TW201936818A - Composition for bonding - Google Patents

Abstract

The invention provides a composition for bonding, which enables bonding without pressurization at relatively low temperatures, and which enables the achievement of excellent bonding strength. A composition for bonding according to the invention contains first metal particles that have an average particle diameter of 20-100 nm and a dispersion medium; and the content of the dispersion medium relative to the entire amount of the composition for bonding is 1.0% by weight or more but less than 5.0% by weight.

Description

接合用組成物Composition for bonding

本發明是有關於一種含有金屬粒子的接合用組成物。The present invention relates to a bonding composition containing metal particles.

先前，為了將金屬零件與金屬零件機械性、電性及/或熱性接合而使用接合材料。作為所述接合材料，例如可列舉：焊料、導電性接著劑、銀糊、各向異性導電性膜等。該些接合材料不僅於金屬零件彼此的接合中使用，而且有時亦於金屬零件、與陶瓷零件、樹脂零件等的接合中使用。例如，近年來，有時於將發光二極體（Light Emitting Diode，LED）等發光元件、半導體晶片等接合於基板的用途、或將該些基板進而接合於放熱構件的用途中使用接合材料。Conventionally, a joining material is used for mechanically, electrically, and / or thermally joining a metal part to a metal part. Examples of the bonding material include solder, a conductive adhesive, a silver paste, and an anisotropic conductive film. These joining materials are used not only for joining metal parts to each other, but also for joining metal parts, ceramic parts, resin parts, and the like. For example, in recent years, a bonding material is sometimes used for a purpose of bonding a light emitting element such as a light emitting diode (LED), a semiconductor wafer, or the like to a substrate, or a purpose of bonding these substrates to a heat radiation member.

包括LED等發光元件的高亮度的照明器件或發光器件、被稱為功率器件的包括在高溫下進行高效率的動作的半導體元件的半導體器件等存在器件使用時的驅動溫度高的傾向。焊料的熔點比該些器件的驅動溫度低，因此並不適於LED等發光元件、半導體晶片等的接合。進而，近年來，就環境保護或「與電氣·電子設備中所含的特定有害物質的使用限制相關的歐洲議會及理事會指令」（RoHS）的規定的觀點而言，要求不含鉛的接合材料。High-luminance lighting devices or light-emitting devices including light-emitting elements such as LEDs, and semiconductor devices including semiconductor devices that perform high-efficiency operations at high temperatures, such as power devices, tend to have high driving temperatures during device use. The melting point of solder is lower than the driving temperature of these devices, so it is not suitable for bonding light-emitting elements such as LEDs and semiconductor wafers. Furthermore, in recent years, lead-free bonding has been required from the viewpoints of environmental protection or "European Parliament and Council Directive (RoHS) concerning restrictions on the use of certain hazardous substances contained in electrical and electronic equipment". material.

作為耐熱性高、且不含鉛的新的接合材料，研究有含有金屬奈米粒子的接合用組成物（例如，參照專利文獻1～專利文獻3等）。As a new bonding material having high heat resistance and containing no lead, a bonding composition containing metal nano particles has been studied (for example, refer to Patent Documents 1 to 3).

專利文獻1中揭示有一種金屬糊，其中於將包含銀粒子的固體成分與溶劑混煉而成的金屬糊中，所述固體成分包括以粒子數基準計而包含30%以上的粒徑100 nm～200 nm的銀粒子的銀粒子，構成固體成分的銀粒子整體的平均粒徑為60 nm～800 nm，進而構成固體成分的銀粒子與作為保護劑的碳數的總和為4～8的胺化合物鍵結，且熱重示差熱分析（Thermogravimetry-Differential Thermal Analysis，TG-DTA）中的因銀粒子的燒結而引起的發熱峰值顯現於小於200℃處。Patent Document 1 discloses a metal paste in which a solid content containing silver particles and a solvent are kneaded, and the solid content includes a particle size of 100 nm or more and a particle size of 100 nm or more. Silver particles of ~ 200 nm silver particles, the average particle diameter of the solid silver particles as a whole is 60 nm to 800 nm, and the total of the silver particles constituting the solid content and the carbon number as the protective agent is 4 to 8 amine The compounds are bonded, and the thermal peak caused by sintering of silver particles in Thermogravimetry-Differential Thermal Analysis (TG-DTA) appears at less than 200 ° C.

專利文獻2中揭示有一種金屬接合用組成物，其特徵在於：含有平均粒徑不同的兩種以上的金屬粒子、有機成分、以及分散劑，且平均粒徑最小的金屬粒子S的平均粒徑D_S 與平均粒徑最大的金屬粒子L的平均粒徑D_L 的粒徑比（D_S /D_L ）為1×10^-4 ～0.5。Patent Document 2 discloses a composition for metal bonding, which is characterized by containing an average particle diameter of two or more kinds of metal particles having different average particle diameters, an organic component, and a dispersant, and the smallest average particle diameter of metal particles S D _S and the maximum average particle diameter of metal particles of an average particle diameter D _L L diameter ratio (D _S / D _L) of 1 × 10 ^-4 ~ 0.5.

專利文獻3中揭示有一種銀微粒子組成物，其特徵在於：含有銀微粒子、包含烷氧基胺的分散劑、以及分散介質，且所述分散劑的含量相對於所述銀微粒子的含量而為0.1質量%～7.0質量%，自室溫加熱至200℃為止時的重量損失為所含有的所有有機成分的70質量%以上。
[現有技術文獻]
[專利文獻]Patent Document 3 discloses a silver fine particle composition including silver fine particles, a dispersant containing an alkoxyamine, and a dispersion medium, and the content of the dispersant relative to the content of the silver fine particles is 0.1% to 7.0% by mass, and the weight loss when heated from room temperature to 200 ° C is 70% by mass or more of all organic components contained.
[Prior Art Literature]
[Patent Literature]

[專利文獻1]日本專利第5795096號說明書
[專利文獻2]國際公開第2014/185073號
[專利文獻3]國際公開第2016/166948號[Patent Document 1] Japanese Patent No. 5795096
[Patent Document 2] International Publication No. 2014/185073
[Patent Document 3] International Publication No. 2016/166948

[發明所欲解決之課題]
先前，於使用金屬奈米粒子的接合中，有時一邊於300℃～350℃的惰性環境下進行加壓一邊進行接合。另外，於LED等發光元件、半導體晶片等的接合中，就防止接合時的該些器件的損傷的觀點而言，理想的是可於小於300℃的煅燒溫度下進行燒結。[Problems to be Solved by the Invention]
Conventionally, in the bonding using metal nano particles, the bonding may be performed while applying pressure in an inert environment at 300 ° C to 350 ° C. In addition, in the bonding of light-emitting elements such as LEDs, semiconductor wafers, and the like, from the viewpoint of preventing damage to these devices at the time of bonding, it is desirable that they can be sintered at a firing temperature of less than 300 ° C.

進而，近年來，對包括LED等發光元件、半導體晶片等的器件有提高輸出的要求，且有時進行高積體化、或增大投入電力。因此，該些器件的驅動溫度進一步變高，存在接合材料的使用環境變得更嚴酷的傾向，因此對LED等發光元件、半導體晶片等的接合要求高的接合強度。所述專利文獻1～專利文獻3中揭示有含有銀奈米粒子的金屬糊等，且揭示有可於比較低的溫度下進行燒結，但為了實現更高的接合強度而有進一步的研究餘地。Furthermore, in recent years, devices including light-emitting elements such as LEDs, semiconductor wafers, and the like have been required to increase their output, and they have been required to be highly integrated or have increased power input. Therefore, the driving temperature of these devices is further increased, and the use environment of the bonding material tends to be more severe. Therefore, high bonding strength is required for the bonding of light-emitting elements such as LEDs and semiconductor wafers. The Patent Documents 1 to 3 disclose metal pastes and the like containing silver nano particles, and also disclose that sintering can be performed at a relatively low temperature, but there is room for further research in order to achieve higher bonding strength.

本發明是鑑於所述課題而成，其目的在於提供一種即便於比較低的溫度下亦可不加壓地進行接合、且可獲得優異的接合強度的接合用組成物。
[解決課題之手段]The present invention has been made in view of the problems described above, and an object thereof is to provide a bonding composition that can be bonded without pressure even at a relatively low temperature and can obtain excellent bonding strength.
[Means for solving problems]

本發明者等人著眼於為了使接合用組成物的燒結體發揮優異的接合強度而重要的是源自接合用組成物中的金屬粒子的固體成分濃度高這一情況，發現藉由減少接合用組成物中所含的分散介質的含量，而即便於LED等發光元件、半導體晶片等的接合中使用亦可獲得充分的接合強度。本發明者等人進一步反覆研究，發現藉由減少接合用組成物中的分散介質量而可提高接合用組成物的燒結體的密度，另一方面，若所述分散介質量過少，則接合用組成物的黏度變高，處理性降低，從而達成了本發明。The present inventors paid attention to the fact that the concentration of solid components derived from the metal particles in the bonding composition is important in order for the sintered body of the bonding composition to exhibit excellent bonding strength, and found that by reducing the bonding The content of the dispersion medium contained in the composition allows sufficient bonding strength to be obtained even when used for bonding light emitting elements such as LEDs and semiconductor wafers. The present inventors and the like have conducted further research and found that the density of the sintered body of the bonding composition can be increased by reducing the amount of the dispersion medium in the bonding composition. On the other hand, if the amount of the dispersion medium is too small, the bonding The viscosity of the composition is increased, and the handleability is reduced, and the present invention has been achieved.

即，本發明為含有平均粒徑為20 nm～100 nm的第一金屬粒子、以及分散介質的接合用組成物，且其特徵在於所述分散介質相對於所述接合用組成物整體的含量為1.0重量%以上且小於5.0重量%。That is, the present invention is a bonding composition containing first metal particles having an average particle diameter of 20 nm to 100 nm and a dispersion medium, and the content of the dispersion medium with respect to the entire bonding composition is 1.0% by weight or more and less than 5.0% by weight.

較佳為所述第一金屬粒子的下述式（1）所表示的一次粒徑的變異係數為25.0%以上且50.0%以下。

變異係數（%）=一次粒徑的標準偏差/平均一次粒徑×100 （1）The coefficient of variation of the primary particle size represented by the following formula (1) of the first metal particle is preferably 25.0% or more and 50.0% or less.

Coefficient of variation (%) = standard deviation of primary particle size / average primary particle size × 100 (1)

較佳為進而含有平均粒徑為200 nm～500 nm的第二金屬粒子。It is preferable to further contain the second metal particles having an average particle diameter of 200 nm to 500 nm.

較佳為所述第一金屬粒子與所述第二金屬粒子的重量比率為20：80～80：20。The weight ratio of the first metal particles to the second metal particles is preferably 20:80 to 80:20.

較佳為所述第一金屬粒子由有機保護成分被覆。Preferably, the first metal particles are covered with an organic protective component.

較佳為所述有機保護成分包含至少一種沸點為150℃以下的胺。Preferably, the organic protective component contains at least one amine having a boiling point of 150 ° C or lower.

較佳為所述接合用組成物進而含有高分子分散劑。
[發明的效果]The bonding composition preferably further contains a polymer dispersant.
[Effect of the invention]

根據本發明，可提供一種即便於比較低的溫度下亦可不加壓地進行接合、且可獲得優異的接合強度的接合用組成物。According to the present invention, it is possible to provide a bonding composition that can be bonded without pressure even at a relatively low temperature and can obtain excellent bonding strength.

本實施形態的接合用組成物為含有平均粒徑為20 nm～100 nm的第一金屬粒子、以及分散介質的接合用組成物，且其特徵在於所述分散介質相對於所述接合用組成物整體的含量為1.0重量%以上且小於5.0重量%。The bonding composition according to this embodiment is a bonding composition containing first metal particles having an average particle diameter of 20 nm to 100 nm and a dispersion medium, and the dispersion medium is relative to the bonding composition. The total content is 1.0% by weight or more and less than 5.0% by weight.

所述第一金屬粒子的平均粒徑為20 nm～100 nm。所述接合用組成物於超過200℃的煅燒溫度下可使金屬粒子彼此燒結，但藉由將所述第一金屬粒子的平均粒徑設為20 nm～100 nm，而產生熔點下降，即便於比較低的溫度（例如，200℃以下、較佳為150℃左右）下亦可使金屬粒子彼此燒結。另外，可使接合用組成物中的第一金屬粒子的分散性難以產生經時變化。若所述第一金屬粒子的平均粒徑小於20 nm，則因第一金屬粒子的表面積變大而接合用組成物的黏度變高，處理性降低。另外，於利用有機保護成分被覆第一金屬粒子的表面的情況下，所述有機保護成分量增加，而於煅燒後殘留有機物，燒結體的密度降低，因此接合強度降低。另一方面，若所述第一金屬粒子的平均粒徑超過100 nm，則難以產生熔點下降，於比較低的溫度下金屬粒子彼此難以燒結。所述第一金屬粒子的平均粒徑的較佳的下限為25 nm，較佳的上限為80 nm。本說明書中，所謂「平均粒徑」，為金屬粒子的一次平均粒徑，且是指數量平均粒徑。所述數量平均粒徑例如可對使用掃描式電子顯微鏡（Scanning Electron Microscope，SEM）（例如，日立股份有限公司製造的S-4800型）獲得的圖像使用圖像處理軟體（例如，三谷公司（MITANI CORPORATION），WinROOF）進行算出。The first metal particles have an average particle diameter of 20 nm to 100 nm. The bonding composition can sinter metal particles with each other at a firing temperature exceeding 200 ° C. However, by setting the average particle diameter of the first metal particles to 20 nm to 100 nm, the melting point decreases, even if the The metal particles can also be sintered at a relatively low temperature (for example, 200 ° C. or lower, preferably about 150 ° C.). In addition, the dispersibility of the first metal particles in the bonding composition can be made less likely to change with time. When the average particle diameter of the first metal particles is less than 20 nm, the surface area of the first metal particles becomes larger, the viscosity of the bonding composition becomes higher, and the handleability decreases. In addition, when the surface of the first metal particles is covered with an organic protective component, the amount of the organic protective component increases, and organic matter remains after firing, and the density of the sintered body decreases, so the bonding strength decreases. On the other hand, if the average particle diameter of the first metal particles exceeds 100 nm, it is difficult to cause a decrease in the melting point, and it is difficult for the metal particles to sinter at a relatively low temperature. A preferred lower limit of the average particle diameter of the first metal particles is 25 nm, and a preferred upper limit is 80 nm. In the present specification, the "average particle diameter" refers to the primary average particle diameter of the metal particles and is an exponential average particle diameter. The number-average particle diameter can be obtained by using an image processing software (for example, Mitani Corporation (for example, Mitani Corporation ( MITANI CORPORATION), WinROOF).

所述第一金屬粒子並無特別限定，例如較佳為選自由金、銀、銅、鎳、鉍、錫及鉑族元素所組成的群組中的至少一種金屬的粒子。所述第一金屬粒子更佳為銅或離子化傾向比銅小（貴）的金屬、即金、鉑、銀及銅中的至少一種金屬的粒子。該些金屬可單獨使用，亦可併用兩種以上。作為併用兩種以上的金屬的方法，有使用包含多種金屬的合金粒子的情況、或使用具有核-殼結構或多層結構的金屬粒子的情況。The first metal particles are not particularly limited, and for example, particles of at least one metal selected from the group consisting of gold, silver, copper, nickel, bismuth, tin, and platinum group elements are preferred. The first metal particles are more preferably particles of copper or a metal having a smaller (more expensive) ionization tendency than copper, that is, at least one metal of gold, platinum, silver, and copper. These metals may be used alone or in combination of two or more. As a method of using two or more metals in combination, there are a case where an alloy particle containing a plurality of metals is used, or a metal particle having a core-shell structure or a multilayer structure is used.

於使用銀微粒子作為所述第一金屬粒子的情況下，使用本實施形態的接合用組成物形成的燒結體（燒結層）的導電率良好。藉由在銀微粒子中併用包含其他金屬的粒子，可難以引起遷移。作為所述「其他金屬」，較佳為所述離子化傾向比氫貴的金屬、即金、銅、鉑、鈀。When silver fine particles are used as the first metal particles, the electrical conductivity of the sintered body (sintered layer) formed using the bonding composition of the present embodiment is good. By using particles containing other metals in combination with the silver fine particles, it is difficult to cause migration. As the "other metal", the metal having a higher ionization tendency than hydrogen, that is, gold, copper, platinum, and palladium is preferable.

所述接合用組成物含有分散介質。藉由含有分散介質，可調整接合用組成物的黏度並使處理性良好。The bonding composition contains a dispersion medium. By containing a dispersion medium, the viscosity of the bonding composition can be adjusted and the handleability can be made good.

所述分散介質相對於接合用組成物整體的含量為1.0重量%以上且小於5.0重量%。若所述分散介質的含量小於1.0重量%，則接合用組成物的剪切黏度過高而處理性差，難以塗敷於被接合構件。另一方面，若所述分散介質的含量為5.0重量%以上，則利用25℃至550℃為止的熱分析而得的重量減少率增大。另外，接合用組成物中的金屬粒子的含量變少，因此燒結體的密度變低，無法獲得充分的接合強度。Content of the said dispersion medium with respect to the whole bonding composition is 1.0 weight% or more and less than 5.0 weight%. When the content of the dispersion medium is less than 1.0% by weight, the shear viscosity of the bonding composition is too high, the handling properties are poor, and it is difficult to apply it to the member to be bonded. On the other hand, if the content of the dispersion medium is 5.0% by weight or more, the weight reduction rate obtained by thermal analysis up to 25 ° C to 550 ° C will increase. In addition, since the content of metal particles in the bonding composition is reduced, the density of the sintered body is reduced, and sufficient bonding strength cannot be obtained.

作為所述分散介質，可於無損本發明的效果的範圍內使用各種分散介質，例如可使用水或有機溶劑。作為所述有機溶劑，例如可列舉烴、醇等。As said dispersion medium, various dispersion media can be used in the range which does not impair the effect of this invention, For example, water or an organic solvent can be used. Examples of the organic solvent include hydrocarbons and alcohols.

作為所述烴，可列舉脂肪族烴、環狀烴、脂環式烴等，可分別單獨使用，亦可併用兩種以上。Examples of the hydrocarbon include aliphatic hydrocarbons, cyclic hydrocarbons, and alicyclic hydrocarbons. These hydrocarbons may be used alone or in combination of two or more kinds.

作為所述脂肪族烴，例如可列舉：十四烷、十八烷、七甲基壬烷、四甲基十五烷、己烷、庚烷、辛烷、壬烷、癸烷、十三烷、甲基戊烷、正鏈烷烴（normal paraffin）、異鏈烷烴等飽和或不飽和脂肪族烴。Examples of the aliphatic hydrocarbon include tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, and tridecane. Saturated or unsaturated aliphatic hydrocarbons such as methylpentane, normal paraffin, and isoparaffin.

作為所述環狀烴，例如可列舉甲苯、二甲苯等。Examples of the cyclic hydrocarbon include toluene and xylene.

作為所述脂環式烴，例如可列舉：檸檬烯（limonene）、雙戊烯、萜品烯、松油烯（亦稱為萜品烯）、薴烯（nesol）、松油精（cinene）、甜橙香精（orange flavor）、萜品油烯、異松油烯（亦稱為萜品油烯）、水芹烯（phellandrene）、薄荷二烯（menthadiene）、芸香烯（terebene）、二氫傘花烴（dihydrocymene）、γ-萜品烯（moslene）、異萜品烯、異松油烯（亦稱為異萜品烯）、海茴香烯（crithmene）、薴（kautschin）、白千層萜（cajeputene）、檸烯（Eulimen）、蒎烯（pinene）、松節油（turpentine）、薄荷烷（menthane）、蒎烷（pinane）、萜烯（terpene）、環己烷等。Examples of the alicyclic hydrocarbon include limonene, dipentene, terpinene, terpinene (also referred to as terpinene), nesol, cinene, Orange flavor, terpineolene, isoterpinene (also known as terpineolene), phellandrene, menthadiene, terebene, dihydroumbrene Dihydrocymene, γ-terpinene (moslene), isoterpinene, isoterpinene (also known as isoterpinene), crienmene, kautschin, lutein (Cajeputene), eulimen, pinene, turpentine, menthane, pinane, terpene, cyclohexane and the like.

所述醇為於分子結構中包含一個以上的OH基的化合物，可列舉脂肪族醇、環狀醇及脂環式醇，可分別單獨使用，亦可併用兩種以上。另外，OH基的一部分亦可於無損本發明的效果的範圍內由乙醯氧基等衍生。The alcohol is a compound containing one or more OH groups in a molecular structure, and examples thereof include aliphatic alcohols, cyclic alcohols, and alicyclic alcohols, which may be used individually or in combination of two or more. In addition, a part of the OH group may be derived from ethoxyl or the like within a range that does not impair the effect of the present invention.

作為所述脂肪族醇，例如可列舉：庚醇、辛醇（1-辛醇、2-辛醇、3-辛醇等）、癸醇（1-癸醇等）、十三醇（異十三醇等）、月桂基醇、十四基醇、鯨蠟醇、2-乙基-1-己醇、十八基醇、十六碳烯醇（hexadecenol）、油烯基醇等碳數為6～30的飽和或不飽和脂肪族醇等。Examples of the aliphatic alcohol include heptanol, octanol (1-octanol, 2-octanol, 3-octanol, etc.), decanol (1-decanol, etc.), and tridecanol (isodecyl alcohol) Triol, etc.), lauryl alcohol, tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, stearyl alcohol, hexadecenol, oleyl alcohol, etc. 6 to 30 saturated or unsaturated aliphatic alcohols.

作為所述環狀醇，例如可列舉甲酚、丁香酚（eugenol）等。進而，作為所述脂環式醇，例如可列舉：環己醇等環烷醇、萜品醇（包含α、β、γ異構體、或該些的任意的混合物）、二氫萜品醇等萜烯醇（單萜烯醇等）、二氫松油醇、桃金孃烯醇（myrtenol）、蘇伯樓醇（sobrerol）、薄荷醇、香旱芹醇（carveol）、紫蘇醇（perillyl alcohol）、松香芹醇（pinocarveol）、蘇伯樓醇（sobrerol）、馬鞭烯醇（verbenol）等。Examples of the cyclic alcohol include cresol, eugenol, and the like. Further, as the alicyclic alcohol, for example, a cycloalkanol such as cyclohexanol, terpineol (including α, β, γ isomers, or any of these mixtures), and dihydroterpineol are exemplified. Isoterpenols (monoterpene alcohols, etc.), dihydroterpineol, myrtenol, sobrerol, menthol, carveol, perillyl alcohol), pinocarveol, sobrerol, verbenol, etc.

所述接合用組成物的於大氣環境下自25℃起以升溫速度10℃/分鐘進行加熱時的至550℃為止的重量減少率W較佳為0.6%≦W≦5.5%。若將接合用組成物加熱至550℃，則分散介質蒸發，被覆金屬粒子的有機物等氧化分解，且大部分氣化而消失。因此，加熱至550℃為止所得的重量減少率W相當於分散介質的量與固體成分中的有機物的量的和。所述重量減少率W越少，則是指接合用組成物中的金屬粒子的含量越高。藉由將所述重量減少率W設為0.6%≦W≦5.5%，而接合用組成物中的金屬粒子的含量高，可獲得高密度的燒結體，因此可實現更優異的接合強度。若重量減少率W小於0.6%，則有時接合用組成物的流動性降低，並且處理性降低。另一方面，若重量減少率W超過5.5%，則接合用組成物中的金屬粒子的含量少，因此有時燒結體的密度降低，並且接合強度降低。重量減少率W的較佳的下限為1%，更佳的下限為2%，較佳的上限為5.4%。所述重量減少率可利用熱重分析法來測定。The weight reduction rate W of the bonding composition when heated at 25 ° C. at a heating rate of 10 ° C./minute to 550 ° C. is preferably 0.6% ≦ W ≦ 5.5%. When the composition for bonding is heated to 550 ° C., the dispersion medium evaporates, and the organic matter covering the metal particles is oxidatively decomposed, and most of it vaporizes and disappears. Therefore, the weight reduction rate W obtained by heating to 550 ° C. corresponds to the sum of the amount of the dispersion medium and the amount of the organic matter in the solid content. The smaller the weight reduction rate W, the higher the content of metal particles in the bonding composition. By setting the weight reduction rate W to 0.6% ≦ W ≦ 5.5%, the content of metal particles in the bonding composition is high, and a high-density sintered body can be obtained, so that more excellent bonding strength can be achieved. When the weight reduction rate W is less than 0.6%, the fluidity of the bonding composition may be reduced, and the handleability may be reduced. On the other hand, when the weight reduction rate W exceeds 5.5%, since the content of the metal particles in the bonding composition is small, the density of the sintered body may decrease and the bonding strength may decrease. The preferable lower limit of the weight reduction rate W is 1%, the more preferable lower limit is 2%, and the preferable upper limit is 5.4%. The weight reduction rate can be measured by a thermogravimetric method.

所述第一金屬粒子較佳為下述式（1）所表示的一次粒徑的變異係數為25.0%以上且50.0%以下。下述一次粒徑的標準偏差可根據所述平均粒徑的測定中使用的圖像資料來算出。

變異係數（%）=一次粒徑的標準偏差/平均一次粒徑×100 （1）The first metal particles are preferably such that the coefficient of variation of the primary particle size represented by the following formula (1) is 25.0% or more and 50.0% or less. The standard deviation of the following primary particle diameter can be calculated from the image data used in the measurement of the average particle diameter.

Coefficient of variation (%) = standard deviation of primary particle size / average primary particle size × 100 (1)

所述變異係數大，是指粒度分佈廣。於所述第一金屬粒子的平均粒徑相同的情況下，使用變異係數大的金屬粒子的情況與使用變異係數小的金屬粒子的情況相比較，接合用組成物的流動性提高。認為其原因在於：金屬粒子的比表面積降低，藉此金屬粒子間的相互作用變小。若所述第一金屬粒子的一次粒徑的變異係數為25.0%以上，則所獲得的接合用組成物的流動性變良好。結果，可減少投入的黏度調整溶劑（分散介質）的量，且可進一步提高接合用組成物中的固體成分濃度。若所述變異係數小於25.0%，則有時無法充分獲得提高接合用組成物的流動性的效果。所述變異係數的上限並無特別限定，就第一金屬粒子的製造方面的問題而言，所述變異係數較佳為50.0%以下。所述變異係數的更佳的下限為27.0%，更佳的上限為45.0%。接合用組成物的流動性亦根據第一金屬粒子的平均粒徑發生變化，且第一金屬粒子的平均粒徑越小，接合用組成物的剪切黏度越變高，流動性越降低，但藉由調整第一金屬粒子的變異係數，即便於使用平均粒徑小的第一金屬粒子的情況下，亦可獲得適當的流動性。The large coefficient of variation means a wide particle size distribution. When the average particle diameter of the first metal particles is the same, when the metal particles having a large coefficient of variation are used, the fluidity of the bonding composition is improved compared with the case where the metal particles having a small coefficient of variation are used. The reason is considered to be that the specific surface area of the metal particles is reduced, and thereby the interaction between the metal particles is reduced. When the coefficient of variation of the primary particle diameter of the first metal particles is 25.0% or more, the fluidity of the obtained bonding composition is improved. As a result, the amount of the viscosity adjustment solvent (dispersion medium) to be input can be reduced, and the solid content concentration in the bonding composition can be further increased. If the coefficient of variation is less than 25.0%, the effect of improving the fluidity of the bonding composition may not be sufficiently obtained in some cases. The upper limit of the coefficient of variation is not particularly limited. In terms of manufacturing problems of the first metal particles, the coefficient of variation is preferably 50.0% or less. A more preferable lower limit of the coefficient of variation is 27.0%, and a more preferable upper limit is 45.0%. The fluidity of the bonding composition also changes according to the average particle diameter of the first metal particles, and the smaller the average particle diameter of the first metal particles, the higher the shear viscosity of the bonding composition and the lower the fluidity, but By adjusting the coefficient of variation of the first metal particles, an appropriate fluidity can be obtained even when the first metal particles having a small average particle diameter are used.

所述接合用組成物較佳為進而含有平均粒徑為200 nm～500 nm的第二金屬粒子。藉由併用平均粒徑為200 nm～500 nm的第二金屬粒子，可抑制煅燒時的體積收縮，且難以產生裂紋，可獲得密度更高的燒結體。若所述第二金屬粒子的平均粒徑小於200 nm，則有時無法充分抑制煅燒時的體積收縮。另一方面，若所述第二金屬粒子的平均粒徑超過500 nm，則於利用被接合構件彼此夾持本實施形態的接合用組成物時，有時因粒徑大的金屬粒子而產生空隙，並且接合強度降低。所述第二金屬粒子的平均粒徑的更佳的下限為250 nm，更佳的上限為400 nm。所述第二金屬粒子的平均粒徑可利用與所述第一金屬粒子的平均粒徑相同的方法進行測定。The bonding composition preferably further contains second metal particles having an average particle diameter of 200 nm to 500 nm. By using the second metal particles having an average particle diameter of 200 nm to 500 nm in combination, volume shrinkage during firing can be suppressed, cracks are hardly generated, and a sintered body having a higher density can be obtained. If the average particle diameter of the second metal particles is less than 200 nm, the volume shrinkage during firing may not be sufficiently suppressed in some cases. On the other hand, if the average particle diameter of the second metal particles exceeds 500 nm, when the bonding composition of the present embodiment is held between the members to be bonded, voids may be generated due to the metal particles having a large particle diameter. , And the joint strength is reduced. A more preferable lower limit of the average particle diameter of the second metal particles is 250 nm, and a more preferable upper limit is 400 nm. The average particle diameter of the second metal particles can be measured by the same method as the average particle diameter of the first metal particles.

所述第二金屬粒子可使用種類與所述第一金屬粒子中例示的金屬粒子相同的金屬粒子。構成所述第二金屬粒子的金屬可與所述第一金屬粒子相同，亦可不同。As the second metal particles, metal particles of the same type as the metal particles exemplified in the first metal particles can be used. The metal constituting the second metal particles may be the same as or different from the first metal particles.

所述第一金屬粒子與所述第二金屬粒子的重量比率較佳為20：80～80：20。藉此，可實現低溫燒結性並且可進一步提高接合強度。若所述第一金屬粒子的重量相對於所述第二金屬粒子80重量份而小於20重量份，則接合用組成物中的平均粒徑為20 nm～100 nm的第一金屬粒子的比例變低，有時於比較低的溫度下金屬粒子彼此難以燒結。另一方面，若所述第一金屬粒子的重量相對於所述第二金屬粒子20重量份而超過80重量份，則煅燒時的體積收縮變大，燒結體中容易產生裂紋，因此存在接合強度降低的傾向。所述第一金屬粒子與所述第二金屬粒子的更佳的重量比率為30：70～60：40。若所述第二金屬粒子的重量較所述第一金屬粒子的重量而言變多，則接合用組成物的流動性降低且處理性降低，另一方面，存在重量減少率降低的傾向，因此所述第一金屬粒子與所述第二金屬粒子的重量比率可考慮到處理性與重量減少率的平衡來決定。The weight ratio of the first metal particles to the second metal particles is preferably 20:80 to 80:20. Thereby, low-temperature sinterability can be achieved, and the bonding strength can be further improved. If the weight of the first metal particles is less than 20 parts by weight with respect to 80 parts by weight of the second metal particles, the proportion of the first metal particles having an average particle diameter in the bonding composition of 20 nm to 100 nm changes. It is low, and metal particles are difficult to sinter with each other at a relatively low temperature. On the other hand, if the weight of the first metal particles exceeds 80 parts by weight with respect to 20 parts by weight of the second metal particles, the volume shrinkage during firing becomes large, and cracks easily occur in the sintered body, so that there is joint strength. Reduced tendency. A better weight ratio of the first metal particles to the second metal particles is 30:70 to 60:40. If the weight of the second metal particles is greater than the weight of the first metal particles, the fluidity and handling properties of the bonding composition are reduced, and the weight reduction rate tends to decrease. Therefore, The weight ratio of the first metal particles to the second metal particles can be determined in consideration of the balance between the handleability and the weight reduction rate.

所述第一金屬粒子較佳為由有機保護成分被覆。所謂所述有機保護成分，是指與第一金屬粒子的表面的至少一部分鍵結且形成膠體的成分。所述有機保護成分無需被覆所述第一金屬粒子的整個表面，只要以可形成膠體的程度被覆第一金屬粒子的表面的至少一部分即可。藉由第一金屬粒子由有機保護成分被覆，可提高所述第一金屬粒子的分散穩定性而防止凝聚。若於煅燒時殘存所述有機保護成分，則阻礙金屬粒子彼此的熔接，因此作為所述有機保護成分，較佳為使用煅燒時蒸發或分解的成分。就此種觀點而言，所述有機保護成分理想的是使用於比較低的溫度下自所述第一金屬粒子的表面脫離的胺。所述第二金屬粒子亦較佳為由有機保護成分被覆。The first metal particles are preferably coated with an organic protective component. The organic protective component is a component that is bonded to at least a part of the surface of the first metal particle and forms a colloid. The organic protective component does not need to cover the entire surface of the first metal particles, as long as it covers at least a part of the surface of the first metal particles to such an extent that a colloid can be formed. By coating the first metal particles with an organic protective component, the dispersion stability of the first metal particles can be improved and aggregation can be prevented. If the organic protective component remains during the firing, the metal particles are prevented from being welded to each other. Therefore, as the organic protective component, a component that evaporates or decomposes during the firing is preferably used. From such a viewpoint, it is desirable that the organic protective component is an amine used to be detached from the surface of the first metal particle at a relatively low temperature. The second metal particles are also preferably covered with an organic protective component.

所述有機保護成分較佳為包含至少一種沸點為150℃以下的胺。若所述胺的沸點超過150℃，則於在比較低的溫度（例如，200℃以下、較佳為150℃左右）下煅燒接合用組成物時，於燒結體中殘存並未揮發的有機保護成分，且有金屬粒子彼此並未充分燒結的擔憂。亦考慮到所述胺與金屬粒子化學性或物理性鍵結的情況、或變化為陰離子或陽離子的情況，而於本實施形態中，所述胺亦可採取源自所述胺的離子、錯合物等狀態。The organic protective component preferably contains at least one amine having a boiling point of 150 ° C or lower. When the boiling point of the amine exceeds 150 ° C, when the composition for bonding is calcined at a relatively low temperature (for example, 200 ° C or lower, preferably about 150 ° C), organic protection which does not volatilize remains in the sintered body. Composition, and there is a concern that the metal particles are not sufficiently sintered with each other. It is also considered that the amine is chemically or physically bonded to the metal particles, or is changed to an anion or a cation. In this embodiment, the amine may also adopt an ion, an ion, or an ion derived from the amine.组合 等等。 State and so on.

所述沸點為150℃以下的胺可為直鏈狀亦可為分支鏈狀，另外，亦可具有側鏈。作為具體例，可列舉：甲基胺、乙基胺、丙基胺。其中，較佳為烷基胺、或烷氧基胺。The amine having a boiling point of 150 ° C. or lower may be linear or branched, and may have a side chain. Specific examples include methylamine, ethylamine, and propylamine. Among these, an alkylamine or an alkoxyamine is preferable.

所述胺例如亦可為包含羥基、羧基、烷氧基、羰基、酯基、巰基等胺以外的官能基的化合物。該情況下，源自胺的氮原子的數量較佳為胺以外的官能基的數量以上。另外，所述胺可分別單獨使用，亦可併用兩種以上。The amine may be, for example, a compound containing a functional group other than an amine such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group, and a mercapto group. In this case, the number of nitrogen atoms derived from the amine is preferably at least the number of functional groups other than the amine. The amines may be used alone or in combination of two or more.

所述有機保護成分更佳為沸點為150℃以下且碳數為1～3的胺。再者，所謂所述胺的碳數，為主鏈的碳數，並不包含官能基的碳數。The organic protective component is more preferably an amine having a boiling point of 150 ° C. or lower and a carbon number of 1 to 3. The carbon number of the amine refers to the carbon number of the main chain and does not include the carbon number of the functional group.

作為所述沸點為150℃以下且碳數為1～3的胺，可列舉3-乙氧基丙基胺、3-甲氧基丙基胺等。Examples of the amine having a boiling point of 150 ° C. or lower and a carbon number of 1 to 3 include 3-ethoxypropylamine, 3-methoxypropylamine, and the like.

接合用組成物中的有機保護成分的含量較佳為0.1重量%～15重量%。若所述有機保護成分的含量為0.1重量%以上，則存在所獲得的接合用組成物的導電性變良好的傾向，若為15重量%以下，則存在接合用組成物的分散穩定性良好的傾向。所述有機保護成分的含量的更佳的下限為0.2重量%，更佳的上限為5重量%，進而佳的下限為0.3重量%，進而佳的上限為4重量%。所述有機保護成分的含量可利用熱重分析來測定。The content of the organic protective component in the bonding composition is preferably from 0.1% by weight to 15% by weight. When the content of the organic protective component is 0.1% by weight or more, the conductivity of the obtained bonding composition tends to be good, and when it is 15% by weight or less, the dispersion stability of the bonding composition is good. tendency. A more preferable lower limit of the content of the organic protective component is 0.2% by weight, a more preferable upper limit is 5% by weight, a further preferable lower limit is 0.3% by weight, and a more preferable upper limit is 4% by weight. The content of the organic protective component can be measured by thermogravimetric analysis.

本實施形態的接合用組成物較佳為進而含有高分子分散劑。藉此，可提高金屬粒子的分散性。The bonding composition of the present embodiment preferably further contains a polymer dispersant. Thereby, the dispersibility of a metal particle can be improved.

作為所述高分子分散劑，亦可使用市售者。作為所述市售品，例如可列舉：索努帕斯（SOLSPERSE）11200、索努帕斯13940、索努帕斯16000、索努帕斯17000、索努帕斯18000、索努帕斯20000、索努帕斯21000、索努帕斯24000、索努帕斯26000、索努帕斯27000、索努帕斯28000（日本路博潤（Lubrizol）（股）製造）；迪斯帕畢克（DISPERBYK）142、迪斯帕畢克160、迪斯帕畢克161、迪斯帕畢克162、迪斯帕畢克163、迪斯帕畢克166、迪斯帕畢克170、迪斯帕畢克180、迪斯帕畢克182、迪斯帕畢克184、迪斯帕畢克190、迪斯帕畢克2155（日本畢克化學（BYK-Chemie Japan）（股）製造）；埃夫卡（EFKA）-46、EFKA-47、EFKA-48、EFKA-49（埃夫卡（EFKA）化學公司製造）；聚合物（polymer）100、聚合物120、聚合物150、聚合物400、聚合物401、聚合物402、聚合物403、聚合物450、聚合物451、聚合物452、聚合物453（埃夫卡（EFKA）化學公司製造）；阿吉斯帕（Ajisper）PB711、阿吉斯帕PA111、阿吉斯帕PB811、阿吉斯帕PW911（味之素公司製造）；弗洛倫（Flowlen）DOPA-15B、弗洛倫DOPA-22、弗洛倫DOPA-17、弗洛倫TG-730W、弗洛倫G-700、弗洛倫TG-720W（共榮社化學工業（股）製造）等。A commercially available one can be used as the polymer dispersant. Examples of the commercially available products include: Sonupas 11200, Sonupas 13940, Sonupas 16000, Sonupas 17000, Sonupas 18000, Sonupas 20000, Sonupas 21000, Sonupas 24000, Sonupas 26000, Sonupas 27000, Sonupas 28000 (manufactured by Lubrizol (Japan)); DISPERBYK ) 142, Disparb 160, Disparb 161, Disparb 162, Disparb 163, Disparb 166, Disparb 170, Disparbike 180, Disparb 182, Disparb 184, Disparb 190, Disparb 2155 (manufactured by BYK-Chemie Japan (stock)); Efka ( EFKA) -46, EFKA-47, EFKA-48, EFKA-49 (manufactured by EFKA Chemical Company); polymer 100, polymer 120, polymer 150, polymer 400, polymer 401 , Polymer 402, polymer 403, polymer 450, polymer 451, polymer 452, polymer 453 (manufactured by EFKA Chemical Company); Ajisper PB711, Agispa PA111, Agispa PB811, Agispa PW911 (manufactured by Ajinomoto); Flolen DOPA-15B, Floren DOPA-22, Floren DOPA-17 , Floren TG-730W, Floren G-700, Floren TG-720W (manufactured by Kyoeisha Chemical Industry Co., Ltd.), etc.

就低溫燒結性的觀點而言，所述高分子分散劑較佳為索努帕斯11200、索努帕斯13940、索努帕斯16000、索努帕斯17000、索努帕斯18000、索努帕斯21000、索努帕斯28000、迪斯帕畢克142或迪斯帕畢克2155。From the viewpoint of low-temperature sinterability, the polymer dispersant is preferably Sonupas 11200, Sonupas 13940, Sonupas 16000, Sonupas 17000, Sonupas 18000, Sonup Perth 21000, Sonupas 28000, Despatch 142 or Despatch 2155.

接合用組成物中的所述高分子分散劑的含量較佳為0.01重量%～15重量%。若所述高分子分散劑的含量為0.01重量%以上，則存在所獲得的接合用組成物的分散穩定性變良好的傾向，若為15重量%以下，則存在接合用組成物的導電性變良好的傾向。所述高分子分散劑的更佳的下限為0.1重量%，更佳的上限為5重量%，進而佳的下限為0.2重量%，進而佳的上限為4重量%。The content of the polymer dispersant in the bonding composition is preferably 0.01 to 15% by weight. When the content of the polymer dispersant is 0.01% by weight or more, the dispersion stability of the obtained bonding composition tends to be good, and when it is 15% by weight or less, the conductivity of the bonding composition is changed. Good tendency. The more preferable lower limit of the polymer dispersant is 0.1% by weight, the more preferable upper limit is 5% by weight, the more preferable lower limit is 0.2% by weight, and the more preferable upper limit is 4% by weight.

本實施形態的接合用組成物除了所述成分以外，亦可於無損本發明的效果的範圍內添加例如發揮作為黏合劑的作用的寡聚物成分、樹脂成分、有機溶劑（可使固體成分的一部分溶解或分散）、界面活性劑、增稠劑或表面張力調整劑等任意成分以賦予與使用目的相應的適度的黏性、密接性、乾燥性或印刷性等功能。所述任意成分並無特別限定。In addition to the components described above, the bonding composition of the present embodiment may add, for example, an oligomer component, a resin component, and an organic solvent (which can make Partially dissolve or disperse), surfactant, thickener, or surface tension adjuster, etc. to impart appropriate viscosity, adhesion, drying, or printability functions to the purpose of use. The arbitrary component is not particularly limited.

作為所述樹脂成分，例如可列舉：聚酯系樹脂、嵌段異氰酸酯等聚胺基甲酸酯系樹脂、聚丙烯酸酯系樹脂、聚丙烯醯胺系樹脂、聚醚系樹脂、三聚氰胺系樹脂、萜烯系樹脂等，該些可分別單獨使用，亦可併用兩種以上。Examples of the resin component include polyurethane resins such as polyester resins and block isocyanates, polyacrylate resins, polypropylene resins, polyether resins, melamine resins, These terpene-based resins may be used alone, or two or more of them may be used in combination.

作為所述有機溶劑，將作為所述分散介質而列舉者除外，例如可列舉：甲基醇、乙基醇、正丙基醇、2-丙基醇、1,3-丙二醇、1,2-丙二醇、1,4-丁二醇、1,2,6-己烷三醇、1-乙氧基-2-丙醇、2-丁氧基乙醇、乙二醇、二乙二醇、三乙二醇，重量平均分子量為200以上且1,000以下的範圍內的聚乙二醇、丙二醇、二丙二醇、三丙二醇，重量平均分子量為300以上且1,000以下的範圍內的聚丙二醇、N,N-二甲基甲醯胺、二甲基亞碸、N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、甘油、丙酮等，該些可分別單獨使用，亦可併用兩種以上。The organic solvent is excluding those listed as the dispersion medium, and examples thereof include methyl alcohol, ethyl alcohol, n-propyl alcohol, 2-propyl alcohol, 1,3-propanediol, and 1,2- Propylene glycol, 1,4-butanediol, 1,2,6-hexanetriol, 1-ethoxy-2-propanol, 2-butoxyethanol, ethylene glycol, diethylene glycol, triethyl Glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol in a weight average molecular weight range of 200 to 1,000, and polypropylene glycol, N, N-diethylene glycol in a weight average molecular weight range of 300 to 1,000. Methylformamide, dimethylmethane, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, glycerol, acetone, etc. These can be used individually or in combination. More than that.

作為所述增稠劑，例如可列舉：黏土、膨潤土（bentonite）或鋰膨潤石（hectorite）等黏土礦物，例如聚酯系乳液樹脂、丙烯酸系乳液樹脂、聚胺基甲酸酯系乳液樹脂或嵌段異氰酸酯等乳液，甲基纖維素、羧基甲基纖維素、羥基乙基纖維素、羥基丙基纖維素、羥基丙基甲基纖維素等纖維素衍生物，三仙膠（xanthan gum）或瓜爾膠（guar gum）等多糖類等，該些可分別單獨使用，亦可併用兩種以上。Examples of the thickener include clay minerals such as clay, bentonite, and hectorite, such as polyester-based emulsion resins, acrylic-based emulsion resins, polyurethane-based emulsion resins, or Emulsions such as block isocyanate, cellulose derivatives such as methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, xanthan gum, or Polysaccharides such as guar gum can be used individually or in combination of two or more.

所述界面活性劑並無特別限定，可使用陰離子性界面活性劑、陽離子性界面活性劑、非離子性界面活性劑的任一種，例如可列舉烷基苯磺酸鹽、四級銨鹽等。因以少量的添加量便獲得效果，因此較佳為氟系界面活性劑。The surfactant is not particularly limited, and any of anionic surfactants, cationic surfactants, and nonionic surfactants can be used, and examples thereof include alkylbenzenesulfonate and quaternary ammonium salts. Since the effect is obtained with a small amount of addition, a fluorine-based surfactant is preferred.

於本實施形態的接合用組成物中，所述第一金屬粒子較佳為作為金屬膠體粒子而存在。關於所述金屬膠體粒子的形態，例如可列舉有機物附著於第一金屬粒子的表面的一部分而構成的金屬膠體粒子、將所述第一金屬粒子作為核且其表面由有機物被覆而構成的金屬膠體粒子、該些混合存在而構成的金屬膠體粒子等，並無特別限定。其中，較佳為將第一金屬粒子作為核且其表面由有機物被覆而構成的金屬膠體粒子。所述第二金屬粒子亦較佳為作為金屬膠體粒子而存在。作為被覆所述第一金屬粒子及/或第二金屬粒子的表面的有機物，可使用所述有機保護成分。In the bonding composition of the present embodiment, the first metal particles are preferably present as metal colloidal particles. Examples of the form of the metal colloidal particles include metal colloidal particles composed of an organic substance attached to a part of the surface of the first metal particle, and metal colloids composed of the first metal particle as a core and whose surface is covered with an organic substance There are no particular restrictions on particles, metal colloidal particles, or the like formed by mixing them. Among these, metal colloidal particles having the first metal particle as a core and the surface of which is coated with an organic substance are preferred. The second metal particles are also preferably present as metal colloid particles. The organic protective component can be used as an organic substance covering the surfaces of the first metal particles and / or the second metal particles.

接合用組成物的剪切黏度只要於無損本發明的效果的範圍內適宜調整即可，25℃下的剪切黏度較佳為於剪切速度10 s^-1 下為15 Pa·S～120 Pa·S。藉由設為所述範圍，例如可於將LED等發光元件、半導體晶片等接合於基板的用途、將該些基板進而接合於放熱構件的用途中適宜地使用。所述剪切黏度的更佳的下限為25 Pa·S，更佳的上限為100 Pa·S。The shear viscosity of the bonding composition may be appropriately adjusted within a range that does not impair the effects of the present invention. The shear viscosity at 25 ° C is preferably 15 Pa · S to 120 Pa at a shear rate of 10 s ^-1 · S. By setting it as the said range, it can use suitably, for example, the use which joins light emitting elements, such as LED, a semiconductor wafer, etc. to a board | substrate, and this board | substrate further to a heat radiation member. The more preferable lower limit of the shear viscosity is 25 Pa · S, and the more preferable upper limit is 100 Pa · S.

所述剪切黏度的調整可藉由金屬粒子的粒徑的調整、有機物的含量的調整、分散介質以外的成分的添加量的調整、各成分的調配比的調整、增稠劑的添加等來進行。所述剪切黏度可利用錐板（cone plate）型黏度計（例如，安東帕（Anton Paar）公司製造的流變儀（Rheometer）MCR301）進行測定。The adjustment of the shear viscosity can be performed by adjusting the particle diameter of the metal particles, adjusting the content of organic matter, adjusting the addition amount of components other than the dispersion medium, adjusting the mixing ratio of each component, adding a thickener, and the like. get on. The shear viscosity can be measured using a cone plate type viscometer (for example, a Rheometer MCR301 manufactured by Anton Paar).

利用接合用組成物接合被接合構件彼此時的接合強度較佳為20 MPa～150 MPa。若接合強度為20 MPa～150 MPa，則可於LED等發光元件、半導體晶片等與基板的接合、所述基板與放熱構件的接合中適宜地使用。所述接合強度的更佳的下限為30 MPa，進而佳的下限為50 MPa。所述接合強度可藉由如下方式評價：將接合用組成物塗敷於其中一被接合構件上，貼附另一被接合構件，之後進行煅燒，對所獲得的積層體使用例如接合試驗機（bond tester）（力世科（rhesca）公司製造）進行接合強度試驗。The joining strength when joining the members to be joined with the joining composition is preferably 20 MPa to 150 MPa. When the bonding strength is 20 MPa to 150 MPa, it can be suitably used for bonding light-emitting elements such as LEDs, semiconductor wafers and the like to a substrate, and bonding the substrate and a heat-radiating member. The more preferable lower limit of the bonding strength is 30 MPa, and the more preferable lower limit is 50 MPa. The bonding strength can be evaluated by applying a composition for bonding to one of the members to be bonded, attaching the other member to be bonded, and then calcining, and using the obtained laminated body, for example, a bonding tester ( A bond tester (manufactured by Rhesca) performs a bond strength test.

本實施形態的接合用組成物具有優異的熱循環可靠性。藉由所述熱循環可靠性良好，而亦可於驅動溫度高的器件的製造中的、LED等發光元件、半導體晶片等的接合中適宜地使用。所述熱循環可靠性例如可藉由如下方式評價：將燒結接合用組成物與被接合構件而成的積層體於大氣環境下、-40℃及150℃下各保持10分鐘，將該操作設為1個循環，並進行500個循環的熱循環試驗。所述熱循環試驗例如可使用冷熱衝擊試驗機（優泰克（Futec）公司製造）進行。相對於積層體的初期強度的、熱循環試驗後的積層體的接合強度的降低率較佳為小於20%，更佳為小於5%。The bonding composition of this embodiment has excellent thermal cycle reliability. The above-mentioned thermal cycle has good reliability, and can be suitably used for bonding of light-emitting elements such as LEDs and semiconductor wafers in the manufacture of devices with high driving temperatures. The thermal cycle reliability can be evaluated, for example, by holding a laminated body formed by sintering a composition for joining and a member to be joined in an atmospheric environment at -40 ° C and 150 ° C for 10 minutes each. For 1 cycle, a 500-cycle thermal cycle test was performed. The thermal cycle test can be performed using, for example, a hot and cold impact tester (manufactured by Futec). The reduction rate of the bonding strength of the laminated body after the thermal cycle test with respect to the initial strength of the laminated body is preferably less than 20%, and more preferably less than 5%.

＜接合用組成物的製備＞
本實施形態的接合用組成物的製造方法並無特別限定，首先，調整金屬粒子分散體，並混合所述金屬粒子分散體與分散介質、以及視需要的所述各種成分，藉此可獲得本實施形態的接合用組成物。<Preparation of a bonding composition>
The method for producing the bonding composition according to this embodiment is not particularly limited. First, by adjusting the metal particle dispersion, mixing the metal particle dispersion and the dispersion medium, and the various components as necessary, the present invention can be obtained. The bonding composition of the embodiment.

作為所述金屬粒子分散體的製備方法，可列舉包括如下步驟的方法：第1步驟，製備可藉由還原而分解並生成金屬原子的金屬化合物、與有機保護成分的混合液；以及第2步驟，藉由使所述混合液中的所述金屬化合物還原而生成於表面的至少一部分附著有有機保護成分的金屬粒子。以下，作為具體的製造方法，列舉將第一金屬粒子設為銀微粒子且使用胺作為有機保護成分的情況為例而進行說明。As the method for preparing the metal particle dispersion, a method including the following steps: a first step of preparing a metal compound which can be decomposed and reduced to generate metal atoms and a mixed solution with an organic protective component; and a second step By reducing the metal compound in the mixed solution, metal particles having an organic protective component attached to at least a part of the surface are generated. Hereinafter, as a specific manufacturing method, a case where the first metal particles are made of silver fine particles and an amine is used as an organic protective component will be described as an example.

於所述第1步驟中，較佳為相對於銀1 mol而添加2 mol以上的胺。藉由將所述胺的添加量設為相對於銀1 mol而為2 mol以上，可使所述胺適量附著於藉由還原而生成的銀微粒子的表面，可對所述銀微粒子賦予對於各種分散介質的優異的分散性與低溫燒結性。In the first step, it is preferable to add 2 mol or more of amine to 1 mol of silver. By setting the addition amount of the amine to be 2 mol or more with respect to 1 mol of silver, an appropriate amount of the amine can be attached to the surface of the silver fine particles generated by reduction, and the silver fine particles can be provided with various properties. Excellent dispersibility and low-temperature sinterability of the dispersion medium.

再者，所述第1步驟中的混合液的組成、及所述第2步驟中的還原條件（例如，加熱溫度及加熱時間等）是以將所獲得的銀微粒子的粒徑設為20 nm～100 nm的方式進行調整。自所述第2步驟中獲得的金屬粒子分散體取出銀微粒子的方法並無特別限定，例如可列舉進行該金屬粒子分散體的清洗的方法等。The composition of the mixed solution in the first step and the reduction conditions (for example, heating temperature and heating time) in the second step are such that the particle size of the obtained silver fine particles is 20 nm ～ 100 nm. The method for taking out silver fine particles from the metal particle dispersion obtained in the second step is not particularly limited, and examples thereof include a method of washing the metal particle dispersion and the like.

作為用於獲得由所述有機成分被覆的銀微粒子的起始材料，可使用各種公知的銀化合物，例如可使用銀鹽或銀鹽的水合物。具體而言，可列舉：硝酸銀、硫酸銀、氯化銀、氧化銀、乙酸銀、草酸銀、甲酸銀、亞硝酸銀、氯酸銀、硫化銀等銀鹽。該些只要可進行還原，則並無特別限定，可溶解於適當的溶媒中，亦可分散於溶媒中而直接使用。另外，該些可單獨使用，亦可併用多種。其中，較佳為草酸銀。草酸銀為最單純的二羧酸銀，使用草酸銀合成的草酸銀胺錯合物於低溫且短時間內進行還原，因此對於本實施形態的第一金屬粒子的合成而言適宜。進而，若使用草酸銀，則於合成時不會產生副產物，僅向系統外排出源自草酸根離子的二氧化碳，因此合成後精製的工夫少。As a starting material for obtaining the silver fine particles coated with the organic component, various known silver compounds can be used, and for example, a silver salt or a hydrate of a silver salt can be used. Specific examples include silver salts such as silver nitrate, silver sulfate, silver chloride, silver oxide, silver acetate, silver oxalate, silver formate, silver nitrite, silver chlorate, and silver sulfide. These are not particularly limited as long as they can be reduced, and they may be dissolved in an appropriate solvent, or they may be dispersed in a solvent and used directly. These may be used alone or in combination. Among them, silver oxalate is preferred. Silver oxalate is the simplest silver dicarboxylate, and the silver oxalate amine complex synthesized using silver oxalate is reduced at a low temperature and in a short time. Therefore, it is suitable for the synthesis of the first metal particles in this embodiment. Furthermore, when silver oxalate is used, by-products are not generated during synthesis, and only carbon dioxide derived from oxalate ions is discharged to the outside of the system. Therefore, there is less time for purification after synthesis.

作為使所述銀化合物還原的方法，較佳為進行加熱的方法。所述加熱方法並無特別限定。作為所述藉由加熱來使所述銀化合物還原的方法，例如可列舉如下方法：對由草酸銀等銀化合物與胺等有機成分生成的錯化合物進行加熱，使所述錯化合物中所含的草酸根離子等金屬化合物分解並使生成的原子狀的銀凝聚。利用所述方法，可製造由胺等有機保護成分被覆的銀微粒子。The method of reducing the silver compound is preferably a method of heating. The heating method is not particularly limited. Examples of the method for reducing the silver compound by heating include a method of heating a compound formed from a silver compound such as silver oxalate and an organic component such as an amine to heat the compound contained in the compound. Metal compounds such as oxalate ions decompose and condense the generated atomic silver. By this method, silver fine particles coated with an organic protective component such as amine can be produced.

如此，於藉由使銀化合物的錯化合物於胺的存在下熱分解而製造由胺被覆的銀微粒子的金屬胺錯合物分解法中，利用為單一種類的分子的銀胺錯合物的分解反應而生成原子狀銀，因此可於反應系統內均勻地生成原子狀銀。因此，與利用多種成分間的反應來生成銀原子的情況相比較，構成反應的成分的組成波動引起的反應的不均勻得到抑制，尤其於以工業規模製造大量的銀粉末時有利。As described above, in the metal amine complex decomposition method for producing amine-coated silver fine particles by thermally decomposing a silver compound complex compound in the presence of an amine, the decomposition of a silver amine complex which is a single type of molecule is used. The reaction generates atomic silver, so atomic silver can be uniformly generated in the reaction system. Therefore, as compared with the case where silver atoms are generated by the reaction between a plurality of components, the non-uniformity of the reaction due to the composition fluctuation of the components constituting the reaction is suppressed, which is particularly advantageous when a large amount of silver powder is produced on an industrial scale.

另外，推測於金屬胺錯合物分解法中，胺分子與生成的銀原子配位鍵結，藉由配位於所述銀原子上的胺分子的作用，產生凝聚時的銀原子的運動得到控制。結果，可根據金屬胺錯合物分解法來製造非常微細、且粒度分佈窄的金屬粒子。In addition, it is presumed that in the metal amine complex decomposition method, the amine molecule is coordinated and bonded with the generated silver atom, and the movement of the silver atom during aggregation is controlled by the action of the amine molecule coordinated to the silver atom. . As a result, very fine metal particles with a narrow particle size distribution can be produced by the metal amine complex decomposition method.

進而，於所製造的銀微粒子的表面，大量的胺分子亦產生比較弱的力的配位鍵結，該些於銀微粒子的表面形成緻密的保護被膜，因此可製造保存穩定性優異、表面潔淨的有機被覆銀微粒子。另外，形成所述被膜的胺分子可藉由加熱等而容易地脫離，因此可製造可於非常低的溫度下進行燒結的銀微粒子。Furthermore, a large number of amine molecules also produce a relatively weak coordination bond on the surface of the produced silver fine particles. The surfaces of the silver fine particles form a dense protective coating, so that they can be manufactured with excellent storage stability and clean surfaces. Organic Coated Silver Particles. In addition, since the amine molecules forming the coating can be easily removed by heating or the like, silver fine particles that can be sintered at a very low temperature can be produced.

另外，於混合固體狀的銀化合物與胺來生成錯化合物等複合化合物時，對於構成被覆銀微粒子的被膜的具有酸價的分散劑混合使用胺，藉此容易生成錯化合物等複合化合物，可藉由短時間的混合來製造複合化合物。另外，藉由混合使用所述胺，可製造具有與各種用途相應的特性的被覆銀微粒子。In addition, when a solid silver compound is mixed with an amine to form a compound such as a compound, an amine is mixed with a dispersant having an acid value that constitutes a film covering the silver fine particles, thereby easily generating a compound such as a compound. A composite compound is produced by short-term mixing. In addition, by using the amine in combination, coated silver fine particles having characteristics corresponding to various uses can be produced.

於以所述方式獲得的包含由胺等有機保護成分被覆的銀微粒子的分散液中，除了銀微粒子以外，亦存在金屬鹽的抗衡離子、分散劑等，且存在液體整體的電解質濃度或有機物濃度高的傾向。此種狀態的液體因導電度高等理由而引起金屬粒子的凝結，容易沈澱。另外，即便未沈澱，若殘留金屬鹽的抗衡離子、分散所需的量以上的過剩的分散劑等，則有導電性惡化的擔憂。因此，對所述包含銀微粒子的溶液進行清洗而將多餘的殘留物除去，藉此可確實地獲得由有機保護成分被覆的銀微粒子。In the dispersion liquid containing silver fine particles coated with an organic protective component such as amine, in addition to the silver fine particles, a counter ion, a dispersant, and the like of a metal salt also exist in the dispersion liquid, and the electrolyte concentration or the organic substance concentration of the entire liquid High tendency. Liquids in this state cause coagulation of metal particles due to reasons such as high electrical conductivity and are liable to precipitate. Moreover, even if it does not precipitate, if there exists a counter ion of a metal salt, an excessive dispersing agent, etc. which are more than the amount required for dispersion, there exists a possibility that electrical conductivity may deteriorate. Therefore, the silver fine particle-containing solution can be reliably obtained by washing the solution containing the silver fine particles to remove excess residues.

作為所述清洗方法，例如可列舉重覆幾次如下步驟的方法：將包含表面由有機保護成分被覆的銀微粒子的分散液靜置固定時間，除去上清液後，添加使銀微粒子沈澱的溶媒（例如，水、甲醇、甲醇/水混合溶媒等）並進行攪框，再次靜置固定期間並除去上清液。作為其他方法，可列舉代替所述靜置而進行離心分離的方法、利用超濾裝置或離子交換裝置等進行脫鹽的方法等。藉由利用此種清洗來除去多餘的殘留物並去除有機溶媒，而可獲得表面由有機保護成分被覆的銀微粒子。As the cleaning method, for example, a method of repeating the following steps can be mentioned: a dispersion liquid containing silver fine particles coated on the surface with an organic protective component is allowed to stand for a fixed time, the supernatant is removed, and a solvent for precipitating the silver fine particles is added. (For example, water, methanol, methanol / water mixed solvent, etc.) and stir the frame, let it stand for a fixed period again, and remove the supernatant. Examples of the other methods include a method of performing centrifugation instead of the standing, a method of desalting using an ultrafiltration device, an ion exchange device, or the like. By using such cleaning to remove excess residues and remove organic solvents, silver fine particles whose surface is covered with an organic protective component can be obtained.

將所述金屬粒子分散體與分散介質混合的方法並無特別限定，可使用攪拌機或攪拌器（stirrer）等並利用先前公知的方法來進行。可利用刮刀（spatula）之類的物品進行攪拌，亦可選擇適當輸出的超音波均質機。The method of mixing the metal particle dispersion and the dispersion medium is not particularly limited, and it can be performed by a conventionally known method using a stirrer, stirrer, or the like. It can be stirred with items such as spatula, and an ultrasonic homogenizer with appropriate output can be selected.

＜接合方法＞
若使用本實施形態的接合用組成物，則即便於比較低的溫度（例如，200℃以下、較佳為150℃左右）下於伴隨加熱的構件彼此的接合中亦可獲得高的接合強度。即，藉由將所述接合用組成物塗佈於第1被接合構件與第2被接合構件之間的接合用組成物塗佈步驟、以及對塗佈於第1被接合構件與第2被接合構件之間的接合用組成物於所需的溫度（例如，200℃以下、較佳為150℃左右）下進行煅燒並加以接合的接合步驟，而可將第1被接合構件與第2被接合構件接合。＜ Joining method ＞
When the bonding composition of this embodiment is used, high bonding strength can be obtained even at a relatively low temperature (for example, 200 ° C. or lower, and preferably about 150 ° C.) for bonding members to be heated. That is, the bonding composition is applied to the bonding composition coating step between the first bonding member and the second bonding member, and the first bonding member and the second bonding member are coated. The bonding composition between the bonding members is subjected to a bonding step of firing and bonding at a desired temperature (for example, 200 ° C. or lower, preferably about 150 ° C.), so that the first bonded member and the second bonded member can be bonded. The joining member is joined.

所述接合步驟中，亦可將第1被接合構件與第2被接合構件向相向的方向加壓，但，尤其是，即便不加壓亦可獲得充分的接合強度亦為本發明的優點之一。所述煅燒亦可階段性升溫或階段性降溫。所述被接合構件亦可預先於表面上塗佈界面活性劑或表面活化劑等。In the joining step, the first member to be joined and the second member to be joined may be pressed in opposite directions, but in particular, it is an advantage of the present invention that sufficient joint strength can be obtained without pressing. One. The calcination may also be carried out stepwise or stepwise. The surface of the member to be joined may be coated with a surfactant or a surfactant on the surface in advance.

所謂所述「塗佈」，為既包含將接合用組成物塗佈為面狀的情況亦包含塗佈（描繪）為線狀的情況的概念。包含藉由加熱而煅燒前的狀態的接合用組成物的塗膜的形狀可設為所需的形狀。因此，藉由煅燒接合用組成物而獲得的燒結體（接合層）的形狀可為面狀亦可為線狀。該些面狀的接合層及線狀的接合層可連續亦可不連續，可包含連續的部分與不連續的部分。The "coating" is a concept that includes both the case where the bonding composition is applied in a planar shape and the case where the composition is applied (drawn) in a linear shape. The shape of the coating film including the bonding composition in a state before being fired by heating can be a desired shape. Therefore, the shape of the sintered body (bonding layer) obtained by firing the composition for joining may be planar or linear. The planar bonding layer and the linear bonding layer may be continuous or discontinuous, and may include a continuous portion and a discontinuous portion.

作為所述第1被接合構件及第2被接合構件，只要為可塗佈接合用組成物並藉由加熱而煅燒並接合的構件即可，並無特別限制，較佳為具備不會因接合時的溫度而損傷的程度的耐熱性的構件。The first to-be-joined member and the second to-be-joined member are not particularly limited as long as they are members that can be coated with a composition for joining and fired and joined by heating. The heat-resistant member is damaged to the extent of temperature.

作為構成所述第1被接合構件及第2被接合構件的材料，例如可列舉：聚醯胺（Polyamide，PA）、聚醯亞胺（Polyimide，PI）、聚醯胺醯亞胺（Polyamide-imide，PAI）、聚對苯二甲酸乙二酯（Polyethylene Terephthalate，PET）、聚對苯二甲酸丁二酯（Polybutylene Terephthalate，PBT）、聚萘二甲酸乙二酯（Polyethylene Naphthalate，PEN）等聚酯、聚碳酸酯（Polycarbonate，PC）、聚醚碸（Polyether Sulfone，PES）、乙烯基樹脂、氟樹脂、液晶聚合物、陶瓷、玻璃、金屬等。Examples of the material constituting the first joined member and the second joined member include polyamide (PA), polyimide (PI), and polyamide-imide imide (PAI), Polyethylene Terephthalate (PET), Polybutylene Terephthalate (PBT), Polyethylene Naphthalate (PEN), etc. Ester, Polycarbonate (PC), Polyether Sulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramic, glass, metal, etc.

所述被接合構件例如可為板狀或帶（strip）狀等各種形狀，可為剛性（rigid）亦可為柔性（flexible）。亦可適宜選擇基材的厚度。出於提高接著性或密接性或者其他目的，亦可使用形成有表面層的構件或實施有親水化處理等表面處理的構件。The member to be joined may have various shapes such as a plate shape or a strip shape, and may be rigid or flexible. The thickness of the substrate can also be appropriately selected. For the purpose of improving adhesion or adhesion, or other purposes, a member having a surface layer formed thereon or a member having a surface treatment such as a hydrophilization treatment may be used.

作為所述第1被接合構件及第2被接合構件，可列舉：樹脂基板、金屬板、LED等發光元件、半導體晶片、形成有電子電路的陶瓷基板等。本實施形態的接合用組成物因所獲得的燒結體的接合強度高，因此亦可於LED等發光元件、半導體晶片等、與金屬基板、陶瓷基板等的接合中適宜地使用。Examples of the first to-be-joined member and the second to-be-joined member include resin substrates, metal plates, light-emitting elements such as LEDs, semiconductor wafers, and ceramic substrates on which electronic circuits are formed. Since the bonding composition of the present embodiment has high bonding strength of the sintered body obtained, it can also be suitably used for bonding a light-emitting element such as an LED, a semiconductor wafer, and the like to a metal substrate, a ceramic substrate, and the like.

作為將接合用組成物塗佈於所述第1被接合構件及第2被接合構件上的步驟，可使用各種方法，例如，可使用浸漬、網版印刷、噴霧式、棒塗式、旋塗式、噴墨式、分配器式、針轉印（pin transfer）法、壓模（stamping）法、利用刷子的塗佈方式、流延式、柔版式、凹版式、平板法、轉印法、親水疏水圖案法、注射器式、針轉印、模版印刷等。其中，本實施形態的接合用組成物因固體成分濃度高而可於分配器式、針轉印、模版印刷中適宜地使用。Various methods can be used as the step of applying the bonding composition to the first member to be joined and the second member to be joined, and for example, dipping, screen printing, spray type, bar coating type, and spin coating can be used. Type, inkjet type, dispenser type, pin transfer method, stamping method, coating method using a brush, cast type, flexo type, gravure type, plate method, transfer method, Hydrophilic and hydrophobic pattern method, syringe type, needle transfer, stencil printing, etc. Among these, the bonding composition of the present embodiment can be suitably used in dispenser type, needle transfer, and stencil printing because of its high solid content concentration.

進行所述煅燒的方法並無特別限定，例如可使用先前公知的烘箱等以塗佈（描繪）於所述第1被接合構件及第2被接合構件上的所述接合用組成物的溫度為例如200℃以下的方式進行煅燒，藉此進行接合。所述煅燒的溫度的下限未必受到限定，較佳為可將所述第1被接合構件及第2被接合構件彼此接合的溫度，且為無損本發明的效果的範圍的溫度。所述煅燒的溫度的下限例如為100℃。The method for performing the firing is not particularly limited. For example, a temperature of the bonding composition applied (painted) on the first member to be joined and the second member to be joined may be using a conventionally known oven or the like. For example, firing is performed at a temperature of 200 ° C. or lower, thereby bonding. The lower limit of the firing temperature is not necessarily limited, but is preferably a temperature at which the first joined member and the second joined member can be joined to each other, and a temperature in a range that does not impair the effect of the present invention. The lower limit of the calcination temperature is, for example, 100 ° C.

再者，本實施形態的接合用組成物與先前的利用環氧樹脂等的熱硬化來獲得煅燒後的接合強度的組成物不同，如上所述，藉由金屬粒子的燒結而可獲得充分的接合強度。因此，即便於在接合後置於溫度較接合時的溫度（煅燒溫度）高的使用環境中而殘存的有機物劣化、分解·消失的情況下，亦無接合強度降低的擔憂，耐熱性優異。In addition, the bonding composition of this embodiment is different from a conventional composition that obtains the bonding strength after firing by thermal curing of an epoxy resin or the like. As described above, sufficient bonding can be obtained by sintering metal particles. strength. Therefore, even if the remaining organic matter is degraded, decomposed, or disappeared in a use environment where the temperature is higher than the temperature at the time of joining (calcination temperature) after joining, there is no fear of lowering the joint strength and the heat resistance is excellent.

根據本實施形態的接合用組成物，例如即便為利用200℃以下、較佳為150℃左右的低溫加熱進行的煅燒，亦可獲得優異的接合強度，因此可將比較不耐熱的被接合構件彼此接合。另外，煅燒時間並無特別限定，根據煅燒溫度，只要為可進行接合的煅燒時間即可。According to the bonding composition of the present embodiment, even if it is calcined by low-temperature heating at a temperature of 200 ° C. or lower, and preferably about 150 ° C., excellent bonding strength can be obtained. Therefore, relatively heat-resistant bonded members can be bonded to each other. Join. In addition, the firing time is not particularly limited, and depending on the firing temperature, any firing time that can be joined may be used.

於本實施形態中，進一步提高所述第1被接合構件及/或第2被接合構件與接合層的密接性，因此亦可進行所述第1被接合構件及/或第2被接合構件的表面處理。作為所述表面處理方法，例如可列舉：進行電暈處理、電漿處理、紫外線（Ultra Violet，UV）處理、電子束處理等乾式處理的方法、或於基材上預先設置底塗層或接合用組成物的接收層的方法等。In this embodiment, since the adhesiveness between the first joined member and / or the second joined member and the bonding layer is further improved, the first joined member and / or the second joined member can also be performed. Surface treatment. Examples of the surface treatment method include a method of performing a dry treatment such as a corona treatment, a plasma treatment, an ultra violet (UV) treatment, an electron beam treatment, or a base coat or a bonding agent provided in advance on the substrate. The method of using the receiving layer of the composition.

以上，對本發明的實施形態進行了說明，但本發明並不僅由該些內容限定。本實施形態的接合用組成物進而亦可含有例如導電性、導熱性、介電性、離子傳導性等優異的摻錫氧化銦、氧化鋁、鈦酸鋇、磷酸鐵鋰等無機粒子。As mentioned above, although embodiment of this invention was described, this invention is not limited only by these contents. The bonding composition according to this embodiment may further contain, for example, inorganic particles such as tin-doped indium oxide, aluminum oxide, barium titanate, and lithium iron phosphate which are excellent in electrical conductivity, thermal conductivity, dielectric properties, and ion conductivity.

以下，揭示實施例對本發明更詳細地進行說明，但本發明並不僅由該些實施例限定。
[實施例]Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited only by these examples.
[Example]

＜第一金屬粒子＞
（1-1）金屬微粒子A1
將3-乙氧基丙基胺（富士軟片和光純藥（股）製造的試劑特級，沸點132℃）11.0 g與3-甲氧基丙基胺（富士軟片和光純藥（股）製造的試劑一級，沸點120℃）7.0 g混合，並利用磁攪拌器充分進行攪拌。一邊進行攪拌一邊向其中添加草酸銀10.0 g，將所獲得的黏性物質加入至120℃的恆溫槽中，反應約15分鐘而獲得反應物。向所述反應物中添加甲醇10 ml並進行攪拌後，利用離心分離使銀微粒子沈澱並加以分離，捨棄上清液。將所述操作再重覆一次而獲得6 g的金屬微粒子A1。＜ First metal particle ＞
(1-1) Metal particles A1
11.0 g of 3-ethoxypropylamine (Fuji Soft Tablets and Kogyo Pure Chemicals Co., Ltd.) with 11.0 g of 3-methoxypropylamine (Fuji Soft Tablets and Kogyo Pure Chemicals Co., Ltd.) One stage, boiling point 120 ° C) 7.0 g are mixed and stirred thoroughly with a magnetic stirrer. While stirring, 10.0 g of silver oxalate was added thereto, and the obtained sticky substance was added to a thermostatic bath at 120 ° C., and reacted for about 15 minutes to obtain a reactant. After 10 ml of methanol was added to the reaction product and stirred, the silver fine particles were precipitated and separated by centrifugation, and the supernatant was discarded. This operation was repeated once more to obtain 6 g of metal fine particles A1.

使用利用SEM（日立股份有限公司製造的S-4800型）拍攝的粒子圖像，算出所獲得的金屬微粒子A1的數量平均一次粒徑（算術平均一次粒徑）。算術平均一次粒徑是根據於不同的拍攝點獲得的5點以上的圖像對合計200個以上的粒子使用圖像處理軟體（三谷公司（MITANI CORPORATION），WinROOF）進行算出。圖1是表示金屬微粒子A1的粒度分佈的圖表。金屬微粒子A1的算術平均一次粒徑為50 nm，標準偏差為14.2 nm。利用下述式（1）獲得的變異係數為28.4%。

變異係數（%）=一次粒徑的標準偏差/平均一次粒徑×100 （1）The number-average primary particle size (arithmetic average primary particle size) of the obtained metal fine particles A1 was calculated using a particle image taken by a SEM (S-4800 type manufactured by Hitachi, Ltd.). The arithmetic average primary particle size is calculated using image processing software (MITANI CORPORATION, WinROOF) for a total of 200 or more particles from images of 5 or more points obtained at different shooting points. FIG. 1 is a graph showing the particle size distribution of the metal fine particles A1. The arithmetic mean primary particle size of the metal fine particles A1 is 50 nm, and the standard deviation is 14.2 nm. The coefficient of variation obtained by the following formula (1) was 28.4%.

Coefficient of variation (%) = standard deviation of primary particle size / average primary particle size × 100 (1)

（1-2）金屬微粒子A2
對將3-乙氧基丙基胺5.0 g與3-甲氧基丙基胺11.0 g混合而成的混合液添加草酸銀，除此以外，與金屬微粒子A1的製法同樣地製作金屬微粒子A2。圖2是表示金屬微粒子A2的粒度分佈的圖表。金屬微粒子A2的算術平均一次粒徑為28 nm，標準偏差為11.1 nm，變異係數為39.6%。(1-2) Metal particles A2
Except that silver oxalate was added to a mixed solution prepared by mixing 5.0 g of 3-ethoxypropylamine and 11.0 g of 3-methoxypropylamine, metal fine particles A2 were produced in the same manner as in the method for producing metal fine particles A1. FIG. 2 is a graph showing a particle size distribution of the metal fine particles A2. The arithmetic mean primary particle size of metal microparticles A2 was 28 nm, the standard deviation was 11.1 nm, and the coefficient of variation was 39.6%.

（1-3）金屬微粒子A3
對將3-乙氧基丙基胺13.0 g與3-甲氧基丙基胺11.0 g混合而成的混合液添加草酸銀，除此以外，與金屬微粒子A1的製法同樣地製作金屬微粒子A3。圖3是表示金屬微粒子A3的粒度分佈的圖表。金屬微粒子A3的算術平均一次粒徑為34 nm，標準偏差為14.8 nm，變異係數為43.5%。(1-3) Metal particles A3
Except that silver oxalate was added to a mixed solution obtained by mixing 13.0 g of 3-ethoxypropylamine and 11.0 g of 3-methoxypropylamine, metal fine particles A3 were produced in the same manner as in the method for producing metal fine particles A1. FIG. 3 is a graph showing a particle size distribution of the metal fine particles A3. The arithmetic average primary particle size of metal microparticles A3 was 34 nm, the standard deviation was 14.8 nm, and the coefficient of variation was 43.5%.

（1-4）金屬微粒子A4
並不調配3-甲氧基丙基胺而是對3-乙氧基丙基胺15.0 g添加草酸銀，除此以外，與金屬微粒子A1的製法同樣地製作金屬微粒子A4。圖4是表示金屬微粒子A4的粒度分佈的圖表。金屬微粒子A4的算術平均一次粒徑為27 nm，標準偏差為6.0 nm，變異係數為22.2%。(1-4) Metal particles A4
Metal microparticles A4 were produced in the same manner as in the method for producing metal microparticles A1 except that silver oxalate was added to 15.0 g of 3-ethoxypropylamine instead of formulating 3-methoxypropylamine. FIG. 4 is a graph showing a particle size distribution of the metal fine particles A4. The arithmetic mean primary particle size of the metal fine particles A4 was 27 nm, the standard deviation was 6.0 nm, and the coefficient of variation was 22.2%.

（1-5）金屬微粒子A5
並不調配3-甲氧基丙基胺而是對3-乙氧基丙基胺10.0 g添加草酸銀，除此以外，與金屬微粒子A1的製法同樣地製作金屬微粒子A5。圖5是表示金屬微粒子A5的粒度分佈的圖表。金屬微粒子A5的算術平均一次粒徑為30 nm，標準偏差為5.9 nm，變異係數為19.7%。(1-5) Metal particles A5
Metal microparticles A5 were produced in the same manner as in the method for producing metal microparticles A1, except that silver oxalate was added to 10.0 g of 3-ethoxypropylamine instead of 3-methoxypropylamine. FIG. 5 is a graph showing a particle size distribution of the metal fine particles A5. The arithmetic average primary particle size of metal microparticles A5 was 30 nm, the standard deviation was 5.9 nm, and the coefficient of variation was 19.7%.

（1-6）金屬微粒子A6
對將3-乙氧基丙基胺10.0 g與2-(2-胺基乙氧基)乙醇（富士軟片和光純藥（股）製造的試劑一級）5.0 g混合而成的混合液添加草酸銀，除此以外，與金屬微粒子A1的製法同樣地製作金屬微粒子A6。圖6是表示金屬微粒子A6的粒度分佈的圖表。金屬微粒子A6的算術平均一次粒徑為45 nm，標準偏差為23.1 nm，變異係數為51.3%。(1-6) Metal particles A6
Silver oxalate was added to a mixed solution prepared by mixing 10.0 g of 3-ethoxypropylamine with 5.0 g of 2- (2-aminoethoxy) ethanol (Fuji film and reagent grade manufactured by Kosuke Pharmaceutical Co., Ltd.). Except for this, metal fine particles A6 were produced in the same manner as in the method for producing metal fine particles A1. FIG. 6 is a graph showing a particle size distribution of the metal fine particles A6. The arithmetic average primary particle size of the metal fine particles A6 was 45 nm, the standard deviation was 23.1 nm, and the coefficient of variation was 51.3%.

（1-7）金屬微粒子A7
並不調配3-乙氧基丙基胺而是對3-甲氧基丙基胺15.0 g添加草酸銀，除此以外，與金屬微粒子A1的製法同樣地製作金屬微粒子A7。圖7是表示金屬微粒子A7的粒度分佈的圖表。金屬微粒子A7的算術平均一次粒徑為83 nm，標準偏差為29.1 nm，變異係數為35.1%。(1-7) Metal particles A7
Metal microparticles A7 were produced in the same manner as in the method for producing metal microparticles A1, except that silver oxalate was added to 15.0 g of 3-methoxypropylamine instead of 3-ethoxypropylamine. FIG. 7 is a graph showing a particle size distribution of the metal fine particles A7. The arithmetic average primary particle size of the metal fine particles A7 was 83 nm, the standard deviation was 29.1 nm, and the coefficient of variation was 35.1%.

（1-8）金屬微粒子A8
並不調配3-甲氧基丙基胺而是對3-乙氧基丙基胺20.0 g添加草酸銀，除此以外，與金屬微粒子A1的製法同樣地製作金屬微粒子A8。圖8是表示金屬微粒子A8的粒度分佈的圖表。金屬微粒子A8的算術平均一次粒徑為19 nm，標準偏差為4.9 nm，變異係數為25.8%。(1-8) Metal particles A8
Metal microparticles A8 were produced in the same manner as in the method for producing metal microparticles A1, except that silver oxalate was added to 20.0 g of 3-ethoxypropylamine instead of formulating 3-methoxypropylamine. FIG. 8 is a graph showing a particle size distribution of the metal fine particles A8. The arithmetic average primary particle size of metal microparticles A8 was 19 nm, the standard deviation was 4.9 nm, and the coefficient of variation was 25.8%.

（1-9）金屬微粒子A9
並不調配3-乙氧基丙基胺而是對3-甲氧基丙基胺20.0 g添加草酸銀，除此以外，與金屬微粒子A1的製法同樣地製作金屬微粒子A9。圖9是表示金屬微粒子A9的粒度分佈的圖表。金屬微粒子A9的算術平均一次粒徑為112 nm，標準偏差為44.9 nm，變異係數為40.1%。(1-9) Metal particles A9
Metal fine particles A9 were produced in the same manner as in the method for producing metal fine particles A1, except that silver oxalate was added to 20.0 g of 3-methoxypropylamine instead of formulating 3-ethoxypropylamine. FIG. 9 is a graph showing a particle size distribution of the metal fine particles A9. The arithmetic mean primary particle size of metal fine particles A9 was 112 nm, the standard deviation was 44.9 nm, and the coefficient of variation was 40.1%.

＜第二金屬粒子＞
（2-1）金屬微粒子B1
將3-乙氧基丙基胺10.0 g與2-(2-胺基乙氧基)乙醇（富士軟片和光純藥（股）製造的試劑一級）20.0 g混合，並利用磁攪拌器充分進行攪拌。一邊進行攪拌一邊向其中添加草酸銀10.0 g，將所獲得的黏性物質加入至120℃的恆溫槽中，反應約15分鐘而獲得反應物。向所述反應物中添加甲醇10 ml並進行攪拌後，利用離心分離使銀微粒子沈澱並加以分離，捨棄上清液。將所述操作再重覆一次而獲得6 g的金屬微粒子B1。圖10是表示金屬微粒子B1的粒度分佈的圖表。金屬微粒子B1的算術平均一次粒徑為300 nm，標準偏差為180 nm，變異係數為60.0%。＜ Second metal particle ＞
(2-1) Metal particles B1
10.0 g of 3-ethoxypropylamine was mixed with 20.0 g of 2- (2-aminoethoxy) ethanol (Fuji film and reagent grade manufactured by Kosuke Pharmaceutical Co., Ltd.), and the mixture was thoroughly stirred with a magnetic stirrer . While stirring, 10.0 g of silver oxalate was added thereto, and the obtained viscous substance was added to a thermostatic bath at 120 ° C. and reacted for about 15 minutes to obtain a reactant. After 10 ml of methanol was added to the reaction product and stirred, the silver fine particles were precipitated and separated by centrifugation, and the supernatant was discarded. This operation was repeated once more to obtain 6 g of metal fine particles B1. FIG. 10 is a graph showing a particle size distribution of the metal fine particles B1. The arithmetic mean primary particle diameter of metal fine particles B1 is 300 nm, the standard deviation is 180 nm, and the coefficient of variation is 60.0%.

（2-2）金屬微粒子B2
將稀有金屬材料研究所製造的算術平均一次粒徑為340 nm、標準偏差為81.6 nm、變異係數為24.0%的銀奈米粒子設為金屬微粒子B2。圖11是表示金屬微粒子B2的粒度分佈的圖表。(2-2) Metal particles B2
Silver fine particles having an arithmetic average primary particle diameter of 340 nm, a standard deviation of 81.6 nm, and a coefficient of variation of 24.0% manufactured by the Institute of Rare Metal Materials were set as metal fine particles B2. FIG. 11 is a graph showing a particle size distribution of the metal fine particles B2.

（2-3）金屬微粒子B3
對將2-(2-胺基乙氧基)乙醇（富士軟片和光純藥（股）製造的試劑一級）10.5 g與草酸銀10.0 g混合而成的混合液添加草酸銀，除此以外，利用與金屬微粒子B1相同的製法來獲得金屬微粒子B3。圖12是表示金屬微粒子B3的粒度分佈的圖表。金屬微粒子B3的算術平均一次粒徑為150 nm，標準偏差為60 nm，變異係數為40.0%。(2-3) Metal particles B3
The silver oxalate was added to a mixed solution prepared by mixing 10.5 g of 2- (2-aminoethoxy) ethanol (Fuji film and Kogyo Pure Chemical Co., Ltd. reagent grade 1) with 10.0 g of silver oxalate. The same method as the metal fine particles B1 was used to obtain the metal fine particles B3. FIG. 12 is a graph showing a particle size distribution of the metal fine particles B3. The arithmetic average primary particle size of metal microparticles B3 was 150 nm, the standard deviation was 60 nm, and the coefficient of variation was 40.0%.

（2-4）金屬微粒子B4
對2-(2-胺基乙氧基)乙醇（富士軟片和光純藥（股）製造的試劑一級）10.5 g添加草酸銀10.0 g，除此以外，利用與金屬微粒子B1相同的製法來獲得金屬微粒子B4。金屬微粒子B4的算術平均一次粒徑為450 nm，標準偏差為189 nm，變異係數為42.0%。(2-4) Metal particles B4
Metal was obtained by the same method as that of metal fine particles B1 except that 10.0 g of 2- (2-aminoethoxy) ethanol (1st grade reagent manufactured by Fujifilm and Kogyo Pure Chemicals Co., Ltd.) was added with silver oxalate. Microparticle B4. The arithmetic mean primary particle diameter of metal fine particles B4 was 450 nm, the standard deviation was 189 nm, and the coefficient of variation was 42.0%.

＜接合用組成物＞
（實施例1）
將4 g的作為第一金屬粒子的金屬微粒子A1、4 g的作為第二金屬粒子的金屬微粒子B1混合，添加0.32 g的作為分散介質的1-癸醇、0.016 g的作為高分子分散劑的索努帕斯16000，並加以攪拌脫泡，藉此製作實施例1的接合用組成物。<Composition for bonding>
(Example 1)
4 g of the metal fine particles A1 as the first metal particles and 4 g of the metal fine particles B1 as the second metal particles were mixed, and 0.32 g of 1-decanol as a dispersion medium and 0.016 g of a polymer dispersant were added. Sonupas 16000 was stirred and degassed to prepare a bonding composition of Example 1.

（實施例2）
將3.2 g的作為第一金屬粒子的金屬微粒子A1、4.8 g的作為第二金屬粒子的金屬微粒子B1混合，除此以外，與實施例1同樣地製作實施例2的接合用組成物。(Example 2)
Except that 3.2 g of the metal fine particles A1 as the first metal particles and 4.8 g of the metal fine particles B1 as the second metal particles were mixed, a bonding composition of Example 2 was prepared in the same manner as in Example 1.

（實施例3）
將2.4 g的作為第一金屬粒子的金屬微粒子A1、5.6 g的作為第二金屬粒子的金屬微粒子B1混合，除此以外，與實施例1同樣地製作實施例3的接合用組成物。(Example 3)
Except that 2.4 g of the metal fine particles A1 as the first metal particles and 5.6 g of the metal fine particles B1 as the second metal particles were mixed, a bonding composition of Example 3 was prepared in the same manner as in Example 1.

（實施例4）
將4 g的作為第一金屬粒子的金屬微粒子A2、4 g的作為第二金屬粒子的金屬微粒子B1混合，除此以外，與實施例1同樣地製作實施例4的接合用組成物。(Example 4)
Except that 4 g of the metal fine particles A2 as the first metal particles and 4 g of the metal fine particles B1 as the second metal particles were mixed, a bonding composition of Example 4 was prepared in the same manner as in Example 1.

（實施例5）
將3.2 g的作為第一金屬粒子的金屬微粒子A2、4.8 g的作為第二金屬粒子的金屬微粒子B1混合，除此以外，與實施例1同樣地製作實施例5的接合用組成物。(Example 5)
Except that 3.2 g of the metal fine particles A2 as the first metal particles and 4.8 g of the metal fine particles B1 as the second metal particles were mixed, a bonding composition of Example 5 was prepared in the same manner as in Example 1.

（實施例6）
使用金屬微粒子B2作為第二金屬粒子，除此以外，與實施例1同樣地製作實施例6的接合用組成物。(Example 6)
A bonding composition of Example 6 was produced in the same manner as in Example 1 except that metal fine particles B2 were used as the second metal particles.

（實施例7）
將3.2 g的作為第一金屬粒子的金屬微粒子A1、4.8 g的作為第二金屬粒子的金屬微粒子B2混合，除此以外，與實施例1同樣地製作實施例7的接合用組成物。(Example 7)
Except that 3.2 g of the metal fine particles A1 as the first metal particles and 4.8 g of the metal fine particles B2 as the second metal particles were mixed, a bonding composition of Example 7 was prepared in the same manner as in Example 1.

（實施例8）
添加0.23 g的作為分散介質的1-癸醇，除此以外，與實施例1同樣地製作實施例8的接合用組成物。(Example 8)
A bonding composition of Example 8 was prepared in the same manner as in Example 1 except that 0.23 g of 1-decanol was added as a dispersion medium.

（實施例9）
添加0.15 g的作為分散介質的1-癸醇，除此以外，與實施例1同樣地製作實施例9的接合用組成物。(Example 9)
A bonding composition of Example 9 was prepared in the same manner as in Example 1 except that 0.15 g of 1-decanol was added as a dispersion medium.

（實施例10）
將4.0 g的作為第一金屬粒子的金屬微粒子A1、4.0 g的作為第二金屬粒子的金屬微粒子B3混合，除此以外，與實施例1同樣地製作實施例10的接合用組成物。(Example 10)
Except that 4.0 g of the metal fine particles A1 as the first metal particles and 4.0 g of the metal fine particles B3 as the second metal particles were mixed, a bonding composition of Example 10 was prepared in the same manner as in Example 1.

（實施例11）
使用金屬微粒子A4作為第一金屬粒子，除此以外，與實施例1同樣地製作實施例11的接合用組成物。(Example 11)
A bonding composition of Example 11 was produced in the same manner as in Example 1 except that metal fine particles A4 were used as the first metal particles.

（實施例12）
使用金屬微粒子A5作為第一金屬粒子，除此以外，與實施例1同樣地製作實施例12的接合用組成物。(Example 12)
A bonding composition of Example 12 was produced in the same manner as in Example 1 except that metal fine particles A5 were used as the first metal particles.

（實施例13）
使用金屬微粒子A3作為第一金屬粒子，除此以外，與實施例1同樣地製作實施例13的接合用組成物。(Example 13)
A bonding composition of Example 13 was produced in the same manner as in Example 1 except that metal fine particles A3 were used as the first metal particles.

（實施例14）
使用金屬微粒子A6作為第一金屬粒子，除此以外，與實施例1同樣地製作實施例14的接合用組成物。(Example 14)
A bonding composition of Example 14 was produced in the same manner as in Example 1 except that metal fine particles A6 were used as the first metal particles.

（實施例15）
使用金屬微粒子A7作為第一金屬粒子，除此以外，與實施例1同樣地製作實施例15的接合用組成物。(Example 15)
A bonding composition of Example 15 was produced in the same manner as in Example 1 except that metal fine particles A7 were used as the first metal particles.

（實施例16）
將4.0 g的作為第一金屬粒子的金屬微粒子A2、4.0 g的作為第二金屬粒子的金屬微粒子B4混合，除此以外，與實施例1同樣地製作實施例16的接合用組成物。(Example 16)
Except that 4.0 g of the metal fine particles A2 as the first metal particles and 4.0 g of the metal fine particles B4 as the second metal particles were mixed, a bonding composition of Example 16 was produced in the same manner as in Example 1.

（實施例17）
並不添加第二金屬粒子而是將6.0 g的作為第一金屬粒子的金屬微粒子A1、0.24 g的作為分散介質的1-癸醇、0.012 g的作為高分子分散劑的索努帕斯16000混合，除此以外，與實施例1同樣地製作實施例17的接合用組成物。(Example 17)
Instead of adding the second metal particles, 6.0 g of the metal fine particles A1 as the first metal particles, 0.24 g of 1-decanol as the dispersion medium, and 0.012 g of Sonopas 16000 as the polymer dispersant were mixed. Other than that, the bonding composition of Example 17 was produced in the same manner as in Example 1.

（比較例1）
並不添加分散介質，除此以外，與實施例1同樣地製作比較例1的接合用組成物。(Comparative Example 1)
A bonding composition of Comparative Example 1 was produced in the same manner as in Example 1 except that the dispersion medium was not added.

（比較例2）
添加0.016 g的作為分散介質的1-癸醇，除此以外，與實施例1同樣地製作比較例2的接合用組成物。(Comparative Example 2)
A joining composition of Comparative Example 2 was produced in the same manner as in Example 1 except that 0.016 g of 1-decanol was added as a dispersion medium.

（比較例3）
添加0.41 g的作為分散介質的1-癸醇，除此以外，與實施例1同樣地製作比較例3的接合用組成物。(Comparative Example 3)
A bonding composition of Comparative Example 3 was produced in the same manner as in Example 1 except that 0.41 g of 1-decanol was added as a dispersion medium.

（比較例4）
添加0.97 g的作為分散介質的1-癸醇，除此以外，與實施例1同樣地製作比較例4的接合用組成物。(Comparative Example 4)
A bonding composition of Comparative Example 4 was prepared in the same manner as in Example 1 except that 0.97 g of 1-decanol was added as a dispersion medium.

（比較例5）
並不添加第二金屬粒子而是添加4 g的作為第一金屬粒子的金屬微粒子A2、0.31 g的作為分散介質的1-癸醇、0.035 g的作為高分子分散劑的索努帕斯16000，除此以外，與實施例1同樣地製作比較例5的接合用組成物。(Comparative Example 5)
Instead of adding the second metal particles, 4 g of the metal fine particles A2 as the first metal particles, 0.31 g of 1-decanol as the dispersion medium, and 0.035 g of Sonopas 16000 as the polymer dispersant, Other than that, the bonding composition of Comparative Example 5 was produced in the same manner as in Example 1.

（比較例6）
並不添加第二金屬粒子而是添加4 g的作為第一金屬粒子的金屬微粒子A1、0.31 g的作為分散介質的1-癸醇、0.035 g的作為高分子分散劑的索努帕斯16000，除此以外，與實施例1同樣地製作比較例6的接合用組成物。(Comparative Example 6)
Rather than adding the second metal particles, 4 g of the metal fine particles A1 as the first metal particles, 0.31 g of 1-decanol as the dispersion medium, and 0.035 g of Sonopas 16000 as the polymer dispersant, Other than that, the bonding composition of Comparative Example 6 was produced in the same manner as in Example 1.

（比較例7）
使用金屬微粒子A8作為第一金屬粒子，除此以外，與實施例1同樣地製作比較例7的接合用組成物。(Comparative Example 7)
A bonding composition of Comparative Example 7 was produced in the same manner as in Example 1 except that the metal fine particles A8 were used as the first metal particles.

（比較例8）
使用金屬微粒子A9作為第一金屬粒子，除此以外，與實施例1同樣地製作比較例8的接合用組成物。(Comparative Example 8)
A bonding composition of Comparative Example 8 was produced in the same manner as in Example 1 except that metal fine particles A9 were used as the first metal particles.

＜評價＞
（1）重量減少率的測定
對於實施例及比較例的接合用組成物，使用差動型示差熱天平（理學（rigaku）公司製造，TG8120）並利用熱重分析法來測定重量減少率。具體而言，於大氣環境下，對接合用組成物以10℃/分鐘的升溫速度進行加熱，測定25℃～550℃為止的重量減少率。＜ Evaluation ＞
(1) Measurement of weight reduction rate The weight reduction rate was measured by the thermogravimetric analysis method using a differential type differential thermal balance (TG8120, manufactured by Rigaku Corporation) for the bonding compositions of the examples and comparative examples. Specifically, the bonding composition was heated at a temperature rising rate of 10 ° C./minute in an atmospheric environment, and the weight reduction rate up to 25 ° C. to 550 ° C. was measured.

（2）剪切黏度
對於實施例及比較例的接合用組成物，使用錐板型黏度計（安東帕（Anton Paar）公司製造的流變儀，MCR301）以如下測定條件測定剪切速度為10 s^-1 時的剪切黏度（Pa·s）。
（測定條件）
測定模式：剪切模式
剪切速度：10 s^-1
測定夾具：錐板CP-50-2
（直徑50 mm、角度2°、間隙0.045 mm）
測定溫度：25℃(2) Shear Viscosity For the compositions for bonding of Examples and Comparative Examples, a cone-plate viscometer (rheometer manufactured by Anton Paar, MCR301) was used to measure the shear rate under the following measurement conditions: Shear viscosity at s ^-1 (Pa · s).
(Measurement conditions)
Measurement mode: Shear mode Shear speed: 10 s ^-1
Measuring fixture: cone plate CP-50-2
(50 mm diameter, 2 ° angle, 0.045 mm clearance)
Measurement temperature: 25 ° C

（3）接合強度
於表面實施有銀鍍敷的銅板（20 mm見方，厚度1 mm）的銀鍍層上，使用裝片機（die bonder）（海索爾（hisol）公司製造）載置10 μg的接合用組成物，並於接合用組成物上積層市售的藍色LED晶片（晶元光電（Epistar）公司製造的ES-CADBV24H，底面積：600 μm×600 μm，高度：150 μm），並且對於各實施例及比較例，製作積層有實施有銀鍍敷的銅板、接合用組成物、以及藍色LED晶片的積層體。(3) Bonding strength On a silver plated copper plate (20 mm square, 1 mm thick) with silver plating on the surface, 10 μg was placed using a die bonder (made by Hisol). A bonding composition, and a commercially available blue LED wafer (ES-CADBV24H manufactured by Epistar Corporation, bottom area: 600 μm × 600 μm, height: 150 μm) is laminated on the bonding composition, In addition, for each of the examples and comparative examples, a laminated body including a copper plate on which silver plating was applied, a composition for bonding, and a blue LED wafer was produced.

將所獲得的積層體放入至熱風循環式烘箱中，於大氣中歷時40分鐘自25℃升溫至190℃，並進行90分鐘煅燒。煅燒處理時，並不對積層體進行加壓。取出積層體後，於常溫下使用接合試驗機（力世科（rhesca）股份有限公司製造接合試驗機（bonding tester）PTR1102）進行接合強度試驗。所述接合強度試驗中，將安裝於接合試驗機的加重感測器的寬度1.2 mm的工具（tool）配置於距所述銅板的表面為10.0 μm的高度處，以0.01 mm/sec使所述工具移動，並按壓利用所述接合用組成物進行接合的接合部分，測定自所述銅板剝離所述藍色LED晶片時的加重，設為剝離時的接合強度。用剝離時的接合強度除以晶片的底面積，算出每單位面積的接合強度（MPa）。The obtained laminated body was put into a hot-air circulation type oven, heated from 25 ° C to 190 ° C in the atmosphere for 40 minutes, and calcined for 90 minutes. During the firing treatment, the laminated body is not pressurized. After taking out the laminated body, the bonding strength test was performed at room temperature using a bonding tester (bonding tester PTR1102 manufactured by Rhesca Co., Ltd.). In the bonding strength test, a tool having a width of 1.2 mm mounted on the weight sensor of the bonding tester was placed at a height of 10.0 μm from the surface of the copper plate, and the tool was set at 0.01 mm / sec. A tool is moved, and a bonding portion to be bonded by the bonding composition is pressed to measure a weight when the blue LED wafer is peeled from the copper plate, and is set as a bonding strength at the time of peeling. The bonding strength at the time of peeling was divided by the bottom area of the wafer to calculate the bonding strength (MPa) per unit area.

（4）熱循環可靠性
將所述接合強度試驗中煅燒的積層體加入至冷熱衝擊試驗機（優泰克（Futec）公司製造）中，於大氣環境下、-40℃及150℃下各保持10分鐘，將該操作設為1個循環，進行500個循環，並取出經過500個循環後的積層體。進行所取出的積層體的接合強度測定，將相對於熱循環試驗前的初期強度的、熱循環試驗後的接合強度的降低率為0～小於5%的情況設為○，將5%以上～小於20%的情況設為△，將20%以上的情況設為×。(4) Reliability of thermal cycle The laminated body calcined in the joint strength test was added to a cold and thermal shock tester (made by Futec), and each was maintained at -40 ° C and 150 ° C in an atmospheric environment for 10 minutes. This operation was set to 1 cycle for 500 minutes, and the laminated body after 500 cycles was taken out. The joint strength of the taken-out laminated body was measured, and when the reduction rate of the joint strength after the thermal cycle test from the initial strength before the thermal cycle test was 0 to less than 5%, it was ○, and 5% or more to When it is less than 20%, it is set to Δ, and when it is 20% or more, it is set to ×.

將實施例及比較例的接合用組成物的組成與評價結果匯總於下述表1、表2及表3中。The composition and evaluation result of the bonding composition of an Example and a comparative example are put together in the following Table 1, Table 2, and Table 3.

[表1]

[Table 1]

[表2]

[Table 2]

[表3]

[table 3]

實施例1～實施例17的接合用組成物均具有適度的剪切黏度，且處理性良好，並且重量減少率為5.5%以下。由實施例1～實施例17的接合用組成物獲得的燒結體的接合強度優異、且熱循環可靠性高。The bonding compositions of Examples 1 to 17 all had moderate shear viscosity, good handling properties, and a weight reduction rate of 5.5% or less. The sintered bodies obtained from the bonding compositions of Examples 1 to 17 have excellent bonding strength and high thermal cycle reliability.

若分別對實施例1～實施例3、實施例4與實施例5、實施例6與實施例7進行比較，則確認到第二金屬粒子的重量比第一金屬粒子的重量多的實施例的剪切黏度降低且流動性變高，另一方面，存在重量減少率降低的傾向。根據實施例1、實施例4、實施例11～實施例15的結果，確認到即便第一金屬粒子的平均粒徑小，藉由調整變異係數亦可獲得適當的流動性。Comparing Example 1 to Example 3, Example 4 and Example 5, Example 6 and Example 7, respectively, it was confirmed that the example of the example in which the weight of the second metal particles is greater than the weight of the first metal particles The shear viscosity is lowered and the fluidity is increased. On the other hand, the weight reduction rate tends to decrease. From the results of Examples 1, 4, and 11 to 15, it was confirmed that even if the average particle diameter of the first metal particles is small, appropriate fluidity can be obtained by adjusting the coefficient of variation.

另一方面，第一金屬粒子的平均粒徑小於20 μm的比較例7、第一金屬粒子的平均粒徑超過100 μm的比較例8均未獲得充分的熱循環可靠性。On the other hand, in Comparative Example 7 in which the average particle diameter of the first metal particles was less than 20 μm and Comparative Example 8 in which the average particle diameter of the first metal particles was more than 100 μm, sufficient thermal cycle reliability was not obtained.

若著眼於分散介質的含量並對實施例1、實施例9、比較例1～比較例4進行比較，則隨著分散介質的含量變低而重量減少量減少，但於分散介質的含量小於1.0重量%的比較例1及比較例2中，接合用組成物的黏度過高而無法測定剪切黏度。比較例1的處理性差，且無法將接合用組成物形成為膜狀，從而無法製作測定用的樣品。另一方面，分散介質的含量為5.0重量%以上的比較例3及比較例4中，重量減少率超過5.5%。When focusing on the content of the dispersion medium and comparing Example 1, Example 9, and Comparative Examples 1 to 4, the weight reduction amount decreases as the content of the dispersion medium becomes lower, but the content of the dispersion medium is less than 1.0. In Comparative Examples 1 and 2 by weight%, the viscosity of the bonding composition was too high to measure the shear viscosity. Comparative Example 1 was inferior in handleability, and the composition for bonding could not be formed into a film, and thus a sample for measurement could not be prepared. On the other hand, in Comparative Examples 3 and 4 in which the content of the dispersion medium was 5.0% by weight or more, the weight reduction rate exceeded 5.5%.

無no

圖1是表示金屬微粒子A1的粒度分佈的圖表。FIG. 1 is a graph showing the particle size distribution of the metal fine particles A1.

圖2是表示金屬微粒子A2的粒度分佈的圖表。 FIG. 2 is a graph showing a particle size distribution of the metal fine particles A2.

圖3是表示金屬微粒子A3的粒度分佈的圖表。 FIG. 3 is a graph showing a particle size distribution of the metal fine particles A3.

圖4是表示金屬微粒子A4的粒度分佈的圖表。 FIG. 4 is a graph showing a particle size distribution of the metal fine particles A4.

圖5是表示金屬微粒子A5的粒度分佈的圖表。 FIG. 5 is a graph showing a particle size distribution of the metal fine particles A5.

圖6是表示金屬微粒子A6的粒度分佈的圖表。 FIG. 6 is a graph showing a particle size distribution of the metal fine particles A6.

圖7是表示金屬微粒子A7的粒度分佈的圖表。 FIG. 7 is a graph showing a particle size distribution of the metal fine particles A7.

圖8是表示金屬微粒子A8的粒度分佈的圖表。 FIG. 8 is a graph showing a particle size distribution of the metal fine particles A8.

圖9是表示金屬微粒子A9的粒度分佈的圖表。 FIG. 9 is a graph showing a particle size distribution of the metal fine particles A9.

圖10是表示金屬微粒子B1的粒度分佈的圖表。 FIG. 10 is a graph showing a particle size distribution of the metal fine particles B1.

圖11是表示金屬微粒子B2的粒度分佈的圖表。 FIG. 11 is a graph showing a particle size distribution of the metal fine particles B2.

圖12是表示金屬微粒子B3的粒度分佈的圖表。 FIG. 12 is a graph showing a particle size distribution of the metal fine particles B3.

Claims (7)

一種接合用組成物，其為含有平均粒徑為20 nm～100 nm的第一金屬粒子、以及分散介質的接合用組成物，且其特徵在於： 所述分散介質相對於所述接合用組成物整體的含量為1.0重量%以上且小於5.0重量%。A bonding composition is a bonding composition containing first metal particles having an average particle diameter of 20 nm to 100 nm and a dispersion medium, and is characterized in that: The content of the dispersion medium with respect to the entire bonding composition is 1.0% by weight or more and less than 5.0% by weight. 如申請專利範圍第1項所述的接合用組成物，其中所述第一金屬粒子的下述式（1）所表示的一次粒徑的變異係數為25.0%以上且50.0%以下， 變異係數（%）=一次粒徑的標準偏差/平均一次粒徑×100 （1）。The bonding composition according to item 1 of the scope of patent application, wherein the coefficient of variation of the primary particle size represented by the following formula (1) of the first metal particle is 25.0% or more and 50.0% or less, Coefficient of variation (%) = standard deviation of primary particle size / average primary particle size × 100 (1). 如申請專利範圍第1項或第2項所述的接合用組成物，其進而含有平均粒徑為200 nm～500 nm的第二金屬粒子。The bonding composition according to claim 1 or claim 2, further comprising second metal particles having an average particle diameter of 200 nm to 500 nm. 如申請專利範圍第3項所述的接合用組成物，其中所述第一金屬粒子與所述第二金屬粒子的重量比率為20：80～80：20。The bonding composition according to item 3 of the scope of patent application, wherein a weight ratio of the first metal particles to the second metal particles is 20:80 to 80:20. 如申請專利範圍第1項至第4項中任一項所述的接合用組成物，其中所述第一金屬粒子由有機保護成分被覆。The bonding composition according to any one of claims 1 to 4, wherein the first metal particles are covered with an organic protective component. 如申請專利範圍第5項所述的接合用組成物，其中所述有機保護成分包含至少一種沸點為150℃以下的胺。The bonding composition according to item 5 of the patent application range, wherein the organic protective component includes at least one amine having a boiling point of 150 ° C. or lower. 如申請專利範圍第1項至第6項中任一項所述的接合用組成物，其進而含有高分子分散劑。The bonding composition according to any one of claims 1 to 6 of the scope of patent application, further comprising a polymer dispersant.