TW202214761A - Metal particle-containing resin composition - Google Patents
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Abstract
Description
發明領域 本發明是有關於一種含金屬粒子之樹脂組成物。 Field of Invention The present invention relates to a resin composition containing metal particles.
背景技術 迄今已知的是將含有金屬粒子的樹脂組成物應用在電子零件封裝體之屏蔽中(專利文獻1)。 Background technique It has hitherto been known to apply a resin composition containing metal particles to a shield of an electronic component package (Patent Document 1).
又，已知會將含有金屬粒子的樹脂組成物作為放熱材料使用。例如，專利文獻2中記載，放熱接著劑是以矽或熱傳導性環氧等作為主材料，且為了提高熱傳導率而混入金屬填料。又，專利文獻3中記載有一種基板，該基板是在熱傳導率高的氮化鋁基板上以電路圖案狀積層導電糊再加以燒成而成，並且記載了前述基板與透過接著劑於基板上積層金屬箔並蝕刻成電路圖案狀的電路基板不同，由於在利用導電燒結體所構成的電路與基板間並無接著劑，因此熱會從電路傳導至氮化鋁基板而進行放熱。In addition, it is known to use a resin composition containing metal particles as a heat-releasing material. For example, Patent Document 2 describes that the exothermic adhesive is mainly composed of silicon, thermally conductive epoxy, or the like, and a metal filler is mixed in order to improve thermal conductivity. In addition, Patent Document 3 describes a substrate obtained by laminating a conductive paste in a circuit pattern on an aluminum nitride substrate with high thermal conductivity, followed by firing, and also describes the substrate and the penetration of an adhesive on the substrate. Unlike a circuit board in which metal foil is laminated and etched into a circuit pattern, since there is no adhesive between the circuit formed by the conductive sintered body and the board, heat is conducted from the circuit to the aluminum nitride board and dissipated.
先前技術文獻 專利文獻 專利文獻1：日本特開2004-063445號公報 專利文獻2：日本特開2015-126674號公報 專利文獻3：日本特開2019-165155號公報 prior art literature Patent Literature Patent Document 1: Japanese Patent Laid-Open No. 2004-063445 Patent Document 2: Japanese Patent Laid-Open No. 2015-126674 Patent Document 3: Japanese Patent Laid-Open No. 2019-165155
發明概要 發明欲解決之課題 本案發明人為了進行矽晶圓或玻璃基板等的放熱，已嘗試在該等之表面塗佈含金屬粒子之樹脂組成物而形成放熱性塗膜，抑或使用含金屬粒子之樹脂組成物將放熱材料接著於矽晶圓或玻璃基板等，然而，由於矽晶圓或玻璃基板之表面平滑，因此以習知含金屬粒子之樹脂組成物來說並無法獲得充分之密著性。 Summary of Invention The problem to be solved by the invention In order to release heat from silicon wafers, glass substrates, etc., the inventors of the present application have tried to coat the surfaces of these with a resin composition containing metal particles to form an exothermic coating film, or to apply a resin composition containing metal particles to heat exothermic materials. Then, on silicon wafers or glass substrates, etc., since the surfaces of silicon wafers or glass substrates are smooth, the conventional resin compositions containing metal particles cannot obtain sufficient adhesion.
本發明是有鑑於上述而成，目的在於提供一種含金屬粒子之樹脂組成物，其兼具優異之導電性、放熱性以及與玻璃基板等平滑表面之密著性。The present invention is made in view of the above, and an object thereof is to provide a metal particle-containing resin composition having excellent electrical conductivity, heat release properties, and adhesion to smooth surfaces such as glass substrates.
用以解決課題之手段 為了解決上述課題，令本發明之含金屬粒子之樹脂組成物中，係相對於含環氧樹脂之黏結劑成分(A)100質量份，含有4000~20000質量份之金屬粒子(B)及50~250質量份之硬化劑(C)；上述金屬粒子(B)含有1500~6800質量份之平均粒徑1~20μm之小片狀覆銀銅粒子(B1)、700~5000質量份之平均粒徑1~20μm之球狀覆銀銅粒子(B2)、及700~6000質量份之平均粒徑100~500nm之由銀或銅構成的球狀粒子(B3)；上述硬化劑(C)含有5~50質量份之咪唑系硬化劑(C1)及45~200質量份之異氰酸酯系硬化劑(C2)。 means of solving problems In order to solve the above-mentioned problems, the metal particle-containing resin composition of the present invention contains 4,000 to 20,000 parts by mass of the metal particles (B) and 50 parts by mass relative to 100 parts by mass of the epoxy resin-containing binder component (A). ~250 parts by mass of hardener (C); the above metal particles (B) contain 1500-6800 parts by mass of small flake silver-coated copper particles (B1) with an average particle size of 1-20 μm, and 700-5000 parts by mass of average particles Spherical silver-coated copper particles (B2) with a diameter of 1 to 20 μm, and 700 to 6000 parts by mass of spherical particles (B3) composed of silver or copper with an average particle size of 100 to 500 nm; the above hardener (C) contains 5 ~50 parts by mass of imidazole-based hardener (C1) and 45-200 parts by mass of isocyanate-based hardener (C2).
上述小片狀覆銀銅粒子(B1)與上述球狀覆銀銅粒子(B2)之含有比例(B1/B2)可設為0.4~6.0。The content ratio (B1/B2) of the above-mentioned platelet-shaped silver-coated copper particles (B1) and the above-mentioned spherical silver-coated copper particles (B2) can be set to 0.4 to 6.0.
上述小片狀覆銀銅粒子(B1)及上述球狀覆銀銅粒子(B2)之合計、與上述球狀粒子(B3)之含有比例((B1+B2)/(B3))可設為1.5~9.2。The sum of the above-mentioned platelet-shaped silver-coated copper particles (B1) and the above-mentioned spherical silver-coated copper particles (B2), and the content ratio of the above-mentioned spherical particles (B3) ((B1+B2)/(B3)) can be set as 1.5~9.2.
發明效果 依據本發明，可製得一種含金屬粒子之樹脂組成物，其兼具優異之導電性、放熱性以及與玻璃基板等平滑表面之密著性。 Invention effect According to the present invention, a resin composition containing metal particles can be obtained, which has both excellent electrical conductivity, heat release properties, and adhesion to smooth surfaces such as glass substrates.
用以實施發明之形態 以下，更具體地說明本發明之實施形態。 Form for carrying out the invention Hereinafter, embodiments of the present invention will be described more specifically.
令本實施形態之含金屬粒子之樹脂組成物中，係相對於含環氧樹脂之黏結劑成分(A)100質量份，含有4000~20000質量份之金屬粒子(B)及50~250質量份之硬化劑(C)；上述金屬粒子(B)含有1500~6800質量份之平均粒徑1~20μm之小片狀覆銀銅粒子(B1)、700~5000質量份之平均粒徑1~20μm之球狀覆銀銅粒子(B2)、及700~6000質量份之平均粒徑100~500nm之由銀或銅構成的球狀粒子(B3)；上述硬化劑(C)含有5~50質量份之咪唑系硬化劑(C1)及45~200質量份之異氰酸酯系硬化劑(C2)。The metal particle-containing resin composition of the present embodiment contains 4,000 to 20,000 parts by mass of the metal particles (B) and 50 to 250 parts by mass relative to 100 parts by mass of the epoxy resin-containing binder component (A). The hardener (C); the above-mentioned metal particles (B) contain 1500-6800 parts by mass of small flake silver-coated copper particles (B1) with an average particle size of 1-20 μm, and 700-5000 parts by mass with an average particle size of 1-20 μm The spherical silver-coated copper particles (B2) and 700-6000 parts by mass of spherical particles (B3) composed of silver or copper with an average particle diameter of 100-500 nm; the above-mentioned hardener (C) contains 5-50 parts by mass The imidazole-based hardener (C1) and 45-200 parts by mass of the isocyanate-based hardener (C2).
本發明之含金屬粒子之樹脂組成物中所含黏結劑成分(A)是以環氧樹脂作為必要成分。黏結劑成分(A)中環氧樹脂之含有比率宜為5~95質量%，較佳為30~90質量%。The binder component (A) contained in the metal particle-containing resin composition of the present invention is an epoxy resin as an essential component. The content rate of the epoxy resin in the binder component (A) is preferably 5 to 95 mass %, preferably 30 to 90 mass %.
環氧樹脂宜包含於常溫下為固體的環氧樹脂及於常溫下為液體的環氧樹脂兩者。此時黏結劑成分(A)中於常溫下為固體的環氧樹脂之含有比率宜為5~30質量%，較佳為5~20質量%。又，黏結劑成分(A)中於常溫下為液體的環氧樹脂之含有比率宜為20~90質量%，較佳為25~80質量%。The epoxy resin preferably includes both epoxy resins that are solid at room temperature and epoxy resins that are liquid at room temperature. In this case, the content ratio of the epoxy resin that is solid at normal temperature in the binder component (A) is preferably 5 to 30 mass %, preferably 5 to 20 mass %. Moreover, 20-90 mass % is preferable, and, as for the content rate of the epoxy resin which is liquid at normal temperature in a binder component (A), 25-80 mass % is preferable.
另，本說明書中，所謂「於常溫下為固體」，意指於25℃下在無溶媒狀態下不具流動性的狀態，所謂「於常溫下為液體」，意指於25℃下在無溶媒狀態下具有流動性的狀態。In addition, in this specification, "solid at room temperature" means a state without fluidity at 25°C without a solvent, and "liquid at room temperature" means at 25°C without a solvent A state of being fluid in a state.
藉由使用於常溫下為固體的環氧樹脂，所製得含金屬粒子之樹脂組成物能形成均勻而無斑駁不一的塗膜。於常溫下為固體的環氧樹脂宜於分子內具有2個以上之環氧丙基，且環氧當量有150~280g/eq。當環氧當量為150g/eq以上時，不易引起裂紋或翹曲等不良情況，當在280g/eq以下時，容易製得耐熱性更優異之硬化物。By using the epoxy resin which is solid at room temperature, the obtained resin composition containing metal particles can form a uniform coating film without unevenness. The epoxy resin that is solid at room temperature is suitable for having more than 2 glycidyl groups in the molecule, and the epoxy equivalent is 150~280g/eq. When the epoxy equivalent is 150 g/eq or more, defects such as cracks and warpage are less likely to occur, and when it is 280 g/eq or less, a cured product with better heat resistance can be easily obtained.
又，於常溫下為固體的環氧樹脂並無特殊限制，例如可使用雙酚A型環氧樹脂、雙酚F型環氧樹脂、雙酚S型環氧樹脂等雙酚型環氧樹脂、螺環型環氧樹脂、萘型環氧樹脂、聯苯型環氧樹脂、萜烯型環氧樹脂、參(環氧丙氧基苯基)甲烷、肆(環氧丙氧基苯基)乙烷等環氧丙基醚型環氧樹脂、四環氧丙基二胺基二苯甲烷等環氧丙基胺型環氧樹脂、四溴雙酚A型環氧樹脂、甲酚酚醛清漆型環氧樹脂、苯酚酚醛清漆型環氧樹脂、α-萘酚酚醛清漆型環氧樹脂、溴化苯酚酚醛清漆型環氧樹脂等酚醛清漆型環氧樹脂、橡膠改質環氧樹脂等。該等可單獨使用1種，亦可併用2種以上。又，於常溫下為固體的環氧樹脂亦可溶解於後述溶劑中來使用。In addition, the epoxy resin that is solid at room temperature is not particularly limited, and for example, bisphenol-type epoxy resins such as bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol S-type epoxy resin, etc. can be used. Spiro-type epoxy resin, naphthalene-type epoxy resin, biphenyl-type epoxy resin, terpene-type epoxy resin, ginseng (glycidoxyphenyl) methane, four (glycidoxyphenyl) ethyl glycidyl ether type epoxy resin such as alkane, glycidylamine type epoxy resin such as tetraglycidyl diamine diphenylmethane, tetrabromobisphenol A type epoxy resin, cresol novolac type epoxy resin Oxygen resin, phenol novolak epoxy resin, α-naphthol novolak epoxy resin, brominated phenol novolak epoxy resin and other novolak epoxy resin, rubber modified epoxy resin, etc. These may be used individually by 1 type, and may use 2 or more types together. Moreover, the epoxy resin which is solid at normal temperature can also be melt|dissolved in the solvent mentioned later, and can be used.
當環氧樹脂含有於常溫下為液體的環氧樹脂時，宜包含液體環氧丙基胺系環氧樹脂及液體環氧丙基醚系環氧樹脂兩者。在此情形下，黏結劑成分(A)中液體環氧丙基胺系環氧樹脂之含有比率宜為5~35質量%，黏結劑成分(A)中液體環氧丙基醚系環氧樹脂之含有比率宜為20~55質量%。當黏結劑成分(A)中以上述比率包含液體環氧丙基胺系環氧樹脂及液體環氧丙基醚系環氧樹脂時，會讓含金屬粒子之樹脂組成物之導電性、放熱性以及與玻璃基板等平滑表面之密著性均衡而優異，再者，容易進一步減少硬化後塗膜之翹曲。When the epoxy resin contains an epoxy resin that is liquid at room temperature, it is preferable to include both a liquid glycidylamine-based epoxy resin and a liquid glycidyl ether-based epoxy resin. In this case, the content ratio of the liquid glycidylamine-based epoxy resin in the binder component (A) is preferably 5 to 35% by mass, and the liquid glycidyl ether-based epoxy resin in the binder component (A) The content ratio is preferably 20 to 55% by mass. When the binder component (A) contains the liquid glycidylamine-based epoxy resin and the liquid glycidyl ether-based epoxy resin in the above ratio, the electrical conductivity and heat release properties of the metal particle-containing resin composition are reduced. Furthermore, the adhesion to smooth surfaces such as glass substrates is well-balanced and excellent, and furthermore, it is easy to further reduce the warpage of the coating film after curing.
液體環氧丙基胺系液體環氧樹脂之環氧當量宜為80~120g/eq。又，液體環氧丙基胺系液體環氧樹脂之黏度宜為1.5Pa．s以下，較佳為0.5~1.5Pa．s。液體環氧丙基醚系環氧樹脂之環氧當量宜為180~220g/eq。又，液體環氧丙基醚系環氧樹脂之黏度宜為6Pa．s以下，較佳為1~6Pa．s。若黏結劑成分(A)包含具上述環氧當量及上述黏度之液體環氧丙基胺系環氧樹脂及液體環氧丙基醚系環氧樹脂，則硬化後塗膜之翹曲會進一步減少，塗膜厚度容易變得更均勻。The epoxy equivalent of the liquid glycidylamine-based liquid epoxy resin is preferably 80~120g/eq. Also, the viscosity of the liquid glycidylamine-based liquid epoxy resin should be 1.5Pa. s or less, preferably 0.5~1.5Pa. s. The epoxy equivalent of the liquid glycidyl ether epoxy resin is preferably 180-220 g/eq. Also, the viscosity of the liquid glycidyl ether epoxy resin should be 6Pa. s or less, preferably 1~6Pa. s. If the binder component (A) contains the liquid glycidylamine-based epoxy resin and the liquid glycidyl ether-based epoxy resin having the above epoxy equivalent and the above viscosity, the warpage of the coating film after curing will be further reduced , the film thickness tends to become more uniform.
本說明書中，液體環氧丙基胺系液體環氧樹脂及液體環氧丙基醚系環氧樹脂之黏度，意指於液溫25℃下利用BH型黏度計(轉子No.5，旋轉數10rpm)測得之值。In this specification, the viscosity of liquid glycidylamine-based liquid epoxy resin and liquid glycidyl ether-based epoxy resin refers to the use of a BH type viscometer (rotor No. 5, number of revolutions) at a liquid temperature of 25°C. 10rpm) measured value.
以提升含金屬粒子之樹脂組成物之物性為目的，黏結劑成分(A)可進一步包含有醇酸樹脂、三聚氰胺樹脂、二甲苯樹脂等改質劑。當黏結劑成分(A)包含改質劑時，黏結劑成分(A)中改質劑之含有比率宜為40質量%以下，較佳為10質量%以下。For the purpose of improving the physical properties of the metal particle-containing resin composition, the binder component (A) may further contain modifiers such as alkyd resin, melamine resin, and xylene resin. When the binder component (A) contains a modifier, the content ratio of the modifier in the binder component (A) is preferably 40% by mass or less, preferably 10% by mass or less.
金屬粒子(B)之含量只要相對於黏結劑成分(A)100質量份為4000~20000質量份，即無特殊限制，宜為5000~19000質量份，較佳為7000~17000質量份。當金屬粒子(B)之含量為4000質量份以上時，容易獲得優異之導電性或放熱性，當在20000質量份以下時，容易獲得優異之密著性。The content of the metal particles (B) is not particularly limited as long as it is 4,000-20,000 parts by mass relative to 100 parts by mass of the binder component (A). When the content of the metal particles (B) is 4,000 parts by mass or more, excellent electrical conductivity or heat release properties are easily obtained, and when it is 20,000 parts by mass or less, excellent adhesion is easily obtained.
令金屬粒子(B)含有：1500~6800質量份之平均粒徑1~20μm之小片狀覆銀銅粒子(B1)；700~5000質量份之平均粒徑1~20μm之球狀覆銀銅粒子(B2)；及700~6000質量份之平均粒徑100~500nm之由銀或銅構成的球狀粒子(B3)。在此，本說明書中，所謂平均粒徑，意指利用雷射繞射散射法求得之粒度分布中在積算值50%的粒徑(一次粒徑)。另，在無損本發明目的之範圍內，金屬粒子(B)亦可含有上述金屬粒子(B1)~(B3)以外的金屬粒子。The metal particles (B) contain: 1500-6800 parts by mass of small flake silver-coated copper particles (B1) with an average particle size of 1-20 μm; 700-5000 parts by mass of spherical silver-coated copper with an average particle size of 1-20 μm Particles (B2); and 700 to 6000 parts by mass of spherical particles (B3) composed of silver or copper with an average particle diameter of 100 to 500 nm. Here, in this specification, an average particle diameter means the particle diameter (primary particle diameter) which is 50% of an integrated value in the particle size distribution calculated|required by the laser diffraction scattering method. Moreover, in the range which does not impair the objective of this invention, the metal particle (B) may contain the metal particle other than the said metal particle (B1)-(B3).
平均粒徑1~20μm之小片狀覆銀銅粒子(B1)之含量只要為1500~6800質量份，即無特殊限制，宜為1600~6700質量份，較佳為2000~6500質量份，更佳為3500~6000質量份。當小片狀覆銀銅粒子(B1)之含量為1500質量份以上時，金屬粒子彼此的接觸會變得良好，容易獲得優異之導電性或放熱性，當在6800質量份以下時，金屬粒子間的空隙少，容易獲得優異之放熱性或密著性。The content of small flake silver-coated copper particles (B1) with an average particle size of 1-20 μm is not particularly limited as long as it is 1500-6800 parts by mass, preferably 1600-6700 parts by mass, preferably 2000-6500 parts by mass, more Preferably, it is 3500-6000 mass parts. When the content of the platelet-shaped silver-coated copper particles (B1) is 1500 parts by mass or more, the contact between the metal particles becomes good, and it is easy to obtain excellent electrical conductivity or heat release. When the content is less than 6800 parts by mass, the metal particles There are few gaps between them, and it is easy to obtain excellent heat dissipation or adhesion.
平均粒徑1~20μm之球狀覆銀銅粒子(B2)之含量只要為700~5000質量份，即無特殊限制，宜為800~4900質量份，較佳為1000~4500質量份，更佳為1500~4500質量份。當球狀覆銀銅粒子(B2)之含量為700質量份以上時，金屬粒子間的空隙會減少，容易獲得優異之密著性，當在5000質量份以下時，金屬粒子彼此的接觸會變得良好，容易獲得優異之導電性或放熱性。The content of spherical silver-coated copper particles (B2) with an average particle size of 1-20 μm is not particularly limited as long as it is 700-5000 parts by mass, preferably 800-4900 parts by mass, preferably 1000-4500 parts by mass, more preferably It is 1500-4500 mass parts. When the content of the spherical silver-coated copper particles (B2) is 700 parts by mass or more, the voids between the metal particles are reduced, and excellent adhesion is easily obtained. If it is good, it is easy to obtain excellent electrical conductivity or exothermicity.
令小片狀覆銀銅粒子(B1)及球狀覆銀銅粒子(B2)為具有銅粒子及被覆該銅粒子之至少一部分的含銀層者。覆銀量以覆銀銅粒子中的比率計宜為1~30質量%，較佳為3~20質量%。若覆銀量為1質量%以上，容易獲得優異之導電性，若覆銀層為30質量%以下，則可維持優異之導電性，並且較銀粒子削減成本。The platelet-shaped silver-coated copper particles (B1) and the spherical silver-coated copper particles (B2) are those having copper particles and a silver-containing layer covering at least a part of the copper particles. The silver-coated amount is preferably 1 to 30 mass %, preferably 3 to 20 mass %, in terms of the ratio in the silver-coated copper particles. When the amount of silver coating is 1 mass % or more, it is easy to obtain excellent conductivity, and when the silver coating layer is 30 mass % or less, excellent conductivity can be maintained, and the cost can be reduced compared with silver particles.
平均粒徑100~500nm之由銀或銅構成的球狀粒子(B3)之含量只要為700~6000質量份，即無特殊限制，當球狀粒子(B3)由銀構成時，較佳為1000~6000質量份，更佳為1500~6000質量份，尤宜為2500~6000質量份，當球狀粒子(B3)由銅構成時，較佳為1000~4000質量份，更佳為1500~4000質量份，尤宜為2500~4000質量份。當球狀粒子(B3)之含量為700質量份以上時，可充分填充小片狀覆銀銅粒子(B1)與球狀覆銀銅粒子(B2)之空隙，容易獲得優異之導電性或放熱性，當在6000質量份以下時，容易獲得優異之密著性。The content of spherical particles (B3) composed of silver or copper with an average particle size of 100 to 500 nm is not particularly limited as long as it is 700 to 6000 parts by mass. When the spherical particles (B3) are composed of silver, it is preferably 1000 ~6,000 parts by mass, more preferably 1,500-6,000 parts by mass, especially 2,500-6,000 parts by mass, when the spherical particles (B3) are made of copper, preferably 1,000-4,000 parts by mass, more preferably 1,500-4,000 parts by mass parts by mass, preferably 2500-4000 parts by mass. When the content of the spherical particles (B3) is 700 parts by mass or more, the gaps between the platelet-shaped silver-coated copper particles (B1) and the spherical silver-coated copper particles (B2) can be fully filled, and it is easy to obtain excellent electrical conductivity or heat release When it is less than 6000 parts by mass, it is easy to obtain excellent adhesion.
小片狀覆銀銅粒子(B1)與球狀覆銀銅粒子(B2)之含有比例(B1/B2)並無特殊限制，宜為0.4~6.0，較佳為1.0~5.0，更佳為1.0~3.0。The content ratio (B1/B2) of the flake silver-coated copper particles (B1) and the spherical silver-coated copper particles (B2) is not particularly limited, and is preferably 0.4~6.0, preferably 1.0~5.0, more preferably 1.0 ~3.0.
小片狀覆銀銅粒子(B1)及球狀覆銀銅粒子(B2)之合計、與球狀粒子(B3)之含有比例((B1+B2)/(B3))並無特殊限制，宜為1.5~9.2，較佳為1.5~6.0，更佳為1.5~3.0。The sum of the flake silver-coated copper particles (B1) and the spherical silver-coated copper particles (B2), and the content ratio of the spherical particles (B3) ((B1+B2)/(B3)) are not particularly limited. It is 1.5-9.2, Preferably it is 1.5-6.0, More preferably, it is 1.5-3.0.
硬化劑(C)之含量只要相對於黏結劑成分(A)100質量份為50~250質量份，即無特殊限制，宜為60~240質量份，較佳為80~200質量份。當含量為50質量份以上時，與塗佈對象物之密著性會變得良好，再者，使用含金屬粒子之樹脂組成物形成的塗膜之導電性或放熱性會變得良好。又，當含量為250質量份以下時，含金屬粒子之樹脂組成物之保存穩定性會提升。The content of the hardener (C) is not particularly limited as long as it is 50 to 250 parts by mass relative to 100 parts by mass of the binder component (A), and is preferably 60 to 240 parts by mass, preferably 80 to 200 parts by mass. When the content is 50 parts by mass or more, the adhesion to the coating object will be good, and furthermore, the conductivity and heat release properties of the coating film formed using the metal particle-containing resin composition will be good. Moreover, when the content is 250 parts by mass or less, the storage stability of the metal particle-containing resin composition is improved.
硬化劑(C)含有咪唑系硬化劑(C1)及異氰酸酯系硬化劑(C2)作為必要成分。The curing agent (C) contains an imidazole-based curing agent (C1) and an isocyanate-based curing agent (C2) as essential components.
咪唑系硬化劑(C1)可舉例如：咪唑、2-十一基咪唑、2-十七基咪唑、2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、2-乙-4-甲-咪唑、1-氰乙基-2-十一基咪唑、2-苯基咪唑。As the imidazole-based curing agent (C1), for example, imidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4 - Methyl-imidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenylimidazole.
咪唑系硬化劑(C1)之含量只要相對於黏結劑成分(A)100質量份為5~50質量份，即無特殊限制，宜為5~45質量份，較佳為10~45質量份。當咪唑系硬化劑(C1)之含量為5質量份以上時，含金屬粒子之樹脂組成物容易硬化，容易獲得優異之密著性，當在50質量份以下時，容易獲得優異之導電性或放熱性。The content of the imidazole-based hardener (C1) is not particularly limited as long as it is 5 to 50 parts by mass relative to 100 parts by mass of the binder component (A). When the content of the imidazole-based hardener (C1) is 5 parts by mass or more, the resin composition containing metal particles is easily hardened, and excellent adhesion is easily obtained, and when it is 50 parts by mass or less, excellent conductivity or Exothermic.
異氰酸酯系硬化劑(C2)可舉例如聚異氰酸酯化合物、封端異氰酸酯化合物等。藉由含有異氰酸酯系硬化劑(C2)，含金屬粒子之樹脂組成物之保存穩定性會提升。As an isocyanate type hardening|curing agent (C2), a polyisocyanate compound, a blocked isocyanate compound, etc. are mentioned, for example. By containing the isocyanate-based hardener (C2), the storage stability of the metal particle-containing resin composition is improved.
異氰酸酯系硬化劑(C2)之含量只要相對於黏結劑成分(A)100質量份為45~200質量份，即無特殊限制，宜為60~190質量份，較佳為80~150質量份。當異氰酸酯系硬化劑(C2)之含量為45質量份以上時，含金屬粒子之樹脂組成物容易硬化，容易獲得優異之密著性，當在200質量份以下時，容易獲得優異之導電性或放熱性。The content of the isocyanate-based hardener (C2) is not particularly limited as long as it is 45 to 200 parts by mass relative to 100 parts by mass of the binder component (A), and is preferably 60 to 190 parts by mass, preferably 80 to 150 parts by mass. When the content of the isocyanate-based hardener (C2) is 45 parts by mass or more, the resin composition containing metal particles is easily hardened, and excellent adhesion is easily obtained, and when it is 200 parts by mass or less, it is easy to obtain excellent electrical conductivity or Exothermic.
在無損本發明目的之範圍內，硬化劑(C)亦可含有咪唑系硬化劑(C1)及異氰酸酯系硬化劑(C2)以外的硬化劑。此種硬化劑可舉例如：酚系硬化劑、胺系硬化劑、陽離子系硬化劑、自由基系硬化劑等。The curing agent (C) may contain curing agents other than the imidazole-based curing agent (C1) and the isocyanate-based curing agent (C2) within a range that does not impair the object of the present invention. As such a curing agent, a phenol-based curing agent, an amine-based curing agent, a cation-based curing agent, a radical-based curing agent, etc. are mentioned, for example.
酚系硬化劑可舉例如酚醛清漆苯酚、萘酚系化合物等。陽離子系硬化劑可舉例如：三氟化硼之胺鹽、對甲氧苯重氮鎓六氟磷酸鹽、二苯基錪六氟磷酸鹽、三苯基鋶、四正丁基鏻四苯基硼酸鹽、四正丁基鏻-o,o-二乙基二硫代磷酸鹽等所代表的鎓系化合物。自由基系硬化劑可舉例如：過氧化二異丙苯、三級丁基過氧化異丙苯、氫過氧化三級丁基、氫過氧化異丙苯等。As a phenolic hardening|curing agent, a novolak phenol, a naphthol-type compound, etc. are mentioned, for example. Examples of cationic hardeners include: amine salt of boron trifluoride, p-methoxybenzenediazonium hexafluorophosphate, diphenyl iodonium hexafluorophosphate, triphenyl perionium, tetra-n-butylphosphonium tetraphenyl Onium-based compounds represented by borate, tetra-n-butylphosphonium-o,o-diethyldithiophosphate, etc. As a radical type hardening|curing agent, dicumyl peroxide, tertiary butyl cumyl peroxide, tertiary butyl hydroperoxide, cumene hydroperoxide, etc. are mentioned, for example.
本發明之含金屬粒子之樹脂組成物可因應塗佈方法摻合溶劑。溶劑含量之理想範圍依照塗佈方法也會有所不同，例如，當進行噴霧塗佈時，宜相對於黏結劑成分(A)100質量份為500~3500質量份。The resin composition containing metal particles of the present invention can be mixed with a solvent according to the coating method. The ideal range of the solvent content varies depending on the coating method. For example, when spray coating is performed, it is preferably 500 to 3500 parts by mass relative to 100 parts by mass of the binder component (A).
溶劑並無特殊限制，例如可使用甲基乙基酮、丙酮、苯乙酮、甲賽璐蘇、乙酸甲賽璐蘇、甲卡必醇、二乙二醇二甲基醚、四氫呋喃、乙酸甲酯、1-甲氧-2-丙醇、乙酸3-甲氧-3-甲-1-丁酯等。該等可單獨使用1種，亦可併用2種以上。The solvent is not particularly limited, for example, methyl ethyl ketone, acetone, acetophenone, methylcellulose, methylcellulose acetate, mecarbitol, diethylene glycol dimethyl ether, tetrahydrofuran, methyl acetate can be used ester, 1-methoxy-2-propanol, 3-methoxy-3-methyl-1-butyl acetate, etc. These may be used individually by 1 type, and may use 2 or more types together.
在無損發明目的之範圍內，本發明之含金屬粒子之樹脂組成物亦可含有抗氧化劑、顏料、染料、賦黏樹脂、塑化劑、紫外線吸收劑、消泡劑、調平劑、填充劑、阻燃劑等公知添加劑。Within the scope of impairing the purpose of the invention, the metal particle-containing resin composition of the present invention may also contain antioxidants, pigments, dyes, tackifying resins, plasticizers, ultraviolet absorbers, defoaming agents, leveling agents, and fillers , flame retardants and other well-known additives.
含金屬粒子之樹脂組成物於液溫25℃下之黏度只要因應塗佈方法適當調整即可，以進行噴霧塗佈時之標準而言，宜為50~600mPa．s，較佳為60~550mPa．s，更佳為100~500mPa．s。當含金屬粒子之樹脂組成物之黏度為50mPa．s以上時，在使含金屬粒子之樹脂組成物硬化而形成塗膜時，可防止在塗佈對象物上液體垂流而形成無斑駁不一的塗膜，同時可防止金屬粒子沈降。當含金屬粒子之樹脂組成物之黏度為600mPa．s以下時，在噴霧塗佈含金屬粒子之樹脂組成物時，可防止噴嘴堵塞，並且容易於塗佈對象物上形成無斑駁不一的塗膜。The viscosity of the resin composition containing metal particles at a liquid temperature of 25°C can be adjusted appropriately according to the coating method. For the standard of spray coating, it should be 50~600mPa. s, preferably 60~550mPa. s, more preferably 100~500mPa. s. When the viscosity of the resin composition containing metal particles is 50mPa. When s is greater than or equal to s, when the resin composition containing metal particles is hardened to form a coating film, the liquid can be prevented from sagging on the coating object to form a coating film without unevenness, and the metal particles can be prevented from settling. When the viscosity of the resin composition containing metal particles is 600mPa. When s is less than s, when the resin composition containing metal particles is spray-coated, nozzle clogging can be prevented, and a coating film without unevenness can be easily formed on the coating object.
另，本說明書中，所謂「含金屬粒子之樹脂組成物之黏度」，意指使用圓錐平板型旋轉黏度計於旋轉數10rpm下測得之黏度。In addition, in this specification, the "viscosity of the resin composition containing metal particles" means the viscosity measured at a rotation number of 10 rpm using a cone-plate rotational viscometer.
本實施形態之含金屬粒子之樹脂組成物可使用通常所用之班布里混合機、捏合機或軋輥等混合機，遵循一般方法進行混練來製造。The metal particle-containing resin composition of the present embodiment can be produced by kneading in accordance with a general method using a commonly used mixer such as a Banbury mixer, a kneader, or a roll.
本實施形態之含金屬粒子之樹脂組成物可應用在電子零件封裝體之屏蔽上，亦可塗佈於矽晶圓或玻璃基板等之表面形成放熱性塗膜，也可以用作將放熱材料接著於矽晶圓或玻璃基板等的接著劑。The resin composition containing metal particles of this embodiment can be applied to the shielding of electronic parts packages, can also be coated on the surface of silicon wafers or glass substrates to form a heat-releasing coating film, and can also be used for bonding heat-releasing materials. Adhesives for silicon wafers or glass substrates.
實施例 以下顯示本發明之實施例，惟本發明並非受限於以下實施例。另，下述中摻合比例等，只要未特別事先聲明，即以質量為基準。 Example Embodiments of the present invention are shown below, but the present invention is not limited to the following embodiments. In addition, the mixing ratio etc. in the following shall be based on the mass unless otherwise stated.
遵循下述表1、2所示之摻合，混合各成分，調製出含金屬粒子之樹脂組成物。In accordance with the blending shown in Tables 1 and 2 below, each component was mixed to prepare a metal particle-containing resin composition.
表中記載的化合物之詳情如下。 ．黏結劑成分(A)：固體環氧樹脂(三菱化學(股)製，商品名「JER157S70」)40質量份、環氧丙基胺系環氧樹脂(艾迪科(ADEKA)(股)製，商品名「EP-3905S」)30質量份及環氧丙基醚系環氧樹脂(艾迪科(ADEKA)(股)製，商品名「EP-4400」)30質量份之混合物 ．覆銀銅粒子(B1)：平均粒徑=5μm、小片狀 ．覆銀銅粒子(B2)：平均粒徑=2μm、球狀 ．銀粒子(B3)：平均粒徑=300nm、球狀 ．銅粒子(B3)：平均粒徑=300nm、球狀 ．咪唑系硬化劑(C1)：2-乙基咪唑(東京化成工業(股)製) ．異氰酸酯系硬化劑(C2)：聚異氰酸酯化合物(DIC(股)製，商品名「DN-992」) ．溶劑：1-甲氧-2-丙醇(岸田(KISHIDA)化學(股)製) Details of the compounds described in the table are as follows. . Binder component (A): 40 parts by mass of solid epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name "JER157S70"), glycidylamine-based epoxy resin (manufactured by ADEKA Co., Ltd., A mixture of 30 parts by mass of trade name "EP-3905S") and 30 parts by mass of glycidyl ether-based epoxy resin (manufactured by ADEKA Corporation, trade name "EP-4400") ． Silver-coated copper particles (B1): average particle size = 5 μm, small flakes . Silver-coated copper particles (B2): average particle size = 2 μm, spherical ． Silver particles (B3): average particle size = 300 nm, spherical ． Copper particles (B3): average particle size = 300 nm, spherical ． Imidazole-based hardener (C1): 2-ethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) ． Isocyanate-based curing agent (C2): polyisocyanate compound (manufactured by DIC Corporation, trade name "DN-992") ． Solvent: 1-methoxy-2-propanol (manufactured by Kishida Chemical Co., Ltd.)
測定所製得含金屬粒子之樹脂組成物之導電性、熱傳導性、密著性及塗佈穩定性，於表1、2中顯示結果。測定方法如下所示。The electrical conductivity, thermal conductivity, adhesion and coating stability of the obtained metal particle-containing resin composition were measured, and the results are shown in Tables 1 and 2. The measurement method is as follows.
．導電性：於玻璃環氧基板上貼合已設有寬度5mm之狹縫且厚度55μm之聚醯亞胺膜作成印刷板。將各實施例及各比較例之含金屬粒子之樹脂組成物線性印刷(長度60mm、寬度5mm、厚度約100μm)於聚醯亞胺膜上，於150℃下加熱60分鐘，藉此使含金屬粒子之樹脂組成物正式硬化。然後，剝離聚醯亞胺膜，藉此製得硬化物試樣。使用測試器，測定所製得硬化物試樣之電阻R(Ω)，並藉由下述式(1)，從硬化物試樣之截面積S(cm 2)與長度L(cm)計算出比電阻(Ω．cm)。當比電阻為4.0×10 -5(Ω．cm)以下時，判斷為導電性優異。 比電阻=截面積S/長度L×電阻R‥‥(1) . Conductivity: A polyimide film with a width of 5mm and a thickness of 55μm was pasted on a glass epoxy substrate to form a printed board. The resin compositions containing metal particles of each example and each comparative example were linearly printed (length 60 mm, width 5 mm, thickness about 100 μm) on a polyimide film, and heated at 150 ° C for 60 minutes, thereby making the metal-containing resin composition. The resin composition of the particles is officially hardened. Then, the polyimide film was peeled off, thereby producing a hardened product sample. Using a tester, measure the resistance R (Ω) of the obtained hardened product sample, and calculate it from the cross-sectional area S (cm 2 ) and length L (cm) of the hardened product sample by the following formula (1). Specific resistance (Ω·cm). When the specific resistance was 4.0×10 −5 (Ω·cm) or less, it was judged that the conductivity was excellent. Specific resistance=cross-sectional area S/length L×resistance R‥‥(1)
．熱傳導性：使用Thermowave Analyzer TA-33(伯特利(BETHEL)製)，評價含金屬粒子之樹脂組成物之熱傳導性。具體而言，準備特夫綸(TEFLON，註冊商標)片(100mm×100mm×3mm)，以於其中央形成寬度50mm、長度50mm之開口部之方式藉由聚醯亞胺膠帶來遮蔽，並且線性印刷各實施例及各比較例之含金屬粒子之樹脂組成物。然後，於150℃下加熱60分鐘，藉此使含金屬粒子之樹脂組成物硬化，再剝離聚醯亞胺膠帶，形成塗膜(寬度50mm、長度50mm、厚度約100μm)。從特夫綸片剝下所製得之塗膜作成硬化物試樣。使用Thermowave Analyzer測定熱擴散率α(m 2/S)，並藉由下述式(2)，從硬化物試樣之密度ρ(kg/m 3)與比熱Cp(J/Kg．K)計算出熱傳導率K(W/m．K)。當熱傳導率為50W/mK以上時，判斷為放熱性優異。 熱傳導率K=熱擴散率α×密度ρ×比熱Cp…(2) . Thermal conductivity: The thermal conductivity of the metal particle-containing resin composition was evaluated using Thermowave Analyzer TA-33 (manufactured by BETHEL). Specifically, a Teflon (TEFLON, registered trademark) sheet (100 mm×100 mm×3 mm) was prepared, covered with a polyimide tape so that an opening with a width of 50 mm and a length of 50 mm was formed in the center, and the linear The resin compositions containing metal particles of each example and each comparative example were printed. Then, the resin composition containing metal particles was hardened by heating at 150° C. for 60 minutes, and the polyimide tape was peeled off to form a coating film (width 50 mm, length 50 mm, thickness about 100 μm). The obtained coating film was peeled off from the Teflon sheet to prepare a hardened product sample. The thermal diffusivity α (m 2 /S) was measured using a Thermowave Analyzer, and calculated from the density ρ (kg/m 3 ) and the specific heat Cp (J/Kg·K) of the hardened sample by the following formula (2). Thermal conductivity K (W/m.K). When the thermal conductivity was 50 W/mK or more, it was judged that the heat dissipation was excellent. Thermal conductivity K=thermal diffusivityα×densityρ×specific heat Cp…(2)
．密著性：根據ASTM D 3359(劃格法)，評價含金屬粒子之樹脂組成物與玻璃基板之密著性。具體而言，準備玻璃基板(微型載玻片(MICRO SLIDE GLASS) 76mm×26mm×1mm 松波硝子)，於各自上以形成寬度20mm、長度50mm之開口部之方式藉由聚醯亞胺膠帶來遮蔽，並使用諾信(Nordson Asymtek)製噴霧裝置，噴霧塗佈各實施例及各比較例之含金屬粒子之樹脂組成物。然後，於150℃下加熱60分鐘，藉此使含金屬粒子之樹脂組成物硬化，再剝離聚醯亞胺膠帶，形成厚度約20μm之塗膜。在形成有塗膜的玻璃基板上進行密著性試驗。． Adhesion: According to ASTM D 3359 (cross-cut method), the adhesion between the resin composition containing metal particles and the glass substrate was evaluated. Specifically, glass substrates (MICRO SLIDE GLASS, 76mm x 26mm x 1mm, Matsuba glass) were prepared, and covered with polyimide tape so as to form openings with a width of 20mm and a length of 50mm on each of them. , and use a spray device made by Nordson Asymtek to spray-coat the resin compositions containing metal particles of each example and each comparative example. Then, the resin composition containing metal particles was hardened by heating at 150° C. for 60 minutes, and then the polyimide tape was peeled off to form a coating film with a thickness of about 20 μm. The adhesion test was performed on the glass substrate on which the coating film was formed.
密著性之評價是藉由以下基準來進行。 5B：劃線邊緣完全平滑，無任何方格剝落。 4B：於劃線交叉處發生塗膜的細小剝落。不過，在劃格部分受到影響的明顯不超過5%。 3B：塗膜沿著劃線邊緣及/或於交叉處剝落。不過，在劃格部分受到影響的明顯大於5%但不超過15%。 2B：塗膜沿著劃線邊緣局部性或全面性發生剝落、及/或格子的許多部分局部性或全面性剝落。不過，在劃格部分受到影響的明顯大於15%但不超過35%。 1B：塗膜沿著劃線邊緣局部性或全面性發生大幅剝落、及/或數個地方的格子局部性或全面性剝落。不過，在劃格部分受到影響的明顯不超過65%。 0B：發生剝落更甚於1B。 The evaluation of adhesiveness was performed according to the following criteria. 5B: The scribed edge is completely smooth without any square peeling. 4B: Fine peeling of the coating film occurred at the intersection of the scribe lines. However, clearly no more than 5% were affected in the cross-cut section. 3B: The coating film peeled off along the edge of the scribe line and/or at the intersection. However, significantly more than 5% but not more than 15% were affected in the cross-cut section. 2B: The coating film peeled off locally or globally along the edge of the scribe line, and/or many parts of the lattice peeled off locally or globally. However, significantly more than 15% but not more than 35% were affected in the cross-cut section. 1B: The coating film peeled off locally or comprehensively along the edge of the scribe line, and/or the grid peeled off locally or comprehensively in several places. However, clearly no more than 65% were affected in the cross-cut section. 0B: Peeling occurred more than 1B.
．塗佈穩定性：圖1、2為示意顯示塗佈穩定性之評價方法之示意圖。使用諾信(Nordson Asymtek)製噴霧裝置，將各實施例及各比較例之含金屬粒子之樹脂組成物藉由以下要領噴霧塗佈於圖1所示正方形之玻璃環氧基板(長100mm×寬100mm×厚度1mm)上，並評價含金屬粒子之樹脂組成物之塗佈穩定性。. Coating stability: Figures 1 and 2 are schematic diagrams showing the evaluation method of coating stability. Using a spraying device made by Nordson Asymtek, the resin compositions containing metal particles of each example and each comparative example were spray-coated on a square glass epoxy substrate (length 100 mm×width as shown in FIG. 1 ) by the following method. 100mm×thickness 1mm), and the coating stability of the resin composition containing metal particles was evaluated.
如圖1所示，於玻璃環氧基板31上，將4片聚醯亞胺膠帶32~35分別貼合於玻璃環氧基板31之各角部附近，並將聚醯亞胺膠帶36貼合於玻璃環氧基板31之中央部。各聚醯亞胺膠帶32~36之面積為10mm×10mm(圖1中尺寸a及b皆為10mm，各聚醯亞胺膠帶32~35是以膠帶的邊與基板的邊呈平行之方式，貼合於距離玻璃環氧基板31的各邊10mm之內側(圖1中尺寸c及d皆為10mm)。As shown in FIG. 1 , on the
將含金屬粒子之樹脂組成物投入噴霧裝置後，緊接著於下述噴霧條件下對玻璃環氧基板31進行噴霧塗佈，且於150℃下加熱60分鐘，藉此形成厚度20μm之含金屬粒子之樹脂組成物之硬化物。再將含金屬粒子之樹脂組成物投入噴霧裝置後經過20分鐘後，以與上述相同的條件進行噴霧塗佈，並於相同條件下以使厚度約為20μm之方式來形成含金屬粒子之樹脂組成物之硬化物。After the resin composition containing metal particles was put into the spray device, the
以下，將含金屬粒子之樹脂組成物投入噴霧裝置後緊接著所形成的含金屬粒子之樹脂組成物之硬化物記載為「硬化物A」，並將含金屬粒子之樹脂組成物投入噴霧裝置後經過20分鐘後所形成的含金屬粒子之樹脂組成物之硬化物記載為「硬化物B」。Hereinafter, the cured product of the metal particle-containing resin composition formed immediately after the metal particle-containing resin composition is put into the spray device is described as "hardened product A", and after the metal particle-containing resin composition is put into the spray device The cured product of the metal particle-containing resin composition formed after the elapse of 20 minutes is described as "cured product B".
＜噴霧條件＞ 諾信(Nordson Asymtek)製 SL-940E 糊擠出壓力：2.8Psi 輔助氣體(霧化氣體)：5Psi 封裝體表面之溫度：22℃ 封裝體表面至噴嘴之距離：約150mm 噴頭移動間距：3mm 噴頭移動速度：250mm/秒 噴霧次數：4次 ＜Spraying Conditions＞ SL-940E by Nordson Asymtek Paste extrusion pressure: 2.8Psi Auxiliary gas (atomizing gas): 5Psi Package surface temperature: 22℃ Distance from package surface to nozzle: about 150mm Nozzle moving distance: 3mm Nozzle moving speed: 250mm/sec Number of sprays: 4 times
加熱結束後於室溫下放置30分鐘後，分別剝下聚醯亞胺膠帶32~36，且如圖2所示，藉由測微計，分別測定已剝下部分(箭號X)的玻璃環氧基板31之厚度、以及與該剝下部分鄰接的在玻璃環氧基板31上形成有含金屬粒子之樹脂組成物之硬化物41的部分(箭號Y)之厚度，並藉由後者減去前者，求得5處含金屬粒子之樹脂組成物之硬化物厚度。After heating, place at room temperature for 30 minutes, peel off the
從硬化物A之厚度及硬化物B之厚度進行塗佈穩定性之評價。評價基準如下述。表1及2中顯示評價結果。 ○：5處所有硬化物A之厚度及5處所有硬化物B之厚度落入20μm±5μm之範圍。 ×：形成有1處以上厚度未落入20μm±5μm之範圍的硬化物A及/或硬化物B。 The coating stability was evaluated from the thickness of the cured product A and the thickness of the cured product B. The evaluation criteria are as follows. The evaluation results are shown in Tables 1 and 2. ○: The thickness of all the hardened objects A in 5 places and the thickness of all the hardened objects B in 5 places fell within the range of 20 μm±5 μm. ×: The cured product A and/or the cured product B whose thickness did not fall within the range of 20 μm±5 μm was formed at one or more places.
[表1]
[表2]
如表1所示，實施例1~14之導電性、熱傳導性、密著性及塗佈穩定性皆優異。As shown in Table 1, Examples 1 to 14 were excellent in electrical conductivity, thermal conductivity, adhesion, and coating stability.
比較例1為小片狀覆銀銅粒子(B1)之含量小於下限值的例子，導電性及熱傳導性差。Comparative Example 1 is an example in which the content of the platelet-shaped silver-clad copper particles (B1) is less than the lower limit, and the electrical conductivity and thermal conductivity are poor.
比較例2為小片狀覆銀銅粒子(B1)之含量大於上限值的例子，導電性、熱傳導性、密著性及塗佈穩定性皆差。Comparative Example 2 is an example in which the content of the platelet-shaped silver-clad copper particles (B1) is larger than the upper limit, and the electrical conductivity, thermal conductivity, adhesion and coating stability are all poor.
比較例3為球狀覆銀銅粒子(B2)之含量小於下限值的例子，密著性及塗佈穩定性差。Comparative Example 3 is an example in which the content of the spherical silver-clad copper particles (B2) is less than the lower limit, and the adhesiveness and coating stability are poor.
比較例4為球狀覆銀銅粒子(B2)之含量大於上限值的例子，導電性、熱傳導性及密著性差。Comparative Example 4 is an example in which the content of the spherical silver-clad copper particles (B2) is larger than the upper limit, and the electrical conductivity, thermal conductivity, and adhesion are poor.
比較例5為銀粒子(B3)之含量小於下限值的例子，導電性及熱傳導性差。Comparative Example 5 is an example in which the content of the silver particles (B3) is less than the lower limit, and the electrical conductivity and thermal conductivity are poor.
比較例6為銀粒子(B3)之含量大於上限值的例子，密著性差。Comparative Example 6 is an example in which the content of the silver particles (B3) is larger than the upper limit, and the adhesion is poor.
比較例7為咪唑系硬化劑(C1)之含量小於下限值的例子，密著性差。Comparative Example 7 is an example in which the content of the imidazole-based curing agent (C1) is less than the lower limit, and the adhesiveness is poor.
比較例8為咪唑系硬化劑(C1)之含量大於上限值的例子，導電性差。Comparative Example 8 is an example in which the content of the imidazole-based curing agent (C1) is larger than the upper limit value, and the conductivity is poor.
比較例9為異氰酸酯系硬化劑(C2)之含量小於下限值的例子，導電性差。Comparative Example 9 is an example in which the content of the isocyanate-based curing agent (C2) is less than the lower limit, and the conductivity is poor.
比較例10為異氰酸酯系硬化劑(C2)之含量大於上限值的例子，導電性及熱傳導性差。Comparative Example 10 is an example in which the content of the isocyanate-based curing agent (C2) exceeds the upper limit value, and the electrical conductivity and thermal conductivity are poor.
比較例11為不含球狀覆銀銅粒子(B)的例子，導電性、密著性及塗佈穩定性差。Comparative Example 11 is an example that does not contain spherical silver-clad copper particles (B), and is inferior in conductivity, adhesion, and coating stability.
比較例12為不含小片狀覆銀銅粒子(B1)的例子，導電性、熱傳導性、密著性及塗佈穩定性皆差。Comparative Example 12 is an example in which the platelet-shaped silver-coated copper particles (B1) are not contained, and the electrical conductivity, thermal conductivity, adhesion, and coating stability are all poor.
31:玻璃環氧基板
32,33,34,35,36:聚醯亞胺膠帶
41:含金屬粒子之樹脂組成物之硬化物
a,b,c,d:尺寸
X,Y:箭號
31:
圖1為顯示塗佈穩定性之評價方法之示意圖，且為貼合有聚醯亞胺膠帶32~36的玻璃環氧基板31之俯視圖。
圖2為顯示塗佈穩定性之評價方法之示意圖，且為玻璃環氧基板31之側視圖，該玻璃環氧基板31係形成有使含金屬粒子之樹脂組成物硬化而成之硬化物A或硬化物B者，該圖顯示在玻璃環氧基板31上測定厚度之位置(已分別剝下聚醯亞胺膠帶32~36的部分(箭號X)、以及與該剝下部分鄰接的在玻璃環氧基板31上形成有含金屬粒子之樹脂組成物之硬化物41的部分(箭號Y))。
FIG. 1 is a schematic diagram showing an evaluation method of coating stability, and is a plan view of a
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