TW202302802A - Silver containing paste - Google Patents

Abstract

This silver-containing paste contains: silver-containing particles; a cyanamide derivative; a solvent; and a polyfunctional compound comprising one or both of (A) an epoxy compound having two or more intramolecular epoxy groups and (B) a (meth)acrylic compound containing two or more intramolecular polymerizable double bonds.

Description

silver paste

The present invention relates to a silver-containing paste.

There is known a technique of manufacturing a semiconductor device using a thermosetting resin composition containing metal particles in order to improve the heat dissipation of the semiconductor device. By making the thermosetting resin composition contain metal particles having a higher thermal conductivity than the resin, the thermal conductivity of the cured product can be improved.

Patent Document 1 discloses a paste-like silver-containing particle composition composed of surface-coated specific sinterable silver-containing particles, a volatile dispersion medium, and two specific resin powders. This document describes that the paste-like silver particle-containing composition is sintered at a temperature of 100° C. or higher and 250° C. or lower under a specific environment. It is also described that this paste-like silver particle-containing composition has good storage stability and can obtain a bonded body excellent in adhesive strength to metal members.

Patent Document 2 discloses a paste-like adhesive composition comprising: metal particles that are sintered by heat treatment to form a particle-connected structure; and a resin that has a decomposition initiation temperature of 40°C to 250°C. This document describes that a sintered body of a paste-like adhesive composition is excellent in metal adhesion. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2019-189936 [Patent Document 2] Japanese Patent Laid-Open No. 2018-98272

[Problem to be Solved by the Invention]

However, as a result of the present inventors' investigations, the silver-containing paste described in the above-mentioned document is improved in terms of the adhesion force between the lead frame and the chip, etc., when bonding a semiconductor chip to a metal surface such as a lead frame. room for. [Technical means to solve the problem]

The inventors of the present invention conducted intensive research based on this knowledge, and found that the adhesion between the lead frame and the chip was improved by appropriately selecting a resin having a property of assisting sintering of metal particles and further adding an adhesion auxiliary agent. , and then completed the present invention.

By the present invention, a kind of silver-containing paste is provided, it comprises: Silver particles; Cyanamide derivatives; solvents; and Consisting of at least one or both of (A) an epoxy compound having two or more epoxy groups in the molecule, and (B) a (meth)acrylic compound containing two or more polymerizable double bonds in the molecule functional compound. [Effect of Invention]

According to this invention, the silver-containing paste excellent in the adhesive force between a lead frame and a chip is provided.

＜Silver-containing paste＞ The outline of the silver-containing paste of this embodiment is demonstrated. The silver-containing paste of this embodiment includes: silver-containing particles, cyanamide derivatives, solvents, and (A) epoxy compounds having two or more epoxy groups in the molecule, and (B) containing two or more epoxy groups in the molecule A polyfunctional compound composed of at least one or both of (meth)acrylic compounds with polymerizable double bonds.

In this embodiment, by including the cyanamide derivative, the adhesion force between the lead frame and the chip is improved. The detailed mechanism is uncertain, but it is considered to be due to the polarity of the cyanamide derivative. The cyanamide derivative has lone electron pairs of two or more nitrogen atoms in the molecule, and also has nitrogen atoms in the cyano group. Since the cyanamide derivative has strong polarity by having this nitrogen atom, it functions as an adhesion aid to a lead frame or a chip. It is considered that the cyanamide derivative adheres to the surface of the silver-containing particles, thereby improving the affinity of the silver-containing particles with the lead frame and the chip, and as a result, the adhesion between the lead frame and the chip during sintering is improved.

In this case, by using the polyfunctional compound used in the silver-containing paste in this embodiment as an epoxy compound having two or more epoxy groups in the molecule (A) and (B) including two or more epoxy groups in the molecule A multifunctional compound composed of at least one or both of the above polymerizable double bond (meth)acrylic compounds can easily introduce cyanamide derivatives into the multifunctional compound, and appropriately increase the content of cyanamide derivatives. The effect of the adhesion force between silver particles, lead frame and chip.

Hereinafter, each component of the silver-containing paste of this embodiment is demonstrated.

[containing silver particles] The silver-containing paste of this embodiment contains silver-containing particles. The silver-containing particles of this embodiment are sintered silver-containing particles that form a particle connection structure (sintered structure) by causing sintering (Sintering) by heat treatment.

In particular, by including silver-containing particles in the silver-containing paste, especially silver-containing particles having a relatively small particle size and a relatively large specific surface area, it is easy to form a sintered structure even when heat treatment is performed at a relatively low temperature (about 180° C.). The preferred particle size will be described later.

The upper limit of the temperature at which the silver-containing particles of this embodiment are sintered by heat treatment is preferably 260°C or lower, more preferably 250°C or lower, further preferably 240°C or lower. The upper limit of the temperature at which sintering occurs is not more than the above upper limit, so that the adhesiveness between the lead frame and the chip is more suitable in the electronic device using the silver-containing paste in this embodiment. Also, the lower limit of the temperature at which sintering occurs is preferably 160°C or higher, more preferably 165°C or higher, and still more preferably 170°C or higher. The lower limit of the temperature at which sintering occurs is more than the above-mentioned lower limit, whereby high-temperature reliability is more suitable for an electronic device using the silver-containing paste in this embodiment.

The shape of the silver-containing particles is not particularly limited. The preferred shape is spherical, but non-spherical shapes such as ellipsoid, flat, plate, flake, needle, scale, agglomerate and polyhedron are also possible. The silver-containing particles can contain at least one of these shapes. In this embodiment, it is preferable to contain two or more kinds of silver-containing particles selected from the group consisting of spherical, flaky, scaly, and aggregated porous polyhedral shapes. Thereby, since the contact rate of silver-containing particle|grains is further improved, it is easy to form a network|network after sintering this silver-containing paste, and in the electronic device using the silver-containing paste in this embodiment, heat dissipation is more suitable.

In addition, in this embodiment, the "spherical shape" is not limited to a perfect true sphere, but also includes a shape with some unevenness on the surface. The surface of silver-containing particles may also be treated with carboxylic acid, saturated fatty acid with 4-30 carbon atoms, unsaturated fatty acid with monovalent carbon number 4-30, long-chain alkyl nitrile, and the like.

The silver-containing particles may be (i) silver particles (silver powder) substantially composed only of silver, or (ii) particles composed of silver and components other than silver. In addition, (i) and (ii) may be used together as the metal-containing particles.

In this embodiment, silver-coated resin particles in which the surfaces of resin particles are coated with silver can also be included as particles composed of silver and components other than silver. In the silver-coated resin particle, the silver layer only needs to cover at least a part of the surface of the resin particle. Of course, silver may also cover the entire surface of the resin particles. Examples of such silver-coated resin particles include silver-plated silicone resins and the like.

Examples of the "resin" in the silver-coated resin particles include silicone resins, (meth)acrylic resins, phenol resins, polystyrene resins, melamine resins, polyamide resins, and polytetrafluoroethylene resins. Of course, other resins may also be used. Moreover, only 1 type may be sufficient as resin, and 2 or more types of resin may be used together.

The polysiloxane resin may be particles composed of organopolysiloxane obtained by polymerizing organochlorosilanes such as methylchlorosilane, trimethyltrichlorosilane, and dimethyldichlorosilane . Also, it may be a polysiloxane resin having a structure obtained by further three-dimensionally crosslinking an organopolysiloxane as a basic skeleton.

The (meth)acrylic resin may be a resin obtained by polymerizing a monomer containing (meth)acrylate as a main component (at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight). Examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, (meth) 2-ethylhexyl acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylic acid 2-Propyl ester, Chloro-2-hydroxyethyl (meth)acrylate, Diethylene glycol mono(meth)acrylate, Methoxyethyl (meth)acrylate, Glycidyl (meth)acrylate , dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate. In addition, the monomer component of the acrylic resin may contain a small amount of other monomers.

Various functional groups can be introduced into silicone resin or (meth)acrylic resin. The functional group that can be introduced is not particularly limited. For example, an epoxy group, an amino group, a methoxy group, a phenyl group, a carboxyl group, a hydroxyl group, an alkyl group, a vinyl group, a mercapto group etc. are mentioned.

The part of the resin particle among the silver-coated resin particles may contain various additive components such as a stress-reducing modifier and the like. Examples of low stress modifiers include butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane (polyurethane) rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane , Liquid synthetic rubber such as liquid polybutadiene, etc.

The median diameter D ₅₀ of the silver-containing particles is, for example, 0.001-1000 μm, preferably 0.01-100 μm, more preferably 0.1-20 μm. By setting D ₅₀ to an appropriate value, it is easy to maintain a balance of thermal conductivity, sinterability, resistance to thermal cycles, and the like. In addition, by setting _D50 to an appropriate value, it may be possible to improve the workability of coating/bonding. The particle size distribution of the silver-containing particles (horizontal axis: particle size, vertical axis: frequency) may be unimodal or multimodal.

(i) The median diameter D ₅₀ of the particles consisting essentially of silver is, for example, 0.8 μm or more, preferably 1.0 μm or more, more preferably 1.2 μm or more. Thereby, the sintered structure can be made strong, and in the electronic device using the silver-containing paste in this embodiment, the adhesiveness between a lead frame and a chip can be made more suitable.

Also, (i) the median diameter D ₅₀ of the particles consisting substantially only of silver is, for example, 10.0 μm, preferably 8.0 μm or less, more preferably 6.0 μm or less. Thereby, the further improvement of sinterability, the improvement of the uniformity of sintering, etc. can be aimed at.

(ii) The median diameter D ₅₀ of the particles composed of silver and components other than silver is, for example, 0.5 μm or more, preferably 1.5 μm or more, more preferably 2.0 μm or more. Thereby, it is easy to set the storage modulus to an appropriate value.

Also, (ii) the median diameter D ₅₀ of the particles composed of silver and components other than silver is, for example, 20 μm or less, preferably 15 μm or less, more preferably 10 μm or less. Thereby, the further improvement of sinterability, the improvement of the uniformity of sintering, etc. can be aimed at.

The median particle diameter D ₅₀ of the silver-containing particles can be obtained, for example, by performing particle image measurement using a flow type particle image analyzer FPIA (registered trademark)-3000 manufactured by Sysmex Corporation. More specifically, the particle diameter of the silver-containing particles can be determined by wet measurement of the volume-based median diameter using the apparatus.

The content of the silver-containing particles in the silver-containing paste is preferably from 80.0% by mass to 99.0% by mass, more preferably from 82.5% by mass to 97.5% by mass, relative to 100% by mass of the solid content excluding the solvent described below. , and more preferably at least 85.0% by mass and 95% by mass. With the content of silver-containing particles in the silver-containing paste of this embodiment within this range, the sintered structure can be made stronger, and in electronic devices using the silver-containing paste of this embodiment, lead frames and chips can be made The closeness between them is more appropriate.

Among the silver-containing particles, those composed of substantially only silver can be obtained from, for example, DOWA HIGHTECH CO., LTD., Fukuda Metal Foil & Powder Co., Ltd., and the like. Moreover, the silver-coated resin particle can be acquired from Mitsubishi Materials Corporation, Sekisui Chemical Co., Ltd., Sanno Co., Ltd., etc., for example.

In the present embodiment, the specific surface area of the silver-containing particles is preferably 0.10 m ² /g or more, preferably 0.15 m ² /g or more, and more preferably 0.20 m ² /g. The upper limit is not particularly limited, but can be set to 2.0 m ² /g or less from the viewpoint of yield. When two or more types of silver-containing particles are contained, the specific surface area of the silver-containing particles is an average value thereof. The specific surface area of the silver-containing particles was set as the BET specific surface area measured using an automatic specific surface area measuring device. With the specific surface area of the silver-containing particles of this embodiment within this range, the sintered structure can be made strong, and in an electronic device using the silver-containing paste of this embodiment, the adhesion between the lead frame and the chip can be improved. suitable. In this embodiment, it is more preferable to use two or more types of silver-containing particles with different specific surface areas from the viewpoint of the effects of the present invention.

In addition, the tap density of the silver-containing particles can be set to preferably 4.0 g/cm ³ or more, more preferably 4.5 g/cm ³ or more, further preferably 5.0 g/cm ^{3 or} more, particularly preferably 5.5 g/cm 3 or more. ³ or more. The upper limit is not particularly limited, but can be set to 8.0 g/cm ³ or less. The tap density was measured in accordance with ISO 3953-1985 (E) "Metal powder-Measurement method of tap density". This tap density makes it easy to set the paste viscosity to an appropriate value.

[cyanamide derivatives] The silver-containing paste of this embodiment further contains a cyanamide derivative. The cyanamide derivative improves the affinity of the silver-containing particles with the lead frame and the chip as described above, and as a result, the adhesive force between the lead frame and the chip during sintering is improved.

Usually, when a cyanamide derivative is added to the polyfunctional compound mentioned later, it functions as a hardening accelerator. On the other hand, the cyanamide derivative in this embodiment has a function as an adhesion aid to improve the adhesion between the lead frame and the chip, and by further adding a hardening accelerator other than the cyanamide derivative, the present invention can be achieved. The mechanical properties of the silver-containing paste of the embodiment and the adhesiveness between the lead frame and the chip are balanced.

Examples of cyanamide derivatives include dicyandiamine; guanidine; guanidine salts such as guanidine sulfamate and phosphate; melamine; These may be used alone or in combination of a plurality of them. Moreover, among these, it is preferable to contain one or more kinds selected from dicyandiamide, guanidine, guanidine salt, melamine, and formamiduron from the viewpoint of the adhesive force between the lead frame and the wafer during sintering. , dicyandiamide is more preferred.

The upper limit of the content of the above-mentioned cyanamide derivative is preferably 3 parts by mass or less, more preferably 2.7 parts by mass or less when the content of the polyfunctional compound of the present embodiment described later is 100 parts by mass, and is further preferably 2.7 parts by mass or less. Preferably, it is 2.5 parts by mass or less. By making content of a cyanamide derivative below the said upper limit, the heat radiation property of a silver-containing paste can be made more suitable. The lower limit of the content of the cyanamide derivative is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and even more preferably 0.01 parts by mass or more when the content of the polyfunctional compound of the present embodiment described later is 100 parts by mass. Preferably, it is 0.1 mass part or more. By making content of a cyanamide derivative more than the said lower limit, the adhesive force of the lead frame and a wafer at the time of sintering can be made more suitable.

[solvent] The silver-containing paste of this embodiment further contains a solvent. With the solvent, for example, adjustment of fluidity of the silver-containing paste, improvement of workability when forming an adhesive layer on a base material, and the like can be achieved.

Examples of solvents include ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether, Propyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, methyl methoxybutanol, α-terpineol, β-terpineol, hexyl Alcohols such as glycol, benzyl alcohol, 2-phenylethyl alcohol, isopalmityl alcohol, isostearyl alcohol, lauryl alcohol, ethylene glycol, propylene glycol, ethyl hexanediol, butyl propylene glycol or glycerin; acetone, methyl ethyl Ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), 2-octanone, isophorone (3,5,5-trimethyl -2-cyclohexen-1-yl) or ketones such as diisobutyl ketone (2,6-dimethyl-4-heptanone); ethyl acetate, butyl acetate, diethyl phthalate , dibutyl phthalate, acetoxyacetic acid, methyl butyrate, methyl caproate, methyl caprylate, methyl caprate, methyl celluloid acetate, ethylene glycol monobutyl ether acetate, propylene glycol Esters such as monomethyl ether acetate, 1,2-diacetyloxyethane, tributyl phosphate, tricresyl phosphate or tripentyl phosphate; tetrahydrofuran, dipropyl ether, ethylene glycol dimethyl ether, Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, propylene glycol dimethyl ether, ethoxyethyl ether, 1,2-bis(2-diethoxy)ethane or 1,2-bis(2-methyl 2-(2-butoxyethoxy)ethane and other ethers; 2-(2-butoxyethoxy)ethane and other ester ethers; 2-(2-methoxyethoxy)ethanol and other ether alcohols ; Hydrocarbons such as toluene, xylene, n-alkane, isoalkane, dodecylbenzene, terpineol, kerosene or diesel; Nitriles such as acetonitrile or propionitrile; Acetamide or N,N-dimethylformamide Amides such as amines; low molecular weight volatile silicone oil or volatile organically modified silicone oil. These may use only 1 type of solvent, and may use 2 or more types of solvents together.

The above solvent has a boiling point of preferably 150°C or higher, more preferably 170°C or higher, further preferably 200°C or higher. The upper limit of the boiling point is not particularly limited as long as it disappears by sintering, but it can be set to 300° C. or lower in the present embodiment. By making the boiling point of a solvent into the said range, the workability|operativity at the time of adhering a silver-containing paste to a base material can be made more suitable.

In 100% by mass of the silver-containing paste of the present embodiment, the above-mentioned solvent can preferably be contained in an amount of 1% by mass to 10% by mass, and more preferably can be contained in an amount of 2% by mass to 8% by mass. By making content of a solvent into the said range, the workability|operativity at the time of adhering a silver-containing paste to a base material can be made more suitable.

[Multifunctional compound] The silver-containing paste of this embodiment contains a polyfunctional compound. The polyfunctional compound of this embodiment is composed of (A) an epoxy compound having two or more epoxy groups in the molecule, and (B) a (meth)acrylic compound having two or more polymerizable double bonds in the molecule. A multifunctional compound composed of at least one or both of them. By using the polyfunctional compound, the sintered structure of the silver-containing particles can be easily formed through the aggregation effect of the resin.

Examples of the epoxy compound in this embodiment include phenol novolak type epoxy compounds, cresol novolac type epoxy compounds, cresol naphthol type epoxy compounds, biphenyl type epoxy compounds, biphenylarane Base type epoxy compound, phenoxy compound, naphthalene skeleton type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, diallyl bisphenol A type epoxy compound, bisphenol A type Diglycidyl ether type epoxy compound, Bisphenol F type Diglycidyl ether type epoxy compound, Bisphenol S type Diglycidyl ether type epoxy compound, o-allyl bisphenol A type Diglycidyl ether, 3,3',5,5'-tetramethyl 4,4'-dihydroxybiphenyl diglycidyl ether type epoxy compound, 1,1,2,2-tetra( Hydroxyphenyl) ethane type epoxy compound, 4,4'-dihydroxybiphenyl diglycidyl ether type epoxy compound, bromocresol novolac type epoxy compound, bisphenol D type epoxypropylene Epoxy compounds such as base ether epoxy compounds, glycidyl ethers of 1,6-naphthalene diol, and triglycidyl ethers of aminophenols. These may be used alone or in combination of a plurality of them. Moreover, among these, it is preferable to contain 1 type or both selected from the bisphenol A type epoxy compound and the bisphenol F type epoxy compound, and it is more preferable to contain the bisphenol F type epoxy compound. By selecting an epoxy compound from the above-mentioned types, further improvement of sinterability, improvement of the uniformity of sintering, etc. can be aimed at. In addition, as the epoxy compound, either a solid or liquid epoxy compound can be used at 25°C.

Examples of the (meth)acrylic compound in this embodiment include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, and triethylene glycol di(meth)acrylate. , tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate and other bifunctional (meth)acrylates; trimethylolpropane tri(meth)acrylate, neopentyl tetra Polyfunctional (meth)acrylates with more than 3 functions such as alcohol tri(meth)acrylates; epoxy (meth)acrylates with more than 2 functions; amine ester (meth)acrylates with more than 2 functions; 2 functions Polyester (meth)acrylate above. These may be used alone or in combination of a plurality of them. Also, among these, it is preferable to include one or both of bifunctional (meth)acrylates and trifunctional or more multifunctional (meth)acrylates, including ethylene glycol di(meth)acrylate ) acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate Bifunctional (meth)acrylates, such as ester, are more preferable, and it is still more preferable to contain ethylene glycol di(meth)acrylate. By selecting the (meth)acrylic compound from the above-mentioned types, it is possible to further improve the sinterability, improve the uniformity of sintering, and the like.

In the present embodiment, the lower limit of the content of the polyfunctional compound is not particularly limited, and for example, it may contain 1% by mass or more, 3% by mass or more, or Contains 5% by mass or more. Thereby, suitable mechanical characteristics can be exhibited as a cured product. In addition, the upper limit of the content of the polyfunctional compound is not particularly limited. For example, it may be 20% by mass or less, 15% by mass or less, or 10% by mass relative to the total solid content of the silver-containing paste. the following.

In this embodiment, the lower limit of the glass transition temperature (Tg) of the cured product of the polyfunctional compound is not particularly limited, for example, it may be 60°C or higher, 65°C or higher, or 70°C. above. The upper limit of the glass transition temperature (Tg) is not particularly limited, and may be, for example, 300° C. or lower, 290° C. or lower, or 280° C. or lower. Thereby, heat resistance can be obtained.

In this embodiment, as a method of measuring the glass transition temperature, for example, a thermomechanical analyzer (TMA SS7100, manufactured by SII Nanotechnology Co., Ltd.) or the like is used.

[other ingredients] In the silver-containing paste of this embodiment, if necessary, it is also possible to add hardeners, hardening accelerators, plasticizers, initiators, antioxidants, dispersants, inorganic fillers such as silica and alumina, and polymers. Other elastomers such as silicone resin or butadiene rubber, coupling agent, initiator, defoamer, leveling agent, fine silicon dioxide (thixotropic modifier) and other components. The contents of these components can be appropriately set according to the application of the silver-containing paste.

(hardener) In the silver-containing paste of this embodiment, for example, a curing agent can be contained. The curing agent is not particularly limited as long as it accelerates the polymerization reaction of polyfunctional compounds (for example, epoxy compounds). Thereby, the polymerization reaction of the above-mentioned polyfunctional compound can be accelerated, which contributes to the improvement of the mechanical properties obtained by using the silver-containing paste.

The hardening agent of this embodiment can be suitably selected from well-known ones, and it can be used as a hardening agent of a polyfunctional compound. Specifically, for example, phenol resin-based curing agents, amine-based curing agents, acid anhydride-based curing agents, mercaptan-based curing agents, and the like can be mentioned. These may be used alone or in combination of two or more.

As the above-mentioned phenolic resin-based hardener, for example, phenol novolac resin, cresol novolac resin, naphthol novolac resin, aminotrisium novolac resin, novolak resin, triphenylmethane type phenol novolak resin, etc. can be used. Varnish-type phenolic resins; modified phenolic resins such as terpene-modified phenolic resins and dicyclopentadiene-modified phenolic resins; Aralkyl type resins such as naphthol aralkyl resins with base skeleton and/or biphenylene skeleton; bisphenol resins with bisphenol skeletons such as bisphenol A and bisphenol F; soluble phenol resins, etc. These may be used alone or in combination of a plurality of them. Also, among these, bisphenol resins having a bisphenol skeleton such as bisphenol A and bisphenol F are preferable, and bisphenol resins having a bisphenol F skeleton are more preferable. By selecting a hardener from the above-mentioned types, it is possible to improve the mechanical properties obtained by using the silver-containing paste, thereby improving the adhesiveness between the lead frame and the chip.

As said amine hardening agent, the compound which has a tertiary amino group can be contained, for example. Compounds having a tertiary amine group include, for example, tertiary amines such as benzyldimethylamine (BDMA), imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole (EMI24), pyridine Azole, 3,5-dimethylpyrazole, pyrazoline and other pyrazoles, triazole, 1,2,3-triazole, 1,2,4-triazole, 1,2,3-benzotriazole Triazoles such as azoles, and imidazolines such as imidazoline, 2-methyl-2-imidazoline, and 2-phenylimidazoline can contain one or two or more selected from these.

The upper limit of the content of the curing agent contained in the silver-containing paste of the present embodiment is not particularly limited, for example, with respect to 100 parts by weight of the polyfunctional compound, preferably 25 parts by weight or less, more preferably 5 parts by weight or less, 3 parts by weight or less is further preferred, and 1 part by weight or less is particularly preferred. The lower limit of the content of the curing agent is not particularly limited, for example, it is preferably 0 part by weight or more, and more preferably 0.1 part by weight or more from the viewpoint of improving the mechanical properties of the silver-containing paste.

(hardening accelerator) In the silver-containing paste of this embodiment, a hardening accelerator can be contained. Here, as the hardening accelerator, hardening accelerators other than the above-mentioned cyanamide derivatives may be contained. The curing accelerator of the present embodiment is not particularly limited, and examples thereof include polyamine-based curing accelerators, imidazole-based curing accelerators, salts of triphenylphosphine or tetraphenylphosphine, and the like. Among them, the curing accelerator of the present embodiment preferably contains at least one selected from polyamine-based curing accelerators and imidazole-based curing accelerators, and more preferably contains imidazole-based curing accelerators.

The upper limit of the content of the hardening accelerator contained in the silver-containing paste of this embodiment is not particularly limited, for example, it is preferably 5 parts by weight or less, more preferably 4 parts by weight or less, based on 100 parts by weight of the polyfunctional compound. , 3 parts by weight or less is further preferred, and 2 parts by weight or less is further preferred. Also, the lower limit of the content of the hardening accelerator is not particularly limited, for example, it is preferably 0 part by weight or more, from the viewpoint of improving the mechanical properties of the silver-containing paste, it is preferably 0.1 part by weight or more, and 0.3 parts by weight The above is more preferable, and 0.5 mass part or more is still more preferable.

(Plasticizer) A plasticizer can be contained in the silver-containing paste of this embodiment. The plasticizer of this embodiment is not particularly limited, and examples thereof include aromatic carboxylic acid esters, aliphatic monocarboxylic acid esters, aliphatic dicarboxylic acid esters, aliphatic tricarboxylic acid esters, phosphoric acid triesters, and petroleum Resins, etc., polyalkylene glycol-based plasticizers, epoxy-based plasticizers, castor oil-based plasticizers, neopentyl glycol dibenzoate, diethylene glycol dibenzoate, triethylene glycol dibenzoate Ethyl diol di-2-butyrate, polyoxyethylene diacetate, polyoxyethylene bis(2-ethylhexanoate), polyoxypropylene monolaurate, polyoxypropylene monostearate Polyol esters such as polyoxyethylene dibenzoate and polyoxypropylene dibenzoate, aliphatic carboxylic acid esters such as butyl oleate, acetyl triethyl citrate, acetyl tributyl citrate esters, oxyesters such as ethoxycarbonylmethyl dibutyl citrate, di-2-ethylhexyl citrate, methyl acetyl ricinoleate or butyl acetyl ricinoleate, soybean oil, Soybean fatty acid, soybean fatty acid ester, epoxidized soybean oil, rapeseed oil, rapeseed fatty acid, rapeseed fatty acid ester, epoxidized rapeseed oil, linseed oil, linseed fatty acid, linseed fatty acid Esters, epoxidized linseed oil, vegetable oil compounds such as coconut oil or coconut fatty acid, neopentylthritol, sorbitol, polyacrylates, polysiloxane oils or alkanes, olefin peroxides, butylglycidyl Base ether, hexyl glycidyl ether, 2-ethylhexyl glycidyl ether, alkyl glycidyl ether, alkylphenol monoglycidyl ether, o-cresyl glycidyl ether, p- n-butyl-phenylglycidyl ether, p-tertiary butyl-phenylglycidyl ether, nonylphenylglycidyl ether, coconut oil fatty acid glycidyl ether, allyl epoxy Propyl Ether, Glycidyl Alcohol, Neopentyl Glycol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether, Glycidyl Alkanoate, Ethylene Glycol Bicyclo Oxypropyl ether and propylene glycol diglycidyl ether, etc.

The content of the plasticizer is preferably 5% by mass or less, more preferably 2% by mass or less, based on the total mass of the silver-containing paste. The adhesiveness of a silver-containing paste can be made more suitable as content of a plasticizer is below the said upper limit. Moreover, the lower limit of content of a plasticizer is not specifically limited, For example, it is 0 mass % or more.

(coupling agent) In the silver-containing paste of this embodiment, a coupling agent can be contained. The coupling agent of this embodiment is not particularly limited, and examples include: methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, Dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane Alkoxysilanes of oxysilanes; chlorosilanes such as methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane; hexamethyldisilazane; such as methacrylic Methacryloxypropyltriethoxysilane, Methacryloxypropyltrimethoxysilane, Methacryloxypropylmethyldiethoxysilane, Methacryloxypropylmethyl Diethoxysilane Alkoxysilanes of methoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane; such as vinyl Trichlorosilane, chlorosilane of vinylmethyldichlorosilane; divinyltetramethyldisilazane.

When the mass of the polyfunctional compound in the silver-containing paste is 100 parts by mass, the content of the coupling agent contained in the silver-containing paste of the present embodiment is preferably 5 parts by mass or less, more preferably 4 parts by mass or less. Preferably, 3 parts by mass or less is still more preferable. The adhesiveness of a silver-containing paste can be made more suitable as content of a coupling agent is below the said upper limit.

(starter) In the silver-containing paste of this embodiment, an initiator can be contained. As an initiator, a radical polymerization initiator etc. are mentioned, for example. Thereby, for example, when the compound to be polymerized by heating includes a compound having a radically polymerizable double bond in the molecule, the polymerization of the compound can be accelerated. The free radical polymerization initiator can contain, for example, one or more compounds selected from the following compounds: octyl peroxide, lauryl peroxide, stearyl peroxide, 1,1,3,3- Tetramethylbutylperoxy 2-ethylhexanoate, oxalic acid peroxide, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 1- Cyclohexyl-1-methylethylperoxy 2-ethylhexanoate, tertiary hexylperoxy 2-ethylhexanoate, tertiary butylperoxy 2-ethylhexanoate, meta Toluyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetyl peroxide, tertiary butyl hydroperoxide, di-tertiary butyl peroxide, Cumene hydroperoxide, dicumyl peroxide, tertiary butyl peroxybenzoate, p-chlorobenzoyl peroxide and cyclohexanone peroxide.

When the mass of the polyfunctional compound in the silver-containing paste is 100 parts by mass, the content of the initiator contained in the silver-containing paste of the present embodiment is preferably 10 parts by mass or less, more preferably 7 parts by mass Part or less, more preferably 5 parts by mass or less. The mechanical characteristics of a silver-containing paste can be made more suitable as content of an initiator is below the said upper limit. Also, the lower limit of the content of the initiator contained in the silver-containing paste of this embodiment is not particularly limited, but when the mass of the polyfunctional compound in the silver-containing paste is 100 parts by mass, it is preferable It is 0.5 mass part or more, More preferably, it is 1 mass part or more, More preferably, it is 2 mass parts or more.

＜Characteristics and physical properties of silver-containing paste＞ Next, the properties and physical properties of the silver-containing paste of this embodiment will be described. The silver-containing paste of this embodiment is preferably in a paste state at 20°C. That is, it is preferable that the silver-containing paste of this embodiment can adhere to a substrate etc. like a paste at 20 degreeC. Thereby, the silver-containing paste of this embodiment can be used suitably as an adhesive agent of a semiconductor element, etc. Of course, depending on the applicable manufacturing process, etc., the silver-containing paste in this embodiment may also be in the form of a relatively low-viscosity varnish.

Using the silver-containing paste of this embodiment, the lower limit value of the grain shear strength measured according to the following <measurement method> is preferably 1.5 N/mm ² or more at 260° C., more preferably 1.9 N/mm ² or more, More preferably, it is 2.2 N/mm ² or more. Thereby, when the silver-containing paste of this embodiment is used, the adhesive strength with a lead frame increases, and the adhesiveness between a lead frame and a chip can be improved. <Measurement method> A silver-containing paste is coated on a copper substrate to form a coating film, and a gold-plated 7×7mm silicon wafer is placed on the coating film, and then the temperature is raised from 30°C to 200°C in 60 minutes. Then heat treatment is performed at 200° C. for 120 minutes, by which the silver-containing paste is hardened or the silicon wafer is bonded to the substrate. Afterwards, the above measurement samples were treated in a constant temperature and humidity chamber at 60°C and humidity of 60% for 48 hours, and the grain shear strength (N/mm ² ) was measured at 260°C using a bare die shear tester.

In addition, the upper limit of the grain shear strength is not particularly limited, and is, for example, 100 N/mm ² or less at 260°C.

In this embodiment, as a method of measuring the grain shear strength, for example, a bare die shear tester (DAGE-4000 type, manufactured by Nordson Advanced Technology K.K.) can be used.

In a preferred aspect of this embodiment, the silver-containing paste of this embodiment is measured with a BF-type viscometer at a temperature of 25°C and a shear rate of 0.5rpm. The lower limit value of the viscosity η of _0.5 at 0.5rpm It is preferably at least 20 Pa·s, more preferably at least 25 Pa·s, and still more preferably at least 30 Pa·s. Thereby, it is possible to prevent the silver-containing paste from spreading on the substrate when the silver-containing paste is applied, and to prevent a short circuit with a wafer of another system. Also, the upper limit of the aforementioned η _0.5 is not particularly limited, and is, for example, 300 Pa·s or less.

In a preferred aspect of this embodiment, the lower limit value of the silver-containing paste of this embodiment is 5Pa when measured with a BF type viscometer at a temperature of 25°C and a shear rate of _5rpm .・s or higher is preferable, more preferably 5.5 Pa・s or higher, further preferably 6 Pa・s or higher. Thereby, it is possible to prevent the silver-containing paste from spreading on the substrate when the silver-containing paste is applied, and to prevent a short circuit with a wafer of another system. In addition, the upper limit of η ₅ is not particularly limited, for example, it may be 40 Pa·s or less, may be 35 Pa·s or less, or may be 30 Pa·s or less.

In a preferred aspect of this embodiment, the lower limit of the viscosity ratio of the above-mentioned η ₅ to the above-mentioned η _0.5 represented by the following formula (1) of the silver-containing paste of the present embodiment is preferably 2 or more, more preferably 2.5 or more, and more preferably 3 or more. Viscosity ratio=η _0.5 /η ₅ (1) When the viscosity ratio is equal to or greater than the above-mentioned lower limit, workability at the time of bonding the silver-containing paste to the substrate can be made more suitable. Moreover, the upper limit of the said viscosity ratio is not specifically limited, For example, it is 10 or less.

In a preferred form of this embodiment, the lower limit value of the storage modulus of the silver-containing paste of this embodiment measured by a dynamic viscoelasticity measuring device at a frequency of 1 Hz and a temperature of 25° C. is preferably 2000 MPa or more , more preferably at least 2500 MPa, further preferably at least 3000 MPa, even more preferably at least 4000 MPa. When the storage modulus is more than the above-mentioned lower limit value, the connection stability between the lead frame and the chip by the silver-containing paste can be made more suitable.

Also, the upper limit of the storage modulus is preferably 20000 MPa or less, more preferably 17500 MPa or less, further preferably 15000 MPa or less, still more preferably 10000 MPa or less, still more preferably 8000 MPa or less. When the storage modulus is below the above-mentioned upper limit, the adhesive strength with the lead frame when using the silver-containing paste of this embodiment improves, and the adhesiveness between a lead frame and a chip can be improved.

In addition, as the dynamic viscoelasticity measuring device for measuring the storage modulus, a known device can be used. As a well-known apparatus, the dynamic viscoelasticity measurement apparatus DMS6100 by SII Nanotechnology company, the dynamic viscoelasticity measurement apparatus HAAKE MARS by Thermo Fisher Scientific, etc. are mentioned, for example.

In the form of the present embodiment, the lower limit value of the thermal conductivity of the silver-containing paste of the present embodiment measured by the laser flash method is preferably 10 W/mK or more, more preferably 12 W/mK or more, still more preferably It is above 14W/mK. Thermal conductivity is more than the above-mentioned lower limit value, and high-temperature reliability is more suitable by this in the electronic device using the silver-containing paste in this embodiment. Moreover, the upper limit of the said thermal conductivity is not specifically limited, For example, it is 200 W/mK or less.

In addition, a known device can be used as a laser flash method thermal constant measuring device for measuring thermal conductivity. As a well-known apparatus, the laser flash method thermal constant measuring apparatus LFA447 etc. which are made from NETZSCH Japan K.K. are mentioned, for example.

＜Applications of silver-containing paste＞ The silver-containing paste of this embodiment can be used for various purposes. For example, a die attach material, a conductive paste, etc. are mentioned. As a die attach material, for example, it can be used in electronic devices, and it can be more preferably used in semiconductor devices. Examples of typical uses of the conductive paste include jumper circuits or through-hole conductors for printed circuit boards, additive circuits, conductor circuits for touch panels, resistor terminals, and solar cells. Formation of electrodes, electrodes of tantalum capacitors, electrodes of film capacitors, external electrodes or internal electrodes of wafer-type ceramic electronic parts, use as an electromagnetic wave shielding layer, etc. In addition, as a substitute for solder, in addition to being used as a conductive adhesive for mounting semiconductor elements or electronic parts on a substrate, it can also be used as a surface of a high-temperature-fired silver electrode of a solar cell covered with solder. A substitute for the solder portion of the gate electrode.

The silver-containing paste of the present embodiment can be cured by hardening. The cured product of this embodiment can be utilized in various applications. For example, used in electronic devices. That is, the electronic device of this embodiment is equipped with the cured body of the silver-containing paste of this embodiment, and the electronic component to which this hardened body was adhered. In the cured product of this embodiment, since silver particles are contained in the cured product, it can be applied to components of various electronic devices in which electrodes and wiring are formed. Moreover, it can also be used suitably as the application which fills the through-hole or the via hole (via hole) of a printed wiring board. Of course, the use mentioned here is an example of an embodiment, and even if it is a use other than this, it is needless to say that the composition of a silver-containing paste can be adjusted and applied simultaneously.

＜Manufacturing method of silver-containing paste＞ Next, the manufacturing method of the silver-containing paste of this embodiment is demonstrated. The silver-containing paste of this embodiment can be manufactured by kneading and mixing the above-mentioned components. This mixing can be performed using, for example, a kneading device such as a kneader, a three-roll mill, or a crushing machine, or various stirring devices.

Also, the method for producing a cured body of the silver-containing paste of the present embodiment has the steps of: preparing the silver-containing paste of the present embodiment by mixing silver particles and resin; and heat-treating the silver-containing paste, The step of causing sintering of silver particles to form a particle interconnected structure.

In the present embodiment, the resin is selected to have the property of assisting sintering. Therefore, in the curing step, the characteristics of the manufacturing process can be improved, that is, the sintering temperature can be lowered, the sintering time can be shortened, and the like. That is, in the hardening step, even if low temperature or short-time sintering conditions are used, both low resistance and adhesiveness of the silver-containing paste can be achieved.

The silver-containing paste of this embodiment is preferably sintered by heat treatment at 260° C. or lower and 160° C. or higher. In this embodiment, the upper limit of the sintering temperature is not particularly limited, for example, it is preferably 260° C. or lower, more preferably 250° C. or lower, and particularly preferably 240° C. or lower. In addition, the lower limit of the sintering temperature is not particularly limited, for example, it is preferably 160°C or higher, more preferably 165°C or higher, and particularly preferably 170°C or higher.

Also, in this embodiment, the lower limit of the sintering time is not particularly limited, for example, it is preferably at least 15 minutes, more preferably at least 18 minutes, and still more preferably at least 20 minutes. The upper limit of the sintering time is not particularly limited, for example, it is preferably 60 minutes or less, more preferably 55 minutes or less, and particularly preferably 50 minutes or less.

As mentioned above, although embodiment of this invention was described, these are only the example of this invention, and various structures other than the above can be employ|adopted. In addition, the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope of attaining the object of the present invention are included in the present invention. [Example]

[Preparation of varnish] Regarding each of Examples 1-4 and Comparative Examples 1-3, varnishes were prepared. The preparation was carried out by uniformly mixing the ingredients according to the incorporation shown in Table 1. In addition, the details of the components shown in Table 1 are as follows. In addition, each component in Table 1 is shown by the blending part. "-" in the table means not measurable.

(epoxy compound) Epoxy compound 1: bisphenol F type liquid epoxy compound, RE-303S, manufactured by Nippon Kayaku Co., Ltd.

(acrylic compound) Acrylic compound 1: Ethylene glycol dimethacrylate, LIGHT ESTER EG, manufactured by Kyoeisha Chemical Co., Ltd.

(hardener) Hardener 1: Bisphenol resin having a bisphenol F skeleton, DIC-BPF (solid at room temperature 25°C), manufactured by DIC Corporation

(cyanamide derivatives) Cyanamide derivative 1: dicyandiamide, EH-3636AS, manufactured by ADEKA CORPORATION

(hardening accelerator) Hardening accelerator 1: Polyamine-based hardening accelerator, EH-5057P, manufactured by ADEKA CORPORATION Hardening accelerator 2: imidazole-based hardening accelerator, 2PHZ-PW, manufactured by SHIKOKU CHEMICALS CORPORATION

(starter) Initiator 1: Dicumyl peroxide, Perkadox BC, manufactured by Kayaku Akzo Corporation

[Preparation of Silver-Containing Paste] Next, a silver-containing paste was prepared using the varnish adjusted in each of Examples 1-4 and Comparative Examples 1-3. 13.0 parts by mass of the varnishes adjusted in Examples 1-4 and Comparative Examples 1-3 were used as silver powder containing silver particles (scale-shaped silver, D ₅₀ : 6.0 μm, manufactured by Fukuda Metal Foil & Powder Co., Ltd. , Sintering temperature: 200°C, Tap density: 5.5g/cm ³ , Specific surface area: 0.2m ² /g) 65 parts by mass, silver-plated silicone resin particles (manufactured by Mitsubishi Materials Corporation, heat-resistant and surface-treated 10μm grade, Spherical shape, D ₅₀ : 10 μm, sintering temperature: 210°C, tap density: 5.5g/cm ³ ) 20 parts by mass, butylpropylene glycol (BFTG, manufactured by Nippon Nyukazai Co., LTd.) as a solvent, boiling point: 274°C ) 2.0 parts by mass and 100 parts by mass in total were used as the silver-containing paste in each of Examples 1-4 and Comparative Examples 1-3.

[evaluate] About each Example and each comparative example, evaluation was performed in the following manner. The results are shown in Table 1.

(Thermal conductivity) Coat the silver-containing paste in each of Examples 1 to 4 and Comparative Examples 1 to 3 in a quadrilateral mold with a thickness of about 1 mm and a side length of 10 mm, heat up from 30°C to 200°C in 60 minutes, and then heat at 200°C for 120 Minutes, thereby making a hardened test piece. After preparing the hardened test piece, thermal diffusivity was measured using laser flash method thermal constant measuring device LFA447 manufactured by NETZSCH Japan K.K., and thermal conductivity was calculated from specific heat and specific gravity.

(volume resistivity) The silver-containing paste in each of Examples 1 to 4 and Comparative Examples 1 to 3 is coated on the substrate with a thickness of 0.1mm×width 4mm×length 50mm, and is heated from 30°C to 200°C in 60 minutes, and then heated at 200°C Heat up for 120 minutes. Next, measure the resistance value by touching the measurement terminals against the upper and lower ends of the substrate. The measurement length is set to 40 mm. Afterwards, the measured resistance value was converted into volume resistivity.

(storage modulus) The silver-containing paste in each of Examples 1 to 4 and Comparative Examples 1 to 3 is coated on a mold of about 0.1mm × about 10mm × about 4mm, and is heated from 30°C to 200°C in 60 minutes, and then heated at 200°C for 120 Minutes, thereby obtaining a strip sample for evaluation. Using this sample, the storage elastic modulus at 25°C (E' ).

(viscosity) Regarding the silver-containing pastes in each of Examples 1-4 and Comparative Examples 1-3, using a BF-type viscometer (manufactured by Brookfield Engineering Co., Ltd., model DV3T), the temperature of the silver-containing paste at room temperature 25° C. was measured immediately after the preparation of the silver-containing paste. viscosity. As the measurement order at this time, the measurement was performed in the order of a shear rate of 0.5 rpm and then a shear rate of 5 rpm. The unit of viscosity is Pa·s.

(Adhesion) As an index of adhesion, grain shear strength was measured by the following method. The silver-containing paste in each of Examples 1-4 and Comparative Examples 1-3 was coated on a copper substrate, and a silicon wafer of 7 mm×7 mm×0.35 mm with a gold-plated surface was mounted on it so that the thickness of the paste became 15 μm. . After that, it took 60 minutes to raise the temperature from 30° C. to 200° C., and then heat-treated at 200° C. for 120 minutes. Through the above, the silver-containing paste was hardened or the silicon wafer was bonded to the substrate. After that, the above-mentioned measurement samples were treated in a constant temperature and humidity chamber at 60°C and humidity of 60% for 48 hours, using a bare die shear tester (manufactured by Nordson Advanced Technology KK, DAGE-4000 type), and at a test speed: 500μm/ The grain shear strength (N/mm ² ) was measured at 260°C under the condition of 2 seconds.

[Table 1] Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 varnish epoxy compound 1 50.0 50.0 50.0 50.0 50.0 50.0 50.0 Acrylic Compound 1 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Hardener 1 20.0 20.0 20.0 20.0 20.0 20.0 20.0 Cyanamide derivatives 0.1 0.2 0.5 1.5 hardening accelerator 1 0.5 1.5 hardening accelerator 2 1.00 1.00 1.00 1.00 1.00 1.00 1.00 Initiator 1 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Paste varnish 13.0 13.0 13.0 13.0 13.0 13.0 13.0 silver powder 65.0 65.0 65.0 65.0 65.0 65.0 65.0 Silver-plated silicone 20.0 20.0 20.0 20.0 20.0 20.0 20.0 solvent 2.0 2.0 2.0 2.0 2.0 2.0 2.0 characteristic Thermal conductivity (W/mK) 28 twenty four 17 14 30 26 twenty two Volume resistivity (μΩ·cm) 41 57 63 88 30 32 40 Storage modulus (MPa) 6400 6400 6500 6500 6400 6600 6300 Viscosity (Pa·s) η _0.5 44 46 53 58 36 47 475 n ₅ 11 12 19 twenty one 10 14 62 η _0.5 /η ₅ 4.0 3.8 2.8 2.8 3.6 3.4 7.7 Grain shear strength (N/mm ² ) 3.4 3.8 2.9 2.3 0.4 0.4 0.2

In Examples 1 to 4, the grain shear strength with the copper plate was specifically higher than that of Comparative Examples 1 to 3, so that the silver-containing pastes of Examples 1 to 4 were closely bonded between the lead frame and the chip. Excellent silver-containing paste.

This application claims priority based on Japanese Patent Application No. 2021-082513 for which it applied on May 14, 2021, and uses all the content disclosed here.

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Claims (12)

A silver-containing paste comprising: Silver particles; Cyanamide derivatives; solvents; and Consisting of at least one or both of (A) an epoxy compound having two or more epoxy groups in the molecule, and (B) a (meth)acrylic compound containing two or more polymerizable double bonds in the molecule functional compound. Such as the silver-containing paste of claim 1, wherein, The aforementioned cyanamide derivatives include one or two or more selected from the group consisting of dicyandiamine, guanidine, guanidine salt, melamine, and formidine urea. Such as the silver-containing paste of claim 1 or 2, wherein, When content of the said polyfunctional compound is 100 mass parts, content of the said cyanamide derivative is 0.01 mass part or more and 3 mass parts or less. Such as the silver-containing paste of claim 1 or 2, wherein, The epoxy compound having two or more epoxy groups in the molecule (A) includes one or both of bisphenol A epoxy compounds and bisphenol F epoxy compounds. Such as the silver-containing paste of claim 1 or 2, its further containing a hardener, The aforementioned hardener contains a bisphenol resin. Such as the silver-containing paste of claim 1 or 2, wherein, The said silver-containing particle is a silver-containing particle which sinters at the temperature of 160 degreeC or more and 260 degreeC or less. The silver-containing paste according to claim 1 or 2, which has a grain shear strength of 1.5 N/mm 2 or more and 100 N/mm ^{2 or} less measured according to the following <measurement method>, <measurement method> coating the silver-containing paste Spread it on a copper substrate to form a coating film, and place a gold-plated 7×7mm silicon wafer on the coating film, then spend 60 minutes heating up from 30°C to 200°C, and then heat treatment at 200°C for 120 minutes, by Harden the silver-containing paste or bond the silicon wafer to the substrate as above, and use it as a measurement sample. After that, treat the above-mentioned measurement sample in a constant temperature and humidity chamber at 60°C and 60% humidity for 48 hours, using bare die scissors A force tester (manufactured by Nordson Advanced Technology KK, model DAGE-4000), and grain shear strength (N/mm ² ) was measured at 260°C. Such as the silver-containing paste of claim 1 or 2, which uses a BF-type viscometer, and stirs the silver-containing paste at a temperature of 25°C and a shear rate of 0.5rpm, and simultaneously measures the viscosity η _0.5 of 0.5rpm when it is 20Pa・s or more and 300Pa・s or less. Such as the silver-containing paste of claim 1 or 2, which uses a BF-type viscometer, and stirs the silver-containing paste at a temperature of 25°C and a shear rate of 5rpm, and simultaneously measures the viscosity η ₅ at 5rpm when it is 5Pa·s Above and below 40Pa・s. As for the silver-containing paste of claim 1 or 2, the viscosity ratio represented by the following formula (1) is not less than 2 and not more than 10, and the viscosity ratio is measured by using a BF type viscometer at a temperature of 25°C and a shear rate of 0.5 Viscosity ratio of viscosity η _0.5 at 0.5 rpm when stirred at rpm and measured simultaneously with viscosity η ₅ at 5 rpm when stirred at temperature: 25°C, shear rate: 5 rpm and measured simultaneously using a BF type viscometer, viscosity ratio = η _0.5 / η ₅ (1). Such as the silver-containing paste of claim 1 or 2, its The storage modulus measured by a dynamic viscoelasticity measuring device at a frequency of 1Hz and a temperature of 25°C is above 2000MPa and below 20000MPa. Such as the silver-containing paste of claim 1 or 2, its The thermal conductivity measured by the laser flash method is not less than 10 W/mK and not more than 200 W/mK.