TW201805391A - Bonding composition and production method thereof, bonding laminate, and cladded silver nanoparticle - Google Patents

Abstract

A bonding composition is disclosed. The bonding composition is provided to obtain a bonding layer that has a low average porosity, high bonding strength and excellent thermal reliability whether in atmospheric baking or inert atmosphere baking, or whether bonding to a coated substrate or an uncoated substrate. The bonding composition is characterized by including silver nanoparticles, a dispersion medium and a first carboxylic acid that is attached to at least one portion of the surface of the silver nanoparticles and has a carbon chain that contains oxygen atoms.

Description

Composition for joining and method for producing same

The present invention relates to a joining composition for joining joined members such as metal parts and a manufacturing method thereof.

In order to mechanically, electrically, or thermally join members to be joined such as metal parts, solder, a conductive adhesive, a silver paste, or an anisotropic conductive film have been used. The joined members include not only metal parts, but also ceramic parts, resin parts, and the like, and different kinds of joined members may be joined in some cases. For example, there is a use in which a light emitting element such as a light emitting diode (LED) is bonded to a substrate, a use in which a semiconductor wafer is bonded to a substrate, or a use in which these substrates are bonded to a heat radiation member.

Among them, Pb-containing solder is also widely used as a joining material for joining members to be joined. However, from the standpoint of environmental protection or Restriction of Hazardous Substances (RoHS) regulation in recent years, Pb-free is required, and the melting point of solder is low, so it is difficult to apply it to silicon carbide or nitrogen with high operating temperature. Problems with power devices such as gallium.

Therefore, a sintered metal paste using metal nano particles as a new bonding material having high heat resistance has attracted attention as a bonding material, and a technique of performing low temperature sintering using silver nano particles as a bonding material is known (for example, (Patent Document 1: Japanese Patent Laid-Open No. 2011-071301, Patent Document 2: Japanese Patent Laid-Open No. 2015-232181, and Patent Document 3: Japanese Patent Laid-Open No. 2011-240406).

More specifically, Patent Document 1 proposes a method of "providing a bonding technology that allows spacers to remain in a bonding layer and improve bonding strength in a bonding technology using metal nano particles", and proposes a method including " The first member 11, the second member 12, and the bonding layer 13 which pressurizes and joins these members 11 and 12, and a bonded body of the plastically deformed spacer 14 remains in the bonding layer 13 ”.

In addition, Patent Document 2 proposes a method of "providing a metal paste for joining that can secure joint strength and reduce unevenness in joint strength even with a structure as simple as possible", and proposes a method that includes "average Metal submicron particles having a primary particle diameter (D50 diameter) of 0.5 μm to 3.0 μm, metal nano particles having an average primary particle diameter of 1 nm to 200 nm and coated with fatty acids having 6 to 8 carbon atoms, and dispersed Dispersion medium for metal bonding paste (bonding material) ".

In addition, in Patent Document 3, "providing a paste containing a flux component that can form a metal phase even in an inert environment" is a subject, and a "including an average primary particle diameter of 1 nm to 200 nm" is proposed. A bonding material of silver nano particles coated with an organic substance having a carbon number of 8 or less, a flux component having at least two carboxyl groups, and a dispersion medium. " [Prior Art Literature] [Patent Literature]

[Patent Literature 1] Japanese Patent Laid-Open No. 2011-071301 [Patent Literature 2] Japanese Patent Laid-Open No. 2015-232181 [Patent Literature 3] Japanese Patent Laid-Open No. 2011-240406

[Problems to be Solved by the Invention] However, in the technologies proposed in the above-mentioned Patent Documents 1 and 2, if a pressure is not applied during firing and bonding, a sufficient bonding state cannot be obtained. In the firing under pressure, there is a problem that the yield is lowered due to the destruction of the wafer or the production steps are complicated. In this respect, it is strongly demanded to develop a mounting technology using non-pressure bonding. In addition, the technique proposed in the aforementioned Patent Document 3 can join a small object to be joined 2 mm × 2 mm, and a large object to be joined that must be joined without pressure under nitrogen and exceeds 5 mm × 5 mm From the viewpoint of sufficient bonding strength, there is still room for improvement in the bonding of the bonded body or the bonded body in the atmosphere.

Therefore, the present invention has been made in view of the problems of the prior art, and an object of the present invention is to provide a bonding composition for obtaining a bonding layer and a method for manufacturing the bonding layer, the bonding layer being free from It needs to be pressurized and whether it is calcined in the atmosphere or in an inert environment, or bonded with or without plated substrates, it has low porosity, strong bonding strength, and excellent heat resistance and reliability. [Means for solving problems]

The present inventors have conducted diligent research in order to achieve the above-mentioned objective, and as a result, have found that, in order to obtain the firing and bonding, it is not necessary to pressurize, whether it is atmospheric firing or inert atmosphere firing, or bonding with or without plating on the substrate Substrate bonding, a bonding layer with low uniform porosity, strong bonding strength, and excellent heat resistance reliability, is extremely effective in specifying the type of carboxylic acid adhering to the surface of silver fine particles in terms of achieving the above-mentioned object, Furthermore, the type of the carboxylic acid contained in the dispersion medium was specified, and the present invention was completed.

That is, the present invention provides a bonding composition comprising: silver nano particles; a dispersion medium; and a first carboxylic acid attached to at least a part of a surface of the silver nano particles and containing O in a carbon chain. atom.

In the joining composition of the present invention having the structure described above, in order to maintain the dispersion stability of the silver nanoparticle and prevent aggregation, an organic substance is adhered and coated on at least a part of the surface of the silver nanoparticle. If the adhered (coated) organic matter remains during firing, it will prevent the silver nano-particles from being welded to each other. Therefore, it is necessary to perform evaporation or decomposition during firing. When the evaporation temperature or the decomposition temperature is near the calcination temperature, the sintering start temperature of the silver nanoparticle and the high-density speed of the sintered layer can be increased, and a denser bonding layer can be formed. Therefore, in the present invention, a carboxylic acid (first carboxylic acid) having a relatively large adsorption energy with respect to the surface of the silver nanoparticle is used as an organic substance adhering to the surface of the silver nanoparticle. This carboxylic acid not only contributes to the stabilization of the silver nanoparticle, but also exerts an effect as a flux, and therefore, it advantageously functions for scale-free Cu bonding. Furthermore, the present invention also relates to a kind of the silver nanoparticle (coated silver nanoparticle) itself, wherein the silver nanoparticle is characterized by including: a silver nanoparticle; and a first carboxylic acid attached to the The silver nanoparticle contains O atoms on at least a part of the surface and in the carbon chain.

In addition, the first carboxylic acid in the present invention contains an O atom having a high electronegativity in the carbon chain. The O atom of the carbon chain means an O atom other than the O atom contained in a carboxyl group (-COOH), and for example, an ether group (-O-), a methoxy group (-OCH ₃ ), and an ethoxy group ( O atoms contained in -OCH ₂ CH ₃ ) and acetamido (-COCH ₃ ). When the silver nano-particles contain O atoms, the wettability with the bonded member is increased, and a strong bond with the bonded member is formed. Specific examples of the first carboxylic acid include acetic acid, methoxyacetic acid, ethoxyacetic acid, and 3-ethoxypropionic acid.

In the bonding composition of the present invention, the carbon number of the carboxylic acid is preferably 5 or less.

The reason is that if the carbon number is increased, the dispersion stability of silver nanoparticle is improved, but if it is too large, the volume occupied by the coated organic matter in the silver nanoparticle is increased, and the bonding layer formed of the bonding composition is increased. It is disadvantageous in terms of high density.

Moreover, in the said bonding composition of this invention, it is preferable that the average primary particle diameter of the said silver nanoparticle is 10 nm-100 nm.

The particle diameter and shape of the silver nanoparticle are not particularly limited as long as the effects of the present invention are not impaired, and various conventionally known silver nanoparticle can be used. Specifically, silver nano particles having an average primary particle diameter of less than 1 μm can be used, and a preferable average particle diameter is 10 nm to 100 nm. When the average primary particle diameter of the silver nanoparticle is 10 nm or more, the silver nanoparticle has good low-temperature sinterability, and the production cost of the silver nanoparticle does not become high, which is practical. Moreover, if it is 100 nm or less, it is preferable that the dispersibility of silver nanoparticle does not change easily with time.

In the bonding composition of the present invention, it is preferable that a second carboxylic acid is contained in the dispersion medium. The second carboxylic acid is preferably a monocarboxylic acid, and more preferably ricinoleic acid or oleic acid.

When a carboxylic acid is contained in a dispersion medium, since this carboxylic acid functions as a flux, a scaleless Cu to-be-joined member can be joined. The larger the number of carboxyl groups, the higher the flux effect. However, even if it is a monocarboxylic acid such as ricinoleic acid or oleic acid in the bonding composition of the present invention, the effect can be sufficiently exhibited, and the scale-free Cu bonded member can be bonded well.

In addition, the bonding composition of the present invention may include silver fine particles having an average particle diameter of 1 μm to 15 μm.

The particle diameter and shape of the silver nanoparticle are not particularly limited as long as the effects of the present invention are not impaired, and various conventionally known silver nanoparticle can be used. Specifically, silver nano particles having an average primary particle diameter of less than 1 μm can be used, and a preferable average particle diameter is 10 nm to 100 nm. When the average primary particle diameter of the silver nanoparticle is 10 nm or more, the silver nanoparticle has good low-temperature sinterability, and the production cost of the silver nanoparticle does not become high, which is practical. Moreover, if it is 100 nm or less, it is preferable that the dispersibility of silver nanoparticle does not change easily with time.

Here, the particle diameter of the silver nanoparticle may not be fixed. As described above, the average primary particle diameter of the silver nanoparticle is preferably 100 nm or less. However, if the composition for bonding is a component that does not cause agglomeration and does not significantly impair the effect of the present invention, the above-mentioned may also be included. Silver nano particles with an average primary particle size in excess of 100 nm. In addition, silver fine particles having an average particle diameter of 1 μm to 15 μm may be added as necessary.

In addition, the present invention relates to a method for producing the bonding composition according to the present invention, the production method comprising: a first step of producing silver nano particles by a silver oxalate complex decomposition method; and In two steps, a first carboxylic acid containing an O atom in a portion other than a carboxyl group is added to the silver nanoparticle obtained in the first step and heated, so that the carboxylic acid is attached to the silver nanoparticle. Rice particles on at least a part of the surface.

According to the manufacturing method of the joining composition of this invention which has such a structure, the joining composition of this invention as mentioned above can be manufactured suitably. [Effect of the invention]

According to the present invention, it is possible to provide a composition for bonding that realizes a bonding layer and a method for manufacturing the bonding layer, which does not need to be pressurized during firing and bonding, whether it is atmospheric firing or inert environment firing, or a plated substrate Bonding or non-plated substrate bonding, low average porosity, strong bonding strength, and excellent heat resistance reliability.

Hereinafter, (1) a preferred embodiment of the bonding composition of the present invention, (2) a preferred embodiment of the manufacturing method of the bonding composition of the present invention, and (3) bonding using the present invention A detailed description will be given of a preferred embodiment of a joining method (a method for producing a bonded body) of a member to be joined of a composition. In addition, in the following description, repeated description may be omitted.

(1) Composition for bonding The composition for bonding according to this embodiment includes silver nano particles, a dispersion medium, and a first carboxylic acid attached to at least a part of the surface of the silver nano particles and The carbon chain contains O atoms. These components and the like are described below.

(1-1) Silver nano particles The particle diameter and shape of the silver nano particles are not particularly limited as long as the effects of the present invention are not impaired, and various conventionally known silver nano particles can be used. Specifically, silver nano particles having an average primary particle diameter of less than 1 μm can be used, and a preferable average particle diameter is 10 nm to 100 nm. When the average primary particle diameter of the silver nanoparticle is 10 nm or more, the silver nanoparticle has good low-temperature sinterability, and the production cost of the silver nanoparticle does not become high, which is practical. Moreover, if it is 100 nm or less, it is preferable that the dispersibility of silver nanoparticle does not change easily with time.

The reason is that if the average primary particle diameter of the silver nano-particles becomes too small, the influence of the increase in the volume occupied by the coating organic matter becomes large; if the average primary particle diameter of the silver nano-particles becomes too large, the welding temperature increases. And the density of the sintered layer is reduced.

Furthermore, in consideration of the problem of migration of the bonding layer formed using the bonding composition of the present invention, it is also possible to add a metal having an ionization series more inert than hydrogen within a range that does not impair the effect of the present invention. , Ie particles of gold, copper, platinum, palladium, etc.

Moreover, the particle diameter of the silver nanoparticle in the bonding composition of this embodiment may not be fixed. As described above, the average primary particle diameter of the silver nanoparticle is preferably 100 nm or less. However, if the composition for bonding is a component that does not cause agglomeration and does not significantly impair the effect of the present invention, the above-mentioned may also be included. Silver nano particles with an average primary particle size in excess of 100 nm.

In addition, if necessary, inorganic fine particles (inorganic coarse particles) such as silver fine particles having an average particle diameter of 1 to 15 μm may be added. In this case, the nanometer-sized silver nanoparticle has a lower melting point around the micron-sized inorganic fine particles, thereby obtaining a good conductive path.

Here, the particle diameters of silver nano particles and inorganic fine particles in the bonding composition of the present embodiment can be measured by a dynamic light scattering method, a small-angle X-ray scattering method, and a wide-angle X-ray diffraction method. In order to show a decrease in the melting point of nano-sized silver fine particles, it is appropriate to use a crystallite diameter determined by a wide-angle X-ray diffraction method. For example, in the wide-angle X-ray diffraction method, more specifically, RINT-Ultima III manufactured by Rigaku Electric Co., Ltd. can be used at a 2θ of 30 ° to 80 ° by the diffraction method. The measurement is performed within the range. In this case, the sample may be measured by being thinly stretched on a glass plate having a recess in the center portion having a depth of about 0.1 mm to about 1 mm, with the surface flattened. In addition, as long as JADE manufactured by Rigaku Electric Co., Ltd. is used, the half-value width of the obtained diffraction spectrum is substituted into the Scherrer's equation below, and the crystallite diameter calculated therefrom is used. (D) The particle diameter may be set. D = Kλ / Bcosθ Here, K: Xerox constant (0.9), λ: X-ray wavelength, B: half-value width around the ray, and θ: Bragg angle.

The particle diameter of the inorganic fine particles is not particularly limited as long as it is larger than the particle diameter of the silver nanoparticle, but the average particle diameter is preferably 1 μm to 50 μm. By setting the average particle size of the inorganic fine particles to 1 μm or more, it is possible to ensure good dispersibility of the inorganic fine particles, and to sufficiently increase the difference from the average particle size of the silver nanoparticle, and to achieve a so-called fine particle size. Densification caused by particle mixing. In addition, by setting the average particle diameter of the inorganic fine particles to 50 μm or less, it is possible to prevent the bonding layer from becoming too thick.

Examples of constituent elements of the inorganic fine particles in the bonding composition of the present embodiment include gold, silver, copper, nickel, bismuth, tin, iron, and platinum group elements (ruthenium, rhodium, palladium, osmium, iridium, and platinum). At least one of. The constituent element is preferably at least one selected from the group consisting of gold, silver, copper, nickel, bismuth, tin, or a platinum group element, and more preferably copper or an ionization tendency less than copper (inert) ) Metal, that is, at least one of gold, platinum, silver, and copper, preferably silver. These elements may be used alone, or two or more of them may be used in combination. As a method of using them in combination, there are a case where an alloy particle containing a plurality of metals is used, or a metal particle having a core-shell structure or a multilayer structure is used.

For example, when silver fine particles are used as the inorganic fine particles, the conductivity of the adhesive layer formed using the bonding composition of the present embodiment is good, but in consideration of migration, a bonding composition containing silver and other metals may be used. This makes it difficult for migration to occur. The "other metal" is preferably a metal whose ionization sequence is more inert than hydrogen, that is, gold, copper, platinum, and palladium.

The combination of the inorganic fine particles and the silver nano particles in the bonding composition of the present embodiment is not particularly limited as long as the effects of the present invention are not impaired, as long as the silver nano particles having low-temperature sinterability are combined. And inorganic fine particles. In addition, two or more kinds of silver nano particles and inorganic fine particles may be combined.

(1-2) First carboxylic acid (organic substance) In the bonding composition of this embodiment, at least a part of the surface of the silver nanoparticle is attached with an organic substance "a first carboxylic acid containing an O atom in the carbon chain" Acid ", and the first carboxylic acid partially or integrally covers the surface of the silver nanoparticle. This first carboxylic acid serves as a so-called dispersant in the bonding composition of the present embodiment to substantially constitute silver colloidal particles together with the silver nanoparticle. The carboxyl group in a molecule of the first carboxylic acid has a relatively high polarity, and interactions caused by hydrogen bonds are liable to occur, but portions other than these functional groups have relatively low polarity. Furthermore, the carboxyl group easily exhibits an acidic property.

In addition, the concept of a compound adhering to the surface of silver nanoparticle is that in addition to the first carboxylic acid, a trace amount of organic matter contained in silver nanoparticle as an impurity at the beginning is not included. A trace amount of organic matter mixed in and adhering to the silver nano particles, such as a residual reducing agent, a residual dispersant, etc. that are not completely removed during the washing process, and a trace amount of organic matter adhering to the silver nano particles. In addition, the "trace amount" specifically refers to less than 1% by mass in the silver colloidal particles.

The first carboxylic acid is an organic substance that can cover the silver nanoparticle to prevent the aggregation of the silver nanoparticle and form silver colloidal particles. The form of the coating is not particularly limited. In this embodiment, the dispersibility and conductivity are described. From the viewpoints of properties, etc., a coated organic substance (for example, an amine) other than the first carboxylic acid may be included within a range that does not impair the effect of the present invention. Furthermore, when these organic substances are chemically or physically combined with the silver nanoparticle, they may be changed into anions or cations. In this embodiment, the ions or errors derived from the coated organic substances are changed. Compounds and the like are also contained in the coated organic matter.

The amine may be linear or branched, and may have a side chain. Examples include: N- (3-methoxypropyl) propane-1,3-diamine, 1,2-ethanediamine, 2-methoxyethylamine, 3-methoxypropylamine , 3-ethoxypropylamine, 1,4-butanediamine, 1,5-pentanediamine, pentanolamine, amino isobutanol and other diamines or alkoxyamines, amino alcohols, In addition, alkylamines (such as propylamine, butylamine, pentylamine, and hexylamine (straight-chain alkylamines may have side chains)), cycloalkylamines (such as cyclopentylamine, and cyclohexylamine) , Primary amines such as aniline, allylamine, secondary amines such as dipropylamine, dibutylamine, piperidine, hexamethyleneimine, tripropylamine, dimethylpropanediamine, cyclohexyldiamine Tertiary amines such as methylamine, pyridine and quinoline.

The amine may be, for example, a compound containing a functional group other than an amine such as a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group, and a mercapto group. The amines may be used alone or in combination of two or more. In addition, the boiling point under normal pressure is preferably 300 ° C or lower, and more preferably 250 ° C or lower.

Here, the first carboxylic acid may include an O atom having a high anion property in a carbon chain. The O atom is an O atom other than the O atom contained in the carboxyl group (-COOH), and is, for example, an ether group (-O-), a methoxy group (-OCH ₃ ), or an ethoxy group (-OCH ₂ CH ₃ ), And O atoms contained in ethenyl (-COCH ₃ ) and the like. When the silver nanoparticle contains O atoms, the wettability with the bonded member is increased, and a strong bond with the bonded member is formed.

Furthermore, in the joining composition of this embodiment, it is preferable that the carbon number of the said carboxylic acid is 5 or less. The reason is that if the carbon number is increased, the dispersion stability of silver nanoparticle is improved, but if it is too large, the volume occupied by the coated organic matter in the silver nanoparticle is increased, and the bonding layer formed of the bonding composition is increased. It is disadvantageous in terms of high density.

Specific examples of the first carboxylic acid include monomethylmalonic acid, acetopropionic acid, methoxyacetic acid, ethoxyacetic acid, and 3-ethoxypropionic acid. Among them, acetic acid, methoxyacetic acid, ethoxyacetic acid, or 3-ethoxypropionic acid is preferred.

The content of the coated organic matter (first carboxylic acid) in the silver colloid in the bonding composition of the present embodiment is preferably 0.1% by mass to 50% by mass. When the organic substance content is 0.1% by mass or more, the storage stability of the obtained bonding composition tends to be good; when it is 50% by mass or less, the conductivity of the bonding composition tends to be good. The more preferable content of the organic substance is 0.3 to 30% by mass, and the more preferable content is 0.5 to 15% by mass.

(1-3) Dispersion medium The bonding composition according to this embodiment may include various dispersion media within a range that does not impair the effects of the present invention, and it is preferable to include a second carboxylic acid in the dispersion medium. When the second carboxylic acid is contained in the dispersion medium, since the second acid acid functions as a flux, the second acid acid is more suitable for joining the scale-free Cu bonded members. The greater the number of carboxyl groups, the higher the flux effect. However, even if it is a monocarboxylic acid such as ricinoleic acid or oleic acid in the bonding composition of the present embodiment, the effect can be fully exhibited, and the scale-free Cu bonded member can be bonded well.

The second carboxylic acid is a monocarboxylic acid different from the first carboxylic acid, as long as it satisfies the condition that it does not adhere to the surface of the silver nanoparticle and has a boiling point of 200 ° C or higher. Furthermore, the second carboxylic acid is preferably ricinoleic acid or oleic acid.

Examples of the dispersion medium include hydrocarbons, alcohols, ethers, and esters. Examples of the hydrocarbon include aliphatic hydrocarbons, cyclic hydrocarbons, and alicyclic hydrocarbons, and they may be used singly or in combination of two or more kinds.

Examples of the hydrocarbon include aliphatic hydrocarbons, cyclic hydrocarbons, alicyclic hydrocarbons, and unsaturated hydrocarbons, and they may be used alone or in combination of two or more kinds. Examples of the aliphatic hydrocarbon include tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, tridecane, and methylformate. Saturated or unsaturated aliphatic hydrocarbons such as pentane, normal paraffin, and isoparaffin. Examples of the cyclic hydrocarbon include toluene and xylene. Examples of the alicyclic hydrocarbon include limonene, dipentene, terpinene, nesol, cinene, orange flavor, terpinolene, and phlene , Menthol, rueene, isopropyltoluene, dihydroisopropyltoluene, berberene, kautschin, cajeputene, pinene, turpentine, mentane, fluorene Alkanes, terpenes, cyclohexane, etc.

Examples of the unsaturated hydrocarbon include ethylene, acetylene, benzene, 1-hexene, 1-octene, 4-vinylcyclohexene, terpene-based alcohol, allyl alcohol, oleyl alcohol, and 2-palm oil Acid, petroselinic acid, oleic acid, oleic acid, tianolic acid, ricinoleic acid, linolenic acid, translinolenic acid, hypolinolenic acid, arachidonic acid, acrylic acid, methacrylic acid, edible Acid and salicylic acid.

Among these, an unsaturated hydrocarbon having a hydroxyl group is preferred. The hydroxyl group is easily disposed on the surface of the silver nanoparticle, and aggregation of the silver nanoparticle can be suppressed. Examples of the unsaturated hydrocarbon having a hydroxyl group include terpene-based alcohols, allyl alcohols, oleyl alcohols, tianolic acid, ricinoleic acid, gallic acid, and salicylic acid. The unsaturated fatty acid having a hydroxyl group is preferred, and examples thereof include tiansolic acid, ricinoleic acid, gallic acid, and salicylic acid.

The unsaturated hydrocarbon is preferably ricinoleic acid. Ricinoleic acid has a carboxyl group and a hydroxyl group, and adsorbs on the surface of the inorganic particles to uniformly disperse the inorganic particles and promotes fusion of the inorganic particles.

The alcohol is a compound containing one or more OH groups in the molecular structure, and examples thereof include aliphatic alcohols, cyclic alcohols, and alicyclic alcohols, which may be used alone or in combination of two or more. In addition, as long as the effect of the present invention is not impaired, a part of the OH group may be derived into ethoxyl or the like.

Examples of the aliphatic alcohol include heptanol, octanol (1-octanol, 2-octanol, 3-octanol, etc.), nonanol, decanol (1-decanol, etc.), lauryl alcohol, and tetradecyl Alcohol, cetyl alcohol, isotridecyl alcohol, 2-ethyl-1-hexanol, stearyl alcohol, cetyl enol, oleyl alcohol, saturated C6-30 aliphatic alcohols or unsaturated C6-30 aliphatic alcohols Wait. Examples of the cyclic alcohol include cresol and eugenol.

Examples of the alicyclic alcohol include cycloalkanols such as cyclohexanol, terpineol (including α isomers, β isomers, γ isomers, and any mixtures thereof), and dihydroterpenes. Terpene alcohols such as pinol (monoterpene alcohols, etc.), dihydroterpineol, myrtenol, sobrerol, menthol, parsanol, perillyl alcohol, rosinol, verbena Enol, Terusolve (MTPH), etc.

The content when the dispersion medium is contained in the bonding composition of the present embodiment may be adjusted according to desired characteristics such as viscosity, and the content of the dispersion medium in the bonding composition is preferably 1% to 30% by mass. When the content of the dispersion medium is from 1% by mass to 30% by mass, the effect of adjusting the viscosity can be obtained within a range in which it is easily used as an adhesive composition. A more preferable content of the dispersion medium is 1 to 20% by mass, and a more preferable content is 1 to 15% by mass. Furthermore, when the content of the dispersion medium is too large, there is a possibility that many voids due to volatilization of the dispersion medium are generated in the bonding layer.

(1-4) Other components In addition to the above-mentioned components in the bonding composition of the present embodiment, in order to impart functions such as appropriate tack, adhesion, drying, or printability according to the purpose of use, To the extent that the effects of the present invention are not impaired, a polymeric dispersant, such as an oligomer component, a resin component, an organic solvent (which can dissolve or disperse a part of the solid component), and a surfactant that functions as a binder is added , Thickener or surface tension adjuster. It does not specifically limit as said arbitrary component.

As the polymer dispersant, a commercially available polymer dispersant can be used. As the commercially available polymer dispersant, for example, as the commercially available product, there may be mentioned: SOSPERSE 11200, SOSPERSE 13940, SOSPERSE 16000, SOSPERSE ) 17000, SOLASPERSE 18000, SOLASPERSE 20000, SOLASPERSE 24000, SOLASPERSE 26000, SOLASPERSE 27000, SOLASPERSE 28000 (Manufactured by Lubrizol, Japan); DISPERBYK-102, DISPERBYK 110, DISPERBYK 111, DISPERBYK (DISPERBYK) 170, DISPERBYK 190, DISPERBYK 194N, DISPERBYK 2015, DISPERBYK 2090, DISPERBYK (DISPERBYK) 2096 (manufactured by BYK Chemie · Japan); Efka-46, Efka-47, Efka-48, Ev Card (EFKA) -49 (manufactured by EFKA Chemical); poly Polymer (Polymer) 100, Polymer (Polymer) 120, Polymer (Polymer) 150, Polymer (Polymer) 400, Polymer (Polymer) 401, Polymer (Polymer) 402, Polymer (Polymer) 403, Polymerization Polymer 450, Polymer 451, Polymer 452, Polymer 453 (manufactured by EFKA Chemical); Ajisper PB711, Aji Ajisper PA111, Ajisper PB811, Ajisper PW911 (manufactured by Ajinomoto); Floren DOPA-15B, Floren ) DOPA-22, Florene DOPA-17, Florene TG-730W, Florene G-700, Florene TG-720W (Kyoeisha Chemical Industry (Manufacturing), BYK Chemie's DISPERBYK series is medium, Evonik's TEGO Dispers series can be listed as 610, 610S , 630, 651, 655, 750W, 755W, etc. (Disparlon) series can include DA-375, DA-1200, etc. From the viewpoint of low-temperature sinterability and dispersion stability, it is preferable to use DISPERBYK-102 and SOLASPERSE. 11200, Solsperse 13940, Solsperse 16000, Solsperse 17000, Solsperse 18000, Solsperse 28000.

The content of the polymer dispersant is preferably from 0.1% by mass to 15% by mass. When the content of the polymer dispersant is 0.1% or more, the dispersion stability of the obtained bonding composition becomes good, but when the content is too large, the dispersion stability decreases. From this viewpoint, the more preferable content of the polymer dispersant is 0.03% by mass to 3% by mass, and the more preferable content is 0.05% by mass to 2% by mass.

Examples of the resin component include polyurethane resins such as polyester resins and blocked isocyanates, polyacrylate resins, polypropylene resins, polyether resins, melamine resins, and terpene resins. These resins may be used alone, or two or more of them may be used in combination.

Here, when the member to be joined is, for example, polyethylene terephthalate (PET), as the resin component, polyvinyl alcohol or polyvinylpyrrole selected from the group having good adhesion to PET by itself can be used. A group consisting of pyridone, vinyl chloride-vinyl acetate copolymer, polyethylene acetal, and polyvinyl butyral. Examples of such ketone-formaldehyde polycondensates or their hydrides include Evonik Degussa Japan (TEGO) (registered trademark) and VariPlus series (SK, AP, etc.) ), As the vinyl chloride-vinyl acetate copolymer, there may be mentioned a SOLBIN (registered trademark) series (SOLBIN AL, etc.) manufactured by Nissin Chemical Industry and Oil Co., Ltd. as polyethylene acetal For polyvinyl butyral, S-REC (registered trademark) series (S-REC KS-1, S-REC BL-1, etc.) manufactured by Sekisui Chemical Industry Co., Ltd. can be cited. Among them, polyvinylpyrrolidone is also highly soluble in highly polar polyols (especially glycol solvents), and can be well dissolved in solvents such as esters and ketones, so it can be preferably used.

Examples of the thickener include clay minerals such as clay, bentonite, and lithium bentonite, such as polyester-based emulsion resins, acrylic-based emulsion resins, polyurethane-based emulsion resins, and block isocyanate-based emulsions. Cellulose derivatives such as cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, polysaccharides such as Sanxian or guar, etc. It can be used alone or in combination of two or more.

A surfactant different from the organic substance may be added. In the multi-component solvent-based inorganic colloidal dispersion liquid, the roughness of the film surface and the shift of the solid content due to the difference in the volatilization speed during drying are liable to occur. By adding a surfactant to the bonding composition of this embodiment, these disadvantages can be suppressed, and a bonding composition capable of forming a uniform conductive film can be obtained. The surfactant that can be used in this embodiment is not particularly limited, and any of anionic surfactants, cationic surfactants, and nonionic surfactants can be used. Examples thereof include alkylbenzenesulfonates, Quaternary ammonium salts, etc. Since the effect can be obtained in a small amount of addition, a fluorine-based surfactant is preferred.

Here, in the bonding composition according to this embodiment, silver colloidal particles obtained by colloidizing silver nanoparticle particles are included as a main component. As for the form of the silver colloidal particles, for example, a first carboxylic acid is attached. Silver colloidal particles formed on a part of the surface of silver nanoparticle; silver colloidal particles composed of the silver nanoparticle as a core and the surface of which is coated with a first carboxylic acid; The colloidal particles and the like are not particularly limited. Among these, silver colloidal particles having silver nanoparticle as a core and whose surface is coated with a first carboxylic acid are preferred. Those skilled in the art can use techniques well known in the art to suitably prepare silver colloidal particles having the morphology.

As described above, the bonding composition according to the present embodiment includes silver nano particles, a first carboxylic acid, and a dispersion medium, but may be other than the silver nano particles, the first carboxylic acid, and a dispersion medium (and other optional components). Contains organic components and residual reducing agents that do not constitute silver colloidal particles.

The viscosity of the bonding composition according to this embodiment may be appropriately adjusted within a range in which the concentration of the solid content does not impair the effect of the present invention. For example, if the viscosity ranges from 0.01 Pa · S to 5000 Pa · S, more It is preferably a viscosity range of 0.1 Pa · S to 1000 Pa · S, and particularly preferably a viscosity range of 1 Pa · S to 100 Pa · S. By setting this viscosity range, the method of apply | coating the composition for joining to a base material can apply a wide range of methods.

As a method of applying the bonding composition to the substrate, for example, self-dipping, screen printing, spray method, bar coating method, spin coating method, inkjet method, dispenser method, needle transfer method, and brush can be used. The coating method, the casting method, the flexographic method, the gravure method, the lithographic method, the transfer method, the hydrophilic-hydrophobic pattern method, or the syringe method are suitably selected for use. From the viewpoint of viscosity, particularly preferred are dispenser method, needle transfer method, or screen printing.

The viscosity can be adjusted by adjusting the particle size of silver nano particles, adjusting the content of organic matter, adjusting the amount of the dispersion medium and other components, adjusting the blending ratio of each component, adding a thickener, and the like. The viscosity of the bonding composition can be measured, for example, by a cone-plate viscometer (for example, a rheometer MCR301 manufactured by Anton Paar).

(2) Production of bonding composition Next, in order to manufacture the bonding composition of the present embodiment, silver nanoparticle (silver colloidal particle) coated with a first carboxylic acid as a main component was prepared.

The first carboxylic acid, the dispersion medium, the other components, and the weight reduction rate are not particularly limited, and it is convenient to adjust by heating. In addition, it can be performed by adjusting the amount of the first carboxylic acid or the like added during the production of the silver nanoparticle, and it is also possible to change the washing conditions or the number of times after the silver nanoparticle is prepared.

Heating can be performed using an oven, an evaporator, or the like. The heating temperature may be in the range of about 50 ° C to 300 ° C, and the heating time may be in the range of several minutes to several hours. Heating can also be performed under reduced pressure. By heating under reduced pressure, the amount of the first carboxylic acid can be adjusted at a lower temperature. When carried out under normal pressure, it can be carried out in the atmosphere or in an inert environment. Furthermore, in order to finely adjust the amount of organic matter, a first carboxylic acid, amine, or the like may be added later.

The method for producing the silver nanoparticle coated with the first carboxylic acid according to this embodiment is not particularly limited, and examples thereof include a method of preparing a dispersion liquid containing silver nanoparticle and then washing the dispersion. As a step of preparing a dispersion liquid containing silver nanoparticle, for example, the metal salt (or metal ion) dissolved in a solvent may be reduced as described below. As the reduction procedure, a procedure based on a chemical reduction method may be used.

That is, as described above, the silver nanoparticle coated with the first carboxylic acid can include a salt containing silver constituting the silver nanoparticle, a first carboxylic acid as a dispersant, and a dispersion medium (essentially, toluene and the like). Organic, but may contain water) is prepared by reducing a raw material liquid (a part of the components may be dispersed without dissolving). By this reduction, silver colloidal particles in which the first carboxylic acid as a dispersant adheres to at least a part of the surface of the silver nanoparticle can be obtained. By adding this silver colloidal particle to a dispersion medium in the process mentioned later, the composition for joining of this invention can be obtained.

As a starting material for obtaining silver nanoparticle particles coated with the first carboxylic acid, various known metal salts or hydrates thereof can be used, and examples thereof include silver nitrate, silver sulfate, silver chloride, silver oxide, and silver acetate. , Silver salts such as silver oxalate, silver formate, silver nitrite, silver chlorate, silver sulfide; for example, gold salts such as chloroauric acid, potassium gold chloride, and sodium sodium chloride; for example, chloroplatinic acid, platinum chloride, and platinum oxide , Such as palladium nitrate, palladium acetate, palladium chloride, palladium oxide, palladium sulfate, etc., but as long as it is soluble in a suitable dispersion medium and can be reduced, there is no Specially limited. These may be used alone or in combination.

In addition, the method of reducing these metal salts in the raw material liquid is not particularly limited, and examples thereof include a method using a reducing agent, a method of irradiating light such as ultraviolet rays, an electron beam, an ultrasonic wave, or thermal energy. Among them, a method using a reducing agent is preferred from the viewpoint of ease of handling.

Examples of the reducing agent include amine compounds such as dimethylaminoethanol, methyldiethanolamine, triethanolamine, phenidone, and hydrazine; for example, sodium borohydride, hydrogen iodide, and hydrogen Isohydrogen compounds; for example, oxides of carbon monoxide and sulfurous acid; for example, ferrous sulfate, iron oxide, iron fumarate, iron lactate, iron oxalate, iron sulfide, tin acetate, tin chloride, tin diphosphate, tin oxalate , Tin oxide, tin sulfate and other low atomic valent metal salts; for example, ethylene glycol, glycerol, formaldehyde, hydroquinone, pyrrogallol, tannin, tannic acid, salicylic acid, D-glucose and other sugars, etc. It is not particularly limited as long as it can be dissolved in a dispersion medium to reduce the metal salt. When the reducing agent is used, light and / or heat may be applied to promote the reduction reaction.

As a specific method for preparing the silver nanoparticle coated with the first carboxylic acid using the metal salt, an organic component, a solvent, and a reducing agent, for example, the following method can be mentioned: the metal salt is dissolved in an organic solvent (for example, Toluene, etc.) to prepare a metal salt solution, add an organic substance as a dispersant to the metal salt solution, and then slowly drop the solution in which the reducing agent is dissolved therein.

In the dispersion liquid containing the silver nanometer particles coated with the first carboxylic acid as a dispersant obtained in the manner described above, in addition to the silver nanometer particles, there is also a counter ion of the metal salt, a residue of the reducing agent, or a dispersion. The electrolyte concentration of the solution tends to be high. Since the solution in this state has high electrical conductivity, it is easy to cause coagulation and precipitation of silver nanoparticle. Alternatively, even if it does not precipitate, if the counter ion of the metal salt, the residue of the reducing agent, or an excessive dispersant remaining in an amount required for dispersion remains, the conductivity may be deteriorated. Therefore, the silver nano particles coated with the first carboxylic acid can be reliably obtained by removing excess residues by washing the solution containing the silver nano particles.

Examples of the cleaning method include a method in which the following steps are repeated several times: a dispersion liquid containing silver nanoparticle particles coated with a first carboxylic acid is allowed to stand for a certain period of time, and the resulting supernatant is removed, Alcohol (methanol, etc.) is added, and the mixture is stirred again to remove the supernatant produced by standing still for a certain period of time; a method of centrifugation instead of standing still; a method of desalination using an ultrafiltration device or an ion exchange device, etc. Wait. By removing the organic solvent by such cleaning, the silver nanoparticle coated with the first carboxylic acid in this embodiment can be obtained.

The bonding composition of the present embodiment can be obtained by mixing the silver nanoparticle particles coated with the first carboxylic acid obtained above with the dispersion medium described in the present embodiment. The method for mixing the silver nanoparticle coated with the first carboxylic acid and the dispersion medium is not particularly limited, and it can be performed by a conventionally known method using a stirrer, a stirrer, or the like. Use a spatula-like stirrer, or an ultrasonic homogenizer with appropriate output power.

When a metal colloidal dispersion liquid containing a plurality of metals is obtained, the method for producing the metal colloidal dispersion liquid is not particularly limited. For example, when a metal colloidal dispersion liquid containing silver and other metals is produced, the silver nanoparticle coated with the first carboxylic acid is used. In the preparation of the particles, a dispersion liquid containing silver nano particles and a dispersion liquid containing other metal nano particles can be separately produced and then mixed, or a silver ion solution can be mixed with other metal ion solutions and then reduced. .

(3) Joining method By using the joining composition of this embodiment, high joining strength can be obtained in joining members with heating. That is, the first to-be-joined member and the second to-be-joined member can be joined by a step of applying the composition for joining step and applying the composition for joining to the first to-be-joined member and Between the second members to be joined; in a joining step, firing and joining the joining composition applied between the first member to be joined and the second member to be joined at a desired temperature (for example, 300 ° C. or lower) . In this case, pressurization is also possible, but it is also one of the advantages of the present invention that sufficient bonding strength can be obtained without particularly pressing. In addition, during the calcination, the temperature may be increased or decreased in stages. In addition, a surface active agent, a surfactant, or the like may be coated on the surface of the member to be joined in advance.

The present inventors have made intensive studies, and as a result, have found that if the bonding composition of the present embodiment is used as the bonding composition in the bonding composition coating step, the bonding strength can be more reliably increased. The first to-be-joined member is joined to the second to-be-joined member (to obtain a bonded body).

Here, the concept of "coating" of the bonding composition of the present embodiment also includes a case where the bonding composition is applied in a planar shape, and also includes a case where it is applied (drawn) in a line shape. The shape of the coating film including the applied composition for bonding and the state before firing by heating can be set to a desired shape. Therefore, in the bonded body of the present embodiment after firing by heating, the concept of a bonding composition includes any of a planar bonding layer and a linear bonding layer, and these planar bonding layers and linear The bonding layer may be continuous or discontinuous, and may include a continuous portion and a discontinuous portion.

The first member to be joined and the second member to be joined that can be used in the present embodiment are not particularly limited as long as they can be coated with a composition for joining and then sintered by heating, but they are preferably A heat-resistant member that is not damaged by the temperature at the time of joining.

Examples of the material constituting such a bonded member include polyamide (PA), polyimide (PI), polyimide (PAI), and polyterephthalic acid. Polyethylene terephthalate (PET), Polybutylene terephthalate (PBT), Polyethylene naphthalate (PEN) and other polyesters, Polycarbonate (PC) Polyethersulfone (PES), vinyl resins, fluororesins, liquid crystal polymers, ceramics, glass, or metals. Among them, metal bonded members are preferred. The reason why a metal-joined member is preferred is that it is excellent in heat resistance and has excellent affinity with the bonding composition of the present invention where the silver nanoparticle is a metal.

In addition, the member to be joined may have various shapes such as a plate shape or a strip shape, and may be rigid or flexible. The thickness of the substrate can also be appropriately selected. In order to improve adhesion or adhesion, or for other purposes, a member having a surface layer formed thereon or a member subjected to a surface treatment such as a hydrophilic treatment may be used.

In the step of applying the bonding composition to the member to be joined, various methods can be used, as described above, for example, self-dipping, screen printing, spraying, bar coating, spin coating, inkjet, and A syringe type, a needle transfer method, a coating method using a brush, a cast type, a flexographic type, a gravure type, or a syringe type are suitably selected for use.

The bonded body of the present embodiment can be obtained by heating the coating film after the coating is performed to a temperature of, for example, 300 ° C. or lower within a range that does not damage the members to be bonded. In this embodiment, as described above, by using the bonding composition of this embodiment, a bonding layer having excellent adhesiveness with respect to a member to be bonded can be obtained, and strong bonding strength can be obtained more reliably. .

In the present embodiment, when the bonding composition contains an adhesive component, the adhesive component is also sintered from the viewpoints of improving the strength of the bonding layer and the bonding strength between the members to be joined, but in some cases, It can be used in various printing methods, and the main purpose of adjusting the viscosity of the bonding composition can be used as the binder component, and the firing conditions can be controlled to remove all the binder components.

The method for performing the firing is not particularly limited. For example, a conventionally known oven or the like can be used to perform firing such that the temperature of the joining composition applied or drawn on the joined member becomes 300 ° C. or lower. This joins. The lower limit of the firing temperature is not necessarily limited, but is preferably a temperature at which members to be joined can be joined to each other, and a temperature in a range that does not impair the effect of the present invention. Here, in the above-mentioned calcined bonding composition, in order to obtain as high a bonding strength as possible, it is preferable that the remaining amount of the organic substance is small, but it is also within a range that does not impair the effect of the present invention. Part of the remaining organic matter.

Furthermore, the first carboxylic acid, which is an organic substance, is included in the bonding composition of the present invention. However, unlike the conventional heat-curing resins such as epoxy resin, the bonding strength after firing is not obtained by the action of organic substances. Instead, sufficient bonding strength is obtained by fusing silver nano-particles that have been welded as described above. Therefore, even after being placed in a use environment having a temperature higher than the joining temperature after the joining, and the remaining organic matter is degraded or decomposed / disappeared, there is no risk that the joining strength is reduced, and therefore the heat resistance is excellent.

According to the bonding composition of the present embodiment, even if it is calcined by low-temperature heating at, for example, about 300 ° C., it is possible to achieve bonding with a bonding layer that exhibits high conductivity. Therefore, the relatively heat-resistant bonded members can be bonded to each other. The firing time is not particularly limited as long as it is a firing time that can be joined in accordance with the firing temperature.

In this embodiment, in order to further improve the adhesion between the member to be joined and the bonding layer, the surface treatment of the member to be joined may be performed. Examples of the surface treatment method include dry treatment methods such as corona treatment, plasma treatment, ultraviolet (UV) treatment, and electron beam treatment. An undercoat layer or a conductive paste is provided on the substrate in advance. The method of the absorbing layer.

As mentioned above, although the typical embodiment of this invention was described, this invention is not limited to these. Hereinafter, the bonding composition of the present invention will be further described in Examples, but the present invention is not limited to these Examples. [Example]

«Example 1» A total of 40 mmol of 3-ethoxypropylamine and 10 mmol of dodecylamine were mixed in 50 mmol, and the mixture was thoroughly stirred with a magnetic stirrer. While stirring, 10 mmol of silver oxalate prepared separately was added thereto to make it thicker. The obtained sticky substance was put into a thermostatic bath at 120 ° C. and reacted for about 15 minutes to obtain a reactant. Then, 100 mmol of methoxyacetic acid was added to the reaction product, and the mixture was again placed in a constant temperature bath at 100 ° C. and stirred for 15 minutes. After 10 ml of methanol was added and stirred, the metallic silver nano particles were precipitated and separated by centrifugation, and the supernatant was removed. This operation was repeated again to obtain metallic silver nano particles. The average primary particle diameter is calculated using a particle image taken with a scanning electron microscope (SEM) (S-4800 model manufactured by Hitachi, Ltd.). Based on the SEM images of 5 or more different shooting points, for a total of 200 or more particles, an image processing software (MITANI CORPORATION, Win ROOF) was used to measure the primary particle size, and the average was calculated by arithmetic mean The primary particle size was 40 nm. In addition, 1 g of microsilver particles (D50 = 2.5 μm, manufactured by Fukuda Metal Foil Industry Co., Ltd.) and 0.3 g of isocyanide as a dispersion medium were added to 2 g of the obtained metallic silver nano particles in a predetermined amount. Tridecyl alcohol and 0.002 g of ricinoleic acid were stirred and mixed to obtain a composition for bonding. Then, the following evaluation tests were performed, and the results are shown in Table 1.

[Evaluation test 1] Measurement of bonding strength This metal-masked composition was applied to a silver plating layer (20 mm square and 1 mm thick) in a size of 1 mm square, and gold plating was laminated thereon. Si wafer (1 mm square). The obtained laminated body was put into a reflow furnace (manufactured by Shinapex), and was calcined in a atmospheric environment at a total temperature of 60 minutes from heating up to taking out, with a maximum temperature of 280 ° C. When the calcination treatment is performed, no pressure is applied without performing pressure. After taking out the laminated body, the joint strength (shear strength) test was performed at room temperature using a joint tester (manufactured by RHESCA).

«Example 2» A composition for bonding was prepared and evaluated in the same manner as in Example 1 except that ricinoleic acid was removed from the dispersion medium. The results are shown in Table 1.

«Example 3» A composition for bonding was prepared and evaluated in the same manner as in Example 1, except that ethoxyacetic acid was added instead of methoxyacetic acid. The results are shown in Table 1. In addition, the following evaluation tests were also performed.

«Example 4» A composition for bonding was prepared and evaluated in the same manner as in Example 1, except that 3-ethoxypropionic acid was added instead of methoxyacetic acid. The results are shown in Table 1.

«Example 5» A composition for bonding was prepared and evaluated in the same manner as in Example 1 except that acetic acid and propionic acid were added instead of methoxyacetic acid. The results are shown in Table 1.

«Example 6» A composition for bonding was prepared and evaluated in the same manner as in Example 1, except that acetic acid was added instead of methoxyacetic acid, and ricinoleic acid was removed from the dispersion medium. The results are shown in Table 1.

Comparative Example 1 A composition for bonding was prepared and evaluated in the same manner as in Example 1, except that 3-ethoxypropylamine was added instead of methoxyacetic acid. The results are shown in Table 1.

Comparative Example 2 A composition for bonding was prepared and evaluated in the same manner as in Example 1, except that 3-ethoxypropylamine was added instead of methoxyacetic acid, and ricinoleic acid was removed from the dispersion medium. . The results are shown in Table 1.

Comparative Example 3 A composition for bonding was prepared in the same manner as in Example 1 except that 3-ethoxypropylamine and a hexylamine mixture (molar ratio = 1: 1) were added instead of methoxyacetic acid. And evaluate. The results are shown in Table 1.

Comparative Example 4 A mixture of 3-ethoxypropylamine and hexylamine (molar ratio = 1: 1) was added instead of methoxyacetic acid, and ricinoleic acid was removed from the dispersion medium. 1 In the same manner, a composition for bonding was prepared and evaluated. The results are shown in Table 1.

Comparative Example 5 A composition for bonding was prepared in the same manner as in Example 1 except that 2- (2-aminoethoxy) ethanol was added instead of methoxyacetic acid, and ricinoleic acid was removed from the dispersion medium. And evaluate. The results are shown in Table 1.

Comparative Example 6 A composition for bonding was prepared in the same manner as in Example 1 except that 2- (2-aminoethylamino) ethanol was added instead of methoxyacetic acid, and ricinoleic acid was removed from the dispersion medium. And evaluated. The results are shown in Table 1.

[Table 1]

«Example 7» A composition for bonding was obtained in the same manner as in Example 1 except that the amount of ricinoleic acid added in the dispersion medium was 0.025 g, and evaluated. The results are shown in Table 2. Here, a 5 mm × 5 mm Si wafer was used here, and the following evaluation test 2 and evaluation test 3 were also performed.

[Evaluation test 2] Porosity measurement For the laminated body subjected to the calcination treatment, an ultrasonic detection device (probe 80 MHz × f3 mm × PF = 10 mm) manufactured by KRAUTKRAMER (stock) was used. ) To evaluate the pores. Fine adjustment was performed to maximize the reflection peak at the bonding interface, and the material sound velocity was set to Si: 9600 mm / s for measurement. The porosity was set to a threshold value of 55% of the reflection intensity, and the porosity was regarded as a porosity.

[Evaluation Test 3] High-temperature reliability The calcined laminated body in [Evaluation Test 1] was placed in a cold and thermal shock tester (made by Futec), and it will be placed in the air at- Each cycle was held at 40 ° C and 200 ° C for 10 minutes as one cycle, and was taken out at any number of cycles. After 20 cycles, the case where the porosity did not increase by 5% or more relative to the zero cycle was designated as "○", and the case where the porosity was increased by 0.5% or more was designated as "×".

«Example 8» Except that acetic acid was used instead of methoxyacetic acid, the amount of ricinoleic acid added in the dispersion medium was set to 0.025 g, and a non-plated oxygen-free copper substrate (in a 10 wt% sulfuric acid aqueous solution) was used. Ultrasonic treatment was performed for 1 min), and a composition for bonding was prepared and evaluated in the same manner as in Example 1 except that the calcination treatment was performed in a nitrogen atmosphere. The results are shown in Table 2.

«Example 9» Except that acetic acid was used instead of methoxyacetic acid, castor oil in the dispersion medium was set to 0.025 g of oleic acid, and a non-plated and oxygen-free copper substrate was used for calcination in a nitrogen atmosphere. Other than that, a composition for bonding was prepared in the same manner as in Example 1 and evaluated. The results are shown in Table 2.

Comparative Example 7 A method was prepared in the same manner as in Example 1 except that 3-ethoxypropylamine was used in place of methoxyacetic acid, and a non-plated and oxygen-free copper substrate was used for calcination in a nitrogen atmosphere. The composition for bonding was evaluated. The results are shown in Table 2.

[Table 2]

It is understood from Table 1 that the bonding composition of the present invention can obtain a bonding layer with sufficient bonding strength that does not require pressure during firing bonding and has a shear strength of 40 MPa or more. In addition, according to Table 2, it is known that if the bonding composition of the present invention is used, it is possible to obtain bonding without plating, whether it is atmospheric firing or inert atmosphere firing, or bonding with or without plating when firing and bonding. Bonded substrates are bonding layers with low average porosity, strong bonding strength, and excellent heat resistance and reliability.

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Claims (11)

A bonding composition comprising: silver nano particles; a dispersion medium; and a first carboxylic acid attached to at least a portion of a surface of the silver nano particles and including O atoms in a carbon chain. The bonding composition according to item 1 of the scope of patent application, wherein the carbon number of the carboxylic acid is 5 or less. The bonding composition according to item 1 or item 2 of the scope of patent application, wherein the silver nanoparticle has an average primary particle diameter of 10 nm to 100 nm. The bonding composition according to any one of claims 1 to 3, wherein the second carboxylic acid is contained in the dispersion medium. The bonding composition according to item 4 of the scope of patent application, wherein the second carboxylic acid is a monocarboxylic acid. The bonding composition according to item 5 of the application, wherein the second carboxylic acid is ricinoleic acid or oleic acid. The bonding composition according to any one of claims 1 to 6, wherein the first carboxylic acid is acetampropionic acid, methoxyacetic acid, ethoxyacetic acid, or 3-ethoxy Propionic acid. The bonding composition according to any one of claims 1 to 7 of the patent application scope, further comprising inorganic fine particles having an average particle diameter of 1 to 15 μm. A joined body comprising: a first joined member; a second joined member; and a joining layer joining the first joined member and the second joined member and including the first The bonding composition according to any one of clauses 8 to 8. A method for manufacturing a bonding composition, comprising: a first step of manufacturing silver nano particles by a silver oxalate complex decomposition method; and a second step of using the obtained in the first step A first carboxylic acid containing an O atom in a portion other than a carboxyl group is added to the silver nanoparticle and heated to attach the carboxylic acid to at least a part of the surface of the silver nanoparticle. A coated silver nanoparticle, comprising: silver nanoparticle; and a first carboxylic acid attached to at least a portion of a surface of the silver nanoparticle and containing O atoms in a carbon chain.