑。 The present invention (4) is the resin compound according to any one of the aforementioned inventions (1) to (3), which contains 1 to 30% by weight of the carbon black relative to the entire resin compound.

本發明(5)係如前述發明(1)至(4)中任一項所述之樹脂化合物，其中，前述石墨為鱗片狀。 The present invention (5) is the resin compound according to any one of the aforementioned inventions (1) to (4), wherein the graphite is in the form of flakes.

本發明(6)係如前述發明(1)至(5)中任一項所述之樹脂化合物，其中，相對於樹脂化合物整體，含有20至80重量%之前述石墨。 The present invention (6) is the resin compound according to any one of the aforementioned inventions (1) to (5), which contains 20 to 80% by weight of the aforementioned graphite with respect to the entire resin compound.

本發明(7)係如前述發明(1)至(6)中任一項所述之樹脂化合物，其中，相對於樹脂化合物整體，更含有1至10重量%之碳奈米管。 The present invention (7) is the resin compound according to any one of the aforementioned inventions (1) to (6), which further contains 1 to 10% by weight of carbon nanotubes relative to the entire resin compound.

本發明(8)係將前述發明(1)至(7)中任一項所述之樹脂化合物成型而成之成形物。 The present invention (8) is a molded product obtained by molding the resin compound according to any one of the aforementioned inventions (1) to (7).

根據本發明可提供熱傳導率及電傳導率高、成型性優異、機械強度高的熱傳導性樹脂化合物及其成形物。進一步根據本發明可提供各種有機物朝零件表面的滲出少的熱傳導性樹脂化合物及其成形物。 According to the present invention, it is possible to provide a thermally conductive resin compound having high thermal conductivity and electrical conductivity, excellent moldability, and high mechanical strength, and a molded product thereof. Furthermore, according to the present invention, it is possible to provide a thermally conductive resin compound and its molded product with little bleeding of various organic substances toward the surface of a part.

第1圖係碳黑的DBP吸收量及形態的示意圖。 Fig. 1 is a schematic diagram of the DBP absorption amount and form of carbon black.

第2圖係碳黑的比表面積及形態的示意圖。 Figure 2 is a schematic diagram of the specific surface area and form of carbon black.

第3圖係說明碳黑的滾子作用及CNT的朝厚度方向提升熱傳導的作用的示意圖。 FIG. 3 is a schematic diagram illustrating the roller action of carbon black and the effect of CNT to increase the heat conduction in the thickness direction.

以下，雖詳細敍述本發明之樹脂化合物的構成、製造方法及用途等，但本發明並不限於此。另外，以下內容中，「氮吸附比表面積」有時亦簡稱為「比表面積」。 Although the structure, manufacturing method, and use of the resin compound of the present invention are described in detail below, the present invention is not limited to this. In addition, in the following, the "nitrogen adsorption specific surface area" is sometimes simply referred to as "specific surface area".

<<構成>>     << Composition >>    

本發明之樹脂化合物係至少包含熱塑性樹脂和熱傳導填充劑。以下，分別針對熱塑性樹脂和熱傳導填充劑進行說明。 The resin compound of the present invention contains at least a thermoplastic resin and a thermally conductive filler. Hereinafter, the thermoplastic resin and the thermally conductive filler will be described separately.

<熱塑性樹脂> <Thermoplastic resin>

本發明所使用之熱塑性樹脂的種類並未限定，可在熱傳導性樹脂化合物中使用的所有熱塑性樹脂均能使用。做 為此種樹脂者，例如可列舉聚醯胺、聚乙酸酯、聚酮、聚烯烴、聚碳酸酯、聚苯乙烯、聚酯、聚醚、聚碸、聚氟聚合物、聚胺酯、聚醯胺醯亞胺、聚芳酯、聚烯丙基碸、聚醚碸、聚烯丙基硫醚、聚氯乙烯、聚醚醯亞胺、聚四氟乙烯、聚醚酮、聚乳酸酯、聚苯硫醚等。另外，從易於經濟性、成型性、捏合性的觀點看來，較佳係使用聚醯胺、聚碳酸酯、聚酯(例如聚對苯二甲酸丁二酯)等。 The type of thermoplastic resin used in the present invention is not limited, and all thermoplastic resins that can be used in the thermally conductive resin compound can be used. Examples of such resins include polyamide, polyacetate, polyketone, polyolefin, polycarbonate, polystyrene, polyester, polyether, polysulfone, polyfluoropolymer, polyurethane, poly Acetamide, imide, polyarylate, polyallyl, polyether, polyallyl sulfide, polyvinyl chloride, polyetherimide, polytetrafluoroethylene, polyetherketone, polylactate , Polyphenylene sulfide, etc. In addition, from the viewpoint of ease of economy, moldability, and kneadability, it is preferable to use polyamide, polycarbonate, polyester (for example, polybutylene terephthalate), or the like.

又，熱塑性樹脂的調配量並未特別限定，相對於樹脂化合物整體，較佳為含有10至90重量%，更佳為含有20至70重量%。 In addition, the compounding amount of the thermoplastic resin is not particularly limited, but it is preferably contained in the range of 10 to 90% by weight, more preferably in the range of 20 to 70% by weight, relative to the entire resin compound.

<熱傳導填充劑> <Heat conduction filler>

本發明之樹脂化合物至少包含石墨及碳黑做為熱傳導填充劑，進一步包含碳奈米管做為適合的任意成分。以下，針對各個熱傳導填充劑進行說明。又，亦可包含該等以外的熱傳導填充劑(其他的熱傳導填充劑)，或是不包含該等以外的熱傳導填充劑。 The resin compound of the present invention contains at least graphite and carbon black as thermally conductive fillers, and further contains carbon nanotubes as suitable optional components. Hereinafter, each thermally conductive filler will be described. Moreover, you may contain the heat conduction filler other than these (other heat conduction filler), or may not contain the heat conduction filler other than these.

(石墨) (Graphite)

石墨係具有六角板狀之結晶構造的層狀石墨，且人造品及天然品的任一者均可。 Graphite is a layered graphite having a hexagonal plate-like crystal structure, and any of artificial and natural products may be used.

石墨的粒徑愈大樹脂化合物的熱傳導率會愈高，但價格也愈高，並且若超過數百微米，調配於樹脂中時會粉碎，因此較佳為平均粒徑在數百微米以下(較佳為 1000μm以下，更佳為500μm以下)者。若石墨的粒徑變小，由於樹脂化合物的熱傳導率會降低，因此以平均粒徑成為10μm以上(較佳為50μm以上)或者粒徑10μm以上的石墨成為石墨整體的90重量%以上為佳。藉由設定為上述粒徑範圍，推測在後述之碳黑的滾子原理更容易動作。又，在此所示的平均粒徑係指重量50%的直徑。 The larger the particle size of graphite, the higher the thermal conductivity of the resin compound, but the higher the price, and if it exceeds hundreds of microns, it will be crushed when formulated in the resin, so it is preferable that the average particle size is less than hundreds of microns (more than It is preferably 1000 μm or less, more preferably 500 μm or less). If the particle size of graphite becomes smaller, the thermal conductivity of the resin compound will decrease. Therefore, it is preferable that graphite having an average particle size of 10 μm or more (preferably 50 μm or more) or graphite having a particle size of 10 μm or more becomes 90% by weight or more of the entire graphite. By setting it to the above-mentioned particle size range, it is estimated that the carbon black roller principle described later is easier to operate. In addition, the average particle diameter shown here refers to a diameter of 50% by weight.

又，做為石墨者，可應用做成鱗片狀、塊狀、球狀等各種形態者，惟為了得到熱傳導率高的石墨，較佳為異向性高的鱗片狀石墨。 In addition, as graphite, those in various forms such as flake, block, and sphere can be used. However, in order to obtain graphite with high thermal conductivity, it is preferably scaly graphite with high anisotropy.

石墨的調配量，相對於樹脂化合物整體，較佳為含有20至80重量%，更佳為含有20至70重量%，又更佳為含有50至70重量%。藉由設定在上述範圍，可更提高本發明的效果。 The blending amount of graphite is preferably 20 to 80% by weight relative to the entire resin compound, more preferably 20 to 70% by weight, and still more preferably 50 to 70% by weight. By setting it in the above range, the effect of the present invention can be further improved.

(碳黑) (Carbon black)

做為第2熱傳導性填充劑的碳黑係以碳為主成分的黑色微粒子，且係使用爐法、熱法、槽法(channel method)、乙炔法等而製成。 The carbon black used as the second thermally conductive filler is black fine particles mainly composed of carbon, and is produced using a furnace method, a thermal method, a channel method, an acetylene method, or the like.

在此，本發明的碳黑必須滿足(A1)比表面積為10至100m²/g，或(B1)DBP吸收量為30至100ml/100g中的至少一個性質。再者，本發明的碳黑較佳為滿足(A2)比表面積為10至60m²/g，更佳為滿足(A3)比表面積為30至60m²/g，又更佳為滿足(A4)比表面積為40至60m²/g，特佳為滿足(A5)比表面積為50至60m²/g。另外，本發明 的碳黑較佳為滿足(B2)DBP吸收量為30至70ml/100g，更佳為滿足(B3)DBP吸收量為40至70ml/100g，又更佳為滿足(B4)DBP吸收量為50至70ml/100g，特佳為滿足(B5)DBP吸收量為60至70ml/100g。在此，本發明的碳黑較佳為滿足關於比表面積之(A1)至(A5)中的任一者，以及關於DBP吸收量之(B1)至(B5)中的任一者的性質。具體而言，較佳為滿足(A1)及(B1)、(A1)及(B2)、(A1)及(B3)、(A1)及(B4)、(A1)及(B5)、(A2)及(B1)、(A2)及(B2)、(A2)及(B3)、(A2)及(B4)、(A2)及(B5)、(A3)及(B1)、(A3)及(B2)、(A3)及(B3)、(A3)及(B4)、(A3)及(B5)、(A4)及(B1)、(A4)及(B2)、(A4)及(B3)、(A4)及(B4)、(A4)及(B5)、(A5)及(B1)、(A5)及(B2)、(A5)及(B3)、(A5)及(B4)、(A5)及(B5)中的任一者。 Here, the carbon black of the present invention must satisfy at least one property of (A1) specific surface area of 10 to 100 m ² / g, or (B1) DBP absorption of 30 to 100 ml / 100 g. Furthermore, the carbon black of the present invention preferably satisfies (A2) specific surface area of 10 to 60 m ² / g, more preferably satisfies (A3) specific surface area of 30 to 60 m ² / g, and even more preferably satisfies (A4) The specific surface area is 40 to 60 m ² / g, and it is particularly preferable that the (A5) specific surface area is 50 to 60 m ² / g. In addition, the carbon black of the present invention preferably satisfies (B2) DBP absorption of 30 to 70 ml / 100g, more preferably satisfies (B3) DBP absorption of 40 to 70 ml / 100g, and even more preferably satisfies (B4) DBP The absorption amount is 50 to 70 ml / 100g, and it is particularly preferable to satisfy (B5) the DBP absorption amount to be 60 to 70 ml / 100g. Here, the carbon black of the present invention preferably satisfies the properties of any one of (A1) to (A5) regarding specific surface area and any one of (B1) to (B5) regarding DBP absorption. Specifically, it is preferable to satisfy (A1) and (B1), (A1) and (B2), (A1) and (B3), (A1) and (B4), (A1) and (B5), (A2 ) And (B1), (A2) and (B2), (A2) and (B3), (A2) and (B4), (A2) and (B5), (A3) and (B1), (A3) and (B2), (A3) and (B3), (A3) and (B4), (A3) and (B5), (A4) and (B1), (A4) and (B2), (A4) and (B3 ), (A4) and (B4), (A4) and (B5), (A5) and (B1), (A5) and (B2), (A5) and (B3), (A5) and (B4), Either (A5) or (B5).

在此，在本發明中，碳黑的氮吸附比表面積係表示以JIS K-6217-2所測量的值。 Here, in the present invention, the nitrogen adsorption specific surface area of carbon black represents the value measured in JIS K-6217-2.

又，在本發明中，碳黑的DBP吸收量係表示以JIS K-6221所測量的值。 In addition, in the present invention, the DBP absorption amount of carbon black represents a value measured in accordance with JIS K-6221.

此外，碳黑的粒徑雖無特別限定，但較佳為25至100nm，更佳為30至60nm。該粒徑係從穿透型顯微鏡的觀察所求得的個數平均徑(1000個的平均值)。 In addition, although the particle size of carbon black is not particularly limited, it is preferably 25 to 100 nm, and more preferably 30 to 60 nm. This particle diameter is the number average diameter (average of 1000) obtained from observation through a transmission microscope.

又，由於結晶度愈高碳黑的熱傳導愈高，故亦可使用在惰性氣體中將碳黑加熱至1000℃以上使結晶度提高的熱處理碳黑。 In addition, since the higher the degree of crystallinity, the higher the thermal conductivity of the carbon black, it is also possible to use heat-treated carbon black in which the carbon black is heated to 1000 ° C. or higher in an inert gas to increase the crystallinity.

再者，本發明的碳黑亦可在其粒子表面具有各種官能基。 Furthermore, the carbon black of the present invention may have various functional groups on the surface of the particles.

做為該等碳黑的代表例者，有三菱化學股份有限公司的# 30B、# 33B、# 25B、# 95、# 85、# 240、MA220等，其他由CABOT、ORION ENGINEERED CARBON、ADITYA BIRLA、東海CARBON各公司販賣。 As representative examples of such carbon blacks, there are # 30B, # 33B, # 25B, # 95, # 85, # 240, MA220, etc. of Mitsubishi Chemical Corporation. Others include CABOT, ORION ENGINEERED CARBON, ADITYA BIRLA, Tokai CARBON companies sell.

碳黑的調配量，相對於樹脂化合物整體，較佳為含有1至30重量%，更佳為含有5至20重量%。藉由設定在上述範圍，可更提高本發明的效果。 The blending amount of carbon black is preferably 1 to 30% by weight, and more preferably 5 to 20% by weight relative to the entire resin compound. By setting it in the above range, the effect of the present invention can be further improved.

針對此，在日本特開平11-71515號公報中，已揭示使用石墨和做為碳黑之科琴導電碳黑(ketjenblack)的樹脂化合物的例子。以科琴導電碳黑為首的所謂的導電性碳黑係使用於賦予樹脂導電性，據稱，該等碳黑在樹脂中產生鏈並顯現導電性。又，該鏈被認為具有熱傳導性。導電性碳黑(預期具有高導電性的碳黑)的特徵為比表面積高、DBP吸收量高。另一方面，本發明所使用之碳黑的特徵為比表面積低及/或DBP吸收量低。 In response to this, Japanese Patent Laid-Open No. 11-71515 has disclosed an example of using graphite and a resin compound of ketjen black as carbon black. The so-called conductive carbon black, led by Ketjen conductive carbon black, is used to impart electrical conductivity to the resin. It is said that such carbon black generates chains in the resin and exhibits electrical conductivity. In addition, the chain is considered to have thermal conductivity. Conductive carbon black (carbon black expected to have high conductivity) is characterized by a high specific surface area and a high DBP absorption. On the other hand, the carbon black used in the present invention is characterized by a low specific surface area and / or a low DBP absorption.

DBP吸收量不同之碳黑的圖像顯示在第1圖，比表面積不同之碳黑的圖像顯示在第2圖。如前述圖式所示，比表面積低、DBP吸收量低的碳黑係異向性低並更接近球，而且成為較大的球。藉由將這種碳黑與成為比碳黑大之平板狀的石墨等的碳材料一起使用，在成型時之熱塑性樹脂融化的狀態，碳黑進入平板與平板之間，宛如發揮滾子的作用(滾子原理)。認為根據該滾子原理，成為平板狀的石墨等碳材料順利地分散在樹脂中，使熱塑性樹脂的流動性良好。結果，可以維持樹脂的流動性(成型性) 並使填充劑更高度調配、維持樹脂中的填充劑量並提高樹脂的流動性(成型性)。另外，DBP吸收量愈大碳黑的凹凸會愈多，在樹脂中流動時碳黑會互相勾住，因而被認為是樹脂的流動性降低的原因。又，碳黑的比表面積與粒徑有成反比之傾向，有藉由碳黑的粒徑決定樹脂中的石墨間的距離之傾向。若碳黑的比表面積小於10m²/g且DBP吸收量小於30ml/g，如第3圖所示，由於滾子變得過大，石墨等填充劑間的距離太寬，而使熱傳導率下降。相反地，認為若碳黑的比表面積大於100m²/g且DBP吸收量大於100ml/100g，滾子會變得過小，各材料彼此的摩擦會增加，且因為石墨等過於接近，而滾子的效果會降低。 The image of carbon black with different DBP absorption is shown in Figure 1, and the image of carbon black with different specific surface area is shown in Figure 2. As shown in the foregoing diagram, the carbon black system having a low specific surface area and a low DBP absorption has a low anisotropy and is closer to a ball, and becomes a larger ball. By using this carbon black together with carbon materials such as graphite that is larger than carbon black in the form of a flat plate, the thermoplastic resin melts during molding, and the carbon black enters between the flat plates and acts like a roller (Roller principle). According to this roller principle, it is thought that carbon materials such as flat graphite and the like are smoothly dispersed in the resin and the thermoplastic resin has good fluidity. As a result, the fluidity (moldability) of the resin can be maintained, the filler can be more highly formulated, the amount of filler in the resin can be maintained, and the fluidity (moldability) of the resin can be improved. In addition, the greater the DBP absorption, the more irregularities of the carbon black, and the carbon black will catch each other when flowing in the resin, which is considered to be the cause of the decrease in the fluidity of the resin. Furthermore, the specific surface area of carbon black tends to be inversely proportional to the particle size, and the distance between graphite in the resin tends to be determined by the particle size of carbon black. If the specific surface area of carbon black is less than 10 m ² / g and the DBP absorption is less than 30 ml / g, as shown in Fig. 3, the distance between fillers such as graphite is too wide due to excessively large rollers, which lowers the thermal conductivity. Conversely, if the specific surface area of carbon black is greater than 100m ² / g and the DBP absorption is greater than 100ml / 100g, the roller will become too small, the friction between the materials will increase, and because the graphite is too close, the roller's The effect will be reduced.

又，從這種觀點看來，做為上述碳黑和石墨的合計調配量，相對於樹脂化合物整體，較佳為30至90重量%，更佳為40至80重量%。 From this point of view, the total blending amount of the carbon black and graphite is preferably 30 to 90% by weight, and more preferably 40 to 80% by weight relative to the entire resin compound.

在此，一般所使用的有機物流動改質劑，例如硬脂酸鈣，其熔點為160℃，松香等的軟化點依據種類而不同，但其熔點大概是150℃以下。由於熱傳導性樹脂化合物係使用在將發熱體所產生的熱予以散熱，故使用時之熱傳導性樹脂化合物的溫度經常超過100℃或150℃。因此，會有有機物流動改質劑的熔點低於熱傳導性樹脂化合物所使用的樹脂軟化的溫度的情況，使用這種有機物流動改質劑時，有機物在樹脂中移動，常常析出表面。如此，由於有機物流動改質劑在表面析出，而於零件使用中會引起環境污染問題。又，為了著色等而進行塗覆、鍍 覆零件時，會引起塗層或鍍層剝落。 Here, a generally used organic fluid modifier, such as calcium stearate, has a melting point of 160 ° C. The softening point of rosin and the like varies depending on the type, but its melting point is approximately 150 ° C or less. Since the heat conductive resin compound is used to dissipate the heat generated by the heating element, the temperature of the heat conductive resin compound during use often exceeds 100 ° C or 150 ° C. Therefore, the melting point of the organic substance flow modifier may be lower than the softening temperature of the resin used for the thermally conductive resin compound. When such an organic substance flow modifier is used, organic substances move in the resin and the surface is often precipitated. In this way, the organic matter flow modifier is precipitated on the surface, which will cause environmental pollution problems in the use of parts. In addition, when coating or plating parts for coloring, etc., the coating or plating may peel off.

由於碳黑的熔點高，在3000℃也難以融化，故即使樹脂融化碳黑也不會融化。因此，在樹脂不會軟化的使用環境中，依據上述滾子原理而發揮做為流動改質劑的功能的上述碳黑不會在零件的表面析出，不會造成因析出而導致的各種困擾。 Since carbon black has a high melting point and is difficult to melt at 3000 ° C, carbon black will not melt even if the resin melts. Therefore, in an environment in which the resin does not soften, the carbon black that functions as a flow modifier based on the roller principle does not precipitate on the surface of the part, and does not cause various troubles due to precipitation.

(碳奈米管) (Carbon Nanotube)

做為第3熱傳導填充劑的碳奈米管(以下稱為CNT)係與碳黑相同，在3000℃不會融化，為熱傳導性高的填充劑。做為一般的CNT的一個例子者，可列舉具有多層構造的圓柱狀且外徑為10nm左右、長度為數微米至數百微米者。 The carbon nanotube (hereinafter referred to as CNT) used as the third thermally conductive filler is the same as carbon black, does not melt at 3000 ° C, and is a filler with high thermal conductivity. As an example of a general CNT, a cylindrical structure having a multilayer structure, an outer diameter of about 10 nm, and a length of several to hundreds of microns can be cited.

石墨具有扁平構造，面方向的熱傳導性良好，但厚度方向的熱傳導性不佳。將調配有石墨的化合物射出成型時，由於石墨沿著樹脂的流動定向，故所成型之零件的流動方向的熱傳導性良好，但也有厚度方向的熱傳導性變差的情況。在包含碳黑及石墨之本發明的系統中，進一步添加CNT，藉此以使CNT進一步進入因做為滾子的碳黑進入石墨與石墨之間而產生的空間。結果，認為石墨與石墨之間的熱傳導增加。又，若碳黑不存在(例如僅包含石墨及CNT的系統的情況)，無法有效地傳遞石墨與石墨之間的熱。 Graphite has a flat structure and good thermal conductivity in the plane direction, but poor thermal conductivity in the thickness direction. When injection molding a compound compounded with graphite, graphite is oriented along the flow of the resin, so the thermal conductivity of the molded part in the flow direction is good, but the thermal conductivity in the thickness direction may be deteriorated. In the system of the present invention including carbon black and graphite, CNT is further added, thereby allowing the CNT to further enter the space created by the carbon black as a roller entering between graphite and graphite. As a result, it is considered that the heat conduction between graphite and graphite increases. In addition, if carbon black does not exist (for example, in the case of a system including only graphite and CNT), the heat between graphite and graphite cannot be efficiently transferred.

如上所述，CNT藉由具有提高石墨與石墨 之熱傳導的作用，而產生零件的厚度方向的熱傳導性變佳的效果。 As described above, the CNT has the effect of improving the thermal conductivity between graphite and graphite, so that the thermal conductivity in the thickness direction of the part is improved.

CNT的調配量，相對於樹脂化合物整體，較佳為1至10重量%，更佳為1至3重量%。若不足1重量%，難以顯現效果，若超過10重量%，樹脂的流動性會變差而成型變得困難。 The compounding amount of CNT is preferably 1 to 10% by weight, and more preferably 1 to 3% by weight relative to the entire resin compound. If it is less than 1% by weight, it is difficult to develop the effect, and if it exceeds 10% by weight, the fluidity of the resin will be deteriorated and molding will become difficult.

又，CNT的線徑雖無特別限定，但較佳為1至100nm，更佳為5至30nm。CNT的線徑係以穿透型顯微鏡觀察所測量之個數平均徑(1000個的平均值)。 Although the wire diameter of CNT is not particularly limited, it is preferably 1 to 100 nm, and more preferably 5 to 30 nm. The wire diameter of CNT is the number-average diameter (average of 1000) measured with a transmission microscope.

(其他的熱傳導填充劑) (Other heat conductive fillers)

本發明的樹脂化合物亦可含有其他的熱傳導填充劑。做為其他的熱傳導填充劑者，只要熱傳導率比樹脂高者均可，可以使用金屬粉、陶瓷粉、其他的碳材料(例如碳纖維)等各種的填充劑。其中，理想為熱傳導高、比重低且經濟效益良好者，例如可使用氮化硼、氮化鋁等。 The resin compound of the present invention may contain other thermally conductive fillers. As other thermally conductive fillers, as long as the thermal conductivity is higher than that of resin, various fillers such as metal powder, ceramic powder, other carbon materials (such as carbon fiber), etc. can be used. Among them, those with high thermal conductivity, low specific gravity, and good economic benefits are ideal. For example, boron nitride and aluminum nitride can be used.

做為其他的熱傳導填充劑的調配量者，相對於樹脂化合物整體，較佳為10重量%以下，更佳為5重量%以下。 The amount of other thermally conductive fillers is preferably 10% by weight or less and more preferably 5% by weight or less relative to the entire resin compound.

<其他的添加劑> <Other additives>

做為其他的添加劑可適當使用周知者，例如樹脂的熱安定劑、抗氧化劑、阻燃劑或流動改質劑等。該等添加劑可單獨使用或是複數使用，但理想為不會析出表面而引起 問題之程度的少量。 As other additives, well-known ones may be suitably used, such as heat stabilizers, antioxidants, flame retardants, or flow modifiers of resins. These additives can be used singly or in plural, but it is ideal that the amount of the surface is not so small as to cause problems.

根據本發明，即使不使用有機物流動改質劑等仍可獲得熱傳導率及電傳導率高、成型性優異、機械強度高的熱傳導性樹脂化合物。因此，也具有抑制有機物朝零件表面滲出的效果。 According to the present invention, a thermally conductive resin compound having high thermal conductivity and electrical conductivity, excellent moldability, and high mechanical strength can be obtained without using an organic substance flow modifier or the like. Therefore, it also has an effect of suppressing organic matter from oozing toward the surface of the part.

<<製造方法>>     << Manufacturing method >>    

接著，針對本發明的樹脂化合物及其成形物(成型零件)的製造方法進行說明。又，關於原料如上所述故省略其說明。 Next, a method of manufacturing the resin compound of the present invention and its molded product (molded part) will be described. In addition, the description of the raw materials is omitted as described above.

本發明的樹脂化合物的製造方法並未限定，但可藉由將原料適當混合而得到。具體而言，例如於成為基質樹脂的原料樹脂(樹脂材料)調配包含前述熱傳導填充劑的其他原料(其他的添加劑等)並進行混合(預先混合)，藉以製造原料組成物，將該原料組成物混合(捏合)，依照需要進一步顆粒化而可製造本發明的樹脂化合物。又，預先混合和捏合係做為混合步驟，可同時或連續進行。 The method for producing the resin compound of the present invention is not limited, but can be obtained by appropriately mixing raw materials. Specifically, for example, the raw material resin (resin material) which becomes the matrix resin is mixed with other raw materials (other additives, etc.) containing the aforementioned heat conductive filler and mixed (pre-mixed) to produce a raw material composition, and the raw material composition The resin compound of the present invention can be produced by mixing (kneading) and further granulating as necessary. In addition, the pre-mixing and kneading system can be carried out simultaneously or continuously as a mixing step.

更具體而言，捏合本發明的樹脂化合物時，可使用一般周知的樹脂捏合機。做為具體的例子，欲效率良好地捏合複數種填充劑、添加劑時，可使用短軸或2軸壓出機、斑伯里混煉機(Banbury mixer)、加壓捏合機、加熱2個輥等。例如，使用2軸壓出機時，可將樹脂及熱傳導填充劑、添加劑預先以超級混合器等混合器混合並捏合，也可以用主螺桿導入樹脂和添加劑，從側進料器另外 導入熱傳導填充劑並捏合。 More specifically, when kneading the resin compound of the present invention, a generally known resin kneader can be used. As a specific example, to efficiently knead a plurality of fillers and additives, a short-axis or two-axis extruder, a Banbury mixer, a pressure kneader, and two heated rollers can be used Wait. For example, when using a 2-axis extruder, the resin, thermally conductive filler, and additives may be mixed and kneaded in advance with a mixer such as a super mixer, or the resin and additives may be introduced with the main screw, and thermally conductive filler may be separately introduced from the side feeder Agent and knead.

又，該熱傳導性樹脂化合物可由一般的成型機成型，製成成型零件。做為成型機可使用射出成型機、壓出成型機、薄膜成型機、加壓成型機等一般的成型機。將本發明的樹脂化合物成型而成的零件可做為各種散熱零件使用。 In addition, the thermally conductive resin compound can be molded by a general molding machine to form molded parts. As the molding machine, general molding machines such as injection molding machines, extrusion molding machines, film molding machines, press molding machines, etc. can be used. The parts molded by the resin compound of the present invention can be used as various heat dissipation parts.

<<用途>>     << Use >>    

根據本發明，可形成熱傳導率及電傳導率高、成型性優異、機械強度高的樹脂化合物及其成形物，故能夠使用在各種用途。例如：可適宜應用在包含LED的各種散熱器、靜電屏蔽、燃料電池用的雙極板等。 According to the present invention, a resin compound having high thermal conductivity and electrical conductivity, excellent moldability, and high mechanical strength and a molded product thereof can be formed, and thus can be used in various applications. For example, it can be suitably applied to various radiators including LEDs, electrostatic shielding, and bipolar plates for fuel cells.

(實施例) (Example)

基於以下的實施例具體說明本發明，但本發明並不僅限於該等實施例。 The present invention is specifically described based on the following examples, but the present invention is not limited to these examples.

使用以下的化合物做為原料。 Use the following compounds as raw materials.

(1)聚醯胺 (1) Polyamide

‧宇部興產公司製 1013B ‧Manufactured by Ube Kosei Corporation 1013B

(2)石墨 (2) Graphite

‧中越黑鉛公司製 CPB-80，平均粒徑316μm ‧CPB-80 manufactured by Sino-Vietnamese Black Lead Company, with an average particle size of 316 μm

(3)碳黑 (3) Carbon black

‧# 25B(三菱化學股份有限公司製) ‧ # 25B (Mitsubishi Chemical Corporation)

平均粒徑47nm、DBP吸收量66ml/100g、氮吸附比表面積為55m²/g Average particle size 47nm, DBP absorption 66ml / 100g, nitrogen adsorption specific surface area 55m ² / g

‧科琴導電碳黑(LION SPECIALTY CHEMICALS公司製) ‧Ketjen conductive carbon black (made by LION SPECIALTY CHEMICALS)

平均粒徑39.5nm、DBP吸收量360ml/100g、氮吸附比表面積為800m²/g Average particle size 39.5nm, DBP absorption 360ml / 100g, nitrogen adsorption specific surface area 800m ² / g

‧# 40B(三菱化學股份有限公司製) ‧ # 40B (Mitsubishi Chemical Corporation)

平均粒徑24nm、DBP吸收量113ml/100g、氮吸附比表面積為115m²/g The average particle size is 24nm, the DBP absorption is 113ml / 100g, and the nitrogen adsorption specific surface area is 115m ² / g

(6)碳奈米管 (6) Carbon nanotube

‧KUMH PETROCHEMICAL公司製 K．Nanos100P 平均粒徑約10nm ‧Made by KUMH PETROCHEMICAL K. Nanos100P average particle size is about 10nm

以表1所示之調配量將原料混合，加熱及捏合後，製成實施例1至5及比較例1至4的試驗用樹脂化合物。又，比較例3和4無法製成所期望的形狀的樹脂化合物。 The raw materials were mixed at the formulation amounts shown in Table 1, and after heating and kneading, the test resin compounds of Examples 1 to 5 and Comparative Examples 1 to 4 were prepared. In addition, Comparative Examples 3 and 4 were unable to produce resin compounds of the desired shape.

針對各實施例及比較例之試驗用樹脂化合物測量流動性(MFR)、機械強度(彎曲彈性模數與最大拉伸應力)、衝擊強度(夏比衝擊值(Charpy Impact Value))、熱傳導率、電傳導率(體積電阻率)。測量結果顯示於表1。又，各性質的測量方法如下述。 For the test compounds of each example and comparative example, the flowability (MFR), mechanical strength (flexural modulus of elasticity and maximum tensile stress), impact strength (Charpy Impact Value), thermal conductivity, Electrical conductivity (volume resistivity). The measurement results are shown in Table 1. In addition, the measurement method of each property is as follows.

(流動性) (fluidity)

依據JIS K-7210進行測量。測量溫度為280℃，測量加重為5kg。 Measured according to JIS K-7210. The measurement temperature is 280 ° C and the measurement weight is 5kg.

流動性(MFR)較佳為0.1g/10分鐘以上。 The fluidity (MFR) is preferably 0.1 g / 10 minutes or more.

(機械強度) (Mechanical strength)

成型1號型啞鈴，拉伸強度依照JIS K-7113、試驗片依照JIS K-7113、彎曲彈性模數依照JIS K-7203進行。 The No. 1 type dumbbell was molded, the tensile strength was in accordance with JIS K-7113, the test piece was in accordance with JIS K-7113, and the bending elastic modulus was in accordance with JIS K-7203.

(夏比衝擊強度) (Charpy impact strength)

依據JIS K-7110以具有缺口的試驗片進行測量。 The measurement was performed with a notched test piece in accordance with JIS K-7110.

衝擊強度較佳在2至20kJ/m²的範圍內。 The impact strength is preferably in the range of 2 to 20 kJ / m ² .

(熱傳導率) (Thermal conductivity)

從1號型啞鈴切出直徑10mm、厚度1mm的圓盤做為厚度方向的熱傳導測量樣品。又，將數片啞鈴層疊，進行熱壓使厚度為10mm以上，以使層疊面成為平面的方式切出直徑10mm、厚度1mm的圓盤做為成型的樹脂的流動方向之熱傳導測量樣品。 A disc with a diameter of 10 mm and a thickness of 1 mm was cut out from the No. 1 dumbbell as the heat conduction measurement sample in the thickness direction. Furthermore, several dumbbells were laminated, and hot-pressed to a thickness of 10 mm or more, and a disk with a diameter of 10 mm and a thickness of 1 mm was cut out so that the laminated surface became a flat surface as a thermal conductivity measurement sample of the molded resin in the flow direction.

熱傳導測量係使用NETZSCH公司的LFA 467 Hyper Flash測量熱擴散係數及熱容量，另外測量啞鈴的密度，從算式：熱傳導率=熱擴散係數×密度×熱容量而求得。 The thermal conductivity measurement system uses LFA 467 Hyper Flash of NETZSCH to measure the thermal diffusivity and thermal capacity, and additionally measures the density of the dumbbell, which is obtained from the formula: thermal conductivity = thermal diffusivity × density × thermal capacity.

(電傳導率(體積電阻率)) (Electrical conductivity (volume resistivity))

使用Mitsubishi Chemical Analytech公司的電阻率計Loresta測量1號型啞鈴的電阻。 The resistance of the No. 1 dumbbell was measured using a resistivity meter Loresta of Mitsubishi Chemical Analytech.

體積電阻率較佳為100Ω‧cm以下(0.01Ωcm以上)。 The volume resistivity is preferably 100 Ω · cm or less (0.01 Ωcm or more).

Claims (8)

一種樹脂化合物，係含有熱塑性樹脂和石墨，該樹脂化合物的特徵為，更含有氮吸附比表面積為10至100m ²/g的碳黑。 A resin compound containing a thermoplastic resin and graphite. The resin compound is characterized by further containing carbon black with a nitrogen adsorption specific surface area of 10 to 100 m ² / g. 一種樹脂化合物，係含有熱塑性樹脂和石墨，該樹脂化合物的特徵為，更含有DBP吸收量為30至100ml/100g的碳黑。     A resin compound containing a thermoplastic resin and graphite. The resin compound is characterized by further containing carbon black with a DBP absorption of 30 to 100 ml / 100 g.     一種樹脂化合物，係含有熱塑性樹脂和石墨，該樹脂化合物的特徵為，更含有氮吸附比表面積為10至100m ²/g且DBP吸收量為30至100ml/100g的碳黑。 A resin compound containing a thermoplastic resin and graphite. The resin compound is characterized by further containing carbon black with a nitrogen adsorption specific surface area of 10 to 100 m ² / g and a DBP absorption of 30 to 100 ml / 100 g. 如申請專利範圍第1項至第3項中任一項所述之樹脂化合物，其中，相對於樹脂化合物整體，含有1至30重量%之前述碳黑。     The resin compound according to any one of claims 1 to 3, which contains 1 to 30% by weight of the aforementioned carbon black relative to the entire resin compound.     如申請專利範圍第1項至第4項中任一項所述之樹脂化合物，其中，前述石墨為鱗片狀。     The resin compound according to any one of items 1 to 4 of the patent application range, wherein the graphite is in the form of flakes.     如申請專利範圍第1項至第5項中任一項所述之樹脂化合物，其中，相對於樹脂化合物整體，含有20至80重量%之前述石墨。     The resin compound according to any one of items 1 to 5 of the patent application range, which contains 20 to 80% by weight of the aforementioned graphite with respect to the entire resin compound.     如申請專利範圍第1項至第6項中任一項所述之樹脂化合物，其中，相對於樹脂化合物整體，更含有1至10重量%之碳奈米管。     The resin compound according to any one of items 1 to 6 of the patent application range, which further contains 1 to 10% by weight of carbon nanotubes relative to the entire resin compound.     一種成形物，係將申請專利範圍第1項至第7項中任一項所述之樹脂化合物成型而成者。     A molded product formed by molding the resin compound described in any one of claims 1 to 7.