WO2022009754A1 - Composition de liaison et procédé de formulation pour composition de liaison - Google Patents

Composition de liaison et procédé de formulation pour composition de liaison Download PDF

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Publication number
WO2022009754A1
WO2022009754A1 PCT/JP2021/024824 JP2021024824W WO2022009754A1 WO 2022009754 A1 WO2022009754 A1 WO 2022009754A1 JP 2021024824 W JP2021024824 W JP 2021024824W WO 2022009754 A1 WO2022009754 A1 WO 2022009754A1
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Prior art keywords
metal
metal particles
bonding composition
particles
bonding
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PCT/JP2021/024824
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English (en)
Japanese (ja)
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尚耶 中島
貴志 西脇
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バンドー化学株式会社
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Priority to JP2021539867A priority Critical patent/JP7025603B1/ja
Publication of WO2022009754A1 publication Critical patent/WO2022009754A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/08—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools with one or more parts not made from powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
    • H01L21/52—Mounting semiconductor bodies in containers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits

Definitions

  • the present invention relates to a bonding composition containing metal particles and a method for preparing the bonding composition.
  • a joining material has been used to mechanically, electrically and / or thermally join a metal part to another.
  • the bonding material include solder, a conductive adhesive, a silver paste, an anisotropic conductive film and the like. These joining materials may be used not only for joining metal parts to each other but also for joining metal parts to ceramic parts, resin parts and the like.
  • a bonding material may be used for bonding a light emitting element such as a light emitting diode (LED), a semiconductor chip, or the like to a substrate, or for further bonding these substrates to a heat radiating member.
  • LED light emitting diode
  • Patent Document 1 discloses a technique of low-temperature sintering (80 to 120 ° C.) using silver nanoparticles as a bonding material, which is coated with an organic substance having 6 or less carbon atoms and has an average primary particle size of 10 to 30 nm.
  • a bonding material in which the nanoparticles are coated with an organic substance having 6 or less carbon atoms and have an average primary particle size of 100 to 200 nm, and two kinds of solvents having different boiling points as dispersants. .. Then, it is described that the occurrence of drying unevenness at the center and the edge, which occurs in the plane of the bonding layer in the desolvation process of the pre-drying step, is reduced, and the heat shock resistance after bonding is enhanced.
  • Patent Document 2 discloses a bonding material composed of a silver paste in which silver fine particles and a solvent are mixed, in which the solvent is diol, triol is mixed as an additive, and dicarboxylic acid is mixed as a sintering accelerator. ing. It is described that the pre-dried film can be prevented from cracking or peeling off, and the non-bonded materials can be satisfactorily bonded to each other even through the protrusions of the pre-dried film.
  • Patent Document 3 has an average particle size of 20 to 100 nm for the purpose of providing a bonding composition which can be bonded even at a relatively low temperature without pressurization and can obtain excellent bonding strength.
  • a bonding material that can be sintered at a relatively low firing temperature (less than 300 ° C.) is disclosed.
  • Patent Documents 1 to 3 disclose metal pastes and the like containing silver nanoparticles and disclose that they can be sintered at a relatively low temperature, the solvent and particles in the bonding material are separated and coated. No description was given regarding stability, and there was room for further study in order to achieve high bonding strength and coating stability.
  • the present invention has been made in view of the above problems, and the solvent and particles in the bonding composition are not separated from each other, have excellent coating stability, and are sintered at a relatively low temperature (200 ° C. or lower). It is an object of the present invention to provide a bonding composition capable of obtaining high bonding strength.
  • the present inventors have focused on the fact that in order to exhibit excellent bonding strength, it is important to exhibit excellent coating stability without separating the solvent and particles of the bonding composition, and the metal.
  • the type and viscosity of the organic substance that coats the particles By setting the type and viscosity of the organic substance that coats the particles to a specific range, the solvent in the bonding composition and the metal particles do not separate from each other, and the coating stability is excellent.
  • sufficient bonding strength can be obtained even when used for bonding elements, semiconductor chips, etc., and completed the present invention.
  • the present invention comprises a first metal particle whose surface is coated with an amine having a polar group and having an average particle size of 20 to 100 nm, a second metal particle having an average particle size of 200 to 500 nm, and a dispersion medium.
  • the bonding composition containing the above and the polymer dispersant, the weight ratio of the first metal particles to the second metal particles is 20:80 to 80:20, and the solid content concentration.
  • the dispersion medium is 90% by weight or more, contains a diol, and has a viscosity at 25 ° C. of 100 to 300 mPa ⁇ s.
  • the surface of the second metal particle is preferably coated with an amine having a polar group.
  • the dispersion medium is at least one selected from the group consisting of 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, and 3-methyl-1,3-butanediol. It is preferable to have.
  • the amine is preferably an alkoxyamine.
  • the present invention comprises a first metal particle whose surface is coated with an amine having a polar group and having an average particle size of 20 to 100 nm, a second metal particle having an average particle size of 200 to 500 nm, and a dispersion medium.
  • a step of preparing a bonding composition by mixing with a polymer dispersant, and the first metal particles so that the solid content concentration in the bonding composition is 90% by weight or more.
  • the second metal particles were blended so as to have a weight ratio of 20:80 to 80:20, the dispersion medium contained a sol, and the viscosity at 25 ° C. was adjusted to 100 to 300 mPa ⁇ s. It is also a method for preparing a bonding composition, which is characterized by being a thing.
  • the solvent and particles in the bonding composition do not separate from each other, and the bonding composition is excellent in coating stability, sintered at a relatively low temperature (200 ° C. or lower), and obtains high bonding strength.
  • a product and a method for preparing the product can be provided. Further, by using such a bonding composition, it is possible to prevent electrical short circuits and contamination of peripheral members of the bonding portion, and it is possible to extend the life of a light emitting element such as an LED.
  • the bonding composition of the present invention comprises a first metal particle whose surface is coated with an amine having a polar group and having an average particle size of 20 to 100 nm, and a second metal particle having an average particle size of 200 to 500 nm.
  • the solid content concentration is 90% by weight or more, the dispersion medium contains a diol, and the viscosity at 25 ° C. is 100 to 300 mPa ⁇ s.
  • the average particle size of the first metal particles is 20 to 100 nm.
  • the bonding composition can sinter metal particles with each other even at a firing temperature exceeding 200 ° C., but by setting the average particle size of the first metal particles to 20 to 100 nm, a melting point drop occurs.
  • the metal particles can be sintered together even at a relatively low temperature (for example, 200 ° C. or lower, preferably about 150 ° C.).
  • the dispersibility of the first metal particles in the bonding composition can be made difficult to change with time.
  • the average particle size of the first metal particles is less than 20 nm, the viscosity of the bonding composition becomes high due to the large surface area of the first metal particles, and the handleability deteriorates.
  • the average particle size of the first metal particles exceeds 100 nm, it becomes difficult for the melting point to drop, and it becomes difficult for the metal particles to sinter with each other at a relatively low temperature.
  • the preferred lower limit of the average particle size of the first metal particles is 25 nm, and the preferred upper limit is 80 nm.
  • the "average particle size” is the primary average particle size of metal particles and means the number average particle size.
  • the number average particle size for example, an image obtained by using a scanning electron microscope (SEM) (for example, S-4800 type manufactured by Hitachi, Ltd.) is used with image processing software (for example, MITANI CORPORATION, WinROOF). It can be calculated using.
  • SEM scanning electron microscope
  • image processing software for example, MITANI CORPORATION, WinROOF. It can be calculated using.
  • the particle size of the metal particles can also be measured by a dynamic light scattering method, a small-angle X-ray scattering method, or a wide-angle X-ray diffraction method.
  • the bonding composition further contains a second metal particle having an average particle size of 200 to 500 nm.
  • the second metal particles having an average particle size of 200 to 500 nm in combination, the solid content concentration in the bonding composition can be increased, and the first metal particles and the second metal particles and the dispersion medium can be increased. Separation from (containing a diol and having a viscosity at 25 ° C. of 100 to 300 mPa ⁇ s) can be reduced. Further, it is possible to suppress the volume shrinkage at the time of firing, to prevent cracks from occurring, and to obtain a sintered body having a higher density. If the average particle size of the second metal particles is less than 200 nm, the volume shrinkage during firing may not be sufficiently suppressed.
  • the average particle size of the second metal particles exceeds 500 nm, when the bonding composition of the present embodiment is sandwiched between the members to be bonded, gaps are generated by the metal particles having a large particle size, and the bonding strength is increased. May decrease.
  • the more preferable lower limit of the average particle size of the second metal particles is 250 nm, and the more preferable upper limit is 400 nm.
  • the average particle size of the second metal particles can be measured by the same method as the average particle size of the first metal particles described above.
  • the surface of the first metal particles is coated with an amine having a polar group.
  • the amine is a component that binds to at least a part of the surface of the first metal particle to form a colloid.
  • the amine does not have to cover the entire surface of the first metal particles, but may cover at least a part of the surface of the first metal particles to such an extent that colloids can be formed.
  • the first metal particles are coated with an amine having a polar group, the dispersion stability of the first metal particles is improved, aggregation is prevented, and when the amine remains at the time of firing, the metal particles It is possible to inhibit the fusion of each other.
  • the amine evaporates or decomposes during firing and separates from the surface of the first metal particles.
  • the polar group is an atomic group containing an oxygen atom or a nitrogen atom having a high electronegativity, and is a polar group such as an alkoxy group (RO-), a hydroxyl group (-OH), or a carboxyl group (-COOH).
  • RO- alkoxy group
  • -OH hydroxyl group
  • -COOH carboxyl group
  • Hydrogen bonds are formed between molecules having polar groups. Therefore, when the first metal particles whose surface is coated with an amine having a polar group and a diol (which has two hydroxyl groups in the molecule) are mixed, the first metal particles in the amine which coats the surface of the first metal particles are mixed. A hydrogen bond is formed between the polar group and the diol, and the separation of the first metal particles and the dispersion medium can be suppressed.
  • the number of nitrogen atoms derived from the amine is preferably equal to or greater than the number of functional groups other than the amine.
  • the above amines may be used alone or in combination of two or more.
  • the surface of the second metal particles may be at least partially coated with an organic protective component such as an amine, and the organic protective component is not particularly limited, but is an amine having a polar group like the first metal particles. It is preferable that the surface is covered.
  • an organic protective component such as an amine
  • the organic protective component is not particularly limited, but is an amine having a polar group like the first metal particles. It is preferable that the surface is covered.
  • the amine having the polar group preferably contains at least one kind of amine having a boiling point of 150 ° C. or lower.
  • the object to be bonded is a light emitting element such as an LED
  • firing at a relatively low temperature for example, 200 ° C. or lower
  • the boiling point of the amine exceeds 150 ° C.
  • the bonding composition is heated at a relatively low temperature (for example, 200 ° C. or lower).
  • the organic protective component amine having a polar group
  • the metal particles may not be sufficiently sintered. ..
  • the amine may be chemically or physically bonded to the metal particles, or may be changed to an anion or a cation.
  • the amine is an ion derived from the amine. It can also be in the state of a complex or the like.
  • the amine having a polar group having a boiling point of 150 ° C. or lower may be linear or branched, or may have a side chain.
  • alkoxyamine is preferable, and 3-methoxypropylamine and / or 3-ethoxypropylamine are more preferable.
  • the surface of the second metal particles may be coated with the same organic protective component as the amine having a polar group that coats the surface of the first metal particles.
  • the organic protective component that coats the surface of the second metal particle may be the same as or different from the amine having a polar group that coats the surface of the first metal particle.
  • the amine that coats the surface of the second metal particle is also described above.
  • the amine covering the second metal particles may be linear or branched, and may have a side chain.
  • the amine content in the bonding composition is preferably 0.1 to 15% by weight.
  • the amine content in the bonding composition is the total value of the amount of amine having a polar group covering the surface of the first metal particle and the amount of amine covering the surface of the second metal particle. Is.
  • the content of the organic protective component in the bonding composition is 0.1% by weight or more, the conductivity of the obtained bonding composition tends to be improved, and when it is 15% by weight or less, the bonding composition tends to be improved. Dispersion stability tends to be good.
  • a more preferable lower limit of the content of the organic protective component is 0.2% by weight, a more preferable upper limit is 5% by weight, a further preferable lower limit is 0.3% by weight, and a further preferable upper limit is 4% by weight.
  • the content of the organic protective component can be measured by thermogravimetric analysis.
  • the first metal particles and the second metal particles are not particularly limited, and are, for example, gold, silver, copper, nickel, bismuth, tin and platinum group elements (ruthenium, rhodium, palladium, osmium, iridium). And platinum), at least one of them.
  • the metal is preferably particles of at least one metal selected from the group consisting of gold, silver, copper, nickel, bismuth, tin or platinum group elements, and further has an ionization tendency higher than that of copper or copper. Is preferably a small (precious) metal, i.e., at least one of gold, platinum, silver and copper. These metals may be used alone or in combination of two or more. As a method of using these metals in combination, alloy particles containing a plurality of metals may be used, or a metal having a core-shell structure or a multilayer structure may be used. Particles may be used.
  • the conductivity of the sintered body (sintered layer) formed by using the bonding composition of the present embodiment is good.
  • silver fine particles in combination with particles made of other metals migration can be made less likely to occur.
  • the "other metal” a metal whose ionization series is noble than hydrogen, that is, gold, copper, platinum, and palladium is preferable.
  • the same kind of metal particle as the metal particle exemplified in the first metal particle can be used.
  • the metal constituting the second metal particle may be the same as or different from the first metal particle.
  • the weight ratio of the first metal particles to the second metal particles is 20:80 to 80:20.
  • the bonding strength can be further improved while achieving low-temperature sinterability.
  • the weight of the first metal particles is less than 20 parts by weight with respect to 80 parts by weight of the second metal particles, the first metal particles having an average particle size of 20 to 100 nm in the bonding composition.
  • the ratio of metal particles becomes low, and it may be difficult for metal particles to sinter with each other at a relatively low temperature.
  • the weight of the first metal particles exceeds 80 parts by weight with respect to 20 parts by weight of the second metal particles, the volume shrinkage during firing becomes large and cracks are likely to occur in the sintered body. , The bonding strength tends to decrease.
  • a more preferable weight ratio between the first metal particles and the second metal particles is 30:70 to 60:40.
  • the weight of the second metal particles is larger than the weight of the first metal particles, the fluidity of the bonding composition is lowered and the handleability is lowered, but the weight reduction rate tends to be lowered.
  • the weight ratio between the first metal particles and the second metal particles can be determined in consideration of the balance between the handleability and the weight reduction rate.
  • the bonding composition has a solid content concentration of 90% by weight or more.
  • the solid content concentration is less than 90% by weight, the content of the metal particles in the bonding composition is low, so that the density of the sintered body is low, and there is a possibility that sufficient bonding strength cannot be obtained. ..
  • the bonding composition contains a dispersion medium, and the dispersion medium contains a diol and has a viscosity at 25 ° C. of 100 to 300 mPa ⁇ s.
  • the dispersion medium contains a diol and has a viscosity at 25 ° C. of 100 to 300 mPa ⁇ s.
  • the concentration of the dispersion medium with respect to the entire bonding composition is 1.0% by weight or more and 8.5% by weight or less. If the concentration of the dispersion medium is less than 1.0% by weight, the shear viscosity of the bonding composition is too high, so that it is difficult to handle and it becomes difficult to apply it to the member to be bonded. On the other hand, when the concentration of the dispersion medium exceeds 8.5% by weight, the fluid density in the bonding composition increases and the sedimentation rate of the metal particles increases, so that the dispersion medium and the metal in the bonding composition increase. Separation from the particles is not effectively prevented and the coating stability may be reduced. Further, since the content of the metal particles in the bonding composition is reduced, the density of the sintered body is reduced, and there is a possibility that sufficient bonding strength cannot be obtained.
  • the dispersion medium may have a viscosity at 25 ° C. of 100 to 300 mPa ⁇ s, and various diols can be used. Specifically, the dispersion medium is selected from the group consisting of 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, and 3-methyl-1,3-butanediol. It is preferable to contain at least one kind.
  • the viscosity at 25 ° C. is a value obtained by measuring a dispersion medium at 25 ° C. with a vibration viscometer.
  • the vibration type viscometer for example, VM-10A manufactured by SEKONIC Corporation can be used, and the measurement may be performed by immersing the liquid (dispersion medium) in the vibrator.
  • the concentration of the diol with respect to the entire bonding composition is preferably 2% by weight or more and 8% by weight or less.
  • the concentration of the above diol is a value derived from the content of all the diols when two or more kinds of diols are contained in the bonding composition. This is because when the concentration of the diol with respect to the entire bonding composition is within the above-mentioned specific range, the separation of the metal particles and the solvent can be effectively prevented, and the coating stability of the bonding composition is improved. ..
  • the dispersion medium has an isotridecanol and a 2,2,4-trimethylpentane-1,3-diol monoisobutyrate (so that the viscosity at 25 ° C. is 100 to 300 mPa ⁇ s). It may contain a compound such as (alias: texanol).
  • the dispersion medium preferably contains a diol and / or 2,2,4-trimethylpentane-1,3-diol monoisobutyrate (also known as texanol).
  • the dispersion medium is a mixture of diol and isotridecanol and / or 2,2,4-trimethylpentane-1,3-diol monoisobutyrate (also known as texanol). It is preferable that the viscosity at ° C. is adjusted to 100 to 300 mPa ⁇ s.
  • the bonding composition of the present embodiment further contains a polymer dispersant. This makes it possible to improve the dispersibility of the metal particles. Further, by adsorbing the polymer dispersant on the particle surface of the first metal particles and / or the second metal particles, the metal particles and the dispersion medium can be uniformly mixed, and the metal particles and the dispersion medium (sol) can be further mixed. Including, the viscosity at 25 ° C. is 100 to 300 mPa ⁇ s) can be prevented from separating.
  • polymer dispersant commercially available ones can also be used.
  • examples of the above-mentioned commercially available products include SOLSPERSE 11200, SOLSPERS 13940, SOLSPERS 16000, SOLSPERS 17000, SOLSPERS 18000, SOLSPERS 20000, SOLSPERS 21000, SOLSPERS 24000, SOLSPARES 26000, SOLSPERS 27000, and SOLSPARS 28000 (Japan Lubrizol Co., Ltd.).
  • Disperbic 142 Disparbic 160, Disparbic 161, Disperbic 162, Disparbic 163, Disparbic 166, Disparbic 170, Disparbic 180, Disparbic 182, Disparbic 184, Disperbic 190, Disperbic 2155 (manufactured by BIC Chemie Japan Co., Ltd.); EFKA-46, EFKA-47, EFKA-48, EFKA-49 (manufactured by EFKA Chemical Co., Ltd.); Polymer 100, Polymer 120, Polymer 150, Polymer 400 , Polymer 401, Polymer 402, Polymer 403, Polymer 450, Polymer 451, Polymer 452, Polymer 453 (manufactured by EFKA Chemical Co., Ltd.); Examples thereof include Floren DOPA-22, Floren DOPA-17, Floren TG-730W, Floren G-700, and Floren TG-720W (manufactured by Kyoeisha Chemical Industry Co., Ltd.
  • the polymer dispersant is preferably Solsparse 11200, Solsporce 13940, Solsporce 16000, Solsporce 17000, Solsporce 18000, Solsperse 21000, Solsperse 28000, Disperbic 118 or Disperbic 190.
  • the content of the polymer dispersant in the bonding composition is preferably 0.01 to 15% by weight.
  • the content of the polymer dispersant is 0.01% by weight or more, the dispersion stability of the obtained bonding composition tends to be improved, and when it is 15% by weight or less, the conductivity of the bonding composition tends to be improved. Tends to improve sex.
  • the more preferable lower limit of the polymer dispersant is 0.1% by weight, the more preferable upper limit is 5% by weight, the further preferable lower limit is 0.2% by weight, and the further preferable upper limit is 4% by weight.
  • the bonding composition of the present embodiment imparts functions such as appropriate viscosity, adhesion, drying property, and printability according to the purpose of use, as long as the effects of the present invention are not impaired. Therefore, for example, an oligomer component that acts as a binder, a resin component, an organic solvent (a part of the solid content may be dissolved or dispersed), a surfactant, a thickener, a surface tension adjuster, or the like. Any component may be added.
  • the optional component is not particularly limited.
  • the resin component examples include polyester resins, polyurethane resins such as blocked isocyanate, polyacrylate resins, polyacrylamide resins, polyether resins, melamine resins, terpene resins and the like. These may be used alone or in combination of two or more.
  • organic solvent examples include those listed as the above dispersion media, such as methyl alcohol, ethyl alcohol, n-propyl alcohol, 2-propyl alcohol, 1,2,6-hexanetriol and 1-ethoxy-2.
  • examples thereof include polypropylene glycol, N, N-dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, glycerin, acetone, etc., which are in the range of 300 or more and 1,000 or less, respectively. It may be used alone or in combination of two or more.
  • the thickener examples include clay minerals such as clay, bentonite or hectrite, for example, emulsions such as polyester emulsion resin, acrylic emulsion resin, polyurethane emulsion resin or blocked isocyanate, methyl cellulose, carboxymethyl cellulose and hydroxy.
  • emulsions such as polyester emulsion resin, acrylic emulsion resin, polyurethane emulsion resin or blocked isocyanate, methyl cellulose, carboxymethyl cellulose and hydroxy.
  • Cellulose derivatives such as ethyl cellulose, hydroxypropyl cellulose and hydroxypropylmethyl cellulose, polysaccharides such as xanthan gum and guar gum can be mentioned, and these may be used alone or in combination of two or more.
  • the surfactant is not particularly limited, and any of anionic surfactant, cationic surfactant, and nonionic surfactant can be used, for example, alkylbenzene sulfonate, quaternary ammonium salt, and the like. Can be mentioned.
  • a fluorosurfactant is preferable because the effect can be obtained with a small amount of addition.
  • the first metal particles are preferably present as metal colloidal particles.
  • the metal colloidal particles formed by adhering amine to a part of the surface of the first metal particles, the first metal particles as a core, and the surface thereof is a polar group.
  • examples thereof include metal colloidal particles coated with an amine having the above, metal colloidal particles composed of a mixture thereof, and the like, but the present invention is not particularly limited.
  • metal colloidal particles having the first metal particle as a core and the surface thereof being coated with an amine having a polar group are preferable.
  • the second metal particles also exist as metal colloidal particles having the second metal particles as a core and whose surface is coated with an amine having a polar group.
  • the shear viscosity of the bonding composition may be appropriately adjusted within a range that does not impair the effects of the present invention, but the shear viscosity at 25 ° C. is preferably 15 to 120 Pa ⁇ S at a shear rate of 10s-1. Within the above range, for example, it can be suitably used for joining a light emitting element such as an LED, a semiconductor chip, or the like to a substrate, or further joining these substrates to a heat radiating member.
  • the more preferable lower limit of the shear viscosity is 25 Pa ⁇ S, and the more preferable upper limit is 100 Pa ⁇ S.
  • the shear viscosity is adjusted by adjusting the particle size of the metal particles, adjusting the content of organic substances, adjusting the amount of dispersion medium and other components added, adjusting the mixing ratio of each component, adding a thickener, and the like. Can be done.
  • the shear viscosity can be measured with a cone plate type viscometer (for example, a rheometer MCR301 manufactured by Anton Pearl Co., Ltd.).
  • the joining strength is preferably 20 to 150 MPa.
  • the bonding strength is 20 to 150 MPa, it can be suitably used for bonding a light emitting element such as an LED, a semiconductor chip or the like to a substrate, or bonding the substrate to a heat radiating member.
  • the more preferable lower limit of the bonding strength is 30 MPa, and the more preferable lower limit is 50 MPa.
  • the bonding strength is determined by applying a bonding composition to one of the members to be bonded, attaching the other member to be bonded, and then firing the laminated body obtained by, for example, a bond tester (manufactured by Reska). It can be evaluated by performing a bonding strength test using.
  • the bonding composition of this embodiment has excellent heat cycle reliability. Since the heat cycle reliability is good, it can be suitably used for joining light emitting elements such as LEDs and semiconductor chips in the manufacture of devices having a high drive temperature.
  • the heat cycle reliability is, for example, 500 cycles in which one cycle is to hold a laminate obtained by sintering a bonding composition and a member to be bonded at -40 ° C and 150 ° C for 10 minutes each in an atmospheric atmosphere. It can be evaluated by performing the heat cycle test of.
  • the heat cycle test can be performed using, for example, a thermal shock tester (manufactured by Hutec).
  • the rate of decrease in the bonding strength of the laminated body after the heat cycle test with respect to the initial strength of the laminated body is preferably less than 20%, more preferably less than 5%.
  • the method for preparing a bonding composition which is one of the embodiments of the present invention, has a first metal particle whose surface is coated with an amine having a polar group and an average particle size of 20 to 100 nm, and a polar group.
  • a step of preparing a bonding composition by mixing a second metal particle coated with amine and having an average particle size of 200 to 500 nm, a dispersion medium, and a polymer dispersant is provided, and is used for bonding.
  • the first metal particles and the second metal particles are blended so that the weight ratio of the first metal particles is 20:80 to 80:20 so that the solid content concentration in the composition is 90% by weight or more.
  • the dispersion medium contains a sol and is characterized in that the viscosity at 25 ° C. is adjusted to 100 to 300 mPa ⁇ s.
  • metal particles metal colloidal particles coated with "amine having a polar group" as a main component are prepared.
  • the amount of "amine having a polar group” and the weight reduction rate are not particularly limited, but it is convenient to adjust by heating. This may be done by adjusting the amount of "amine having a polar group” added when producing the metal particles.
  • the cleaning conditions and the number of times after adjusting the metal particles may be changed.
  • heating can be performed in an oven, an evaporator or the like.
  • the heating temperature may be in the range of about 50 to 300 ° C., and the heating time may be several minutes to several hours.
  • Heating may be performed under reduced pressure. By heating under reduced pressure, the amount of organic matter can be adjusted at a lower temperature. When it is carried out under normal pressure, it can be carried out in the atmosphere or in an inert atmosphere.
  • amines can be added later for fine adjustment of the organic content.
  • the method for preparing the metal particles coated with the "amine having a polar group" of the present embodiment is not particularly limited, but for example, a dispersion liquid containing the metal particles is prepared, and then the dispersion liquid is washed.
  • the method and the like can be mentioned.
  • a step of preparing a dispersion liquid containing metal particles for example, a metal salt (or a metal ion) dissolved in a solvent may be reduced as described below, and the reduction procedure is based on a chemical reduction method. The procedure may be adopted. Further, the metal amine complex method can also be used (details will be described later).
  • the metal particles coated with the "amine having a polar group" as described above include the metal salt of the metal constituting the metal particles, the "amine having a polar group", the polymer dispersant, and the dispersion. It can be prepared by reducing the raw material liquid containing the medium. In addition, a part of the components of the raw material liquid may not be dissolved but dispersed, or may contain water.
  • metal colloidal particles in which "amines with polar groups" are attached to at least a portion of the surface of the metal particles.
  • the metal colloidal particles can also be obtained as a bonding composition composed of a metal colloidal dispersion liquid by adding them to a dispersion medium in a step described later.
  • various known metal salts or hydrates thereof can be used, for example, silver nitrate, silver sulfate, silver chloride, oxidation.
  • Silver salts such as silver, silver acetate, silver oxalate, silver formate, silver nitrite, silver chlorate, silver sulfide; for example, gold salts such as gold chloride acid, potassium gold chloride, sodium gold chloride; for example, platinum chloride acid, Platinum salts such as platinum chloride, platinum oxide, potassium platinum chloride and the like; for example, palladium salts such as palladium nitrate, palladium acetate, palladium chloride, palladium oxide, palladium sulfate and the like, which can be dissolved in a suitable dispersion medium. , And is not particularly limited as long as it can be reduced. In addition, these may be used alone or in combination of two or more.
  • the method for reducing these metal salts in the raw material liquid is not particularly limited, and examples thereof include a method using a reducing agent, a method of irradiating light such as ultraviolet rays, an electron beam, ultrasonic waves, or heat energy. Of these, a method using a reducing agent is preferable from the viewpoint of ease of operation.
  • the reducing agent examples include amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone and hydrazine; for example, hydrogen compounds such as sodium boron hydride, hydrogen iodide and hydrogen gas; for example, carbon monoxide. , Oxides such as sulfite; for example, ferrous sulfate, iron oxide, iron fumarate, iron lactate, iron oxalate, iron sulfide, tin acetate, tin chloride, tin diphosphate, tin oxalate, tin oxide, sulfate.
  • amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone and hydrazine
  • hydrogen compounds such as sodium boron hydride, hydrogen iodide and hydrogen gas
  • carbon monoxide for example, carbon monoxide.
  • Oxides such as sulfite; for example, ferrous
  • Low valence metal salts such as tin; for example, sugars such as ethylene glycol, glycerin, formaldehyde, hydroquinone, pyrogallol, tannin, tannic acid, salicylic acid, D-glucose, etc. may be mentioned. It is not particularly limited as long as it can be reduced. When the above reducing agent is used, light and / or heat may be applied to accelerate the reduction reaction.
  • the metal salt As a specific method for preparing metal particles coated with the "amine having a polar group" by using the metal salt, the "amine having a polar group", a dispersion solvent and a reducing agent, for example, the metal salt is used.
  • the dispersion liquid containing the metal particles coated with the "amine having a polar group" obtained as described above in addition to the metal particles, the counter ion of the metal salt, the residue of the reducing agent and the dispersant are present. Therefore, the electrolyte concentration and organic substance concentration of the entire liquid tend to be high. Since the liquid in such a state has high conductivity, coagulation of metal particles occurs and it is easy to precipitate. Alternatively, even if it does not precipitate, if the counterion of the metal salt, the residue of the reducing agent, or the excess dispersant in excess of the amount required for dispersion remains, the conductivity may be deteriorated. Therefore, by washing the solution containing the metal particles to remove the excess residue, the metal particles coated with the organic substance can be surely obtained.
  • a dispersion liquid containing metal particles coated with "amine having a polar group” is allowed to stand for a certain period of time, the generated supernatant liquid is removed, and then alcohol (methanol, etc.) is added.
  • alcohol methanol, etc.
  • the metal particles coated with the "amine having a polar group" used in the present embodiment can be obtained.
  • the bonding composition of the present embodiment contains the metal particles coated with the "amine having a polar group" obtained above and the dispersion medium described in the above embodiment (containing a diol and having a viscosity at 25 ° C. of 100 to 100. (300 mPa ⁇ s) and is obtained by mixing.
  • the mixing method of the metal particles coated with the "amine having a polar group" and the dispersion medium is not particularly limited, and can be carried out by a conventionally known method using a stirrer, a stirrer or the like. An ultrasonic homogenizer with an appropriate output may be applied by stirring with a spatula or the like.
  • the production method thereof is not particularly limited.
  • a metal colloidal dispersion composed of silver and other metals the above-mentioned organic substance (In the preparation of metal particles coated with an amine having a polar group), a dispersion containing the metal particles and a dispersion containing other metal particles may be separately produced and then mixed, or may be mixed with a silver ion solution. It may be mixed with other metal ion solutions and then reduced.
  • the above metal amine complex method for example, in the first step of mixing an amine solution containing an amine having a polar group with a metal compound containing a metal atom to produce a complex compound containing the metal compound and the amine.
  • the metal particles may be produced by the second step of decomposing the complex compound to generate metal particles by heating.
  • a complex compound produced from a metal compound such as silver oxalate containing silver and an amine having a polar group is heated in the presence of an amine having a polar group to obtain oxalate ions and the like contained in the complex compound.
  • a metal compound such as silver oxalate containing silver and an amine having a polar group
  • an amine having a polar group By aggregating the atomic silver produced by decomposing a metal compound, silver particles protected by a protective film of an amine having a polar group can be produced.
  • the metal amine complex decomposition method for producing metal particles coated with an amine having a polar group by thermally decomposing the complex compound of the metal compound in the presence of an amine having a polar group a single species is used. Since the atomic metal is generated by the decomposition reaction of the metal amine complex which is the molecule of the above, it is possible to uniformly generate the atomic metal in the reaction system, and when the metal atom is generated by the reaction between a plurality of components. In comparison with, the non-uniformity of the reaction caused by the composition fluctuation of the components constituting the reaction is suppressed, which is particularly advantageous in producing a large amount of metal powder on an industrial scale.
  • an amine molecule having a polar group is coordinated to the generated metal atom, and aggregation is caused by the action of the amine molecule having a polar group coordinated to the metal atom. It is presumed that the movement of metal atoms is controlled. As a result, according to the metal amine complex decomposition method, it becomes possible to produce metal particles having a very fine particle size distribution.
  • amine molecules having a large number of polar groups also form coordination bonds with relatively weak force on the surface of the produced metal fine particles, and these form a dense protective film on the surface of the metal particles, so that they are preserved. It is possible to produce coated metal particles having a clean surface with excellent stability. Further, among the amines having polar groups forming the film, the alkoxyamine molecules can be easily desorbed by heating or the like, so that metal particles that can be sintered at a relatively low temperature (200 ° C. or lower) should be produced. Is possible.
  • the bonding composition of the present embodiment containing the metal particles coated with the amine having a polar group obtained as described above contains the metal particles and a dispersion medium (containing a diol and having a viscosity at 25 ° C. of 100 to 300 mPa. It is possible to add various inorganic components and organic components as long as the separation from (s) is prevented and the coating stability is not impaired. It was
  • the metal particles coated with the "amine having a polar group” described above When preparing the second metal particles whose surface is coated with an organic protective component different from the "amine having a polar group", the metal particles coated with the "amine having a polar group" described above.
  • the surface of the second metal particle is coated with an organic protective component different from that of the first metal particle by using a desired organic protective component instead of the "amine having a polar group”.
  • Metal particles can be prepared.
  • a joining step of firing and joining the bonding composition applied between them at a desired temperature for example, 200 ° C. or lower, preferably about 150 ° C.
  • the first bonded member and the second bonded member are bonded. It can be joined to a member.
  • this joining step it is possible to apply pressure in the direction in which the first member to be joined and the second member to be joined face each other, but it is also possible to obtain sufficient joining strength without particularly pressing. This is one of the advantages of the present invention. Further, when firing, the temperature can be raised or lowered step by step. It is also possible to apply a surfactant, a surface activator, or the like to the surface of the member to be joined in advance.
  • the present inventor has obtained that if the above-mentioned bonding composition of the present embodiment is used as the bonding composition in the bonding composition coating step, the dispersion medium and the metal are used in the bonding composition. It has been found that separation from particles is prevented, coating stability is high, and the first member to be bonded and the second member to be bonded can be more reliably bonded with high bonding strength (a bonded body can be obtained). ..
  • the "coating" of the bonding composition of the present embodiment is a concept including both the case where the bonding composition is applied in a planar shape and the case where the bonding composition is applied (drawn) in a linear shape.
  • the shape of the coating film made of the bonding composition in a state before being applied and fired by heating can be a desired shape. Therefore, in the bonded body of the present embodiment after firing by heating, the bonding composition is a concept including both a planar bonding layer and a linear bonding layer, and these planar bonding layers and linear bonding layers are included.
  • the bonding layer may be continuous or discontinuous, and may include continuous portions and discontinuous portions.
  • the first member to be joined and the second member to be joined that can be used in the present embodiment are particularly limited as long as they can be joined by applying a bonding composition and firing by heating. However, it is preferable that the member has heat resistance to the extent that it is not damaged by the temperature at the time of joining.
  • Examples of the material constituting such a member to be joined include polyamide (PA), polyimide (PI), polyamideimide (PAI), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene naphthalate (PEN).
  • Examples thereof include polyester, polycarbonate (PC), polyether sulfone (PES), vinyl resin, fluororesin, liquid crystal polymer, ceramics, glass, metal and the like, and among them, a metal bonded member is preferable.
  • the metal bonded member is preferable because it has excellent heat resistance and has an excellent affinity with the metal bonding composition of the present invention in which the inorganic particles are metal.
  • the member to be joined may have various shapes such as a plate shape or a strip shape, and may be rigid or flexible.
  • the thickness of the base material can also be appropriately selected.
  • a member having a surface layer formed therein or a member having undergone a surface treatment such as a hydrophilization treatment may be used.
  • first and second members to be joined examples include a resin substrate, a metal plate, a light emitting element such as an LED, a semiconductor chip, and a ceramic substrate on which an electronic circuit is formed. Since the bonding composition of the present embodiment has high bonding strength of the obtained sintered body, it can be suitably used for bonding a light emitting element such as an LED, a semiconductor chip, or the like with a metal substrate, a ceramic substrate, or the like. ..
  • Various methods can be used as the step of applying the bonding composition to the first and second members to be bonded, for example, dipping, screen printing, spraying, bar coating, spin coating, and inkjet.
  • the bonding composition of the present embodiment has a high solid content concentration, and therefore can be suitably used for a dispenser type, pin transfer, and stencil printing.
  • the coated film after being applied as described above can be fired by heating to a temperature of, for example, 200 ° C. or lower within a range that does not damage the member to be joined, to obtain the bonded body of the present embodiment.
  • a bonding layer having high coating stability and excellent adhesion to the member to be bonded can be obtained and is strong. Bonding strength can be obtained more reliably.
  • the binder component when the bonding composition contains a binder component, the binder component is also sintered from the viewpoint of improving the strength of the bonding layer and the bonding strength between the members to be bonded, but in some cases, the binder component is also sintered. May remove all the binder components by controlling the firing conditions, with the main purpose of adjusting the viscosity of the bonding composition for application to various printing methods.
  • the method for performing the firing is not particularly limited, and the temperature of the bonding composition coated or drawn on the member to be bonded using, for example, a conventionally known oven is set to, for example, 200 ° C. or lower. It can be joined by firing.
  • the lower limit of the firing temperature is not always limited, and it is preferable that the temperature is such that the members to be bonded can be bonded to each other and the effect of the present invention is not impaired.
  • the bonding composition after firing it is preferable that the residual amount of the organic substance is small in terms of obtaining the bonding strength as high as possible, but a part of the organic substance remains as long as the effect of the present invention is not impaired. It doesn't matter if you do.
  • the bonding composition of the present invention contains an organic substance, it does not obtain the bonding strength after firing by the action of the organic substance, unlike the conventional one using thermosetting such as an epoxy resin. As described above, sufficient bonding strength can be obtained by fusing the fused metal particles. Therefore, even if the organic matter that remains after being placed in a usage environment higher than the joining temperature deteriorates, decomposes, or disappears after joining, there is no risk of the joining strength decreasing, and therefore the heat resistance is excellent. There is.
  • the bonding composition of the present embodiment it is possible to realize a bonding having a bonding layer that exhibits high conductivity even by firing by heating at a low temperature of 200 ° C. or lower, so that the members to be bonded that are relatively weak to heat can be realized. Can be joined.
  • the firing time is not particularly limited, and any firing time may be used as long as it can be bonded according to the firing temperature.
  • the surface treatment of the bonded member may be performed.
  • the surface treatment method include a method of performing a dry treatment such as corona treatment, plasma treatment, UV treatment, and electron beam treatment, and a method of providing a primer layer and a conductive paste receiving layer on a substrate in advance.
  • the present invention is not limited to these.
  • the metal colloid dispersion using metal particles as inorganic particles has been described.
  • tin-doped indium oxide and alumina which are excellent in conductivity, thermal conductivity, dielectric property, ionic conductivity, etc.
  • Inorganic particles such as barium titanate and lithium iron phosphate can also be used.
  • the arithmetic mean primary particle size of the metal fine particles A1 was 50 nm, and the standard deviation was 14.2 nm.
  • the coefficient of variation obtained by the following equation (1) was 28.4%.
  • Coefficient of variation (%) standard deviation of primary particle size / average primary particle size x 100 (1)
  • (1-2) Metal fine particles A2 Except for the addition of 25.0 g of hexylamine (first-class reagent manufactured by Wako Pure Chemical Industries, Ltd., boiling point 130 ° C) in place of 11.0 g of 3-ethoxypropylamine and 7.0 g of 3-methoxypropylamine. Made the metal fine particles A2 in the same manner as the method for producing the metal fine particles A1.
  • the arithmetic mean primary particle size of the metal fine particles A2 was 59 nm, the standard deviation was 15.4 nm, and the coefficient of variation was 35.0%.
  • Metal fine particles B1 instead of 11.0 g of 3-ethoxypropylamine and 7.0 g of 3-methoxypropylamine, 10.0 g of 3-ethoxypropylamine and 2- (2-aminoethoxy) ethanol (manufactured by Wako Pure Chemical Industries, Ltd.)
  • the metal fine particles B1 were produced in the same manner as in the production method of the metal fine particles A1 except that 20.0 g of the reagent (first-class reagent, boiling point 220 ° C.) was added.
  • the arithmetic mean primary particle size of the metal fine particles B1 was 300 nm, the standard deviation was 180 nm, and the coefficient of variation was 60.0%.
  • Example 1 2 g of metal fine particles A1 as the first metal particles and 4.1 g of metal fine particles B1 as the second metal particles are mixed, and 0.11 g of isotridecanol and 2,4-diethyl-1,5-pentane as dispersion media are mixed. 0.16 g of diol and 0.018 g of sol sparse as a polymer dispersant were added, and the mixture was stirred and defoamed to prepare a bonding composition of Example 1.
  • Example 2 Same as in Example 1 except that 0.15 g of isotridecanol and 0.23 g of 2,4-diethyl-1,5-pentanediol were added as the dispersion medium, and 0.025 g of Solsparse 16000 was added as the polymer dispersant.
  • the bonding composition of Example 2 was prepared.
  • Example 3 2 g of metal fine particles A1 as the first metal particles and 2.1 g of metal fine particles B1 as the second metal particles are mixed, and 0.09 g of isotridecanol and 2,4-diethyl-1,5-pentane as dispersion media are mixed.
  • the bonding composition of Example 3 is the same as in Example 1 except that 0.07 g of diol, 0.07 g of 2-ethyl-1,3-hexanediol, and 0.015 g of Solsparse 16000 as a polymer dispersant are added. I made a thing.
  • Example 4 2 g of metal fine particles A1 as the first metal particles and 2.1 g of metal fine particles B1 as the second metal particles are mixed, and 0.07 g of isotridecanol and 2,4-diethyl-1,5-pentane as dispersion media are mixed.
  • the bonding composition of Example 4 is the same as in Example 1 except that 0.07 g of diol, 0.09 g of 2-ethyl-1,3-hexanediol, and 0.015 g of Solsparse 16000 as a polymer dispersant are added. I made a thing.
  • Example 5 2 g of metal fine particles A1 as the first metal particles and 2.1 g of metal fine particles B1 as the second metal particles are mixed, and 0.04 g of isotridecanol and 2,4-diethyl-1,5-pentane as dispersion media are mixed.
  • the bonding composition of Example 5 is the same as in Example 1 except that 0.07 g of diol, 0.11 g of 2-ethyl-1,3-hexanediol, and 0.015 g of Solsparse 16000 as a polymer dispersant are added. I made a thing.
  • Example 6 2 g of metal fine particles A1 as the first metal particles and 2.1 g of metal fine particles B1 as the second metal particles are mixed, and 2-ethyl-1,3-hexanediol 0.14 g and 3-methyl-1 are mixed as dispersion media.
  • a bonding composition of Example 6 was prepared in the same manner as in Example 1 except that 0.14 g of 3-butanediol and 0.019 g of DISPERBYK-118 as a polymer dispersant were added.
  • Example 7 2 g of metal fine particles A1 are mixed as the first metal particles, 2.1 g of metal fine particles B1 are mixed as the second metal particles, and 0.08 g of 2-ethyl-1,3-hexanediol and 3-methyl-1 are used as dispersion media.
  • a bonding composition of Example 7 was prepared in the same manner as in Example 1 except that 0.20 g of 3-butanediol and 0.023 g of DISPERBYK-190 as a polymer dispersant were added.
  • Example 8 2 g of metal fine particles A1 as the first metal particles and 2.1 g of metal fine particles B1 as the second metal particles are mixed, 3-methyl-1,3-butanediol as a dispersion medium 0.33 g, and as a polymer dispersant.
  • a bonding composition of Example 8 was prepared in the same manner as in Example 1 except that 0.022 g of DISPERBYK-190 was added.
  • Example 9 2 g of metal fine particles A1 as the first metal particles, 2 g of metal fine particles B1 as the second metal particles are mixed, 0.28 g of 2-ethyl-1,3-hexanediol as a dispersion medium, and DISPERBYK- as a polymer dispersant.
  • the bonding composition of Example 9 was prepared in the same manner as in Example 1 except that 0.017 g of 118 was added.
  • Comparative Example 1 2 g of metal fine particles A1 as the first metal particles, 2.1 g of metal fine particles B1 as the second metal particles are mixed, 0.20 g of isotridecanol as a dispersion medium, and 0.013 g of sol sparse 16000 as a polymer dispersant.
  • a bonding composition of Comparative Example 1 was prepared in the same manner as in Example 1 except that the particles were added.
  • Comparative Example 2 2 g of metal fine particles A1 are mixed as the first metal particles, 2.1 g of metal fine particles B1 are mixed as the second metal particles, and 0.14 g of isotridecanol and 2,4-diethyl-1,5-pentane are mixed as dispersion media.
  • a bonding composition of Comparative Example 2 was prepared in the same manner as in Example 1 except that 0.07 g of a diol and 0.014 g of Solsparse 16000 as a polymer dispersant were added.
  • Comparative Example 3 2 g of metal fine particles A1 as the first metal particles and 2.1 g of metal fine particles B1 as the second metal particles are mixed, and 0.19 g of isotridecanol and 2,4-diethyl-1,5-pentane as dispersion media are mixed.
  • a bonding composition of Comparative Example 3 was prepared in the same manner as in Example 1 except that 0.05 g of diol and 0.016 g of Solsparse as a polymer dispersant were added.
  • Comparative Example 4 2 g of metal fine particles A1 as the first metal particles and 2.1 g of metal fine particles B1 as the second metal particles are mixed, and 0.06 g of isotridecanol and 2,4-diethyl-1,5-pentane as dispersion media are mixed.
  • a bonding composition of Comparative Example 4 was prepared in the same manner as in Example 1 except that 0.18 g of a diol and 0.016 g of Solsperse 16000 as a polymer dispersant were added.
  • Comparative Example 5 2 g of metal fine particles A1 as the first metal particles and 2.1 g of metal fine particles B1 as the second metal particles are mixed, and 0.04 g of isotridecanol and 2,4-diethyl-1,5-pentane as dispersion media are mixed.
  • a bonding composition of Comparative Example 5 was prepared in the same manner as in Example 1 except that 0.18 g of a diol and 0.015 g of Solsparse 16000 as a polymer dispersant were added.
  • Comparative Example 6 1 g of metal fine particles A1 as the first metal particles and 4.3 g of metal fine particles B1 as the second metal particles are mixed, and 0.10 g of isotridecanol and 2,4-diethyl-1,5-pentane as dispersion media are mixed.
  • a bonding composition of Comparative Example 6 was prepared in the same manner as in Example 1 except that 0.15 g of a diol and 0.017 g of Solsperse 16000 as a polymer dispersant were added.
  • Comparative Example 7 2 g of metal fine particles A1 are mixed as the first metal particles, 2.1 g of metal fine particles B1 are mixed as the second metal particles, and 2,4-diethyl-1,5-pentanediol 0.12 g and 2-ethyl are used as dispersion media.
  • a bonding composition of Comparative Example 7 was prepared in the same manner as in Example 1 except that 0.28 g of -1,3-hexanediol was added and no polymer dispersant was added.
  • Comparative Example 8 2 g of metal fine particles A1 are mixed as the first metal particles, 2.1 g of metal fine particles B1 are mixed as the second metal particles, and 2-ethyl-1,3-hexanediol 0.15 g and 3-methyl-1 are used as dispersion media.
  • a bonding composition of Comparative Example 8 was prepared in the same manner as in Example 1 except that 0.15 g of 3-butanediol and 0.22 g of DISPERBYK-118 as a polymer dispersant were added.
  • Comparative Example 9 2 g of metal fine particles A2 are mixed as the first metal particles, 2 g of metal fine particles B1 are mixed as the second metal particles, and 2-ethyl-1,3-hexanediol 0.14 g and 3-methyl-1,3 are used as dispersion media.
  • the bonding composition of Comparative Example 9 was prepared in the same manner as in Example 1 except that 0.32 g of butanediol and 0.03 g of DISPERBYK-190 as a polymer dispersant were added.
  • Shear Viscosity For the bonding compositions of Examples and Comparative Examples, the shear rate is 10 s -1 under the following measurement conditions using a cone plate type viscometer (Rheometer manufactured by Anton Pearl Co., Ltd., MCR301). Shear viscosity (Pa ⁇ s) was measured. (Measurement condition) Measurement mode: Shear mode Shear velocity: 10s -1 Measuring jig: Cone plate CP-25-2 (Diameter 25 mm, angle 2 °, gap 0.105 mm) Measurement temperature: 25 ° C
  • a bond strength test was performed at room temperature using a bond tester (bonding tester PTR1102 manufactured by Reska Co., Ltd.).
  • a tool with a width of 1.2 mm attached to the weight sensor of the bond tester was placed at a height of 10.0 ⁇ m from the surface of the copper plate, and the tool was moved at 0.01 mm / sec.
  • the bonding portion of the bonding composition was pressed, and the load when the sapphire was peeled from the copper plate was measured and used as the bonding strength at the time of peeling.
  • the bonding strength at the time of peeling was divided by the bottom area of the chip to calculate the bonding strength (MPa) per unit area.
  • the bonding compositions of Examples 1 to 9 all had appropriate bonding strength and were excellent in continuous coating stability.
  • Comparing Examples 1 to 9 and Comparative Examples 1 to 5 with a focus on the viscosity of the dispersion medium those having a viscosity of the dispersion medium outside the specific range (100 to 300 mPa ⁇ s) contain a sol as the dispersion medium. Even so, the coating stability could not be maintained satisfactorily due to the separation of the metal particles and the dispersion medium or the occurrence of stringing during coating. Further, when Comparative Example 6 was confirmed, although the viscosity of the dispersion medium was within a specific range, the metal particles and the dispersion medium were separated from each other, resulting in inferior continuous coating stability.

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Abstract

La présente invention concerne une composition de liaison qui présente une excellente stabilité de revêtement, qui est frittée à une température relativement basse (200°C ou moins) et qui fournit une force de liaison élevée, sans provoquer de séparation entre un solvant et des particules dans la composition. La composition de liaison selon la présente invention contient : des premières particules métalliques dont les surfaces sont recouvertes d'une amine présentant un groupe polaire et qui présentent une grosseur moyenne de particule de 20 à 100 nm ; des deuxièmes particules métalliques présentant une grosseur moyenne de particule de 200 à 500 nm ; un milieu de dispersion ; et un agent dispersant de polymère. Le rapport pondéral des premières particules métalliques aux deuxièmes particules métalliques est de 20:80 à 80:20. La concentration de sa teneur en solides est d'au moins 90 % en poids. Le milieu dispersant contient un diol et présente une viscosité de 100-300 mPa·s à 25°C.
PCT/JP2021/024824 2020-07-06 2021-06-30 Composition de liaison et procédé de formulation pour composition de liaison WO2022009754A1 (fr)

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JP7332226B1 (ja) 2022-11-11 2023-08-23 株式会社フェクト 銀合金ナノ粒子含有組成液の調製方法、銀合金被膜の形成方法及びこの銀合金被膜を用いた配線回路の製造方法
WO2023189846A1 (fr) * 2022-03-30 2023-10-05 バンドー化学株式会社 Composition de microparticules d'argent

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WO2019142633A1 (fr) * 2018-01-22 2019-07-25 バンドー化学株式会社 Composition pour liaison
WO2020040184A1 (fr) * 2018-08-23 2020-02-27 バンドー化学株式会社 Composition d'assemblage

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WO2019142633A1 (fr) * 2018-01-22 2019-07-25 バンドー化学株式会社 Composition pour liaison
WO2020040184A1 (fr) * 2018-08-23 2020-02-27 バンドー化学株式会社 Composition d'assemblage

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023189846A1 (fr) * 2022-03-30 2023-10-05 バンドー化学株式会社 Composition de microparticules d'argent
JP7365530B1 (ja) 2022-03-30 2023-10-19 バンドー化学株式会社 銀微粒子組成物
JP7332226B1 (ja) 2022-11-11 2023-08-23 株式会社フェクト 銀合金ナノ粒子含有組成液の調製方法、銀合金被膜の形成方法及びこの銀合金被膜を用いた配線回路の製造方法

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