WO2017204238A1 - 導電性接着剤 - Google Patents

導電性接着剤 Download PDF

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Publication number
WO2017204238A1
WO2017204238A1 PCT/JP2017/019311 JP2017019311W WO2017204238A1 WO 2017204238 A1 WO2017204238 A1 WO 2017204238A1 JP 2017019311 W JP2017019311 W JP 2017019311W WO 2017204238 A1 WO2017204238 A1 WO 2017204238A1
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WIPO (PCT)
Prior art keywords
fine particles
protective layer
amine
metal fine
conductive adhesive
Prior art date
Application number
PCT/JP2017/019311
Other languages
English (en)
French (fr)
Inventor
崇充 森
淳一郎 三並
岩佐　成人
Original Assignee
株式会社大阪ソーダ
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 株式会社大阪ソーダ filed Critical 株式会社大阪ソーダ
Priority to KR1020187032860A priority Critical patent/KR102305794B1/ko
Priority to US16/304,098 priority patent/US20200172767A1/en
Priority to JP2018519575A priority patent/JP6962321B2/ja
Priority to CN202311099183.2A priority patent/CN117285876A/zh
Priority to CN201780024674.7A priority patent/CN109072012A/zh
Priority to EP17802824.7A priority patent/EP3467062A4/en
Publication of WO2017204238A1 publication Critical patent/WO2017204238A1/ja

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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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
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    • B22—CASTING; POWDER METALLURGY
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • B22F1/056—Submicron particles having a size above 100 nm up to 300 nm
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    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B22F1/102—Metallic powder coated with organic material
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    • 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
    • B22F7/062—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 involving the connection or repairing of preformed parts
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    • 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
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    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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Definitions

  • the present invention relates to a conductive adhesive, a method for producing the same, a sintered body of the conductive adhesive, and a circuit or apparatus including the sintered body between members.
  • Conductive adhesives such as die bonds and die attach agents are bonding materials used for semiconductors, LEDs, power semiconductors and the like.
  • As a joining method it is generally known to join to a substrate by joining by pressurization and heating, or sintering by heating or the like without applying pressure.
  • development of a non-pressurized bonding material has been advanced from the viewpoint of the simplicity and efficiency of the manufacturing process.
  • Non-pressure bonding material is a conductive adhesive containing an epoxy resin.
  • This bonding material is used by curing an epoxy resin by low-temperature treatment, and can suppress the generation of voids and improve the bonding strength with a base material (Patent Document 1).
  • Patent Document 1 the epoxy resin itself becomes a resistor, the obtained conductivity and thermal conductivity are lowered.
  • a bonding material that does not contain a thermosetting resin such as an epoxy resin a conductive adhesive made of only silver can be cited.
  • This bonding material uses micro silver or sub-micron silver (particle diameter 300 to 900 nm) (Patent Document 2), however, voids are likely to occur, and a normal sintering reaction is performed at 200 to 250 ° C. for 1 hour. Is required. For this reason, development of the joining material which can obtain high shear strength (material with high joining property) by processing at a low temperature for a short time and can suppress generation
  • silver nanoparticles are characterized by being easily sintered at a low temperature by a short heat treatment.
  • silver nanoparticle having a particle diameter of about 20 nm it can be easily sintered at a relatively low temperature (200 ° C. or lower) to form a dense film.
  • a relatively low temperature 200 ° C. or lower
  • stress is generated in the coating film as the film thickness increases, resulting in cracks and chipping. For this reason, development of a material with less stress on the coating film is required.
  • Patent Document 3 As a material that satisfies this requirement, a conductive adhesive containing nano-sized metal nanoparticles has been proposed (see, for example, Patent Document 3).
  • the conductive adhesive containing nano-sized metal nanoparticles is placed between the members, and a sintered body heated and sintered at a high temperature (eg, 200 ° C. or higher) adheres between the members. High conductivity can be exhibited.
  • a high temperature eg, 200 ° C. or higher
  • the conventional sintered adhesive containing nano-sized silver fine particles causes cracking, chipping, etc. in the obtained sintered body, resulting in a decrease in mechanical strength. I found it.
  • the heating time at the time of sintering is increased or the heating temperature is increased, the problem of cracking and chipping of the sintered body occurs remarkably.
  • the main object of the present invention is to provide a conductive adhesive that is less susceptible to cracking or chipping due to sintering and that provides a sintered body having excellent mechanical strength. Furthermore, another object of the present invention is to provide a method for producing a conductive adhesive, a sintered body of a conductive adhesive, and a circuit or device including the sintered body between members.
  • the present inventor has intensively studied to solve the above problems.
  • conductive adhesives with metal fine particles that have a protective layer containing a specific amine and have an average particle diameter in a specific range effectively suppress cracking and chipping of the sintered body of the conductive adhesive. And found that a sintered body excellent in mechanical strength can be obtained.
  • the conductive adhesive includes a metal fine particle A having a protective layer containing an amine and having an average particle diameter of 30 nm to 300 nm, and the amine is a monoalkyl having 5 to 7 carbon atoms.
  • this invention provides the invention of the aspect hung up below.
  • Item 1 Comprising a protective layer containing an amine, containing metal fine particles A having an average particle size of 30 nm to 300 nm,
  • the amine includes a monoalkylamine having 5 to 7 carbon atoms and / or an alkoxyamine represented by the following general formula (1): NH 2 —R 2 —O—R 1 (1) [Wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 4 carbon atoms.
  • the ratio of the monoalkylamine having 5 to 7 carbon atoms and / or the alkoxyamine represented by the general formula (1) to an amine different from these is 100: 0 to 10:90.
  • a method for producing a conductive adhesive comprising a step of mixing a metal fine particle A having a protective layer containing an amine and having an average particle diameter of 30 nm to 300 nm,
  • the amine contains a monoalkylamine having 5 to 7 carbon atoms and / or an alkoxyamine represented by the following general formula (1): NH 2 —R 2 —O—R 1 (1) [Wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 4 carbon atoms.
  • the ratio of the monoalkylamine having 5 to 7 carbon atoms and / or the alkoxyamine represented by the general formula (1) to an amine different from these is 100: 0 to 10:90.
  • the amine contained in the protective layer of the metal fine particle with the monoalkylamine having 5 to 7 carbon atoms and the alkoxyamine represented by the general formula (1), the monoalkylamine having 5 to 7 carbon atoms and / or
  • the manufacturing method of the said conductive adhesive, the sintered compact of the said conductive adhesive, and the circuit or apparatus provided with the said sintered compact between members can be provided.
  • the conductive adhesive of the present invention includes a metal fine particle A having an amine-containing protective layer and an average particle diameter of 30 nm to 300 nm, and the amine is a monoalkylamine having 5 to 7 carbon atoms and / or the following: It contains an alkoxyamine represented by the general formula (1), and the protective layer is different from the monoalkylamine having 5 to 7 carbon atoms and / or the alkoxyamine represented by the general formula (1).
  • the ratio with the amine is in the range of 100: 0 to 10:90.
  • NH 2 —R 2 —O—R 1 (1) wherein R 1 represents an alkyl group having 1 to 4 carbon atoms, and R 2 represents an alkylene group having 1 to 4 carbon atoms. ]
  • the conductive adhesive of the present invention the method for producing the conductive adhesive, the sintered body of the conductive adhesive, and the circuit or device provided with the sintered body between the members will be described in detail.
  • Conductive adhesive The conductive adhesive of the present invention contains the aforementioned metal fine particles A in a predetermined ratio.
  • Metal fine particle A The metal fine particles A of the present invention are provided with a protective layer containing an amine and have an average particle diameter of 30 nm to 300 nm. As will be described later, the metal fine particles A have the protective layer on the surface layer of particles (metal particles) made of metal.
  • the amine contained in the protective layer of the metal fine particle A is represented by a monoalkylamine having 5 to 7 carbon atoms (hereinafter sometimes referred to as “C5-7 monoalkylamine”) and the general formula (1). At least one of the above-mentioned alkoxyamines (hereinafter sometimes referred to as “alkoxyamine (1)”).
  • a total of amine (1): a total of amines different from C5-7 monoalkylamine and / or alkoxyamine (1)) is in the range of 100: 0 to 10:90.
  • the average particle size of the metal fine particles A of the present invention can be used without particular limitation as long as it is in the range of 30 nm to 300 nm, preferably in the range of 30 nm to 250 nm, and more preferably in the range of 30 nm to 230 nm. . If the average particle size is smaller than 30 nm, sufficient mechanical strength (shear strength) cannot be obtained, and if it is larger than 300 nm, sufficient conductivity cannot be obtained.
  • the average particle diameter of the metal fine particles A in the present invention is only when a metal fine particle having an average particle diameter in the above range is used alone or in combination with a plurality of metal fine particles having an average particle diameter in the above range. Alternatively, a case where metal fine particles having an average particle size outside the above range are mixed to obtain an average particle size within the above range may be included.
  • the metal fine particle A contains a monoalkylamine having 5 to 7 carbon atoms (particularly preferably n-hexylamine) as the amine contained in the protective layer.
  • metal fine particles S having an average particle diameter in the range of 180 nm to 210 nm.
  • the amine contained in the protective layer of the metal fine particles S preferably contains 80% or more, more preferably 90% or more of a monoalkylamine having 5 to 7 carbon atoms.
  • the ratio of the said metal fine particle S in the metal fine particle A is 20 mass% or more.
  • the amount of amine contained in the protective layer in the metal fine particles of the present invention can be determined by the measurement method described later.
  • the metal fine particles A may be substantially composed only of the metal fine particles S (the ratio of the metal fine particles S is 99% by mass or more), and may contain other metal fine particles.
  • the amine contained in the protective layer contains a monoalkylamine having 5 to 7 carbon atoms (particularly preferably n-hexylamine) and an average particle size of 50 nm to 100 nm.
  • a range of fine metal particles P is preferred.
  • the amine contained in the protective layer of the metal fine particles P preferably contains 80% or more, more preferably 90% or more of a monoalkylamine having 5 to 7 carbon atoms.
  • the proportion of the metal fine particles P in the metal fine particles A is preferably about 20% by mass to 80% by mass.
  • the metal fine particles having an average particle size in the above range can be arbitrarily selected, and metal fine particles having different average particle sizes can be combined to form metal fine particles A. it can.
  • combinations of different average particle sizes include, for example, metal fine particles having an average particle size of 30 nm or more and less than 100 nm (preferably a range of average particle size of 30 nm or more and less than 100 nm, and more preferably a range of average particle size of 50 nm or more and less than 100 nm).
  • metal fine particles (I) having a small average particle size and an average particle size of 100 nm to 300 nm (preferably a range of average particle size of 100 nm to 250 nm, and a range of average particle size of 100 nm to 230 nm is more preferable).
  • a combination with metal fine particles for example, metal fine particles (II) having a large average particle diameter) can be exemplified.
  • the ratio in the case of using a combination of metal fine particles having different average particle diameters can be selected as appropriate, but the mass ratio of the metal fine particles (I) having a small average particle diameter and the metal fine particles (II) having a large average particle (I: II) may be in the range of 99: 1 to 1:99, preferably in the range of 90:10 to 10:90, more preferably in the range of 90:10 to 20:80, and 90:10 to 40:60. The range of is more preferable.
  • metal fine particles outside the above average particle diameter range (outside the range of 30 nm to 300 nm, for example, less than 30 nm, 1 to 25 nm, more than 300 nm, more than 300 nm and less than 500 nm) are used in combination. Can do.
  • metal fine particles outside the above average particle diameter range are used in combination, if the average particle diameter after mixing the metal fine particles is within the above average particle diameter range, addition of metal fine particles outside the above average particle diameter range
  • the amount is not particularly limited, and may be, for example, 15% by mass or less, preferably 10% by mass or less, and more preferably 5% by mass or less based on the total amount of the metal fine particles.
  • the fine metal particles outside the above average particle diameter range preferably have a protective layer.
  • a protective layer having a ratio of the C5-7 monoalkylamine and / or alkoxyamine (1) to an amine different from these is in the range of 100: 0 to 10:90. It is also possible to use one outside this range.
  • the protective layer of the metal fine particles outside the above range of the average particle diameter may be composed of those that can be used as a component of the protective layer of the metal fine particles A described later.
  • the average particle diameter of the metal fine particles A is an average value of the lengths of the long sides of 30 or more particles included in an image observed with a scanning electron microscope.
  • grains contained in the image at the time of observing with a scanning electron microscope It can be an average value.
  • the average particle diameter in the case of using a combination of metal fine particles having different average particle diameters is the average value of the long side lengths of 30 or more particles of each metal fine particle included in an image observed with a scanning electron microscope. And the mixing ratio of each metal fine particle.
  • the content of the metal fine particles is not particularly limited, but is preferably 80% by mass or more, more preferably about 85% by mass to 95% by mass.
  • Examples of the metal species of the metal fine particles A of the present invention include gold, silver, copper, platinum, palladium, nickel, aluminum and the like.
  • gold, silver, and platinum are preferable in terms of conductivity
  • silver, copper, and nickel are preferable in terms of cost and low-temperature sinterability
  • silver is particularly preferable.
  • the metal fine particles A of the present invention have a protective layer on the surface layer of particles (metal particles) made of metal.
  • the material for forming the protective layer is not particularly limited as long as it can form a surface layer of metal particles and can function as a protective layer (for example, a layer that suppresses aggregation of metal fine particles A). From the viewpoint of effectively increasing the mechanical strength of the sintered body of the adhesive, preferably, fatty acids, amines, hydroxy fatty acids and the like are mentioned.
  • the protective layer may be composed of one type of material, or may be composed of two or more types of materials.
  • a fatty acid in a fatty- acid protective layer Preferably it is C3-C18 fatty acid, More preferably, C4-C18 fatty acid of an alkyl group is mentioned.
  • preferred 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, linoleic acid , ⁇ -linolenic acid and the like.
  • fatty acids include cyclic alkyl carboxylic acids such as cyclohexane carboxylic acid.
  • caproic acid, 2-ethylhexylic acid, oleic acid, linoleic acid, and ⁇ -linolenic acid are preferable from the viewpoint of effectively increasing the mechanical strength of the sintered body of the conductive adhesive.
  • the fatty acid in the protective layer may be composed of one type of fatty acid or may be composed of two or more types of fatty acid.
  • the amine contained in the protective layer of the amine metal fine particle A contains at least one of C5-7 monoalkylamine and alkoxyamine (1).
  • the amine contained in the protective layer if it contains at least one of C5-7 monoalkylamine (especially monoalkylamine having 6 carbon atoms) and alkoxyamine (1), it should be used without any problem. Can do.
  • the amine in the protective layer may be formed from at least one of C5-7 monoalkylamine and alkoxyamine (1), and may contain other amines.
  • the ratio of C5-7 monoalkylamine and / or alkoxyamine (1) to an amine different from these may be in the range of 100: 0 to 10:90, and 100: 0 to 20: 80 is preferable, 100: 0 to 30:70 is more preferable, 100: 0 to 40:60 is more preferable, and 100: 0 to 50:50 is preferable. Particularly preferred. If it is the said range, when it sinters, the sintered compact which is excellent in mechanical strength (shear strength) will be obtained.
  • the ratio of each amine contained in the protective layer can be calculated from gas chromatography. Specifically, after dispersing 1 g of metal fine particles in 4 g of methanol, adding a few drops of concentrated hydrochloric acid and stirring well, the amine in the protective layer is liberated in methanol, and the solution is neutralized with sodium hydroxide. The product is introduced into gas chromatography. The ratio of each amine can be determined by the peak area of the amine obtained by chromatography. The amount of amine contained in the protective layer is expressed as content (%) from the value of the peak area obtained by the above measuring method.
  • Examples of the monoalkylamine having 5 to 7 carbon atoms include n-amylamine, n-hexylamine, n-heptylamine, cyclohexylamine, cycloheptylamine and the like. Of these, n-amylamine, n-hexylamine and n-heptylamine are preferable, and n-hexylamine is particularly preferable.
  • the C5-7 monoalkylamine in the protective layer may be composed of one type of monoalkylamine or may be composed of two or more types of monoalkylamine.
  • R 1 may be linear or branched as long as it is an alkyl group having 1 to 4 carbon atoms, and is preferably alkyl having 1 to 3 carbon atoms. A group, an ethyl group, a propyl group, and an isopropyl group are more preferable.
  • R 2 may be linear or branched as long as it is an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl, propyl, isopropyl More preferably, it is a group.
  • the alkoxyamine represented by the general formula (1) may be composed of one kind of alkoxyamine or may be composed of two or more kinds of alkoxyamine.
  • alkoxyamine represented by the general formula (1) examples include 1-methoxymethylamine, 1-ethoxymethylamine, 1-propoxymethylamine, 1-isopropoxymethylamine, 1-butoxymethylamine, -Methoxyethylamine, 2-ethoxyethylamine, 2-propoxyethylamine, 2-isopropoxyethylamine, 2-butoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-isopropoxypropylamine, Examples include 3-butoxypropylamine, 4-methoxybutylamine, 4-ethoxybutylamine, 4-propoxybutylamine, 4-isopropoxybutylamine, 4-butoxybutylamine and the like.
  • 2-ethoxyethylamine, 2-propoxyethylamine, 2-isopropoxyethylamine, 2-butoxyethylamine, 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, and 3-isopropoxypropylamine are preferable.
  • the amine contained in the protective layer may be either one of C5-7 monoalkylamine and alkoxyamine (1), or may contain both.
  • the ratio when both are included is not particularly limited, and can be arbitrarily included. The ratio includes, for example, 70:30 to 30:70.
  • the amine contained in the protective layer may contain an amine different from C5-7 monoalkylamine and / or alkoxyamine (1).
  • the amine contained in the protective layer of the metal fine particles A is detached from the surface of the metal fine particles A when the conductive adhesive is sintered. It has virtually no effect on sex.
  • amines contained in the protective layer specific examples of amines different from C5-7 monoalkylamine and / or alkoxyamine (1) are not particularly limited, but include primary amines, secondary amines, Examples thereof include tertiary amines, and diamine compounds having two amino groups in one compound.
  • Primary amines include ethylamine, n-propylamine, isopropylamine, 1,2-dimethylpropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, isoamylamine, n-octylamine, 2- Octylamine, tert-octylamine, 2-ethylhexylamine, n-nonylamine, n-aminodecane, n-aminoundecane, n-dodecylamine, n-tridecylamine, 2-tridecylamine, n-tetradecylamine, n -Pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-oleylamine, 3-methoxypropylamine, 3-ethoxy
  • cyclopropylamine, cyclobutylamine, cyclopropylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine which are alicyclic amines, aniline which is an aromatic amine, and the like can be exemplified.
  • ether amines such as 3-isopropoxypropylamine and isobutoxypropylamine can also be exemplified.
  • Secondary amines include N, N-dipropylamine, N, N-dibutylamine, N, N-dipentylamine, N, N-dihexylamine, N, N-dipeptylamine, N, N-dioctylamine, N , N-dinonylamine, N, N-didecylamine, N, N-diundecylamine, N, N-didodecylamine, N, N-distearylamine, N-methyl-N-propylamine, N-ethyl-N- Examples thereof include dialkyl monoamines such as propylamine, N-propyl-N-butylamine, and cyclic amines such as piperidine.
  • tertiary amine examples include triethylamine, tributylamine, trihexylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, and dilaurylmonomethylamine.
  • a diamine compound having two amino groups in one compound can also be used.
  • the diamine compound include ethylenediamine, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-diethylethylenediamine, N, N′-diethylethylenediamine, 1,3-propanediamine, and 2,2-dimethyl- 1,3-propanediamine, N, N-dimethyl-1,3-propanediamine, N, N'-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N '-Diethyl-1,3-propanediamine, 1,4-butanediamine, N, N-dimethyl-1,4-butanediamine, N, N'-dimethyl-1,4-butanediamine, N, N-diethyl -1,4-butanediamine, N, N′-diethyl-1,4-
  • n-butylamine, n-octylamine, N, N-dimethyl-1,3-diaminopropane, N, N-diethyl- 1,3-diaminopropane is preferred.
  • Different amines in the protective layer may contain one kind of the above-described amines or may contain two or more kinds.
  • the molar ratio of amine to fatty acid is preferably in the range of about 90:10 to about 99.9: 0.1, and about 95: 5 A range of from about 99.5: 0.5 is more preferred.
  • the protective layer of the metal fine particles A in the present invention may contain a hydroxy fatty acid.
  • the hydroxy fatty acid that can be contained in the protective layer is a hydroxy fatty acid having 3 to 24 carbon atoms and 1 hydroxyl group.
  • a compound having more than one (for example, one) can be used.
  • hydroxy fatty acids include 2-hydroxydecanoic acid, 2-hydroxydodecanoic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 2-hydroxyoctadecanoic acid, 2-hydroxyeicosanoic acid, 2-hydroxydocosanoic acid, 2-hydroxytricosanoic acid, 2-hydroxytetracosanoic acid, 3-hydroxyhexanoic acid, 3-hydroxyoctanoic acid, 3-hydroxynonanoic acid, 3-hydroxydecanoic acid, 3-hydroxyundecanoic acid, 3-hydroxydodecanoic acid, 3-hydroxytridecanoic acid, 3-hydroxytetradecanoic acid, 3-hydroxyhexadecanoic acid, 3-hydroxyheptadecanoic acid, 3-hydroxyoctadecanoic acid, ⁇ -hydroxy-2-decenoic acid, ⁇ -hydroxypentadecanoic acid, ⁇ -hydroxy Heptade Acid, ⁇ -hydroxyeicosanoic acid
  • hydroxy fatty acids having 4 to 18 carbon atoms and having one hydroxyl group other than the ⁇ position (particularly the 12th position) are preferable, and ricinoleic acid and 12-hydroxystearic acid are more preferable.
  • the hydroxy fatty acid contained in the second protective layer may be one type or two or more types.
  • the content of the hydroxy fatty acid may be in the range of 0.1 to 10 mol, preferably in the range of 0.2 to 5 mol, with respect to 1 mol of the amine. .
  • the ratio (mass%) of the protective layer in the metal fine particle A is not particularly limited, but from the viewpoint of effectively increasing the mechanical strength of the sintered body of the conductive adhesive while protecting the surface of the metal fine particle A, about 0.1 to 10% by mass is preferable, about 0.2 to 8% by mass is more preferable, and about 0.2 to 5% by mass is more preferable.
  • the metal fine particles A used in the present invention may be purchased and used as long as they have the characteristics described above, and are usually used for producing metal fine particles (for example, silver fine particles) used (for example, , JP-A-2015-40319) may be used. Details of the method for producing the metal fine particles will be described later. Further, in the metal fine particles A of the present invention, the ratio of C5-7 monoalkylamine and / or alkoxyamine (1) in the protective layer to an amine different from these is out of the range of 100: 0 to 10:90. It is also possible to use a metal fine particle having the ratio adjusted within a range of 100: 0 to 10:90 by a method described later.
  • the conductive adhesive of the present invention preferably further contains a solvent.
  • a solvent By containing a solvent, fluidity
  • the solvent is not particularly limited as long as it can disperse the metal fine particles A, but preferably contains a polar organic solvent.
  • 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, 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 Diols such as 2-methyl-2,4-pentanediol, 3-methyl-1,5-pentanediol, 1,2-octanediol,
  • a linear or branched alcohol having 3 to 5 carbon atoms, 3-methoxy-3-methyl-1- Butanol, 3-methoxy-1-butanol, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, and terpineol are preferred.
  • the solvent may further contain a nonpolar or hydrophobic solvent in addition to the polar organic solvent.
  • Non-polar 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 Alcohols such as benzene, toluene and benzonitrile; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; methyl-n-amyl ketone; methyl ethyl ketone oxime; and triacetin.
  • 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 preferable.
  • a solvent can be used individually by 1 type or in mixture of 2 or more types.
  • the ratio of the polar organic solvent is preferably 5% by volume or more, more preferably 10% by volume or more, and further preferably 15% by volume or more with respect to the total amount of the solvent. More preferred. Moreover, it can be 60 volume% or less, can also be 55 volume% or less, and can also be 50 volume% or less.
  • the solvent may consist of only a polar organic solvent.
  • the conductive adhesive of the present invention has good dispersibility of the metal fine particles A even when it contains a large amount of polar organic solvent.
  • the ratio of the solvent is not particularly limited, but is preferably 20% by mass or less, more preferably about 5% by mass to 15% by mass.
  • the conductive adhesive of the present invention includes a step of mixing metal fine particles A having an amine-containing protective layer and having an average particle diameter of 30 nm to 300 nm (more specifically, mixing the metal fine particles A and a solvent). It can manufacture by the method of providing.
  • the amine contains a monoalkylamine having 5 to 7 carbon atoms and / or an alkoxyamine represented by the general formula (1).
  • the metal in which the ratio of the monoalkylamine of formula 5 to 7 and / or the alkoxyamine represented by the general formula (1) to an amine different from these is in the range of 100: 0 to 10:90 Fine particles A are used.
  • a metal fine particle having an amine-containing protective layer and having an average particle diameter of 30 nm to 300 nm is prepared, and the amine contained in the metal fine particle protective layer and carbon
  • the monoalkylamine having 5 to 7 and / or the alkoxyamine represented by the general formula (1) is substituted to represent the monoalkylamine having 5 to 7 carbon and / or the general formula (1).
  • a step of preparing the metal fine particles A may be further provided by adjusting the ratio of the alkoxyamine and the amine different from these to be in the range of 100: 0 to 10:90.
  • the following method can be employed as a method for preparing the metal fine particles A by substituting the amine.
  • Method for producing metal fine particles A An example of a method for producing metal fine particles A (for example, silver fine particles) used in the present invention is shown below.
  • a composition for producing metal fine particles A (a composition for preparing silver fine particles) is prepared. Specifically, a silver compound (preferably, silver nitrate, silver oxalate, etc.) that is a raw material for the silver fine particles, components (such as the aforementioned fatty acid, amine, hydroxy fatty acid, etc.) constituting the protective layer, and an organic solvent are prepared. . Next, these components are mixed to obtain a silver fine particle preparation composition. What is necessary is just to adjust suitably the ratio of each component in the said composition so that it may become the structure of the above-mentioned metal microparticle A.
  • the content of silver oxalate in the composition is preferably about 20 to 70% by mass relative to the total amount of the composition.
  • the content of the fatty acid is preferably about 0.1% by mass to 20% by mass with respect to the total amount of the composition.
  • the amine content in the protective layer is preferably about 5% by mass to 55% by mass with respect to the total amount of the composition.
  • the content of the hydroxy fatty acid is preferably about 0.1% by mass to 15% by mass with respect to the total amount of the composition.
  • the amine may be used by adjusting the ratio of C5-7 monoalkylamine and / or alkoxyamine (1) to an amine different from these within the above range. Further, silver fine particles were synthesized using a composition for preparing silver fine particles adjusted so that the ratio in the protective layer was outside the above range, and the ratio was adjusted within the above range by the method described later (the amine was added). (Replacement) is also possible.
  • the mixing means of each component is not particularly limited, and can be mixed by a general-purpose apparatus such as a mechanical stirrer, a magnetic stirrer, a vortex mixer, a planetary mill, a ball mill, a three roll, a line mixer, a planetary mixer, or a dissolver.
  • a general-purpose apparatus such as a mechanical stirrer, a magnetic stirrer, a vortex mixer, a planetary mill, a ball mill, a three roll, a line mixer, a planetary mixer, or a dissolver.
  • the temperature of the composition is, for example, 60 ° C. or less, particularly 40 ° C. It is preferable to mix while keeping below.
  • the composition for preparing silver fine particles by subjecting the composition for preparing silver fine particles to a reaction in a reaction vessel, usually a reaction by heating, a thermal decomposition reaction of the silver compound occurs to produce silver fine particles.
  • the composition may be introduced into a previously heated reaction vessel, or may be heated after the composition is introduced into the reaction vessel.
  • the reaction temperature may be any temperature at which the thermal decomposition reaction proceeds and silver fine particles are generated, and it may be about 50 to 250 ° C., for example. Further, the reaction time may be appropriately selected according to the desired average particle size and the composition of the composition corresponding thereto. Examples of the reaction time include 1 minute to 100 hours.
  • the silver fine particles produced by the thermal decomposition reaction are obtained as a mixture containing unreacted raw materials, it is preferable to purify the silver fine particles.
  • the purification method include a solid-liquid separation method, a precipitation method using a specific gravity difference between silver fine particles and an unreacted raw material such as an organic solvent.
  • the solid-liquid separation method include filter filtration, centrifugal separation, cyclone type, and decanter methods.
  • the viscosity of the mixture may be adjusted by diluting a mixture containing silver fine particles with a low-boiling solvent such as acetone or methanol.
  • the average particle diameter of the obtained silver fine particles can be adjusted.
  • Method for adjusting (substituting) the ratio of each amine in the protective layer The ratio (C5-7 monoalkylamine and / or alkoxyamine (C5-7 monoalkylamine and / or alkoxyamine) in the protective layer described in the section “2.
  • Method for producing metal fine particles A” 1) and a ratio of amines different from these) are adjusted (substitute) so that the ratio of the fine metal particles obtained by adjusting the ratio to be outside the above range is within the above range. State.
  • metal fine particles in which the ratio of C5-7 monoalkylamine and / or alkoxyamine (1) to an amine different from these is outside the above range is dispersed in a solvent, and C5-7 Adding at least one of monoalkylamine and alkoxyamine (1) in a range of 0.1 to 5 times the mass of the metal fine particles, and stirring at room temperature to 80 ° C. for 1 minute to 24 hours
  • the ratio of each amine in a protective layer can be adjusted (substitution) in the said range.
  • the solvent for dispersing the metal fine particles a solvent that can be used for the synthesis of the metal fine particles may be used, or a solvent that can be used for the conductive adhesive may be used.
  • the metal fine particles in which the ratio of each amine in the protective layer is adjusted (substituted) to the above range can be recovered by the solid-liquid separation method described in the section “2. Method for producing metal fine particles A”.
  • the method for adjusting (substituting) the ratio of each amine in the protective layer is as follows: in the case of metal fine particles having an average particle diameter outside the above range, C5-7 monoalkylamine and / or alkoxyamine (1) in the protective layer It is also possible to adjust the ratio of amines different from these to a desired ratio.
  • Sintered body of conductive adhesive 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 the above-mentioned "1. Conductive adhesive”. .
  • the sintered body of the conductive adhesive of the present invention most of the components constituting the protective layer of the conductive adhesive are detached due to the high heat during sintering, and the sintered body is substantially In general, it is made of metal.
  • the sintering temperature is not particularly limited, but is preferably about 150 ° C. to 200 ° C. from the viewpoint of effectively increasing the mechanical strength while the obtained sintered body exhibits high conductivity and high adhesive force.
  • the temperature is about 150 ° C. to 185 ° C.
  • the sintering time is preferably about 0.4 to 2.0 hours, more preferably about 0.5 to 1.2 hours.
  • Sintering can be performed in an atmosphere such as air or an inert gas (nitrogen gas, argon gas).
  • the sintering means is not particularly limited, and examples thereof include an oven, a hot air drying furnace, an infrared drying furnace, laser irradiation, flash lamp irradiation, and microwave.
  • circuit or Device of the present invention includes a portion where members are bonded by the sintered body of the present invention.
  • the circuit or device of the present invention is obtained by disposing the conductive adhesive of the present invention described in detail in “1. Conductive adhesive” between the members of the circuit or device, and sintering the conductive adhesive. And the members are bonded together.
  • the sintered body of the present invention exhibits high electrical conductivity and high adhesive force, and the mechanical strength is effectively enhanced. Excellent electrical conductivity and adhesion, and excellent mechanical strength.
  • the amine in the protective layer of the synthesized silver fine particles was measured by the following method.
  • the sample was analyzed using gas chromatography (GC-2010 manufactured by Shimadzu Corporation, column: Rtx-5 Amine manufactured by RESTEK), and the ratio of amine contained in the protective layer (GC%) was determined from the peak area ratio obtained. Quantification was performed. The results are shown in Table 1-3.
  • HA is n-hexylamine
  • MP is methoxypropylamine
  • DA is N, N-diethyl-1,3-diaminopropane or N, N-dimethyl-1,3-diaminopropane
  • BuNH 2 means n-butylamine
  • PrNH 2 means n-propylamine.
  • these glass centrifuge tubes were set up on a hot stirrer equipped with an aluminum block (HHE-19G-U manufactured by Koike Seimitsu Seisakusho), stirred at 40 ° C. for 30 minutes, and further at 30 ° C. for 30 minutes. Stir for minutes.
  • the magnetic stir bar was taken out, 15 g of methanol was added to each composition, and the mixture was stirred with a vortex mixer, and then centrifuged at 3000 rpm (about 1600 ⁇ G) for 1 minute with a centrifuge (CF7D2 manufactured by Hitachi Koki). A sedimentation operation was performed, and the supernatant was removed by tilting the centrifuge tube.
  • the steps of adding 15 g of methanol, stirring, centrifuging, and removing the supernatant were repeated twice to recover the produced silver fine particles 1.
  • the silver fine particles 1 obtained in Synthesis Example 1 were observed with a scanning electron microscope (S-4500, manufactured by Hitachi High-Tech), and the length of the long side of any 30 particles included in the image was measured. The average value was obtained. The average particle size was 200 nm.
  • Example 1 In Example 1, silver fine particles 1A and in Example 2 silver fine particles 1B were used, and terpineol corresponding to 10% of the total mass was added to obtain each dispersion. This solution was mixed twice in a stirring priority mode using a Mazerustar manufactured by Kurabo Industries, and each conductive adhesive was prepared.
  • each conductive adhesive may have a film thickness of 50 micrometers
  • a silicon wafer (size 2 mm ⁇ 2 mm) having a gold plating or gold sputtering process on the back surface (the surface in contact with the conductive adhesive) was placed on top. This was heated with a dryer (circulation type) at a predetermined temperature (150 ° C.) for 60 minutes to obtain a coating film in which each conductive adhesive was sintered.
  • these glass centrifuge tubes were set up on a hot stirrer equipped with an aluminum block (HHE-19G-U manufactured by Koike Seimitsu Seisakusho), stirred at 40 ° C. for 30 minutes, and further at 30 ° C. for 30 minutes. Stir for minutes.
  • the magnetic stir bar was taken out, 15 g of methanol was added to each composition, and the mixture was stirred with a vortex mixer, and then centrifuged at 3000 rpm (about 1600 ⁇ G) for 1 minute with a centrifuge (CF7D2 manufactured by Hitachi Koki). A sedimentation operation was performed, and the supernatant was removed by tilting the centrifuge tube.
  • the steps of adding 15 g of methanol, stirring, centrifuging, and removing the supernatant were repeated twice to recover the produced silver fine particles 2.
  • the silver fine particles 2 obtained in Synthesis Example 2 were observed with a scanning electron microscope (S-4500, manufactured by Hitachi High-Tech), and the length of the long side of any 30 particles included in the image was measured. The average value was obtained. The average particle size was 75 nm.
  • the silver fine particle 2 obtained by the synthesis example 2 was used for the Example as the silver fine particle 2C.
  • Example 3 used silver fine particles 2A
  • Example 4 used silver fine particles 2B
  • Comparative Example 1 used silver fine particles 2C
  • Comparative Example 2 used silver fine particles 2D
  • Comparative Example 3 used silver fine particles 2E.
  • Each of these liquids was mixed twice in a stirring priority mode using a Mazerustar manufactured by Kurabo Industries, and each conductive adhesive was prepared.
  • each conductive adhesive may have a film thickness of 50 micrometers
  • a silicon wafer (size 2 mm ⁇ 2 mm) having a gold plating or gold sputtering process on the back surface (the surface in contact with the conductive adhesive) was placed on top. This was heated with a dryer (circulation type) at a predetermined temperature (150 ° C.) for 60 minutes to obtain a coating film in which each conductive adhesive was sintered.
  • these glass centrifuge tubes were set up on a hot stirrer equipped with an aluminum block (HHE-19G-U manufactured by Koike Seimitsu Seisakusho), stirred at 40 ° C. for 30 minutes, and further at 30 ° C. for 30 minutes. Stir for minutes.
  • the magnetic stir bar was taken out, 15 g of methanol was added to each composition, and the mixture was stirred with a vortex mixer, and then centrifuged at 3000 rpm (about 1600 ⁇ G) for 1 minute with a centrifuge (CF7D2 manufactured by Hitachi Koki). A sedimentation operation was performed, and the supernatant was removed by tilting the centrifuge tube.
  • the steps of adding 15 g of methanol, stirring, centrifuging, and removing the supernatant were repeated twice to recover the produced silver fine particles 6.
  • the silver fine particles 3 obtained in Synthesis Example 3 were observed with a scanning electron microscope (S-4500 manufactured by Hitachi High-Tech), and the length of the long side of any 30 particles included in the image was measured. The average value was obtained. The average particle size was 20 nm.
  • a base material having an electroless silver plating of 0.5 ⁇ m on a copper plate is prepared, and a conductive adhesive is uniformly coated thereon so that the coating thickness is 50 ⁇ m.
  • a silicon wafer (size 2 mm ⁇ 2 mm) on which gold plating or gold sputtering treatment was performed on the back surface (surface in contact with the conductive adhesive) was placed on top. This was heated with a dryer (circulation type) at a predetermined temperature (150 ° C.) for 60 minutes to obtain a coating film in which the conductive adhesive was sintered.
  • the average particle diameter of the metal fine particles is in the range of 30 nm to 300 nm
  • the amine in the protective layer is a monoalkylamine having 5 to 7 carbon atoms and / or the above general formula
  • the ratio of the alkoxyamine represented by 1) and having 5 to 7 carbon atoms and / or the alkoxyamine represented by the general formula (1) and an amine different from these is 100:
  • the conductive adhesives of Examples 1 to 4 in the range of 0 to 10:90 had high coating film shear strength, and there was no cracking or chipping of the coating film.
  • the conductive adhesive of Comparative Example 1-3 in which the proportion of N, N-diethyl-1,3-diaminopropane, n-butylamine, or n-propylamine in the amine contained in the protective layer is 100% is The shearing force of the coating film was low. Further, the conductive adhesive of Comparative Example 4 in which the average particle diameter of the metal fine particles was 20 nm also had a low coating film shear force.
  • Example 5 to 11 The silver fine particles 1A, 1B, 2A, 2B, and 2C obtained above were mixed at a ratio shown in Table 2, and terpineol corresponding to 10% of the total mass was added to obtain each dispersion. This solution was mixed twice in a stirring priority mode using a Mazerustar manufactured by Kurabo Industries, and each conductive adhesive was prepared. In addition, the average particle diameter after mixing was calculated
  • each conductive adhesive may have a film thickness of 50 micrometers
  • a silicon wafer (size 2 mm ⁇ 2 mm) having a gold plating or gold sputtering process on the back surface (the surface in contact with the conductive adhesive) was placed on top. This was heated with a dryer (circulation type) at a predetermined temperature (150 ° C.) for 60 minutes to obtain a coating film in which each conductive adhesive was sintered.
  • the conductive adhesives of Examples 5 to 11 were obtained by mixing metal fine particles having different average particle sizes or amines contained in the protective layer.
  • the particle diameter is in the range of 30 nm to 300 nm
  • the amine in the protective layer contains a monoalkylamine having 5 to 7 carbon atoms and / or an alkoxyamine represented by the above general formula (1), and further has a carbon number Since the ratio of the monoalkylamine of 5 to 7 and / or the alkoxyamine represented by the general formula (1) and the amine different from these is in the range of 100: 0 to 10:90, sintering At a temperature of 150 ° C., the shear strength of the coating film was high, and there was no cracking or chipping of the coating film.
  • Example 12 Each silver fine particle 1A, 1B, 2A, 2B, 2C, 3A obtained above was mixed at a ratio shown in Table 3, and terpineol corresponding to 10% of the total mass was added to obtain each dispersion.
  • This solution was mixed twice in a stirring priority mode using a Mazerustar manufactured by Kurabo Industries, and each conductive adhesive was prepared.
  • the average particle diameter after mixing was calculated
  • each conductive adhesive may have a film thickness of 50 micrometers
  • a silicon wafer (size 2 mm ⁇ 2 mm) having a gold plating or gold sputtering process on the back surface (the surface in contact with the conductive adhesive) was placed on top. This was heated with a dryer (circulation type) at a predetermined temperature (150 ° C.) for 60 minutes to obtain a coating film in which each conductive adhesive was sintered.
  • the conductive adhesive of Example 12 is a mixture of three types of metal fine particles having different average particle sizes and amines contained in the protective layer.
  • the particle diameter is in the range of 30 nm to 300 nm
  • the amine in the protective layer contains a monoalkylamine having 5 to 7 carbon atoms and / or an alkoxyamine represented by the above general formula (1), and further has a carbon number Since the ratio of the monoalkylamine of 5 to 7 and / or the alkoxyamine represented by the general formula (1) and the amine different from these is in the range of 100: 0 to 10:90, sintering At a temperature of 150 ° C., the shear strength of the coating film was high, and there was no cracking or chipping of the coating film. On the other hand, in Comparative Examples 5 and 6 having an average particle diameter of less than 30 ⁇ m, the shear strength of the coating film was low.

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Abstract

焼結による割れや欠け等が発生し難く、機械的強度に優れた焼結体が得られる、導電性接着剤を提供する。　アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子Ａを含有し、　前記アミンは、炭素数５～７のモノアルキルアミン及び／又は下記一般式（１）で表されるアルコキシアミンを含み、 ＮＨ2－Ｒ2－Ｏ－Ｒ1　…（１） [式中、Ｒ1は炭素数１～４のアルキル基を示し、Ｒ2は炭素数１～４のアルキレン基を示す。]　前記保護層において、前記炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にある、導電性接着剤。

Description

導電性接着剤
　本発明は、導電性接着剤、その製造方法、当該導電性接着剤の焼結体、及び当該焼結体を部材間に備えている回路又は装置に関する。
　ダイボンドやダイアタッチ剤等を始めとする導電性接着剤は、半導体、ＬＥＤ、パワー半導体等に使われる接合材料である。接合方式として、加圧と加熱による接合、もしくは無加圧で加熱等による焼結によって基材と接合させることが一般に知られている。近年、製造プロセスの簡便さや効率の観点から、無加圧方式の接合材料の開発が進んでいる。
　無加圧方式の接合材料として、一つはエポキシ樹脂を含む導電性接着剤が挙げられる。この接合材料は、低温処理でエポキシ樹脂を硬化させて使用するものであり、ボイド発生の抑制や基材との接合強度を向上させることができる（特許文献１）。しかしながら、エポキシ樹脂自体が抵抗体となるために、得られる導電性や熱伝導性が低くなる。
　一方、エポキシ樹脂等の熱硬化性樹脂を含まない接合材料として、銀のみからなる導電性接着剤が挙げられる。この接合材料は、ミクロ銀、もしくはサブミクロン銀（粒子径３００～９００ｎｍ）を用いているが（特許文献２）、ボイドが発生しやすく、通常の焼結反応として、２００～２５０℃で１時間の処理が必要である。このため、より低温で短時間の処理で高いせん断強度（接合性の高い材料）が得られ、ボイド発生を抑制することのできる接合材料の開発が求められている。
　近年、銀ナノ微粒子の開発が進んでおり、銀ナノ微粒子は低温で短時間の熱処理で容易に焼結する特徴がある。特に、粒子径が２０ｎｍ程度の銀ナノ微粒子を用いた場合、比較的低温（２００℃以下）で容易に焼結し、緻密な膜を形成することができる。
　しかしながら、接合材料中に２０ｎｍ程度の粒子を多く配合した場合、膜厚が厚くなるに従って塗膜に応力が発生し、その結果として割れや欠けが生じる。このことから、塗膜の応力が少ない材料の開発が求められている。
　この要求を満たす材料として、ナノサイズの金属ナノ微粒子を含む導電性接着剤が提案されている（例えば、特許文献３を参照）。
国際公開２０１０/１８７１２ 国際公開２０１４/１０４０４６ 特開２００６－８３３７７号公報
　ナノサイズの金属ナノ微粒子を含む導電性接着剤は、部材間に配置された状態で、高温（例えば、２００℃以上）に加熱・焼結された焼結体が、部材間を接着しつつ、高い導電性を発揮することが可能となる。
　しかしながら、本発明者が検討を行ったところ、ナノサイズの銀微粒子を含む従来の導電性接着剤では、得られる焼結体に、割れ、欠け等が発生し、機械的強度が低下することを見出した。特に、導電性をより一層高める観点から、焼結時の加熱時間を長くしたり、加熱温度を高くしたりすると、焼結体の割れや欠けの問題が顕著に発生することを見出した。
　このような状況下、本発明は、焼結による割れや欠け等が発生し難く、機械的強度に優れた焼結体が得られる、導電性接着剤を提供することを主な目的とする。さらに、本発明は、導電性接着剤の製造方法、導電性接着剤の焼結体、及び当該焼結体を部材間に備えている回路又は装置を提供することも目的とする。
　本発明者は、上記の課題を解決すべく鋭意検討を行った。その結果、特定のアミンを含む保護層を備え、かつ、特定範囲の平均粒子径を有する金属微粒子を含む導電性接着剤は、導電性接着剤の焼結体の割れや欠けが効果的に抑制され、機械的強度に優れた焼結体が得られることを見出した。より具体的には、導電性接着剤が、アミンを含む保護層を備え、かつ、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子Ａを含有し、前記アミンは、炭素数５～７のモノアルキルアミン及び／又は下記一般式（１）で表されるアルコキシアミンを含み、さらに、前記保護層において、前記炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にある導電性接着剤は、導電性接着剤の焼結体の割れや欠けが効果的に抑制され、機械的強度に優れた焼結体が得られることを見出した。
ＮＨ2－Ｒ2－Ｏ－Ｒ1　　…（１）
[式中、Ｒ1は炭素数１～４のアルキル基を示し、Ｒ2は炭素数１～４のアルキレン基を示す。]
　さらに、このような焼結体は、高い導電性を備え、接着性に優れることも見出した。本発明は、このような知見に基づいて、さらに検討を重ねることにより完成したものである。
　即ち、本発明は、下記に掲げる態様の発明を提供する。
項１．　アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子Ａを含有し、
　前記アミンは、炭素数５～７のモノアルキルアミン及び／又は下記一般式（１）で表されるアルコキシアミンを含み、
ＮＨ2－Ｒ2－Ｏ－Ｒ1　　…（１）
[式中、Ｒ1は炭素数１～４のアルキル基を示し、Ｒ2は炭素数１～４のアルキレン基を示す。]
　前記保護層において、前記炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にある、導電性接着剤。
項２．　前記保護層が、さらに脂肪酸を含む、項１に記載の導電性接着剤。
項３．　溶媒をさらに含む、項１又は２に記載の導電性接着剤。
項４．　項１～３のいずれかに記載の導電性接着剤の焼結体。
項５．　項４に記載の焼結体により部材間が接着された部分を備えている、回路又は装置。
項６．　アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子Ａを混合する工程を備える、導電性接着剤の製造方法であって、
　前記アミンが炭素数５～７のモノアルキルアミン及び／又は下記一般式（１）で表されるアルコキシアミンを含み、
ＮＨ2－Ｒ2－Ｏ－Ｒ1　　…（１）
[式中、Ｒ1は炭素数１～４のアルキル基を示し、Ｒ2は炭素数１～４のアルキレン基を示す。]
　前記保護層において、前記炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にある、前記金属微粒子Ａを用いる、導電性接着剤の製造方法。
項７．　アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子を準備する工程と、
　当該金属微粒子の保護層に含まれるアミンと、炭素数５～７のモノアルキルアミン及び一般式（１）で表されるアルコキシアミンとを置換して、炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内となるように調整し、前記金属微粒子Ａを調製する工程と、
をさらに備える、項６に記載の導電性接着剤の製造方法。
項８．　項１～６のいずれかに記載の導電性接着剤を部材間に配置する工程と、
　前記導電性接着剤を加熱して焼結させる工程と、
を備える、部材の接着方法。
　本発明によれば、焼結による割れや欠け等が発生し難く、機械的強度（せん断強度）に優れた焼結体が得られる導電性接着剤を提供することができる。さらに、本発明によれば、当該導電性接着剤の製造方法、当該導電性接着剤の焼結体、及び当該焼結体を部材間に備えている回路又は装置を提供することができる。
　本発明の導電性接着剤は、アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子Ａを含有し、前記アミンは、炭素数５～７のモノアルキルアミン及び／又は下記一般式（１）で表されるアルコキシアミンを含み、前記保護層において、前記炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にあることを特徴とする。
ＮＨ2－Ｒ2－Ｏ－Ｒ1　　…（１）
[式中、Ｒ1は炭素数１～４のアルキル基を示し、Ｒ2は炭素数１～４のアルキレン基を示す。]
　以下、本発明の導電性接着剤、当該導電性接着剤の製造方法、当該導電性接着剤の焼結体、及び当該焼結体を部材間に備えている回路又は装置について詳述する。
１．導電性接着剤
　本発明の導電性接着剤は、前述の金属微粒子Ａを所定の割合で含んでいる。
金属微粒子Ａ
　本発明の金属微粒子Ａは、アミンを含む保護層を備えており、平均粒子径が３０ｎｍ～３００ｎｍである。後述の通り、金属微粒子Ａは、金属により構成された粒子（金属粒子）の表層に、当該保護層を有している。
　また、金属微粒子Ａの保護層に含まれるアミンは、炭素数５～７のモノアルキルアミン（以下、「Ｃ５－７モノアルキルアミン」ということがある。）及び前記一般式（１）で表されるアルコキシアミン（以下、「アルコキシアミン（１）」ということがある。）の少なくとも一方を含んでいる。さらに、保護層において、炭素数５～７のモノアルキルアミン及び／又は一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率（Ｃ５－７モノアルキルアミン及び／又はアルコキシアミン（１）の合計：Ｃ５－７モノアルキルアミン及び／又はアルコキシアミン（１）とは異なるアミンの合計）が、１００：０～１０：９０の範囲内にある。
　本発明の金属微粒子Ａの平均粒子径は、３０ｎｍ～３００ｎｍの範囲であれば特に制限なく用いることができ、３０ｎｍ～２５０ｎｍの範囲であることが好ましく、３０ｎｍ～２３０ｎｍの範囲であることがより好ましい。平均粒子径が３０ｎｍより小さいと、十分な機械的強度（せん断強度）が得られず、３００ｎｍより大きいと十分な導電性が得られない。なお、本発明における金属微粒子Ａの平均粒子径には、上記範囲の平均粒子径を有する金属微粒子を単独で、又は、上記範囲の平均粒子径を有する金属微粒子を複数組み合わせて用いた場合だけでなく、上記範囲外の平均粒子径の金属微粒子を混合し、上記範囲の平均粒子径となった場合も含まれ得る。
　さらに、特に高い機械的強度（せん断強度）を発揮する観点から、金属微粒子Ａには、保護層に含まれるアミンが炭素数５～７のモノアルキルアミン（特に好ましくはｎ－ヘキシルアミン）を含み、かつ、平均粒子径が１８０ｎｍ～２１０ｎｍの範囲の金属微粒子Ｓを含んでいることが好ましい。当該金属微粒子Ｓの保護層に含まれるアミンは、炭素数５～７のモノアルキルアミンを８０％以上含んでいることが好ましく、９０％以上含んでいることがさらに好ましい。また、金属微粒子Ａ中における、当該金属微粒子Ｓの割合は、２０質量％以上であることが好ましい。
　なお、本発明の金属微粒子における保護層に含まれるアミンの量は、後述の測定方法によって、求めることができる。
　さらに、金属微粒子Ａは、実質的に金属微粒子Ｓのみにより構成されていてもよい（金属微粒子Ｓの割合が９９質量％以上）し、他の金属微粒子を含んでいてもよい。当該金属微粒子Ｓと共に含まれる金属微粒子としては、保護層に含まれるアミンが炭素数５～７のモノアルキルアミン（特に好ましくはｎ－ヘキシルアミン）を含み、かつ、平均粒子径が５０ｎｍ～１００ｎｍの範囲の金属微粒子Ｐが好ましい。当該金属微粒子Ｐの保護層に含まれるアミンは、炭素数５～７のモノアルキルアミンを８０％以上含んでいることが好ましく、９０％以上含んでいることがさらに好ましい。また、金属微粒子Ａ中における、当該金属微粒子Ｐの割合は、２０質量％～８０質量％程度であることが好ましい。
　上記範囲の平均粒子径を有する金属微粒子を複数組み合わせて用いる場合、上記範囲の平均粒子径を有する金属微粒子を任意で選択し、異なる平均粒子径の金属微粒子を組み合せて金属微粒子Ａとすることができる。異なる平均粒子径の組み合わせとして、例えば、平均粒子径３０ｎｍ以上１００ｎｍ未満（平均粒子径３０ｎｍ以上１００ｎｍ未満の範囲が好ましく、平均粒子径５０ｎｍ以上１００ｎｍ未満の範囲がより好ましい）の平均粒子径の金属微粒子（例えば、小さい平均粒子径の金属微粒子（Ｉ））と、平均粒子径１００ｎｍ以上３００ｎｍ以下（平均粒子径１００ｎｍ以上２５０ｎｍ以下の範囲が好ましく、平均粒子径１００ｎｍ以上２３０ｎｍ以下の範囲がより好ましい）の金属微粒子（例えば、大きい平均粒子径の金属微粒子（ＩＩ））との組み合せを例示することができる。異なる平均粒子径の金属微粒子を組み合わせて用いる場合の比率は、適宜選択することができるが、小さい平均粒子径の金属微粒子（Ｉ）と大きい平均粒子の金属微粒子（ＩＩ）の質量比（Ｉ：ＩＩ）が、９９：１～１：９９の範囲であればよく、９０：１０～１０：９０の範囲が好ましく、９０：１０～２０：８０の範囲がより好ましく、９０：１０～４０：６０の範囲がさらに好ましい。
　さらに、金属微粒子としては、上記平均粒子径の範囲外（３０ｎｍ～３００ｎｍの範囲外であり、例えば、３０ｎｍ未満、１～２５ｎｍ、３００ｎｍ超、３００ｎｍ超５００ｎｍ以下程度）の金属微粒子を組み合わせて用いることができる。上記平均粒子径の範囲外の金属微粒子を組み合わせて用いる場合、金属微粒子を混合した後の平均粒子径が上記平均粒子径の範囲内であれば、上記平均粒子径の範囲外の金属微粒子の添加量は特に制限されず、例えば、金属微粒子の全量に対して、１５質量％以下であればよく、１０質量％以下であることが好ましく、５質量％以下であることがより好ましい。
　上記平均粒子径の範囲外の金属微粒子は、保護層を有しているものが好ましい。当該金属微粒子の保護層において、前記Ｃ５－７モノアルキルアミン及び／又はアルコキシアミン（１）と、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲にあるものを用いてもよく、当該範囲外のものを用いてもよい。なお、上記平均粒子径の範囲外の金属微粒子の保護層は、後述する金属微粒子Ａの保護層の成分として用いることのできるものから構成されていてもよい。
　本発明において、金属微粒子Ａの平均粒子径は、走査型電子顕微鏡で観察される画像に含まれる３０個以上の粒子の長辺の長さの平均値である。なお、本発明の金属微粒子Ａについて、単独の平均粒子径の金属微粒子を用いる場合は、走査型電子顕微鏡で観察する場合の画像に含まれる任意の３０個以上の粒子の長辺の長さの平均値とすることができる。また、異なる平均粒子径の金属微粒子を組み合わせて用いる場合の平均粒子径は、走査型電子顕微鏡で観察される画像に含まれる各金属微粒子の３０個以上の粒子の長辺の長さの平均値と各金属微粒子の混合比率により求めることができる。
　より具体的には、例えば２種類の異なる平均粒子径の金属微粒子を組み合わせて用いる場合、金属微粒子の真密度を一定と仮定することで、次の式（Ａ）より求めることができる。
　混合した金属微粒子の平均粒子径＝２×（（Ａ/Ｒ1 2+Ｂ/Ｒ2 2）/（Ａ/Ｒ1 3+Ｂ/Ｒ2 3））…（Ａ）
[式中、小さい平均粒子径の金属微粒子：大きい平均粒子径の金属微粒子の比率をＡ：Ｂ、小さい平均粒子径の金属微粒子の半径をＲ1、大きい平均粒子径の金属微粒子の半径をＲ2で表す。]
　また、例えば３種類の異なる平均粒子径の金属微粒子を組み合わせて用いる場合、金属微粒子の真密度を一定と仮定することで、次の式（Ｂ）より求めることができる。
　混合した金属微粒子の平均粒子径＝２×（（Ａ/Ｒ1 2+Ｂ/Ｒ2 2+Ｃ/Ｒ3 2）/（Ａ/Ｒ1 3+Ｂ/Ｒ2 3+Ｃ/Ｒ3 3））…（Ｂ）
[式中、小さい平均粒子径の金属微粒子：中間の平均粒子径の金属微粒子：大きい平均粒子径の金属微粒子の比率をＡ：Ｂ：Ｃ、小さい平均粒子径の金属微粒子の半径をＲ1、中間の平均粒子径の金属微粒子の半径をＲ2、大きい平均粒子径の金属微粒子の半径をＲ3で表す。]
　本発明の導電性接着剤において、金属微粒子の含有量としては、特に制限されないが、好ましくは、８０質量％以上、より好ましくは８５質量％～９５質量％程度が挙げられる。
　本発明の金属微粒子Ａの金属種としては、金、銀、銅、白金、パラジウム、ニッケル、アルミニウム等を例示することができる。中でも、導電性の点では、金、銀、白金が好ましく、コスト及び低温焼結性の点では、銀、銅、ニッケルが好ましく、銀が特に好ましい。
　本発明の金属微粒子Ａは、金属により構成された粒子（金属粒子）の表層に、保護層を有している。保護層を形成する材料としては、金属粒子の表層を形成でき、かつ、保護層として機能できるもの（例えば、金属微粒子Ａ同士の凝集を抑制する層）であれば、特に制限されないが、導電性接着剤の焼結体の機械的強度を効果的に高める観点からは、好ましくは脂肪酸、アミン、ヒドロキシ脂肪酸等が挙げられる。保護層は、１種類の材料により構成されていてもよいし、２種類以上の材料により構成されていてもよい。
脂肪酸
　保護層における脂肪酸としては、特に制限されないが、好ましくはアルキル基の炭素数が３以上１８以下の脂肪酸、より好ましくはアルキル基の炭素数が４以上１８以下の脂肪酸が挙げられる。脂肪酸の好ましい具体例としては、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、２－エチルヘキサン酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、α－リノレン酸等が挙げられる。また、脂肪酸の具体例としては、シクロヘキサンカルボン酸のような環状アルキルカルボン酸等も挙げられる。これらの中でも、導電性接着剤の焼結体の機械的強度を効果的に高める観点から、カプロン酸、２－エチルヘキシル酸、オレイン酸、リノール酸、α－リノレン酸が好ましい。保護層における脂肪酸は、１種類の脂肪酸から構成されていてもよいし、２種類以上の脂肪酸により構成されていてもよい。
アミン
　金属微粒子Ａの保護層に含まれるアミンは、Ｃ５－７モノアルキルアミン及びアルコキシアミン（１）の少なくとも一方を含んでいることを特徴とする。保護層に含まれるアミンとしては、Ｃ５－７モノアルキルアミン（特には、炭素数６のモノアルキルアミンが好ましい）及びアルコキシアミン（１）の少なくとも一方を含むものであれば、特に問題なく用いることができる。なお、保護層中におけるアミンは、Ｃ５－７モノアルキルアミン及びアルコキシアミン（１）の少なくとも一方のみから形成されていてもよく、それ以外のアミンを含有していてもよい。
　保護層において、Ｃ５－７モノアルキルアミン及び／又はアルコキシアミン（１）と、これらとは異なるアミンとの比率は、１００：０～１０：９０の範囲であればよく、１００：０～２０：８０に範囲であれば好ましく、１００：０～３０：７０に範囲であればより好ましく、１００：０～４０：６０に範囲であればさらに好ましく、１００：０～５０：５０に範囲であれば特に好ましい。上記範囲であれば、焼結した際に、機械的強度（せん断強度）に優れる焼結体が得られる。
　なお、保護層に含まれる各アミンの比率は、ガスクロマトグラフィーから計算することができる。具体的には、金属微粒子１ｇをメタノール４ｇに分散させた後、濃塩酸を数滴加えよく撹拌することで保護層中のアミンをメタノール中に遊離させ、その溶液を水酸化ナトリウムで中和処理したものをガスクロマトグラフィーに導入する。クロマトグラフィーにより得られたアミンのピーク面積により各アミンの比率を定量できる。保護層に含まれるアミンの量は上記測定方法によって得られたピーク面積の値より、含有量（％）で表す。
　炭素数５～７のモノアルキルアミンとしては、ｎ‐アミルアミン、ｎ‐ヘキシルアミン、ｎ‐ヘプチルアミン、シクロヘキシルアミン、シクロヘプチルアミン等を例示することができる。中でもｎ－アミルアミン、ｎ－ヘキシルアミン、ｎ－ヘプチルアミンが好ましく、ｎ－ヘキシルアミンが特に好ましい。保護層におけるＣ５－７モノアルキルアミンは、１種類のモノアルキルアミンから構成されていてもよく、２種類以上のモノアルキルアミンから構成されていてもよい。
　また、前記一般式（１）中、Ｒ1は、炭素数１～４のアルキル基であれば、直鎖又は分岐鎖のいずれでもよく、炭素数１～３のアルキルであることが好ましく、メチル基、エチル基、プロピル基、イソプロピル基であることがより好ましい。Ｒ2は、炭素数１～４のアルキル基であれば、直鎖又は分岐鎖のいずれでもよく、炭素数１～３のアルキル基であることが好ましく、メチル基、エチル基、プロピル基、イソプロピル基であることがより好ましい。前記一般式（１）で表されるアルコキシアミンは、１種類のアルコキシアミンから構成されていてもよく、２種以上のアルコキシアミンから構成されていてもよい。
　前記一般式（１）で表されるアルコキシアミンの具体例としては、１－メトキシメチルアミン、１－エトキシメチルアミン、１－プロポキシメチルアミン、１－イソプロポキシメチルアミン、１－ブトキシメチルアミン、２－メトキシエチルアミン、２－エトキシエチルアミン、２－プロポキシエチルアミン、２－イソプロポキシエチルアミン、２－ブトキシエチルアミン、３－メトキシプロピルアミン、３－エトキシプロピルアミン、３－プロポキシプロピルアミン、３－イソプロポキシプロピルアミン、３－ブトキシプロピルアミン、４－メトキシブチルアミン、４－エトキブチルアミン、４－プロポキシブチルアミン、４－イソプロポキシブチルアミン、４－ブトキシブチルアミン等を例示することができる。中でも、２－エトキシエチルアミン、２－プロポキシエチルアミン、２－イソプロポキシエチルアミン、２－ブトキシエチルアミン、３－メトキシプロピルアミン、３－エトキプロピルアミン、３－プロポキシプロピルアミン、３－イソプロポキシプロピルアミンが好ましい。
　保護層に含まれるアミンは、Ｃ５－７モノアルキルアミン及びアルコキシアミン（１）のいずれか一方のみであってもよいし、両者を含んでいてもよい。両者を含む場合の比率も特に制限されず、任意に比率で含むことができ、比率としては、例えば７０：３０～３０：７０などが挙げられる。
　前述の通り、保護層に含まれるアミンには、Ｃ５－７のモノアルキルアミン及び／又はアルコキシアミン（１）とは異なるアミンが含まれていてもよい。なお、本発明の導電性接着剤において、金属微粒子Ａの保護層に含まれているアミンは、導電性接着剤の焼結時に金属微粒子Ａの表面から離脱するため、得られる焼結体の導電性には実質的に影響を与えない。
　保護層に含まれるアミンのうち、Ｃ５－７モノアルキルアミン及び／又はアルコキシアミン（１）とは異なるアミンの具体例としては、特に制限をされないが、第１級アミン、第２級アミン、第３級アミン、さらに、ひとつの化合物中に２つのアミノ基を有するジアミン化合物等を例示することができる。
　第１級アミンとしては、エチルアミン、ｎ－プロピルアミン、イソプロピルアミン、１,２－ジメチルプロピルアミン、ｎ－ブチルアミン、イソブチルアミン、ｓｅｃ－ブチルアミン、ｔｅｒｔ－ブチルアミン、イソアミルアミン、ｎ－オクチルアミン、２－オクチルアミン、ｔｅｒｔ－オクチルアミン、２－エチルヘキシルアミン、ｎ－ノニルアミン、ｎ－アミノデカン、ｎ－アミノウンデカン、ｎ－ドデシルアミン、ｎ－トリデシルアミン、２－トリデシルアミン、ｎ－テトラデシルアミン、ｎ－ペンタデシルアミン、ｎ－ヘキサデシルアミン、ｎ－ヘプタデシルアミン、ｎ－オクタデシルアミン、ｎ－オレイルアミン、３－メトキシプロピルアミン、３－エトキシプロピルアミン、３－プロポキシプロピルアミン、３－イソプロポキシプロピルアミン、３－ブトキシプロピルアミン、Ｎ‐エチル‐１,３‐ジアミノプロパン、Ｎ,Ｎ‐ジイソプロピルエチルアミン、Ｎ，Ｎ－ジメチル‐１,３‐ジアミノプロパン、Ｎ,Ｎ‐ジブチル‐１,３‐アミノプロパン、Ｎ,Ｎ‐ジイソブチル‐１,３‐ジアミノプロパン、Ｎ‐ラウリルジアミノプロパン等の直鎖又は分岐炭化水素基を有するアミン等を例示できる。
　また、脂環式アミンであるシクロプロピルアミン、シクロブチルアミン、シクロプロピルアミン、シクロヘキシルアミン、シクロヘプチルアミン、シクロオクチルアミンや、芳香族アミンであるアニリン等も例示できる。
　また、３－イソプロポキシプロピルアミン、イソブトキシプロピルアミン等のエーテルアミンも例示できる。
　第２級アミンとしては、Ｎ，Ｎ－ジプロピルアミン、Ｎ，Ｎ－ジブチルアミン、Ｎ，Ｎ－ジペンチルアミン、Ｎ，Ｎ－ジヘキシルアミン、Ｎ，Ｎ－ジペプチルアミン、Ｎ，Ｎ－ジオクチルアミン、Ｎ，Ｎ－ジノニルアミン、Ｎ，Ｎ－ジデシルアミン、Ｎ，Ｎ－ジウンデシルアミン、Ｎ，Ｎ－ジドデシルアミン、Ｎ，Ｎ－ジステアリルアミン、Ｎ－メチル－Ｎ－プロピルアミン、Ｎ－エチル－Ｎ－プロピルアミン、Ｎ－プロピル－Ｎ－ブチルアミン等のジアルキルモノアミン、及びピペリジン等の環状アミンを例示することができる。
　第３級アミンとしては、トリエチルアミン、トリブチルアミン、トリヘキシルアミン、ジメチルオクチルアミン、ジメチルデシルアミン、ジメチルラウリルアミン、ジメチルミリスチルアミン、ジメチルパルミチルアミン、ジメチルステアリルアミン、ジラウリルモノメチルアミン等を例示できる。
　さらに、異なるアミンとしては、ひとつの化合物中に２つのアミノ基を有するジアミン化合物も用いることができる。ジアミン化合物としては、エチレンジアミン、Ｎ，Ｎ－ジメチルエチレンジアミン、Ｎ，Ｎ’－ジメチルエチレンジアミン、Ｎ，Ｎ－ジエチルエチレンジアミン、Ｎ，Ｎ’－ジエチルエチレンジアミン、１，３－プロパンジアミン、２，２－ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジメチル‐１，３‐プロパンジアミン、Ｎ，Ｎ’‐ジメチル－１，３－プロパンジアミン、Ｎ，Ｎ－ジエチル－１，３－プロパンジアミン、Ｎ，Ｎ’－ジエチル－１，３－プロパンジアミン、１，４－ブタンジアミン、Ｎ，Ｎ－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ’－ジメチル－１，４－ブタンジアミン、Ｎ，Ｎ－ジエチル－１，４－ブタンジアミン、Ｎ，Ｎ’－ジエチル－１，４－ブタンジアミン、１，５－ペンタンジアミン、１，５－ジアミノ－２－メチルペンタン、１，６－ヘキサンジアミン、Ｎ，Ｎ－ジメチル－１，６－ヘキサンジアミン、Ｎ，Ｎ’－ジメチル－１，６－ヘキサンジアミン、１，７－ヘプタンジアミン、１，８－オクタンジアミン等を例示できる。
　中でも、導電性接着剤の焼結体の機械的強度を効果的に高める観点から、ｎ－ブチルアミン、ｎ－オクチルアミン、Ｎ，Ｎ－ジメチル‐１,３‐ジアミノプロパン、Ｎ，Ｎ‐ジエチル‐１,３‐ジアミノプロパンが好ましい。保護層中における異なるアミンは、上述したものを１種類含んでいるものでもよく、２種類以上を含んでいるものでもよい。
　保護層において、アミンと脂肪酸とを併用する場合、アミンと脂肪酸とのモル比（アミン：脂肪酸）としては、約９０：１０～約９９．９：０．１の範囲が好ましく、約９５：５～約９９．５：０．５の範囲がより好ましい。
　さらに、本発明における金属微粒子Ａの保護層には、ヒドロキシ脂肪酸を含有してもよい、保護層に含まれ得るヒドロキシ脂肪酸としては、ヒドロキシ脂肪酸としては、炭素数３～２４で、かつ水酸基を１個以上（例えば、１個）有する化合物を使用できる。ヒドロキシ脂肪酸として、例えば、２－ヒドロキシデカン酸、２－ヒドロキシドデカン酸、２－ヒドロキシテトラデカン酸、２－ヒドロキシヘキサデカン酸、２－ヒドロキシオクタデカン酸、２－ヒドロキシエイコサン酸、２－ヒドロキシドコサン酸、２－ヒドロキシトリコサン酸、２－ヒドロキシテトラコサン酸、３－ヒドロキシヘキサン酸、３－ヒドロキシオクタン酸、３－ヒドロキシノナン酸、３－ヒドロキシデカン酸、３－ヒドロキシウンデカン酸、３－ヒドロキシドデカン酸、３－ヒドロキシトリデカン酸、３－ヒドロキシテトラデカン酸、３－ヒドロキシヘキサデカン酸、３－ヒドロキシヘプタデカン酸、３－ヒドロキシオクタデカン酸、ω－ヒドロキシ－２－デセン酸、ω－ヒドロキシペンタデカン酸、ω－ヒドロキシヘプタデカン酸、ω－ヒドロキシエイコサン酸、ω－ヒドロキシドコサン酸、６－ヒドロキシオクタデカン酸、リシノール酸、１２－ヒドロキシステアリン酸、［Ｒ－（Ｅ）］－１２－ヒドロキシ－９－オクタデセン酸等が挙げられる。中でも、炭素数４～１８で、かつω位以外（特に、１２位）に１個の水酸基を有するヒドロキシ脂肪酸が好ましく、リシノール酸、１２－ヒドロキシステアリン酸がより好ましい。第２の保護層に含まれるヒドロキシ脂肪酸は、１種類であってもよいし、２種類以上であってもよい。
　保護層において、ヒドロキシ脂肪酸を含む場合、ヒドロキシ脂肪酸の含有量は、アミン１モルに対して、０．１～１０モルの範囲であればよく、０．２～５モルの範囲であることが好ましい。
　金属微粒子Ａにおける保護層の割合（質量％）としては、特に制限されないが、金属微粒子Ａの表面を保護しつつ、導電性接着剤の焼結体の機械的強度を効果的に高める観点から、０．１質量％～１０質量％程度が好ましく、０．２質量％～８質量％程度がより好ましく、０．２質量％～５質量％程度がさらに好ましい。
　本発明に用いる金属微粒子Ａは、上述した特徴を有するものであれば、市販されているものを購入して用いてもよく、通常、用いられる金属微粒子（例えば、銀微粒子）の製造方法（例えば、特開２０１５－４０３１９号公報）によって製造したものを用いてもよい。なお、金属微粒子の製造方法については、後で詳細を述べる。また、本発明の金属微粒子Ａには、保護層におけるＣ５－７モノアルキルアミン及び／又はアルコキシアミン（１）と、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲外である金属微粒子を用い、後述する方法によって、当該比率を、１００：０～１０：９０の範囲内に調整したものを用いることも可能である。
溶媒
　本発明の導電性接着剤は、金属微粒子Ａに加えて、さらに溶媒を含むことが好ましい。溶媒を含むことにより、流動性が高まり、本発明の導電性接着剤を所望の場所に配置しやすくなる。
　溶媒としては、金属微粒子Ａを分散できるものであれば、特に制限されないが、極性有機溶媒を含むことが好ましい。極性有機溶媒としては、アセトン、アセチルアセトン、メチルエチルケトン等のケトン類；ジエチルエーテル、ジプロピルエーテル、ジブチルエーテル、テトラヒドロフラン、１，４－ジオキサン等のエーテル類；１，２－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、１，２－ヘキサンジオール、１，６－ヘキサンジオール、１，２－ペンタンジオール、１，５－ペンタンジオール、２－メチル－２，４－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，２－オクタンジオール、１，８－オクタンジオール、２－エチル－１，３－ヘキサンジオール等のジオール類；グリセロール；炭素数１～５の直鎖又は分岐鎖のアルコール、シクロヘキサノール、３－メトキシ－３－メチル－１－ブタノール、３－メトキシ－１－ブタノール等のアルコール類；酢酸エチル、酢酸ブチル、酪酸エチル、蟻酸エチル等の脂肪酸エステル類；ポリエチレングリコール、トリエチレングリコールモノメチルエーテル、テトラエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、トリエチレングリコールジメチルエーテル、テトラエチレングリコールジメチルエーテル、３－メトキシブチルアセテート、エチレングリコールモノブチルエーテル、エチレングリコールモノブチルエーテルアセテート、エチレングリコールモノヘキシルエーテル、エチレングリコールモノオクチルエーテル、エチレングリコールモノ－２－エチルヘキシルエーテル、エチレングリコールモノベンジルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテルアセテート、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、ポリプロピレングリコール、プロピレングリコールモノプロピルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノプロピルエーテル、トリプロピレングリコールモノブチルエーテル等のグリコール又はグリコールエーテル類；Ｎ，Ｎ－ジメチルホルムアミド；ジメチルスルホキシド；テルピネオール等のテルペン類；アセトニトリル；γ－ブチロラクトン；２－ピロリドン；Ｎ－メチルピロリドン；Ｎ－(２－アミノエチル)ピペラジン等が挙げられる。これらの中でも、導電性接着剤の焼結体の機械的強度をより一層効果的に高める観点から、炭素数３～５の直鎖又は分岐鎖のアルコール、３－メトキシ－３－メチル－１－ブタノール、３－メトキシ－１－ブタノール、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノブチルエーテルアセテート、テルピネオールが好ましい。
　溶媒は、極性有機溶媒に加えて、さらに非極性又は疎水性溶媒を含んでいてもよい。非極性有機溶媒としては、ヘキサン、ヘプタン、オクタン、ノナン、デカン、２－エチルヘキサン、シクロヘキサン等の直鎖、分枝、又は環状の飽和炭化水素；炭素数６以上の直鎖又は分岐鎖のアルコール等のアルコール類；ベンゼン、トルエン、ベンゾニトリル等の芳香族化合物；ジクロロメタン、クロロホルム、ジクロロエタン等のハロゲン化炭化水素類；メチル－ｎ－アミルケトン；メチルエチルケトンオキシム；トリアセチン等が挙げられる。これらの中でも、飽和炭化水素及び炭素数６以上の直鎖又は分岐鎖のアルコール類が好ましく、ヘキサン、オクタン、デカン、オクタノール、デカノール、ドデカノールがより好ましい。溶媒は、１種を単独で、又は２種以上を混合して使用できる。
　極性有機溶媒と非極性有機溶媒との双方を含む場合、極性有機溶媒の比率は、溶媒の全量に対して、５容量％以上が好ましく、１０容量％以上がより好ましく、１５容量％以上がさらにより好ましい。また、６０容量％以下とすることができ、５５容量％以下とすることもでき、５０容量％以下とすることもできる。溶媒は極性有機溶媒のみからなるものとすることもできる。本発明の導電性接着剤は、このように極性有機溶媒を多く含む場合にも、金属微粒子Ａの分散性が良い。
　本発明の導電性接着剤において、溶媒の割合としては、特に制限されないが、２０質量％以下が好ましく、５質量％～１５質量％程度がより好ましい。
　本発明の導電性接着剤は、アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子Ａを混合する（より具体的には、金属微粒子Ａと溶媒を混合する）工程を備える方法により製造することができる。本発明の導電性接着剤の製造方法においては、前記アミンが炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンを含み、前記保護層において、前記炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にある、前記金属微粒子Ａを用いる。
　また、本発明の導電性接着剤の製造方法において、アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子を準備し、当該金属微粒子の保護層に含まれるアミンと、炭素数５～７のモノアルキルアミン及び／又は一般式（１）で表されるアルコキシアミンとを置換して、炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内となるように調整し、前記金属微粒子Ａを調製する工程をさらに備えていてもよい。アミンを置換して金属微粒子Ａを調製する方法としては、例えば後述の方法を採用することができる。
２．金属微粒子Ａの製造方法
　本発明に用いる金属微粒子Ａ（例えば、銀微粒子）の製造方法の一例を以下に示す。
　まず、金属微粒子Ａを製造するための組成物（銀微粒子調製用組成物）を用意する。具体的には、銀微粒子の原料となる銀化合物（好ましくは、硝酸銀、シュウ酸銀等）と、保護層を構成する成分（前述の脂肪酸、アミン、ヒドロキシ脂肪酸等）、及び有機溶媒を準備する。次に、これらの各成分を混合して銀微粒子調製用組成物を得る。当該組成物における各成分の割合は、前述の金属微粒子Ａの構成となるように、適宜調整すればよい。例えば、組成物中のシュウ酸銀の含有量は、組成物の全量に対して、２０～７０質量％程度とすることが好ましい。また、保護層に脂肪酸を含有させる場合、脂肪酸の含有量としては、組成物の全量に対して、０．１質量％～２０質量％程度とすることが好ましい。保護層におけるアミンの含有量としては、組成物の全量に対して、５質量％～５５質量％程度とすることが好ましい。保護層にヒドロキシ脂肪酸を含有させる場合、ヒドロキシ脂肪酸の含有量としては、組成物の全量に対して、０．１質量％～１５質量％程度とすることが好ましい。
　なお、アミンは、Ｃ５－７モノアルキルアミン及び／又はアルコキシアミン（１）と、これらとは異なるアミンとの比率が、上記範囲内になるように調整して用いればよい。また、保護層における当該比率が、上記範囲外となるように調整した銀微粒子調製用組成物を用いて、銀微粒子を合成し、後述する方法によって、当該比率を上記範囲内に調整（アミンを置換）することも可能である。
　また、各成分の混合手段も特に制限されず、例えば、メカニカルスターラー、マグネティックスターラー、ボルテックスミキサー、遊星ミル、ボールミル、三本ロール、ラインミキサー、プラネタリーミキサー、ディゾルバー等の汎用の装置で混合できる。混合時の溶解熱、摩擦熱等の影響で組成物の温度が上昇し、銀微粒子の熱分解反応が開始することを回避するために、組成物の温度を、例えば６０℃以下、特に４０℃以下に抑えながら混合することが好ましい。
　次に、銀微粒子調製用組成物を、反応容器内で反応、通常は加熱による反応に供することにより、銀化合物の熱分解反応が起こり、銀微粒子が生成する。反応に当たっては、予め加熱しておいた反応容器内に組成物を導入してもよく、組成物を反応容器内に導入した後に加熱してもよい。
　反応温度は、熱分解反応が進行し、銀微粒子が生成する温度であればよく、例えば５０～２５０℃程度が挙げられる。また、反応時間は、所望する平均粒子径の大きさや、それに応じた組成物の組成に合せて、適宜選択すればよい。反応時間としては、例えば１分間～１００時間が挙げられる。
　熱分解反応により生成した銀微粒子は、未反応原料を含む混合物として得られるため、銀微粒子を精製することが好ましい。精製方法としては、固液分離方法、銀微粒子と有機溶媒等の未反応原料との比重差を利用した沈殿方法等が挙げられる。固液分離方法としては、フィルター濾過、遠心分離、サイクロン式、又はデカンタ等の方法が挙げられる。精製時の取り扱いを容易にするために、アセトン、メタノール等の低沸点溶媒で銀微粒子を含有する混合物を希釈して、その粘度を調整してもよい。
　銀微粒子製造用組成物の組成や反応条件を調整することにより、得られる銀微粒子の平均粒子径を調整することができる。
３．保護層における各アミンの比率を調整（置換）する方法
　「２．金属微粒子Ａの製造方法」の欄で述べた保護層における各アミンの前記比率（Ｃ５－７モノアルキルアミン及び／又はアルコキシアミン（１）と、これらとは異なるアミンとの比率）が、上記範囲外となるように調整して得られた金属微粒子の当該比率が、上記範囲内となるように調整（置換）する方法について、述べる。
　保護層に含まれるアミンにおいて、Ｃ５－７モノアルキルアミン及び／又はアルコキシアミン（１）と、これらとは異なるアミンとの比率が、上記範囲外の金属微粒子を溶媒中に分散させ、Ｃ５－７モノアルキルアミン及びアルコキシアミン（１）の少なくとも一方を、金属微粒子の質量に対して、０．１～５倍量の範囲で添加し、室温～８０℃で、１分～２４時間撹拌を行う工程に付することで、保護層中における各アミンの比率を上記範囲に調整（置換）することができる。また、予め各アミンの比率を特定の割合に調整した溶媒中に、金属微粒子を加えることで、金属微粒子の保護層中におけるＣ５－７モノアルキルアミン及び／又はアルコキシアミン（１）と、これらとは異なるアミンとの比率を所望する比率に調整することも可能である。
　金属微粒子を分散させる溶媒は、金属微粒子の合成に用いることができる溶媒を用いてもよく、導電性接着剤に用いることのできる溶媒を用いても良い。保護層中における各アミンの比率を上記範囲に調整（置換）した金属微粒子は、「２．金属微粒子Ａの製造方法」の欄で述べた固液分離方法によって回収することができる。なお、本保護層における各アミンの比率を調整（置換）する方法は、上記範囲外の平均粒子径の金属微粒子において、保護層中におけるＣ５－７モノアルキルアミン及び／又はアルコキシアミン（１）と、これらとは異なるアミンとの比率を所望する比率に調整することも可能である。
４．導電性接着剤の焼結体
　本発明の導電性接着剤の焼結体は、前述の「１．導電性接着剤」で詳述した本発明の導電性接着剤を焼結することにより得られる。本発明の導電性接着剤の焼結体においては、導電性接着剤の保護層を構成している成分が、焼結の際の高熱により、ほとんどが離脱しており、焼結体は、実質的に金属により構成されている。
　焼結温度としては、特に制限されないが、得られる焼結体が高い導電性と高い接着力を発揮しつつ、機械的強度を効果的に高める観点から、好ましくは１５０℃～２００℃程度、より好ましくは１５０℃～１８５℃程度が挙げられる。同様の観点から、焼結時間としては、好ましくは０．４時間～２．０時間程度、より好ましくは０．５時間～１．２時間程度が挙げられる。焼結は、大気、不活性ガス（窒素ガス、アルゴンガス）等の雰囲気下で行うことができる。焼結手段としては、特に制限されず、オーブン、熱風式乾燥炉、赤外線乾燥炉、レーザー照射、フラッシュランプ照射、マイクロウェーブ等が挙げられる。
５．回路又は装置
　本発明の回路又は装置は、それぞれ、本発明の焼結体により部材間が接着された部分を備えている。すなわち、本発明の回路又は装置は、前述の「１．導電性接着剤」で詳述した本発明の導電性接着剤を、回路又は装置の部材間に配置し、導電性接着剤を焼結させて、部材間を接着したものである。
　前述の通り、本発明の焼結体は、高い導電性と高い接着力を発揮しつつ、機械的強度が効果的に高められていることから、これを備える回路又は装置においても、部材間の導電性及び密着性に優れており、機械的強度も優れている。
　以下の実施例において本発明をより具体的に説明するが、本発明はこれらに限定されない。
　実施例及び比較例において使用した各成分の詳細は、以下の通りである。
・シュウ酸銀（（ＣＯＯＡｇ）2）特許文献１（特許第５５７４７６１号公報）に記載の方法で合成した。
・オレイン酸（和光純薬工業株式会社製）
・Ｎ,Ｎ－ジメチル－１,３－ジアミノプロパン（和光純薬工業株式会社製）
・Ｎ,Ｎ－ジエチル－１,３－ジアミノプロパン（和光純薬工業株式会社製）
・ｎ－ヘキシルアミン（炭素数６、和光純薬工業株式会社製）
・ｎ－プロピルアミン（炭素数３、和光純薬工業株式会社製）
・ｎ－ブチルアミン（炭素数４、和光純薬工業株式会社製）
・３－メトキシプロピルアミン（炭素数４、和光純薬工業株式会社製）
・２‐（２－エチルへキシルオキシ）エタノール（和光純薬工業株式会社製）
・ブタノール（和光純薬工業株式会社製）
・ペンタノール（和光純薬工業株式会社製）
　以下の実施例及び比較例において、合成した銀微粒子の保護層におけるアミンの測定は、以下の方法により行った。
（銀微粒子の保護層に含まれる各アミンの比率の測定方法）
　銀微粒子１ｇに対して、メタノール４ｇを添加し、１分間撹拌した。その後、撹拌しながら濃塩酸１００ｍｇを添加し、さらに１０分間撹拌を続け、保護層を遊離させた。さらに撹拌を続けながら、４８％水酸化ナトリウム水溶液を１５０ｍｇ添加し、ｐＨ＞７とした。その固液混合物を濾過することで、保護層に含まれるアミンを抽出したメタノール溶液が得られ、ガスクロマトグラフィー用の試料とした。その試料をガスクロマトグラフィー（島津製作所製　ＧＣ－２０１０、カラム：ＲＥＳＴＥＫ製　Ｒｔｘ－５　Ａｍｉｎｅ）を用いて分析を行い、得られたピーク面積比より保護層に含まれるアミンの比率（ＧＣ％）の定量を行った。結果を表１－３に示す。
　なお、表１－３において、ＨＡはｎ－ヘキシルアミン、ＭＰはメトキシプロピルアミン、ＤＡはＮ,Ｎ－ジエチル－１,３－ジアミノプロパン又はＮ,Ｎ－ジメチル－１,３－ジアミノプロパン、ＢｕＮＨ2はｎ－ブチルアミン、ＰｒＮＨ2はｎ－プロピルアミンを意味する。
　以下の実施例及び比較例において、機械的強度、及び塗膜の割れや欠けは、それぞれ、以下のようにして評価した。結果は表１－３に示す。
（機械的強度の評価）
　各実施例及び比較例で得られた各塗膜のせん断強度は、ボンドテスター（西進商事製ＳＳ３０－ＷＤ）を用いてダイシェアテストを実施して測定した。
（塗膜の割れや欠けの評価）
　各実施例及び比較例で得られた各塗膜の表面を目視で観察し、塗膜の割れや欠けの有無を評価した。
＜合成例１＞　平均粒子径２００ｎｍの金属微粒子の合成例
　磁気撹拌子を入れた５０ｍＬガラス製遠沈管に、オレイン酸（０．１ｇ）、Ｎ,Ｎ－ジエチル－１,３－ジアミノプロパン（３．２５ｇ）、及びペンタノール（４．０ｇ）を投入し、１分間程度攪拌したのち、シュウ酸銀（４．０ｇ）を投入し、約１０分間攪拌することで、銀微粒子調製用組成物を得た。その後、アルミブロックを備えたホットスターラー（小池精密機器製作所製ＨＨＥ－１９Ｇ－Ｕ）上に、これらのガラス製遠沈管を立てて設置し、４０℃で３０分間攪拌し、さらに、９０℃で３０分間攪拌した。放冷後、磁気撹拌子を取り出し、各組成物にメタノール１５ｇを添加してボルテックスミキサーで攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノール１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、製造された銀微粒子１を回収した。合成例１で得られた銀微粒子１を、走査型電子顕微鏡（日立ハイテク製Ｓ－４５００）にて観察し、画像に含まれる任意の３０個の粒子の長辺の長さを測定して、平均値を求めた。平均粒子径は２００ｎｍであった。
銀微粒子１の保護層に含まれるアミンの比率の調整（置換）方法
　合成例１で得られた銀微粒子１の分散液（メタノール溶液）を用いて、ｎ－ヘキシルアミン（銀微粒子１Ａの調製に使用）、メトキシプロピルアミン（銀微粒子１Ｂの調製に使用）の各アミンを銀微粒子１の質量の３倍量を添加し、室温で４時間撹拌した。撹拌後、磁気撹拌子を取り出し、各組成物にメタノール１５ｇを添加してボルテックスミキサーで攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノール１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、保護層におけるアミンの比率を調整（置換）した銀微粒子１Ａ，１Ｂを回収した。なお、平均粒子径は変化しなかった。
（実施例１，２）
　実施例１では銀微粒子１Ａ、実施例２では銀微粒子１Ｂを用い、それぞれ、総質量の１０％相当のテルピネオールを添加し、各分散液を得た。この液をクラボウ社製のマゼルスターを用い、２回撹拌優先モードにて混合し、各導電性接着剤を調製した。
　次に、銅板上に無電解銀めっきを０．５μｍ施した基材を準備し、その上に各導電性接着剤を塗膜厚みが５０μｍとなるように、均一に塗膜を行い、その上に裏面（導電性接着剤と接する面）に金めっきもしくは金スパッタ処理が施されたシリコンウエハ（サイズ２ｍｍ×２ｍｍ）を上に乗せた。これを乾燥器（循環式）により、所定温度（１５０℃）にて６０分間加熱させ、各導電性接着剤が焼結した塗膜を得た。
＜合成例２＞　平均粒子径７５ｎｍの金属微粒子の合成例
　磁気撹拌子を入れた５０ｍＬガラス製遠沈管に、オレイン酸（０．１ｇ）、Ｎ,Ｎ－ジエチル－１,３－ジアミノプロパン（３．２５ｇ）、及びブタノール（６．０ｇ）を投入し、１分間程度攪拌したのち、シュウ酸銀（４．０ｇ）を投入し、約１０分間攪拌することで、銀微粒子調製用組成物を得た。その後、アルミブロックを備えたホットスターラー（小池精密機器製作所製ＨＨＥ－１９Ｇ－Ｕ）上に、これらのガラス製遠沈管を立てて設置し、４０℃で３０分間攪拌し、さらに、９０℃で３０分間攪拌した。放冷後、磁気撹拌子を取り出し、各組成物にメタノール１５ｇを添加してボルテックスミキサーで攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノール１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、製造された銀微粒子２を回収した。合成例２で得られた銀微粒子２を、走査型電子顕微鏡（日立ハイテク製Ｓ－４５００）にて観察し、画像に含まれる任意の３０個の粒子の長辺の長さを測定して、平均値を求めた。平均粒子径は７５ｎｍであった。なお、合成例２で得られた銀微粒子２は、銀微粒子２Ｃとして、実施例に用いた。
銀微粒子２の保護層に含まれる各アミンの比率の調整（置換）方法
　合成例２で得られた銀微粒子２の分散液（メタノール溶液）を用いて、ｎ－ヘキシルアミン（銀微粒子２Ａの調製に使用）、メトキシプロピルアミン（銀微粒子２Ｂの調製に使用）、ｎ－ブチルアミン（銀微粒子２Ｄの調製に使用）、ｎ－プロピルアミン（銀微粒子２Ｅの調製に使用）の各アミンを銀微粒子２の質量の３倍量を添加し、室温で４時間撹拌した。撹拌後、磁気撹拌子を取り出し、各組成物にメタノール１５ｇを添加してボルテックスミキサーで攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノール１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、保護層における各アミンの比率を調整（置換）した銀微粒子２Ａ～２Ｅを回収した。なお、平均粒子径は変化しなかった。
（実施例３，４及び比較例１～３）
　上記で得られた各銀微粒子２Ａ～２Ｅを用い、総質量の１０％相当のテルピネオールを添加し、各分散液を得た。実施例３では銀微粒子２Ａ、実施例４では銀微粒子２Ｂ、比較例１では銀微粒子２Ｃ、比較例２では銀微粒子２Ｄ、比較例３では銀微粒子２Ｅを用いた。これらの液をそれぞれクラボウ社製のマゼルスターを用い、２回撹拌優先モードにて混合し、各導電性接着剤を調製した。
　次に、銅板上に無電解銀めっきを０．５μｍ施した基材を準備し、その上に各導電性接着剤を塗膜厚みが５０μｍとなるように、均一に塗膜を行い、その上に裏面（導電性接着剤と接する面）に金めっきもしくは金スパッタ処理が施されたシリコンウエハ（サイズ２ｍｍ×２ｍｍ）を上に乗せた。これを乾燥器（循環式）により、所定温度（１５０℃）にて６０分間加熱させ、各導電性接着剤が焼結した塗膜を得た。
＜合成例３＞　平均粒子径２０ｎｍの金属微粒子の合成例
　磁気撹拌子を入れた５０ｍＬガラス製遠沈管に、オレイン酸（０．０６ｇ）、ヘキシルアミン（１．４ｇ）、Ｎ,Ｎ－ジメチル－１,３－ジアミノプロパン（０．３ｇ）、ブチルアミン（０．６ｇ）及び２－（２－エチルヘキシルオキシ）エタノール（４．０ｇ）を投入し、１分間程度攪拌したのち、シュウ酸銀（４．０ｇ）を投入し、約１０分間攪拌することで、銀微粒子調製用組成物を得た。その後、アルミブロックを備えたホットスターラー（小池精密機器製作所製ＨＨＥ－１９Ｇ－Ｕ）上に、これらのガラス製遠沈管を立てて設置し、４０℃で３０分間攪拌し、さらに、９０℃で３０分間攪拌した。放冷後、磁気撹拌子を取り出し、各組成物にメタノール１５ｇを添加してボルテックスミキサーで攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノール１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、製造された銀微粒子６を回収した。合成例３で得られた銀微粒子３を、走査型電子顕微鏡（日立ハイテク製Ｓ－４５００）にて観察し、画像に含まれる任意の３０個の粒子の長辺の長さを測定して、平均値を求めた。平均粒子径は２０ｎｍであった。
　銀微粒子３の保護層に含まれる各アミンの比率の調整（置換）方法
　合成例３で得られた銀微粒子３の分散液（メタノール溶液）を用いて、ｎ－ヘキシルアミンを銀微粒子の質量の３倍量を添加し、室温で４時間撹拌した。撹拌後、磁気撹拌子を取り出し、各組成物にメタノール１５ｇを添加してボルテックスミキサーで攪拌した後、遠心分離機（日立工機製ＣＦ７Ｄ２）にて３０００ｒｐｍ（約１６００×Ｇ）で１分間の遠沈操作を実施し、遠沈管を傾けることにより上澄みを除去した。メタノール１５ｇの添加、撹拌、遠心分離、及び上澄み除去の工程を２回繰り返し、保護層に含まれるアミンの比率を調整（置換）した銀微粒子３Ａを回収した。なお、平均粒子径は変化しなかった。
（比較例４）
　上記で得られた銀微粒子３Ａを用い、総質量の１０％相当のテルピネオールを添加し、各分散液を得た。この液をクラボウ社製のマゼルスターを用い、２回撹拌優先モードにて混合し、導電性接着剤を調製した。
　次に、銅板上に無電解銀めっきを０．５μｍ施した基材を準備し、その上に導電性接着剤を塗膜厚みが５０μｍとなるように、均一に塗膜を行い、その上に裏面（導電性接着剤と接する面）に金めっきもしくは金スパッタ処理が施されたシリコンウエハ（サイズ２ｍｍ×２ｍｍ）を上に乗せた。これを乾燥器（循環式）により、所定温度（１５０℃）にて６０分間加熱させ、導電性接着剤が焼結した塗膜を得た。
Figure JPOXMLDOC01-appb-T000001
　表１に示される結果から明らかな通り、金属微粒子の平均粒子径が３０ｎｍ～３００ｎｍの範囲内であり、保護層中のアミンが、炭素数５～７のモノアルキルアミン及び／又は上記一般式（１）で表されるアルコキシアミンを含み、さらに、炭素数５～７のモノアルキルアミン及び／又は一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にある実施例１～４の導電性接着剤は、塗膜のせん断強度が高く、塗膜の割れや欠けも無かった。一方、保護層に含まれるアミンにおいて、Ｎ，Ｎ－ジエチル－１，３－ジアミノプロパン、ｎ－ブチルアミン、またはｎ－プロピルアミンの割合が１００％である比較例１－３の導電性接着剤は、塗膜のせん断力が低かった。また、金属微粒子の平均粒子径が２０ｎｍである比較例４の導電性接着剤についても、塗膜のせん断力が低かった。
（実施例５～１１）
　上記で得られた各銀微粒子１Ａ，１Ｂ，２Ａ，２Ｂ，２Ｃを表２に示す割合で混合し、総質量の１０％相当のテルピネオールを添加し、各分散液を得た。この液をクラボウ社製のマゼルスターを用い、２回撹拌優先モードにて混合し、各導電性接着剤を調製した。なお、混合後の平均粒子径は上述した方法により求めた。
　次に、銅板上に無電解銀めっきを０．５μｍ施した基材を準備し、その上に各導電性接着剤を塗膜厚みが５０μｍとなるように、均一に塗膜を行い、その上に裏面（導電性接着剤と接する面）に金めっきもしくは金スパッタ処理が施されたシリコンウエハ（サイズ２ｍｍ×２ｍｍ）を上に乗せた。これを乾燥器（循環式）により、所定温度（１５０℃）にて６０分間加熱させ、各導電性接着剤が焼結した塗膜を得た。
Figure JPOXMLDOC01-appb-T000002
　表２に示される結果から明らかな通り、実施例５～１１の導電性接着剤は、平均粒子径または保護層中に含まれるアミンが異なる金属微粒子を混合したものであるが、金属微粒子の平均粒子径が３０ｎｍ～３００ｎｍの範囲内であり、保護層中のアミンが、炭素数５～７のモノアルキルアミン及び／又は上記一般式（１）で表されるアルコキシアミンを含み、さらに、炭素数５～７のモノアルキルアミン及び／又は一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にあることから、焼結温度が１５０℃において、塗膜のせん断強度が高く、塗膜の割れや欠けもなかった。
（実施例１２，比較例５，６）
　上記で得られた各銀微粒子１Ａ，１Ｂ，２Ａ，２Ｂ，２Ｃ，３Ａを表３に示す割合で混合し、総質量の１０％相当のテルピネオールを添加し、各分散液を得た。この液をクラボウ社製のマゼルスターを用い、２回撹拌優先モードにて混合し、各導電性接着剤を調製した。なお、混合後の平均粒子径は上述した方法により求めた。
　次に、銅板上に無電解銀めっきを０．５μｍ施した基材を準備し、その上に各導電性接着剤を塗膜厚みが５０μｍとなるように、均一に塗膜を行い、その上に裏面（導電性接着剤と接する面）に金めっきもしくは金スパッタ処理が施されたシリコンウエハ（サイズ２ｍｍ×２ｍｍ）を上に乗せた。これを乾燥器（循環式）により、所定温度（１５０℃）にて６０分間加熱させ、各導電性接着剤が焼結した塗膜を得た。
Figure JPOXMLDOC01-appb-T000003
　表３に示される結果から明らかな通り、実施例１２の導電性接着剤は、平均粒子径及び保護層中に含まれるアミンが異なる金属微粒子を３種類混合したものであるが、金属微粒子の平均粒子径が３０ｎｍ～３００ｎｍの範囲内であり、保護層中のアミンが、炭素数５～７のモノアルキルアミン及び／又は上記一般式（１）で表されるアルコキシアミンを含み、さらに、炭素数５～７のモノアルキルアミン及び／又は一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にあることから、焼結温度が１５０℃において、塗膜のせん断強度が高く、塗膜の割れや欠けもなかった。一方、平均粒子径が３０μｍを下回る比較例５，６では、塗膜のせん断強度が低かった。

Claims (8)

  1. 　アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子Ａを含有し、
    　前記アミンは、炭素数５～７のモノアルキルアミン及び／又は下記一般式（１）で表されるアルコキシアミンを含み、
    ＮＨ2－Ｒ2－Ｏ－Ｒ1　　…（１）
    [式中、Ｒ1は炭素数１～４のアルキル基を示し、Ｒ2は炭素数１～４のアルキレン基を示す。]
    　前記保護層において、前記炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にある、導電性接着剤。
  2. 　前記保護層が、さらに脂肪酸を含む、請求項１に記載の導電性接着剤。
  3. 　溶媒をさらに含む、請求項１又は２に記載の導電性接着剤。
  4. 　請求項１～３のいずれかに記載の導電性接着剤の焼結体。
  5. 　請求項４に記載の焼結体により部材間が接着された部分を備えている、回路又は装置。
  6. 　アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子Ａを混合する工程を備える、導電性接着剤の製造方法であって、
    　前記アミンが炭素数５～７のモノアルキルアミン及び／又は下記一般式（１）で表されるアルコキシアミンを含み、
    ＮＨ2－Ｒ2－Ｏ－Ｒ1　　…（１）
    [式中、Ｒ1は炭素数１～４のアルキル基を示し、Ｒ2は炭素数１～４のアルキレン基を示す。]
    　前記保護層において、前記炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内にある、前記金属微粒子Ａを用いる、導電性接着剤の製造方法。
  7. 　アミンを含む保護層を備え、平均粒子径が３０ｎｍ～３００ｎｍである金属微粒子を準備する工程と、
    　当該金属微粒子の保護層に含まれるアミンと、炭素数５～７のモノアルキルアミン及び一般式（１）で表されるアルコキシアミンとを置換して、炭素数５～７のモノアルキルアミン及び／又は前記一般式（１）で表されるアルコキシアミンと、これらとは異なるアミンとの比率が、１００：０～１０：９０の範囲内となるように調整し、前記金属微粒子Ａを調製する工程と、
    をさらに備える、請求項６に記載の導電性接着剤の製造方法。
  8. 　請求項１～６のいずれかに記載の導電性接着剤を部材間に配置する工程と、
    　前記導電性接着剤を加熱して焼結させる工程と、
    を備える、部材の接着方法。
PCT/JP2017/019311 2016-05-26 2017-05-24 導電性接着剤 WO2017204238A1 (ja)

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