TW201247859A - Thermal conductive composition and thermal conductive body - Google Patents

Thermal conductive composition and thermal conductive body Download PDF

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Publication number
TW201247859A
TW201247859A TW101111644A TW101111644A TW201247859A TW 201247859 A TW201247859 A TW 201247859A TW 101111644 A TW101111644 A TW 101111644A TW 101111644 A TW101111644 A TW 101111644A TW 201247859 A TW201247859 A TW 201247859A
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TW
Taiwan
Prior art keywords
silver
conductive composition
thermally conductive
amine
acid
Prior art date
Application number
TW101111644A
Other languages
Chinese (zh)
Other versions
TWI564381B (en
Inventor
Ayuko Suzuki
Original Assignee
Namics Corp
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Publication date
Application filed by Namics Corp filed Critical Namics Corp
Publication of TW201247859A publication Critical patent/TW201247859A/en
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Publication of TWI564381B publication Critical patent/TWI564381B/en

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • C09K5/14—Solid materials, e.g. powdery or granular
    • 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
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29199—Material of the matrix
    • H01L2224/2929—Material of the matrix with a principal constituent of the material being a polymer, e.g. polyester, phenolic based polymer, epoxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/28—Structure, shape, material or disposition of the layer connectors prior to the connecting process
    • H01L2224/29—Structure, shape, material or disposition of the layer connectors prior to the connecting process of an individual layer connector
    • H01L2224/29001—Core members of the layer connector
    • H01L2224/29099—Material
    • H01L2224/29198—Material with a principal constituent of the material being a combination of two or more materials in the form of a matrix with a filler, i.e. being a hybrid material, e.g. segmented structures, foams
    • H01L2224/29298—Fillers
    • H01L2224/29299—Base material
    • H01L2224/293—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/29338—Base material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/29339—Silver [Ag] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32245—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/83855—Hardening the adhesive by curing, i.e. thermosetting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/838—Bonding techniques
    • H01L2224/8385—Bonding techniques using a polymer adhesive, e.g. an adhesive based on silicone, epoxy, polyimide, polyester
    • H01L2224/8388—Hardening the adhesive by cooling, e.g. for thermoplastics or hot-melt adhesives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Conductive Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

The present invention provides a thermal conductive composition capable of obtaining a thermal conductive body having high thermal conductivity. The thermal conductive composition of the present invention includes: (A)silver powders, (B) silver microparticles, (C) silver aliphatate, and (D) amine. (A) silver powders are preferably with average particle size in 0.3 μ m to 100 μ m. (B) silver microparticles are preferably with average particle diameters of primary particles in 50 to 150nm, and crystallite diameter in 20 to 50nm, and the ratio of the average particle diameter to the crystallite diameter is l to 7.5. (B) silver microparticles are preferably manufactured by mixing silver salts of carboxylic acid and aliphatic primary amine, thereafter, adding a reductant at reaction temperature of 20 to 80 DEG C for precipitating the silver microparticles.

Description

201247859 六、發明說明： 【發明所屬之技術領域】 本發明係關於熱傳導性組成物及將其加工處理所得 之熱傳導體。 【先前技術】 以往’為了將半導體晶片（chip)接著/固定（晶片接 合；die bonding)於導線架（lead frame)等金屬板，而使 用包含銀粉末、熱固性樹脂、及溶劑的銀膏（silverpaste)。 當使用該銀膏接著/固定晶片時，由於銀具有高熱傳導率， 可將於晶片產生的熱迅速地散逸至導線架。此外，由於樹 脂的硬化溫度較低’接著/固定晶片時，晶片不易因熱而發 生劣化。此外’銀膏所包含之銀或樹脂與金等相比係屬價 格低廉。另外，藉由調整銀膏所包含之黏度調製劑（溶劑） 之添加量’可控制銀膏的黏度或搖變性（thixotropy)。由 於銀膏係處理容易，故可藉由印刷塗佈，或藉由注入、滴 下等方式選擇性地賦予一定量至接著面。因此，銀膏大多 被使用於接著/固定晶片。 作為此種銀膏，於專利文獻1係揭示一種銀膏，其係 使較銀粉小之球狀銀微粒子混合存在於含有銀粉、熱固性 樹脂及溶劑係導電性膏體中而製成者。於專利文獻2係揭 示一種包含具有銀粉、熱固性樹脂、及硫鍵與經基的化合 物之熱傳導性樹脂组成物。於專利文獻3係揭示將經高級 脂肪酸或高級脂肪酸的衍生物被覆之銀粒子進行加熱處 理，而得到電子回路連接用幫浦之製造方法。專利文獻4 324149 4 201247859 係揭示一種包含將銀離子還原所得之銀微粒子、作為接著 劑成分之熱固性樹脂，而熱傳導性優異之接著膏體。 [先前技術文獻] [專利文獻] [專利文獻1]曰本特開平11-150135號公報 [專利文獻2]日本特開2009-191214號公報 [專利文獻3]日本特開2009-289745號公報 [專利文獻4]日本特開2003-183616號公報 【發明内容】 (發明欲解決之課題） 近年來，因使用半導體晶片之電子零件的高性能化， 來自晶片的發熱量增加，而正更強烈地要求用以將晶片接 著/固定於導線架之銀膏具有高熱傳導率。 在此，本發明之目的係提供可得到具有高熱傳導率之 熱傳導體之熱傳導性組成物。 (解決課題之手段） 本發明者等係為解決上述課題而進行研究。 其結果為本發明者等發現藉由使用含有銀粉、銀微粒 子、脂肪酸銀、胺之熱傳導性組成物，可得到所具有的熱 傳導率高於以往包含銀粉及銀微粒子的銀膏之熱傳導體。 本發明係基於此種新穎的發現而完成者。 本發明係一種含有：（A)銀粉、（B)銀微粒子、（C)脂 肪酸銀與（D)胺之熱傳導性組成物。 前述（A)銀粉，較佳為平均粒徑係0. 3//m至100/zm。 324149 5 201247859 刖述（B)銀微粒子較佳為：初級粒子之平均粒徑係5〇 至150簡’微晶徑（^%仏1111；6(14脱切〇係2〇至5〇簡， 且，平均粒徑相對於微晶徑之比為丨至7 5。 前述（B)銀錄子，較料II由下述方式製造者：混合 缓酸之銀鹽與脂肪族-級胺，其次，添加縣劑，於反應 溫度20至80°C使銀微粒子析出。 本發明之熱傳導性組成物較佳為復含有（e)樹脂酸銀 (silver resinate)。 本發明之熱傳導性組成物較佳為復含有（F)樹脂。 本發明係提供-種熱傳導體，其係將上述之任一熱傳 導性組成物於100 i 40(TC之溫度範圍進行加熱處理所得 者0 本發明提供—種接著劑，其係包含上述之任一熱傳導 性組成物。 本發明係提供-種電子零件，其之熱傳導 體。 (發明之效果） 依據本發明，可提供一種可得到具有高熱傳導率之熱 傳導體之熱傳導性組成物。 【實施方式】 以下，詳細說明用以實施本發明之形態。 本發明之實施形態之熱傳導性組成物的特徵為含 有：（A)銀粉、⑻銀微粒子、（c)脂肪酸銀、及（D)胺。 (A)銀粉 324149 6 201247859 由純銀或銀合金製成的粉 可使用例如球狀、粒狀或 作為本發明之銀粉，可使用 末。銀粉的形狀係無特別限定， 者片狀（鱗片狀）之銀粉。 本發明中所使用之銀粉的/ l〇〇"m為較佳，1/zm至5〇"爪/ /仫，係以0·3以m至 為最佳。在此所謂之平均粒^ ^佳’ 2.4_至16/ζιη 式粒度分布測定法求得之I糸忍指藉由雷射繞射散射 為了提高熱傳導體之埶傳二:之平均粒徑⑽)。 含之銀粉的粒徑以大者為較佳，熱傳導性組成物所包 會損及熱傳導性組成物對I、⑽’銀粉的粒徑過大時， 此，以不損及對裝置之塗佈特性^作業性。因 使用粒徑大之銀粉。料 ^作紐為讀，較佳為 銀粉的平均粒徑以於上;範j:=佳本發明中所使用之 一此外，藉由使用填充密度（敲緊密度 ’可增加銀粉彼此間之接觸點或者接觸面。其妹 果為可〜加銀粉彼此間之熱傳導點或者熱傳導面。為^ 二步提高銀粉的填充密度，混合使驗度分布及/或形 同之複數種銀粉為較佳。 本發明之熱傳導性組成物係含有用以促進銀粉彼此 間之熱傳導點之金屬熔融接合的添加劑。藉由包含此種添 加劑，於加熱熱傳導性組成物所得之熱傳導體的内部會形 成更大的熱傳導路徑（heat conduction path)。本發明係 使用後述之（C)脂肪酸銀及（D)胺作為此種添加劑。 銀粉的製造方法並無特別限定。例如可藉由還原法、 324149 7 201247859 粉碎法、電解法、霧化法（atomizing method)、熱處理法、 或者該等之組合而製造銀粉。片狀的銀粉例如可藉由球磨 機將球狀或粒狀的銀粒子等壓碎而製造 (B)銀微粒子 本發明之銀微粒子係例如具有相對於上述銀粉而言 為小之平均粒徑，而由純銀或者銀合金構成的粒子。 本發明銀微粒子之初級粒子的平均粒徑為4〇至 150nm，較佳為50至150nm，更佳為70至140nm。銀微粒 子之平均粒徑若於此範圍，銀微粒子的凝集會受抑制、銀 膏的保存安定性會變得良好。又，在此所謂之平均粒徑， 意指以掃描式電子顯微鏡（SEM)觀察粒子而藉由影像分析 求出的投影面積直徑（Heywood Diameter)之平均值。 本發明中所使用之銀微粒子，微晶徑為15至5〇nm， 較佳為20至5Onm。微晶徑若於此範圍，則在抑制熱傳導 性組成物經加熱處理時的體積收縮的同時，於加熱處理後 所形成的熱傳導體之緻密性或表面平滑性會提升。又，該 微晶徑，意指藉由以Cu之Κα射線作為射線源之粉末X射 線繞射法進行測定，求出平面指數為（11，1)面之波峰的半 高寬（half width) ’ 再以謝樂公式（Scherrer formula)計 算出之值。 本發明中所使用之銀微粒子，初級銀微粒子的平均粒 徑相對於微晶徑之比（平均粒徑/微晶徑）為1至1〇，較佳 為1至7· 5,更佳為1至5之範圍。 本發明中所使用之銀微粒子可藉由下述方式製造：混 324149 201247859 合紐之銀難m級胺，其:欠，添加還原劑，於反 應溫度2 0至8 0 °C使銀微粒子析出。 首先，混合羧酸的銀鹽與脂肪族一級胺，得到溶解 竣酸的銀鹽的溶液。在溶液巾，可認為脂㈣—級胺會配 位於羧酸的銀鹽，形成一種胺錯合物。 羧酸的銀鹽可為脂肪族、芳香族之任一者之緩酸的銀 鹽。此外，羧酸的銀鹽也可為單綾酸的銀鹽，亦可為二元 竣酸等多元It酸的銀鹽。脂㈣驗的銀鹽也可為鍵狀脂 肪族紐的銀鹽’亦可為環狀脂肪峨酸的銀鹽。脂肪族 幾^的銀鹽’較佳為鏈狀脂肪族單敌酸的銀鹽，更佳為醋 酸銀、丙酸銀或丁酸銀，特佳為醋酸銀。該等可僅使用曰】 種類’亦可將2種以上併用。 ^月曰肪知一級胺係可為鏈狀脂肪族一級胺，亦可為環狀 脂肪族-級胺。此外’亦可係—元胺化合物、二元胺化合 物等多7L胺化合物。於脂肪族_級胺，脂肪族烴基之氣原 子’亦可為經經基、曱氧基、6氧基等烧氧基取代者。脂 肪族一級胺’更佳為3-曱氧基丙基胺、3_胺基丙醇、或丨，2一 〜胺基環己:^該等可僅使用丨種類，亦可將2種以上併 用。 相對於鲮酸的銀鹽1當量，脂肪族一級胺的使用量以201247859 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a thermally conductive composition and a heat conductor obtained by processing the same. [Prior Art] In the past, in order to attach/fix a semiconductor chip to a metal plate such as a lead frame, silver paste containing silver powder, a thermosetting resin, and a solvent was used (silverpaste). ). When the silver paste is used to subsequently/fix the wafer, the heat generated by the wafer can be quickly dissipated to the lead frame due to the high thermal conductivity of the silver. In addition, since the curing temperature of the resin is low, when the wafer is fixed/fixed, the wafer is less likely to deteriorate due to heat. In addition, the silver or resin contained in the silver paste is less expensive than gold. Further, the viscosity or thixotropy of the silver paste can be controlled by adjusting the amount of addition of the viscosity modifier (solvent) contained in the silver paste. Since the silver paste is easy to handle, it can be selectively imparted to the adhesive surface by printing or by injection, dripping or the like. Therefore, silver paste is mostly used for the subsequent/fixed wafer. Patent Document 1 discloses a silver paste which is prepared by mixing spherical silver fine particles smaller than silver powder in a paste containing silver powder, a thermosetting resin, and a solvent-based conductive paste. Patent Document 2 discloses a thermally conductive resin composition comprising a compound having silver powder, a thermosetting resin, and a sulfur bond and a warp group. Patent Document 3 discloses a method of producing a pump for electronic circuit connection by subjecting silver particles coated with a derivative of a higher fatty acid or a higher fatty acid to heat treatment. Patent Document 4 324149 4 201247859 discloses a paste comprising a silver fine particle obtained by reducing silver ions and a thermosetting resin as a binder component, and having excellent thermal conductivity. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2009-289745 [Patent Document 2] JP-A-2009-289214 (Patent Document 3) JP-A-2009-289745 [Problem to be Solved by the Invention] In recent years, the amount of heat generated from the wafer has increased due to the high performance of electronic components using semiconductor wafers, and is becoming more intense. The silver paste required to bond/fix the wafer to the lead frame has a high thermal conductivity. Here, an object of the present invention is to provide a thermally conductive composition which can obtain a heat conductor having high thermal conductivity. (Means for Solving the Problem) The inventors of the present invention have studied to solve the above problems. As a result, the inventors have found that by using a thermally conductive composition containing silver powder, silver fine particles, fatty acid silver, or amine, it is possible to obtain a heat conductor having a thermal conductivity higher than that of the conventional silver paste containing silver powder and silver fine particles. The present invention has been accomplished based on such novel findings. The present invention is a thermally conductive composition comprising: (A) silver powder, (B) silver fine particles, (C) silver fatty acid and (D) amine. The above-mentioned (A) silver powder, preferably having an average particle diameter of from 0.3/m to 100/zm. 324149 5 201247859 Describing (B) Silver microparticles are preferably: the average particle size of the primary particles is 5 〇 to 150 ' 'microcrystalline diameter (^% 仏 1111; 6 (14 cleavage 〇 2 〇 to 5 〇, Moreover, the ratio of the average particle diameter to the crystallite diameter is from 丨 to 75. The above (B) silver record, the material II is produced by the following method: mixing the acid salt of the acid with the aliphatic-grade amine, followed by The precipitant is added to precipitate silver fine particles at a reaction temperature of 20 to 80 ° C. The thermally conductive composition of the present invention preferably further comprises (e) silver resinate. The thermally conductive composition of the present invention is preferably. The invention provides a (F) resin. The present invention provides a thermal conductor which is obtained by heat-treating any of the above thermally conductive compositions at a temperature range of 100 i 40 (TC). The present invention provides any of the above-described thermally conductive compositions. The present invention provides an electronic component and a thermal conductor thereof. (Effect of the Invention) According to the present invention, it is possible to provide a heat conduction of a heat conductor having high thermal conductivity. Sex composition. [Embodiment] The following is detailed The heat conductive composition according to the embodiment of the present invention is characterized by comprising: (A) silver powder, (8) silver fine particles, (c) fatty acid silver, and (D) an amine. (A) Silver powder 324149 6 201247859 A powder made of pure silver or a silver alloy may be, for example, a spherical shape, a granular shape or a silver powder of the present invention, and may be used. The shape of the silver powder is not particularly limited, and is a sheet-like (scale-like) silver powder. The silver powder used in the medium is preferably l/zm to 5〇"claw/ /仫, which is preferably 0. 3 to m. The average grain in this case ^ ^佳' 2.4_ to 16/ζιη type particle size distribution measurement method I 糸 finger by laser diffraction scattering in order to improve the thermal conductivity of the 埶 2: the average particle size (10)). The larger one is preferable, and the heat conductive composition may damage the heat conductive composition. When the particle size of the silver powder is too large, the coating property of the device is not impaired. Silver powder with a large diameter. The material is used for reading, preferably the average particle size of the silver powder is above; Van j: = good in the invention In addition, by using the packing density (knock tightness), the contact points or contact faces of the silver powders can be increased. The sisters are the heat conduction points or heat conduction surfaces between the silver powders and the silver powder. The packing density is preferably such that the mixing distribution and/or the plurality of silver powders are similar. The thermally conductive composition of the present invention contains an additive for promoting metal fusion bonding of the thermal conduction points of the silver powders. Such an additive forms a larger heat conduction path inside the heat conductor obtained by heating the thermally conductive composition. In the present invention, (C) fatty acid silver and (D) amine described later are used as such an additive. The method for producing the silver powder is not particularly limited. For example, silver powder can be produced by a reduction method, a pulverization method of 324149 7 201247859, an electrolysis method, an atomizing method, a heat treatment method, or a combination thereof. The sheet-like silver powder can be produced, for example, by crushing spherical or granular silver particles or the like by a ball mill. (B) Silver fine particles The silver fine particle of the present invention has, for example, a small average particle diameter with respect to the above silver powder. A particle composed of pure silver or a silver alloy. The primary particles of the silver fine particles of the present invention have an average particle diameter of from 4 to 150 nm, preferably from 50 to 150 nm, more preferably from 70 to 140 nm. When the average particle diameter of the silver fine particles is within this range, the aggregation of the silver fine particles is suppressed, and the storage stability of the silver paste is improved. Here, the average particle diameter herein means an average value of a projected area diameter (Heywood Diameter) obtained by image analysis by scanning electron microscopy (SEM). The silver fine particles used in the present invention have a crystallite diameter of 15 to 5 Å, preferably 20 to 5 nm. When the crystallite diameter is within this range, the volume shrinkage of the thermally conductive composition during heat treatment is suppressed, and the heat conductivity or surface smoothness of the heat conductor formed after the heat treatment is improved. Further, the microcrystalline diameter means that the half-height width of the peak of the (11, 1) plane is obtained by measuring the powder X-ray diffraction method using Κα rays of Cu as a ray source. ' Calculate the value by the Scherrer formula. In the silver fine particles used in the present invention, the ratio of the average particle diameter of the primary silver fine particles to the crystallite diameter (average particle diameter / crystallite diameter) is 1 to 1 Torr, preferably 1 to 7.5, more preferably Range of 1 to 5. The silver fine particles used in the present invention can be produced by mixing 324149 201247859 with a silver-doped m-amine, which is: owing, adding a reducing agent, and depositing silver fine particles at a reaction temperature of 20 to 80 ° C. . First, a silver salt of a carboxylic acid and an aliphatic primary amine are mixed to obtain a solution in which a silver salt of citric acid is dissolved. In solution towels, it is believed that the lipid (tetra)-amine will be coordinated to the silver salt of the carboxylic acid to form an amine complex. The silver salt of the carboxylic acid may be a slow acid silver salt of either aliphatic or aromatic. Further, the silver salt of the carboxylic acid may be a silver salt of monodecanoic acid or a silver salt of a polyvalent It acid such as dibasic citric acid. The silver salt of the lipid (4) may also be a silver salt of a key aliphatic group, or a silver salt of a cyclic fatty acid. The aliphatic silver salt ' is preferably a silver salt of a chain aliphatic monobasic acid, more preferably silver acetate, silver propionate or silver butyrate, and particularly preferably silver acetate. These may be used alone or in combination of two or more. ^月曰肥 know that the primary amine system can be a chain aliphatic primary amine, or a cyclic aliphatic-grade amine. Further, it may be a 7 L amine compound such as a monoamine compound or a diamine compound. The aliphatic atom-amine, the aliphatic hydrocarbon group gas atom ' may also be substituted with an alkyl group such as a thiol group, a decyloxy group or a oxy group. The aliphatic primary amine 'more preferably 3-methoxypropylamine, 3-aminopropanol, or hydrazine, 2-aminocyclohexene: ^ These may be used alone or in combination of two or more And use it. The amount of the aliphatic primary amine used is 1 equivalent to the silver salt of citric acid.

I CT 田以上為較佳。相對於羧酸的銀鹽1當量，脂肪族一 級胺的使用量以1〇至3。0當量為較佳，1.0至2.0當量 為更佳’ 1.2至1.8當量為特佳。 護酸的銀鹽與脂肪族一級胺之混合，可於有機溶劑未 324149 201247859 存在下或存在下進杆。 行。作為有機溶劑之例二:用有：溶劑，可易於混合進 丙二醇二丁. w %、叫、丁醇等醇類； 劑可僅使用i種類U笨等芳香族煙等。該等有機溶 用量為住立曰 將2種以上併用。有機溶劑之使 用里為任進行混 ㈣㈣之便 之銀微粒子的生產料·定。 -、在之後的步驟 為了混合綾酸鹽之銀略 攪拌第-級脂肪族胺、戋；、曰、一級胺，係例如-邊 .备 或第一級脂肪族胺與有機溶密丨丨之、、早 合物，-邊將_的銀•力。於 n劑之混 適宜地繼續攪拌。_ # 、、 +加結束後’亦可 間内’溫度係以維持於20至80 C為較佳’以維持於20至6(TC為更佳。 f ；δ 後於級的銀鹽與脂肪族—級胺之混合物中添加 、'^、使銀微粒子析出。就反應的控制之點而言，還原 劑係以甲酸、Μ、抗壞血酸或肼（hydrazine)為較佳，甲 酸為更佳。該等可僅使用1種類，亦可將2種以上併用。 相對於麟的銀鹽，還原劑之使用量係以氧化還原當量以 上為較佳，氧化還原當量的丨至3倍為更佳。 在還原劑的添加及之後的反應之間，溫度係維持於2〇 C至80C。溫度係以20至70°C為較佳，20至60°C為更佳。 溫度若於該範圍，隨著銀微粒子充分地成長，生產性會變 同，銀微粒子之二次凝集亦會受到抑制。還原劑的添加及 之後的反應所需要的時間雖因反應裝置的規模.而異.，惟通 吊係10分鐘至10小時。又，於還原劑的添加及之後的反 應之際，可視需要追加乙醇、丙醇、丁醇等醇類；丙二醇 324149 10 201247859 二丁基鱗等醚類；甲苯等芳香族烴等有機溶劑。 於還原劑的添加及之後的反應中，相對於混合有羧酸 的銀鹽與脂肪族一級胺之溶液、還原劑、與有機溶劑之總 計容積（L) ’羧酸的銀鹽的量（111〇1)以1〇至6.0 m〇i/L為 較佳，2. 0至5. 0 mol/L為更佳、2. 0至4. Omol/L為又更 佳。當羧酸的銀鹽之濃度於該範圍時，能充分地進行反應 液的擾拌，而可去除反應熱。其結果為，由於析出的銀微 粒子之平均粒徑為適當，故可防止於後續步驟進行之沈降 傾析、置換溶劑等操作發生障礙。 將混合有羧酸的銀鹽與脂肪族一級胺之溶液與任意 的有機溶劑放入反應容器後，於反應容器中連續地供給還 原劑。以此種半批次（semibatch)方式進行反應時，從還原 劑的添加開始至反應結束為止之每1小時的銀微粒子析出 量，係例如為〇. 3至1. 〇m〇 1 /h/L。因此，以半批次方式進 行反應時’銀微粒子之生產性變得非常大。在此所謂之銀 微粒子的析出量，意指相對於混合有羧酸的銀鹽與脂肪族 一級胺之溶液、還原劑、有機溶劑的總計容積1L之銀微粒 子的析出量。以連續反應方式（連續式完全混合槽，流通式） 進行反應時，銀微粒子之生產性變得更大。 使藉由上述反應析出的銀微粒子沈降後，係藉由傾析 等去除上清液，或添加醇等溶劑，例如添加曱醇、乙醇、 萜品醇等。藉此’可從反應液分離出銀微粒子。 又，上述所說明之銀微粒子的製造方法本身已屬公知 者，例如係揭示於日本特開2006-183072號公報。 324149 11 201247859 (c)脂肪酸銀 作為本發明之脂肪酸銀，可使用例如醋酸、丙酸、丁 酸、辛酸、月桂酸、肉菫蔻酸、軟脂酸、硬脂酸、山荼酸 (behenic acid)、丙烯酸、油酸、亞麻油酸、花生油酸 (arachidonic acid)等的銀鹽。其中，以使用醋酸的銀鹽 為最佳。 此外，作為（C)脂肪酸銀，可使用上述為（B)銀微粒子 原料之羧酸的銀鹽。 ⑻胺 作為本發明之胺，可使用1級胺、2級胺、3級胺中 之任一者。作為胺之例，可舉：脂肪族胺、芳香族胺、改質 多元胺（例如、聚胺基醯胺、聚胺基醯亞胺、聚胺基酯、聚 胺基脲、聚醚改質胺等）、三級胺化合物、咪唑化合物（例 如2-曱基咪唑、2-苯基咪唑、2-苯基-4-曱基咪唑、2-苯 基-4-曱基-5-羥基曱基咪唑、2-十一基咪唑、2-十七基咪 ^、之^-二胺基^^-^’-曱基哺吐基-^’”-乙基-已-三啡 等）、醯肼化合物、二氰二胺（dicyandiamid)化合物、三聚 氰胺（melamine)化合物等。 此外，作為（D)胺，亦可使用上述（B)銀微粒子的原料 之脂肪族第1級胺。 (E)樹脂酸銀 本發明之熱傳導性組成物以復含有（E)樹脂酸銀為較 佳。 本發明中所使用之樹脂酸銀係以下式（1)所表示之化 324149 12 201247859 合物。 R-S-Ag ···(〇 於上式（1)中’ Ag係表示銀原子’ S係表示硫原子，r 係表示烷基。R所表示之烷基的碳數並無特別限制，碳數 為任意數。此外’烧基可為直鏈狀、分枝狀、環狀之任— 者。此外，烷基可為從飽和烴去除1個氫之燒基，亦可為 從不飽和烴去除1個氫之烷基。此外，烷基亦可為連續的 碳原子彼此間被氧原子隔開。此外，烷基之氫原子的一部 份可經羥基等其他的官能基取代。 上式（1)所表示之樹脂酸銀，較佳係羧酸的銀鹽與硫 醇的反應物，更佳係敌酸的銀鹽與第三_十二基硫醇的反應 物。 玫吸的銀鹽 J 日肋妷々日妨π —乏羧醍的ί 鹽。此外’賴的銀鹽，可為單紐的銀鹽，亦可為二; 緩酸等多紐的銀鹽。此外，賴的銀鹽，可為键狀脂月 族錢的銀鹽’亦可為環狀脂肪族紐的銀鹽。_的； ^較佳為醋酸銀、丙酸銀、或丁酸銀，特佳為醋酸銀( μ等可僅使用1種類，亦可將2種以上併用。 ^醇咖。丨）係於分子中具有丨個以上㈣基卜s价 :。硫醇較佳為苯f基硫醇、第三_十二基硫醇，更信 : 十二基硫醇。該等可僅使用1種類，亦可將2種以 上併用。 猎由一邊 製造樹脂酸銀 324149 授拌上述之麟的銀鹽—邊與硫醇混合，可 羧酉文的銀鹽與硫醇之混合，可於有機溶劑 13 201247859 未存在下或存在下進行。藉由使用有機溶劑，可容易地進 行混合。作為有機溶劑之例，可列舉乙醇、丙醇、丁醇等 醇類；丙二醇二丁基醚等醚類；環己烷等環狀烴；甲苯等 芳香族烴等。該等有機溶劑可僅使用1種類，亦可將2種 以上併用。 (F) 樹脂 本發明之熱傳導性組成物可復含有（F)樹脂。 本發明中所使用之樹脂，可為熱固性樹脂，亦可為熱 塑性樹脂。 熱固性樹脂並無特別限制，只要是藉由加熱進行硬化 之樹脂即可。熱固性樹脂之例，可列舉環氧樹脂、胺酯樹 脂、乙稀醋樹脂、聚^夕氧（silicone)樹脂、盼樹脂、尿素 樹脂（urea resin)、三聚氰胺樹脂、不飽和聚醋樹脂、二 烯丙基酞酸酯樹脂、聚醯亞胺樹脂等。 熱塑性樹脂並無特別限制，只要是藉由加熱進行軟化 之樹脂即可。作為熱塑性樹脂之例，可列舉乙基纖維素、 硝化織維素等纖維素系樹脂；丙烯酸樹脂、醇酸樹脂、飽 和聚酯樹脂、丁醛樹脂、聚乙烯醇、羥基丙基纖維素等可。 該等樹脂可僅使用1種類，亦可將2種類以上併用。 (G) 溶劑 本發明之熱傳導性組成物可為了黏度調整等而復含 有（G)溶劑。 溶劑係可使用該領域之公知者。溶劑之例可列舉甲 醇、乙二醇、丙二醇、二氫松油醇等醇系溶劑；甲苯、二 324149 14 201247859 甲苯、乙基苯、二乙基苯、異丙基苯、戊基苯、對異丙基 曱苯（p-cymene)、四氫萘及石油系芳香族烴混合物等芳香 族烴系溶劑；萜品醇、沈香醇（linalool)、香葉醇、香茅 醇等IS烯醇；乙二醇單乙基醚、乙二醇單丁基醚、丙二醇 單曱基醚、丙二醇單乙基醚、丙二醇單-正丁基醚、丙二醇 單-第三丁基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、 二丙二醇單甲基醚、二丙二醇單丁基醚、三丙二醇單曱基 醚等醚醇系溶劑；曱基異丁基酮等酮系溶劑；以及乙二醇 單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙二醇單丁基 乙醋酸酯、丙二醇單曱基醚乙酸酯、丙二醇單乙基醚乙酸+ 酯等酯系溶劑；水等。該等溶劑可僅使用1種類，亦可將 2種類以上併用。 (H)其他 另外，本發明之熱傳導性組成物亦可含有以下物質中 之任1種以上。 •無機填充劑（例如燻石夕（fumed si 1 ica)、碳酸辦、滑石等） •偶合劑（例如7 _縮水甘油氧基丙基三曱氧石夕烧等石夕烧偶 合劑；四辛基雙（二（十三基）亞磷酸酯）鈦酸酯等鈦酸酯偶 合劑等） •矽烷單體（例如、參（3-(三曱氧矽基）丙基）異氰酸酯） •可塑劑（例如羧基末端聚丁二烯-丙烯腈等共聚物；聚矽 氧橡膠（silicon gum)、聚^夕氧橡膠粉末、聚碎氧樹脂粉 末、丙烯酸樹脂粉末等樹脂粉末） •難燃劑 324149 15 201247859 •抗氧化劑 •消泡劑 藉由添加上述（A)銀粉、（B)銀微粒子、（c)脂肪酸銀、 及（D)胺並進行混合，可調製本發明之熱傳導性組成物。 此外，藉由添加1種以上選自上述（E)樹脂酸銀、（F) 樹脂、（G)溶劑、及（Η)其他成分之任意成分並進行混合， 可調製本發明之熱傳導性組成物。 又，上述（Α)至（Η)成分之加入順序為任意順序，可同 時加入上述（Α)至（Η)成分並進行混合，亦可依序加入上述 (Α)至（Η)成分並進行混合。 其次’說明使用以上述方式得到的熱傳導性組成物於 基板上形成熱傳導體之方法。 將上述（Α)至（D)成分、及視需要之（Ε)至（Η)成分進行 混合，調製膏狀的熱傳導性組成物。將前述所調製的熱傳 導性組成物塗佈在基板上。塗佈方法為任意方法，例如可 藉由为’主（dispense)、喷射分注（jet dispense)、漏版印 刷（stencil printing)、網版印刷、針式轉印、捺印 (stamping)等方法進行塗佈。 於基板上塗佈膏狀熱傳導性組成物後，將該熱傳導性 組成物於100至400°C，較佳為於150至35(TC，更佳為於 200至300°C之溫度範圍進行加熱處理。藉此，可於基板上 形成由熱傳導體構成的膜。 如此操作所得之熱傳導體膜係具有非常高之熱傳導 率特性。雖尚未明瞭其原因，但可認為是（(：）脂肪酸銀、及 324149 16 201247859 (D)胺2種成分形成某種錯合物，該錯合物係藉由使銀粉及 銀微粒子彼此間互相接近，而促進於加熱處理時銀粉及銀 微粒子彼此間之熔融接合。 本發明之熱傳導性組成物可使用於形成各種電子零 件之導電回路，例如使用於形成印刷電路板（printed substrate)之回路圖形。 此外，本發明之熱傳導性組成物可使用作為用以將半 導體晶片接著/固定於導線架之接著劑（晶片接合劑）。 加熱本發明之熱傳導性組成物所得之熱傳導體，熱傳 導率非常地高。藉由使用本發明之熱傳導性組成物，可製 造可容易地將例如由晶片所產生的熱散逸出之高放熱性電 子零件。 此外，本發明之熱傳導性組成物除了使用於晶片之接 著/固定以外，尚可使用於例如將電容器、電阻、二極體、 記憶體、運算元件（CPU)等接著/固定至基板。 (實施例） 以下說明本發明之實施例，惟本發明不限定於該等。 (A)銀粉 銀粉係將以下2種類（A1及A2)之銀片以1 : 1之比例 進行混合而使用。 (A1) 組成為「銀」、形狀為「球狀」、粒度分布為「D50:1.4 em，D10:0.7 /zm，D90:4。1 ym」、敲緊密度為「5. 1 g/ml」 (A2) 324149 17 201247859 r D50:4. 2 5. 2 g/ml」 組成為「銀」、形狀為「片狀」、粒度分布為 "m D1G. 1. 9 μ m，刪：7. 9 β m」、敲緊密度為「 (B )銀微粒子 銀微粒子係以以下方法所調製。 、先於10 L玻璃製反應容器中放入甲氧基丙基 :4二kg(45· 〇 mol)。將該3_甲氧基丙基胺維持於反應溫 又 C以下，一邊攪拌一邊添加醋酸銀5. 〇 kg(3〇. 〇 mol)。在剛添加醋酸銀時，醋酸銀係溶解於恥甲氧基丙基 胺’，透明溶液^若再添加醋酸銀，醋酸銀會慢慢開始混 蜀右添加全部量的醋酸銀，醋酸銀會變成現濁之灰色、 具有黏性的溶液。徐緩地滴下95重量％之甲酸0.7 g( 5· 0 mol)至該溶液。剛滴入曱酸後溶液會急劇地發 熱。該段時間内，將反應溫度維持於30至45。〇混濁之 灰色、具有黏性的溶液，係變為茶色，再進一步變為黑色。 部滴下之後’反應結束。若將藉由反應而得到的滿 。物靜置於4(Tc，則該混合物會分離成二層。上層係黃色 透明的液體。下層係已沉澱之黑色銀微粒子。上層的液體 中係不含銀β以傾析去除上層的液體。藉由使用曱醇之分 離，得到銀含有率90重量％之正球狀銀微粒子。 所得到的銀微粒子之平均粒徑為13〇nm，微晶徑為 40⑽，平均粒徑/微晶徑=3. 2卜平均粒徑係以掃描式電子 顯U鏡（SEM)觀察並藉由影像分析而求出的投影面積直徑 之平均值。微晶徑係以MAC Science股份有限公司製X射 線繞射測定裝置（M18XHF22)測定之值，而係由cu的Κα射 324149 18 201247859 線作為射線源並藉由粉末X射線繞射法測定，求出平面指 數（1，1，1)面之波峰的半高寬，並藉由謝樂公式計算之值。 (c)脂肪酸銀 脂肪酸銀係使用醋酸銀。 ⑻胺 胺係使用以下2種類的胺。 (D1)曱氧基丙基胺 (D2)二胺基環己烷 (E) 樹脂酸銀 樹脂酸銀係使用第三-十二基硫醇與醋酸銀之反應 物。 (F) 樹脂 樹脂係使用聚酯粉末。 (G) 溶劑 溶劑係使用以下2種類（G1至G2)的溶劑。 (G1)甲醇 (G2)正烧烴（Normal Paraffin)混合物（碳數C14至 C16之混合物） 依以下的表1所示之比例混合上述（A)至（G)成分。藉 此，調製實施例1至3、及比較例1至3之熱傳導性組成 物。又，表1所示之各成分調配比例係以總重量％表示。 324149 19 201247859 [表1] 實施例1 實施例2 實施例3 比較例1 比較例2 比較例3 銀粉 (A1) 41.75 41.75 41.75 41.75 41.75 ΓΙΓΫΓ (A2) 41.75 41.75 41.75 41.75 41.75 41.75 銀微粒 子 (B) 0.40 0.40 0.40 0.40 0. 40 脂肪酸 銀 (C) 0.13 0.13 0.13 胺 (D1) 0.10 0.10 (D2) 0.10 樹脂酸 銀 (E) 0.23 0.23 樹脂 (F) 8.64 8. 64 8.64 8.64 8.64 8.64 溶劑 (G1) 0.10 (G2) 7. 23 7.13 7.00 7.86 7.23 7.46 熱傳導率[W/mK] 47.1 46.8 54.4 — 24.4 —4·6·「 29.0 藉由漏版印刷法’將實施例1至3及比較例1至3之 熱傳導性組成物構成的銀膏、分別塗佈至鐵氟龍（註冊商標） 製的基板。其次，將基板於200°C進行加熱處理30分鐘。 加熱處理後，將塗膜由鐵氟龍（註冊商標）製的基板剝離。 藉此’付到厚度300 /zm之熱傳導體構成的膜。以雷射閃 光（laser flash)法分別測定熱傳導體構成的膜之熱傳導 率。測定結果係如上述表1所示。 又’雷射閃光法係測定熱擴散率之方法，對樣品内面 照射脈衝（pulse)狀氙閃光’以紅外線檢測器測定熱傳至樣 品表面者。熱傳導率係可以熱擴散率x比熱X密度算出。 由表1所示之結果瞭解到，將實施例1至3之熱傳導 性組成物進行加熱處理而得到的熱傳導體，熱傳導 324149 20 201247859 45.0[W/mK]以上，具有高熱傳導率。 由此結果可證實，含有（A)銀粉、（B)銀微粒子、（C) 脂肪酸銀、及（D)胺之熱傳導性組成物較僅含有（A)銀粉、 或者是僅含有（A)銀粉及（B)銀微粒子之熱傳導性組成物係 可得到具有高熱傳導率之熱傳導體。 比較實施例1與實施例3之結果即可知，包含（E)樹 脂酸銀之熱傳導性組成物較未含（E)樹脂酸銀之熱傳導性 組成物係可得到具有高熱傳導率之熱傳導體。 比較實施例3與比較例2之結果即可知，含有（A)銀 粉、（B)銀微粒子、（〇脂肪酸銀、（D)胺、及（E)樹脂酸銀 之熱傳導性組成物較僅含有（A)銀粉、（B)銀微粒子、及（E) 樹脂酸銀之熱傳導性組成物係可得到具有高熱傳導率之熱 傳導體。 第1圖係表示將實施例1至3之熱傳導性組成物加熱 而得之熱傳導體膜的剖面之電子顯微鏡照片。第2圖係表 示將比較例1至3之熱傳導性組成物加熱而得之熱傳導體 膜的剖面之電子顯微鏡照片。 比較第1圖及第2圖即可知，將實施例1至3之熱傳 導性組成物加熱而得之熱傳導體膜，銀粉及銀微粒子彼此 間係互相炫融接合而形成大的熱傳導路徑，故具有高熱傳 導率。相對於此，將比較例1至3之熱傳導性組成物加熱 而得之熱傳導體膜，銀粉及銀微粒子彼此間並未熔融接 合，不具有高熱傳導率。 【圖式簡單說明】 324149 21 201247859 第1圖係表示由實施例1至'3之熱傳導性組成物而得 之熱傳導體膜的剖面之電子顯微鏡照片。 第2圖係表示由比較例1至3之熱傳導性組成物而得 之熱傳導體膜的剖面之電子顯微鏡照片。 【主要元件符號說明】 無 324149 22I CT above is preferred. The aliphatic primary amine is preferably used in an amount of from 1 Torr to 3.0 equivalents, more preferably from 1.0 to 2.0 equivalents, more preferably from 1.2 to 1.8 equivalents, per equivalent of the silver salt of the carboxylic acid. The acid-protected silver salt is mixed with the aliphatic primary amine and can be fed in the presence or absence of an organic solvent 324149 201247859. Row. Example 2 as an organic solvent: It can be easily mixed with a solvent such as propylene glycol dibutyl ketone, an alcohol such as butanol, or the like. These organic solvents are used in combination with two or more kinds. In the use of the organic solvent, the production of silver fine particles for the mixing of (4) and (4) is determined. - in the subsequent step, in order to mix the citrate silver, stir the first-grade aliphatic amine, hydrazine, hydrazine, primary amine, such as - side or first-grade aliphatic amine and organic solvent ,, early compound, - the silver will force _. Stirring is continued as appropriate in the mixture of agents. _ # , , + After the end of the addition, the 'temperature can be maintained at 20 to 80 C is better' to maintain 20 to 6 (TC is better. f ; δ after the grade of silver salt and fat The mixture of the group-grade amine is added, and the silver fine particles are precipitated. In terms of the control of the reaction, the reducing agent is preferably formic acid, hydrazine, ascorbic acid or hydrazine, and formic acid is more preferable. The above-mentioned type may be used alone or in combination of two or more kinds. The amount of the reducing agent to be used is preferably a redox equivalent or more, and more preferably 3 times the redox equivalent of the silver salt. Between the addition of the reducing agent and the subsequent reaction, the temperature is maintained at 2 ° C to 80 C. The temperature is preferably 20 to 70 ° C, more preferably 20 to 60 ° C. If the temperature is within this range, The silver particles are sufficiently grown, the productivity will be the same, and the secondary agglomeration of the silver particles will be suppressed. The time required for the addition of the reducing agent and the subsequent reaction varies depending on the scale of the reaction device. 10 minutes to 10 hours. In addition, when the addition of the reducing agent and the subsequent reaction, it is possible to chase Alcohols such as ethanol, propanol and butanol; propylene glycol 324149 10 201247859 Ethers such as dibutyl sulphate; organic solvents such as aromatic hydrocarbons such as toluene. In the addition of a reducing agent and subsequent reactions, carboxylic acid is mixed with The solution of the silver salt and the aliphatic primary amine, the reducing agent, and the total volume of the organic solvent (L) 'the amount of the silver salt of the carboxylic acid (111〇1) is preferably from 1 〇 to 6.0 m〇i/L. 2. 0 to 5. 0 mol / L is more preferable, 2. 0 to 4. Omol / L is more preferably. When the concentration of the silver salt of the carboxylic acid is within this range, the reaction liquid can be sufficiently disturbed. The heat of reaction can be removed. As a result, since the average particle diameter of the precipitated silver fine particles is appropriate, it is possible to prevent the operation of sedimentation decantation, replacement of the solvent, and the like in the subsequent step. After the solution with the aliphatic primary amine and any organic solvent are placed in the reaction vessel, the reducing agent is continuously supplied to the reaction vessel. When the reaction is carried out in such a semibatch manner, the reaction is started from the addition of the reducing agent to the reaction. The amount of silver fine particles deposited per hour until the end is, for example,至. 3 to 1. 〇m〇1 /h/L. Therefore, when the reaction is carried out in a semi-batch manner, the productivity of silver microparticles becomes very large. The amount of silver microparticles precipitated here means relative to The amount of silver fine particles in a total volume of 1 L of a solution of a silver salt of a carboxylic acid and an aliphatic primary amine, a reducing agent, and an organic solvent is mixed. When the reaction is carried out by a continuous reaction method (continuous complete mixing tank, flow type), silver is mixed. After the silver fine particles deposited by the above reaction are allowed to settle, the supernatant is removed by decantation or the like, or a solvent such as an alcohol is added, for example, decyl alcohol, ethanol, terpineol or the like is added. Thereby, silver fine particles can be separated from the reaction liquid. Further, the method for producing the silver fine particles described above is known per se, and is disclosed, for example, in Japanese Laid-Open Patent Publication No. 2006-183072. 324149 11 201247859 (c) Fatty acid silver As the fatty acid silver of the present invention, for example, acetic acid, propionic acid, butyric acid, octanoic acid, lauric acid, capric acid, palmitic acid, stearic acid, behenic acid (behenic acid) can be used. ), silver salts of acrylic acid, oleic acid, linoleic acid, arachidonic acid, and the like. Among them, silver salt using acetic acid is preferred. Further, as the (C) fatty acid silver, the silver salt of the carboxylic acid of the above (B) silver fine particle raw material can be used. (8) Amine As the amine of the present invention, any of a primary amine, a secondary amine, and a tertiary amine can be used. As an example of the amine, an aliphatic amine, an aromatic amine, a modified polyamine (for example, polyamine amide, polyamine amide, polyamine, polyamine urea, polyether modification) Amine, etc.), tertiary amine compound, imidazole compound (eg 2-mercaptoimidazole, 2-phenylimidazole, 2-phenyl-4-mercaptoimidazole, 2-phenyl-4-indolyl-5-hydroxyindole) Imidazole, 2-undecyl imidazole, 2-pyridyl imidazolium, ^-diaminol^^-^'-indenyl-based thiol-^'"-ethyl-hexyl-triphthyl, etc. An anthracene compound, a dicyandiamid compound, a melamine compound, etc. Further, as the (D) amine, an aliphatic first-grade amine of the above (B) silver fine particle raw material may be used. Silver resinate The thermally conductive composition of the present invention preferably contains (E) silver resinate. The resin acid silver used in the present invention is a compound represented by the following formula (1): 324149 12 201247859. Ag ··· (In the above formula (1), 'Ag is a silver atom', S represents a sulfur atom, and r represents an alkyl group. The carbon number of the alkyl group represented by R is not particularly limited, and the carbon number is arbitrary. number In addition, the 'alkyl group may be linear, branched or cyclic. In addition, the alkyl group may be a base for removing one hydrogen from a saturated hydrocarbon, or one hydrogen may be removed from the unsaturated hydrocarbon. Further, the alkyl group may be such that consecutive carbon atoms are separated from each other by an oxygen atom. Further, a part of the hydrogen atom of the alkyl group may be substituted with another functional group such as a hydroxyl group, as represented by the above formula (1). The silver resin resin is preferably a reaction product of a silver salt of a carboxylic acid and a mercaptan, more preferably a reaction product of a silver salt of a dicarboxylic acid and a third-dodecyl mercaptan. 々 妨 π — 乏 carboxy 醍 ί salt. In addition, 'Lai's silver salt, can be a single silver salt, can also be two; slow acid and other multi-new silver salt. In addition, Lai silver salt, can be The silver salt of the key fatty moon money may also be a silver salt of a cyclic aliphatic group. _; ^ is preferably silver acetate, silver propionate, or silver butyrate, particularly preferably silver acetate (μ, etc. Only one type may be used, and two or more types may be used in combination. ^Alcohol. 丨) has more than one (4) s-valent valence in the molecule: thiol is preferably benzene-f- thiol, and third-twelfth Base thiol, more faith : Dodecyl mercaptan. These may be used in only one type, or two or more types may be used together. Hunting from the side to produce silver resin 324149, mixing the silver salt of the above-mentioned Lin - mixed with mercaptan, can be carboxy The mixing of the silver salt and the mercaptan can be carried out in the absence or presence of the organic solvent 13 201247859. The mixing can be easily carried out by using an organic solvent. Examples of the organic solvent include ethanol, propanol and butanol. An alcohol such as an ether such as propylene glycol dibutyl ether; a cyclic hydrocarbon such as cyclohexane; or an aromatic hydrocarbon such as toluene. These organic solvents may be used alone or in combination of two or more. (F) Resin The thermally conductive composition of the present invention may further comprise (F) a resin. The resin used in the present invention may be a thermosetting resin or a thermoplastic resin. The thermosetting resin is not particularly limited as long as it is a resin which is cured by heating. Examples of the thermosetting resin include epoxy resin, amine ester resin, ethylene vinegar resin, silicone resin, expectant resin, urea resin, melamine resin, unsaturated polyester resin, and diene. A propyl phthalate resin, a polyimide resin, or the like. The thermoplastic resin is not particularly limited as long as it is a resin which is softened by heating. Examples of the thermoplastic resin include cellulose resins such as ethyl cellulose and nitrification, and acrylic resins, alkyd resins, saturated polyester resins, butyral resins, polyvinyl alcohol, and hydroxypropyl cellulose. . These resins may be used alone or in combination of two or more. (G) Solvent The thermally conductive composition of the present invention may contain a (G) solvent for viscosity adjustment or the like. Solvents can be used by those skilled in the art. Examples of the solvent include alcohol solvents such as methanol, ethylene glycol, propylene glycol, and dihydroterpineol; toluene, two 324149 14 201247859 toluene, ethylbenzene, diethylbenzene, cumene, pentylbenzene, and An aromatic hydrocarbon solvent such as p-cymene, tetrahydronaphthalene or a petroleum aromatic hydrocarbon mixture; IS enol such as terpineol, linalool, geraniol or citronellol; Ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monodecyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol mono-telebutyl ether, diethylene glycol single An ether alcohol solvent such as ethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monobutyl ether or tripropylene glycol monodecyl ether; a ketone solvent such as mercaptoisobutyl ketone; And ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl acetate, propylene glycol monodecyl ether acetate, propylene glycol monoethyl ether acetate + ester Equivalent ester solvent; water, etc. These solvents may be used alone or in combination of two or more. (H) Others The heat conductive composition of the present invention may contain any one or more of the following. • Inorganic fillers (eg fumed si 1 ica, carbonated, talc, etc.) • coupling agents (eg 7 _ glycidoxypropyl trioxon oxylate, etc.; a bis (tris(tridecyl) phosphite) titanate coupling agent such as titanate, etc.) • a decane monomer (for example, ginseng (3-(trioxanyl)propyl)isocyanate) • plasticizer (For example, copolymers such as carboxyl-terminated polybutadiene-acrylonitrile; resin powders such as polysilicon rubber, polyoxyethylene rubber powder, polyacetal resin powder, and acrylic resin powder) • Flame retardant 324149 15 201247859 • Antioxidant/antifoaming agent The thermally conductive composition of the present invention can be prepared by adding and mixing the above (A) silver powder, (B) silver fine particles, (c) fatty acid silver, and (D) amine. Further, the heat conductive composition of the present invention can be prepared by adding one or more optional components selected from the group consisting of the above (E) resin acid silver, (F) resin, (G) solvent, and other components. . Further, the order of addition of the above (Α) to (Η) components is in any order, and the above (Α) to (Η) components may be simultaneously added and mixed, and the above (Α) to (Η) components may be sequentially added and carried out. mixing. Next, a method of forming a heat conductor on a substrate using the thermally conductive composition obtained in the above manner will be described. The above-mentioned (Α) to (D) components and, if necessary, (Ε) to (Η) components are mixed to prepare a paste-like heat conductive composition. The heat-conductive composition prepared as described above is coated on a substrate. The coating method is any method, for example, by a method of 'dispense, jet dispense, stencil printing, screen printing, pin transfer, stamping, and the like. Coating. After coating the paste-like thermally conductive composition on the substrate, the thermally conductive composition is heated at a temperature ranging from 100 to 400 ° C, preferably from 150 to 35 (TC, more preferably from 200 to 300 ° C). Therefore, a film made of a heat conductor can be formed on the substrate. The heat conductor film obtained in this way has very high thermal conductivity characteristics. Although the reason is not known, it can be considered as ((:) fatty acid silver, And 324149 16 201247859 (D) The two components of the amine form a complex compound which promotes the fusion bonding of the silver powder and the silver fine particles to each other during the heat treatment by bringing the silver powder and the silver fine particles closer to each other. The thermally conductive composition of the present invention can be used to form a conductive circuit for various electronic parts, for example, a circuit pattern for forming a printed circuit board. Further, the thermally conductive composition of the present invention can be used as a semiconductor The wafer is subsequently/fixed to the lead frame of the lead frame (wafer bonding agent). The heat conductor obtained by heating the thermally conductive composition of the present invention has a very high thermal conductivity. By using the thermally conductive composition of the present invention, a highly exothermic electronic component that can easily dissipate heat generated, for example, by a wafer can be manufactured. Further, the thermally conductive composition of the present invention is used in addition to/after attachment to a wafer. In addition, for example, a capacitor, a resistor, a diode, a memory, an arithmetic element (CPU), and the like may be attached/fixed to the substrate. (Embodiment) Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto. (A) Silver powder silver powder is used by mixing the following two types of silver sheets (A1 and A2) in a ratio of 1:1. (A1) The composition is "silver", the shape is "spherical", and the particle size distribution is "D50: 1.4 em, D10: 0.7 /zm, D90: 4. 1 ym", and the knocking degree is "5. 1 g/ml" (A2) 324149 17 201247859 r D50: 4. 2 5. 2 g/ml The composition is "silver", the shape is "flaky", the particle size distribution is "m D1G. 1. 9 μ m, deleted: 7. 9 β m", and the knock tightness is "(B) silver microparticle silver microparticle system It was prepared by the following method: methoxypropyl: 4 2 kg (45·〇mol) was placed in a 10 L glass reaction vessel. The 3-methoxypropylamine is maintained at a reaction temperature of C or less, and silver acetate is added while stirring 5. 〇kg(3〇. 〇mol). When silver acetate is added, silver acetate is dissolved in the smear Propylamine', transparent solution ^ If silver acetate is added, the silver acetate will slowly start to mix and add the entire amount of silver acetate. The silver acetate will become a turbid gray, sticky solution. Slowly drip 95 0.7 g (5.0 mol) of formic acid by weight to the solution. The solution will heat up sharply just after the addition of citric acid. During this time, the reaction temperature was maintained at 30 to 45. The turbid gray, viscous solution turns into brown and then turns black again. After the drip, the reaction is over. If it will be obtained by reaction. When the object is statically placed at 4 (Tc, the mixture is separated into two layers. The upper layer is a yellow transparent liquid. The lower layer is precipitated black silver microparticles. The upper layer of liquid contains no silver beta to decanted to remove the upper layer of liquid. By using the separation of decyl alcohol, positive spherical silver fine particles having a silver content of 90% by weight are obtained. The obtained silver fine particles have an average particle diameter of 13 〇 nm, a crystallite diameter of 40 (10), and an average particle diameter / crystallite diameter = 3. The average particle size is the average of the projected area diameters observed by scanning electron microscopy (SEM) and obtained by image analysis. The microcrystalline diameter is X-ray diffraction by MAC Science Co., Ltd. The value measured by the measuring device (M18XHF22) is determined by the Κα 324 149 18 201247859 line of cu as a ray source and measured by a powder X-ray diffraction method to obtain a half of the peak of the plane index (1,1,1) plane. Height and width, calculated by the Xerox formula. (c) Fatty acid Silver fatty acid silver is made of silver acetate. (8) Amine amines use the following two types of amines. (D1) methoxypropylamine (D2) diamine Base cyclohexane (E) resin silver acid resin silver acid using third-dodecyl sulfur (F) A resin powder is a polyester powder. (G) A solvent solvent is a solvent of the following two types (G1 to G2). (G1) Methanol (G2) is a hydrocarbon (Normal Paraffin) Mixture (mixture of carbon numbers C14 to C16) The above components (A) to (G) were mixed in the proportions shown in Table 1 below, whereby the heat conductivity of Examples 1 to 3 and Comparative Examples 1 to 3 was prepared. The composition ratio of each component shown in Table 1 is expressed by the total weight %. 324149 19 201247859 [Table 1] Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Silver powder (A1) 41.75 41.75 41.75 41.75 41.75 ΓΙΓΫΓ (A2) 41.75 41.75 41.75 41.75 41.75 41.75 Silver granules (B) 0.40 0.40 0.40 0.40 0. 40 Fatty acid silver (C) 0.13 0.13 0.13 Amine (D1) 0.10 0.10 (D2) 0.10 Silver resinate (E) 0.23 0.23 Resin (F) 8.64 8. 64 8.64 8.64 8.64 8.64 Solvent (G1) 0.10 (G2) 7. 23 7.13 7.00 7.86 7.23 7.46 Thermal conductivity [W/mK] 47.1 46.8 54.4 — 24.4 —4·6·“ 29.0 Example 1 to 3 and comparison by stencil printing method 1-3 silver paste of the thermally conductive composition consisting of, respectively, applied to the substrate Teflon (registered trademark) manufactured. Next, the substrate was heat-treated at 200 ° C for 30 minutes. After the heat treatment, the coating film was peeled off from a substrate made of Teflon (registered trademark). This is a film made of a heat conductor having a thickness of 300 / zm. The thermal conductivity of the film composed of the heat conductor was measured by a laser flash method. The measurement results are shown in Table 1 above. Further, the laser flash method is a method of measuring the thermal diffusivity, and the inner surface of the sample is irradiated with a pulse-like flash. The heat is transmitted to the surface of the sample by an infrared detector. The thermal conductivity can be calculated from the thermal diffusivity x and the thermal X density. As is apparent from the results shown in Table 1, the heat conductor obtained by heat-treating the thermally conductive compositions of Examples 1 to 3 has a high thermal conductivity of 324149 20 201247859 45.0 [W/mK] or more. From this result, it was confirmed that the thermally conductive composition containing (A) silver powder, (B) silver fine particles, (C) fatty acid silver, and (D) amine contained only (A) silver powder or only (A) silver powder. And (B) a thermally conductive composition of silver microparticles to obtain a thermal conductor having high thermal conductivity. As is apparent from the results of Comparative Example 1 and Example 3, a thermally conductive composition containing (E) silver sulphate can obtain a heat conductor having a high thermal conductivity than a thermally conductive composition containing no (E) resin acid silver. Comparing the results of Example 3 and Comparative Example 2, it is understood that the thermally conductive composition containing (A) silver powder, (B) silver fine particles, (anthracene fatty acid silver, (D) amine, and (E) resin acid silver contains only (A) Silver powder, (B) silver fine particles, and (E) thermal conductive composition of resin silver acid can obtain a heat conductor having high thermal conductivity. Fig. 1 shows the heat conductive compositions of Examples 1 to 3. An electron micrograph of a cross section of a heat conductor film obtained by heating. Fig. 2 is an electron micrograph showing a cross section of a heat conductor film obtained by heating the heat conductive compositions of Comparative Examples 1 to 3. Comparing Fig. 1 and Fig. 2, it can be seen that the thermal conductive film obtained by heating the thermally conductive compositions of Examples 1 to 3, the silver powder and the silver fine particles are mutually fused to each other to form a large heat conduction path, and thus have high thermal conductivity. Thus, the thermal conductive film obtained by heating the thermally conductive compositions of Comparative Examples 1 to 3, the silver powder and the silver fine particles were not melt-bonded to each other, and did not have high thermal conductivity. [Simplified Schematic] 324149 21 201247859 Fig. 1 is an electron micrograph showing a cross section of a thermal conductor film obtained from the thermally conductive compositions of Examples 1 to 3. Fig. 2 is a view showing heat conduction obtained by the thermally conductive compositions of Comparative Examples 1 to 3. Electron micrograph of the section of the body membrane. [Key element symbol description] No 324149 22

Claims (1)

201247859 七、申請專利範圍： 1. 一種熱傳導性組成物，其係含有以下（A)至（D)成分：（A) 銀粉、（B)銀微粒子、（C)脂肪酸銀、（D)胺。 2. 如申請專利範圍第1項所述之熱傳導性組成物，其中， 前述（A)銀粉之平均粒徑為0. 3 # m至1〇〇以m。 3. 如申請專利範圍第1項或第2項所述之熱傳導性組成 物’其中，前述（B)銀微粒子之初級粒子平均粒徑為50 至150nm，微晶徑為20至50nm，且平均粒徑相對於微 晶徑之比為1至7. 5。 4·如申請專利範圍第1項至第3項中任一項所述之熱傳導 性組成物’其中’前述（B)銀微粒子係藉由下述方式製 造者：混合敌酸的銀鹽與脂肪族一級胺，其次，添加還 原劑，並於反應溫度20至8(TC使銀微粒子析出。 5·如申請專利範圍第1項至第4項中任一項所述之熱傳導 性組成物，復含有（E)樹脂酸銀。 6.如申請專利範圍第1項至第5項中任一項所述之熱傳導 性組成物，復含有（F)樹脂。 7· —種熱傳導體，其係將申請專利範圍第1項至第6項中 任一項所述之熱傳導性組成物於100至400°C之溫度範 圍進行加熱處理所得者。 8. —種接著劑，其係包含申請專利範圍第丨項至第6項令 任一項所述之熱傳導性組成物。 9. 一種電子零件，其係包含申請專利範圍第7項所述之熱 傳導體。 ^ 324149201247859 VII. Patent Application Range: 1. A thermally conductive composition comprising the following components (A) to (D): (A) silver powder, (B) silver microparticles, (C) fatty acid silver, and (D) amine. 2. The average particle size of the (A) silver powder is 0.3 m to 1 m in m. 3. The thermally conductive composition according to claim 1 or 2, wherein the primary particle of the (B) silver microparticles has an average particle diameter of 50 to 150 nm, a microcrystal diameter of 20 to 50 nm, and an average 5。 The ratio of the particle diameter to the crystallite diameter is from 1 to 7.5. 4. The thermally conductive composition according to any one of claims 1 to 3, wherein the (B) silver microparticles are manufactured by mixing silver salt and fat of a diacid acid. a primary amine, followed by a reducing agent, and a reaction temperature of 20 to 8 (TC to precipitate silver fine particles. 5. The thermally conductive composition according to any one of claims 1 to 4, (E) a resinous silver oxide. The thermally conductive composition according to any one of claims 1 to 5, further comprising (F) a resin. The heat conductive composition according to any one of the items 1 to 6 is heat-treated at a temperature ranging from 100 to 400 ° C. 8. An adhesive comprising a patent application scope The thermally conductive composition according to any one of the preceding claims, wherein the heat conductive composition according to any one of claims 7 is provided.
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