WO2019138558A1 - Composition pour frittage en phase liquide, agent adhésif, corps fritté, structure de liaison, et corps lié ainsi que procédé de fabrication de celui-ci - Google Patents

Composition pour frittage en phase liquide, agent adhésif, corps fritté, structure de liaison, et corps lié ainsi que procédé de fabrication de celui-ci Download PDF

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Publication number
WO2019138558A1
WO2019138558A1 PCT/JP2018/000723 JP2018000723W WO2019138558A1 WO 2019138558 A1 WO2019138558 A1 WO 2019138558A1 JP 2018000723 W JP2018000723 W JP 2018000723W WO 2019138558 A1 WO2019138558 A1 WO 2019138558A1
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Prior art keywords
composition
metal
liquid phase
phase sintering
resin
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PCT/JP2018/000723
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English (en)
Japanese (ja)
Inventor
史貴 上野
雅記 竹内
斉藤　晃一
貴耶 山本
Original Assignee
日立化成株式会社
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Priority to PCT/JP2018/000723 priority Critical patent/WO2019138558A1/fr
Publication of WO2019138558A1 publication Critical patent/WO2019138558A1/fr

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    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only

Definitions

  • the present invention relates to a composition for liquid phase sintering, an adhesive, a sintered body, a bonded structure, a bonded body, and a method of manufacturing a bonded body.
  • solder powder is dispersed as a filler in thermosetting resin such as epoxy resin to make a paste, which is used as a conductive adhesive Methods (see, for example, Patent Document 1).
  • thermosetting resin such as epoxy resin
  • a paste-like conductive adhesive is applied to a die pad of a support member using a dispenser, a printing machine, a stamping machine or the like, then the semiconductor element is die-bonded and the conductive adhesive is heat-cured to obtain a semiconductor Equipment
  • an adhesive composition in which silver particles are sintered by heating at 100 ° C. to 400 ° C. by using micro-sized or smaller silver particles which have been subjected to a special surface treatment (for example, patent documents 3).
  • the silver particles proposed in Patent Document 3 are sintered, the silver particles form a metal bond, and therefore, it is considered that the connection reliability at high temperature is excellent.
  • transitional liquid phase sintering type metal adhesive As an example using metal particles other than silver, development of a transitional liquid phase sintering type metal adhesive is in progress (see, for example, Patent Document 4).
  • a combination of metal particles for example, copper and tin
  • an interfacial liquid phase is formed by heating. Thereafter, the melting point of the liquid phase gradually rises due to the progress of the reaction diffusion, so that the melting point of the composition of the bonding layer finally exceeds the bonding temperature.
  • connection reliability under high temperature is improved by joining copper and a copper-tin alloy.
  • the composition for liquid phase sintering used for the transitional liquid phase sintering type metal adhesive is, for example, a relatively high melting point first metal as a combination of metals capable of transitional liquid phase sintering, And a second metal having a relatively low melting point.
  • the second metal is melted by heat to form a liquid phase, and the first metal diffuses in the liquid phase, whereby the melting point is higher than the melting point of the second metal. Alloy.
  • the first metal and the separate metal particles are used as a form of the composition for liquid phase sintering.
  • the form etc. which contain each of a 2nd metal are mentioned.
  • the form containing resin other than these metal particles is also mentioned as a form of the said composition for liquid phase sintering.
  • a composition for liquid phase sintering containing a first metal particle containing a first metal, a second metal particle containing a second metal, and a resin.
  • One aspect of the present invention is a composition for liquid phase sintering capable of forming a sintered body by a transient liquid phase sintering method in which the occurrence of cracks is suppressed in a thermal cycle test, and the composition for liquid phase sintering
  • An object of the present invention is to provide a contained adhesive, a sintered body using this composition for liquid phase sintering, a bonded structure, a bonded body, and a method of manufacturing a bonded body.
  • ⁇ 3> In the particle diameter distribution of the second metal particle, a volume cumulative distribution curve is drawn from the small diameter side, the particle diameter at 10% of accumulation is D10, and the particle diameter at 90% of accumulation is D90
  • the elastic modulus in tension after heating the composition for liquid phase sintering for 30 minutes at 250 degreeC in low oxygen concentration atmosphere is 1 GPa-10 GPa in any one of ⁇ 1>- ⁇ 3> described in any one of ⁇ 1>- ⁇ 3> Composition for liquid phase sintering.
  • ⁇ 7> The composition for liquid phase sintering according to any one of ⁇ 1> to ⁇ 6>, wherein the volume average particle diameter of the second metal particles is 3.1 ⁇ m to 10.0 ⁇ m.
  • ⁇ 9> An adhesive containing the composition for liquid phase sintering according to any one of ⁇ 1> to ⁇ 8>.
  • ⁇ 10> A sintered body of the composition for liquid phase sintering according to any one of ⁇ 1> to ⁇ 9>.
  • ⁇ 11> The sintered body according to ⁇ 10>, which has a tensile modulus of 1 to 10 GPa.
  • the junction structure where the ⁇ 12> 1st to-be-joined thing and the 2nd to-be-joined thing are joined through the sintered compact as described in ⁇ 10> or ⁇ 11>.
  • composition for liquid phase sintering according to any one of ⁇ 1> to ⁇ 8> in at least one of a joining part of the element in the supporting member and a joining part with the element in the element Applying a substance to form a composition layer, Bringing the support member into contact with the element through the composition layer; And heating the composition layer to sinter.
  • a composition for liquid phase sintering capable of forming a sintered body by the transient liquid phase sintering method in which the occurrence of cracks is suppressed in a thermal cycle test, and the composition for liquid phase sintering It is possible to provide an adhesive containing a substance and a method for producing a sintered body, a bonded structure, a bonded body, and a bonded body using this composition for liquid phase sintering.
  • the present invention is not limited to the following embodiments.
  • the constituent elements including element steps and the like
  • the term “step” includes, in addition to steps independent of other steps, such steps as long as the purpose of the step is achieved even if it can not be clearly distinguished from other steps. .
  • numerical values described before and after “to” are included in the numerical range indicated using “to” as the minimum value and the maximum value, respectively.
  • each component may contain a plurality of corresponding substances.
  • the content of each component means the total content of the plurality of substances present in the composition unless otherwise specified.
  • particles corresponding to each component may contain a plurality of types.
  • the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
  • the term “layer” may mean that when the region in which the layer is present is observed, it is formed in only a part of the region, in addition to the case where the region is entirely formed. included.
  • composition for liquid phase sintering includes a first metal particle containing a first metal and having a melting point of 400 ° C. or more, and the first metal. It contains a second metal particle that contains a second metal capable of transient liquid phase sintering, has a melting point of 300 ° C. or less, and has a volume average particle diameter of 1.0 ⁇ m to 10.0 ⁇ m, and a resin.
  • the second metal particles are first melted to form a liquid phase, and the periphery of the first metal particles is surround. Then, the first metal contained in the first metal particles reacts and diffuses to the surrounding liquid phase, whereby an alloy containing the first metal and the second metal is formed. On the other hand, in the region where the second metal particles were present, the second metal particles melted and flowed out around the first metal particles to form voids, and the resin extruded as the alloy grew. It is considered that the resin part is formed by the penetration of the resin into the void.
  • the volume average particle diameter of the second metal particles is 1.0 ⁇ m to 10.0 ⁇ m. Therefore, as compared with the case where the volume average particle size of the second metal particles exceeds 10.0 ⁇ m, the voids formed after the melting of the second metal particles are smaller, and the small voids are filled with the resin, It is considered that the resin portion in the sintered body is finely dispersed, and uneven distribution of the resin portion is suppressed. And, by suppressing the uneven distribution of the resin part, it becomes difficult to produce a place where stress concentrates in the sintered body, so it is difficult to apply thermal stress to the alloy part, and the thermal cycle test is carried out on the sintered body However, it is presumed that cracking is less likely to occur.
  • the composition of the present disclosure comprises a first metal particle containing a first metal and having a melting point of 400 ° C. or higher, and a second metal capable of performing a transient liquid phase sintering with the first metal. And second metal particles having a melting point of 300 ° C. or less and a volume average particle diameter of 1.0 ⁇ m to 10.0 ⁇ m.
  • transitional liquid phase sintering in the present disclosure is also referred to as Transient Liquid Phase Sintering (TLPS), and the transition to the liquid phase by heating at the particle interface of the low melting point metal and the liquid phase of the high melting point metal It refers to a phenomenon that proceeds by reaction diffusion to the surface.
  • the transitional liquid phase sintering allows the melting point of the sintered body to exceed the heating temperature.
  • the combination of metals capable of transient liquid phase sintering is not particularly limited, and the combination of Au and In, Cu and Sn Combinations of Ag and Sn, combinations of Co and Sn, combinations of Ni and Sn, and the like.
  • a combination of Cu and Sn is preferable as a combination of metals capable of transient liquid phase sintering. Since the reaction to form the copper-tin metal compound (Cu 6 Sn 5 ) by sintering proceeds at around 250 ° C., using Cu and Sn in combination allows sintering by general equipment such as a reflow furnace. It is possible.
  • the composition of the present disclosure may also include other metal particles (ie, particles composed of metals other than the first metal and the second metal) in addition to the first metal particles and the second metal particles.
  • other metal particles ie, particles composed of metals other than the first metal and the second metal
  • the ratio of the other metal particles to the whole metal particles is 10% by mass or less Is preferable, 5% by mass or less is more preferable, and 1% by mass or less is more preferable.
  • each of the first metal particle and the second metal particle will be described.
  • the first metal particles contain the first metal and have a melting point of 400 ° C. or higher.
  • the first metal particles may be in the form of containing the first metal as a single metal, or in the form of containing an alloy containing the first metal.
  • the first metal particles are preferably particles containing Cu as a single metal.
  • the first metal particle only needs to contain the first metal in at least a part of the region in the particle, and in view of facilitating the reaction diffusion of the first metal into the liquid phase in the process of sintering, at least It is preferable that the surface of the particle contains a first metal.
  • a first metal particle containing the first metal on the surface of the particle for example, a core particle, and a coating layer which covers the core particle and contains the first metal (for example, a first metal simple substance or a first metal) And a covering layer composed of an alloy containing a metal of The core particle may contain the first metal or may not contain the first metal.
  • Examples of core particles containing a first metal include particles consisting of a first metal single particle, particles consisting of an alloy containing a first metal, and particles in which some of the particles contain the first metal. Moreover, as a particle which does not contain a 1st metal, the particle
  • the first metal is Cu
  • the melting point of the first metal particles is 400 ° C. or higher, preferably 400 ° C. to 2500 ° C., more preferably 400 ° C. to 2000 ° C., and still more preferably 400 ° C. to 1300 ° C.
  • a measuring pan made of platinum is used by DSC (differential scanning calorimetry) and 50 ml It can measure on the conditions heated from 25 degreeC to 1300 degreeC with the temperature increase rate of 10 degree-C / min under nitrogen flow of 1 / minute.
  • the melting point of the first metal-containing region is preferably in the above range.
  • the volume average particle diameter of the first metal particles is not particularly limited, and is preferably 0.5 ⁇ m to 80 ⁇ m, and more preferably 1 ⁇ m to 50 ⁇ m, from the viewpoints of application stability and suppression of sintering unevenness. More preferably, it is 1 ⁇ m to 30 ⁇ m. Also, in the particle diameter distribution of the first metal particles, a volume cumulative distribution curve is drawn from the small diameter side, the particle diameter at 10% of accumulation is D10, and the particle diameter at 90% of accumulation is D90, D90
  • the value of / D10 is preferably 1 to 3, and more preferably 1.5 to 2.5, from the viewpoint of the reliability of the high temperature region after sintering (that is, the durability to the thermal cycle test). Preferably, it is 1.5 to 2.0.
  • the volume average particle size of the first metal particles is calculated from the particle size distribution measured by a laser diffraction type particle size distribution analyzer (for example, LS 13 320 type laser scattering / diffraction particle size distribution measuring device manufactured by Beckman Coulter, Inc.) Be done. Specifically, in the obtained particle size distribution, a volume cumulative distribution curve is drawn from the small diameter side, and D50, which is the particle size at which the cumulative 50% is achieved, is defined as the volume average particle size. Further, the value of D90 / D10 is obtained from D10, which is the particle diameter when the cumulative 10% of the volume cumulative distribution curve is obtained, and D90, which is the particle diameter when the cumulative 90% is obtained.
  • the measurement of the particle size distribution is performed as follows.
  • a metal particle is added in the range of 0.01% by mass to 0.3% by mass to 125 g of a solvent (terpineol) to prepare a dispersion.
  • a solvent terpineol
  • About 100 ml of this dispersion is injected into the cell and measured at 25 ° C.
  • the particle size distribution is measured with the refractive index of the solvent being 1.48.
  • the measurement and calculation method of the volume average particle diameter and D90 / D10 in the following 2nd metal particle are also the same.
  • the content of the first metal particles is the reliability of the high temperature region after sintering (that is, the durability to the thermal cycle test) with respect to the total volume of the first metal particles, the second metal particles, and the resin. From the viewpoint of the above, 50% by volume to 80% by volume is preferable, 60% by volume to 80% by volume is more preferable, and 65% by volume to 70% by volume is more preferable.
  • the content rate of the 1st metal particle with respect to the total volume of a 1st metal particle, a 2nd metal particle, and resin is calculated
  • Content rate of first metal particle (volume%) (Aw / Ad) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd)) ⁇ 100
  • Ad Specific gravity of first metal particle
  • Bd Specific gravity of second metal particle
  • Cd Specific gravity of resin
  • the second metal particles contain a second metal and have a melting point of 300 ° C. or less and a volume average particle diameter of 1.0 ⁇ m to 10.0 ⁇ m.
  • the second metal particles may contain the second metal as a single metal, or may contain an alloy containing the second metal.
  • the second metal particles are preferably particles containing an alloy containing Sn. Examples of the alloy containing Sn include Sn-3.0Ag-0.5Cu alloy and the like.
  • the notation in the alloy indicates that the tin alloy contains A mass% of element X and B mass% of element Y.
  • the second metal particles may contain the second metal in at least a part of the region, and in view of facilitating the second metal particles to be in a liquid phase in the process of sintering, the entire particles are second It is preferable to contain the following metals.
  • the melting point of the second metal particles is 300 ° C. or less, preferably 120 ° C. to 300 ° C., more preferably 130 ° C. to 250 ° C., and still more preferably 135 ° C. to 225 ° C.
  • the melting point of the second metal particles is measured by DSC (Differential scanning calorimetry) using a platinum pan at a heating rate of 10 ° C./min under a nitrogen stream of 50 ml / min.
  • the difference between the melting point of the first metal particle and the melting point of the second metal particle is preferably 500 ° C. or more, more preferably 600 ° C. or more, and still more preferably 800 ° C. or more.
  • the volume average particle size of the second metal particles is 1.0 ⁇ m to 10.0 ⁇ m, and preferably 3.1 ⁇ m to 10.0 ⁇ m.
  • the volume average particle diameter of the second metal particles is in the above range, generation of cracks in the thermal cycle test after sintering is suppressed as compared with the case where the volume average particle diameter is larger than the above range.
  • the volume average particle diameter of the second metal particles is in the above range, the aggregation of the particles can be suppressed as compared to the case where the volume average particle diameter is smaller than the above range. .
  • the volume average particle diameter of the second metal particles is preferably 3.0 ⁇ m to 5.0 ⁇ m, and preferably 3.1 ⁇ m to 5 ⁇ m, from the viewpoint of suppression of cracks and printability in a thermal cycle test after sintering. More preferably, it is .0 ⁇ m.
  • the particle size at 10% of accumulation is D10
  • the particle size at 90% of accumulation is D90 / D10
  • the value of is preferably 2.2 to 7.0, and 2.75 to 6.5, from the viewpoint of the reliability of the high temperature region after sintering (that is, the durability to the thermal cycle test). Is more preferable, and 2.9 to 3.5 is more preferable.
  • the content of the second metal particles is the reliability of the high temperature region after sintering (that is, the durability to the thermal cycle test) with respect to the total volume of the first metal particles, the second metal particles and the resin. From the viewpoint of the above, 15% by volume to 30% by volume is preferable, 18% by volume to 28% by volume is more preferable, and 20% by volume to 26% by volume is more preferable.
  • the total content of the first metal particles and the second metal particles is not particularly limited, and is preferably 80% by volume or more and 85% by volume or more with respect to the entire composition. More preferably, it is 88% by volume or more. In addition, the total content of the first metal particles and the second metal particles may be 98 volume% or less with respect to the entire composition.
  • the ratio of the content of the first metal particles (based on volume) to the content of the second metal (based on volume) ie, the content of the first metal particles / the content of the second metal particles
  • the ratio of the content of the first metal particles (based on volume) to the content of the second metal (based on volume) is preferably 2.0 to 4.0, and more preferably 2.2 to 3.5.
  • the resin contained in the composition of the present disclosure is not particularly limited, and may be a thermoplastic resin or a thermosetting resin.
  • the thermoplastic resin include polyamide resin, polyamide imide resin, polyimide resin, polyurethane resin, thermoplastic epoxy resin and the like.
  • the thermosetting resin include epoxy resin, oxazine resin, bismaleimide resin, phenol resin, unsaturated polyester resin, silicone resin and the like.
  • epoxy resins bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthalene type epoxy resin, biphenol type epoxy resin, biphenyl novolac type Epoxy resin, cyclic aliphatic epoxy resin and the like can be mentioned.
  • the above resins may be used alone or in combination of two or more.
  • a thermoplastic resin is preferable from the viewpoint of facilitating flow without inhibiting alloy formation of metal particles in the process of sintering.
  • the resin preferably exhibits a softening point lower than the melting point of the second metal particles from the viewpoint of making it difficult to inhibit the alloy formation of the metal particles in the process of sintering.
  • the softening point of the resin refers to the value measured by thermomechanical analysis. Specifically, for example, a resin film with a thickness of 100 ⁇ m is heated at 10 ° C./min using a thermomechanical analyzer (TMA 8320, manufactured by Rigaku Corporation, measurement probe: compression weighted standard type) While compressing with a force of 49 mN, the temperature displaced 80 ⁇ m is taken as the softening point of the resin.
  • TMA 8320 thermomechanical analyzer
  • the softening point of the resin is preferably 5 ° C.
  • the softening point of the resin is preferably 40 ° C. or higher, more preferably 50 ° C. or higher, and 60 ° C. or higher, from the viewpoint of shape retention of the layer of the transient liquid phase sintering composition. Is more preferred.
  • the elastic modulus at 25 ° C. of the resin is preferably 0.01 GPa to 1.0 GPa, more preferably 0.01 GPa to 0.5 GPa, and more preferably 0.01 GPa to 0, from the viewpoint of securing connection reliability. More preferably, it is .3 GPa.
  • the elastic modulus at 25 ° C. of the resin is a value measured by the method of JIS K 7161-1: 2014.
  • the thermal decomposition rate of the resin measured under a stream of nitrogen using a thermogravimetry apparatus is preferably 2.0% by mass or less. If the thermal decomposition rate of the resin measured under a nitrogen stream using a thermogravimetry device is 2.0 mass% or less, the elastic modulus of the sintered body before and after the thermal history is given to the sintered body Changes are easily suppressed.
  • the thermal decomposition rate of the resin is more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less.
  • the thermal decomposition rate of a resin refers to a value measured by the following method.
  • 10 mg of resin placed in a platinum pan is heated from 25 ° C. to 400 ° C. at a heating rate of 10 ° C./min under a nitrogen stream of 50 ml / min using a thermogravimetry apparatus
  • the weight loss rate between 200 ° C. and 300 ° C. is taken as the thermal decomposition rate.
  • thermoplastic resin As the resin, as described above, a thermoplastic resin is preferable, and among them, a thermoplastic resin having a functional group or a structure which easily forms a hydrogen bond with the surface of metal particles is preferable from the viewpoint of the dispersibility of the resin in the composition.
  • functional groups that easily form hydrogen bonds with the surface of metal particles include amino groups and carboxy groups.
  • an amide bond, an imide bond, a urethane bond etc. are mentioned as a structure which is easy to form a hydrogen bond with the surface of metal particle.
  • thermoplastic resin what contains at least 1 sort (s) selected from the group which consists of an amide bond, an imide bond, and a urethane bond is preferable.
  • thermoplastic resin at least one selected from the group consisting of a polyamide resin, a polyamideimide resin, a polyimide resin and a polyurethane resin can be mentioned.
  • the thermoplastic resin is preferably a polyamideimide resin.
  • the thermoplastic resin preferably has a molecular structure exhibiting flexibility.
  • the molecular structure exhibiting flexibility at least one of a polyalkylene oxide structure and a polysiloxane structure can be mentioned.
  • the polyalkylene oxide structure is not particularly limited.
  • the polyalkylene oxide structure preferably includes, for example, a structure represented by the following general formula (1).
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 100
  • “*” represents a bonding position to an adjacent atom.
  • m represents a rational number that is an average value.
  • the alkylene group represented by R 1 is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms.
  • the alkylene group may be linear, branched or cyclic.
  • Examples of the alkylene group represented by R 1 include methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, decylene group and the like.
  • the alkylene group represented by R 1 one kind may be used alone, or two or more kinds of different alkylene groups may be used in combination.
  • m is preferably 20 to 60, and more preferably 30 to 40.
  • the structure represented by General formula (1) contains the structure represented by following General formula (1A).
  • m represents an integer of 1 to 100, and "*" represents a bonding position to an adjacent atom.
  • the preferred range of m is the same as in the case of the general formula (1).
  • the proportion of the polyalkylene oxide structure represented by the general formula (1) in all the polyalkylene oxide structures is preferably 75% by mass to 100% by mass, The content is more preferably 85% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.
  • the polyalkylene oxide represented by the general formula (1A) accounts for all the polyalkylene oxide structures represented by the general formula (1)
  • the proportion of the structure is preferably 50% by mass to 100% by mass, more preferably 75% by mass to 100% by mass, and still more preferably 90% by mass to 100% by mass.
  • the polysiloxane structure is not particularly limited.
  • the polysiloxane structure preferably contains, for example, a structure represented by the following general formula (2).
  • R 2 and R 3 each independently represent a divalent organic group
  • R 4 to R 7 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms
  • N represents an integer of 1 to 50
  • “*” represents a bonding position to an adjacent atom.
  • n indicates a rational number that is an average value.
  • the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the alkyl group or the aryl group.
  • Examples of the divalent organic group represented by R 2 and R 3 in the general formula (2) include a divalent saturated hydrocarbon group, a divalent aliphatic ether group, and a divalent aliphatic ester group. .
  • the divalent saturated hydrocarbon group may be linear, branched or cyclic.
  • the divalent saturated hydrocarbon group may have a substituent such as a fluorine atom or a halogen atom such as a chlorine atom.
  • Examples of the divalent saturated hydrocarbon group represented by R 2 and R 3 include methylene group, ethylene group, propylene group, butylene group, pentylene group, cyclopropylene group, cyclobutylene group and cyclopentylene group.
  • the divalent saturated hydrocarbon groups represented by R 2 and R 3 can be used alone or in combination of two or more. As R 2 and R 3 , a propylene group is preferable.
  • examples of the alkyl group having 1 to 20 carbon atoms represented by R 4 to R 7 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and a t-butyl group, Examples include n-octyl group, 2-ethylhexyl group, n-dodecyl group and the like. Among these, a methyl group is preferable.
  • the aryl group having 6 to 18 carbon atoms represented by R 4 to R 7 may be unsubstituted or substituted by a substituent.
  • the substituent include a halogen atom, an alkoxy group, and a hydroxy group.
  • the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group and a benzyl group. Among these, a phenyl group is preferable.
  • the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms represented by R 4 to R 7 can be used singly or in combination of two or more.
  • n is preferably 5 to 25 and more preferably 10 to 25.
  • the polyamideimide resin When a polyamideimide resin is used as the thermoplastic resin, the polyamideimide resin preferably has a structural unit derived from a diimide carboxylic acid or a derivative thereof and a structural unit derived from an aromatic diisocyanate or an aromatic diamine.
  • the polyamideimide resin is a resin having a structural unit derived from diimide carboxylic acid or a derivative thereof and a structural unit derived from aromatic diisocyanate or aromatic diamine
  • the following general formula is occupied in the structural unit derived from diimide carboxylic acid or a derivative thereof
  • the proportion of the structural unit represented by the following general formula (4) in the structural unit derived from the diimide carboxylic acid or its derivative is 30 mol% or more, and the proportion of the structural unit represented by (3) is 25 mol% or more
  • the sum of the ratio of the structural unit represented by the following general formula (3) and the ratio of the structural unit represented by the following general formula (4) is 60 mol% or more, and the following general It is more preferable that the sum of the ratio of the structural unit represented by the formula (3) and the ratio of the structural unit represented by the following general formula (4) is 70 mol% or more
  • 60 mol% or less of the ratio of the structural unit represented by following General formula (3) to the structural unit derived from diimide carboxylic acid or its derivative (s) may be sufficient.
  • 60 mol% or less of the ratio of the structural unit represented by following General formula (4) to the structural unit derived from diimide carboxylic acid or its derivative (s) may be sufficient.
  • the total of the ratio of the structural unit represented by the following general formula (3) to the structural unit derived from the following general formula (4) in the structural units derived from the diimide carboxylic acid or its derivative is 100 mol% or less It may be.
  • R 8 represents a divalent group including a structure represented by the following general formula (1), and “*” represents a bonding position to an adjacent atom.
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 100
  • “*” represents a bonding position to an adjacent atom.
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 100
  • “*” represents a bonding position to an adjacent atom.
  • Specific examples of R 1 , preferable ranges of m, and the like are as described above.
  • the structural unit represented by the general formula (3) is preferably a structural unit represented by the following general formula (3A), and more preferably a structural unit represented by the following general formula (3B).
  • R 1 represents an alkylene group
  • m represents an integer of 1 to 100
  • “*” represents a bonding position to an adjacent atom.
  • m represents an integer of 1 to 100, and "*" represents a bonding position to an adjacent atom.
  • the preferable range etc. of m are the same as that of the case of General formula (1).
  • R 9 is a bivalent group containing the structure represented by the following general formula (2), "*" represents a bonding position between the adjacent atoms.
  • R 2 and R 3 each independently represent a divalent organic group
  • R 4 to R 7 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms
  • N represents an integer of 1 to 50
  • “*” represents a bonding position to an adjacent atom.
  • Specific examples of R 2 to R 7 and preferable ranges of n and the like are as described above.
  • the structural unit represented by the general formula (4) is preferably a structural unit represented by the following general formula (4A).
  • R 2 and R 3 each independently represent a divalent organic group
  • R 4 to R 7 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms
  • N represents an integer of 1 to 50
  • “*” represents a bonding position to an adjacent atom.
  • the specific examples of R 2 to R 7 and the preferred range of n are the same as in the case of the general formula (2).
  • the method for producing the polyamideimide resin is not particularly limited, and examples thereof include an isocyanate method and an acid chloride method.
  • a polyamideimide resin is synthesized using a diimide carboxylic acid and an aromatic diisocyanate.
  • acid chloride method a polyamideimide resin is synthesized using a diimide carboxylic acid chloride and an aromatic diamine.
  • An isocyanate method synthesized from a diimide carboxylic acid and an aromatic diisocyanate is more preferable because the structure of the polyamideimide resin can be optimized easily.
  • the diimidic carboxylic acids used in the isocyanate method are synthesized, for example, using trimellitic anhydride and diamines.
  • a diamine used for the synthesis combination of a diimide carboxylic acid, a siloxane modified diamine, an alicyclic diamine, an aliphatic diamine etc. are suitable.
  • siloxane modified diamine As a siloxane modified diamine, what has the following structural formula is mentioned, for example.
  • R 2 and R 3 each independently represent a divalent organic group
  • R 4 to R 7 each independently represent an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 18 carbon atoms.
  • n represents an integer of 1 to 50. Specific examples of R 2 to R 7 and preferable ranges of n are the same as in the case of the general formula (2).
  • Examples of commercially available siloxane-modified diamines include KF-8010, KF-8012, X-22-161A, X-22-161B, and X-22-9409 (all manufactured by Shin-Etsu Chemical Co., Ltd.).
  • Alicyclic diamines include 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] propane, bis [4- (3-aminocyclohexyloxy) cyclohexyl] sulfone, bis [4- (4-aminocyclohexyl) Oxy) cyclohexyl] sulfone, 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] hexafluoropropane, bis [4- (4-aminocyclohexyloxy) cyclohexyl] methane, 4,4'-bis (4 -Aminocyclohexyloxy) dicyclohexyl, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ether, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ketone, 1,3-
  • oxypropylene diamine is preferred.
  • Commercially available oxypropylene diamines include Jeffamine D-230 (Mitsui Chemical Fine Co., Ltd., amine equivalent: 115, trade name), Jeffamine D-400 (Mitsui Chemical Fine Co., Ltd., amine equivalent: 200, trade name) ), Jeffamine D-2000 (manufactured by Mitsui Chemicals Fine Inc., amine equivalent: 1,000, trade name), Jeffamine D-4000 (manufactured by Mitsui Chemicals Fine Inc., amine equivalent: 2,000, trade name), etc. Can be mentioned.
  • One of the above diamines may be used alone, or two or more thereof may be used in combination.
  • Polyamideimide resin synthesized by using 60 mol% to 100 mol% of the above diamine with respect to the total amount of diamine is preferable, and among them, in order to simultaneously achieve heat resistance and low elastic modulus, it is synthesized including siloxane modified diamine Siloxane-modified polyamideimide resin is more preferred.
  • aromatic diamine can also be used together as needed.
  • aromatic diamines include p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminoxylene, diaminodurene, 1 3,5-diaminonaphthalene, 2,6-diaminonaphthalene, benzidine, 4,4'-diaminoterphenyl, 4,4 '' '-diaminoquaterphenyl, 4,4'-diaminodiphenylmethane, 1,2-bis (anilino) ) Ethane, 4,4'-diaminodiphenylether, diaminodiphenylsulfone, 2,2-bis (p-aminophenyl) propane, 2,2-bis (p-aminophenyl) hexafluoroprop
  • the aromatic diisocyanate may, for example, be a diisocyanate obtained by the reaction of an aromatic diamine with phosgene or the like.
  • Specific examples of the aromatic diisocyanate include aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, phenylene-1,3-diisocyanate and the like.
  • aromatic diisocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene diisocyanate, diphenyl ether diisocyanate, phenylene-1,3-diisocyanate and the like.
  • 4,4'-diphenylmethane diisocyanate, diphenylether diisocyanate and the like are preferable.
  • the polymerization reaction of a polyamideimide resin by the isocyanate method is usually N-methyl-2-pyrrolidone (NMP), N, N-dimethylformamide (DMF), N, N-dimethylacetamide (DMAC), dimethylsulfoxide (DMSO), It is carried out in a solvent such as dimethyl sulfate, sulfolane, ⁇ -butyrolactone, cresol, halogenated phenol, cyclohexane, dioxane and the like.
  • the reaction temperature is preferably 0 ° C. to 200 ° C., more preferably 100 ° C. to 180 ° C., and still more preferably 130 ° C. to 160 ° C.
  • the compounding ratio (diimide carboxylic acid / aromatic diisocyanate) on a molar basis of diimide carboxylic acid and aromatic diisocyanate in the polymerization reaction of a polyamideimide resin by the isocyanate method is preferably 1.0 to 1.5, and 1.
  • the ratio is more preferably 05 to 1.3, and still more preferably 1.1 to 1.2.
  • the composition of the present disclosure may contain a solvent from the viewpoint of improving the printability when the composition of the present disclosure is used as a paste.
  • the solvent is preferably a polar solvent, and from the viewpoint of preventing the composition from being dried in the step of applying the composition, the solvent preferably has a boiling point of 200 ° C. or higher It is more preferable that the solvent has a boiling point of 300 ° C. or less in order to suppress the generation of voids during sintering.
  • solvents examples include terpineol, stearyl alcohol, tripropylene glycol methyl ether, diethylene glycol, diethylene glycol monoethyl ether (ethoxyethoxyethanol), diethylene glycol monohexyl ether, diethylene glycol monomethyl ether, dipropylene glycol-n-propyl ether, Alcohols such as dipropylene glycol n-butyl ether, tripropylene glycol n-butyl ether, 1,3-butanediol, 1,4-butanediol, propylene glycol phenyl ether, tributyl citrate, 4-methyl-1,3 -Dioxolan-2-one, ⁇ -butyrolactone, sulfolane, 2- (2-butoxyethoxy) ethanol, diethylene Esters such as recalled monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether,
  • the content of the solvent is not particularly limited, and the proportion by mass of the solvent in the entire composition of the present disclosure is 0.1% by mass to 10% by mass. Is preferable, 2 to 7% by mass is more preferable, and 3 to 5% by mass is more preferable.
  • composition of the present disclosure may optionally contain other components such as rosin, activators, and thixotropic agents.
  • Rosins that may be used in the compositions of the present disclosure include dehydroabietic acid, dihydroabietic acid, neoabietic acid, dihydropimaric acid, pimaric acid, isopimaric acid, tetrahydroabietic acid, parastronic acid and the like.
  • Activators that may be used in the compositions of the present disclosure include aminodecanoic acid, pentane-1,5-dicarboxylic acid, triethanolamine, diphenylacetic acid, sebacic acid, phthalic acid, benzoic acid, dibromosalicylic acid, anisic acid, iodo Examples thereof include salicylic acid and picolinic acid.
  • the activator is not particularly limited, and among them, from the viewpoint of the reliability of the high temperature region, a secondary amine or a tertiary amine is preferable, a tertiary amine is more preferable, and triethanol is preferable. More preferably, it is an amine.
  • Thixo agents that may be used in the compositions of the present disclosure include 12-hydroxystearic acid, 12-hydroxystearic acid triglyceride, ethylenebisstearic acid amide, hexamethylene bisoleic acid amide, N, N'-distearyl adipic acid Amide etc. are mentioned.
  • the proportion of the resin in the solid content excluding metal particles is preferably 5% by mass to 30% by mass, more preferably 6% by mass to 28% by mass, and 8% by mass. More preferably, it is% to 25% by mass. If the proportion of the resin in the solid content excluding metal particles is 5% by mass or more, the composition of the present disclosure is likely to be in the form of a paste. If the proportion of the resin in the solid content excluding metal particles is 30% by mass or less, sintering of the metal particles is less likely to be inhibited.
  • solid content means the remaining component except a volatile component (solvent etc.) from a composition.
  • the method for producing the composition of the present disclosure is not particularly limited. It can be obtained by mixing the metal particles, the resin, the solvent used if necessary, and other components constituting the composition of the present disclosure, and further performing processing such as stirring, melting, dispersion and the like.
  • the apparatus for mixing, stirring, dispersing and the like is not particularly limited, and a three-roll mill, a planetary mixer, a planetary mixer, a rotation and revolution type stirring apparatus, a grinder, a twin screw kneader, A thin layer shear disperser or the like can be used. Also, these devices may be used in combination as appropriate. In the case of the said process, you may heat as needed. After treatment, the maximum particle size of the composition may be adjusted by filtration. The filtration can be performed using a filtration device. As a filter for filtration, a metal mesh, a metal filter, and a nylon mesh are mentioned, for example.
  • the tensile elastic modulus after heating the composition at 250 ° C. for 30 minutes in a low oxygen concentration atmosphere is preferably 1 GPa to 10 GPa, more preferably 1 GPa to 7 GPa, and further preferably 1 GPa to 5 GPa. preferable.
  • the tensile modulus of elasticity is obtained by measurement with a tensile tester (Autograph AGS-X, manufactured by Shimadzu Corporation) using a 1 kN load cell at a tensile speed of 50 mm / min.
  • the adhesive of the present disclosure contains the composition of the present disclosure.
  • the composition of the present disclosure can be used as an adhesive as it is, or may contain other components as an adhesive if necessary.
  • Preferred embodiments of the adhesive of the present disclosure are the same as those of the composition of the present disclosure described above.
  • the sintered body of the present disclosure is a sintered product of the composition of the present disclosure.
  • the method of sintering the composition of the present disclosure is not particularly limited.
  • the electrical resistivity of the sintered body is preferably 1 ⁇ 10 ⁇ 4 ⁇ ⁇ cm or less.
  • the tensile modulus of the sintered body is preferably 1 GPa to 10 GPa, more preferably 1 GPa to 7 GPa, and still more preferably 1 GPa to 5 GPa.
  • the joint structure of the present disclosure is a structure in which a first object to be joined and a second object to be joined are joined via the sintered body of the present disclosure.
  • the combination of the first object and the second object is not particularly limited, and examples thereof include a combination of an element and a support member in a joined body described later.
  • the structure of the junction part in the joined body mentioned later is mentioned as a joining structure of this indication.
  • the bonded body of the present disclosure is obtained by bonding the element and the support member via the sintered body of the present disclosure. It does not specifically limit as a supporting member, What is a metal of the material of the location where the element is joined is used. Gold, silver, copper, nickel etc. are mentioned as a metal which is a material of the location where the element is joined. Further, the support member may be configured by patterning a plurality of metals among the above on the base material. Specific examples of the support member include a lead frame, a tape carrier with wiring, a rigid wiring board, a flexible wiring board, a glass substrate with wiring, a silicon wafer with wiring, and a wafer level chip size package (CSP). And the like.
  • CSP wafer level chip size package
  • the element is not particularly limited, and may be a semiconductor chip, an active element such as a transistor, a diode, a light emitting diode, or a thyristor, a capacitor, a resistor, a resistor array, a coil, a passive element such as a switch, and the like. Moreover, a semiconductor device, an electronic component, etc. are mentioned as a joined object of this indication.
  • the semiconductor device include a diode, a rectifier, a thyristor, a MOS (Metal Oxide Semiconductor) gate driver, a power switch, a power MOSFET (Metal Oxide Semiconductor Field-Effect Transistor), an IGBT (Insulated Gate Bipolar Transistor), a Schottky diode, Examples include a power module provided with a fast recovery diode and the like, a transmitter, an amplifier, an LED module and the like.
  • MOS Metal Oxide Semiconductor
  • MOSFET Metal Oxide Semiconductor Field-Effect Transistor
  • IGBT Insulated Gate Bipolar Transistor
  • Schottky diode Examples include a power module provided with a fast recovery diode and the like, a transmitter, an amplifier, an LED module and the like.
  • the composition according to the present disclosure is applied to at least one of the joining site of the element in the support member and the joining site with the support member in the element to form a composition layer. And contacting the support member with the element through the composition layer, and sintering the composition layer by heating.
  • the step of applying the composition to form a composition layer may include the step of drying the applied composition.
  • the composition layer is formed by applying the composition of the present disclosure to at least one of the joining portion of the element in the support member and the joining portion with the support member in the element.
  • the method of applying the composition include a coating method and a printing method.
  • a method of applying the composition for example, dipping, spray coating, bar coating, die coating, comma coating, slit coating, and application by an applicator can be used.
  • a printing method for printing the composition for example, a dispenser method, a stencil printing method, an intaglio printing method, a screen printing method, a needle dispenser method, and a jet dispenser method can be used.
  • the composition layer formed by the application of the composition is preferably dried from the viewpoint of suppressing the flow of the composition and the generation of voids during heating.
  • the composition layer may be dried by standing at ordinary temperature (for example, 25 ° C.), drying by heating, or drying under reduced pressure.
  • a hot plate warm air dryer, warm air heater, nitrogen dryer, infrared dryer, infrared heater, far infrared heater, microwave heater, laser heater, electromagnetic heater
  • a heater heating device, a steam heating furnace, a hot plate press device or the like can be used.
  • the temperature and time for drying can be appropriately adjusted in accordance with the type and amount of the solvent used, and for example, drying at 50 ° C. to 180 ° C. for 1 minute to 120 minutes is preferable.
  • the element and the support member are attached to each other through the composition layer by bringing the element and the support member into contact with each other.
  • the step of drying the applied composition may be performed at any stage before or after the step of contacting the support member with the element.
  • the composition layer is heated to form a sintered body.
  • Sintering of the composition layer may be performed by heat treatment or heat and pressure treatment.
  • heat treatment hot plate, warm air dryer, warm air heater, nitrogen dryer, infrared dryer, infrared heater, far infrared heater, microwave heater, laser heater, electromagnetic heater, heater heater An apparatus, a steam heating furnace, etc. can be used.
  • a hot plate press apparatus or the like may be used for the heat and pressure treatment, or the above-described heat treatment may be performed while being pressurized.
  • the heating temperature in sintering of the composition layer is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, and still more preferably 220 ° C.
  • the heating time for sintering the composition layer is preferably 5 seconds to 10 hours, more preferably 1 minute to 30 minutes, and preferably 3 minutes to 10 minutes, depending on the type of metal particles. More preferable.
  • the oxygen concentration is 1000 ppm or less, preferably 500 ppm or less.
  • the composition prepared by the method to be described later is 10 mm long ⁇ 100 mm wide using a printing form on an aluminum foil (Separium 50B2C-ET manufactured by Toyo Aluminum Co., Ltd.) release-treated with an epoxy resin It printed in the size of 250 micrometers in thickness.
  • the printed matter is placed on a hot plate and dried at 100 ° C. for 30 minutes, and then, using a nitrogen oven (P-P50-3AO2 manufactured by Yashima Industry Co., Ltd.), under conditions of 250 ° C. and nitrogen flow of 30 L / min. It was heated and sintered for 30 minutes to obtain a sintered sample piece. This sintered sample piece was used as a sample piece (normal state).
  • the sintered sample piece was subjected to a heat treatment in an oven at 275 ° C. for 4 hours in an air atmosphere to obtain a sample piece (after the heat treatment).
  • the change in elastic modulus was confirmed by measuring the elastic modulus of these sample pieces with a tensile tester (Autograph AGS-X, manufactured by Shimadzu Corporation). The measurement was performed using a 1 kN load cell at a tension speed of 50 mm / min.
  • composition prepared by the method described later was applied onto a copper lead frame using a pointed tweezers to form a composition layer.
  • a Si chip having a size of 2 mm ⁇ 2 mm and gold-plated on the adhesion surface was placed on the composition layer and lightly pressed with tweezers to obtain a sample before sintering of the composition.
  • the sample before sintering is dried on a hot plate at 100 ° C. for 30 minutes, and then set on a conveyor of a nitrogen reflow apparatus (Tamura Seisakusho Co., Ltd .: 1 zone 50 cm, 7 zones configuration, under nitrogen stream), oxygen concentration 200 ppm It transported at a speed of 0.3 m / min.
  • cross-sectional SEM observation of the sample for investigating the presence or absence of a crack was performed as follows.
  • a sample is fixed in a cup with a sample clip (Samplklip I, manufactured by Buehler), an epoxy casting resin (Epomount, manufactured by Refintech Co., Ltd.) is poured around it until the whole sample is embedded, and left in a vacuum desiccator The pressure was reduced for a second for degassing. Thereafter, the epoxy casting resin was cured by standing at room temperature (25 ° C.) for 8 hours or more.
  • a stainless steel metal mask (30 cm ⁇ 30 cm, line width 1.0 mm, line interval 0.2 mm, 5 lines) was placed on the substrate and fixed to the substrate with an adhesive tape so as not to shift. 20 g of the composition was taken out, uniformly applied to the top of the metal mask, and filled with the composition into the grooves of the metal mask using a polypropylene squeegee. Then, the metal mask was removed and it was set as printed matter. The above process was repeated five times without washing of the metal mask, and it was visually confirmed that the lines of each printed material were not connected and the corners of the lines were not crushed. Thereafter, the printed matter was heated at 200 ° C. in the atmosphere for 1 minute, and it was confirmed that the lines were not connected.
  • Continuous printing 8 hours or more in Table 1 means that the printing machine is filled with 200 g of the composition and the connection between the lines of the printed matter, even if the printing is carried out continuously for 8 hours by the above method, And means that there is no connection between the lines after heating.
  • “1 hour continuous printing” or “2 hours continuous printing” means that 200 g of the composition is filled in a printing machine and printing is continuously performed for 8 hours by the above method after 1 hour or 2 hours respectively Later, it means that at least one of the connection between the lines of the printed matter, the collapse of the corners of the lines, and the connection between the lines after heating has occurred.
  • composition In a 100 ml polyethylene bottle, 0.8 parts by mass of polyamideimide resin 1 (1.6 parts by mass as a resin solution), 0.3 parts by mass of 12-hydroxystearic acid (manufactured by Wako Pure Chemical Industries, Ltd.), dehydroabietic acid ( 1.9 parts by weight of Wako Pure Chemical Industries, Ltd., 0.3 parts by weight of triethanolamine (Wako Pure Chemical Industries, Ltd.), and hexyl carbitol (alias: diethylene glycol monohexyl ether, Wako Pure Chemical Industries, Ltd. 4.1 parts by mass was weighed, tightly capped, stirred by a rotor stirrer for 30 minutes, and mixed.
  • Tin alloy particles 2 (SAC 305, Sn-3.0Ag-0.5Cu, manufactured by Mitsui Mining & Smelting Co., Ltd., spherical, volume average particle diameter: 1.5 ⁇ m, D90 / D) instead of tin alloy particles 1 in the preparation of composition 1
  • the contents (volume basis) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles are shown in Table 1.
  • Tin alloy particles 3 (SAC 305, Sn-3.0Ag-0.5Cu, manufactured by Mitsui Mining & Smelting Co., Ltd., spherical, volume average particle diameter: 5.0 ⁇ m, D90 / Dia instead of tin alloy particles 1 in the preparation of composition 1
  • the contents (volume basis) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles are shown in Table 1.
  • Tin alloy particles 4 (SAC 305, Sn-3.0Ag-0.5Cu, manufactured by Mitsui Mining & Smelting Co., Ltd., spherical, volume average particle diameter: 10.0 ⁇ m, D90 /, instead of tin alloy particles 1 in the preparation of composition 1
  • the contents (volume basis) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles are shown in Table 1.
  • Tin alloy particles 5 (SAC305, Sn-3.0Ag-0.5Cu, manufactured by Mitsui Mining & Smelting Co., Ltd., spherical, volume average particle diameter: 25.0 ⁇ m, D90 / D, instead of tin alloy particles 1 in the preparation of composition 1
  • the contents (volume basis) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles are shown in Table 1.
  • the contents (volume basis) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles are shown in Table 1.
  • Example B1 and Comparative Example B1 Epoxy resin 1 (jER 828, manufactured by Mitsubishi Chemical Corporation, softening point: room temperature (25 ° C.) or less instead of using 0.8 parts by mass (1.6 parts by mass as a resin solution) of polyamideimide resin 1 in the preparation of composition 1
  • the composition 5 was prepared using 0.8 parts by mass of a thermal decomposition rate of 5% by mass.
  • the contents (volume basis) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles are shown in Table 2.
  • the composition C3 was manufactured using 0.8 parts by mass of a product having a softening point of room temperature (25 ° C. or less, a thermal decomposition rate of 5% by mass).
  • the contents (volume basis) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles are shown in Table 2.
  • Example A1 to A4 the occurrence of cracks in the thermal cycle test was suppressed as compared with Comparative Example A1.
  • the printability was good as compared with Comparative Example A2.
  • Example B1 the generation of cracks in the thermal cycle test was suppressed as compared to Comparative Example B1.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne une composition pour frittage en phase liquide qui contient : des premières particules de métal comprenant un premier métal, et présentant un point de fusion supérieur ou égal à 400°C ; des secondes particules de métal comprenant ledit premier métal et un second métal permettant un frittage en phase liquide transitoire, et présentant un point de fusion inférieur ou égal à 300°C, et un diamètre particulaire moyen en volume compris entre １,０μｍ et １０,０μｍ ; et une résine.
PCT/JP2018/000723 2018-01-12 2018-01-12 Composition pour frittage en phase liquide, agent adhésif, corps fritté, structure de liaison, et corps lié ainsi que procédé de fabrication de celui-ci WO2019138558A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013199648A (ja) * 2012-03-26 2013-10-03 E I Du Pont De Nemours & Co ポリマー厚膜はんだ合金／金属導電体組成物
WO2016039056A1 (fr) * 2014-09-09 2016-03-17 株式会社村田製作所 Composition métallique et matériau de liaison
EP3244461A1 (fr) * 2015-07-21 2017-11-15 LG Chem, Ltd. Module thermoélectrique et son procédé de fabrication

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013199648A (ja) * 2012-03-26 2013-10-03 E I Du Pont De Nemours & Co ポリマー厚膜はんだ合金／金属導電体組成物
WO2016039056A1 (fr) * 2014-09-09 2016-03-17 株式会社村田製作所 Composition métallique et matériau de liaison
EP3244461A1 (fr) * 2015-07-21 2017-11-15 LG Chem, Ltd. Module thermoélectrique et son procédé de fabrication

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