WO2019013230A1 - Conductive adhesive composition - Google Patents

Conductive adhesive composition Download PDF

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Publication number
WO2019013230A1
WO2019013230A1 PCT/JP2018/026103 JP2018026103W WO2019013230A1 WO 2019013230 A1 WO2019013230 A1 WO 2019013230A1 JP 2018026103 W JP2018026103 W JP 2018026103W WO 2019013230 A1 WO2019013230 A1 WO 2019013230A1
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WO
WIPO (PCT)
Prior art keywords
conductive adhesive
adhesive composition
particles
conductive
thermoplastic resin
Prior art date
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PCT/JP2018/026103
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French (fr)
Japanese (ja)
Inventor
真太郎 阿部
近藤　剛史
力亜 古正
Original Assignee
田中貴金属工業株式会社
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Publication of WO2019013230A1 publication Critical patent/WO2019013230A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C09J177/06—Polyamides derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the present invention relates to conductive adhesive compositions.
  • Patent Document 1 a conductive paste for die bonding comprising a metal powder and an organic solvent, wherein the metal powder has a purity of 99.9% by mass or more and an average particle diameter of 0.01 ⁇ m to 1.0 ⁇ m.
  • a conductive paste comprising one or more metal particles selected from palladium powder and copper powder, and a coating layer made of gold covering at least a part of the metal particles.
  • Patent Document 2 gold, silver, copper, platinum, palladium, palladium, rhodium, nickel, iron, cobalt, tin, indium, aluminum, zinc, at least any of these compounds or alloys, having an average particle diameter of 0.1 to 100 ⁇ m.
  • Conductive adhesive comprising: a plurality of solid conductive particles including iron; solid lubricating particles not metal-bonded to the solid conductive particles; and having higher lubricity than the solid conductive particles; and water or an organic solvent Agents have been reported.
  • the semiconductor element In electronic components, the semiconductor element generates heat due to current flow during use, so the die bonding material is subject to repeated temperature changes, which may degrade adhesion by the die bonding material and cause the semiconductor element to separate from the support member is there. Further, in recent years, with the progress of miniaturization and high functionality of electronic parts, the calorific value by energization of the semiconductor element tends to increase, and the risk of the above peeling is further increased.
  • the present invention has been invented in view of the above problems, and an object thereof is to provide a conductive adhesive composition in which peeling of a material to be adhered is unlikely to occur even when subjected to repeated temperature changes. is there.
  • the present inventors repeatedly subjected to temperature changes in the conductive adhesive composition by including particles of thermoplastic resin in solid form at 25 ° C. consisting of a polyamide containing an aliphatic skeleton. It has been found that adhesion which is less likely to be peeled off can be formed, and the present invention has been completed.
  • the conductive adhesive composition of the present invention is a conductive adhesive composition comprising particles (A) of a thermoplastic resin which is solid at 25 ° C. and a conductive filler (B), and the thermal adhesive as described above
  • the plastic resin is a polyamide comprising an aliphatic backbone having a melting point of 250 ° C. or less.
  • the thermoplastic resin contains at least one of nylon 11, nylon 12 and nylon 6.
  • the average particle diameter of the thermoplastic resin particles (A) is 1 to 30 ⁇ m.
  • the conductive adhesive composition according to one aspect of the present invention contains the particles (A) of the thermoplastic resin in a range of 0.5 to 10% by mass with respect to the total amount of the conductive adhesive composition. .
  • the conductive filler (B) contains silver.
  • the conductive adhesive composition according to one aspect of the present invention contains the conductive filler (B) in the range of 80 to 95% by mass with respect to the total amount of the conductive adhesive composition.
  • the conductive adhesive cured product of the present invention is a cured product of any one of the above-mentioned conductive adhesive compositions.
  • the electronic device of the present invention uses any one of the conductive adhesive compositions described above for bonding of parts.
  • the conductive adhesive composition of the present invention is characterized in that it comprises particles (A) of a thermoplastic resin in solid form at 25 ° C. comprising a polyamide containing an aliphatic skeleton, which has been subjected to repeated temperature changes. Also in this case, peeling of the adherend material is less likely to occur.
  • the average particle size is taken as the 50% average particle size (D50) of the particle size distribution measured using a laser diffraction / scattering type particle size analyzer.
  • D50 50% average particle size
  • measurement can be performed using a laser diffraction / scattering particle size analyzer MT-3000 manufactured by Nikkiso Co., Ltd.
  • the conductive adhesive composition according to the present invention contains particles (A) of a thermoplastic resin solid at 25 ° C. (hereinafter, also simply referred to as “particles of thermoplastic resin (A)”).
  • the particles (A) of the thermoplastic resin are particles of a polyamide containing an aliphatic skeleton having a melting point of 250 ° C. or less.
  • thermoplastic resin particles (A) melt at the time of heat curing of the conductive adhesive composition since the melting point thereof is 250 ° C. or less, and as a result, the conductive adhesive It will have high adhesiveness with the conductive filler (B) in the cured product.
  • thermoplastic resin having high adhesiveness with the conductive filler (B) is elastically deformed when stressed as described above, and the stress can be effectively relieved. Therefore, it is considered that the cured conductive adhesive of the present invention is excellent in stress relaxation performance, and peeling of the material to be adhered is difficult to occur even when the stress load as described above is applied.
  • the particles (A) of the thermoplastic resin are melted at the time of heat curing of the conductive adhesive composition to fill the voids existing at the bonding interface between the conductive adhesive cured product and the material to be bonded, The improvement of the adhesive strength is also considered to contribute to the suppression of peeling due to repeated temperature changes.
  • the particles (A) of the thermoplastic resin may be particles of a polyamide containing an aliphatic skeleton having a melting point of 250 ° C. or less, and there is no particular limitation.
  • particles of resin having a melting point in the range of 50 to 250 ° C. are preferable, particles of resin having a melting point in the range of 100 to 225 ° C. are more preferable, and melting point is 150 to 150 More preferred are particles of resin in the range of 200 ° C.
  • the thermoplastic resin contains at least one of nylon 11, nylon 12 and nylon 6.
  • Particles made of either nylon 11, nylon 12, nylon 6 may be used alone, or multiple types of particles may be used. It is also possible to use particles made of at least two copolymers of nylon 11, nylon 12, and nylon 6. In particular, particles of nylon 11, particles of nylon 12, and particles of a copolymer of nylon 12 and nylon 6 are preferred.
  • the average particle diameter of the particles (A) of the thermoplastic resin in the present invention is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and still more preferably 15 ⁇ m or less in order to secure the adhesion strength.
  • the average particle diameter of the particles (A) of the thermoplastic resin in the present invention is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, in order to secure the stress relaxation performance of the cured conductive adhesive. And 5 ⁇ m or more.
  • the shape of the particles (A) of the thermoplastic resin in the present invention is not particularly limited, and examples thereof include substantially spherical, cubic, cylindrical, prismatic, conical, conical, pyramidal, flake, foil and dendritic shapes, etc. However, a substantially spherical or cubic shape is preferable.
  • the content of the particles (A) of the thermoplastic resin is the composition of the conductive adhesive in order to prevent peeling of the material to be bonded at a high level when subjected to repeated temperature changes.
  • the content is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more based on the total amount of the substance.
  • the conductive filler (B) in the present invention is not particularly limited as long as it is a component that contributes to the conductivity in the conductive adhesive composition.
  • metals, carbon nanotubes and the like are preferable.
  • metal all metal powders treated as a general conductor can be used.
  • simple substances such as silver, copper, gold, nickel, aluminum, chromium, platinum, palladium, tungsten, and molybdenum, alloys comprising these two or more metals, coated articles of these metals, oxides of these metals, or oxides of these metals And compounds having good conductivity, and the like.
  • metals having silver or copper as a main component are more preferable because they are resistant to oxidation and high thermal conductivity, and metals having silver as a main component are particularly preferable because they are excellent in conductivity and antioxidative property.
  • the term "main component" refers to the component with the highest content among the components in the conductive filler.
  • the average particle size (D50) of the conductive filler (B) is not particularly limited, but the cost at the time of pulverizing the conductive filler (B), easiness of paste formation, securing of adhesion to a material to be adhered, etc. From the viewpoint, it is preferably 0.5 to 10 ⁇ m, more preferably 0.7 to 8 ⁇ m, and still more preferably 0.8 to 6 ⁇ m.
  • the tap density of the conductive filler (B) is not particularly limited, but is preferably 4 g / cm 3 or more, more preferably 5 g / cm 3 or more, in order to ensure the adhesion strength to the adherend material Preferably, it is more preferably 5.5 g / cm 3 or more. Moreover, in order to prevent the conductive filler (B) from settling and becoming unstable when the conductive adhesive composition is stored for a long period of time, it is preferably 8 g / cm 3 or less, and 7.5 g / cm 3 or less Is more preferably 7 g / cm 3 or less.
  • the tap density is measured and calculated, for example, by the metal powder-tap density measuring method of JIS standard Z 2512: 2012.
  • the specific surface area of the conductive filler (B) is not particularly limited, but is preferably 0.1 to 3 m 2 / g, more preferably 0.2 to 2 m 2 / g, and still more preferably 0.3. It is ⁇ 1 m 2 / g.
  • the specific surface area of the conductive filler (B) is 0.1 m 2 / g or more, the surface area of the conductive filler (B) in contact with the adherend material can be secured.
  • the specific surface area of the conductive filler (B) is 3 m 2 / g or less, the amount of solvent added to the conductive composition can be reduced.
  • the shape of the conductive filler (B) is not particularly limited, and examples thereof include powder, sphere, flake, foil, plate, dendritic and the like. In general, flakes or spheres are selected. In addition to particles of a single metal, metal particles surface-coated with other metals, or mixtures of these can be used.
  • the conductive filler (B) may have its surface coated with a coating agent.
  • a coating agent the coating agent containing carboxylic acid is mentioned, for example.
  • the carboxylic acid contained in the coating agent is not particularly limited, and examples thereof include monocarboxylic acid, polycarboxylic acid and oxycarboxylic acid.
  • the carboxylic acid contained in the coating agent may be a mixture of two or more. Further, higher fatty acids which are saturated fatty acids or unsaturated fatty acids having 12 to 24 carbon atoms are preferable.
  • a method of coating the surface of the conductive filler (B) with a coating agent for example, a method of stirring and kneading both in a mixer, impregnating the conductive filler (B) with a solution of carboxylic acid to volatilize the solvent
  • a coating agent for example, a method of stirring and kneading both in a mixer, impregnating the conductive filler (B) with a solution of carboxylic acid to volatilize the solvent
  • the content of the conductive filler (B) is preferably 80% by mass or more based on the total amount of the conductive adhesive composition to improve the conductivity and the thermal conductivity, and is 82% by mass or more. It is more preferable to make it 84 mass% or more. Further, in order to secure the ease of paste formation, the content is preferably 95% by mass or less, more preferably 92% by mass or less, and still more preferably 90% by mass or less.
  • the particles (A) of the thermoplastic resin and the conductive filler (B) may be dispersed in the binder resin.
  • the binder resin is not particularly limited, for example, an epoxy resin, a phenol resin, a urethane resin, an acrylic resin, a silicone resin, a polyimide resin, etc. can be used, and these may be used alone or in combination.
  • the binder resin in the present invention is preferably a thermosetting resin, and particularly preferably an epoxy resin. When a binder resin is contained, it is preferable to use 0.5 mass% or more.
  • the content of the binder resin is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less based on the total amount of the conductive adhesive composition. .
  • the content of the binder resin is 15% by mass or less, a network due to necking of the conductive filler is easily formed, and stable conductivity and thermal conductivity can be obtained.
  • the conductive adhesive composition of the present invention may also contain, for example, a curing agent.
  • a curing agent examples include amine-based curing agents such as tertiary amines, alkyl ureas and imidazoles, and phenol-based curing agents.
  • the content of the curing agent is preferably 5% by mass or less based on the total amount of the conductive adhesive composition.
  • a curing accelerator can also be incorporated into the conductive adhesive composition of the present invention.
  • a curing accelerator for example, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methyl-4-methylimidazole, 1-cyano-2-ethyl Examples thereof include imidazoles such as -4-methylimidazole, tertiary amines, triphenylphosphines, urea compounds, phenols, alcohols, and carboxylic acids.
  • the curing accelerator may be used alone or in combination of two or more.
  • the compounding quantity of a hardening accelerator is not limited and may be determined suitably, when using it, it is generally 1.5 mass% or less with respect to the whole quantity of the conductive adhesive composition of this invention .
  • the conductive adhesive composition of the present invention may further contain a solvent to paste the conductive adhesive composition.
  • a solvent which does not dissolve it is used.
  • Others are not particularly limited, but those having a boiling point of 350 ° C. or less are preferable, and those having a boiling point of 300 ° C. or less are more preferable because the solvent is easily volatilized during curing of the conductive adhesive composition.
  • acetate, ether, hydrocarbon and the like can be mentioned, and more specifically, dibutyl carbitol, butyl carbitol acetate and the like are preferably used.
  • the content of the solvent is usually 15% by mass or less with respect to the conductive adhesive composition, and preferably 10% by mass or less from the viewpoint of workability.
  • the conductive adhesive composition of the present invention in addition to the above components, antioxidants, ultraviolet light absorbers, tackifiers, viscosity modifiers, dispersants, coupling agents, toughness imparting agents, elastomers, etc. It can be suitably blended in the range which does not impair the effect of the present invention.
  • the conductive adhesive composition of the present invention can be obtained by mixing and stirring the above (A) and (B) and other components in any order.
  • a dispersion method for example, a system such as two rolls, three rolls, a sand mill, a roll mill, a ball mill, a colloid mill, a jet mill, a bead mill, a kneader, a homogenizer, and a propellerless mixer can be adopted.
  • the cured conductive adhesive of the present invention is obtained by curing the above-described conductive adhesive composition of the present invention.
  • the method of curing is not particularly limited, for example, a conductive adhesive cured product can be obtained by heat treating the conductive adhesive composition at 100 to 250 ° C. for 0.5 to 3 hours.
  • the thermal conductivity of the conductive adhesive cured product of the present invention is preferably 5 W / m ⁇ K or more, more preferably 10 W / m ⁇ K or more, in order to ensure the heat radiation of the material to be bonded. Preferably, it is 20 W / m ⁇ K or more.
  • the thermal conductivity of the conductive adhesive cured product can be calculated using the method described in the section of the example.
  • the conductive adhesive composition is generally cured by heating to perform bonding.
  • the temperature of heating at that time is not particularly limited, but the conductive fillers (B), and the adhesive material and the conductive filler (B) form close contact with each other, and the adhesion portion is formed.
  • the temperature is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, and still more preferably 150 ° C. or higher, in order to stabilize the shape.
  • the bonding between the conductive fillers (B) proceeds excessively, necking between the conductive fillers (B) occurs, and the conductive fillers (B) are firmly bonded to each other so as to avoid being too hard.
  • the temperature is preferably 230 ° C. or less, more preferably 210 ° C. or less.
  • a method of performing a thermal cycle test by the method described later in the section of the example and measuring the ratio of the peeled area after the test by the method described later in the section of the example can be mentioned. It is preferable that the ratio of the peeling area measured by the said method is 15% or less, It is more preferable that it is 10% or less, It is more preferable that it is 5% or less.
  • the conductive adhesive composition of the present invention can be used for bonding parts in electronic devices.
  • Thermoplastic resin particles (3) “4000 EDX NAT COS” (trade name), Arkema Co., copolymer of nylon 6 and nylon 12, average particle diameter d50: 10 ⁇ m, spherical, melting point: 170 to 210 ° C.
  • thermoplastic resin particles (1) “SX-500H” (trade name), manufactured by Soken Chemical Co., Ltd., made of styrene copolymer, average particle diameter d50: 5 ⁇ m, spherical, decomposition start at 260 to 300 ° C., etc.
  • Silver particles (1) flake-like, average particle diameter d50: 4 ⁇ m, tap density: 6.7 g / cm 3 , manufactured by Tanaka Kikinzoku Kogyo Co., Ltd.
  • Epoxy resin (1) bisphenol F type (“EPICLON 831-S” (trade name), manufactured by Dainippon Ink and Chemicals, Inc., liquid at room temperature, epoxy equivalent: 169 g / eq -Epoxy resin (2): Phenol novolak type ("EPALLOY 8330" (trade name), manufactured by Emerald Performance Materials, liquid at room temperature, epoxy equivalent: 177 g / eq Epoxy resin (3): 1,4 butanediol glycidyl ether ("ERISYS GE-21” (trade name), manufactured by CVC, liquid at room temperature, epoxy equivalent: 125 g / eq Curing agent: Phenolic curing agent (MEH 8000 H, manufactured by Meiwa Kasei Co., Ltd.) Hardener acceleration: 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ) Solvent: butyl carbitol acetate (made by Tokyo Chemical Industry Co
  • the obtained conductive adhesive composition is applied to a 10 mm ⁇ 10 mm silver-plated copper lead frame, and a 5 mm ⁇ 5 mm silver sputtering silicon chip is placed on the coated surface, and then 60 at 250 ° C. in a nitrogen atmosphere.
  • a silver bonded body (hereinafter, also simply referred to as a “silver bonded body”) was prepared by heating a silver lead-plated copper lead frame and a silver-sputtered silicon chip using a conductive adhesive cured product.
  • the thermal conductivity of the obtained silver bonded body is shown in Table 1.
  • the silver bonded body obtained in the example had a smaller peeled area after the thermal cycle test compared to the silver bonded body obtained in the comparative example. From this result, it was confirmed that the conductive adhesive composition of the present invention can achieve adhesion which is hard to cause peeling of the material to be adhered even when the temperature change is repeated.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Inorganic Chemistry (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The purpose of the present invention is to provide a conductive adhesive composition that, even when repeatedly subjected to temperature changes, is unlikely to result in peeling off of an adherend material. The present invention pertains to a conductive adhesive composition comprising: particles (A) of a thermoplastic resin that is in the form of a solid at 25°C; and a conductive filler (B), wherein the thermoplastic resin is a polyamide that has a melting point of at most 250°C and includes an aliphatic skeleton.

Description

導電性接着剤組成物Conductive adhesive composition
　本発明は、導電性接着剤組成物に関する。 The present invention relates to conductive adhesive compositions.
　近年、半導体素子の支持部材へのダイボンド等、各種部材の接合において、従来広く用いられていた、ろう材やはんだによる接合に替えて、導電性金属からなるフィラーを含有する導電性接着剤組成物による接着が注目されている。 In recent years, in bonding various members such as die bonding to a supporting member of a semiconductor element, a conductive adhesive composition containing a filler made of a conductive metal in place of bonding by brazing material and solder, which has been widely used conventionally Adhesion by is attracting attention.
　例えば特許文献１において、金属粉末と有機溶剤とからなるダイボンド用の導電性ペーストであって、前記金属粉末は、純度９９．９質量％以上、平均粒径０．０１μｍ～１．０μｍである銀粉、パラジウム粉、銅粉から選択される一種以上の金属粒子と、前記金属粒子の少なくとも一部を覆う金からなる被覆層とからなる導電性ペーストが報告されている。 For example, in Patent Document 1, a conductive paste for die bonding comprising a metal powder and an organic solvent, wherein the metal powder has a purity of 99.9% by mass or more and an average particle diameter of 0.01 μm to 1.0 μm. There has been reported a conductive paste comprising one or more metal particles selected from palladium powder and copper powder, and a coating layer made of gold covering at least a part of the metal particles.
　また、特許文献２において、平均粒径０．１～１００μｍの金、銀、銅、白金、パラジウム、ロジウム、ニッケル、鉄、コバルト、錫、インジウム、アルミニウム、亜鉛、これらの化合物もしくは合金の少なくともいずれかを含む複数の固体導電性粒子と、前記固体導電性粒子と金属接合されず、かつ前記固体導電性粒子より潤滑性の高い固体潤滑性粒子と、水または有機溶剤とを備えた導電性接着剤が報告されている。 Further, in Patent Document 2, gold, silver, copper, platinum, palladium, palladium, rhodium, nickel, iron, cobalt, tin, indium, aluminum, zinc, at least any of these compounds or alloys, having an average particle diameter of 0.1 to 100 μm. Conductive adhesive comprising: a plurality of solid conductive particles including iron; solid lubricating particles not metal-bonded to the solid conductive particles; and having higher lubricity than the solid conductive particles; and water or an organic solvent Agents have been reported.
日本国特開２０１３－２０６７６５号公報Japan JP 2013-206765 gazette 日本国特開２０１０－２６７５７９号公報Japanese Unexamined Patent Publication No. 2010-267579
　電子部品において、半導体素子は使用時に通電により発熱するため、ダイボンド材は繰り返し温度変化を受けることとなるが、これによりダイボンド材による接着が劣化し、半導体素子が支持部材から剥離してしまうことがある。
　また、近年は電子部品の小型化・高機能化が進展するに伴い半導体素子の通電による発熱量は増大傾向にあり、上記のような剥離の危険性はより一層高まっている。 In electronic components, the semiconductor element generates heat due to current flow during use, so the die bonding material is subject to repeated temperature changes, which may degrade adhesion by the die bonding material and cause the semiconductor element to separate from the support member is there.
Further, in recent years, with the progress of miniaturization and high functionality of electronic parts, the calorific value by energization of the semiconductor element tends to increase, and the risk of the above peeling is further increased.
　本発明は上記のような課題に鑑みて発明されたものであり、その目的は、繰り返し温度変化を受けた場合にも被接着材料の剥離が生じにくい導電性接着剤組成物を提供することである。 The present invention has been invented in view of the above problems, and an object thereof is to provide a conductive adhesive composition in which peeling of a material to be adhered is unlikely to occur even when subjected to repeated temperature changes. is there.
　本発明者らは、鋭意研究した結果、導電性接着剤組成物において、脂肪族骨格を含むポリアミドからなる２５℃において固体状の熱可塑性樹脂の粒子を含有させることによって、繰り返し温度変化を受けた場合にも剥離が生じにくい接着を形成できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors repeatedly subjected to temperature changes in the conductive adhesive composition by including particles of thermoplastic resin in solid form at 25 ° C. consisting of a polyamide containing an aliphatic skeleton. It has been found that adhesion which is less likely to be peeled off can be formed, and the present invention has been completed.
　すなわち、本発明の導電性接着剤組成物は２５℃において固体状の熱可塑性樹脂の粒子（Ａ）と、導電性フィラー（Ｂ）とを含有する導電性接着剤組成物であって、前記熱可塑性樹脂は、２５０℃以下の融点を有する脂肪族骨格を含むポリアミドである。 That is, the conductive adhesive composition of the present invention is a conductive adhesive composition comprising particles (A) of a thermoplastic resin which is solid at 25 ° C. and a conductive filler (B), and the thermal adhesive as described above The plastic resin is a polyamide comprising an aliphatic backbone having a melting point of 250 ° C. or less.
　本発明の一態様に係る導電性接着剤組成物は、熱可塑性樹脂が、ナイロン１１、ナイロン１２及びナイロン６の少なくともいずれか一つを含有する。 In the conductive adhesive composition according to one aspect of the present invention, the thermoplastic resin contains at least one of nylon 11, nylon 12 and nylon 6.
　本発明の一態様に係る導電性接着剤組成物は、熱可塑性樹脂の粒子（Ａ）の平均粒径が１～３０μｍである。 In the conductive adhesive composition according to one aspect of the present invention, the average particle diameter of the thermoplastic resin particles (A) is 1 to 30 μm.
　本発明の一態様に係る導電性接着剤組成物は、導電性接着剤組成物の全体量に対して、前記熱可塑性樹脂の粒子（Ａ）を０．５～１０質量％の範囲で含有する。 The conductive adhesive composition according to one aspect of the present invention contains the particles (A) of the thermoplastic resin in a range of 0.5 to 10% by mass with respect to the total amount of the conductive adhesive composition. .
　本発明の一態様に係る導電性接着剤組成物は、導電性フィラー（Ｂ）が、銀を含有する。 In the conductive adhesive composition according to one aspect of the present invention, the conductive filler (B) contains silver.
　本発明の一態様に係る導電性接着剤組成物は、導電性接着剤組成物の全体量に対して、導電性フィラー（Ｂ）を８０～９５質量％の範囲で含有する。 The conductive adhesive composition according to one aspect of the present invention contains the conductive filler (B) in the range of 80 to 95% by mass with respect to the total amount of the conductive adhesive composition.
　また、本発明の導電性接着剤硬化物は、前記いずれか１の導電性接着剤組成物を硬化したものである。 The conductive adhesive cured product of the present invention is a cured product of any one of the above-mentioned conductive adhesive compositions.
　また、本発明の電子機器は、前記いずれか１の導電性接着剤組成物を部品の接着に使用したものである。 Moreover, the electronic device of the present invention uses any one of the conductive adhesive compositions described above for bonding of parts.
　本発明の導電性接着剤組成物は、脂肪族骨格を含むポリアミドからなる２５℃において固体状の熱可塑性樹脂の粒子（Ａ）を含むことを特徴とし、このことにより繰り返しの温度変化を受けた場合にも被接着材料の剥離が生じにくくなる。 The conductive adhesive composition of the present invention is characterized in that it comprises particles (A) of a thermoplastic resin in solid form at 25 ° C. comprising a polyamide containing an aliphatic skeleton, which has been subjected to repeated temperature changes. Also in this case, peeling of the adherend material is less likely to occur.
　以下に、本発明を実施するための形態を説明するが、本発明は以下の実施形態に限定されるものではなく、本発明の要旨を逸脱しない範囲において、任意に変形して実施することができる。また、本明細書において数値範囲を示す「～」とは、その前後に記載された数値を下限値、及び上限値として含む意味で使用される。 Although the form for implementing this invention is demonstrated below, this invention is not limited to the following embodiment, In the range which does not deviate from the summary of this invention, it can deform | transform arbitrarily and to implement it can. Further, in the present specification, “to” indicating a numerical range is used in the meaning including the numerical values described before and after that as the lower limit and the upper limit.
　また、本明細書において平均粒子径はレーザー回折・散乱式粒度分析計を用いて測定された粒子径分布の５０％平均粒子径（Ｄ５０）とする。例えば、日機装株式会社製のレーザー回折・散乱式粒度分析計ＭＴ－３０００を用いて測定することができる。 Further, in the present specification, the average particle size is taken as the 50% average particle size (D50) of the particle size distribution measured using a laser diffraction / scattering type particle size analyzer. For example, measurement can be performed using a laser diffraction / scattering particle size analyzer MT-3000 manufactured by Nikkiso Co., Ltd.
　［２５℃において固体状の熱可塑性樹脂の粒子（Ａ）］
　本発明に係る導電性接着剤組成物は、２５℃において固体状の熱可塑性樹脂の粒子（Ａ）（以下、単に「熱可塑性樹脂の粒子（Ａ）」ともいう）を含有する。本発明において熱可塑性樹脂の粒子（Ａ）は、２５０℃以下の融点を有する脂肪族骨格を含むポリアミドの粒子である。 [Particles of Thermoplastic Resin Solid at 25 ° C. (A)]
The conductive adhesive composition according to the present invention contains particles (A) of a thermoplastic resin solid at 25 ° C. (hereinafter, also simply referred to as “particles of thermoplastic resin (A)”). In the present invention, the particles (A) of the thermoplastic resin are particles of a polyamide containing an aliphatic skeleton having a melting point of 250 ° C. or less.
　導電性接着剤組成物を用いた接着が繰り返し温度変化を受けることにより劣化する原因の一つとして、被接着材料同士の線熱膨張率の差により生じる、導電性接着剤の硬化物（以下、単に「導電性接着剤硬化物」ともいう）または接合界面への応力負荷が挙げられる。
　本発明の導電性接着剤組成物では、熱可塑性樹脂の粒子（Ａ）がその融点が２５０℃以下であることから導電性接着剤組成物の熱硬化時に溶融し、その結果、導電性接着剤硬化物内において導電性フィラー（Ｂ）と高い密着性を有することとなる。このように導電性フィラー（Ｂ）と高い密着性を有する熱可塑性樹脂は、上述のような応力負荷がかかった際に弾性変形し、応力を効果的に緩和することができる。そのため、本発明の導電性接着剤硬化物は応力緩和性能に優れ、上記のような応力負荷がかかった際にも被接着材料の剥離が生じにくくなっているものと考えられる。
　他にも、熱可塑性樹脂の粒子（Ａ）が導電性接着剤組成物の熱硬化時に溶融して、導電性接着剤硬化物と被接着材料の接着界面に存在する空隙を充填することにより、接着強度が向上することも、繰り返しの温度変化による剥離の抑制に寄与していると考えられる。 A cured product of a conductive adhesive (hereinafter referred to as "cured" of the conductive adhesive, which is caused by the difference in the linear thermal expansion coefficient between the materials to be bonded, as one of the causes of deterioration due to repeated temperature changes due to adhesion using the conductive adhesive composition. Stress loading on the “conductive adhesive cured product” or bonding interface may be mentioned.
In the conductive adhesive composition of the present invention, the thermoplastic resin particles (A) melt at the time of heat curing of the conductive adhesive composition since the melting point thereof is 250 ° C. or less, and as a result, the conductive adhesive It will have high adhesiveness with the conductive filler (B) in the cured product. As described above, the thermoplastic resin having high adhesiveness with the conductive filler (B) is elastically deformed when stressed as described above, and the stress can be effectively relieved. Therefore, it is considered that the cured conductive adhesive of the present invention is excellent in stress relaxation performance, and peeling of the material to be adhered is difficult to occur even when the stress load as described above is applied.
Besides, the particles (A) of the thermoplastic resin are melted at the time of heat curing of the conductive adhesive composition to fill the voids existing at the bonding interface between the conductive adhesive cured product and the material to be bonded, The improvement of the adhesive strength is also considered to contribute to the suppression of peeling due to repeated temperature changes.
　本発明において熱可塑性樹脂の粒子（Ａ）は、２５０℃以下の融点を有する脂肪族骨格を含むポリアミドの粒子であればよく、特に限定はされないが、導電性接着剤硬化物において熱可塑性樹脂と導電性フィラー（Ｂ）の密着性を担保するために、融点が５０～２５０℃の範囲の樹脂の粒子が好ましく、融点が１００～２２５℃の範囲の樹脂の粒子がより好ましく、融点が１５０～２００℃の範囲の樹脂の粒子がさらに好ましい。 In the present invention, the particles (A) of the thermoplastic resin may be particles of a polyamide containing an aliphatic skeleton having a melting point of 250 ° C. or less, and there is no particular limitation. In order to secure the adhesion of the conductive filler (B), particles of resin having a melting point in the range of 50 to 250 ° C. are preferable, particles of resin having a melting point in the range of 100 to 225 ° C. are more preferable, and melting point is 150 to 150 More preferred are particles of resin in the range of 200 ° C.
　具体的には、熱可塑性樹脂が、ナイロン１１、ナイロン１２及びナイロン６の少なくともいずれか一つを含有することが好ましい。ナイロン１１、ナイロン１２、ナイロン６のいずれかからなる粒子を単独で使用することもできるし、複数種の粒子を使用することもできる。また、ナイロン１１、ナイロン１２、ナイロン６の少なくとも２種類からなる共重合体からなる粒子を使用することも可能である。特に、ナイロン１１の粒子、ナイロン１２の粒子、ナイロン１２とナイロン６の共重合体の粒子が好ましい。 Specifically, it is preferable that the thermoplastic resin contains at least one of nylon 11, nylon 12 and nylon 6. Particles made of either nylon 11, nylon 12, nylon 6 may be used alone, or multiple types of particles may be used. It is also possible to use particles made of at least two copolymers of nylon 11, nylon 12, and nylon 6. In particular, particles of nylon 11, particles of nylon 12, and particles of a copolymer of nylon 12 and nylon 6 are preferred.
　本発明における熱可塑性樹脂の粒子（Ａ）の平均粒径は、接着強度を担保するために３０μｍ以下であることが好ましく、２０μｍ以下であることがより好ましく、１５μｍ以下であることがさらに好ましい。
　また、本発明における熱可塑性樹脂の粒子（Ａ）の平均粒径は、導電性接着剤硬化物の応力緩和性能を担保するために１μｍ以上であることが好ましく、３μｍ以上であることがより好ましく、５μｍ以上であることがさらに好ましい。 The average particle diameter of the particles (A) of the thermoplastic resin in the present invention is preferably 30 μm or less, more preferably 20 μm or less, and still more preferably 15 μm or less in order to secure the adhesion strength.
In addition, the average particle diameter of the particles (A) of the thermoplastic resin in the present invention is preferably 1 μm or more, more preferably 3 μm or more, in order to secure the stress relaxation performance of the cured conductive adhesive. And 5 μm or more.
　本発明における熱可塑性樹脂の粒子（Ａ）の形状は特に限定されず、例えば、略球状、立方体状、円柱状、角柱状、円錐状、角錐状、フレーク状、箔状および樹枝状等が挙げられるが、略球状、立方体状が好ましい。 The shape of the particles (A) of the thermoplastic resin in the present invention is not particularly limited, and examples thereof include substantially spherical, cubic, cylindrical, prismatic, conical, conical, pyramidal, flake, foil and dendritic shapes, etc. However, a substantially spherical or cubic shape is preferable.
　本発明の導電性接着剤組成物において、繰り返し温度変化を受けた場合の被接着材料の剥離を高い水準で防止するために、熱可塑性樹脂の粒子（Ａ）の含有量は導電性接着剤組成物の全体量に対して０．５質量％以上であることが好ましく、１質量％以上であることがより好ましく、２質量％以上であることがさらに好ましい。また、熱可塑性樹脂の粒子（Ａ）を過剰に含有することによって導電性接着剤硬化物の熱伝導率が低下することを防止するため、１０質量％以下であることが好ましく、７質量％以下であることがより好ましく、５質量％以下であることがさらに好ましい。 In the conductive adhesive composition of the present invention, the content of the particles (A) of the thermoplastic resin is the composition of the conductive adhesive in order to prevent peeling of the material to be bonded at a high level when subjected to repeated temperature changes. The content is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more based on the total amount of the substance. Moreover, in order to prevent that the heat conductivity of electroconductive adhesive hardened | cured material falls by containing the particle | grains (A) of a thermoplastic resin excessively, it is preferable that it is 10 mass% or less, and 7 mass% or less. Is more preferably 5% by mass or less.
　［導電性フィラー（Ｂ）］
　本発明における導電性フィラー（Ｂ）は、導電性接着剤組成物における導電性に寄与する成分であれば特に制限されない。中でも、金属やカーボンナノチューブ等が好ましい。金属としては、一般的な導体として扱われる金属の粉末は全て利用することができる。例えば、銀、銅、金、ニッケル、アルミニウム、クロム、白金、パラジウム、タングステン、モリブデン等の単体、これら２種以上の金属からなる合金、これら金属のコーティング品、これら金属の酸化物、あるいはこれら金属の化合物で良好な導電性を有するもの等が挙げられる。中でも、酸化しづらく熱伝導性が高いことから、銀または銅を主成分とする金属がより好ましく、電導性や抗酸化性に優れることから銀を主成分とする金属が特により好ましい。ここで「主成分」とは、導電性フィラー中の成分の中で、最も含有量の多い成分のことをさす。 [Conductive filler (B)]
The conductive filler (B) in the present invention is not particularly limited as long as it is a component that contributes to the conductivity in the conductive adhesive composition. Among them, metals, carbon nanotubes and the like are preferable. As metal, all metal powders treated as a general conductor can be used. For example, simple substances such as silver, copper, gold, nickel, aluminum, chromium, platinum, palladium, tungsten, and molybdenum, alloys comprising these two or more metals, coated articles of these metals, oxides of these metals, or oxides of these metals And compounds having good conductivity, and the like. Among them, metals having silver or copper as a main component are more preferable because they are resistant to oxidation and high thermal conductivity, and metals having silver as a main component are particularly preferable because they are excellent in conductivity and antioxidative property. Here, the term "main component" refers to the component with the highest content among the components in the conductive filler.
　導電性フィラー（Ｂ）の平均粒子径（Ｄ５０）は特に限定されないが、導電性フィラー（Ｂ）を微粉化する際のコスト、ペースト化の容易性、被接着材料との密着性の確保等の観点から、好ましくは０．５～１０μｍ、より好ましくは０．７～８μｍ、さらに好ましくは０．８～６μｍである。 The average particle size (D50) of the conductive filler (B) is not particularly limited, but the cost at the time of pulverizing the conductive filler (B), easiness of paste formation, securing of adhesion to a material to be adhered, etc. From the viewpoint, it is preferably 0.5 to 10 μm, more preferably 0.7 to 8 μm, and still more preferably 0.8 to 6 μm.
　導電性フィラー（Ｂ）のタップ密度は、特に限定されないが、被接着材料への接着強度を確保するために、４ｇ／ｃｍ３以上であることが好ましく、５ｇ／ｃｍ３以上であることがより好ましく、５．５ｇ／ｃｍ３以上であることがさらに好ましい。また、導電性接着剤組成物を長期保管した際に導電性フィラー（Ｂ）が沈降し不安定になることを防ぐために、８ｇ／ｃｍ３以下であることが好ましく、７．５ｇ／ｃｍ３以下であることがより好ましく、７ｇ／ｃｍ３以下であることがさらに好ましい。タップ密度は、例えばＪＩＳ規格Ｚ２５１２：２０１２の金属粉－タップ密度測定方法により測定され算出される。 The tap density of the conductive filler (B) is not particularly limited, but is preferably 4 g / cm 3 or more, more preferably 5 g / cm 3 or more, in order to ensure the adhesion strength to the adherend material Preferably, it is more preferably 5.5 g / cm 3 or more. Moreover, in order to prevent the conductive filler (B) from settling and becoming unstable when the conductive adhesive composition is stored for a long period of time, it is preferably 8 g / cm 3 or less, and 7.5 g / cm 3 or less Is more preferably 7 g / cm 3 or less. The tap density is measured and calculated, for example, by the metal powder-tap density measuring method of JIS standard Z 2512: 2012.
　導電性フィラー（Ｂ）の比表面積は、特に限定されないが、０．１～３ｍ２／ｇであることが好ましく、より好ましくは０．２～２ｍ２／ｇであり、さらに好ましくは０．３～１ｍ２／ｇである。導電性フィラー（Ｂ）の比表面積が０．１ｍ２／ｇ以上であることにより、被接着材料に接する導電性フィラー（Ｂ）の表面積が確保できる。また導電性フィラー（Ｂ）の比表面積が３ｍ２／ｇ以下であることにより、導電性組成物に添加する溶剤量を少なくできる。 The specific surface area of the conductive filler (B) is not particularly limited, but is preferably 0.1 to 3 m 2 / g, more preferably 0.2 to 2 m 2 / g, and still more preferably 0.3. It is ̃1 m 2 / g. When the specific surface area of the conductive filler (B) is 0.1 m 2 / g or more, the surface area of the conductive filler (B) in contact with the adherend material can be secured. When the specific surface area of the conductive filler (B) is 3 m 2 / g or less, the amount of solvent added to the conductive composition can be reduced.
　導電性フィラー（Ｂ）の形状は特に限定されず、例えば、粉状、球状、フレーク状、箔状、プレート状、樹枝状等が挙げられる。一般的にはフレーク状または球状が選択される。また、単一の金属の粒子の他、他の金属で表面被覆された金属粒子、又はこれらの混合物を用いることができる。 The shape of the conductive filler (B) is not particularly limited, and examples thereof include powder, sphere, flake, foil, plate, dendritic and the like. In general, flakes or spheres are selected. In addition to particles of a single metal, metal particles surface-coated with other metals, or mixtures of these can be used.
　導電性フィラー（Ｂ）は、その表面がコーティング剤で被覆されていてもよい。コーティング剤としては、例えば、カルボン酸を含むコーティング剤が挙げられる。カルボン酸を含むコーティング剤を用いることによって、導電性接着剤組成物の放熱性をより一層向上させることができる。 The conductive filler (B) may have its surface coated with a coating agent. As a coating agent, the coating agent containing carboxylic acid is mentioned, for example. By using the coating agent containing a carboxylic acid, the heat dissipation of the conductive adhesive composition can be further improved.
　コーティング剤に含まれるカルボン酸は特に限定されず、例えば、モノカルボン酸、ポリカルボン酸およびオキシカルボン酸等が挙げられる。
　コーティング剤に含まれるカルボン酸は２種以上の混合物であってもよい。また、炭素数１２～２４の飽和脂肪酸または不飽和脂肪酸である高級脂肪酸が好ましい。 The carboxylic acid contained in the coating agent is not particularly limited, and examples thereof include monocarboxylic acid, polycarboxylic acid and oxycarboxylic acid.
The carboxylic acid contained in the coating agent may be a mixture of two or more. Further, higher fatty acids which are saturated fatty acids or unsaturated fatty acids having 12 to 24 carbon atoms are preferable.
　導電性フィラー（Ｂ）の表面をコーティング剤で被覆する方法としては、例えば、両者をミキサー中で撹拌、混練する方法、該導電性フィラー（Ｂ）にカルボン酸の溶液を含浸して溶剤を揮発させる方法等の公知の方法が挙げられる。 As a method of coating the surface of the conductive filler (B) with a coating agent, for example, a method of stirring and kneading both in a mixer, impregnating the conductive filler (B) with a solution of carboxylic acid to volatilize the solvent Known methods such as the method of
　導電性フィラー（Ｂ）の含有量は、導電性や熱伝導率を向上させるために、導電性接着剤組成物の全体量に対して８０質量％以上とすることが好ましく、８２質量％以上とすることがより好ましく、８４質量％以上とすることがさらに好ましい。また、ペースト化の容易性を担保するために、９５質量％以下とすることが好ましく、９２質量％以下とすることがより好ましく、９０質量％以下とすることがさらに好ましい。 The content of the conductive filler (B) is preferably 80% by mass or more based on the total amount of the conductive adhesive composition to improve the conductivity and the thermal conductivity, and is 82% by mass or more. It is more preferable to make it 84 mass% or more. Further, in order to secure the ease of paste formation, the content is preferably 95% by mass or less, more preferably 92% by mass or less, and still more preferably 90% by mass or less.
　［その他の成分］
　＜バインダ樹脂＞
　本発明の導電性接着剤組成物において、熱可塑性樹脂の粒子（Ａ）、及び導電性フィラー（Ｂ）は、バインダ樹脂中に分散されてもよい。バインダ樹脂は特に限定されないが、例えば、エポキシ樹脂、フェノール樹脂、ウレタン樹脂、アクリル樹脂、シリコーン樹脂又はポリイミド樹脂等を用いることができ、これらを単独で用いても、複数種類組み合わせて用いてもよい。作業性の観点から本発明におけるバインダ樹脂は熱硬化性樹脂であることが好ましく、エポキシ樹脂であることが特に好ましい。またバインダ樹脂を含有させる場合は、０．５質量％以上用いることが好ましい。 [Other ingredients]
<Binder resin>
In the conductive adhesive composition of the present invention, the particles (A) of the thermoplastic resin and the conductive filler (B) may be dispersed in the binder resin. Although the binder resin is not particularly limited, for example, an epoxy resin, a phenol resin, a urethane resin, an acrylic resin, a silicone resin, a polyimide resin, etc. can be used, and these may be used alone or in combination. . From the viewpoint of workability, the binder resin in the present invention is preferably a thermosetting resin, and particularly preferably an epoxy resin. When a binder resin is contained, it is preferable to use 0.5 mass% or more.
　バインダ樹脂の含有量は、導電性接着剤組成物の全体量に対して１５質量％以下であることが好ましく、１０質量％以下であることがより好ましく、８質量％以下であることがさらに好ましい。バインダ樹脂の含有量が１５質量％以下であると、導電性フィラーのネッキングによるネットワークが形成され易く、安定した導電性および熱伝導性が得られる。 The content of the binder resin is preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 8% by mass or less based on the total amount of the conductive adhesive composition. . When the content of the binder resin is 15% by mass or less, a network due to necking of the conductive filler is easily formed, and stable conductivity and thermal conductivity can be obtained.
　＜硬化剤＞
　また、本発明の導電性接着剤組成物は、上記成分のほかにも、例えば、硬化剤を含有していてもよい。硬化剤としては、例えば、三級アミン、アルキル尿素、イミダゾール等のアミン系硬化剤や、フェノール系硬化剤等が挙げられる。 <Hardening agent>
In addition to the above components, the conductive adhesive composition of the present invention may also contain, for example, a curing agent. Examples of the curing agent include amine-based curing agents such as tertiary amines, alkyl ureas and imidazoles, and phenol-based curing agents.
　硬化剤の含有量は導電性接着剤組成物の全体量に対して５質量％以下であることが好ましい。そうすることで未硬化の硬化剤が残りにくくなり、被接着材料との密着性が良好となるためである。 The content of the curing agent is preferably 5% by mass or less based on the total amount of the conductive adhesive composition. By doing so, the uncured curing agent hardly remains, and the adhesion to the material to be bonded becomes good.
　＜硬化促進剤＞
　本発明の導電性接着剤組成物には硬化促進剤を配合することもできる。硬化促進剤としては、例えば、２－フェニル－４，５－ジヒドロキシメチルイミダゾール、２－フェニル－４―メチル－５－ヒドロキシメチルイミダゾール、２―メチル－４－メチルイミダゾール、１－シアノ－２－エチル－４－メチルイミダゾール等のイミダゾール類、第３級アミン類、トリフェニルフォスフィン類、尿素系化合物、フェノール類、アルコール類、カルボン酸類等が例示される。硬化促進剤は１種類だけ使用しても２種類以上を併用してもよい。 <Hardening accelerator>
A curing accelerator can also be incorporated into the conductive adhesive composition of the present invention. As a curing accelerator, for example, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-methyl-4-methylimidazole, 1-cyano-2-ethyl Examples thereof include imidazoles such as -4-methylimidazole, tertiary amines, triphenylphosphines, urea compounds, phenols, alcohols, and carboxylic acids. The curing accelerator may be used alone or in combination of two or more.
　硬化促進剤の配合量は限定されるものではなく適宜決定すればよいが、使用する場合は一般には、本発明の導電性接着剤組成物の全体量に対して１．５質量％以下である。 Although the compounding quantity of a hardening accelerator is not limited and may be determined suitably, when using it, it is generally 1.5 mass% or less with respect to the whole quantity of the conductive adhesive composition of this invention .
　＜溶剤＞
　本発明の導電性接着剤組成物には、さらに導電性接着剤組成物をペースト状にするために溶剤を含んでいてもよい。溶剤を含む場合は、ペースト中において熱可塑性樹脂の粒子（Ａ）の形状を維持するために、これを溶解しない性質の溶剤を用いる。その他は特に限定されないが、導電性接着剤組成物の硬化の際に溶剤が揮発しやすいことから沸点３５０℃以下のものが好ましく、沸点３００℃以下のものがより好ましい。具体的にはアセテート、エーテル、炭化水素等が挙げられ、より具体的には、ジブチルカルビトール、ブチルカルビトールアセテート等が好ましく用いられる。
　溶剤の含有率は、導電性接着剤組成物に対して通常１５質量％以下であり、作業性の観点から好ましくは１０質量％以下である。 <Solvent>
The conductive adhesive composition of the present invention may further contain a solvent to paste the conductive adhesive composition. When the solvent is contained, in order to maintain the shape of the particles (A) of the thermoplastic resin in the paste, a solvent which does not dissolve it is used. Others are not particularly limited, but those having a boiling point of 350 ° C. or less are preferable, and those having a boiling point of 300 ° C. or less are more preferable because the solvent is easily volatilized during curing of the conductive adhesive composition. Specifically, acetate, ether, hydrocarbon and the like can be mentioned, and more specifically, dibutyl carbitol, butyl carbitol acetate and the like are preferably used.
The content of the solvent is usually 15% by mass or less with respect to the conductive adhesive composition, and preferably 10% by mass or less from the viewpoint of workability.
　本発明の導電性接着剤組成物には、上記成分の他にも、酸化防止剤、紫外線吸収剤、粘着付与剤、粘性調整剤、分散剤、カップリング剤、強靭性付与剤、エラストマー等を、本発明の効果を損なわない範囲で適宜配合することができる。 In the conductive adhesive composition of the present invention, in addition to the above components, antioxidants, ultraviolet light absorbers, tackifiers, viscosity modifiers, dispersants, coupling agents, toughness imparting agents, elastomers, etc. It can be suitably blended in the range which does not impair the effect of the present invention.
　本発明の導電性接着剤組成物は、上記の（Ａ）及び（Ｂ）並びにその他の成分を任意の順序で混合、撹拌することにより得ることができる。分散方法としては、例えば、二本ロール、三本ロール、サンドミル、ロールミル、ボールミル、コロイドミル、ジェットミル、ビーズミル、ニーダー、ホモジナイザー、及びプロペラレスミキサー等の方式を採用することができる。 The conductive adhesive composition of the present invention can be obtained by mixing and stirring the above (A) and (B) and other components in any order. As a dispersion method, for example, a system such as two rolls, three rolls, a sand mill, a roll mill, a ball mill, a colloid mill, a jet mill, a bead mill, a kneader, a homogenizer, and a propellerless mixer can be adopted.
　また、本発明の導電性接着剤硬化物は、上記の本発明の導電性接着剤組成物を硬化させることにより得られる。硬化の方法は特に限定されないが、例えば、導電性接着剤組成物を１００～２５０℃で０．５～３時間熱処理することで、導電性接着剤硬化物を得ることができる。 The cured conductive adhesive of the present invention is obtained by curing the above-described conductive adhesive composition of the present invention. Although the method of curing is not particularly limited, for example, a conductive adhesive cured product can be obtained by heat treating the conductive adhesive composition at 100 to 250 ° C. for 0.5 to 3 hours.
　本発明の導電性接着剤硬化物の熱伝導率は、被接着材料の放熱性を確保するために、５Ｗ／ｍ・Ｋ以上であることが好ましく、１０Ｗ／ｍ・Ｋ以上であることがより好ましく、２０Ｗ／ｍ・Ｋ以上であることがさらに好ましい。なお、導電性接着剤硬化物の熱伝導率は、実施例の欄に記載の方法を用いて算出することができる。 The thermal conductivity of the conductive adhesive cured product of the present invention is preferably 5 W / m · K or more, more preferably 10 W / m · K or more, in order to ensure the heat radiation of the material to be bonded. Preferably, it is 20 W / m · K or more. The thermal conductivity of the conductive adhesive cured product can be calculated using the method described in the section of the example.
　また、本発明の導電性接着剤組成物を用いて接着を行う際には、通常加熱により導電性接着剤組成物を硬化させて接着を行う。その際の加熱の温度は特に限定はされないが、導電性フィラー（Ｂ）同士、及び、被接着材料と導電性フィラー（Ｂ）との間に、互いに点接触した近接状態を形成させ、接着部としての形状を安定させるために１００℃以上であることが好ましく、１３０℃以上であることがより好ましく、１５０℃以上であることがさらに好ましい。
　また、導電性フィラー（Ｂ）同士の結合が過度に進行し導電性フィラー（Ｂ）間のネッキングが生じて強固に結合し、硬すぎる状態となることを避けるために２５０℃以下であることが好ましく、２３０℃以下であることがより好ましく、２１０℃以下であることがさらに好ましい。 When bonding is performed using the conductive adhesive composition of the present invention, the conductive adhesive composition is generally cured by heating to perform bonding. The temperature of heating at that time is not particularly limited, but the conductive fillers (B), and the adhesive material and the conductive filler (B) form close contact with each other, and the adhesion portion is formed. The temperature is preferably 100 ° C. or higher, more preferably 130 ° C. or higher, and still more preferably 150 ° C. or higher, in order to stabilize the shape.
In addition, the bonding between the conductive fillers (B) proceeds excessively, necking between the conductive fillers (B) occurs, and the conductive fillers (B) are firmly bonded to each other so as to avoid being too hard. The temperature is preferably 230 ° C. or less, more preferably 210 ° C. or less.
　本発明の導電性接着剤組成物を用いて被接着材料を接着した場合に、繰り返し温度変化を受けた場合にも被接着材料の剥離が生じにくくなっていることを評価する方法としては、種々の方法が挙げられるが、例えば、実施例の欄において後述する方法で冷熱サイクル試験を行い、試験後の剥離面積の割合を実施例の欄において後述する方法で測定する方法が挙げられる。当該方法で測定した剥離面積の割合は１５％以下であることが好ましく、１０％以下であることがより好ましく、５％以下であることがさらに好ましい。 When a material to be bonded is bonded using the conductive adhesive composition of the present invention, various methods can be used to evaluate that peeling of the material to be bonded is less likely to occur even when the temperature changes repeatedly. However, for example, a method of performing a thermal cycle test by the method described later in the section of the example and measuring the ratio of the peeled area after the test by the method described later in the section of the example can be mentioned. It is preferable that the ratio of the peeling area measured by the said method is 15% or less, It is more preferable that it is 10% or less, It is more preferable that it is 5% or less.
　本発明の導電性接着剤組成物は、電子機器における部品の接着に用いることができる。 The conductive adhesive composition of the present invention can be used for bonding parts in electronic devices.
　以下、実施例により本発明をさらに具体的に説明するが、本発明はこれらの実施例により何ら限定されるものではない。 Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.
　Ａ．導電性接着剤組成物の調製
　表１に記載された各材料を三本ロールにて混練し、表１に示す組成の導電性接着剤組成物を調製した（各材料の数値は導電性接着剤組成物の総質量に対する質量％を表す）。使用した材料は下記の通りである。なお、混練の順番は、導電性フィラー（Ｂ）、熱可塑性樹脂の粒子（Ａ）、バインダ樹脂、硬化剤、硬化促進剤、溶剤の順である。 A. Preparation of Conductive Adhesive Composition Each material listed in Table 1 was kneaded with three rolls to prepare a conductive adhesive composition having the composition shown in Table 1 (the numerical value of each material is a conductive adhesive) Represents% by mass relative to the total mass of the composition). The materials used are as follows. The order of kneading is the order of the conductive filler (B), the particles of the thermoplastic resin (A), the binder resin, the curing agent, the curing accelerator, and the solvent.
　［熱可塑性樹脂の粒子（Ａ）］
・熱可塑性樹脂粒子（１）：「ＳＰ－５００」（商品名）、東レ社製、ナイロン１２製、平均粒子径ｄ５０：５μｍ、球状、融点：１６５～１７１℃
・熱可塑性樹脂粒子（２）：「ＳＰ－１０」（商品名）、東レ社製、ナイロン１２製、平均粒子径ｄ５０：１０μｍ、球状、融点：１６５～１７１℃
・熱可塑性樹脂粒子（３）：「４０００ＥＤＸ　ＮＡＴ　ＣＯＳ」（商品名）、アルケマ社製、ナイロン６とナイロン１２の共重合体、平均粒子径ｄ５０：１０μｍ、球状、融点：１７０～２１０℃ [Particles of Thermoplastic Resin (A)]
Thermoplastic resin particles (1): “SP-500” (trade name), manufactured by Toray Industries, Inc., made of nylon 12, average particle diameter d50: 5 μm, spherical, melting point: 165 to 171 ° C.
Thermoplastic resin particles (2): “SP-10” (trade name), manufactured by Toray Industries, Inc., made of nylon 12, average particle diameter d50: 10 μm, spherical, melting point: 165 to 171 ° C.
Thermoplastic resin particles (3): “4000 EDX NAT COS” (trade name), Arkema Co., copolymer of nylon 6 and nylon 12, average particle diameter d50: 10 μm, spherical, melting point: 170 to 210 ° C.
　［他の熱可塑性樹脂の粒子］
・他の熱可塑性樹脂粒子（１）：「ＳＸ－５００Ｈ」（商品名）、綜研化学社製、スチレン共重合体製、平均粒子径ｄ５０：５μｍ、球状、２６０～３００℃で分解開始
・他の熱可塑性樹脂粒子（２）：「ＫＭＰ－６００」（商品名）、信越化学社製、シリコーン樹脂製、平均粒子径ｄ５０：５μｍ、球状、融点：３００℃前後 [Particles of other thermoplastic resin]
Other thermoplastic resin particles (1): “SX-500H” (trade name), manufactured by Soken Chemical Co., Ltd., made of styrene copolymer, average particle diameter d50: 5 μm, spherical, decomposition start at 260 to 300 ° C., etc. Thermoplastic resin particles (2): “KMP-600” (trade name), manufactured by Shin-Etsu Chemical Co., Ltd., silicone resin, average particle diameter d50: 5 μm, spherical, melting point: around 300 ° C.
　［導電性フィラー（Ｂ）］
・銀粒子（１）：フレーク状、平均粒子径ｄ５０：４μｍ、タップ密度：６．７ｇ／ｃｍ３、田中貴金属工業社製
・銀粒子（２）：球状、平均粒子径ｄ５０：０．８μｍ、タップ密度：５．５ｇ／ｃｍ３、田中貴金属工業社製 [Conductive filler (B)]
Silver particles (1): flake-like, average particle diameter d50: 4 μm, tap density: 6.7 g / cm 3 , manufactured by Tanaka Kikinzoku Kogyo Co., Ltd. Silver particles (2): spherical, average particle diameter d50: 0.8 μm, Tap density: 5.5 g / cm 3 , manufactured by Tanaka Kikinzoku Kogyo
　［バインダ樹脂・硬化剤・硬化促進剤・溶剤］
・エポキシ樹脂（１）：ビスフェノールＦ型（「ＥＰＩＣＬＯＮ　８３１－Ｓ」（商品名）、大日本インキ化学工業社製、室温で液状、エポキシ当量：１６９ｇ／ｅｑ
・エポキシ樹脂（２）：フェノールノボラック型（「ＥＰＡＬＬＯＹ　８３３０」（商品名）、Ｅｍｅｒａｌｄ　Ｐｅｒｆｏｒｍａｎｃｅ　Ｍａｔｅｒｉａｌｓ社製、室温で液状、エポキシ当量：１７７ｇ／ｅｑ
・エポキシ樹脂（３）：１，４ブタンジオールグリシジルエーテル（「ＥＲＩＳＹＳ　ＧＥ－２１」（商品名）、ＣＶＣ社製、室温で液状、エポキシ当量：１２５ｇ／ｅｑ
・硬化剤：フェノール系硬化剤（ＭＥＨ８０００Ｈ、明和化成社製）
・硬化剤促進：２－フェニル－４，５－ジヒドロキシメチルイミダゾール（２ＰＨＺ）
・溶剤：ブチルカルビトールアセテート（東京化成工業社製） [Binder resin, curing agent, curing accelerator, solvent]
Epoxy resin (1): bisphenol F type (“EPICLON 831-S” (trade name), manufactured by Dainippon Ink and Chemicals, Inc., liquid at room temperature, epoxy equivalent: 169 g / eq
-Epoxy resin (2): Phenol novolak type ("EPALLOY 8330" (trade name), manufactured by Emerald Performance Materials, liquid at room temperature, epoxy equivalent: 177 g / eq
Epoxy resin (3): 1,4 butanediol glycidyl ether ("ERISYS GE-21" (trade name), manufactured by CVC, liquid at room temperature, epoxy equivalent: 125 g / eq
Curing agent: Phenolic curing agent (MEH 8000 H, manufactured by Meiwa Kasei Co., Ltd.)
Hardener acceleration: 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ)
Solvent: butyl carbitol acetate (made by Tokyo Chemical Industry Co., Ltd.)
　Ｂ．物性評価
　得られた導電性接着剤組成物を１０ｍｍ×１０ｍｍの銀メッキした銅リードフレームに塗布し、塗布面に５ｍｍ×５ｍｍの銀スパッタリングシリコンチップを戴置後、窒素雰囲気下、２５０℃で６０分加熱し、銀メッキした銅リードフレームと銀スパッタリングしたシリコンチップが導電性接着剤硬化物により接合された銀接合体（以下、単に「銀接合体」ともいう）を作製した。
　得られた銀接合体の熱伝導率を表１に示す。
　なお、熱伝導率λ（Ｗ／ｍ・Ｋ）は、レーザーフラッシュ法熱定数測定装置（「ＴＣ－７０００」（商品名）、ＵＬＶＡＣ‐ＲＩＫＯ社製）を用いてＡＳＴＭ－Ｅ１４６１に準拠して熱拡散ａを測定し、ピクノメーター法により室温での比重ｄを算出し、また、示差走査熱量測定装置（「ＤＳＣ７０２０」（商品名）、セイコー電子工業社製）を用いてＪＩＳ－Ｋ７１２３　２０１２に準拠して室温での比熱Ｃｐを測定して、関係式λ＝ａ×ｄ×Ｃｐにより算出した。 B. Physical Property Evaluation The obtained conductive adhesive composition is applied to a 10 mm × 10 mm silver-plated copper lead frame, and a 5 mm × 5 mm silver sputtering silicon chip is placed on the coated surface, and then 60 at 250 ° C. in a nitrogen atmosphere. A silver bonded body (hereinafter, also simply referred to as a “silver bonded body”) was prepared by heating a silver lead-plated copper lead frame and a silver-sputtered silicon chip using a conductive adhesive cured product.
The thermal conductivity of the obtained silver bonded body is shown in Table 1.
The thermal conductivity λ (W / m · K) is measured in accordance with ASTM-E1461 using a laser flash method thermal constant measurement apparatus (“TC-7000” (trade name) manufactured by ULVAC-RIKO). Diffusion a is measured, specific gravity d at room temperature is calculated by the pycnometer method, and it conforms to JIS-K7123 2012 using a differential scanning calorimeter ("DSC 7020" (trade name), manufactured by Seiko Instruments Inc.) Then, the specific heat Cp at room temperature was measured and calculated by the relational expression λ = a × d × Cp.
　また、得られた銀接合体を用いて冷熱サイクル試験を行い、剥離面積を測定した。この試験では、基板を－５０℃に３０分間保持した後に１５０℃に３０分間保持する操作を１サイクルとして２０００サイクル繰返し、試験後のシリコンチップの剥離面積の割合を測定した。結果を表１に示す。
　なお、剥離面積の割合は、２０００サイクル後の超音波映像・検査装置「Ｆｉｎｅ　ＳＡＴ」（商品名）で得られた剥離状態の画像を二値化ソフト「ｉｍａｇｅ　Ｊ」で濃淡を白と黒の二階調に画像変換し、以下の関係式で求めた。
　剥離面積の割合（％）＝剥離面積（黒色画素数）÷チップ面積（黒色画素数＋白色画素数）×１００ Moreover, a thermal cycle test was performed using the obtained silver bonded body, and the peeling area was measured. In this test, the operation of holding the substrate at -50.degree. C. for 30 minutes and then holding it at 150.degree. C. for 30 minutes was repeated 2000 cycles as one cycle, and the ratio of the peeling area of the silicon chip after the test was measured. The results are shown in Table 1.
In addition, the ratio of the peeled area is the image in the peeled state obtained by the ultrasonic image and inspection apparatus “Fine SAT” (trade name) after 2000 cycles, and the gray level is white and black by the binarization software “image J”. The image was converted into two gradations, and the following relational expression was obtained.
Peeling area ratio (%) = Peeling area (number of black pixels) / chip area (number of black pixels + number of white pixels) × 100
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例で得られた銀接合体は、比較例で得られた銀接合体と比べて冷熱サイクル試験後の剥離面積が少なかった。
　この結果から、本発明の導電性接着剤組成物によれば、繰り返し温度変化を受けた場合にも被接着材料の剥離が生じにくい接着を達成できることが確認された。 As shown in Table 1, the silver bonded body obtained in the example had a smaller peeled area after the thermal cycle test compared to the silver bonded body obtained in the comparative example.
From this result, it was confirmed that the conductive adhesive composition of the present invention can achieve adhesion which is hard to cause peeling of the material to be adhered even when the temperature change is repeated.
　本発明を特定の態様を参照して詳細に説明したが、本発明の精神と範囲を離れることなく様々な変更および修正が可能であることは、当業者にとって明らかである。なお、本出願は、２０１７年７月１１日付けで出願された日本特許出願（特願２０１７－１３５２０３）に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。 Although the present invention has been described in detail with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application (Japanese Patent Application No. 2017-135203) filed on July 11, 2017, which is incorporated by reference in its entirety. Also, all references cited herein are taken as a whole.

Claims (8)

  1. 　２５℃において固体状の熱可塑性樹脂の粒子（Ａ）と、
    　導電性フィラー（Ｂ）と、
    　を含有する導電性接着剤組成物であって、
    　前記熱可塑性樹脂は、２５０℃以下の融点を有する脂肪族骨格を含むポリアミドである導電性接着剤組成物。     Particles of thermoplastic resin solid at 25 ° C. (A),
    Conductive filler (B),
    A conductive adhesive composition containing
    The conductive adhesive composition, wherein the thermoplastic resin is a polyamide including an aliphatic skeleton having a melting point of 250 ° C. or less.
  2. 　前記熱可塑性樹脂が、ナイロン１１、ナイロン１２及びナイロン６の少なくともいずれか一つを含有する請求項１に記載の導電性接着剤組成物。 The conductive adhesive composition according to claim 1, wherein the thermoplastic resin contains at least one of nylon 11, nylon 12 and nylon 6.
  3. 　前記熱可塑性樹脂の粒子（Ａ）の平均粒径が１～３０μｍである請求項１または２に記載の導電性接着剤組成物。 The conductive adhesive composition according to claim 1, wherein the average particle diameter of the particles (A) of the thermoplastic resin is 1 to 30 μm.
  4. 　前記導電性接着剤組成物の全体量に対して、前記熱可塑性樹脂の粒子（Ａ）を０．５～１０質量％の範囲で含有する請求項１～３のいずれか１項に記載の導電性接着剤組成物。 The conductive material according to any one of claims 1 to 3, which contains the particles (A) of the thermoplastic resin in a range of 0.5 to 10% by mass with respect to the total amount of the conductive adhesive composition. Adhesive composition.
  5. 　前記導電性フィラー（Ｂ）は、銀を含有する請求項１～４のいずれか１項に記載の導電性接着剤組成物。 The conductive adhesive composition according to any one of claims 1 to 4, wherein the conductive filler (B) contains silver.
  6. 　前記導電性接着剤組成物の全体量に対して、前記導電性フィラー（Ｂ）を８０～９５質量％の範囲で含有する請求項１～５のいずれか１項に記載の導電性接着剤組成物。 The conductive adhesive composition according to any one of claims 1 to 5, wherein the conductive filler (B) is contained in a range of 80 to 95% by mass with respect to the total amount of the conductive adhesive composition. object.
  7. 　請求項１～６のいずれか１項に記載の導電性接着剤組成物を硬化した、導電性接着剤硬化物。 A conductive adhesive cured product obtained by curing the conductive adhesive composition according to any one of claims 1 to 6.
  8. 　請求項１～６のいずれか１項に記載の導電性接着剤組成物を部品の接着に使用した電子機器。 An electronic device using the conductive adhesive composition according to any one of claims 1 to 6 for bonding parts.
PCT/JP2018/026103 2017-07-11 2018-07-10 Conductive adhesive composition WO2019013230A1 (en)

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KR20230009942A (en) 2020-05-18 2023-01-17 다나카 기킨조쿠 고교 가부시키가이샤 A conductive composition, a conductive sintered portion, and a member having a conductive sintered portion

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