WO2019138556A1 - Liquid phase sintering composition, adhesive agent, sintered body, joint structure, joint body, and production method for joint body - Google Patents

Abstract

This liquid phase sintering composition comprises: first metal particles containing a first metal and having a melting point of 400°C or higher; second metal particles having a melting point of 300°C or lower and containing a second metal which can be transient-liquid-phase sintered together with the first metal; and a resin, wherein the contained amount of the second metal particles per 1 m2 of the surface area of the first metal particles is 3.7-11.0 g.

Description

Liquid phase sintering composition, adhesive, sintered body, bonded structure, bonded body, and method of manufacturing bonded body

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.

When manufacturing a semiconductor device, as a method of bonding a semiconductor element and a supporting member, a method of dispersing solder powder in thermosetting resin such as epoxy resin to make a paste and using it as a conductive adhesive is known. (See, for example, Patent Document 1).
In this method, 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

In recent years, with the progress of high speed and high integration of semiconductor devices, in order to operate the semiconductor device at high temperature, bonding property at low temperature and connection reliability at high temperature are required for the conductive adhesive.

In order to improve the reliability of the solder paste in which the solder powder is dispersed, a low elastic material typified by an acrylic resin has been studied (see, for example, Patent Document 2).

In addition, an adhesive composition is proposed 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). In the adhesive composition in which silver particles are sintered in Patent Document 3, it is described that the silver particles form a metal bond, and therefore, it is considered that the connection reliability at high temperature is excellent. .

On the other hand, 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). In the transitional liquid phase sintering type metal adhesive, a combination of metal particles (for example, copper and tin) which generates a liquid phase at a bonding interface is used as a metal component. By combining metal particles that generate a liquid phase at the bonding interface, 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.
In the transitional liquid phase sintering type metal adhesive described in Patent Document 4, it is described that an electrically mechanically stable connection is formed by joining copper and a copper-tin alloy.

JP 2005-93996 A WO 2009/104693 JP, 2015-224263, A Japanese Patent Application Publication No. 2013-510240

In the transitional liquid phase sintering type metal adhesive described in Patent Document 4, although it is supposed that an electrically mechanically stable connection is formed, heating is performed while suppressing generation of whiskers after sintering. It is difficult and difficult to obtain die shear strength after repeated cooling process.
Therefore, one aspect of the present invention is a composition for liquid phase sintering that provides a sintered body having high die shear strength after repeated heating and cooling treatment and that is less likely to cause whiskers, and the composition for liquid phase sintering It is an object of the present invention to provide an adhesive containing an object 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 specific means for achieving the said subject are as follows.
<1> A first metal particle containing a first metal and having a melting point of 400 ° C. or higher, and a second metal containing the first metal and capable of transient liquid phase sintering having a melting point of 300 ° C. Containing a second metal particle, which is
A composition for liquid phase sintering, wherein the content of the second metal particles per 1 m ² of surface area of the first metal particles is 3.7 g to 11.0 g.
<2> In <1>, the content of the second metal particle is 20% by volume to 30% by volume with respect to the total volume of the first metal particle, the second metal particle, and the resin. The composition for liquid phase sintering as described.
<3> The average BET specific surface area in the whole of the first metal particles is ^{0.02m 2 /g~0.1m 2 / g <1} > or liquid phase sintering composition according to <2>.
<4> The composition for liquid phase sintering according to any one of <1> to <3>, wherein the first metal contains Cu.
<5> The composition for liquid phase sintering according to any one of <1> to <4>, wherein the second metal contains Sn.
<6> An adhesive containing the composition for liquid phase sintering according to any one of <1> to <5>.
<7> A sintered body of the composition for liquid phase sintering according to any one of <1> to <5>.
The junction structure where the <8> 1st to-be-joined thing and the 2nd to-be-joined thing are joined through the sintered compact as described in <7>.
The joined body by which the <9> element and the supporting member are joined through the sintered compact as described in <7>.
<10> The composition for liquid phase sintering according to any one of <1> to <5> 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.

According to one aspect of the present invention, a composition for liquid phase sintering which provides a sintered body having high die shear strength after repeated heating and cooling treatment and in which whiskers are not easily generated, 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.

Hereinafter, modes for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps and the like) are not essential unless otherwise specified. The same applies to numerical values and ranges thereof, and does not limit the present invention.
In the present disclosure, 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. .
In the present disclosure, 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.
The upper limit value or the lower limit value described in one numerical value range may be replaced with the upper limit value or the lower limit value of the other stepwise description numerical value range in the numerical value range described stepwise in the present disclosure. . In addition, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the example.
In the present disclosure, each component may contain a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, the content of each component means the total content of the plurality of substances present in the composition unless otherwise specified.
In the present disclosure, particles corresponding to each component may contain a plurality of types. When there are a plurality of particles corresponding to each component in the composition, the particle diameter of each component means the value for the mixture of the plurality of particles present in the composition unless otherwise specified.
In the present disclosure, 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>
The composition for liquid phase sintering (hereinafter, also simply referred to as “composition”) of the present disclosure includes a first metal particle containing a first metal and having a melting point of 400 ° C. or more, and the first metal. and the second metal particles melting point and containing a second metal capable of transitional liquid phase sintering is 300 ° C. or less, wherein a resin, wherein the per surface area 1 m ² of the first metal particles first The content of the metal particles of 2 is 3.7 g to 11.0 g.
When the above composition is used, a sintered body having high die shear strength after repeated heating and cooling treatment and in which whiskers are not easily generated can be obtained. Although the reason is not clear, it is guessed as follows.

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. In the composition for liquid phase sintering, 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.
Here, as a form of the composition for liquid phase sintering, in addition to a form containing both the first metal and the second metal in one metal particle, the first metal and the separate metal particles are used. The form etc. which contain each of a 2nd metal are mentioned. Moreover, the form containing resin other than these metal particles is also mentioned as a form of the said composition for liquid phase sintering.

According to studies by the present inventors, a composition for liquid phase sintering containing a first metal particle containing a first metal and a second metal particle containing a second metal among these forms and a resin. In the material, it was found that the die shear strength of the sintered body and the easiness of generation of whiskers were changed depending on the content of the second metal particles relative to the total surface area of the first metal particles contained in the composition.

In the process of heating and sintering a composition containing the first metal particles, the second metal particles, and the resin, the second metal particles are first melted to form a liquid phase, and the periphery of the first metal particles is The surrounding, the first metal contained in the first metal particles react and diffuse into the surrounding liquid phase. Thereby, an alloy containing the first metal and the second metal is formed.
Here, in the region separated from the surface of the first metal particle in the liquid phase formed by melting the second metal particle, the first metal reacted and diffused at the time of sintering hardly reaches, It is believed that the metal of the metal remains unalloyed. In addition, if the second metal remains without being alloyed, it is conceivable that whiskers due to a low melting point (that is, a phenomenon in which a needle-like or nodule-like metal is naturally grown on the surface of a sintered body) may occur. .

In contrast, in the compositions of the present disclosure, the content of the second metal particles per surface area 1 m ² of the first metal particles (hereinafter, also referred to as "second metal particles per unit surface area") is It is 3.7 g to 11.0 g. Therefore, compared with the case where the amount of the second metal particles per unit surface area is larger than 11.0 g, it is inferred that the first metal does not reach and the second metal which is not alloyed is small and whiskers are hardly generated. Ru.
In addition, when the amount of the second metal particles per unit surface area is in the above range, a sufficient amount of the second metal particles melted at the time of sintering is the first metal, as compared to the case where the amount is smaller than 3.7 g. The surface of the particles is contacted and a sufficient amount of alloy is formed. Therefore, it is inferred that sintering defects are unlikely to occur, and the die shear strength after repeating the heating and cooling treatment is high.
As described above, it is presumed that in the composition of the present disclosure, a sintered body having high die shear strength after repeated heating and cooling treatment and in which whiskers are not easily generated can be obtained.

The “second metal particle amount per unit surface area” is preferably 3.7 g to 11.0 g, and is 3.8 g from the viewpoint of suppression of remelting in addition to high die shear strength and suppression of whiskers. It is more preferable that it is ̃10.8 g, more preferably 3.9 g to 10.4 g, particularly preferably 4.0 g to 10.0 g, and it is 4.5 g to 9.0 g Very preferred.
Here, “the amount of the second metal particles per unit surface area” is the ^second metal particles in a composition including the first metal particles in an amount such that the surface area of the first metal particles is 1 m ^{2 in} total. Is a value indicating how many g are included.
Also, the sum of the surface areas of the first metal particles is the sum of all the surface areas of the first metal particles contained in the composition. The total surface area of the first metal particles may be determined by multiplying the average BET specific surface area of the entire first metal particles by the mass of the first metal particles contained in the composition.

The “average BET specific surface area of the entire first metal particles” is a value of specific surface area obtained by measuring the entire first metal particles contained in the composition. That is, when the first metal particle contains a plurality of types of metal particles having different specific surface areas, the “average BET specific surface area” is a value obtained by averaging the specific surface areas of the plurality of types of metal particles.
Specifically, for example, a _first metal particle composed of ₁ gram of metal particles M of specific surface area S ₁ , ₂ grams of metal particles M of specific surface area S ₂ , and ₃ grams of metal particles M of specific surface area S ₃ The specific surface area S _{T of the} entire M ₁ + M ₂ + M ₃ ) gram is represented by the following formula.
Formula: S _T = (S ₁ × M ₁ + S ₂ × M ₂ + S ₃ × M ₃ ) / (M ₁ + M ₂ + M ₃ )
Moreover, the sum total of the surface area of a 1st metal particle is represented by a following formula.
Formula: Sum of the surface area of the first metal particle = S _T × (M ₁ + M ₂ + M ₃ )
The above formula is an example of the first metal particle composed of three kinds of metal particles different in specific surface area, but the first metal particle composed of two or less kinds of metal particles and the four kinds of metal particles The same applies to the first metal particle composed of the above metal particles.
The value of the average BET specific surface area of the entire first metal particles can be obtained by measuring the entire first metal particles by the BET method according to JIS-Z-8830: 2013.

Hereinafter, each component which comprises the composition of this indication is demonstrated in detail.

(Metal particles)
The composition of the present disclosure includes a first metal particle containing a first metal and having a melting point higher than 300 ° C., and a second metal having a transitional liquid phase sintering with the first metal. And second metal particles having a temperature of 300 ° C. or less.

Here, “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.
Further, the combination of metals capable of transient liquid phase sintering (that is, the combination of the first metal and the second metal) 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.

In the present disclosure, 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. Good. However, the ratio of the other metal particles to the whole metal particles (that is, the whole of the first metal particles, the second metal particles, and other metal particles optionally contained) 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.
Hereinafter, each of the first metal particle and the second metal particle will be described.

-1st metal particle-
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. When the first metal is Cu, 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.
As the 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 | grains which consist of metals other than a 1st metal, a carbon particle, etc. are mentioned.
When the first metal is Cu, it is preferable that at least the surface of the first metal particle is composed of copper or a copper alloy, and the entire first metal particle is copper or copper. It is preferable to be made of a copper alloy.

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.
When the melting point of the first metal particle is measured, for example, with respect to the first metal particle having a melting point of 1300 ° C. or less, 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.
In the case where the first metal particle contains the first metal in a partial region, 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 μm to 80 μm, and more preferably 1 μm to 50 μm, from the viewpoints of application stability and suppression of sintering unevenness. More preferably, it is 1 μm to 30 μm.
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.
The measurement of the particle size distribution is performed as follows. Specifically, 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. 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 in the following 2nd metal particle are also the same.

The average BET specific surface area in the entire first metal particles is preferably from the viewpoint of imparting stability and whisker suppression during continuous ^grant, a ^{0.01m 2 /g~0.15m 2 / g, 0.02m} 2 more preferably /g~0.1m is ² / ^g, more preferably from 0.04m ² /g~0.08m 2 / g.

The content of the first metal particles is 56% by volume to 85% by volume from the viewpoint of application stability at the time of continuous application with respect to the total volume of the first metal particles, the second metal particles, and the resin. It is preferably 70% by volume to 83% by volume, and more preferably 65% by volume to 80% by volume.

In addition, 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 | required by following Formula.
Content rate of first metal particle (volume%) = (Aw / Ad) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd)) × 100
Aw: mass composition ratio of the first metal particle (mass%)
Bw: mass composition ratio of second metal particles (mass%)
Cw: mass composition ratio of resin (mass%)
Ad: Specific gravity of first metal particle Bd: Specific gravity of second metal particle Cd: Specific gravity of resin

-Second metal particle-
The second metal particles contain the second metal and have a melting point of 300 ° C. or less.
The second metal particles may contain the second metal as a single metal, or may contain an alloy containing the second metal.
When the second metal is Sn, 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. In the case of Sn-AX-BY, for example, in the case of Sn-AX-BY, 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. It can measure on the conditions heated from 300C to 300C.
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 diameter of the second metal particles is not particularly limited, and is preferably 0.5 μm to 80 μm, and more preferably 1 μm to 50 μm from the viewpoint of application stability and high-temperature reliability in the sintered body. More preferably, the thickness is 1 μm to 30 μm.

The content of the second metal particles is 12% by volume from the viewpoint of the application stability at the time of continuous application and suppression of whiskers with respect to the total volume of the first metal particles, the second metal particles, and the resin. The content is preferably 40% by volume, more preferably 12% by volume to 30% by volume, and still more preferably 20% by volume to 30% by volume.
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. If the total content of the first metal particles and the second metal particles is 98 volume% or less with respect to the entire composition, the printability (i.e., the composition) when the composition of the present disclosure is used as a paste The tendency to lose the ability to
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) From the viewpoint of suppression of at least 1.0, it is preferably at least greater than 1.0, preferably 2.0 to 4.0, and more preferably 2.2 to 3.5.

The average BET specific surface area in the whole second metal particles ^is preferably 0.01m ² /g~0.45m 2 / ^g, more to be 0.02m ² /g~0.40m 2 / g ^preferably, it is more preferably 0.03m ² /g~0.35m 2 / g.
The average BET specific surface area of the entire second metal particles is determined in the same manner as the average BET specific surface area of the entire first metal particles described above.

(resin)
The resin contained in the composition of the present disclosure is not particularly limited, and may be a thermoplastic resin or a thermosetting resin.
Examples of the thermoplastic resin include polyamide resin, polyamide imide resin, polyimide resin, polyurethane resin, thermoplastic epoxy resin and the like.
Examples of the thermosetting resin include epoxy resin, oxazine resin, bismaleimide resin, phenol resin, unsaturated polyester resin, silicone resin and the like. Further, as 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.
Among these, as a resin contained in the composition, 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 μm 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 μm is taken as the softening point of the resin.
The softening point of the resin is preferably 5 ° C. or more lower than the melting point of the second metal particles, more preferably 10 ° C. or more lower, from the viewpoint of flowing without inhibiting alloy formation in the process of sintering. It is more preferable that the temperature be lower than ° 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.

In the present disclosure, the thermal decomposition rate of a resin refers to a value measured by the following method.
When 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.

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. Examples of functional groups that easily form hydrogen bonds with the surface of metal particles include amino groups and carboxy groups. Moreover, 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.
As a 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.
As such a 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.

From the viewpoint of relaxation of stress due to deformation of the thermoplastic resin, the thermoplastic resin preferably has a molecular structure exhibiting flexibility. As the molecular structure exhibiting flexibility, at least one of a polyalkylene oxide structure and a polysiloxane structure can be mentioned.

When the thermoplastic resin has a polyalkylene oxide structure, 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).

In the general formula (1), R ¹ represents an alkylene group, m represents an integer of 1 to 100, and “*” represents a bonding position to an adjacent atom. When the polyalkylene oxide structure is an assembly of a plurality of species, m represents a rational number that is an average value.

In the general formula (1), 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. As 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.

In the general formula (1), m is preferably 20 to 60, and more preferably 30 to 40.

It is preferable that the structure represented by General formula (1) contains the structure represented by following General formula (1A).

In the 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).

When the thermoplastic resin has a polyalkylene oxide structure, 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.
When the thermoplastic resin has a polyalkylene oxide structure represented by the general formula (1), 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.

When the thermoplastic resin has a polysiloxane structure, the polysiloxane structure is not particularly limited. The polysiloxane structure preferably contains, for example, a structure represented by the following general formula (2).

In formula (2), R ² and R ³ each independently represent a divalent organic group, and 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, and “*” represents a bonding position to an adjacent atom. When the polysiloxane structure is an assembly of a plurality of types, n indicates a rational number that is an average value.
In addition, 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. .
When R ² and R ³ are a divalent saturated hydrocarbon 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.

In the general formula (2), 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.
In the general formula (2), the aryl group having 6 to 18 carbon atoms represented by R ⁴ to R ⁷ may be unsubstituted or substituted by a substituent. When the aryl group has a substituent, examples of the substituent include a halogen atom, an alkoxy group, and a hydroxy group.
Examples of 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.

In the general formula (2), n is preferably 5 to 25 and more preferably 10 to 25.

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.

When 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 It is preferable that 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, It is particularly preferred that the total proportion of the structural unit represented by the general formula (3) in a proportion and the following formula of the structural unit represented (4) is 85 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.

In the general formula (3), 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.

In the general formula (1), R ¹ represents an alkylene group, m represents an integer of 1 to 100, and “*” 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).

In the general formula (3A), R ¹ represents an alkylene group, m represents an integer of 1 to 100, and “*” represents a bonding position to an adjacent atom. Specific examples of R ¹ , preferable ranges of m and the like are the same as in the case of the general formula (1).

In the general formula (3B), 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).

In the general formula (4), R ⁹ is a bivalent group containing the structure represented by the following general formula (2), "*" represents a bonding position between the adjacent atoms.

In formula (2), R ² and R ³ each independently represent a divalent organic group, and 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, and “*” 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).

In formula (4A), R ² and R ³ each independently represent a divalent organic group, and 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, and “*” 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.
In the isocyanate method, a polyamideimide resin is synthesized using a diimide carboxylic acid and an aromatic diisocyanate. In the 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.

Hereinafter, the synthesis method of the polyamideimide resin by the isocyanate method will be described in detail.
The diimidic carboxylic acids used in the isocyanate method are synthesized, for example, using trimellitic anhydride and diamines. As 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.

As a siloxane modified diamine, what has the following structural formula is mentioned, for example.

In general formula (5), R ² and R ³ each independently represent a divalent organic group, and 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. And 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-bis (4-aminocyclohexyloxy) benzene , 1, 4 -Bis (4-aminocyclohexyloxy) benzene, 2,2'-dimethylbicyclohexyl-4,4'-diamine, 2,2'-bis (trifluoromethyl) dicyclohexyl-4,4'-diamine, 2,6 2,2 ′, 6′-Tetramethyldicyclohexyl-4,4′-diamine, 5,5′-dimethyl-2,2′-sulfonyl-dicyclohexyl-4,4′-diamine, 3,3′-dihydroxydicyclohexyl-4 4,4'-diamine, 4,4'-diaminodicyclohexyl ether, 4,4'-diaminodicyclohexyl sulfone, 4,4'-diaminodicyclohexyl ketone, 4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether , 3,3'-Diaminodicyclohexyl ether, 2,2-bis (4-aminocyclohexyl) Propane and the like, can be used alone or in combinations of two or more.
Among these, 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] propane, bis [4- (3-aminocyclohexyloxy) cyclohexyl] sulfone, bis [4- (4-aminocyclohexyloxy) cyclohexyl Sulfone, 2,2-bis [4- (4-aminocyclohexyloxy) cyclohexyl] hexafluoropropane, bis [4- (4-aminocyclohexyloxy) cyclohexyl] methane, 4,4'-bis (4-aminocyclohexyl It is selected from the group consisting of oxy) dicyclohexyl, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ether, bis [4- (4-aminocyclohexyloxy) cyclohexyl] ketone, and 4,4'-diaminodicyclohexylmethane Small Kutomo one cycloaliphatic diamines are preferred.

As aliphatic diamine, 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.

As diamine, aromatic diamine can also be used together as needed. Specific examples of 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) hexafluoropropane, 3,3 ' -Dimethylbenzidine, 3,3'-dimethyl-4,4'-diaminodiphenyl ether, , 3'-dimethyl-4,4'-diaminodiphenylmethane, diaminobenzotrifluoride, 1,4-bis (p-aminophenoxy) benzene, 4,4'-bis (p-aminophenoxy) biphenyl, 2,2- Bis {4- (p-aminophenoxy) phenyl} propane, diaminoanthraquinone, 4,4'-bis (3-aminophenoxyphenyl) diphenyl sulfone, 1,3-bis (anilino) hexafluoropropane, 1,4-bis (Anilino) octafluorobutane, 1,5-bis (anilino) decafluoropentane, 1,7-bis (anilino) tetradecafluoroheptane, 2,2-bis {4- (p-aminophenoxy) phenyl} hexafluoro Propane, 2,2-bis {4- (3-aminophenoxy) phenyl} hexaful Ropropane, 2,2-bis {4- (2-aminophenoxy) phenyl} hexafluoropropane, 2,2-bis {4- (4-aminophenoxy) -3,5-dimethylphenyl} hexafluoropropane, 2, 2-Bis {4- (4-aminophenoxy) -3,5-ditrifluoromethylphenyl} hexafluoropropane, p-bis (4-amino-2-trifluoromethylphenoxy) benzene, 4,4'-bis ( 4-amino-2-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4,4'-bis (4-amino-2-trifluoromethylphenoxy) ) Diphenyl sulfone, 4,4'-bis (3-amino-5-trifluoromethylphenoxy) diphenyl sulfone, Examples thereof include 2,2-bis {4- (4-amino-3-trifluoromethylphenoxy) phenyl} hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane and the like. The aromatic diamine can be optionally used in the range of 0 mol% to 40 mol% with respect to the total amount of diamine.

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. Among these, 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, γ-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.

(solvent)
The composition of the present disclosure may contain a solvent from the viewpoint of improving the impartability (for example, the printability of the composition) when the composition of the present disclosure is used as a paste.
From the viewpoint of dissolving the resin, 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.

Examples of such solvents 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, γ-butyrolactone, sulfolane, 2- (2-butoxyethoxy) ethanol, diethylene Esters such as recalled monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monobutyl ether acetate, glycerin triacetate; ketones such as isophorone; lactams such as N-methyl-2-pyrrolidone; and nitriles such as phenylacetonitrile be able to. The solvents may be used alone or in combination of two or more.

When the composition of the present disclosure contains a solvent, 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.

(Other ingredients)
The 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.
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.

In the composition of the present disclosure, 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.
In addition, "solid content" means the remaining component except a volatile component (solvent etc.) from a composition.

(Method of producing 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, a nylon mesh etc. are mentioned.

<Adhesive>
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.

<Sintered body>
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 Ω · cm or less.

<Joint structure>
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.
Moreover, the structure of the junction part in the joined body mentioned later is mentioned as a joining structure of this indication.

<Joint and Method of Manufacturing the Same>
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.
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. Specific examples of 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.

In the method of producing a joined body according to the present disclosure, 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.
Examples of the method of applying the composition include a coating method and a printing method.
As 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. As 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. For heat drying or reduced pressure drying, 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.
After forming the composition layer, 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.

Next, 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.
For 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.
In addition, 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. or higher, although it depends on the type of metal particles. Although the upper limit in particular of the heating temperature concerned is not restricted, it is 300 ° C or less, for example.
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.
In the method of producing a joined body of the present disclosure, it is preferable to sinter the composition layer under an atmosphere of low oxygen concentration. Under a low oxygen concentration atmosphere, the oxygen concentration is 1000 ppm or less, preferably 500 ppm or less.

Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to the following examples.

The measurement of each characteristic in each example and comparative example was carried out as follows.

(1) Whisker The composition prepared by the method described later was applied on 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. Under the present circumstances, it heated at 250 degreeC or more for 1 minute or more, and was set as the sintered sample of the composition.
The sintered sample of the composition was treated in an 85 ° C. 85% constant temperature and humidity chamber for 96 hours and then observed with an electron microscope (SEM) JSM-59 to measure the length of the generated whisker. The “whisker length” when no whisker is generated is “0 μm”.

(2) Die shear strength after repeated heating and cooling treatment A sintered sample of the composition was prepared in the same manner as "(1) whisker". A sintered sample of the composition was set in a thermal shock tester (Lifetech Co., Ltd., model 6015), and cooling and heating cycles were repeated. The thermal cycle is, specifically, first cooling at a rate of room temperature (25 ° C.) to -10 ° C. per minute, maintaining for 30 minutes at -65 ° C., and then heating at a rate of + 10 ° C. per minute at 175 ° C. The operation was maintained for 30 minutes and then cooled to room temperature (25 ° C.) at a rate of −10 ° C./minute as one cycle. The die shear strength of the sample after 3000 cycles was measured as follows.
Using a universal bond tester (4000 series, manufactured by DAGE) equipped with a 1 kN load cell, the Si chip was pressed horizontally at a measurement speed of 500 μm / s and a measurement height of 100 μm, and the die shear strength of the sample after 3000 cycles was measured. . The average of nine measurement results was taken as die shear strength. If the die shear strength is less than 7.0 N / mm ² , it can be said that the adhesion is defective.

(3) Re-melting temperature A sintered sample of the composition was prepared in the same manner as "(1) whisker". The remelting temperature of the sintered sample of the composition is raised by 10 ° C./min under nitrogen flow of 50 ml / min using a platinum pan according to DSC (differential scanning calorimetry). It measured on the conditions heated from 25 degreeC to 400 degreeC by a temperature rate.
In addition, in Table 1, "ND" means that a remelting peak was not observed even if it heated to 400 degreeC.

[Examples 1 to 5 and Comparative Examples 1 to 2]
(Synthesis of thermoplastic resin)
Siloxane-modified diamine (trade name: X-22-161A, manufactured by Shin-Etsu Chemical Co., Ltd., general, while flowing nitrogen gas at about 250 ml / min through a 300 ml separable flask equipped with a thermocouple, a stirrer, and a nitrogen inlet. In the formula (5), 32.0 g of a diamine in which R ² and R ³ are ethylene groups (—CH ₂ CH ₂ —), R ⁴ to R ⁷ are all methyl groups, and n is about 20, 0.935 g of 4,4'-diaminodicyclohexylmethane (trade name: Wandamine HM (WHM), manufactured by Shin Nippon Rika Co., Ltd.), oxypropylene diamine (trade name: Jeffamine D-2000, manufactured by Mitsui Chemicals Fine Co., Ltd. _{-OCH 2 CH (CH 3) -} ) diamine number structural units m is about 33) 40.0 g, trimellitic anhydride 17.9 g, and N- main Added and stirred-2-pyrrolidone 100 g, was dissolved. To this solution is added 50 g of toluene, and the ring closure reaction of imide ring is carried out by dehydration reflux at a temperature of 150 ° C. or more for 6 hours. After distilling off the toluene, after cooling, 13.4 g of 4,4'-diphenylmethane diisocyanate (MDI) In addition, they were reacted at 150 ° C. for 2 hours to synthesize polyamideimide resin 1. The solid content was 50% by mass.
The softening point and the thermal decomposition rate of the obtained polyamideimide resin 1 were measured by the above-mentioned method and found to be 210 ° C. and 0.8% by mass, respectively.

(Preparation of 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. In this mixture, 67.4 parts by mass of copper particles 1 (made by Mitsui Metal Mining Co., Ltd., spherical, volume average particle diameter: 25 μm, average BET specific surface area: 0.04 m ² / g, melting point: 1083 ° C.), tin alloy particles 1 (SAC 305, Sn-3.0Ag-0.5Cu, manufactured by Mitsui Mining & Smelting Co., Ltd., spherical, volume average particle diameter: 3.0 μm, melting point: 220 ° C.) 27.0 parts by mass is weighed and mixed, and a spatula The mixture was stirred until no dry powder was found, and the assembly was sealed up and stirred at 2000 rpm for 1 minute using a rotation and rotation type stirring device (Planetary Vacuum Mixer ARV-310, manufactured by Shinky Co., Ltd.) to obtain Composition 1.
The amount of surface area 1 m ² per tin alloy particles of the copper particles are shown in Table 1.
Further, the content (volume based) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles is shown in Table 1 (“tin alloy particle content” in Table 1).
In addition, it was 0.04 m < ² > / g when the average BET specific surface area in the tin alloy particle 1 was measured by the above-mentioned method.

In place of copper particle 1, 67.4 parts by mass of copper particle 2 (manufactured by Mitsui Mining & Smelting Co., Ltd., spherical, volume average particle diameter: 20 μm, average BET specific surface area: 0.1 m ² / g) was used, A composition 2 was obtained in the same manner as the composition 1. The amount of surface area 1 m ² per tin alloy particles of the copper particles are shown in Table 1. Further, the content (volume based) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles is shown in Table 1 (“tin alloy particle content” in Table 1).
A composition 3 was obtained in the same manner as the composition 1, except that the addition amount of the copper particles 1 was changed to 70.8 parts by mass. The amount of surface area 1 m ² per tin alloy particles of the copper particles are shown in Table 1. Further, the content (volume based) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles is shown in Table 1 (“tin alloy particle content” in Table 1).
The same as composition 1 except using epoxy resin 1 (jER 828, manufactured by Mitsubishi Chemical Corporation, softening point: room temperature (25 ° C. or less, thermal decomposition rate: 5% by mass) instead of polyamideimide resin 1 Composition 4 was obtained. The amount of surface area 1 m ² per tin alloy particles of the copper particles are shown in Table 1. Further, the content (volume based) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles is shown in Table 1 (“tin alloy particle content” in Table 1).
A composition 5 was obtained in the same manner as the composition 1 except that the addition amount of 27.0 parts by mass of the tin alloy particles 1 was changed to 23.6% by mass. The amount of surface area 1 m ² per tin alloy particles of the copper particles are shown in Table 1. Further, the content (volume based) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles is shown in Table 1 (“tin alloy particle content” in Table 1).

A composition C1 was obtained in the same manner as the composition 1 except that the addition amount of 27.0 parts by mass of the tin alloy particles 1 was changed to 9.7 parts by mass. The amount of surface area 1 m ² per tin alloy particles of the copper particles are shown in Table 1. Further, the content (volume based) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles is shown in Table 1 (“tin alloy particle content” in Table 1).
A composition C2 was obtained in the same manner as the composition 1 except that the addition amount of the tin alloy particles 1 was changed to 31.5 parts by mass. The amount of surface area 1 m ² per tin alloy particles of the copper particles are shown in Table 1. Further, the content (volume based) of tin alloy particles relative to the total volume of the resin, copper particles, and tin alloy particles is shown in Table 1 (“tin alloy particle content” in Table 1).

In Examples 1 to 5, the die shear strength was higher than that in Comparative Example 1. In Examples 1 to 5, generation of whiskers was suppressed as compared with Comparative Example 2. That is, in Examples 1 to 5, coexistence of die shear strength and whisker suppression was realized as compared with Comparative Example 1 and Comparative Example 2.

All documents, patent applications, and technical standards described herein are as specifically and individually indicated that the individual documents, patent applications, and technical standards are incorporated by reference. Incorporated herein by reference.

Claims (10)

1. A first metal particle containing a first metal and having a melting point of 400 ° C. or more, and a second metal capable of performing a transient liquid phase sintering with the first metal and having a melting point of 300 ° C. or less Containing a second metal particle and a resin,
   A composition for liquid phase sintering, wherein the content of the second metal particles per 1 m ² of surface area of the first metal particles is 3.7 g to 11.0 g.
2. The liquid according to claim 1, wherein the content of the second metal particles is 20% by volume to 30% by volume with respect to the total volume of the first metal particles, the second metal particles, and the resin. Composition for phase sintering.
3. Claim 1 or the liquid phase sintering composition according to claim 2 first average BET specific surface area in the whole metal particles is 0.02m ² /g~0.1m ² / g.
4. The composition for liquid phase sintering according to any one of claims 1 to 3, wherein the first metal contains Cu.
5. The composition for liquid phase sintering according to any one of claims 1 to 4, wherein the second metal contains Sn.
6. An adhesive containing the composition for liquid phase sintering according to any one of claims 1 to 5.
7. A sintered body of the composition for liquid phase sintering according to any one of claims 1 to 5.
8. A bonded structure in which the first object and the second object are joined via the sintered body according to claim 7.
9. A joined body in which the element and the support member are joined via the sintered body according to claim 7.
10. The composition for liquid phase sintering according to any one of claims 1 to 5 is applied to at least one of a portion of the support member to which the element is bonded and a portion of the element to be bonded to the support member. Forming a composition layer;
    Bringing the support member into contact with the element through the composition layer;
    And heating the composition layer to sinter.