TW202413537A - Heat conductive composition, heat conductive sheet, heat conductive composition manufacturing method, and heat conductive sheet manufacturing method - Google Patents
Heat conductive composition, heat conductive sheet, heat conductive composition manufacturing method, and heat conductive sheet manufacturing method Download PDFInfo
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- TW202413537A TW202413537A TW112130461A TW112130461A TW202413537A TW 202413537 A TW202413537 A TW 202413537A TW 112130461 A TW112130461 A TW 112130461A TW 112130461 A TW112130461 A TW 112130461A TW 202413537 A TW202413537 A TW 202413537A
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- Prior art keywords
- thermally conductive
- conductive composition
- rosin
- particles
- melting
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L93/00—Compositions of natural resins; Compositions of derivatives thereof
- C08L93/04—Rosin
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K7/00—Constructional details common to different types of electric apparatus
- H05K7/20—Modifications to facilitate cooling, ventilating, or heating
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Thermal Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
本發明系關於導熱組合物、導熱片、導熱組合物的製造方法和導熱片的製造方法。The present invention relates to a thermally conductive composition, a thermally conductive sheet, a method for manufacturing the thermally conductive composition, and a method for manufacturing the thermally conductive sheet.
各種電子設備中的LSI(Large Scale Integration)等中，由於使用的元件的發熱而LSI本身長時間暴露於高溫，從而導致動作不良或故障的擔憂。因此，為了防止LSI等的升溫，廣泛使用導熱材料。導熱材料使元件的發熱進行擴散，或藉由傳導至放出至大氣等體系外的放熱構件以能夠降低設備的升溫。In various electronic devices such as LSI (Large Scale Integration), the heat generated by the components used causes the LSI itself to be exposed to high temperatures for a long time, which can lead to concerns about malfunction or failure. Therefore, in order to prevent the temperature of LSI, etc., thermal conductive materials are widely used. Thermal conductive materials diffuse the heat generated by the components or reduce the temperature of the equipment by conducting it to a heat dissipating component that releases it to the outside of the system such as the atmosphere.
如果作為這樣的導熱材料使用金屬或陶瓷，則存在難以輕量化，加工性差，或柔軟性變低這樣的問題。因此，提出各種將由樹脂或橡膠等形成的高分子材料作為母材的導熱組合物。If metal or ceramic is used as such a thermal conductive material, there are problems such as difficulty in weight reduction, poor processability, or low flexibility. Therefore, various thermal conductive compositions using polymer materials such as resins and rubbers as base materials have been proposed.
作為將高分子材料作為母材的導熱組合物，例如，提出了在分子内，含有高分子化合物、環氧樹脂、導熱填料和活性酯固化劑的樹脂組合物(例如，参照專利文獻1)。As a thermally conductive composition using a polymer material as a base material, for example, a resin composition containing a polymer compound, an epoxy resin, a thermally conductive filler, and an active ester curing agent in a molecule has been proposed (for example, refer to Patent Document 1).
在使用專利文獻1的樹脂組合物以製作樹脂片時，將樹脂組合物溶解於有機溶劑以調製樹脂清漆，將調製的樹脂清漆塗佈於支持體上使其乾燥，從而製造在支持體上形成有樹脂組合物層的樹脂片。 現有技術文獻 專利文獻 When the resin composition of Patent Document 1 is used to prepare a resin sheet, the resin composition is dissolved in an organic solvent to prepare a resin varnish, and the prepared resin varnish is applied to a support and dried to prepare a resin sheet having a resin composition layer formed on the support. Prior Art Document Patent Document
專利文獻1:日本專利第6787210號公報Patent document 1: Japanese Patent No. 6787210
＜發明欲解決之問題＞＜Problems to be solved＞
然而，專利文獻1中，關於導熱組合物中残留的揮發成分沒有研究。在使用使專利文獻1所記載的樹脂組合物溶解於有機溶劑的樹脂清漆來製作樹脂片時，樹脂清漆的乾燥時，揮發成分沒有完全乾燥，有時樹脂組合物中残留微量的揮發成分。樹脂組合物中残留的微量的揮發成分由於使固化反應開始的加熱而膨脹，產生空隙。這樣的空隙如果存在於基材與樹脂組合物的界面，則形成導熱率低的空氣的空間，因此不僅導致樹脂組合物層的面内的熱傳遞的偏差，而且會發生導熱率的降低這樣的問題。However, Patent Document 1 does not study the volatile components remaining in the thermally conductive composition. When a resin sheet is produced using a resin varnish in which the resin composition described in Patent Document 1 is dissolved in an organic solvent, the volatile components are not completely dried when the resin varnish is dried, and a trace amount of volatile components may remain in the resin composition. The trace amount of volatile components remaining in the resin composition expands due to the heating that starts the curing reaction, generating voids. If such voids exist at the interface between the substrate and the resin composition, spaces for air with low thermal conductivity are formed, which not only causes a deviation in heat transfer within the surface of the resin composition layer, but also causes a problem of reduced thermal conductivity.
本發明的一方式的目的在於提供使其固化時，抑制基材與導熱組合物的固化物的界面所存在的空隙的發生，能夠實現高導熱率的導熱組合物。 [用於解決課題的方法] One aspect of the present invention aims to provide a thermally conductive composition that can achieve high thermal conductivity by suppressing the generation of voids at the interface between a substrate and a cured product of the thermally conductive composition when the composition is cured. [Method for Solving the Problem]
作為用於解決上述課題的方法，如下。 即， ＜1＞一種導熱組合物，其為包含熱塑性樹脂、松香系樹脂、導熱粒子和低熔點金屬粒子的導熱組合物， 上述熱塑性樹脂和上述松香系樹脂具有揮發成分， 上述揮發成分的含有比例為5.0wt%以下。 ＜2＞根據＜1＞所述的導熱組合物，上述熱塑性樹脂和上述松香系樹脂的熔點為上述低熔點金屬粒子的熔點以下。 ＜3＞根據＜1＞或＜2＞所述的導熱組合物，上述熱塑性樹脂和上述松香系樹脂的熔點為上述低熔點金屬粒子的熔點的-10℃以下。 ＜4＞根據＜1＞～＜3＞的任一項所述的導熱組合物，上述熱塑性樹脂和上述松香系樹脂的熔點為110℃～140℃。 ＜5＞根據＜1＞～＜4＞的任一項所述的導熱組合物，上述熱塑性樹脂為選自由聚醯胺系樹脂、聚酯系樹脂、聚氨酯系樹脂、聚烯烴系樹脂、苯氧基系樹脂所組成的組中的1種以上的成分。 ＜6＞根據＜1＞～＜5＞的任一項所述的導熱組合物，上述松香系樹脂為松香和改性松香的至少任一者。 ＜7＞根據＜1＞～＜6＞的任一項所述的導熱組合物，上述導熱粒子為銅粒子、銀被覆粒子和銀粒子的至少任一者。 ＜8＞根據＜1＞～＜7＞的任一項所述的導熱組合物，上述低熔點金屬粒子包含Sn以及選自Bi、Ag、Cu和In中的至少1種。 ＜9＞根據＜1＞～＜8＞的任一項所述的導熱組合物，上述導熱粒子的體積平均粒徑為1μm～100μm。 ＜10＞根據＜1＞～＜9＞的任一項所述的導熱組合物，上述低熔點金屬粒子的平均粒徑為10μm以下。 ＜11＞一種導熱片，其包含＜1＞～＜10＞的任一項所述的導熱組合物的固化物。 ＜12＞根據＜11＞所述的導熱片，上述固化物的主表面處的空隙面積的比例為20%以下。 ＜13＞一種導熱組合物的製造方法，其包括下述工序: 將包含揮發成分的熱塑性樹脂和包含揮發成分的松香系樹脂在非活性氣體氣氛下一邊加熱一邊混合，製作第1混合物的樹脂混合工序， 在上述第1混合物中混合導熱粒子和低熔點金屬粒子，製作第2混合物的粒子混合工序，以及 將上述第2混合物在上述熱塑性樹脂和上述松香系樹脂的熔點以上的溫度一邊加熱處理一邊成型為膜狀，製作具有膜狀的形狀的導熱組合物的加熱成型工序， 上述熱塑性樹脂和上述松香系樹脂所包含的上述揮發成分的含有比例為5.0wt%以下。 ＜14＞一種導熱片的製造方法，其包括下述工序: 將藉由＜13＞所述的導熱組合物的製造方法獲得的上述導熱組合物配置於一對基材之間的狀態下加熱處理並固化，獲得固化物的工序， 上述固化物與上述基材相接的主表面處的空隙面積的比例為20%以下。 ＜15＞根據＜14＞所述的導熱片的製造方法，上述加熱處理的溫度為140℃～200℃，加熱時間為30分鐘～3小時。 ＜發明之功效＞ The method for solving the above-mentioned problem is as follows. That is, <1> A thermally conductive composition comprising a thermoplastic resin, a rosin-based resin, thermally conductive particles and low-melting-point metal particles, wherein the thermoplastic resin and the rosin-based resin have volatile components, and the content of the volatile components is 5.0 wt% or less. <2> According to the thermally conductive composition described in <1>, the melting points of the thermoplastic resin and the rosin-based resin are lower than the melting point of the low-melting-point metal particles. <3> According to the thermally conductive composition described in <1> or <2>, the melting points of the thermoplastic resin and the rosin-based resin are lower than -10°C of the melting point of the low-melting-point metal particles. <4> The thermally conductive composition according to any one of <1> to <3>, wherein the melting points of the thermoplastic resin and the rosin-based resin are 110°C to 140°C. <5> The thermally conductive composition according to any one of <1> to <4>, wherein the thermoplastic resin is one or more components selected from the group consisting of polyamide resins, polyester resins, polyurethane resins, polyolefin resins, and phenoxy resins. <6> The thermally conductive composition according to any one of <1> to <5>, wherein the rosin-based resin is at least one of rosin and modified rosin. <7> The thermally conductive composition according to any one of <1> to <6>, wherein the thermally conductive particles are at least one of copper particles, silver-coated particles, and silver particles. <8> The thermally conductive composition according to any one of <1> to <7>, wherein the low-melting-point metal particles include Sn and at least one selected from Bi, Ag, Cu, and In. <9> The thermally conductive composition according to any one of <1> to <8>, wherein the volume average particle size of the thermally conductive particles is 1 μm to 100 μm. <10> The thermally conductive composition according to any one of <1> to <9>, wherein the average particle size of the low-melting-point metal particles is 10 μm or less. <11> A thermally conductive sheet comprising a cured product of the thermally conductive composition according to any one of <1> to <10>. <12> The thermally conductive sheet according to <11>, wherein the ratio of the void area at the main surface of the cured product is 20% or less. <13> A method for producing a thermally conductive composition, comprising the following steps: A resin mixing step of mixing a thermoplastic resin containing a volatile component and a rosin-based resin containing a volatile component under an inert gas atmosphere while heating to produce a first mixture, A particle mixing step of mixing thermally conductive particles and low-melting-point metal particles into the first mixture to produce a second mixture, and A heat-molding step of forming the second mixture into a film while heating it at a temperature above the melting point of the thermoplastic resin and the rosin-based resin to produce a thermally conductive composition having a film-like shape, The content ratio of the volatile component contained in the thermoplastic resin and the rosin-based resin is 5.0 wt% or less. <14> A method for manufacturing a thermally conductive sheet, comprising the following steps: The thermally conductive composition obtained by the method for manufacturing a thermally conductive composition described in <13> is placed between a pair of substrates and heat-treated and cured to obtain a cured product, wherein the ratio of the void area at the main surface where the cured product contacts the substrate is 20% or less. <15> According to the method for manufacturing a thermally conductive sheet described in <14>, the temperature of the heat treatment is 140°C to 200°C, and the heating time is 30 minutes to 3 hours. <Effects of the invention>
本發明的一方式能夠提供進行固化時，抑制基材與導熱組合物的固化物的界面所存在的空隙的發生，能夠實現高導熱率的導熱組合物。One aspect of the present invention can provide a thermally conductive composition capable of achieving high thermal conductivity by suppressing the generation of voids at the interface between a substrate and a cured product of the thermally conductive composition during curing.
以下，詳細地說明本發明的實施方式。另外，在本說明書中表示數值範圍的「～」只要沒有特別規定，表示包含其前後所記載的數值作為下限值和上限值。In the following, the embodiments of the present invention are described in detail. In addition, in the present specification, "to" indicating a numerical range includes the numerical values described before and after as the lower limit and the upper limit unless otherwise specified.
＜導熱組合物＞ 說明本發明實施方式涉及的導熱組合物。本實施方式涉及的導熱組合物包含熱塑性樹脂、松香系樹脂、導熱粒子和低熔點金屬粒子。 <Thermal conductive composition> Description of the thermal conductive composition involved in the embodiment of the present invention. The thermal conductive composition involved in this embodiment includes a thermoplastic resin, a rosin resin, thermal conductive particles and low melting point metal particles.
一般而言，從高溫下的接著、可靠性的觀點和提高導熱粒子的填充率的觀點考慮，導熱組合物使用將熱固性樹脂作為主體的粘合劑樹脂。在使用這些粘合劑樹脂的情況下，需要溶解於溶劑，將包含粘合劑樹脂和溶劑的塗佈液塗佈於基材以使其乾燥。然而，溶劑存在乾燥時不能完全除去而残留，易於作為氣泡残留的傾向。本發明人等着眼於在使用導熱組合物時，不使用溶劑，從而減少導熱組合物所包含的氣泡量。而且，本發明人等發現代替溶劑，使用熔點比較低的熱塑性樹脂和松香系樹脂，從而能夠降低傳導體組合物所包含的揮發性成分的量。Generally speaking, thermally conductive compositions use adhesive resins containing thermosetting resins as the main component from the viewpoints of adhesion at high temperatures, reliability, and increasing the filling rate of thermally conductive particles. When using these adhesive resins, they need to be dissolved in a solvent, and a coating liquid containing the adhesive resin and the solvent is applied to a substrate and dried. However, the solvent cannot be completely removed during drying and remains, and tends to remain as bubbles. The inventors of the present invention have focused on reducing the amount of bubbles contained in the thermally conductive composition by not using a solvent when using the thermally conductive composition. Furthermore, the inventors have found that the amount of volatile components contained in the conductor composition can be reduced by using a thermoplastic resin or a rosin-based resin having a relatively low melting point instead of a solvent.
(熱塑性樹脂) 作為熱塑性樹脂，能夠使用聚醯胺系樹脂、聚酯系樹脂、聚氨酯系樹脂、聚烯烴系樹脂、苯氧基系樹脂等。它們可以單独使用一種，可以並用二種以上。這些之中，從接著性和可靠性的觀點考慮，優選為聚醯胺系樹脂。 (Thermoplastic resin) As the thermoplastic resin, polyamide resin, polyester resin, polyurethane resin, polyolefin resin, phenoxy resin, etc. can be used. They can be used alone or in combination of two or more. Among these, polyamide resin is preferred from the viewpoint of adhesion and reliability.
作為聚醯胺系樹脂，可舉出例如，聚醯胺、聚醯胺共聚體、它們的混合物。聚醯胺系樹脂可以包含藉由氨基羧酸的自縮合、內醯胺的開環聚合、二胺與二羧酸的縮聚而得的聚合體。Examples of the polyamide resin include polyamide, polyamide copolymer, and mixtures thereof. The polyamide resin may include polymers obtained by self-condensation of aminocarboxylic acid, ring-opening polymerization of lactamide, and condensation of diamine and dicarboxylic acid.
作為聚醯胺，可舉出藉由二胺與二羧酸的縮聚而得的尼龍66、尼龍610、尼龍612、尼龍46、尼龍1212等藉由內醯胺的開環聚合而得的尼龍6、尼龍12等。Examples of the polyamide include nylon 66, nylon 610, nylon 612, nylon 46, nylon 1212, etc., which are obtained by polycondensation of diamine and dicarboxylic acid; and nylon 6 and nylon 12, which are obtained by ring-opening polymerization of lactamide.
作為聚醯胺共聚體，可舉出例如，尼龍6/66、尼龍66/6、尼龍66/610、尼龍66/612、尼龍66/6T(T表示對苯二甲酸成分)、尼龍66/6I(I表示間苯二甲酸成分)、尼龍6T/6I等共聚聚醯胺(無規共聚聚醯胺)。作為無規共聚聚醯胺，可以使用例如，改性的脂肪族聚醯胺的共聚體。Examples of the polyamide copolymer include copolymer polyamides (random copolymer polyamides) such as nylon 6/66, nylon 66/6, nylon 66/610, nylon 66/612, nylon 66/6T (T represents a terephthalic acid component), nylon 66/6I (I represents an isophthalic acid component), and nylon 6T/6I. As the random copolymer polyamide, for example, a copolymer of a modified aliphatic polyamide can be used.
作為它們的混合物，可舉出例如，尼龍66與尼龍6的混合物、尼龍66與尼龍612的混合物、尼龍66與尼龍610的混合物、尼龍66與尼龍6I的混合物、尼龍66與尼龍6T的混合物等。Examples of the mixtures thereof include a mixture of nylon 66 and nylon 6, a mixture of nylon 66 and nylon 612, a mixture of nylon 66 and nylon 610, a mixture of nylon 66 and nylon 6I, and a mixture of nylon 66 and nylon 6T.
聚醯胺、聚醯胺共聚體、它們的混合物等可以單独使用一種，可以組合使用二種以上。The polyamide, polyamide copolymer, mixture thereof, and the like may be used alone or in combination of two or more.
作為聚酯系樹脂，可舉出例如，聚對苯二甲酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚環己烷二亞甲基對苯二甲酸酯等聚亞烷基對苯二甲酸酯；聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯等聚亞烷基萘二甲酸酯等芳香族聚酯；聚四亞甲基對苯二甲酸酯等直鏈聚酯；聚羥基丁酸酯、聚己內酯、聚琥珀酸丁二醇酯、聚琥珀酸乙二醇酯、聚乳酸、聚蘋果酸、聚二醇酸、聚二惡烷、聚(2-氧雜環丁酮)等分解性脂肪族聚酯等。Examples of the polyester resin include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane dimethylene terephthalate; aromatic polyesters such as polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; linear polyesters such as polytetramethylene terephthalate; and decomposable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxohexycyclobutanone).
作為聚氨酯系樹脂，可舉出例如，聚醚系聚氨基甲酸酯樹脂、聚酯系聚氨基甲酸酯樹脂、聚碳酸酯系聚氨基甲酸酯樹脂。聚氨酯系樹脂可以為氨基甲酸酯系彈性體。氨基甲酸酯系彈性體例如，具有硬鏈段和軟鏈段。硬鏈段由聚氨酯構成。軟鏈段由聚碳酸酯系多元醇、醚系多元醇、己內酯系聚酯、己二酸酯系聚酯等構成。As polyurethane resins, for example, polyether polyurethane resins, polyester polyurethane resins, and polycarbonate polyurethane resins can be cited. Polyurethane resins can be urethane elastomers. For example, urethane elastomers have a hard segment and a soft segment. The hard segment is composed of polyurethane. The soft segment is composed of polycarbonate polyols, ether polyols, caprolactone polyesters, adipate polyesters, and the like.
作為聚烯烴系樹脂，可舉出例如，聚乙烯、低密度聚乙烯、直鏈狀低密度聚乙烯、高密度聚乙烯、交聯聚乙烯、超高分子量聚乙烯、聚丙烯、均聚丙烯、沖擊共聚物聚丙烯、無規共聚物聚丙烯、嵌段共聚物聚丙烯、等規聚丙烯、間規聚丙烯、半等規聚丙烯、聚丁烯、環烯烴聚合物、立體嵌段聚丙烯、聚-3-甲基-1-丁烯、聚-3-甲基-1-戊烯、聚-4-甲基-1-戊烯等α-烯烴聚合體、乙烯-丙烯的嵌段或無規共聚體、乙烯-甲基甲基丙烯酸酯共聚體、乙烯-甲基丙烯酸酯共聚體、乙烯-乙基丙烯酸酯共聚體、乙烯-丁基丙烯酸酯共聚體、乙烯-乙酸乙烯酯共聚體等α-烯烴共聚體、聚氟烯烴、進一步聚烯烴系熱塑性彈性體，可以為它們的2種以上的共聚體。Examples of the polyolefin resin include polyethylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, crosslinked polyethylene, ultra-high molecular weight polyethylene, polypropylene, homopolypropylene, impact copolymer polypropylene, random copolymer polypropylene, block copolymer polypropylene, isotactic polypropylene, syndiotactic polypropylene, semi-isotactic polypropylene, polybutene, cycloolefin polymers, stereoblock polypropylene, α-olefin polymers such as poly-3-methyl-1-butene, poly-3-methyl-1-pentene, and poly-4-methyl-1-pentene, block or random copolymers of ethylene-propylene, α-olefin copolymers such as ethylene-methyl methacrylate copolymers, ethylene-methacrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, and ethylene-vinyl acetate copolymers, polyfluoroolefins, and further polyolefin thermoplastic elastomers, and copolymers of two or more thereof may be used.
作為苯氧基系樹脂，可舉出例如，具有雙酚A型的骨架、雙酚F型的骨架、雙酚S型的骨架、聯苯骨架、酚醛清漆骨架、萘骨架和醯亞胺骨架等骨架的苯氧基樹脂等。Examples of the phenoxy resin include phenoxy resins having a skeleton such as a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a biphenyl skeleton, a novolac skeleton, a naphthalene skeleton, and an imide skeleton.
熱塑性樹脂具有揮發成分。揮發成分為熱塑性樹脂和松香系樹脂所包含的氣體成分。熱塑性樹脂所包含的揮發成分的含量只要以揮發成分與松香系樹脂所包含的揮發成分的含量成為5.0wt%以下的範圍得以包含即可。揮發成分的含量的測定方法的詳細情況進行後述。Thermoplastic resins have volatile components. Volatile components are gas components contained in thermoplastic resins and rosin-based resins. The content of volatile components contained in the thermoplastic resin can be contained as long as the content of the volatile components and the volatile components contained in the rosin-based resin is less than 5.0wt%. The details of the method for measuring the content of volatile components will be described later.
熱塑性樹脂的熔點優選為低熔點金屬粒子的熔點以下，熱塑性樹脂的熔點更優選為低熔點金屬粒子的熔點的-10℃以下，進一步優選為110℃～140℃。The melting point of the thermoplastic resin is preferably lower than the melting point of the low-melting-point metal particles, more preferably -10°C lower than the melting point of the low-melting-point metal particles, and further preferably 110°C to 140°C.
(松香系樹脂) 松香系樹脂具有除去低熔點金屬粒子的表面所形成的氧化膜的功能。作為松香系樹脂，可舉出例如，松香和改性松香。作為松香，可舉出例如，松樹酯原料、托爾油所包含的脂松香、木蒸松香和浮油松香等天然樹脂松香(未改性松香)。作為改性松香，可舉出歧化松香、聚合松香、氫化松香、酯化松香和它們的衍生物等。作為氫化松香，可舉出氫化松香(完全氫化松香、部分氫化松香)、和不飽和有機酸((甲基)丙烯酸等脂肪族的不飽和一元酸、富馬酸、馬來酸等α,β-不飽和羧酸等脂肪族不飽和二元酸、肉桂酸等具有芳香族環的不飽和羧酸等)作為改性松香的不飽和有機酸改性松香的氫化物(也稱為「氫化酸改性松香」)等。作為酯化松香，可舉出將松香、歧化松香或氫化松香等利用甘油、季戊四醇、乙二醇等醇進行了改性的酯化合物。它們可以單独使用一種，可以並用二種以上。作為上述松香系樹脂，可以直接使用市售的松香系樹脂，進一步可以進行精製而使用，可以將松香系樹脂所包含的特定的有機酸(例如，松香酸、新松香酸、副海松酸、海松酸、異海松酸等)、其改性物單独使用或複數組合使用。 (Rosin-based resin) Rosin-based resin has the function of removing the oxide film formed on the surface of low-melting-point metal particles. Examples of rosin-based resins include rosin and modified rosin. Examples of rosin include natural resin rosins (unmodified rosins) such as rosin ester raw materials, gum rosin contained in toll oil, wood distilled rosin, and tall oil rosin. Examples of modified rosin include disproportionated rosin, polymerized rosin, hydrogenated rosin, esterified rosin, and derivatives thereof. Examples of hydrogenated rosin include hydrogenated rosin (completely hydrogenated rosin, partially hydrogenated rosin), and unsaturated organic acid (aliphatic unsaturated monobasic acid such as (meth) acrylic acid, aliphatic unsaturated dibasic acid such as α,β-unsaturated carboxylic acid such as fumaric acid, unsaturated carboxylic acid having an aromatic ring such as cinnamic acid) as a modified rosin, and hydrogenated products of unsaturated organic acid-modified rosin (also referred to as "hydrogenated acid-modified rosin"). Examples of esterified rosin include ester compounds obtained by modifying rosin, disproportionated rosin, or hydrogenated rosin with alcohols such as glycerin, pentaerythritol, and ethylene glycol. These may be used alone or in combination of two or more. As the above-mentioned rosin resin, commercially available rosin resin can be used directly, or it can be used after being purified. Specific organic acids (e.g., abietic acid, neoabietic acid, parapimaric acid, pimaric acid, isopimaric acid, etc.) and their modified products contained in the rosin resin can be used alone or in combination.
松香系樹脂具有揮發成分。松香系樹脂所包含的揮發成分的含量如上述那樣，只要以使揮發成分和松香系樹脂所包含的揮發成分的含量成為5.0wt%以下的範圍得以包含即可。揮發成分的含量的測定方法的詳細情況進行後述。Rosin-based resins have volatile components. The content of the volatile components contained in the rosin-based resin is as described above, and it is sufficient that the volatile components and the content of the volatile components contained in the rosin-based resin are contained in a range of 5.0 wt % or less. The details of the method for measuring the content of the volatile components will be described later.
松香系樹脂的熔點與熱塑性樹脂同樣，優選為低熔點金屬粒子的熔點以下。即，松香系樹脂的熔點優選為低熔點金屬粒子的熔點的-10℃以下。松香系樹脂的熔點更優選為110℃～140℃。 如果松香系樹脂的熔點為110℃～140℃，則能夠抑制對於本實施方式涉及的導熱組合物的固化物的耐熱性產生影響，並且在本實施方式涉及的導熱組合物的製作時進行熔融成型。 The melting point of the rosin resin is preferably below the melting point of the low-melting-point metal particles, similar to the thermoplastic resin. That is, the melting point of the rosin resin is preferably below -10°C of the melting point of the low-melting-point metal particles. The melting point of the rosin resin is more preferably 110°C to 140°C. If the melting point of the rosin resin is 110°C to 140°C, the influence on the heat resistance of the cured product of the thermally conductive composition involved in the present embodiment can be suppressed, and melt molding can be performed during the preparation of the thermally conductive composition involved in the present embodiment.
熱塑性樹脂和松香系樹脂的至少一者如上所述，具有揮發成分。熱塑性樹脂和松香系樹脂所包含的揮發成分的合計的含量為5.0wt%以下，優選為4.5wt%以下，進一步優選為4.0wt%以下。At least one of the thermoplastic resin and the rosin-based resin has a volatile component as described above. The total content of the volatile components contained in the thermoplastic resin and the rosin-based resin is 5.0 wt % or less, preferably 4.5 wt % or less, and more preferably 4.0 wt % or less.
熱塑性樹脂和松香系樹脂所包含的揮發成分的合計的含量的測定方法能夠如以下那樣進行測定。 首先，將預定量的質量(例如，1g～2g)的熱塑性樹脂或松香系樹脂的試樣迅速地採集至已知的稱量罐，使其在鋁杯的底部均勻地展開。然後，對於鋁杯加蓋，直接使用電子天平進行稱量。稱量後，除去蓋，置於稱量罐下，設置於乾燥器内，在預定溫度(例如，(135±2)℃)乾燥預定時間(例如，3小時)。乾燥後，對於稱量罐直接加蓋，放入乾燥器中，放冷直至室溫之後，稱量。由下式(1)，求出乾燥的試樣的固體成分(%)。而且，由下式(2)，從100減去求得的固體成分，算出熱塑性樹脂和松香系樹脂所包含的揮發成分的合計的含有比例。 固體成分(%)＝((稱量罐＋乾燥後的試樣的質量)-(稱量罐的質量))/((稱量罐＋試樣的質量)-(稱量罐的質量))×100 ・・・(1) 揮發成分的合計的含有比例(%)＝100-固體成分 ・・・(2) The total content of volatile components contained in thermoplastic resins and rosin-based resins can be measured as follows. First, a predetermined amount of mass (e.g., 1g to 2g) of a thermoplastic resin or rosin-based resin sample is quickly collected into a known weighing pot and evenly spread on the bottom of an aluminum cup. Then, the aluminum cup is covered and weighed directly using an electronic balance. After weighing, the cover is removed, placed under the weighing pot, set in a desiccator, and dried at a predetermined temperature (e.g., (135±2)°C) for a predetermined time (e.g., 3 hours). After drying, the weighing pot is directly covered, placed in a desiccator, cooled to room temperature, and weighed. The solid content (%) of the dried sample is calculated from the following formula (1). Then, the total content ratio of volatile components contained in the thermoplastic resin and the rosin-based resin is calculated by subtracting the obtained solid content from 100 according to the following formula (2). Solid content (%) = ((Weighing tank + mass of sample after drying) - (mass of weighing tank)) / ((Weighing tank + mass of sample) - (mass of weighing tank)) × 100 ... (1) Total content ratio of volatile components (%) = 100 - solid content ... (2)
另外，在測定僅僅熱塑性樹脂或松香系樹脂所包含的揮發成分的含量的情況下，與上述同樣地準備僅僅熱塑性樹脂或松香系樹脂的試樣進行測定而求出。When the content of volatile components contained in only a thermoplastic resin or a rosin-based resin is to be measured, a sample of only a thermoplastic resin or a rosin-based resin is prepared in the same manner as above and the content of volatile components is determined by measurement.
(導熱粒子) 作為導熱粒子，優選為銅粒子、銀被覆粒子和銀粒子的至少任一者。這些之中，從穩定地維持高導熱率的方面考慮，更優選為銀被覆粒子。 (Thermal Conductive Particles) As thermal conductive particles, at least one of copper particles, silver-coated particles, and silver particles is preferred. Among these, silver-coated particles are more preferred from the perspective of stably maintaining high thermal conductivity.
作為銀被覆粒子，可舉出例如，銀被覆銅粒子、銀被覆鎳粒子、銀被覆鋁粒子等。Examples of the silver-coated particles include silver-coated copper particles, silver-coated nickel particles, and silver-coated aluminum particles.
作為導熱粒子的形狀，沒有特別限制，能夠根據目的適當選擇，可舉出例如，球狀、扁平狀、粒狀、針狀等。The shape of the thermally conductive particles is not particularly limited and can be appropriately selected according to the purpose. For example, spherical, flat, granular, needle-shaped, etc. can be cited.
導熱粒子的體積平均粒徑優選為1μm～100μm，更優選為10μm～70μm，進一步優選為10μm～50μm。如果導熱粒子的體積平均粒徑為1μm～100μm，則能夠增大導熱粒子相對於低熔點金屬粒子的體積比例，能夠實現高導熱率。另外，體積平均粒徑例如，能夠利用鐳射衍射-散乱式粒徑分佈測定装置(製品名：Microtrac MT3300EXII，Microtrac bel株式會社製)來測定。The volume average particle size of the thermally conductive particles is preferably 1 μm to 100 μm, more preferably 10 μm to 70 μm, and further preferably 10 μm to 50 μm. If the volume average particle size of the thermally conductive particles is 1 μm to 100 μm, the volume ratio of the thermally conductive particles to the low-melting-point metal particles can be increased, and high thermal conductivity can be achieved. In addition, the volume average particle size can be measured, for example, using a laser diffraction-scattered particle size distribution measuring device (product name: Microtrac MT3300EXII, manufactured by Microtrac bel Co., Ltd.).
(低熔點金屬粒子) 作為低熔點金屬粒子，例如，適合使用JIS Z3282-1999所規定的焊料粒子。 (Low-melting-point metal particles) As low-melting-point metal particles, for example, solder particles specified in JIS Z3282-1999 are suitable.
作為焊料粒子，可舉出例如，Sn-Pb系焊料粒子、Pb-Sn-Sb系焊料粒子、Sn-Sb系焊料粒子、Sn-Pb-Bi系焊料粒子、Sn-Bi系焊料粒子、Sn-Bi-Ag系焊料粒子、Sn-Cu系焊料粒子、Sn-Pb-Cu系焊料粒子、Sn-In系焊料粒子、Sn-Ag系焊料粒子、Sn-Pb-Ag系焊料粒子、Pb-Ag系焊料粒子、Sn-Ag-Cu系焊料粒子等。它們可以單独使用1種，可以並用2種以上。這些之中，優選為包含Sn以及選自Bi、Ag、Cu和In中的至少1種的焊料粒子，更優選為Sn-Bi系焊料粒子、Sn-Bi-Ag系焊料粒子、Sn-Ag-Cu系焊料粒子、Sn-In系焊料粒子，從熔點的觀點考慮，進一步優選為Sn-Bi系焊料粒子、Sn-Bi-Ag系焊料粒子。Examples of the solder particles include Sn-Pb solder particles, Pb-Sn-Sb solder particles, Sn-Sb solder particles, Sn-Pb-Bi solder particles, Sn-Bi solder particles, Sn-Bi-Ag solder particles, Sn-Cu solder particles, Sn-Pb-Cu solder particles, Sn-In solder particles, Sn-Ag solder particles, Sn-Pb-Ag solder particles, Pb-Ag solder particles, Sn-Ag-Cu solder particles, etc. These may be used alone or in combination of two or more. Among these, preferred are solder particles containing Sn and at least one selected from Bi, Ag, Cu and In, more preferred are Sn-Bi solder particles, Sn-Bi-Ag solder particles, Sn-Ag-Cu solder particles, and Sn-In solder particles, and from the perspective of melting point, Sn-Bi solder particles and Sn-Bi-Ag solder particles are further preferred.
作為低熔點金屬粒子的形狀，沒有特別限制，能夠根據目的適當選擇，可舉出例如，球狀、扁平狀、粒狀、針狀等。The shape of the low-melting-point metal particles is not particularly limited and can be appropriately selected depending on the purpose. For example, spherical, flat, granular, needle-like, etc. can be cited.
低熔點金屬粒子的熔點優選為100℃～250℃，更優選為120℃～200℃。The melting point of the low-melting-point metal particles is preferably 100°C to 250°C, more preferably 120°C to 200°C.
從在導熱組合物的固化物中，通過熔融的低熔點金屬粒子而藉由導熱粒子能夠形成網路(金屬的連續相)，能夠實現高導熱率方面考慮，優選低熔點金屬粒子的熔點比導熱組合物的熱固化處理溫度低。In order to achieve high thermal conductivity by forming a network (continuous phase of metal) through the melted low-melting-point metal particles in the cured thermally conductive composition, the melting point of the low-melting-point metal particles is preferably lower than the heat curing temperature of the thermally conductive composition.
低熔點金屬粒子在導熱組合物的熱固化處理條件下與上述導熱粒子進行反應，製成顯示比低熔點金屬粒子高的熔點的合金，從而能夠防止高溫下的熔融，可靠性提高。此外，導熱組合物的固化物的耐熱性提高。The low melting point metal particles react with the above-mentioned heat conductive particles under the heat curing treatment conditions of the heat conductive composition to produce an alloy showing a higher melting point than the low melting point metal particles, thereby preventing melting at high temperatures and improving reliability. In addition, the heat resistance of the cured product of the heat conductive composition is improved.
導熱組合物的熱固化處理例如，以150℃～200℃的溫度在30分鐘～2小時以下的條件下進行。The heat curing treatment of the thermally conductive composition is performed, for example, at a temperature of 150° C. to 200° C. for 30 minutes to 2 hours.
低熔點金屬粒子的體積平均粒徑優選為10μm以下，更優選為1μm～5μm。如果低熔點金屬粒子的體積平均粒徑為10μm以下，則能夠減小低熔點金屬粒子相對於導熱粒子的體積比例，能夠實現高導熱率。另外，低熔點金屬粒子的體積平均粒徑能夠與上述導熱粒子的體積平均粒徑同樣地操作來測定。The volume average particle size of the low melting point metal particles is preferably 10 μm or less, and more preferably 1 μm to 5 μm. If the volume average particle size of the low melting point metal particles is 10 μm or less, the volume ratio of the low melting point metal particles to the thermally conductive particles can be reduced, and high thermal conductivity can be achieved. In addition, the volume average particle size of the low melting point metal particles can be measured in the same manner as the volume average particle size of the thermally conductive particles described above.
導熱粒子的體積平均粒徑比低熔點金屬粒子的體積平均粒徑大，導熱粒子與低熔點金屬粒子的體積平均粒徑比優選為2以上，更優選為3以上，進一步優選為5以上。體積平均粒徑比的上限值優選為20以下，更優選為10以下。The volume average particle size of the thermally conductive particles is larger than that of the low melting point metal particles, and the volume average particle size ratio of the thermally conductive particles to the low melting point metal particles is preferably 2 or more, more preferably 3 or more, and further preferably 5 or more. The upper limit of the volume average particle size ratio is preferably 20 or less, and more preferably 10 or less.
藉由使用與導熱粒子相比體積平均粒徑小的低熔點金屬粒子，從而導熱組合物中的導熱粒子成為主成分，導熱粒子與導熱粒子之間存在的低熔點金屬粒子由於加熱而熔融，與導熱粒子合金化以形成網路，因此能夠實現高導熱率。By using low-melting-point metal particles having a smaller average particle size than the thermally conductive particles, the thermally conductive particles in the thermally conductive composition become the main component, and the low-melting-point metal particles between the thermally conductive particles are melted by heating and alloyed with the thermally conductive particles to form a network, thereby achieving high thermal conductivity.
導熱組合物中的導熱粒子與低熔點金屬粒子的體積比優選為1以上，更優選為1.5以上，進一步優選為2以上。體積比的上限值優選為5以下，更優選為4以下，進一步優選為3以下。如果體積比為1以上，則與低熔點金屬粒子相比體積平均粒徑大的導熱粒子的體積比例增多，因此能夠抑制熔融的低熔點金屬粒子的流動。此外，低熔點金屬粒子即使對於不易潤濕的界面(例如，鋁)也難以發生分離，因此能夠抑制界面的材質的影響，界面材質的選擇性提高。The volume ratio of the thermally conductive particles to the low-melting-point metal particles in the thermally conductive composition is preferably 1 or more, more preferably 1.5 or more, and further preferably 2 or more. The upper limit of the volume ratio is preferably 5 or less, more preferably 4 or less, and further preferably 3 or less. If the volume ratio is 1 or more, the volume ratio of the thermally conductive particles having a larger volume average particle size than the low-melting-point metal particles increases, thereby suppressing the flow of the molten low-melting-point metal particles. In addition, the low-melting-point metal particles are difficult to separate even at an interface that is not easily wetted (for example, aluminum), thereby suppressing the influence of the material of the interface and improving the selectivity of the interface material.
(其它成分) 本實施方式涉及的導熱組合物優選含有固化成分和固化劑，進一步根據需要，只要不損害本實施方式的效果，可以包含其它成分。作為其它成分，沒有特別限制，能夠根據目的適當選擇，可舉出例如，金屬以外的導熱粒子(例如，氮化鋁、氧化鋁、碳纖維等)、添加劑(例如，抗氧化劑、紫外線吸收劑、固化促進劑、矽烷偶聯劑、流平劑、阻燃劑等)等。 (Other components) The thermally conductive composition involved in this embodiment preferably contains a curing component and a curing agent, and may further contain other components as needed, as long as the effect of this embodiment is not impaired. As other components, there is no particular limitation, and they can be appropriately selected according to the purpose, and examples thereof include thermally conductive particles other than metals (for example, aluminum nitride, aluminum oxide, carbon fiber, etc.), additives (for example, antioxidants, ultraviolet absorbers, curing accelerators, silane coupling agents, leveling agents, flame retardants, etc.), etc.
-固化成分- 作為固化成分，優選使用環氧乙烷環化合物和氧雜環丁烷化合物的至少任一者。 -Curing component- As the curing component, it is preferred to use at least one of an oxirane cyclic compound and an oxirane cyclobutane compound.
--環氧乙烷環化合物-- 上述環氧乙烷環化合物為具有環氧乙烷環的化合物，可舉出例如，環氧樹脂等。 --Oxyethylene oxide ring compound-- The above-mentioned oxirane ring compound is a compound having an oxirane ring, and examples thereof include epoxy resins, etc.
作為環氧樹脂，沒有特別限制，能夠根據目的適當選擇，可舉出例如，縮水甘油基醚型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、雙酚A型環氧樹脂、三苯酚型環氧樹脂、四苯酚型環氧樹脂、苯酚-苯二亞甲基型環氧樹脂、萘酚-苯二亞甲基型環氧樹脂、苯酚-萘酚型環氧樹脂、苯酚-二環戊二烯型環氧樹脂、脂環式環氧樹脂、脂肪族環氧樹脂等。它們可以單独使用1種，可以並用2種以上。The epoxy resin is not particularly limited and can be appropriately selected according to the purpose, and examples thereof include glycidyl ether type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A type epoxy resins, trisphenol type epoxy resins, tetraphenol type epoxy resins, phenol-xylylene type epoxy resins, naphthol-xylylene type epoxy resins, phenol-naphthol type epoxy resins, phenol-dicyclopentadiene type epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. These may be used alone or in combination of two or more.
--氧雜環丁烷化合物-- 氧雜環丁烷化合物為具有氧雜環丁烷基的化合物，可以為脂肪族化合物、脂環式化合物或芳香族化合物。 --Oxycyclobutane compounds-- Oxycyclobutane compounds are compounds with an oxycyclobutane group, and can be aliphatic compounds, alicyclic compounds or aromatic compounds.
氧雜環丁烷化合物可以為僅僅具有1個氧雜環丁烷基的1官能的氧雜環丁烷化合物，可以為具有2個以上氧雜環丁烷基的多官能的氧雜環丁烷化合物。The oxycyclobutane compound may be a monofunctional oxycyclobutane compound having only one oxycyclobutane group, or may be a polyfunctional oxycyclobutane compound having two or more oxycyclobutane groups.
作為氧雜環丁烷化合物，沒有特別限制，能夠根據目的適當選擇，可舉出例如，3,7-雙(3-氧雜環丁烷基)-5-氧雜-壬烷、1,4-雙((3-乙基-3-氧雜環丁烷基甲氧基)甲基)苯、1,2-雙((3-乙基-3-氧雜環丁烷基甲氧基)甲基)乙烷、1,3-雙((3-乙基-3-氧雜環丁烷基甲氧基)甲基)丙烷、乙二醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、三甘醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、四甘醇雙(3-乙基-3-氧雜環丁烷基甲基)醚、1,4-雙(3-乙基-3-氧雜環丁烷基甲氧基)丁烷、1,6-雙(3-乙基-3-氧雜環丁烷基甲氧基)己烷、3-乙基-3-(苯氧基)甲基氧雜環丁烷、3-乙基-3-(環己基氧基甲基)氧雜環丁烷、3-乙基-3-(2-乙基己基氧基甲基)氧雜環丁烷、3-乙基-3-羥基甲基氧雜環丁烷、3-乙基-3-(氯甲基)氧雜環丁烷、3-乙基-3｛((3-乙基氧雜環丁烷-3-基)甲氧基)甲基｝氧雜環丁烷、苯二亞甲基雙氧雜環丁烷、4,4′-雙((3-乙基-3-氧雜環丁烷基)甲氧基甲基)聯苯(OXBP)等。它們可以單独使用1種，可以並用2種以上。The oxacyclobutane compound is not particularly limited and can be appropriately selected according to the purpose. For example, 3,7-bis(3-oxacyclobutane)-5-oxa-nonane, 1,4-bis((3-ethyl-3-oxacyclobutanemethoxy)methyl)benzene, 1,2-bis((3-ethyl-3-oxacyclobutanemethoxy)methyl )ethane, 1,3-bis((3-ethyl-3-oxocyclobutanemethyloxy)methyl)propane, ethylene glycol bis(3-ethyl-3-oxocyclobutanemethyl)ether, triethylene glycol bis(3-ethyl-3-oxocyclobutanemethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxocyclobutanemethyl)ether, 1,4-bis(3-ethyl-3-oxocyclobutanemethyloxy)butane, 1,6-bis(3-ethyl-3-oxocyclobutanemethyloxy)hexane, 3-ethyl-3-(phenoxy)methyloxycyclobutane, 3-ethyl-3-(cyclohexyloxymethyl)oxycyclobutane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxycyclobutane, 3-ethyl-3 -hydroxymethyl cyclohexane, 3-ethyl-3-(chloromethyl)cyclohexane, 3-ethyl-3{((3-ethylcyclohexane-3-yl)methoxy)methyl}cyclohexane, xylylenebiscyclohexane, 4,4′-bis((3-ethyl-3-cyclohexane-butane-methoxymethyl)biphenyl (OXBP), etc. These may be used alone or in combination of two or more.
作為氧雜環丁烷化合物，能夠使用市售品，作為市售品，可舉出例如，由東亞合成株式會社銷售的「ARONE OXETANE(注冊商標)」系列、由宇部興產株式會社銷售的「ETERNACOLL(注冊商標)」系列等。As the oxacyclobutane compound, a commercially available product can be used. Examples of the commercially available product include the "ARONE OXETANE (registered trademark)" series sold by Toagosei Co., Ltd. and the "ETERNACOLL (registered trademark)" series sold by Ube Industries, Ltd.
環氧乙烷環化合物和氧雜環丁烷化合物之中，優選為縮水甘油基醚型環氧樹脂、苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、苯酚-二環戊二烯型環氧樹脂、雙酚A型環氧樹脂、脂肪族環氧樹脂、4,4′-雙((3-乙基-3-氧雜環丁烷基)甲氧基甲基)聯苯(OXBP)。Among the ethylene oxide cyclic compounds and oxycyclobutane compounds, preferred are glycidyl ether type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, phenol-dicyclopentadiene type epoxy resins, bisphenol A type epoxy resins, aliphatic epoxy resins, and 4,4′-bis((3-ethyl-3-oxycyclobutane)methoxymethyl)biphenyl (OXBP).
固化成分的含量沒有特別限制，能夠根據目的適當選擇，相對於導熱粒子含有層的總量，優選為0.5質量%～60質量%。The content of the curing component is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.5 mass % to 60 mass % relative to the total amount of the thermally conductive particle-containing layer.
-固化劑- 作為固化劑，為與上述固化成分對應的固化劑，可舉出例如，酸酐系固化劑、脂肪族胺系固化劑、芳香族胺系固化劑、苯酚系固化劑、硫醇系固化劑等加聚型固化劑、咪唑等觸媒型固化劑等。它們可以單独使用1種，可以並用2種以上。這些之中，優選為酸酐系固化劑。酸酐系固化劑在固化成分為環氧樹脂的情況下，熱固化時沒有氣體的發生，與環氧樹脂混合時能夠實現長的儲存期，此外，從能夠實現所得的固化物的電特性、化學的特性和機械特性間的良好的平衡的方面考慮，是優選的。 -Curing agent- As the curing agent, for example, a curing agent corresponding to the above-mentioned curing component can be cited, such as anhydride curing agents, aliphatic amine curing agents, aromatic amine curing agents, phenol curing agents, thiol curing agents and other addition-type curing agents, imidazole and other catalytic curing agents, etc. They can be used alone or in combination of two or more. Among these, anhydride curing agents are preferred. When the curing component is an epoxy resin, anhydride curing agents do not generate gas during thermal curing, and can achieve a long storage period when mixed with an epoxy resin. In addition, they are preferred from the perspective of being able to achieve a good balance between the electrical properties, chemical properties and mechanical properties of the resulting cured product.
作為酸酐系固化劑，可舉出例如，環己烷-1,2-二羧酸酐、三羧酸的單酸酐等。作為三羧酸的單酸酐，可舉出例如，環己烷-1,2,4-三羧酸-1,2-酸酐等。Examples of the acid anhydride curing agent include cyclohexane-1,2-dicarboxylic anhydride and tricarboxylic acid monoanhydride. Examples of tricarboxylic acid monoanhydride include cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride.
固化劑具有助焊劑活性，從提高相對於導熱粒子的熔融的低熔點金屬粒子的潤濕性方面考慮是優選的。作為固化劑表現助焊劑活性的方法，可舉出例如，對於固化劑利用公知的方法導入羧基、磺醯基、磷酸基等質子酸基的方法等。這些之中，從與作為固化成分的環氧樹脂或氧雜環丁烷化合物的反應性方面考慮，優選導入羧基，可舉出例如，戊二酸、琥珀酸等含有羧基的有機酸等。此外，可以為由戊二酸酐或琥珀酸酐改性的化合物或戊二酸銀等有機酸的金屬鹽等。The curing agent has flux activity, and is preferred from the perspective of improving the wettability of the molten low-melting-point metal particles relative to the thermally conductive particles. As a method for the curing agent to exhibit flux activity, for example, a method of introducing a protonic acid group such as a carboxyl group, a sulfonyl group, or a phosphoric acid group into the curing agent by a known method can be cited. Among these, from the perspective of reactivity with epoxy resins or cyclohexane compounds as curing components, it is preferred to introduce a carboxyl group, and for example, organic acids containing a carboxyl group such as glutaric acid and succinic acid can be cited. In addition, it can be a compound modified by glutaric anhydride or succinic anhydride, or a metal salt of an organic acid such as silver glutarate.
固化劑的含量沒有特別限制，能夠根據目的適當選擇，相對於導熱組合物的總量，優選為0.1質量%～30質量%。The content of the curing agent is not particularly limited and can be appropriately selected according to the purpose, but is preferably 0.1 mass % to 30 mass % relative to the total amount of the thermally conductive composition.
固化成分與固化劑的莫耳当量基準的当量比根據使用的固化成分和固化劑的種類而不同，不能籠統地規定，優選為0.5～3.0，更優選為0.5～2.0，進一步優選為0.7～1.5。如果当量比為0.5～3.0，則具有導熱組合物的熱固化時，低熔點金屬粒子充分地熔融而能夠形成網路這樣的優點。The equivalent ratio of the curing component to the curing agent on a molar equivalent basis varies depending on the types of the curing component and curing agent used and cannot be generally specified, but is preferably 0.5 to 3.0, more preferably 0.5 to 2.0, and further preferably 0.7 to 1.5. If the equivalent ratio is 0.5 to 3.0, it has the advantage that the low-melting-point metal particles are sufficiently melted during the heat curing of the thermally conductive composition to form a network.
-聚合物- 本實施方式涉及的導熱組合物為了賦予柔軟性等，優選含有聚合物。作為聚合物，沒有特別限制，能夠根據目的適當選擇，可舉出例如，分子内具有選自聚丁二烯結構、聚矽氧烷結構、聚(甲基)丙烯酸酯結構、聚亞烷基結構、聚亞烷基氧基結構、聚異戊二烯結構、聚異丁烯結構、聚醯胺結構、聚碳酸酯結構中的至少1種結構的聚合物等。 -Polymer- The thermally conductive composition involved in this embodiment preferably contains a polymer in order to impart flexibility, etc. The polymer is not particularly limited and can be appropriately selected according to the purpose. For example, a polymer having at least one structure selected from a polybutadiene structure, a polysiloxane structure, a poly(meth)acrylate structure, a polyalkylene structure, a polyalkyleneoxy structure, a polyisoprene structure, a polyisobutylene structure, a polyamide structure, and a polycarbonate structure in the molecule can be cited.
聚合物的含量相對於導熱組合物的總量，優選為1質量%～50質量%，更優選為1質量%～30質量%，進一步優選為1質量%～10質量%。The content of the polymer is preferably 1% to 50% by mass, more preferably 1% to 30% by mass, and further preferably 1% to 10% by mass, relative to the total amount of the thermally conductive composition.
＜導熱組合物的製造方法＞ 說明本實施方式涉及的導熱組合物的製造方法的一例。本實施方式涉及的導熱組合物的製造方法中，將包含揮發成分的熱塑性樹脂和包含揮發成分的松香系樹脂***帶有夾套的燒瓶中，在作為非活性氣體氣氛的狀態下一邊加熱一邊混合預定時間，製作第1混合物(樹脂混合工序)。 <Method for producing a thermally conductive composition> An example of a method for producing a thermally conductive composition according to the present embodiment is described. In the method for producing a thermally conductive composition according to the present embodiment, a thermoplastic resin containing a volatile component and a rosin-based resin containing a volatile component are inserted into a jacketed flask, and the mixture is mixed for a predetermined time while being heated in an inert gas atmosphere to produce a first mixture (resin mixing step).
非活性氣體能夠使用氮氣、氬氣等。As the inert gas, nitrogen, argon, etc. can be used.
加熱溫度優選為100℃～150℃，更優選為115℃～145℃，進一步優選為125℃～140℃。The heating temperature is preferably 100°C to 150°C, more preferably 115°C to 145°C, and further preferably 125°C to 140°C.
加熱時間優選為5分鐘～1小時，更優選為10分鐘～40分鐘，進一步優選為20分鐘～30分鐘。The heating time is preferably 5 minutes to 1 hour, more preferably 10 minutes to 40 minutes, and further preferably 20 minutes to 30 minutes.
作為熱塑性樹脂與松香系樹脂的混合方法，能夠使用利用攪拌葉片的攪拌等。As a method for mixing the thermoplastic resin and the rosin-based resin, stirring using a stirring blade or the like can be used.
接下來，在第1混合物中混合導熱粒子和低熔點金屬粒子，製作第2混合物(粒子混合工序)。Next, thermally conductive particles and low-melting-point metal particles are mixed into the first mixture to prepare a second mixture (particle mixing step).
第1混合物與導熱粒子和低熔點金屬粒子的混合方法與上述同樣，能夠使用利用攪拌葉片的攪拌等。The method of mixing the first mixture with the thermally conductive particles and the low-melting-point metal particles is the same as described above, and stirring using a stirring blade or the like can be used.
在第1混合物中混合導熱粒子和低熔點金屬粒子時，與樹脂混合工序同樣，可以在非活性氣體氣氛下一邊加熱一邊混合。非活性氣體能夠使用與上述樹脂混合工序同樣的非活性氣體。加熱溫度和加熱時間可以適當調製，可以設為與上述樹脂混合工序同樣的加熱溫度和加熱時間。When the thermally conductive particles and the low melting point metal particles are mixed in the first mixture, the mixture may be mixed while being heated in an inert gas atmosphere, similarly to the resin mixing step. The inert gas may be the same inert gas as in the resin mixing step. The heating temperature and heating time may be appropriately adjusted and may be the same as in the resin mixing step.
接下來，將第2混合物在熱塑性樹脂和松香系樹脂的熔點以上的溫度一邊加熱處理一邊成型為膜狀，製作具有膜狀的形狀的導熱組合物(加熱成型工序)。Next, the second mixture is molded into a film while being heat-treated at a temperature not lower than the melting point of the thermoplastic resin and the rosin-based resin, thereby producing a thermally conductive composition having a film shape (heat molding step).
第2混合物的成型可以使用加熱至預定的加熱溫度的壓制装置來進行。加熱溫度可以設為與上述的樹脂混合工序同樣的加熱溫度。第2混合物可以在設置於壓制装置的具有預定的形狀的大小的離形膜上，一定量灌注，利用縫隙規夾持，以預定的壓力(例如，3.3MPa(0.6MPa的空氣壓))，預定時間(例如，5分鐘)加熱壓着而成型。The second mixture can be molded using a press device heated to a predetermined heating temperature. The heating temperature can be set to the same heating temperature as the resin mixing step described above. The second mixture can be molded by pouring a certain amount of it on a release film of a predetermined shape and size set in the press device, clamping it with a slit gauge, and heating and pressing it at a predetermined pressure (for example, 3.3 MPa (0.6 MPa air pressure)) for a predetermined time (for example, 5 minutes).
獲得的導熱組合物的主表面處的揮發成分的含量為5.0wt%以下。The content of volatile components on the main surface of the obtained thermally conductive composition is 5.0 wt % or less.
由此，獲得形成為片狀的本實施方式涉及的導熱組合物。Thus, the thermally conductive composition according to the present embodiment formed into a sheet shape is obtained.
這樣，本實施方式涉及的導熱組合物包含熱塑性樹脂、松香系樹脂、導熱粒子和低熔點金屬粒子，使熱塑性樹脂和松香系樹脂所包含的揮發成分的合計的含量為5.0wt%以下。本實施方式涉及的導熱組合物使揮發成分的合計的含量為5.0wt%以下，從而能夠抑制作為母材的熱塑性樹脂和松香系樹脂中所包含的間隙的量。本實施方式涉及的導熱組合物能夠抑制塗佈於基材時與基材的接触面所存在的揮發成分的量。因此，本實施方式涉及的導熱組合物在將導熱組合物加熱以使其固化時，能夠抑制由於揮發成分而產生的空隙的發生。由此，本實施方式涉及的導熱組合物在固化時，抑制基材與導熱組合物的固化物的界面所存在的空隙的發生，能夠實現高導熱率。Thus, the thermally conductive composition involved in the present embodiment includes a thermoplastic resin, a rosin-based resin, thermally conductive particles, and low-melting-point metal particles, so that the total content of volatile components contained in the thermoplastic resin and the rosin-based resin is 5.0wt% or less. The thermally conductive composition involved in the present embodiment makes the total content of volatile components less than 5.0wt%, thereby being able to suppress the amount of gaps contained in the thermoplastic resin and the rosin-based resin as the base material. The thermally conductive composition involved in the present embodiment is able to suppress the amount of volatile components present on the contact surface with the substrate when applied to the substrate. Therefore, when the thermally conductive composition involved in the present embodiment is heated to cure the thermally conductive composition, the occurrence of gaps caused by volatile components can be suppressed. Thus, when the thermally conductive composition according to the present embodiment is cured, the generation of voids at the interface between the substrate and the cured product of the thermally conductive composition is suppressed, thereby achieving high thermal conductivity.
本實施方式涉及的導熱組合物能夠使熱塑性樹脂和松香系樹脂的熔點為低熔點金屬粒子的熔點以下。在將本實施方式涉及的導熱組合物進行加熱處理時，熱塑性樹脂和松香系樹脂與低熔點金屬粒子快地熔融，因此低熔點金屬粒子能夠以維持粒子的狀態的狀態包含於熱塑性樹脂和松香系樹脂中。由此，本實施方式涉及的導熱組合物即使加熱處理，也能夠將低熔點金屬粒子以粒子狀的狀態分散於熱塑性樹脂和松香系樹脂中而包含，因此能夠更確實地具有高導熱率。The thermally conductive composition of the present embodiment can make the melting point of the thermoplastic resin and the rosin-based resin lower than the melting point of the low-melting-point metal particles. When the thermally conductive composition of the present embodiment is subjected to heat treatment, the thermoplastic resin and the rosin-based resin and the low-melting-point metal particles melt quickly, so that the low-melting-point metal particles can be contained in the thermoplastic resin and the rosin-based resin in a state of maintaining the particle state. Therefore, even if the thermally conductive composition of the present embodiment is subjected to heat treatment, the low-melting-point metal particles can be dispersed in the thermoplastic resin and the rosin-based resin in a particle state and contained, so that it can have a higher thermal conductivity more reliably.
本實施方式涉及的導熱組合物能夠使熱塑性樹脂和松香系樹脂的熔點為110℃～140℃。如果將本實施方式涉及的導熱組合物在110℃～140℃進行加熱處理，則熱塑性樹脂和松香系樹脂能夠確實地熔融，在熱塑性樹脂和松香系樹脂中包含低熔點金屬粒子。由此，本實施方式涉及的導熱組合物如果在110℃～140℃進行加熱處理，則能夠將低熔點金屬粒子以粒子狀的狀態分散於熱塑性樹脂和松香系樹脂中而包含，因此能夠確實地具有高導熱率。The thermally conductive composition of the present embodiment can make the melting point of the thermoplastic resin and the rosin-based resin be 110°C to 140°C. If the thermally conductive composition of the present embodiment is heated at 110°C to 140°C, the thermoplastic resin and the rosin-based resin can be surely melted, and the low-melting-point metal particles can be contained in the thermoplastic resin and the rosin-based resin. Therefore, if the thermally conductive composition of the present embodiment is heated at 110°C to 140°C, the low-melting-point metal particles can be dispersed in the thermoplastic resin and the rosin-based resin in a particle state and contained, so that it can surely have a high thermal conductivity.
本實施方式涉及的導熱組合物中，作為熱塑性樹脂，能夠使用選自由聚醯胺系樹脂、聚酯系樹脂、聚氨酯系樹脂、聚烯烴系樹脂、苯氧基系樹脂所組成的組中的1種以上的成分。本實施方式涉及的導熱組合物藉由作為熱塑性樹脂包含上述成分，從而加熱處理時，熱塑性樹脂能夠變得柔軟。由此，本實施方式涉及的導熱組合物進行加熱處理，從而能夠將低熔點金屬粒子以分散於熱塑性樹脂和松香系樹脂中的狀態而包含，能夠確實地發揮導熱率。In the thermally conductive composition of the present embodiment, as the thermoplastic resin, one or more components selected from the group consisting of polyamide resins, polyester resins, polyurethane resins, polyolefin resins, and phenoxy resins can be used. The thermally conductive composition of the present embodiment contains the above components as a thermoplastic resin, so that the thermoplastic resin can become soft when heat-treated. Therefore, the thermally conductive composition of the present embodiment can contain low-melting-point metal particles in a state of being dispersed in the thermoplastic resin and the rosin resin by heat treatment, and can surely exert thermal conductivity.
本實施方式涉及的導熱組合物中，松香系樹脂能夠使用松香和改性松香的至少任一者。本實施方式涉及的導熱組合物作為松香系樹脂包含上述成分，從而在加熱處理時，松香系樹脂能夠變得柔軟。由此，本實施方式涉及的導熱組合物進行加熱處理，從而能夠將低熔點金屬粒子以分散於熱塑性樹脂和松香系樹脂中的狀態而包含，能夠確實地發揮導熱率。In the thermally conductive composition of the present embodiment, the rosin-based resin can use at least one of rosin and modified rosin. The thermally conductive composition of the present embodiment contains the above-mentioned components as the rosin-based resin, so that the rosin-based resin can become soft during heat treatment. Therefore, the thermally conductive composition of the present embodiment can contain low-melting-point metal particles in a state of being dispersed in the thermoplastic resin and the rosin-based resin by heat treatment, and can surely exert thermal conductivity.
本實施方式涉及的導熱組合物中，導熱粒子能夠使用銅粒子、銀被覆粒子和銀粒子的至少任一者。由此，導熱粒子能夠確實地發揮導電性，因此本實施方式涉及的導熱組合物能夠確實地實現導熱率。In the thermally conductive composition according to the present embodiment, the thermally conductive particles can be at least one of copper particles, silver-coated particles, and silver particles. As a result, the thermally conductive particles can reliably exhibit electrical conductivity, and thus the thermally conductive composition according to the present embodiment can reliably achieve thermal conductivity.
本實施方式涉及的導熱組合物中，低熔點金屬粒子能夠使用包含Sn以及選自Bi、Ag、Cu、和In中的至少1種的粒子。由此，低熔點金屬粒子能夠確實地發揮導電性，因此本實施方式涉及的導熱組合物能夠確實地實現導熱率。In the thermally conductive composition according to the present embodiment, the low-melting-point metal particles can be particles containing Sn and at least one selected from Bi, Ag, Cu, and In. As a result, the low-melting-point metal particles can reliably exhibit electrical conductivity, and thus the thermally conductive composition according to the present embodiment can reliably achieve thermal conductivity.
本實施方式涉及的導熱組合物能夠使導熱粒子的體積平均粒徑為1μm～100μm。由此，本實施方式涉及的導熱組合物能夠提高導熱粒子相對於低熔點金屬粒子的體積比例，因此本實施方式涉及的導熱組合物能夠進一步確實地具有高導熱率。The thermally conductive composition of the present embodiment can make the volume average particle size of the thermally conductive particles be 1 μm to 100 μm. Therefore, the thermally conductive composition of the present embodiment can increase the volume ratio of the thermally conductive particles relative to the low melting point metal particles, so the thermally conductive composition of the present embodiment can further reliably have a high thermal conductivity.
本實施方式涉及的導熱組合物能夠使低熔點金屬粒子的體積平均粒徑為10μm以下。由此，能夠提高導熱粒子相對於低熔點金屬粒子的體積比例，因此本實施方式涉及的導熱組合物能夠確實地具有導熱率。The thermally conductive composition according to the present embodiment can make the volume average particle size of the low melting point metal particles be 10 μm or less. This can increase the volume ratio of the thermally conductive particles to the low melting point metal particles, so that the thermally conductive composition according to the present embodiment can have a reliable thermal conductivity.
＜導熱片＞ 使用附圖說明包含本實施方式涉及的導熱組合物的固化物的導熱片。另外，為了使說明的理解變得容易，各附圖中，對於同一構成要素附上同一符號，有時省略重複的說明。此外，附圖中的各構件的比例尺有時與實時不同。進一步，下述構成構件的數目、位置、形狀等不限定於本實施方式，能夠在實施本實施方式的基礎上，設為優選的數目、位置、形狀等。 <Thermal Conductive Sheet> The thermal conductive sheet of the cured product of the thermal conductive composition according to the present embodiment is described using the attached drawings. In addition, in order to facilitate the understanding of the description, the same symbol is attached to the same component in each attached drawing, and repeated descriptions are sometimes omitted. In addition, the scale of each component in the attached drawings is sometimes different from that in real time. Furthermore, the number, position, shape, etc. of the following components are not limited to the present embodiment, and can be set to a preferred number, position, shape, etc. based on the implementation of the present embodiment.
圖1為表示導熱片的構成的一例的斷面圖。圖1所示那樣，導熱片10從第1基材11側依次層疊而具備第1基材11、導熱粒子含有層12和第2基材13。另外，導熱片10將導熱粒子含有層12和第2基材13作為一組，可以在第2基材13的上進一步層疊1層以上而具備，進一步根據需要可以具有其它構件。以下的說明中，為了說明的方便，將第2基材13側設為上，將第1基材11側設為下，不表示普遍的上下關係。FIG. 1 is a cross-sectional view showing an example of the structure of a thermally conductive sheet. As shown in FIG. 1 , the thermally conductive sheet 10 includes the first substrate 11, the thermally conductive particle-containing layer 12, and the second substrate 13, which are stacked in order from the first substrate 11 side. In addition, the thermally conductive sheet 10 includes the thermally conductive particle-containing layer 12 and the second substrate 13 as a set, and may further include one or more layers stacked on the second substrate 13, and may further include other components as needed. In the following description, for the convenience of explanation, the second substrate 13 side is set as the upper side and the first substrate 11 side is set as the lower side, which does not represent a general upper and lower relationship.
[第1基材] 第1基材11的形狀、結構、大小、材質等沒有特別限制，能夠根據目的適當選擇。 [First substrate] The shape, structure, size, material, etc. of the first substrate 11 are not particularly limited and can be appropriately selected according to the purpose.
作為第1基材11的形狀，可舉出例如，板狀、片狀等。作為第1基材11的結構，可舉出單層結構、層疊結構等。第1基材11的大小能夠根據用途等適當選擇。Examples of the shape of the first substrate 11 include a plate shape, a sheet shape, etc. Examples of the structure of the first substrate 11 include a single layer structure, a stacked structure, etc. The size of the first substrate 11 can be appropriately selected according to the application, etc.
第1基材11的材質為焊料不易潤濕的材質，可舉出矽(Si)、鋁、鎢、鉬、玻璃、模塑樹脂、不鏽鋼、陶瓷等。它們可以單独使用1種，可以並用2種以上。作為陶瓷，可舉出例如，氮化鋁、炭化矽、氧化鋁、氮化鎵等。作為上述模塑樹脂，可舉出例如，環氧樹脂、有機矽樹脂、氨基甲酸酯樹脂、丙烯酸系樹脂等。這些之中，作為第1基材11的材質，矽(Si)或玻璃是適合的。The material of the first substrate 11 is a material that is not easily wetted by solder, and examples thereof include silicon (Si), aluminum, tungsten, molybdenum, glass, molding resin, stainless steel, and ceramics. They may be used alone or in combination of two or more. Examples of ceramics include aluminum nitride, silicon carbide, aluminum oxide, and gallium nitride. Examples of the above-mentioned molding resins include epoxy resins, organic silicone resins, urethane resins, and acrylic resins. Among these, silicon (Si) or glass is suitable as the material of the first substrate 11.
第1基材11的平均厚度沒有特別限制，能夠根據目的適當選擇。The average thickness of the first substrate 11 is not particularly limited and can be appropriately selected according to the purpose.
第1基材11可以為放熱結構體中的發熱體(電子部件)自身。The first substrate 11 may be the heat generating body (electronic component) itself in the heat dissipating structure.
[導熱粒子含有層] 圖1所示那樣，導熱粒子含有層12為設置於第1基材11的上面，由本實施方式涉及的導熱組合物的固化物形成的層。 [Thermal Conductive Particle-Containing Layer] As shown in FIG. 1 , the thermally conductive particle-containing layer 12 is a layer provided on the first substrate 11 and formed of a cured product of the thermally conductive composition involved in this embodiment.
導熱粒子含有層12的主表面處的空隙面積的比例優選為20%以下，更優選為15%以下，進一步優選為10%以下。導熱粒子含有層12的主表面為導熱粒子含有層12與第1基材11的上面和第2基材13的下面的界面。如果導熱粒子含有層12的主表面處的空隙面積的比例為20%以下，則易於將導熱粒子含有層12從第1基材11或第2基材13的一方的基材傳導的熱沿著導熱粒子含有層12的厚度方向而朝向另一方的基材而傳達。The ratio of the void area at the main surface of the thermally conductive particle containing layer 12 is preferably 20% or less, more preferably 15% or less, and further preferably 10% or less. The main surface of the thermally conductive particle containing layer 12 is the interface between the thermally conductive particle containing layer 12 and the upper surface of the first substrate 11 and the lower surface of the second substrate 13. If the ratio of the void area at the main surface of the thermally conductive particle containing layer 12 is 20% or less, it is easy to transfer the heat conducted from the thermally conductive particle containing layer 12 from one of the first substrate 11 or the second substrate 13 to the other substrate along the thickness direction of the thermally conductive particle containing layer 12.
導熱粒子含有層12的平均厚度沒有特別限制，能夠根據目的適當選擇，優選為5μm～500μm，更優選為10μm～200μm，進一步優選為30μm～100μm。The average thickness of the thermally conductive particle-containing layer 12 is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 5 μm to 500 μm, more preferably 10 μm to 200 μm, and further preferably 30 μm to 100 μm.
(導熱粒子不含有層) 導熱粒子含有層12可以具有不含有導熱粒子的導熱粒子不含有層。導熱粒子不含有層在導熱粒子含有層12中優選具有至少1層，可以具有2層以上。 (Thermal Conductive Particle-Free Layer) The thermally conductive particle-containing layer 12 may include a thermally conductive particle-free layer that does not include thermally conductive particles. The thermally conductive particle-free layer preferably includes at least one layer in the thermally conductive particle-containing layer 12, and may include two or more layers.
在設置有複數層的導熱粒子含有層12的情況下，優選為導熱粒子含有層12彼此之間具有導熱粒子不含有層的方式。在該情況下，複數的導熱粒子含有層12可以為同一的組成，也可以為不同的組成。此外，複數的導熱粒子含有層12的平均厚度可以相同，也可以不同。When a plurality of thermally conductive particle-containing layers 12 are provided, it is preferred that a thermally conductive particle-free layer is provided between the thermally conductive particle-containing layers 12. In this case, the plurality of thermally conductive particle-containing layers 12 may have the same composition or different compositions. In addition, the average thickness of the plurality of thermally conductive particle-containing layers 12 may be the same or different.
導熱粒子不含有層其形狀、材質、結構、大小等沒有特別限制，能夠根據目的適當選擇。The thermally conductive particles do not contain any layer and their shape, material, structure, size, etc. are not particularly limited and can be appropriately selected according to the purpose.
作為導熱粒子不含有層的形狀，可舉出例如，箔狀、板狀、片狀等。Examples of the shape of the thermally conductive particles that do not include a layer include a foil shape, a plate shape, and a sheet shape.
作為導熱粒子不含有層的材質，優選為導熱率高，比較柔軟的材質，可舉出例如，銅、金、鉑、鈀、銀、鋅、鐵、錫、鎳、鎂、銦、或這些合金等。這些之中，優選為由上述金屬形成的金屬箔，從導熱率、穩定性和經濟性的觀點考慮，更優選為銅箔。As the material of the thermally conductive particles without a layer, a relatively soft material with high thermal conductivity is preferred, and examples thereof include copper, gold, platinum, palladium, silver, zinc, iron, tin, nickel, magnesium, indium, or alloys thereof. Among these, metal foils formed of the above metals are preferred, and copper foils are more preferred from the viewpoints of thermal conductivity, stability, and economy.
作為導熱粒子不含有層的結構，可舉出單層結構、層疊結構等。Examples of the structure in which the thermally conductive particles do not have a layer include a single-layer structure and a stacked structure.
作為導熱粒子不含有層的大小，能夠根據用途等適當選擇。The size of the thermally conductive particles does not include a layer, and can be appropriately selected according to the application, etc.
導熱粒子不含有層的平均厚度沒有特別限制，能夠根據目的適當選擇，優選為1μm～50μm，優選為5μm～30μm。The average thickness of the thermally conductive particle-free layer is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1 μm to 50 μm, more preferably 5 μm to 30 μm.
[第2基材] 圖1所示那樣，第2基材13與第1基材11對置而配置，其形狀、結構、大小、材質等沒有特別限制，能夠根據目的適當選擇。 [Second substrate] As shown in FIG. 1 , the second substrate 13 is arranged opposite to the first substrate 11. Its shape, structure, size, material, etc. are not particularly limited and can be appropriately selected according to the purpose.
作為第2基材13的形狀，可舉出例如，板狀、片狀等。Examples of the shape of the second substrate 13 include a plate shape and a sheet shape.
作為第2基材13的結構，可舉出單層結構、層疊結構等。As the structure of the second substrate 13, a single layer structure, a stacked structure, etc. can be cited.
作為第2基材13的大小，能夠根據用途等適當選擇。The size of the second substrate 13 can be appropriately selected according to the application, etc.
第2基材13的材質為焊料易於潤濕的材質，可舉出銅、金、鉑、鈀、銀、鋅、鐵、錫、鎳、鎂、銦、或這些合金等。它們可以單独使用1種，可以並用2種以上。這些之中，作為第2基材13的材質，銅是適合的。The material of the second substrate 13 is a material that is easily wetted by solder, and examples thereof include copper, gold, platinum, palladium, silver, zinc, iron, tin, nickel, magnesium, indium, or alloys thereof. One of these materials may be used alone, or two or more of these materials may be used in combination. Among these, copper is suitable as the material of the second substrate 13.
第2基材13的平均厚度沒有特別限制，能夠根據目的適當選擇。The average thickness of the second substrate 13 is not particularly limited and can be appropriately selected according to the purpose.
第2基材13可以為放熱結構體中的散熱器自身。The second substrate 13 may be the heat sink itself in the heat dissipation structure.
[其它構件] 作為其它構件，沒有特別限制，能夠根據目的適當選擇，可舉出例如，中間層、保護層等。 [Other components] As other components, there are no particular restrictions and they can be appropriately selected according to the purpose. For example, an intermediate layer, a protective layer, etc. can be cited.
本實施方式中，第1基材11和第2基材13的至少任一者與導熱粒子含有層12的界面處的空隙面積的比例優選小於20%，更優選為10%以下，進一步優選為5%以下。如果空隙面積的比例小於20%，則導熱粒子含有層12的面内的熱傳遞的偏差變小，能夠實現高導熱率。In the present embodiment, the ratio of the void area at the interface between at least one of the first substrate 11 and the second substrate 13 and the thermally conductive particle containing layer 12 is preferably less than 20%, more preferably 10% or less, and further preferably 5% or less. When the ratio of the void area is less than 20%, the deviation of heat transfer within the surface of the thermally conductive particle containing layer 12 becomes small, and high thermal conductivity can be achieved.
第1基材11和第2基材13的至少任一者與導熱粒子含有層12的界面處的空隙面積的比例例如，能夠如以下那樣來求出。 製作在Si基板(例如，30mm×30mm×2mm)與玻璃基板(例如，30mm×30mm×2mm)之間，設置有平均厚度100μm的導熱粒子含有層12的層疊體。從層疊體的玻璃基板側使用光學顯微鏡，將玻璃基板與導熱粒子含有層12的界面從玻璃基板側進行拍攝，獲得玻璃基板與導熱粒子含有層12的界面的圖像1。接下來，從層疊體的Si基板側使用紅外線顯微鏡，將Si基板與導熱粒子含有層的界面從Si基板側進行拍攝，獲得Si基板與導熱粒子含有層12的界面的圖像2。將所得的界面的圖像1和空隙的圖像2如以下那樣處理，從而算出空隙面積的比例(%)。 使用Microsoft公司製的Excel，將圖像1和圖像2以白黑50%(閾值128)進行二值化，作為位圖圖像進行保存。接下來，將製作的二值化位圖圖像作為二進製數據讀入Excel，取得圖像整體的像素數和白色部的像素數，藉由計數白色部的像素數/整體的像素數，從而算出空隙面積的比例(%)。另外，空隙的圖像1(玻璃基板)和空隙的圖像2(Si基板)中，採用空隙面積的比例多的一側的值。 The ratio of the void area at the interface between at least one of the first substrate 11 and the second substrate 13 and the thermally conductive particle-containing layer 12 can be obtained, for example, as follows. A stacked body having a thermally conductive particle-containing layer 12 with an average thickness of 100 μm is prepared between a Si substrate (e.g., 30 mm×30 mm×2 mm) and a glass substrate (e.g., 30 mm×30 mm×2 mm). An optical microscope is used to photograph the interface between the glass substrate and the thermally conductive particle-containing layer 12 from the glass substrate side of the stacked body, and an image 1 of the interface between the glass substrate and the thermally conductive particle-containing layer 12 is obtained. Next, an infrared microscope was used to photograph the interface between the Si substrate and the thermally conductive particle containing layer from the Si substrate side of the laminate, and an image 2 of the interface between the Si substrate and the thermally conductive particle containing layer 12 was obtained. The obtained image 1 of the interface and the image 2 of the void were processed as follows to calculate the ratio (%) of the void area. Using Excel made by Microsoft, images 1 and 2 were binarized at 50% black and white (threshold 128) and saved as bitmap images. Next, the binary bitmap image was read into Excel as binary data, the number of pixels of the entire image and the number of pixels of the white portion were obtained, and the ratio (%) of the void area was calculated by counting the number of pixels of the white portion/the number of pixels of the entire image. In addition, in the void image 1 (glass substrate) and the void image 2 (Si substrate), the value of the side with a larger void area ratio is adopted.
本實施方式涉及的導熱片10為使用由本實施方式涉及的導熱組合物形成的固化物以形成導熱粒子含有層12。由此，導熱片10能夠抑制導熱粒子含有層12與第1基材11或第2基材13的界面處的空隙的發生，因此能夠發揮高導熱率。由此，導熱片10能夠對於導熱片10的主面沿垂直方向(面間方向，即，導熱片10的厚度方向)穩定地傳導熱。The thermally conductive sheet 10 of the present embodiment uses a cured product formed from the thermally conductive composition of the present embodiment to form the thermally conductive particle-containing layer 12. As a result, the thermally conductive sheet 10 can suppress the generation of voids at the interface between the thermally conductive particle-containing layer 12 and the first substrate 11 or the second substrate 13, and thus can exhibit high thermal conductivity. As a result, the thermally conductive sheet 10 can stably conduct heat in a direction perpendicular to the main surface of the thermally conductive sheet 10 (inter-plane direction, i.e., the thickness direction of the thermally conductive sheet 10).
＜導熱片的製造方法＞ 說明本實施方式涉及的導熱片10的製造方法的一例。本實施方式涉及的導熱片的製造方法中，在作為準備的一組基材的第1基材11和第2基材13之間配置本實施方式涉及的導熱組合物(層疊工序)。 <Method for manufacturing thermally conductive sheet> An example of a method for manufacturing the thermally conductive sheet 10 according to the present embodiment is described. In the method for manufacturing the thermally conductive sheet according to the present embodiment, the thermally conductive composition according to the present embodiment is arranged between a first substrate 11 and a second substrate 13 as a set of prepared substrates (lamination process).
在第1基材11和第2基材13中的一者的基材上，賦予本實施方式涉及的導熱組合物之後，在本實施方式涉及的導熱組合物上，配置第1基材11和第2基材13中的另一者的基材。由此，獲得在第1基材11和第2基材13之間以夾持有本實施方式涉及的導熱組合物的狀態得以層疊的層疊體。After the thermally conductive composition according to the present embodiment is applied to one of the first substrate 11 and the second substrate 13, the other of the first substrate 11 and the second substrate 13 is disposed on the thermally conductive composition according to the present embodiment. Thus, a stacked body is obtained in which the first substrate 11 and the second substrate 13 are stacked in a state where the thermally conductive composition according to the present embodiment is sandwiched between them.
作為導熱組合物的賦予手法，可舉出例如，噴墨法、刮板塗佈法、凹版塗佈法、凹版膠版塗佈法、棒塗法、輥塗法、刀塗佈法、氣刀塗佈法、逗點塗佈法、U逗點塗佈法、AKKU塗佈法、平滑塗佈法、微凹版塗佈法、反向輥塗法、4根輥塗法、5根輥塗法、浸漬塗佈法、簾式塗佈法、滑動塗佈法、模塗法等。Examples of the method for applying the thermally conductive composition include inkjet coating, scraper coating, gravure coating, gravure offset coating, rod coating, roller coating, knife coating, air knife coating, comma coating, U-comma coating, AKKU coating, smooth coating, micro-gravure coating, reverse roll coating, 4-roll coating, 5-roll coating, dip coating, curtain coating, slide coating, and die coating.
接下來，加熱處理層疊體，使本實施方式涉及的導熱組合物進行固化，從而形成由本實施方式涉及的導熱組合物的固化物形成的導熱粒子含有層12(導熱粒子含有層形成工序)。Next, the layer stack is heat-treated to cure the thermally conductive composition according to the present embodiment, thereby forming a thermally conductive particle-containing layer 12 composed of a cured product of the thermally conductive composition according to the present embodiment (thermally conductive particle-containing layer forming step).
加熱溫度優選為140℃～200℃，更優選為145℃～180℃，進一步優選為150℃～160℃。The heating temperature is preferably 140°C to 200°C, more preferably 145°C to 180°C, and further preferably 150°C to 160°C.
加熱時間優選為10分鐘～3小時，更優選為30分鐘～2小時，進一步優選為60分鐘～1小時。The heating time is preferably 10 minutes to 3 hours, more preferably 30 minutes to 2 hours, and further preferably 60 minutes to 1 hour.
由此，獲得導熱片10。Thus, the thermal conductive sheet 10 is obtained.
另外，可以在本實施方式涉及的導熱片10的製造方法中，將本實施方式涉及的導熱組合物賦予至第1基材11和第2基材13的任一者上，使其固化，製作導熱粒子含有層12之後，在導熱粒子含有層12的第1基材11和第2基材13的一者被層疊的面的不同的面上，層疊第1基材11和第2基材13的另一者，製作導熱片10。In addition, in the method for manufacturing the thermally conductive sheet 10 involved in the present embodiment, the thermally conductive composition involved in the present embodiment is applied to either the first substrate 11 or the second substrate 13 and cured to produce the thermally conductive particle-containing layer 12, and then the other of the first substrate 11 and the second substrate 13 is stacked on a surface different from the surface on which the first substrate 11 and the second substrate 13 of the thermally conductive particle-containing layer 12 are stacked, thereby producing the thermally conductive sheet 10.
表示導熱片10的其它構成的一例。例如，可以如圖2所示那樣，導熱片10在第2基材13的上面，層疊導熱粒子含有層12和第2基材13，將第1基材11、導熱粒子含有層12、第2基材13、導熱粒子含有層12和第2基材13依次層疊的構成。Another example of the configuration of the thermally conductive sheet 10 is shown. For example, as shown in FIG. 2 , the thermally conductive sheet 10 may be configured such that the thermally conductive particle containing layer 12 and the second substrate 13 are stacked on the second substrate 13, or the first substrate 11, the thermally conductive particle containing layer 12, the second substrate 13, the thermally conductive particle containing layer 12, and the second substrate 13 are stacked in this order.
導熱片10如上所述，具有高導熱率，例如，藉由填充LSI等熱源與散熱器之間的微小的間隙，從而能夠適合用作兩者之間熱得以順利地流動那樣的熱界面材料(TIM)。因此，導熱片10中，作為TIM，例如，能夠用於根據溫度對於元件動作的效率、寿命等產生不良影響的CPU、MPU、功率電晶體、LED、鐳射二極體等各種電氣器件周邊等。由此，導熱片10能夠適合用於將實装有LED芯片或IC芯片的放熱基板與散熱器接著，構成功率LED模組或功率IC模組等時。As described above, the heat conductive sheet 10 has a high thermal conductivity, and can be used as a thermal interface material (TIM) to smoothly flow heat between a heat source such as an LSI, for example, by filling a tiny gap between the heat source and the heat sink. Therefore, the heat conductive sheet 10 can be used as a TIM, for example, around various electrical devices such as CPUs, MPUs, power transistors, LEDs, and laser diodes, which have adverse effects on the efficiency and life of the component operation due to temperature. Therefore, the heat conductive sheet 10 can be used to connect a heat dissipation substrate mounted with an LED chip or an IC chip to a heat sink to form a high-efficiency LED module or a power IC module.
另外，作為功率LED模組，具有引線接合實装類型的模組和倒裝晶片實装類型的模組，作為功率IC模組，具有引線接合實装類型的模組。In addition, as a power LED module, there are a wire bonding mounting type module and a flip chip mounting type module, and as a power IC module, there is a wire bonding mounting type module.
導熱片10能夠作為放熱結構體使用。放熱結構體具有發熱體、本實施方式涉及的導熱片10以及放熱構件。The heat-conducting sheet 10 can be used as a heat-dissipating structure. The heat-dissipating structure includes a heat-generating element, the heat-conducting sheet 10 according to the present embodiment, and a heat-dissipating member.
作為發熱體，沒有特別限制，能夠根據目的適當選擇，可舉出例如，CPU(Central Processing Unit)、MPU(Micro Processing Unit)、GPU(Graphics Processing Unit)等電子部件等。There is no particular limitation on the heat generating body, and it can be appropriately selected according to the purpose. For example, electronic components such as CPU (Central Processing Unit), MPU (Micro Processing Unit), and GPU (Graphics Processing Unit) can be cited.
作為放熱構件，如果為放熱電子部件(發熱體)發的熱的結構體，則沒有特別限制，能夠根據目的適當選擇，可舉出例如，散熱器、散熱具、波室和熱管等。The heat dissipating member is not particularly limited as long as it is a structure that dissipates heat generated by electronic components (heat generating body), and can be appropriately selected according to the purpose. For example, a heat sink, a heat sink, a wave chamber, and a heat pipe can be cited.
散熱器和散熱器一般而言，為内部不具有空間的實心結構。Heat sinks and heat sinks are generally solid structures with no space inside.
散熱器為用於將電子部件的熱有效率地傳導至其它部件的構件。作為散熱器的材質，沒有特別限制，能夠根據目的適當選擇，可舉出例如，銅、鋁等。散熱器通常為平板形狀。A heat sink is a component for efficiently transferring heat from an electronic component to other components. The material of the heat sink is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include copper and aluminum. A heat sink is generally in the form of a flat plate.
散熱器為用於將電子部件的熱放出至空氣中的構件。作為散熱器的材質，沒有特別限制，能夠根據目的適當選擇，可舉出例如，銅、鋁等。散熱器例如，具有複數的扇片。散熱器例如，具有基部，以及相對於基部的一個面，朝向非平行方向(例如，正交的方向)延伸的設置的複數的扇片。The heat sink is a component for releasing heat from electronic components into the air. The material of the heat sink is not particularly limited and can be appropriately selected according to the purpose. For example, copper, aluminum, etc. can be cited. The heat sink, for example, has a plurality of fins. The heat sink, for example, has a base and a plurality of fins extending in a non-parallel direction (for example, an orthogonal direction) relative to one surface of the base.
波室為中空結構體。中空結構體的内部空間封入有揮發性的液體。作為波室，可舉出例如，使散熱器為中空結構的波室，使散熱器為中空結構那樣的板狀的中空結構體等。The wave chamber is a hollow structure. A volatile liquid is sealed in the inner space of the hollow structure. Examples of the wave chamber include a wave chamber in which a radiator is a hollow structure, and a plate-shaped hollow structure in which a radiator is a hollow structure.
熱管為圓筒狀、大致圓筒狀、或扁平筒狀的中空結構體。中空結構體的内部空間封入有揮發性的液體。The heat pipe is a cylindrical, substantially cylindrical, or flat cylindrical hollow structure, in which a volatile liquid is sealed.
放熱結構體具備導熱片10，因此能夠作為半導體装置使用。對於使用具備導熱片10的放熱結構體作為半導體装置的情況下的一例進行說明。圖3為表示半導體装置的一例的概略斷面圖。圖3所示那樣，半導體装置20具備導熱片21、電子部件22、散熱器23和散熱器24，放熱電子部件22的發熱。Since the heat dissipation structure has a heat conducting sheet 10, it can be used as a semiconductor device. An example of using the heat dissipation structure having the heat conducting sheet 10 as a semiconductor device is described. FIG3 is a schematic cross-sectional view showing an example of a semiconductor device. As shown in FIG3, the semiconductor device 20 has a heat conducting sheet 21, an electronic component 22, a heat sink 23, and a heat sink 24, and dissipates the heat generated by the electronic component 22.
導熱片21具有2個導熱片21A和21B。導熱片21A和21B的至少一者使用上述本實施方式涉及的導熱片10。The thermally conductive sheet 21 includes two thermally conductive sheets 21A and 21B. The thermally conductive sheet 10 according to the present embodiment described above is used as at least one of the thermally conductive sheets 21A and 21B.
導熱片21A被固定於與散熱器23的電子部件22對置的主面23a，被挟持於電子部件22的上面22a與散熱器23的主面23a之間。導熱片21A與電子部件22相接，因此吸收電子部件22的發熱而傳熱至散熱器24，由散熱器24向外部放熱。The heat conductive sheet 21A is fixed to the main surface 23a of the heat sink 23 that is opposite to the electronic component 22, and is sandwiched between the upper surface 22a of the electronic component 22 and the main surface 23a of the heat sink 23. The heat conductive sheet 21A is in contact with the electronic component 22, so it absorbs the heat generated by the electronic component 22 and transfers the heat to the heat sink 24, and the heat is released to the outside by the heat sink 24.
導熱片21B設置於散熱器23的主面23a，被挟持於散熱器23與散熱器24之間。The heat conducting sheet 21B is provided on the main surface 23 a of the heat sink 23 , and is sandwiched between the heat sink 23 and the heat sink 24 .
電子部件22為例如，BGA等半導體元件，被實装於配線基板25。The electronic component 22 is, for example, a semiconductor element such as BGA, and is mounted on the wiring substrate 25 .
散熱器23例如，形成為方形板狀，具有與電子部件22對峙的主面23a、沿著主面23a的外周而立設的側壁23b以及主面23a的相反側的主面23c。The heat sink 23 is formed in a square plate shape, for example, and has a main surface 23a facing the electronic component 22, a side wall 23b standing along the outer periphery of the main surface 23a, and a main surface 23c opposite to the main surface 23a.
散熱器23在被側壁23b包圍的主面23a設置導熱片21，在主面23c設置導熱片21B。散熱器23中，側壁23b的前端面實装於配線基板25。散熱器23藉由側壁23b而隔開預定的距離以包圍電子部件22。Heat sink 23 has heat conducting sheet 21 provided on main surface 23a surrounded by side wall 23b, and heat conducting sheet 21B provided on main surface 23c. Heat sink 23 is mounted on wiring board 25 at the front end surface of side wall 23b. Heat sink 23 surrounds electronic component 22 at a predetermined distance by side wall 23b.
散熱器23具有高導熱率時，熱電阻減少，能夠效率良好地吸熱電子部件22的熱，例如，因此能夠使用導熱性良好的銅、鋁等來形成。When the heat sink 23 has high thermal conductivity, the thermal resistance is reduced and the heat of the electronic component 22 can be efficiently absorbed. Therefore, for example, the heat sink 23 can be formed using copper, aluminum, etc. having high thermal conductivity.
散熱器24設置於與導熱片21B的散熱器23側相反側的主面，在散熱器23的主面23c隔著導熱片21B而設置。The heat sink 24 is provided on the main surface of the heat conducting sheet 21B on the opposite side to the heat sink 23 side, and is provided on the main surface 23c of the heat sink 23 via the heat conducting sheet 21B.
半導體装置20中，在散熱器23的主面23a設置導熱片21A，在主面23c設置導熱片21B，因此利用導熱片21A和21B吸收電子部件22的發熱，由散熱器24得以放熱。In the semiconductor device 20 , the heat conducting sheet 21A is provided on the main surface 23 a of the heat sink 23 , and the heat conducting sheet 21B is provided on the main surface 23 c . Therefore, the heat generated by the electronic component 22 is absorbed by the heat conducting sheets 21A and 21B and dissipated by the heat sink 24 .
如以上那樣，說明實施方式，上述實施方式作為例子進行提示，沒有藉由上述實施方式而限定本發明。上述實施方式能夠以其它各種形態來實施，在不脫離發明的主旨的範圍內，能夠進行各種組合、省略、置換，變更等。這些實施方式、其變形包含於發明的範圍、主旨，並且包含於請求項所記載的發明和其均等的範圍內。 實施例 As described above, the embodiments are described. The embodiments are provided as examples, and the present invention is not limited by the embodiments. The embodiments can be implemented in various other forms, and can be combined, omitted, replaced, and changed in various ways without departing from the subject matter of the invention. These embodiments and their variations are included in the scope and subject matter of the invention, and are included in the invention described in the claims and their equivalents. Embodiments
以下，說明本發明的實施例，本發明不受這些實施例的任何限定。Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.
＜導熱組合物的調製＞ [實施例1] 將作為基礎的熱塑性樹脂(M2513，無規共聚聚醯胺，Arkema株式會社製，熔點：125℃～135℃)3.26質量份、松香系樹脂(氫化酸改性松香，KE-604，荒川工業株式會社製)4.48質量份***能夠加熱的帶有夾套的燒瓶，在氮氣氣氛下保持於125℃的同時，攪拌30分鐘。接著，在該燒瓶内添加導熱粒子(Ag塗佈Cu粒子，福田金屬箔粉工業株式會社製，體積平均粒徑Dv：40μm)56.30質量份和低熔點金屬粒子(Sn 58Bi 42流子，三井金屬礦業株式會社製，體積平均粒徑Dv：4μm)35.96質量份%，進行均勻地混合。接著，在將上下的熱工具(170mm×70mm) 加熱至125℃的壓制装置(迷你壓制機，Dexerials公司製)中，設置將38μm離形膜(38GS，Lintec公司製)切割成定型的膜，在該膜上將由上述調整的混合物以一定量灌注之後，用厚度計100μm的縫隙規進行夾持。接著，將38μm的離形膜覆蓋縫隙規，以3.3MPa(0.6MPa的空氣壓)加熱壓着5分鐘後，冷却至常溫，製作出膜狀的導熱組合物。 <Preparation of thermally conductive composition> [Example 1] 3.26 parts by weight of a base thermoplastic resin (M2513, random copolymer polyamide, manufactured by Arkema Co., Ltd., melting point: 125°C-135°C) and 4.48 parts by weight of a rosin-based resin (hydrogenated acid-modified rosin, KE-604, manufactured by Arakawa Industries, Ltd.) are placed in a heating jacketed flask, maintained at 125°C under a nitrogen atmosphere, and stirred for 30 minutes. Next, 56.30 parts by mass of thermally conductive particles (Ag-coated Cu particles, manufactured by Fukuda Metal Foil & Powder Industries, Ltd., volume average particle size Dv: 40 μm) and 35.96 parts by mass of low melting point metal particles (Sn 58 Bi 42 particles, manufactured by Mitsui Mining & Co., Ltd., volume average particle size Dv: 4 μm) were added to the flask and uniformly mixed. Next, a 38μm release film (38GS, manufactured by Lintec) was cut into a fixed film in a press device (mini press, manufactured by Dexerials) with upper and lower hot tools (170mm×70mm) heated to 125°C. A certain amount of the mixture prepared above was poured on the film and then clamped with a 100μm thickness gauge. Next, the 38μm release film was placed over the slit gauge, heated and pressed at 3.3MPa (0.6MPa air pressure) for 5 minutes, and then cooled to room temperature to produce a film-shaped thermal conductive composition.
[實施例2] 實施例1中，作為熱塑性樹脂，代替M2513(聚醯胺化合物，Arkema株式會社製)而使用M1276(無規共聚聚醯胺，Arkema株式會社製，熔點：110℃～115℃)，除此以外，進行與實施例1同樣地操作，調製出膜狀的導熱組合物。 [Example 2] In Example 1, M1276 (random copolymer polyamide, manufactured by Arkema Co., Ltd., melting point: 110°C to 115°C) was used as the thermoplastic resin instead of M2513 (polyamide compound, manufactured by Arkema Co., Ltd.). The same operation as in Example 1 was performed to prepare a film-like thermal conductive composition.
[實施例3] 實施例1中，作為熱塑性樹脂，代替M2513(聚醯胺化合物，Arkema株式會社製)而使用GM-920(聚酯，東洋紡株式會社製)，除此以外，進行與實施例1同樣地操作，調製出膜狀的導熱組合物。 [Example 3] In Example 1, GM-920 (polyester, manufactured by Toyobo Co., Ltd.) was used as the thermoplastic resin instead of M2513 (polyamide compound, manufactured by Arkema Co., Ltd.). The same operation as in Example 1 was performed to prepare a film-like thermal conductive composition.
[實施例4] 實施例1中，作為松香系樹脂，代替KE-604(氫化酸改性松香，荒川工業株式會社製)而使用KR-120(酸改性超淺色松香，荒川工業株式會社製)，除此以外，進行與實施例1同樣地操作，調製出膜狀的導熱組合物。 [Example 4] In Example 1, the same operation as in Example 1 was performed except that KR-120 (acid-modified ultra-light rosin, manufactured by Arakawa Industries, Ltd.) was used as the rosin-based resin instead of KE-604 (hydrogenated acid-modified rosin, manufactured by Arakawa Industries, Ltd.) to prepare a film-like thermally conductive composition.
[實施例5] 實施例1中，代替氮氣氣氛下而設為空氣氣氛下，除此以外，進行與實施例1同樣地操作，調製出膜狀的導熱組合物。 [Example 5] In Example 1, the same operation as in Example 1 was performed except that the atmosphere was changed to air atmosphere instead of nitrogen atmosphere to prepare a film-like thermal conductive composition.
[比較例1] 將作為基礎的熱塑性樹脂(M2513，聚醯胺化合物，Arkema株式會社製)3.26質量份在以使甲苯(富士膠片和光純藥社製)和乙醇(富士膠片和光純藥公司製)以1：1的比例包含的溶液中，熱塑性樹脂的含量成為20wt%的方式進行了溶解。在該溶液中，加入低熔點助焊劑(KE-604，東京化成工業株式會社製)4.48質量份，均勻地混合。而且，在該燒瓶内添加導熱粒子(Ag塗佈Cu粒子，福田金屬箔粉工業株式會社製，體積平均粒徑Dv：40μm)56.30質量份和低熔點金屬粒子(Sn 58Bi 42流子，三井金屬礦業株式會社製，體積平均粒徑Dv：4μm)35.96質量份%，使用攪拌装置(泡筒煉太郎-自動公轉混合機，株式會社THINKY製)，進一步均勻地混合，製作出導熱組合物。將製作的導熱組合物塗覆於38μm離形膜(38GS，Lintec公司製)，在80℃乾燥15分鐘。層厚調整為100μm。 [Comparative Example 1] 3.26 parts by weight of a base thermoplastic resin (M2513, a polyamide compound, manufactured by Arkema Co., Ltd.) was dissolved in a solution containing toluene (manufactured by Fuji Film Co., Ltd. and ethanol (manufactured by Fuji Film Co., Ltd. and Koh Jun Chemical Co., Ltd.) at a ratio of 1:1 so that the content of the thermoplastic resin was 20 wt%. 4.48 parts by weight of a low melting point flux (KE-604, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the solution and mixed uniformly. Furthermore, 56.30 parts by mass of thermally conductive particles (Ag-coated Cu particles, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., with a volume average particle size Dv: 40 μm) and 35.96 parts by mass of low melting point metal particles (Sn 58 Bi 42 particles, manufactured by Mitsui Metal Mining Co., Ltd., with a volume average particle size Dv: 4 μm) were added to the flask, and further uniformly mixed using a stirring device (Cellular Retinaro-Automatic Rotating Mixer, manufactured by THINKY Co., Ltd.) to prepare a thermally conductive composition. The prepared thermally conductive composition was coated on a 38 μm release film (38GS, manufactured by Lintec) and dried at 80°C for 15 minutes. The layer thickness was adjusted to 100 μm.
[比較例2] 實施例1中，作為熱塑性樹脂，代替M2513(聚醯胺化合物，Arkema株式會社製)而使用NOXTITE PA-521(氫化丁二烯橡膠，UNIMATEC株式會社製)，除此以外，進行與實施例1同樣地操作，調製出膜狀的導熱組合物。 [Comparative Example 2] In Example 1, a film-like thermal conductive composition was prepared by performing the same operation as in Example 1 except that NOXTITE PA-521 (hydrogenated butadiene rubber, manufactured by UNIMATEC Co., Ltd.) was used as the thermoplastic resin instead of M2513 (polyamide compound, manufactured by Arkema Co., Ltd.).
[比較例3] 比較例1中，代替熱塑性樹脂M2513而設為M1276(無規共聚聚醯胺，Arkema株式會社製，熔點：110℃～115℃)，除此以外，進行與比較例1同樣地操作，調製出膜狀的導熱組合物。 [Comparative Example 3] In Comparative Example 1, the thermoplastic resin M2513 was replaced with M1276 (random copolymer polyamide, manufactured by Arkema Co., Ltd., melting point: 110°C to 115°C). The same operation as in Comparative Example 1 was performed to prepare a film-like thermal conductive composition.
＜特性＞ 接下來，以下那樣操作，測定並評價所得的各導熱組合物所包含的揮發成分的含量、各導熱組合物的成膜性以及各導熱組合物的固化物的空隙面積的比例和導熱率。將結果顯示於表1。 <Characteristics> Next, the content of volatile components contained in each thermally conductive composition, the film-forming property of each thermally conductive composition, and the ratio of the void area and thermal conductivity of the cured product of each thermally conductive composition were measured and evaluated as follows. The results are shown in Table 1.
[揮發成分的含量] 首先，從包含熱塑性樹脂和低熔點助焊劑的混合物中作為試樣取質量1g～2g，迅速地採集於稱量罐，均勻地展開於鋁杯的底部。然後，對於鋁杯加蓋，直接使用電子天平進行稱量。稱量後，取蓋，置於稱量罐下，設置於乾燥器内，在(135±2)℃乾燥3小時。乾燥後，對於稱量罐直接加蓋，放入乾燥器，放冷直至室溫之後，稱量。由下式(1)，求出熱塑性樹脂和低熔點助焊劑所包含的固體成分(%)。而且，由下式(2)，從100減去求得的固體成分，從而算出熱塑性樹脂和松香系樹脂所包含的揮發成分的合計的含有比例。 固體成分(%)＝((稱量罐＋乾燥後的試樣的質量)-(稱量罐的質量))/((稱量罐＋試樣的質量)-(稱量罐的質量))×100 ・・・(1) 揮發成分的合計的含有比例(%)＝100-固體成分 ・・・(2) [Content of volatile components] First, take 1g to 2g of the mixture containing the thermoplastic resin and the low-melting point flux as a sample, quickly collect it in a weighing pot, and evenly spread it on the bottom of the aluminum cup. Then, cover the aluminum cup and weigh it directly using an electronic balance. After weighing, remove the lid, place it under the weighing pot, set it in a desiccator, and dry it at (135±2)℃ for 3 hours. After drying, cover the weighing pot directly, put it in a desiccator, cool it to room temperature, and then weigh it. From the following formula (1), calculate the solid content (%) contained in the thermoplastic resin and the low-melting point flux. Then, the total content ratio of volatile components contained in the thermoplastic resin and the rosin-based resin is calculated by subtracting the obtained solid content from 100 according to the following formula (2). Solid content (%) = ((Weighing tank + mass of sample after drying) - (mass of weighing tank)) / ((Weighing tank + mass of sample) - (mass of weighing tank)) × 100 ... (1) Total content ratio of volatile components (%) = 100 - solid content ... (2)
[成膜性] 目視確認獲得的導熱組合物，基於下述評價基準評價膜的狀態。 (評價基準) A：形成均勻的膜 B：形成一部分不均勻的膜 C：不能製膜 [Film-forming property] The obtained thermal conductive composition was visually checked, and the film state was evaluated based on the following evaluation criteria. (Evaluation criteria) A: Uniform film was formed B: Partially uneven film was formed C: Film could not be formed
[空隙面積的比例] (層疊體的製作) 在基材上塗佈導熱組合物之後，在導熱組合物上載置銅基板(30mm×30mm×2mm)，基材與銅基板之間，將導熱組合物以使厚度為0.1mm，1邊為20mm的方式夾持，從而製作出層疊體。將層疊體放入熱處理乾燥装置(STPH-102，ESPEC株式會社製)，在150℃進行60分鐘連續固化，以使導熱組合物固化，從而製作出基材與銅基板之間包含導熱組合物的固化物的層疊體。將作為基材使用玻璃基板(20mm×20mm×1mm)而製作的層疊體設為「層疊體1」，將作為基材使用Si基板(20mm×20mm×0.775mm)而製作的層疊體設為「層疊體2」。 [Ratio of void area] (Preparation of laminated body) After applying the thermally conductive composition on the substrate, a copper substrate (30 mm × 30 mm × 2 mm) is placed on the thermally conductive composition, and the thermally conductive composition is sandwiched between the substrate and the copper substrate so that the thickness is 0.1 mm and one side is 20 mm, thereby preparing a laminated body. The laminated body is placed in a heat treatment drying device (STPH-102, manufactured by ESPEC Co., Ltd.) and continuously cured at 150°C for 60 minutes to cure the thermally conductive composition, thereby preparing a laminated body containing a cured product of the thermally conductive composition between the substrate and the copper substrate. The stacked body made using a glass substrate (20 mm × 20 mm × 1 mm) as a base material is referred to as "Stacked body 1", and the stacked body made using a Si substrate (20 mm × 20 mm × 0.775 mm) as a base material is referred to as "Stacked body 2".
使用金屬顯微鏡(奧林巴斯株式會社製，商品名：MX63)公司製)，從層疊體1的玻璃基板側拍攝導熱組合物的固化物與玻璃基板的界面，使用紅外線顯微鏡(奧林巴斯株式會社製，商品名：MX63，浜松Photonics株式會社製，商品名：InGaAs照相機 C12741-03)，從層疊體2的Si基板側拍攝導熱組合物的固化物與Si基板的界面。將拍攝了固化物與玻璃基板的界面的圖像設為圖像1，將拍攝了固化物與Si基板的界面的圖像設為圖像2。圖4表示將實施例1中的導熱組合物的固化物與玻璃基板的界面利用金屬顯微鏡觀察得到的圖像，圖5表示將實施例1中的導熱組合物的固化物與Si基板的界面利用紅外線顯微鏡觀察得到的圖像。另外，圖4和圖5中，白色部分為導熱粒子，灰色部分為空隙，黑色部分為樹脂。The interface between the cured product of the heat conductive composition and the glass substrate was photographed from the glass substrate side of the laminate 1 using a metal microscope (product name: MX63 manufactured by Olympus Corporation) and the interface between the cured product of the heat conductive composition and the Si substrate was photographed from the Si substrate side of the laminate 2 using an infrared microscope (product name: MX63 manufactured by Olympus Corporation, product name: InGaAs camera C12741-03 manufactured by Hamamatsu Photonics Co., Ltd.). The image of the interface between the cured product and the glass substrate was set as image 1, and the image of the interface between the cured product and the Si substrate was set as image 2. FIG4 shows an image obtained by observing the interface between the cured product of the thermally conductive composition in Example 1 and the glass substrate using a metal microscope, and FIG5 shows an image obtained by observing the interface between the cured product of the thermally conductive composition in Example 1 and the Si substrate using an infrared microscope. In FIG4 and FIG5, the white portion is the thermally conductive particle, the gray portion is the void, and the black portion is the resin.
(空隙面積的比例的測定) 將灰色部分進行2值化處理，從而算出空隙部分的面積。所得的圖像1和圖像2的空隙面積的比例(%)如以下那樣算出。 圖像中的面積計算使用Microsoft公司製的Excel。首先，將圖像以白黑50%(閾值128)進行二值化而作為位圖圖像進行保存。接下來，將製作的二值化位圖圖像作為二進製數據讀入Excel，取得圖像整體的像素數和白色部的像素數，計數白色部的像素數/整體的像素數，從而算出空隙面積的比例(%)，圖像1(玻璃基板)和圖像2(Si基板)中，採用空隙面積的比例大的一者，採用下述基準進行評價。 -評價基準- A：空隙面積的比例小於5% B：空隙面積的比例為5%以上且小於20% C：空隙面積的比例為20%以上 (Measurement of the ratio of the void area) The gray part is binarized to calculate the area of the void part. The ratio (%) of the void area of the obtained image 1 and image 2 is calculated as follows. The area calculation in the image uses Excel made by Microsoft. First, the image is binarized at 50% white and black (threshold 128) and saved as a bitmap image. Next, the binary bitmap image is read into Excel as binary data, the number of pixels of the entire image and the number of pixels of the white part are obtained, and the number of pixels of the white part/the total number of pixels are counted to calculate the ratio (%) of the void area. The image 1 (glass substrate) and the image 2 (Si substrate) with the larger ratio of the void area are used for evaluation using the following criteria. -Evaluation criteria- A: The ratio of void area is less than 5% B: The ratio of void area is more than 5% and less than 20% C: The ratio of void area is more than 20%
圖6表示將比較例1中的導熱組合物的固化物與玻璃基板的界面利用金屬顯微鏡觀察得到的圖像，圖7表示將比較例1中的導熱組合物的固化物與Si基板的界面利用紅外線顯微鏡觀察得到的圖像。FIG6 shows an image of the interface between the cured product of the thermally conductive composition in Comparative Example 1 and the glass substrate observed using a metal microscope, and FIG7 shows an image of the interface between the cured product of the thermally conductive composition in Comparative Example 1 and the Si substrate observed using an infrared microscope.
[導熱率] (層疊體的製作) 在銅基板(30mm×30mm×2mm)上塗佈導熱組合物之後，配置高度0.125mm的隔離物，在隔離物上載置其它銅基板(30mm×30mm×2mm)，在2張銅基板之間將導熱組合物以使厚度為0.125mm，1邊為20mm的方式夾持以製作出層疊體。將層疊體放入熱處理乾燥装置(STPH-102，ESPEC株式會社製)，在150℃進行60分鐘連續固化，以使導熱組合物固化，從而製作出2張銅基板之間包含導熱組合物的固化物的層疊體。 [Thermal conductivity] (Preparation of a laminate) After applying a thermally conductive composition on a copper substrate (30 mm × 30 mm × 2 mm), a spacer with a height of 0.125 mm was placed, and another copper substrate (30 mm × 30 mm × 2 mm) was placed on the spacer. The thermally conductive composition was sandwiched between two copper substrates so that the thickness was 0.125 mm and one side was 20 mm to prepare a laminate. The laminate was placed in a heat treatment drying device (STPH-102, manufactured by ESPEC Co., Ltd.) and continuously cured at 150°C for 60 minutes to cure the thermally conductive composition, thereby preparing a laminate containing a cured product of the thermally conductive composition between two copper substrates.
(熱電阻的測定) 關於獲得的各層疊體，採用基於ASTM-D5470的方法，測定導熱組合物的固化物的一方與銅基板的界面的熱電阻(單位：℃・cm 2/W)。由其結果，減去2張銅基板的熱電阻，算出導熱組合物的固化物的熱電阻，由熱電阻與固化物的厚度，求出導熱率(W/m・K)，基於下述評價基準進行評價。 -評價基準- A：導熱率為20W/m・K以上 B：導熱率為8.0W/m・K以上且小於20W/m・K C：導熱率小於8.0W/m・K (Measurement of thermal resistance) For each obtained stack, the thermal resistance (unit: ℃・cm 2 /W) of the interface between one side of the cured thermally conductive composition and the copper substrate was measured using a method based on ASTM-D5470. The thermal resistance of the two copper substrates was subtracted from the result to calculate the thermal resistance of the cured thermally conductive composition. The thermal conductivity (W/m・K) was calculated from the thermal resistance and the thickness of the cured product, and the evaluation was performed based on the following evaluation criteria. -Evaluation Criteria- A: Thermal conductivity is 20W/m・K or more B: Thermal conductivity is 8.0W/m・K or more and less than 20W/m・K C: Thermal conductivity is less than 8.0W/m・K
【表1】 【Table 1】
由表1，各實施例中，形成均勻的膜，導熱率為20W/m・K以上，但是各比較例中，導熱率小於20W/m・K，低。From Table 1, in each embodiment, a uniform film was formed, and the thermal conductivity was 20 W/m·K or more, but in each comparative example, the thermal conductivity was less than 20 W/m·K, which was low.
由此，確認了上述各實施例的導熱組合物包含熱塑性樹脂和松香系樹脂，將這些樹脂所包含的揮發成分的含量抑制為預定值以下，從而空隙面積的比例被抑制為20%以下，發揮優異的成膜性和導熱性。因此，本實施方式涉及的導熱組合物作為TIM能夠發揮高導熱性，因此例如，可以說能夠適合用於CPU、MPU、功率電晶體、LED、鐳射二極體等各種電氣器件的周邊等。Thus, it was confirmed that the thermally conductive composition of each of the above-mentioned embodiments contains a thermoplastic resin and a rosin-based resin, and the content of the volatile components contained in these resins is suppressed to below a predetermined value, thereby suppressing the ratio of the void area to below 20%, and exhibiting excellent film-forming properties and thermal conductivity. Therefore, the thermally conductive composition involved in this embodiment can exhibit high thermal conductivity as a TIM, so it can be said that it can be suitably used for the periphery of various electrical devices such as CPUs, MPUs, power transistors, LEDs, and laser diodes.
本申請基於2022年9月26日於日本特許庁申請的特願2022-152864號和2023年7月7日於日本特許庁申請的特願2023-112482號而主張優先權，援用這些上述申請中記載的全部内容。This application claims priority based on Tokugawa 2022-152864 filed with the Japan Patent Office on September 26, 2022, and Tokugawa 2023-112482 filed with the Japan Patent Office on July 7, 2023, and all the contents described in these applications are incorporated herein by reference.
10:導熱片 11:第1基材 12:導熱粒子含有層 13:第2基材 20:半導體装置 21A、21B:導熱片 22:電子部件 23:散熱器 23a、23c:主面 23b:側壁 24:散熱器 25:配線基板 10: Thermally conductive sheet 11: First substrate 12: Thermally conductive particle-containing layer 13: Second substrate 20: Semiconductor device 21A, 21B: Thermally conductive sheet 22: Electronic component 23: Heat sink 23a, 23c: Main surface 23b: Side wall 24: Heat sink 25: Wiring board
圖1為表示導熱片的構成的一例的斷面圖。 圖2為表示導熱片的其它構成的一例的斷面圖。 圖3為表示作為放熱結構體的半導體装置的一例的概略斷面圖。 圖4為將實施例1中的導熱組合物的固化物與玻璃基板的界面利用金屬顯微鏡觀察得到的圖像。 圖5為將實施例1中的導熱組合物的固化物與Si基板的界面利用紅外線顯微鏡觀察得到的圖像。 圖6為將比較例1中的導熱組合物的固化物與玻璃基板的界面利用金屬顯微鏡觀察得到的圖像。 圖7為將比較例1中的導熱組合物的固化物與Si基板的界面利用紅外線顯微鏡觀察得到的圖像。 FIG1 is a cross-sectional view showing an example of the structure of a thermally conductive sheet. FIG2 is a cross-sectional view showing an example of another structure of a thermally conductive sheet. FIG3 is a schematic cross-sectional view showing an example of a semiconductor device as a heat dissipating structure. FIG4 is an image obtained by observing the interface between the cured product of the thermally conductive composition in Example 1 and the glass substrate using a metal microscope. FIG5 is an image obtained by observing the interface between the cured product of the thermally conductive composition in Example 1 and the Si substrate using an infrared microscope. FIG6 is an image obtained by observing the interface between the cured product of the thermally conductive composition in Comparative Example 1 and the glass substrate using a metal microscope. FIG7 is an image obtained by observing the interface between the cured product of the thermally conductive composition in Comparative Example 1 and the Si substrate using an infrared microscope.
10:導熱片 10: Heat conducting sheet
11:第1基材 11: The first substrate
12:導熱粒子含有層 12: Thermally conductive particles containing layer
13:第2基材 13: Second base material
Claims (15)
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| JP2022-152864 | 2022-09-26 | ||
| JP2022152864 | 2022-09-26 | ||
| JP2023-112482 | 2023-07-07 | ||
| JP2023112482A JP2024047538A (en) | 2022-09-26 | 2023-07-07 | Heat conductive composition, heat conductive sheet, heat conductive composition manufacturing method, and heat conductive sheet manufacturing method |
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| JP2021113308A (en) * | 2020-01-20 | 2021-08-05 | ユニチカ株式会社 | Thermally conductive resin composition and molded article comprising the same |
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