WO2022176809A1 - 導電性接着剤、導電性接着剤の焼結体、焼結体の製造方法、電子部品、及び電子部品の製造方法 - Google Patents

導電性接着剤、導電性接着剤の焼結体、焼結体の製造方法、電子部品、及び電子部品の製造方法 Download PDF

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Publication number
WO2022176809A1
WO2022176809A1 PCT/JP2022/005713 JP2022005713W WO2022176809A1 WO 2022176809 A1 WO2022176809 A1 WO 2022176809A1 JP 2022005713 W JP2022005713 W JP 2022005713W WO 2022176809 A1 WO2022176809 A1 WO 2022176809A1
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Prior art keywords
silver particles
conductive adhesive
mass
sintered body
acid
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Ceased
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PCT/JP2022/005713
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English (en)
French (fr)
Japanese (ja)
Inventor
英也 川▲崎▼
優 橋立
諒 加藤
崇充 森
淳一郎 三並
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Osaka Soda Co Ltd
Kansai University
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Osaka Soda Co Ltd
Kansai University
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Application filed by Osaka Soda Co Ltd, Kansai University filed Critical Osaka Soda Co Ltd
Priority to EP22756127.1A priority Critical patent/EP4296326A4/en
Priority to JP2023500827A priority patent/JPWO2022176809A1/ja
Priority to US18/546,658 priority patent/US12534651B2/en
Priority to CN202280015214.9A priority patent/CN116867873A/zh
Publication of WO2022176809A1 publication Critical patent/WO2022176809A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/50—Additional features of adhesives in the form of films or foils characterized by process specific features

Definitions

  • the present invention relates to a conductive adhesive, a sintered body of the conductive adhesive, a method for manufacturing the sintered body, an electronic component, and a method for manufacturing an electronic component.
  • Conductive adhesives including die bonding agents, are bonding materials used for electronic components such as semiconductors, LEDs, and power semiconductors.
  • As a bonding method it is generally known to bond to a base material by bonding by pressurization and heating, or by sintering by heating or the like without pressure. In recent years, from the viewpoint of simplicity and efficiency of the manufacturing process, the development of non-pressure bonding materials has progressed.
  • Patent Document 1 describes a metal paste obtained by kneading a solid content of silver particles and a solvent, wherein the solid content contains 30% or more silver particles having a particle size of 100 to 200 nm based on the number of particles. Furthermore, the silver particles constituting the solid content are a metal paste in which an amine compound having a total number of carbon atoms of 4 to 8 is bonded as a protective agent. According to the metal paste, silver particles can be sintered in a low temperature range, and a sintered body with low resistance and excellent thermal conductivity can be formed.
  • thermosetting resin in addition to silver particles has a problem that the specific resistance tends to increase due to the presence of the thermosetting resin.
  • the main object of the present invention is to provide a novel conductive adhesive that provides a sintered body with a low specific resistance value even though it contains a thermosetting resin in addition to silver particles.
  • Another object of the present invention is to provide a sintered body of the conductive adhesive, a method for manufacturing the sintered body, an electronic component, and a method for manufacturing the electronic component.
  • the inventor of the present invention has made intensive studies to solve the above problems. As a result, the present inventors have found that a sintered body having a low specific resistance can be obtained by forming a protective layer containing a predetermined compound on silver particles in a conductive adhesive containing silver particles and a thermosetting resin. The present invention has been completed through further studies based on such findings.
  • Section 1 silver particles; a thermosetting resin; A conductive adhesive comprising A conductive adhesive, wherein the silver particles are provided with a protective layer containing a compound represented by the following general formula (1).
  • R 1 is an alkyl group having 1 to 5 carbon atoms
  • R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • Section 2. Item 2. The conductive adhesive according to Item 1, wherein the thermosetting resin is an epoxy resin.
  • Item 3. Item 3.
  • the conductive adhesive according to Item 1 or 2 wherein the content of the silver particles is 70% by mass or more.
  • Section 4. Item 4. The conductive adhesive according to any one of Items 1 to 3, further comprising a solvent.
  • Item 5. The conductive adhesive according to Item 4, wherein the solvent has an octanol/water partition coefficient (Log Pow) of ⁇ 2 or more and 4 or less.
  • Item 6. A sintered body of the conductive adhesive according to any one of Items 1 to 5.
  • Item 7. An electronic component in which members are joined together by the sintered body according to item 6.
  • Item 8. A method for producing a sintered body, comprising a step of sintering the conductive adhesive according to any one of Items 1 to 5 at a temperature of 100°C or higher and 250°C or lower.
  • a method for manufacturing an electronic component in which members are joined by a sintered body A step of disposing the conductive adhesive according to any one of Items 1 to 5 between the members; sintering the conductive adhesive at a temperature of 100° C. or higher and 250° C. or lower;
  • a method of manufacturing an electronic component comprising:
  • the present invention it is possible to provide a novel conductive adhesive that provides a sintered body with a low specific resistance value despite containing a thermosetting resin in addition to silver particles. Furthermore, according to the present invention, it is also possible to provide a sintered body of the conductive adhesive, a method for manufacturing the sintered body, an electronic component, and a method for manufacturing the electronic component.
  • the conductive adhesive of the present invention is a conductive adhesive containing silver particles and a thermosetting resin, wherein the silver particles are provided with a protective layer containing a compound represented by the following general formula (1): It is characterized by With the conductive adhesive of the present invention having this configuration, a sintered body having a small specific resistance value can be obtained in spite of containing a thermosetting resin in addition to silver particles.
  • R 1 is an alkyl group having 1 to 5 carbon atoms
  • R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • a numerical value connected by "-" means a numerical range including numerical values before and after "-" as a lower limit value and an upper limit value. If multiple lower limits and multiple upper limits are listed separately, any lower limit and upper limit can be selected and connected with "-".
  • the conductive adhesive of the present invention contains silver particles and a thermosetting resin.
  • the silver particles are equipped with a protective layer. Specifically, the silver particles have a protective layer on the surface of the particles made of silver. Moreover, the protective layer contains the compound represented by the general formula (1).
  • the conductive adhesive of the present invention contains the compound represented by the general formula (1) in the protective layer, so that the silver particles have good dispersibility in the solvent and the sintered body has a small specific resistance value. is obtained.
  • R 1 is an alkyl group having 1 to 5 carbon atoms. and more preferably an alkyl group having 1 carbon atom (that is, a methyl group).
  • R 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and from the viewpoint of more preferably exhibiting the effects of the present invention, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is preferably a group, more preferably a hydrogen atom or an alkyl group having 1 carbon atom (ie, methyl group), and particularly preferably an alkyl group having 1 carbon atom (ie, methyl group).
  • 2-hydroxyisobutyric acid and lactic acid are particularly preferred, and 2-hydroxyisobutyric acid is most preferred.
  • the compound represented by general formula (1) contained in the protective layer may be of one type or two or more types.
  • the protective layer may contain a compound different from the compound represented by general formula (1).
  • different compounds include amine compounds, fatty acids, and hydroxy fatty acids (provided that the hydroxy fatty acid is different from the compound represented by general formula (1)).
  • the different compound contained in the protective layer may be one kind or two or more kinds.
  • alkylamines are preferable from the viewpoint of more preferably exhibiting the effects of the present invention.
  • the alkylamine is not particularly limited, but preferably an alkylamine having an alkyl group having 3 or more and 18 or less carbon atoms, more preferably an alkylamine having an alkyl group having 4 or more and 12 or less carbon atoms.
  • alkylamines include ethylamine, n-propylamine, isopropylamine, 1,2-dimethylpropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, isoamylamine, tert-amylamine, 3 -pentylamine, n-amylamine, n-hexylamine, n-heptylamine, n-octylamine, 2-octylamine, 2-ethylhexylamine, n-nonylamine, n-aminodecane, n-aminoundecane, n-dodecylamine , n-tridecylamine, 2-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-hepta
  • dibutylamine as a secondary amine and cyclopropylamine
  • cyclobutylamine cyclopropylamine
  • cyclohexylamine cycloheptylamine
  • cyclooctylamine cyclic alkylamines.
  • n-hexylamine, cyclohexylamine, n-octylamine, 2-ethylhexylamine, n-dodecylamine, n-oleylamine, N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3 -diaminopropane is preferred
  • n-butylamine, n-hexylamine, cyclohexylamine, n-octylamine, n-dodecylamine, N,N-dimethyl-1,3-diaminopropane, N,N-diethyl-1,3 - diaminopropane is more preferred.
  • An amine compound may be used individually by 1 type, and may be used in combination of 2 or more types.
  • Fatty acids are not particularly limited, but preferably fatty acids having alkyl groups of 3 to 18 carbon atoms, more preferably fatty acids having alkyl groups of 4 to 18 carbon atoms.
  • Preferred specific examples of fatty acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and linoleic acid. , ⁇ -linolenic acid and the like.
  • specific examples of fatty acids include cyclic alkylcarboxylic acids such as cyclohexanecarboxylic acid.
  • hydroxy fatty acid a compound having 3 to 24 carbon atoms and having one or more (eg, one) hydroxyl group can be used.
  • Hydroxy fatty acids different from the compound represented by general formula (1) include, for example, 2-hydroxydecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, and 2-hydroxyoctadecanoic acid.
  • hydroxy fatty acids having 4 to 18 carbon atoms and having one hydroxyl group other than the ⁇ -position are preferred, and ricinoleic acid and 12-hydroxystearic acid are more preferred.
  • a fatty acid and a hydroxy fatty acid may each be used individually, and may be used in combination of 2 or more types.
  • the content of silver contained in the silver particles is not particularly limited as long as the effect of the present invention is exhibited. Preferably, it is 98% by mass or more.
  • the content of the protective layer for silver particles is not particularly limited as long as the effect of the present invention is exhibited. 0.3% by mass or less, and the lower limit is preferably 0.05% by mass or more.
  • the content of the protective layer of silver particles can be measured by differential thermal analysis or thermogravimetric differential thermal analysis.
  • the proportion of the compound represented by general formula (1) in the protective layer of the silver particles is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more. Particularly preferably, it is 99% by mass or more, and may be 100% by mass.
  • the silver particle protective layer is preferably formed by attaching an amine compound or the like to the surface of the silver particles and then substituting the amine compound with a compound represented by the general formula (1). . Therefore, the protective layer may contain the amine compound remaining without being substituted.
  • the average particle size of the silver particles is not particularly limited as long as the effects of the present invention are exhibited, and is, for example, 20 nm or more, preferably 30 nm or more, more preferably 60 nm or more, and for example, 500 nm or less, preferably 400 nm. Below, it is more preferably 250 nm or less. 400 nm, 60 to 250 nm.
  • the average particle size of the silver particles is the volume-based average particle size measured for 200 randomly selected particles using image analysis software (e.g., Macview (manufactured by Mountec)) for SEM images.
  • image analysis software e.g., Macview (manufactured by Mountec)
  • an SED mode secondary electron detector
  • an accelerating voltage is 20 kV
  • an observation magnification is 5000 to 30000 times
  • a width range of 1 to 20 ⁇ m is observed.
  • the width is such that 200 or more (generally, about 200 to 300) silver particles are included in the width range of 1 to 20 ⁇ m.
  • the volume-based average particle diameter is a value measured assuming that the particles observed in the SEM image are spherical having the diameter.
  • the content of silver particles is not particularly limited as long as the effects of the present invention are exhibited, and is, for example, 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass. % or more, and, for example, 95% by mass or less, preferably 93% by mass or less, more preferably 90% by mass or less. % by mass, 75 to 95% by mass, 75 to 93% by mass, 75 to 90% by mass, 80 to 95% by mass, 80 to 93% by mass, 80 to 90% by mass.
  • the conductive adhesive of the present invention may contain silver particles different from the silver particles provided with the protective layer containing the compound represented by general formula (1).
  • the content of silver particles provided with a protective layer containing a compound represented by general formula (1) is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and further It is preferably 98% by mass or more, more preferably 99% by mass or more, and still more preferably 100% by mass.
  • silver particles having a single average particle size for example, a range of 20 to 500 nm
  • different average particle sizes for example, 20 to 500 nm. within the range
  • the ratio may be appropriately adjusted so as to obtain the desired physical properties.
  • silver particles A1 and silver particles A2 having a large average particle size are used, the ratio of silver particles A1:silver particles A2 may be in the range of 1-30:70-99.
  • Silver particles containing the compound represented by the general formula (1) and having an average particle diameter within the range of 20 to 500 nm are sometimes referred to as silver particles A.
  • silver particles in addition to the silver particles A having an average particle size of 20 to 500 nm, silver particles having a larger average particle size (for example, in the range of 0.5 to 5.5 ⁇ m) silver It may contain particles. Silver particles having an average particle size in the range of 0.5 to 5.5 ⁇ m are sometimes referred to as silver particles B.
  • the protective layer of the silver particles may contain the compound represented by the general formula (1), or may contain a compound different from the compound represented by the general formula (1) (a specific example is as described above).
  • the average particle size of the silver particles B preferably has a lower limit of 0.6 ⁇ m or more, and an upper limit of preferably 3.0 ⁇ m or less, more preferably 3.0 ⁇ m or less. 2.5 ⁇ m or less, more preferably 2.0 ⁇ m or less. .0 ⁇ m, 0.6-2.5 ⁇ m, 0.6-2.0 ⁇ m.
  • the average particle size of silver particles B can be measured by laser diffraction.
  • silver particles B in the present invention commercially available ones may be used, or those synthesized by a known synthesis method may be used.
  • silver particles A may be used alone, or silver particles A and silver particles B may be used in combination.
  • the mass ratio of silver particles A and silver particles B may be in the range of (silver particles A:silver particles B) 30-70:70-30.
  • a range of ⁇ 65:65-35 is preferred, and a range of 40-60:60-40 is more preferred.
  • a higher shear strength can be obtained by using the silver particles A and the silver particles B together in a ratio within the above range.
  • thermosetting resin is not particularly limited as long as it does not inhibit the effects of the present invention.
  • examples include epoxy resin, acrylic resin, silicone resin, urethane resin, vinyl ester resin, phenol resin, urea resin, and melamine resin. , unsaturated polyester resins, diallyl phthalate resins, and polyimide resins. Among these, epoxy resins are particularly preferred.
  • the thermosetting resin contained in the conductive adhesive of the present invention may be of one type or two or more types.
  • the content of the thermosetting resin is not particularly limited as long as the effects of the present invention are exhibited, and is, for example, 0.001% by mass or more, preferably 0.005% by mass or more. , more preferably 0.01% by mass or more, and for example, 10% by mass or less, preferably 7% by mass or less, more preferably 3% by mass or less, and a preferable range is 0.001 to 10% by mass. , 0.001 to 7% by mass, 0.001 to 3% by mass, 0.005 to 10% by mass, 0.005 to 7% by mass, 0.005 to 3% by mass, 0.01 to 10% by mass, 0 0.01 to 7% by mass, 0.01 to 3% by mass.
  • the conductive adhesive of the present invention preferably further contains a solvent.
  • the type of solvent is not particularly limited as long as it does not impair the effects of the present invention.
  • the octanol/water partition coefficient (Log Pow) of the solvent is preferably -2 to 4, more preferably 0.5 to 3.75, and still more preferably 1 to 3.5.
  • octanol/water partition coefficient (Log Pow)
  • the dispersibility of the silver particles provided with the protective layer and the thermosetting resin becomes particularly good, which is preferable.
  • specific examples of preferred solvents include hexylcarbitol (Log Pow: 1.7), texanol (Log Pow: 3.2), isopropyl alcohol (Log Pow: 0.05), ⁇ -terpineol (Log Pow: 2.98), diethylene glycol (Log Pow: -1.98), ethylene glycol (Log Pow: -1.36), 2-ethyl-1,3-hexanediol (Log Pow: 1.60), diethylene glycol Mono-2-ethylhexyl ether (Log Pow: 2.23), butyl carbitol (Log Pow: 0.56), butyl carbitol acetate (Log Pow: 2.9), butanediol (Log Pow: -0.34
  • Particularly preferred solvents are hexylcarbitol (Log Pow: 1.7) and Texanol (Log Pow: 3.2).
  • the number of solvents contained in the conductive adhesive may be one or two or more.
  • the content of the solvent is not particularly limited as long as the effect of the present invention is exhibited, and is, for example, 2% by mass or more, preferably 3% by mass or more, more preferably 5% by mass. or more, for example, 20% by mass or less, preferably 17% by mass or less, more preferably 15% by mass or less, and preferable ranges are about 2 to 20% by mass, about 2 to 17% by mass, About 15% by mass, about 3 to 20% by mass, about 3 to 17% by mass, about 3 to 15% by mass, about 5 to 20% by mass, about 5 to 17% by mass, and about 5 to 15% by mass.
  • the conductive adhesive of the present invention can contain a curing agent (initiator) as another component in addition to the components described above.
  • a curing agent initiator
  • it is not particularly limited as long as it promotes curing by mixing the silver particles and the thermosetting resin, imidazole-based, hydrazide-based, boron trifluoride-amine complex, amine imide, polyamine-based, tertiary amine, Amines such as alkylureas, dicyandiamides, acid anhydrides, phenols, and modified products thereof are exemplified, and these can be used alone or in combination of two or more.
  • imidazole-based curing agents are preferably used from the viewpoint of excellent storage stability at low temperatures and rapid curing.
  • the imidazole curing agent a known imidazole curing agent can be used. More specifically, adducts of imidazole compounds with epoxy resins are exemplified. Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 2-propylimidazole, 2-dodecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 4-methylimidazole.
  • the content of the curing agent in the conductive adhesive of the present invention is preferably 0.5% by mass or more and 20% by mass or less. This is because if the content of the curing agent is less than 0.5% by mass, the curing of the thermosetting resin may be insufficient and the adhesiveness may be insufficient. This is because if the amount is more than % by mass, the curing agent may react during storage and the stability may decrease.
  • the specific resistance value of the sintered body obtained by heating the conductive adhesive at 200 ° C. for 60 minutes is preferably 30 ⁇ cm or less, or more. It is preferably 20 ⁇ cm or less, more preferably 10 ⁇ cm or less. In addition, the lower limit of the specific resistance value is, for example, 5 ⁇ cm or more.
  • the method for measuring the specific resistance value of the sintered body is as follows, and specifically, it is measured by the method described in Examples.
  • a conductive adhesive is uniformly applied on a polyimide film in a size of 2 mm ⁇ 60 mm ⁇ 50 ⁇ m in film thickness, and baked at a predetermined temperature (200° C.) for 60 minutes to obtain a sintered body.
  • the resistance value of the sintered body is measured at room temperature with a resistance meter (eg, HIOKI RM3548), and the specific resistance (volume resistance) value is obtained from the value obtained by measuring the actual film thickness with a micrometer.
  • This specific resistance value is the average value of the values measured at four points of the sintered body.
  • the conductive adhesive of the present invention can be produced by mixing silver particles and a thermosetting resin, and the silver particles and the thermosetting resin are as described above. Moreover, as described above, the conductive adhesive of the present invention may contain a solvent, and when the solvent is contained, the solvent is mixed.
  • a composition for producing silver particles (silver particle preparation composition).
  • a silver compound that is a raw material for silver particles a compound represented by general formula (1) that forms a protective layer, and, if necessary, a compound different from general formula (1) described above ( amine compounds, etc.) and solvents.
  • preferred silver compounds include silver nitrate and silver oxalate, and silver oxalate is particularly preferred.
  • the solvent the same solvents as those exemplified as the solvent mixed with the conductive adhesive are preferably exemplified.
  • a solvent different from the solvent blended in the above-described conductive adhesive is used, and finally replaced with the solvent blended in the conductive adhesive.
  • the different solvent is not particularly limited as long as it can disperse the silver particles, and for example, a polar organic solvent can be used.
  • Polar organic solvents include ketones such as acetone, acetylacetone and methyl ethyl ketone; ethers such as diethyl ether, dipropyl ether, dibutyl ether, tetrahydrofuran and 1,4-dioxane; 1,2-propanediol and 1,2-butane.
  • Diol 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,2-hexanediol, 1,6-hexanediol, 1,2-pentanediol, 1,5-pentanediol , 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol, 1,8-octanediol, 2-ethyl-1,3-hexanediol, etc.
  • Glycerol straight or branched chain alcohols having 1 to 5 carbon atoms, alcohols such as cyclohexanol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol; ethyl acetate, butyl acetate , ethyl butyrate, ethyl formate, texanol and other fatty acid esters; polyethylene glycol, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene Glycol dimethyl ether, 3-methoxybutyl acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monohexyl ether, ethylene glycol monooctyl ether, ethylene glycol mono-2
  • non-polar organic solvents hydrophobic organic solvents
  • Nonpolar organic solvents include linear, branched, or cyclic saturated hydrocarbons such as hexane, heptane, octane, nonane, decane, 2-ethylhexane, and cyclohexane; linear or branched alcohols having 6 or more carbon atoms; aromatic compounds such as benzene, toluene and benzonitrile; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; methyl-n-amyl ketone; methyl ethyl ketone oxime; Among these, saturated hydrocarbons and linear or branched alcohols having 6 or more carbon atoms are preferable, and hexane, octane, decane, octanol, decanol and dodecanol are more
  • a composition for preparing silver particles is obtained by mixing each component.
  • the ratio of each component in the composition is adjusted as appropriate.
  • the content of silver oxalate in the composition is preferably about 20 to 70% by mass with respect to the total amount of the composition.
  • the content of the compound represented by the general formula (1) to be adhered to the surface of the silver particles is preferably about 5% by mass to 55% by mass with respect to the total amount of the composition.
  • the amine compound is attached to the surface of the silver particles, the content of the amine compound is preferably about 5% by mass to 55% by mass with respect to the total amount of the composition.
  • the fatty acid content is preferably about 0.1% by mass to 20% by mass with respect to the total amount of the composition.
  • the content of the hydroxy fatty acid is 0.1% by mass with respect to the total amount of the composition. It is preferably about 15% by mass.
  • a silver particle-preparing composition to which a compound (amine compound) or the like different from the compound represented by the general formula (1) is attached is used to once synthesize silver particles to which the amine compound or the like is attached. It is also possible to substitute the compound represented by the general formula (1) with an amine compound or the like to form the protective layer.
  • the means for mixing each component is not particularly limited, and for example, it can be mixed with a general-purpose device such as a mechanical stirrer, a magnetic stirrer, a vortex mixer, a planetary mill, a ball mill, a triple roll, a line mixer, a planetary mixer, and a dissolver.
  • a general-purpose device such as a mechanical stirrer, a magnetic stirrer, a vortex mixer, a planetary mill, a ball mill, a triple roll, a line mixer, a planetary mixer, and a dissolver.
  • the temperature of the composition is set to, for example, 60°C or less, particularly 40°C. It is preferable to mix while suppressing the following.
  • the composition for silver particle preparation is subjected to a reaction, usually by heating, in a reaction vessel to cause a thermal decomposition reaction of the silver compound to generate silver particles.
  • a reaction usually by heating, in a reaction vessel to cause a thermal decomposition reaction of the silver compound to generate silver particles.
  • the composition may be introduced into a preheated reaction vessel, or the composition may be introduced into the reaction vessel and then heated.
  • the reaction temperature may be any temperature at which the thermal decomposition reaction proceeds and silver particles are generated, for example, about 50 to 250°C.
  • the reaction time may be appropriately selected according to the desired average particle size and the composition of the composition accordingly. Examples of the reaction time include 1 minute to 100 hours.
  • the silver particles generated by the thermal decomposition reaction are obtained as a mixture containing unreacted raw materials, it is preferable to purify the silver particles.
  • the purification method include a solid-liquid separation method, a precipitation method utilizing a difference in specific gravity between silver particles and an unreacted raw material such as an organic solvent, and the like.
  • the solid-liquid separation method include filter filtration, centrifugal separation, cyclone method, and decanter method.
  • the mixture containing silver particles may be diluted with a low boiling point solvent such as acetone or methanol to adjust its viscosity.
  • the average particle size of the resulting silver particles can be adjusted.
  • Silver particles (with an amine compound adhering to the surface) once synthesized by the above method are prepared and dispersed in a solvent.
  • the solvent are the same as those exemplified above as the solvent.
  • a step of adding a compound represented by the general formula (1) in an amount ranging from 0.1 to 5 times the mass of the silver particles, and stirring at room temperature to 80°C for 1 minute to 24 hours. can replace the amine compound adhering to the surface of the silver particles with the compound represented by the general formula (1).
  • the silver particles substituted with the amine compound can be recovered by the above solid-liquid separation method or the like.
  • the sintered body of the conductive adhesive of the present invention is obtained by sintering the conductive adhesive of the present invention described in detail in "1. Conductive Adhesive" above. .
  • the components adhering to the surface of the silver particles (the compound represented by the general formula (1), etc.) and the solvent are almost completely destroyed by the high heat during sintering. is separated, and the sintered body is substantially composed of silver and thermosetting resin.
  • the sintering temperature is not particularly limited, but from the viewpoint of increasing the shear strength and density of the obtained sintered body while suitably sintering at a low temperature, for example, 250 ° C. or less, preferably about 100 ° C. to 250 ° C., More preferably, it is about 150°C to 250°C.
  • the sintering time is preferably about 0.4 hours to 2.0 hours, more preferably about 0.5 hours to 1.2 hours. No pressure is required during sintering of the conductive adhesive of the present invention. In other words, the conductive adhesive of the present invention can be suitably used for applications in which pressure is not applied during sintering.
  • pressure may be applied during sintering of the conductive adhesive of the present invention, and the pressure when applying pressure is, for example, about 10 to 30 MPa.
  • Sintering can be performed in an atmosphere such as the atmosphere or an inert gas (nitrogen gas, argon gas).
  • the sintering means is not particularly limited, and examples thereof include an oven, hot air drying oven, infrared drying oven, laser irradiation, flash lamp irradiation, microwave and the like.
  • the sintered body of the present invention preferably satisfies the specific resistance value shown in the column "1. Conductive adhesive”.
  • the electronic part of the present invention has a portion where members are bonded together by the sintered body of the present invention. That is, the electronic component of the present invention is obtained by disposing the conductive adhesive of the present invention described in detail in "1. Conductive Adhesive" above between members of the electronic component (for example, between members included in a circuit). , sintering a conductive adhesive to bond the members together.
  • the specific resistance value of the electronic component of the present invention can also be made low.
  • Example 1 Using the dispersion liquid (isopropyl alcohol) of the silver particles a obtained above, 2-hydroxyisobutyric acid was added in an amount 0.5 times the mass of the silver particles, and the mixture was stirred at room temperature for 2 hours. After stirring, remove the magnetic stirrer, add 15 g of methanol to each composition, stir with a vortex mixer, and then centrifuge at 3000 rpm (approximately 1600 ⁇ G) for 1 minute in a centrifuge (CF7D2 manufactured by Hitachi Koki). The operation was carried out and the supernatant was removed by tilting the centrifuge tube.
  • a centrifuge C7D2 manufactured by Hitachi Koki
  • the resulting hexyl carbitol dispersion of silver particles a1 and silver particles b was mixed with 0.1 g of an epoxy resin (bisphenol A type epoxy resin) to obtain a conductive adhesive.
  • an epoxy resin bisphenol A type epoxy resin
  • the content of silver particles in the conductive adhesive is 84.2% by mass (the mass ratio of silver particles a1 and silver particles b is 1:1)
  • the content of hexyl carbitol is 15.0% by mass
  • the content of epoxy resin is 15.0% by mass.
  • the content is 1.0% by mass.
  • Example 2 In Example 1, a hexyl carbitol dispersion of silver particles a1 and silver particles b was mixed with 0.3 g of an epoxy resin (bisphenol A type epoxy resin) to determine the content of silver particles in the conductive adhesive. 82.5% by mass (mass ratio of silver particles a1 and silver particles b is 1:1), the content of hexylcarbitol was 15.0% by mass, and the content of epoxy resin was 2.9% by mass.
  • a conductive adhesive was obtained in the same manner as in Example 1 except for the above.
  • Example 3 In Example 1, a hexyl carbitol dispersion of silver particles a1 and silver particles b was mixed with 0.5 g of an epoxy resin (bisphenol A type epoxy resin) to determine the content of silver particles in the conductive adhesive. 81.0 mass % (the mass ratio of silver particles a1 and silver particles b is 1:1), the content of hexyl carbitol was 14.9 mass %, and the content of epoxy resin was 4.8 mass %.
  • a conductive adhesive was obtained in the same manner as in Example 1 except for the above.
  • Example 4 Using the dispersion liquid (isopropyl alcohol) of the silver particles a obtained above, L-lactic acid was added in an amount 0.5 times the mass of the silver particles, and the mixture was stirred at room temperature for 2 hours. After stirring, remove the magnetic stirrer, add 15 g of methanol to each composition, stir with a vortex mixer, and then centrifuge at 3000 rpm (approximately 1600 ⁇ G) for 1 minute in a centrifuge (CF7D2 manufactured by Hitachi Koki). The operation was carried out and the supernatant was removed by tilting the centrifuge tube.
  • a centrifuge C7D2 manufactured by Hitachi Koki
  • the resulting hexyl carbitol dispersion of silver particles a2 and silver particles b was mixed with 0.1 g of an epoxy resin (bisphenol A type epoxy resin) to obtain a conductive adhesive.
  • an epoxy resin bisphenol A type epoxy resin
  • the content of silver particles in the conductive adhesive is 84.2% by mass (the mass ratio of silver particles a2 to silver particles b is 1:1)
  • the content of hexyl carbitol is 15.0% by mass
  • the content of epoxy resin is 15.0% by mass.
  • the content is 1.0% by mass.
  • Example 5 a hexyl carbitol dispersion of silver particles a2 and silver particles b was mixed with 0.3 g of an epoxy resin (bisphenol A type epoxy resin) to determine the content of silver particles in the conductive adhesive. 82.5% by mass (the mass ratio of silver particles a2 and silver particles b is 1:1), the content of hexylcarbitol was 15.0% by mass, and the content of epoxy resin was 2.9% by mass.
  • a conductive adhesive was obtained in the same manner as in Example 4, except for the above.
  • Example 6 a hexyl carbitol dispersion of silver particles a2 and silver particles b was mixed with 0.5 g of an epoxy resin (bisphenol A type epoxy resin) to determine the content of silver particles in the conductive adhesive. 81.0% by mass (the mass ratio of silver particles a2 and silver particles b is 1:1), the content of hexylcarbitol was 14.9% by mass, and the content of epoxy resin was 4.8% by mass.
  • a conductive adhesive was obtained in the same manner as in Example 4, except for the above.
  • the resulting hexyl carbitol dispersion of silver particles a3 and silver particles b was mixed with 0.1 g of an epoxy resin (bisphenol A type epoxy resin) to obtain a conductive adhesive.
  • an epoxy resin bisphenol A type epoxy resin
  • the content of silver particles in the conductive adhesive is 84.2% by mass (the mass ratio of silver particles a and silver particles b is 1:1)
  • the content of hexyl carbitol is 15.0% by mass
  • the content of epoxy resin is 15.0% by mass.
  • the content is 1.0% by mass.
  • Comparative example 2 In Comparative Example 1, a hexyl carbitol dispersion of silver particles a3 and silver particles b was mixed with 0.30 g of an epoxy resin (bisphenol A type epoxy resin) to determine the content of silver particles in the conductive adhesive. 82.5% by mass (mass ratio of silver particles a and silver particles b is 1:1), the content of hexyl carbitol was 15.0% by mass, and the content of epoxy resin was 2.9% by mass. A conductive adhesive was obtained in the same manner as in Comparative Example 1 except for the above.
  • an epoxy resin bisphenol A type epoxy resin
  • Comparative Example 3 In Comparative Example 1, a hexyl carbitol dispersion of silver particles a3 and silver particles b was mixed with 0.5 g of an epoxy resin (bisphenol A type epoxy resin) to determine the content of silver particles in the conductive adhesive. 81.0% by mass (the mass ratio of silver particles a and silver particles b is 1:1), the content of hexylcarbitol was 14.9% by mass, and the content of epoxy resin was 4.8% by mass. A conductive adhesive was obtained in the same manner as in Comparative Example 1 except for the above.
  • an epoxy resin bisphenol A type epoxy resin
  • a conductive adhesive was evenly applied on a polyimide film in a size of 2 mm ⁇ 60 mm ⁇ 50 ⁇ m in film thickness, and baked at a predetermined temperature (200° C. or 250° C.) for 60 minutes to obtain a sintered body.
  • the resistance value of the sintered body is measured under room temperature conditions by a two-terminal measurement method using a resistance meter (HIOKI RM3548), and the specific resistance (volume resistance ) values were obtained.
  • This specific resistance value is the average value of the values measured at four points of the sintered body. Table 1 and FIG. 1 show the measurement results of the specific resistance value.
  • the n-hexylamine-substituted silver particles a3 do not disperse in polar solvents with a solvent octanol/water partition coefficient (Log Pow) of -1.98 to -0.34, but settle.
  • silver particles a1 substituted with 2-hydroxyisobutyric acid and silver particles a2 substituted with L-lactic acid have improved dispersibility.
  • the silver particles a1 have good dispersibility in low-polar solvents with octanol/water partition coefficients (Log Pow) of 1.7 to 3.2. It was suggested that it can be used as a solvent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Conductive Materials (AREA)
  • Adhesives Or Adhesive Processes (AREA)
PCT/JP2022/005713 2021-02-18 2022-02-14 導電性接着剤、導電性接着剤の焼結体、焼結体の製造方法、電子部品、及び電子部品の製造方法 Ceased WO2022176809A1 (ja)

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EP22756127.1A EP4296326A4 (en) 2021-02-18 2022-02-14 ELECTROCONDUCTIVE ADHESIVE, ELECTROCONDUCTIVE ADHESIVE SINTERED BODY, METHOD FOR PRODUCING SINTERED BODY, ELECTRONIC COMPONENT, AND METHOD FOR PRODUCING ELECTRONIC COMPONENT
JP2023500827A JPWO2022176809A1 (https=) 2021-02-18 2022-02-14
US18/546,658 US12534651B2 (en) 2021-02-18 2022-02-14 Electrically conductive adhesive, sintered body of electrically conductive adhesive, method for producing sintered body, electronic component, and method for producing electronic component
CN202280015214.9A CN116867873A (zh) 2021-02-18 2022-02-14 导电性粘接剂、导电性粘接剂的烧结体、烧结体的制造方法、电子部件及电子部件的制造方法

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JP5574761B2 (ja) 2009-04-17 2014-08-20 国立大学法人山形大学 被覆銀超微粒子とその製造方法
JP2015159096A (ja) 2014-02-25 2015-09-03 田中貴金属工業株式会社 低温焼結性に優れる銀ペースト及び該銀ペーストの製造方法
WO2016204105A1 (ja) * 2015-06-15 2016-12-22 株式会社大阪ソーダ 金属ナノ微粒子製造用組成物
WO2017169534A1 (ja) * 2016-03-30 2017-10-05 株式会社大阪ソーダ 導電性接着剤
WO2021039361A1 (ja) * 2019-08-26 2021-03-04 京セラ株式会社 銀粒子、銀粒子の製造方法、ペースト組成物及び半導体装置並びに電気・電子部品
WO2021044817A1 (ja) * 2019-09-02 2021-03-11 株式会社大阪ソーダ 銀粒子

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JP5574761B2 (ja) 2009-04-17 2014-08-20 国立大学法人山形大学 被覆銀超微粒子とその製造方法
JP2012022795A (ja) * 2010-07-12 2012-02-02 Yokohama Rubber Co Ltd:The 導電性組成物および太陽電池セル
JP2015159096A (ja) 2014-02-25 2015-09-03 田中貴金属工業株式会社 低温焼結性に優れる銀ペースト及び該銀ペーストの製造方法
WO2016204105A1 (ja) * 2015-06-15 2016-12-22 株式会社大阪ソーダ 金属ナノ微粒子製造用組成物
WO2017169534A1 (ja) * 2016-03-30 2017-10-05 株式会社大阪ソーダ 導電性接着剤
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See also references of EP4296326A4

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US12534651B2 (en) 2026-01-27
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