JP7577949B2 - Paste-like resin composition, highly thermally conductive material, and semiconductor device - Google Patents

Description

The present invention relates to a paste-like resin composition, a highly thermally conductive material, and a semiconductor device.

A technique is known for manufacturing semiconductor devices using a thermosetting resin composition containing metal particles, with the intention of increasing the heat dissipation of the semiconductor device. By including metal particles, which have a higher thermal conductivity than the resin, in the thermosetting resin composition, the thermal conductivity of the cured product can be increased.

Specific examples of applications to semiconductor devices include a technique for bonding/joining a semiconductor element to a substrate (support member) using a thermosetting resin composition containing metal particles, as described in the following Patent Documents 1 and 2.

Patent Document 1 discloses a thermosetting resin composition for semiconductor bonding that contains a (meth)acrylic acid ester compound of a specific structure, a radical initiator, silver fine particles, silver powder, and a solvent, and a semiconductor device in which a semiconductor element and a substrate are bonded with the composition. The document also discloses that the connection reliability against temperature cycles after mounting can be improved (paragraph 0011).

Patent Document 2 discloses a resin paste composition containing an imide acrylate compound, a radical initiator, a filler, and a liquid rubber component, and a semiconductor device in which a semiconductor element and a substrate are bonded with the composition. The document also discloses that the occurrence of chip cracks and chip warpage can be suppressed by reducing the stress of the resin paste composition (paragraph 0003).

Patent Document 3 discloses a silver paste composition consisting of silver particles, a solvent, and additives that satisfy predetermined physical properties, and a semiconductor device having a structure in which a semiconductor element and a support member for mounting the semiconductor element are bonded via the composition. The document describes an example in which dipropylene glycol methyl ether acetate and isobornylcyclohexanol are used as solvents.

JP 2014-74132 A JP 2000-239616 A JP 2014-225350 A

However, the electrical conductivity of semiconductor devices in which a semiconductor element and a substrate are bonded using the resin compositions described in Patent Documents 1 to 3 leaves room for improvement.

The inventors have discovered that if the difference between the Hansen solubility parameter of silver-containing particles measured by a specified method and the Hansen solubility parameter of a certain solvent is within a specific range, the silver-containing particles have an excellent balance between dispersion and aggregation in the paste-like resin composition, and the material obtained from the paste-like resin composition has excellent electrical conductivity, thus completing the present invention.

That is, the present invention can be shown as follows.
According to the present invention,
The present invention comprises silver-containing particles A, a solvent B, and a thermosetting resin C,
There is provided a paste-like resin composition, in which the difference between the Hansen solubility parameter a of silver-containing particles A and the Hansen solubility parameter b of solvent B, measured by the following method, is 4.3 or more and 9.8 or less.
[method]
2 mL of any solvent selected from the evaluation solvents listed below is added to 0.2 g of silver-containing particles A in a 10 mL glass container, and the mixture is stirred for 5 seconds with a vortex mixer, after which the dispersibility is visually evaluated according to the following four-point scale: The evaluation solvent and the evaluation results of the dispersibility in that solvent are input into the Sphere program of computer software HSPiP (version 5.2.02), and the Hansen solubility parameter is calculated.
(Solvent for evaluation)
Water, methanol, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, acetonitrile, ethyl acetate, methyl ethyl ketone, 1-butanol, cyclohexanol, isopropyl alcohol (Evaluation)
0: Does not disperse.
1: Settling is complete in less than 10 minutes.
2: Settling is complete after 10 minutes or more but less than 1 hour.
3: Settling is complete after 1 hour or more and 12 hours or less.

According to the present invention,
A highly thermally conductive material is provided by sintering the paste-like resin composition.

According to the present invention,
A substrate;
A semiconductor element mounted on the base material via an adhesive layer,
The adhesive layer is formed by sintering the paste-like resin composition, thereby providing a semiconductor device.

According to the present invention,
measuring the Hansen solubility parameter a of the silver-containing particles A and the Hansen solubility parameter of the solvent measured by the above method;
A step of selecting a solvent B having a difference in Hansen solubility parameter from the Hansen solubility parameter a of 4.3 to 9.8;
mixing silver-containing particles A, a selected solvent B, and a thermosetting resin C;
The present invention provides a method for producing a paste-like resin composition, comprising the steps of:

According to the present invention,
Measuring the Hansen solubility parameter of the metal particles and the Hansen solubility parameter of the solvent measured by the above method;
Selecting the metal particles and/or the solvent such that the difference between the Hansen solubility parameter of the metal particles and the Hansen solubility parameter of the solvent is 4.3 or more and 9.8 or less;
mixing the selected metal particles, the selected solvent, and a thermosetting resin;
A method for producing a resin composition is provided, comprising:

The present invention provides a paste-like resin composition that can produce a material with improved electrical conductivity.

1 is a cross-sectional view illustrating an example of a semiconductor device. 1 is a cross-sectional view illustrating an example of a semiconductor device.

The following describes an embodiment of the present invention with reference to the drawings. In all drawings, similar components are given similar reference symbols and descriptions will be omitted where appropriate. In addition, "~" indicates "above" to "below" unless otherwise specified.

<Paste-like resin composition>
The paste-like resin composition of the present embodiment comprises silver-containing particles A, a solvent B, a thermosetting resin C, and
The difference between the Hansen solubility parameter (HSP) a of the silver-containing particles A and the Hansen solubility parameter (HSP) b of the solvent B, as measured by the following method, is 4.3 or more and 9.8 or less.
[method]
2 mL of any solvent selected from the evaluation solvents listed below is added to 0.2 g of silver-containing particles A in a 10 mL glass container, and the mixture is stirred for 5 seconds with a vortex mixer, after which the dispersibility is visually evaluated according to the following four-point scale: All evaluation solvents and the evaluation results of dispersibility for each solvent are input into the Sphere program of computer software HSPiP (version 5.2.02), and the Hansen solubility parameter is calculated.
(Solvent for evaluation)
Water, methanol, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, acetonitrile, ethyl acetate, methyl ethyl ketone, 1-butanol, cyclohexanol, isopropyl alcohol (Evaluation)
0: Does not disperse.
1: Settling is complete in less than 10 minutes.
2: Settling is complete after 10 minutes or more but less than 1 hour.
3: Settling is complete after 1 hour or more and 12 hours or less.

Note that "sedimentation is completed" by visual inspection means that when a glass container containing the evaluation solvent in which silver-containing particles A are dispersed is observed directly under a 32 W fluorescent lamp, the silver-containing particles A dispersed in the evaluation solvent can no longer be visually confirmed.

In this way, by having the difference between parameters a and b within a specified range, the balance between dispersion and aggregation of the silver-containing particles A in the paste-like resin composition is optimized, and the contact rate between the silver-containing particles A is improved, so that it is believed that a network is formed after sintering, making it possible to provide a material with improved thermal conductivity and electrical conductivity.

From the viewpoint of the effects of the present invention, the difference between the Hansen solubility parameter a of the silver-containing particles A and the Hansen solubility parameter b of the solvent B can be preferably 5.0 or more and 9.0 or less, and more preferably 5.5 or more and 9.0 or less.

The dispersion term (δD) of the Hansen solubility parameter a of the silver-containing particles A is 15.0 MPa ^1/2 or more and 17.0 MPa ^1/2 or less, preferably 15.5 MPa ^1/2 or more and 16.5 MPa ^1/2 or less;
The polarization term (δP) is 7.0 MPa ^1/2 or more and 10.0 MPa ^1/2 or less, preferably 7.5 MPa ^1/2 or more and 9.5 MPa ^1/2 or less,
The hydrogen bond parameter (δH) is 8.0 MPa ^1/2 or more and 11.0 MPa ^1/2 or less, and preferably 8.5 MPa ^1/2 or more and 10.5 MPa ^1/2 or less.

The dispersion term (δD) of the Hansen solubility parameter b of the solvent B is 14.0 MPa ^1/2 or more and 25.0 MPa ^1/2 or less, preferably 16.0 MPa ^1/2 or more and 19.5 MPa ^1/2 or less;
The polarization term (δP) is 5.0 MPa ^1/2 or more and 19.0 MPa ^1/2 or less, preferably 5.0 MPa ^1/2 or more and 16.0 MPa ^1/2 or less,
The hydrogen bond parameter (δH) is 4.0 MPa ^1/2 or more and 15.5 MPa ^1/2 or less, and preferably 4.0 MPa ^1/2 or more and 8.0 MPa ^1/2 or less.
When the content is within the above range, compatibility with the silver-containing particles A is appropriate, and furthermore, the solubility in the thermosetting resin C is excellent.

Hansen solubility parameter (HSP) is an index that indicates the solubility of a substance, i.e., how much a substance dissolves in another substance. HSP expresses solubility as a three-dimensional vector. This three-dimensional vector can be typically expressed by a dispersion term (δD), a polarization term (δP), and a hydrogen bond term (δH). Substances with similar vectors can be judged to have high solubility. The similarity of vectors can be judged by the distance of the Hansen solubility parameter (ΔHSP, expressed by the following formula).
In the following formula, the Hansen solubility parameter of substance 1 is expressed using the dispersion term (δD1), the polarization term (δP1), and the hydrogen bond term (δH1), and the Hansen solubility parameter of substance 2 is expressed using the dispersion term (δD2), the polarization term (δP2), and the hydrogen bond term (δH2). The smaller the ΔHSP, the more compatible the two substances are.

This embodiment was completed by focusing on the relationship between the Hansen solubility parameter calculated from the dispersibility evaluation of insoluble silver-containing particles A in the evaluation solvent and the Hansen solubility parameter of solvent B. In other words, it was discovered that if the difference between these Hansen solubility parameters (ΔHSP) is within a predetermined range, the balance between the dispersion and aggregation of silver-containing particles A in the paste-like resin composition is optimized, and the contact rate between the silver-containing particles A is improved, so that a network is formed after sintering and electrical conductivity is improved.

The Hansen Solubility Parameter (HSP value) can be calculated using computer software called HSPiP (Hansen Solubility Parameters in Practice). In this embodiment, the Sphere program version 5.2.02 is used as the computer software HSPiP.
Here, the computer software HSPiP developed by Hansen and Abbott includes a function for calculating HSP distances and a database that lists the Hansen parameters of solvents or non-solvents. The Hansen solubility parameter (HSP) b of solvent B can be estimated from the database or by inputting the molecular structure in SMILE notation into the DIY (Do It Yourself) program of the computer software HSPiP.

[Silver-containing particles A]
The silver-containing particles A can be sintered by an appropriate heat treatment to form a particle-connected structure (sintered structure).

In particular, when the paste-like resin composition contains silver-containing particles, particularly silver particles with a relatively small particle size and a relatively large specific surface area, a sintered structure is easily formed even when heat-treated at a relatively low temperature (about 180°C). The preferred particle size will be described later.

The shape of the silver-containing particles A is not particularly limited. A preferred shape is spherical, but non-spherical shapes such as ellipsoidal, flat, plate-like, flake-like, needle-like, scale-like, aggregated, and polyhedral shapes are also acceptable. The silver-containing particles A may contain at least one type of silver-containing particles having these shapes.
In this embodiment, it is preferable to include two or more types selected from spherical, scaly, aggregated, and polyhedral silver-containing particles, and it is more preferable to include spherical silver-containing particles a1 and one or more types of silver-containing particles a2 selected from scaly, aggregated, and polyhedral shapes. This further improves the contact rate between the silver-containing particles, and therefore a network is easily formed after sintering of the paste-like resin composition, thereby further improving the thermal conductivity and electrical conductivity.
When the silver-containing particles A contain the silver-containing particles a2, resin cracks in a molded product obtained from the paste resin composition can be suppressed, and the linear expansion coefficient can be suppressed.

In this embodiment, the term "spherical" is not limited to a perfect sphere, but also includes shapes with slight irregularities on the surface.
The silver-containing particles A may have their surfaces treated with a carboxylic acid, a saturated fatty acid having 4 to 30 carbon atoms, a monovalent unsaturated fatty acid having 4 to 30 carbon atoms, a long-chain alkylnitrile, or the like.

The silver-containing particles A may be (i) particles consisting essentially of silver, or (ii) particles consisting of silver and components other than silver. In addition, (i) and (ii) may be used in combination as metal-containing particles.

In this embodiment, it is particularly preferable that the silver-containing particles A include silver-coated resin particles in which the surfaces of resin particles are coated with silver. This makes it possible to prepare a paste-like resin composition that provides a cured product with superior thermal conductivity and storage modulus.

Because silver-coated resin particles have a silver surface and a resin interior, they are thought to have good thermal conductivity and are softer than particles made only of silver. For this reason, it is thought that the use of silver-coated resin particles makes it easier to design the thermal conductivity and storage modulus to appropriate values.

Normally, increasing the amount of silver-containing particles would be considered to increase thermal conductivity. However, metals are usually "hard," so if the amount of silver-containing particles is too high, the elastic modulus after sintering may become too large. By using silver-coated resin particles in part or in whole, it is possible to easily design a paste-like resin composition that can give a cured product with the desired thermal conductivity and storage elastic modulus.

In silver-coated resin particles, it is sufficient that at least a portion of the surface of the resin particle is covered with a silver layer. Of course, the entire surface of the resin particle may be covered with silver.

Specifically, in the silver-coated resin particles, the silver layer covers preferably 50% or more, more preferably 75% or more, and even more preferably 90% or more of the surface of the resin particle, and particularly preferably, in the silver-coated resin particles, the silver layer covers substantially the entire surface of the resin particle.
From another viewpoint, it is preferable that when a silver-coated resin particle is cut at a cross section, a silver layer is observed all around the periphery of the cross section.

From another perspective, the mass ratio of resin to silver in the silver-coated resin particles is, for example, 90/10 to 10/90, preferably 80/20 to 20/80, and more preferably 70/30 to 30/70.

Examples of the "resin" in the silver-coated resin particles include silicone resin, (meth)acrylic resin, phenol resin, polystyrene resin, melamine resin, polyamide resin, polytetrafluoroethylene resin, etc. Of course, other resins may also be used. In addition, only one type of resin may be used, or two or more types of resins may be used in combination.
From the viewpoint of elasticity and heat resistance, the resin is preferably a silicone resin or a (meth)acrylic resin.

The silicone resin may be particles composed of organopolysiloxane obtained by polymerizing organochlorosilane such as methylchlorosilane, trimethyltrichlorosilane, or dimethyldichlorosilane. It may also be a silicone resin whose basic structure is a structure in which organopolysiloxane is further crosslinked in three dimensions.

The (meth)acrylic resin can be a resin obtained by polymerizing a monomer containing a (meth)acrylic acid ester as the main component (50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more). Examples of the (meth)acrylic acid ester include at least one compound selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-propyl (meth)acrylate, 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. The monomer components of the acrylic resin may contain small amounts of other monomers. Examples of such other monomer components include styrene-based monomers. For information on silver-coated (meth)acrylic resins, see, for example, JP 2017-126463 A.

Various functional groups may be introduced into the silicone resin or (meth)acrylic resin. There are no particular limitations on the functional groups that can be introduced. Examples include epoxy groups, amino groups, methoxy groups, phenyl groups, carboxyl groups, hydroxyl groups, alkyl groups, vinyl groups, and mercapto groups.

The resin particle portion of the silver-coated resin particles may contain various additive components, such as low-stress modifiers. Examples of low-stress modifiers include liquid synthetic rubbers such as butadiene styrene rubber, butadiene acrylonitrile rubber, polyurethane rubber, polyisoprene rubber, acrylic rubber, fluororubber, liquid organopolysiloxane, and liquid polybutadiene. In particular, when the resin particle portion contains silicone resin, the elastic properties of the silver-coated resin particles can be made favorable by including a low-stress modifier.

The shape of the resin particle portion of the silver-coated resin particles is not particularly limited. Preferably, the shape is a combination of a sphere and an irregular shape other than a sphere, such as a flat, plate-like, or needle-like shape.

The specific gravity of the silver-coated resin particles is not particularly limited, but the lower limit is, for example, 2 or more, preferably 2.5 or more, and more preferably 3 or more. The upper limit of the specific gravity is, for example, 10 or less, preferably 9 or less, and more preferably 8 or less. An appropriate specific gravity is preferable in terms of the dispersibility of the silver-coated resin particles themselves and the uniformity when the silver-coated resin particles are used in combination with other silver-containing particles.

When silver-coated resin particles are used, the proportion of silver-coated resin particles in the entire silver-containing particles A is preferably 1 to 50 mass%, more preferably 3 to 45 mass%, and even more preferably 5 to 40 mass%. By appropriately adjusting this proportion, it is possible to further improve heat dissipation while suppressing the decrease in adhesive strength due to heat cycles.

Incidentally, when the proportion of silver-coated resin particles in the entire silver-containing particles A is not 100% by mass, the silver-containing particles other than the silver-coated resin particles are, for example, particles that are substantially composed of only silver.

The median diameter _D50 of the silver-containing particles A is, for example, 0.001 to 1000 μm, preferably 0.01 to 100 μm, and more preferably 0.1 to 20 μm. By setting _D50 to an appropriate value, it is easy to balance thermal conductivity, sinterability, resistance to heat cycles, and the like. In addition, by setting D50 to an appropriate value, it may be possible to improve workability in coating/adhesion, etc.
The particle size distribution of the silver-containing particles (abscissa: particle diameter, ordinate: frequency) may be unimodal or multimodal.

The median diameter _D50 of the particles consisting essentially of silver is, for example, 0.8 μm or more, preferably 1.0 μm or more, and more preferably 1.2 μm or more. This can further increase the thermal conductivity.

The median diameter _D50 of the particles consisting essentially of silver is, for example, 7.0 μm or less, preferably 5.0 μm or less, and more preferably 4.0 μm or less, which can further improve the ease of sintering and the uniformity of sintering.

The median diameter _D50 of the silver-containing particles A is, for example, 0.5 μm or more, preferably 1.5 μm or more, and more preferably 2.0 μm or more, which makes it easy to adjust the storage modulus E′ to an appropriate value.

The median diameter D50 of the silver-containing particles A is, for example, 20 μm or less, preferably 15 μm or less, and more preferably 10 μm or less. This makes it easier to achieve sufficiently high thermal conductivity.

The median diameter _D50 of the silver-containing particles A can be determined by particle image measurement using, for example, a flow particle image analyzer FPIA (registered trademark)-3000 manufactured by Sysmex Corp. More specifically, the particle diameter of the silver-containing particles A can be determined by measuring the volume-based median diameter in a wet manner using this device.

The proportion of silver-containing particles A in the entire paste-like resin composition is, for example, 1 to 98% by mass, preferably 30 to 95% by mass, and more preferably 50 to 90% by mass. By making the proportion of metal-containing particles 1% by mass or more, it is easy to increase thermal conductivity. By making the proportion of silver-containing particles A 98% by mass or less, it is possible to improve the workability of application/adhesion.

Among the silver-containing particles A, particles consisting essentially of silver alone can be obtained, for example, from Dowa Hightec Co., Ltd. and Fukuda Metal Foil and Powder Co., Ltd. In addition, silver-coated resin particles can be obtained, for example, from Mitsubishi Materials Corporation, Sekisui Chemical Co., Ltd., Sanno Co., Ltd., etc.

[Solvent B]
Solvent B may be used without any particular limitation as long as the difference between the Hansen solubility parameter b of solvent B and the Hansen solubility parameter a of silver-containing particles A is within a predetermined range. Solvent B is a compound that is liquid at room temperature (25° C.) and may contain a monofunctional monomer.
Solvent B may be one type of solvent, or two or more types may be mixed to adjust the Hansen solubility parameter.

When solvent B consists of one kind of solvent, it can be used as long as the difference between the Hansen solubility parameter a and the Hansen solubility parameter b in relation to the silver-containing particles A falls within a predetermined range. Examples of such solvents include tripropylene glycol mono-n-butyl ether, dimethyl sulfoxide, benzyl benzoate, diacetone alcohol, triethylene glycol dimethyl ether, γ-butyrolactone, isobornylcyclohexanol, terpineol, isobornylcyclohexanol, and diethylene glycol.
Among these, tripropylene glycol mono-n-butyl ether, dimethyl sulfoxide, benzyl benzoate, γ-butyrolactone, isobornylcyclohexanol, or terpineol is preferred.

When solvent B is composed of two or more solvents, two or more solvents selected from tripropylene glycol mono-n-butyl ether, propylene carbonate, diacetone alcohol, triethylene glycol dimethyl ether, dimethyl sulfoxide, benzyl benzoate, ethylene glycol, diethylene glycol, γ-butyrolactone, carbitol, n-dodecane, isobornylcyclohexanol, terpineol, propylene glycol phenyl ether, ethylene glycol mono-2-ethylhexyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, δ-valerolactone, butyl carbitol, phenoxypropanol, diethylene glycol monobutyl ether acetate, ethylene glycol mono-n-butyl ether acetate, dimethyl isosorbide, isophorone, butyl diglycol acetate, hexylene glycol, butyl benzoate, 2-phenoxyethanol, benzyl alcohol, dihydrolevoglucosenone, dipropylene glycol, and caprolactone can be mixed and used by adjusting the Hansen solubility parameter.

The boiling point of solvent B is 220° C. or higher and 350° C. or lower, preferably 240° C. or higher and 320° C. or lower, and more preferably 250° C. or higher and 300° C. or lower. When two or more solvents are used in combination, the boiling point is the boiling point of the mixed solvent.
When the boiling point of the solvent B is within the above range, the generation of voids in the material obtained by sintering the paste-like resin composition can be suppressed.

From the viewpoint of the effects of the present invention, the proportion of solvent B in the entire paste-like resin composition is, for example, 1 to 20 mass %, preferably 1.5 to 15 mass %, and more preferably 2 to 10 mass %.

[Thermosetting resin C]
The paste-like resin composition of the present embodiment may further contain a thermosetting resin C.

The thermosetting resin C usually contains a group that polymerizes/crosslinks when acted upon by an active chemical species such as a radical, and/or a chemical structure that reacts with a curing agent D described below. The thermosetting resin C contains, for example, one or more of an epoxy group, an oxetanyl group, a group containing an ethylenic carbon-carbon double bond, a hydroxy group, an isocyanate group, a maleimide structure, and the like.
As the thermosetting resin C, preferably, an epoxy resin can be used.
The epoxy resin may be a compound having only one epoxy group in one molecule, or may be a compound having two or more epoxy groups in one molecule.

Epoxy resins include, for example, bifunctional or crystalline epoxy resins such as biphenyl type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, stilbene type epoxy resins, and hydroquinone type epoxy resins; novolac type epoxy resins such as cresol novolac type epoxy resins, phenol novolac type epoxy resins, and naphthol novolac type epoxy resins; phenol aralkyl type epoxy resins such as phenylene skeleton-containing phenol aralkyl type epoxy resins, biphenylene skeleton-containing phenol aralkyl type epoxy resins, and phenylene skeleton-containing naphthol aralkyl type epoxy resins; trifunctional type epoxy resins such as triphenol methane type epoxy resins and alkyl-modified triphenol methane type epoxy resins; modified phenol type epoxy resins such as dicyclopentadiene-modified phenol type epoxy resins and terpene-modified phenol type epoxy resins; heterocyclic ring-containing epoxy resins such as triazine nucleus-containing epoxy resins, etc.

Furthermore, the epoxy group-containing compound may also include monofunctional epoxy group-containing compounds such as 4-tert-butylphenyl glycidyl ether, m,p-cresyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether.
The paste-like resin composition of the present embodiment may contain only one type of thermosetting component, or may contain two or more types of thermosetting components.

In this embodiment, it is also preferable to use a combination of thermosetting resin C and a (meth)acryloyl group-containing compound. When these are used in combination, the ratio (mass ratio) is not particularly limited, but for example, thermosetting resin C/(meth)acryloyl group-containing compound=95/5 to 50/50, preferably thermosetting resin C/((meth)acryloyl group-containing compound=90/10 to 60/40.

Examples of (meth)acrylic group-containing compounds include diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol #200 di(meth)acrylate (n:4), polyethylene glycol #400 di(meth)acrylate (n:9), polyethylene glycol #600 di(meth)acrylate (n:14), polyethylene glycol #1000 di(meth)acrylate (n:23), etc.

An epoxy resin is preferable as the thermosetting resin C. Preferred examples of the epoxy resin include bisphenol A type epoxy resin and bisphenol F type epoxy resin.
The amount of the thermosetting resin C in the paste-like resin composition of this embodiment is, for example, 3 to 20 mass %, preferably 5 to 15 mass %, of the total non-volatile components.

[Curing agent D]
The paste-like resin composition of the present embodiment may further contain a curing agent D.

The curing agent D may be one having a reactive group that reacts with the thermosetting resin C. The curing agent D may include, for example, a reactive group that reacts with a functional group, such as an epoxy group, a maleimide group, or a hydroxyl group, contained in the thermosetting resin C.

The hardener D preferably comprises a phenolic hardener and/or an imidazole hardener, which are particularly preferred when the thermosetting component comprises epoxy groups.
The phenolic curing agent may be a low molecular weight compound or a high molecular weight compound (i.e., a phenolic resin).

Examples of phenol-based hardeners, which are low molecular weight compounds, include bisphenol compounds (phenolic resins having a bisphenol F skeleton) such as bisphenol A and bisphenol F (dihydroxydiphenylmethane); compounds having a biphenylene skeleton such as 4,4'-biphenol; etc.

Specific examples of the phenol resin include novolac-type phenol resins such as phenol novolac resin, cresol novolac resin, bisphenol novolac resin, and phenol-biphenyl novolac resin; polyvinylphenol; multifunctional phenol resins such as triphenylmethane-type phenol resin; modified phenol resins such as terpene-modified phenol resin and dicyclopentadiene-modified phenol resin; and phenol aralkyl-type phenol resins such as phenol aralkyl resins having a phenylene skeleton and/or biphenylene skeleton and naphthol aralkyl resins having a phenylene and/or biphenylene skeleton.
When the curing agent D is used, only one type may be used, or two or more types may be used in combination.

When the paste-like resin composition of this embodiment contains the curing agent D, the amount of the curing agent D is, for example, 30 to 300 parts by mass, preferably 50 to 200 parts by mass, per 100 parts by mass of the thermosetting resin C.

(Cure Accelerator)
The paste-like resin composition of the present embodiment may further contain a curing accelerator.
The curing accelerator typically accelerates the reaction between the thermosetting resin C and the curing agent D.

Specific examples of the curing accelerator include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, and adducts of phosphonium compounds and silane compounds; amidines and tertiary amines such as dicyandiamide, 1,8-diazabicyclo[5.4.0]undecene-7, and benzyldimethylamine; and nitrogen atom-containing compounds such as quaternary ammonium salts of the above amidines or the above tertiary amines.
When a curing accelerator is used, only one type may be used, or two or more types may be used in combination.

When the paste-like resin composition of this embodiment contains a curing accelerator, the amount of the curing accelerator is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the thermosetting resin C.

(Silane coupling agent)
The paste-like resin composition of the present embodiment may further contain a silane coupling agent, which can further improve the adhesive strength.

Examples of the silane coupling agent include known silane coupling agents, specifically, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane;
Epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane;
Styrylsilanes such as p-styryltrimethoxysilane;
Methacrylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane;
Acrylsilanes such as 3-(trimethoxysilyl)propyl methacrylate and 3-acryloxypropyltrimethoxysilane;
Aminosilanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, and N-phenyl-γ-aminopropyltrimethoxysilane;
Isocyanurate silane;
Alkylsilane;
Ureidosilanes such as 3-ureidopropyltrialkoxysilane;
Mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
Examples include isocyanate silanes such as 3-isocyanate propyl triethoxy silane.
When a silane coupling agent is used, only one type may be used, or two or more types may be used in combination.

When the paste-like resin composition of this embodiment contains a silane coupling agent, the amount of the silane coupling agent is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, when the amount of the thermosetting component (the total amount of the (meth)acrylic group-containing compound (A) and the thermosetting resin C) is taken as 100 parts by mass.

(Plasticizer)
The paste-like resin composition of the present embodiment may contain a plasticizer. The use of a plasticizer makes it easier to design the storage modulus to be smaller. In addition, it becomes easier to prevent the adhesive strength from decreasing due to heat cycles.

Specific examples of the plasticizer include polyester compounds, silicone compounds such as silicone oil and silicone rubber, polybutadiene compounds such as polybutadiene maleic anhydride adducts, and acrylonitrile butadiene copolymer compounds.
When a plasticizer is used, only one type may be used, or two or more types may be used in combination.

When the paste-like resin composition of this embodiment contains a plasticizer, the amount of the plasticizer is, for example, 5 to 50 parts by mass, preferably 10 to 30 parts by mass, when the amount of the thermosetting component (the total amount of the (meth)acrylic group-containing compound (A) and the thermosetting resin C) is taken as 100 parts by mass.

(Radical initiator)
The paste-like resin composition of the present embodiment may contain a radical initiator.
The use of a radical initiator can, for example, prevent insufficient curing, allow the curing reaction to proceed sufficiently at a relatively low temperature (e.g., 180° C.), and further improve adhesive strength.
The radical initiator may include peroxides, azo compounds, and the like.

Examples of the peroxide include organic peroxides such as diacyl peroxides, dialkyl peroxides, and peroxyketals. More specifically, examples of the peroxides include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; peroxyketals such as 1,1-di(t-butylperoxy)cyclohexane and 2,2-di(4,4-di(t-butylperoxy)cyclohexyl)propane;
Hydroperoxides such as p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, and t-butyl hydroperoxide;
Dialkyl peroxides such as di(2-t-butylperoxyisopropyl)benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-hexyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, and di-t-butyl peroxide;
Diacyl peroxides such as dibenzoyl peroxide and di(4-methylbenzoyl) peroxide;
Peroxydicarbonates such as di-n-propyl peroxydicarbonate and diisopropyl peroxydicarbonate;
Examples of the peroxyester include 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate, and t-butylperoxy 2-ethylhexanoate.

Examples of the azo compound include 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), and 2,2'-azobis(2,4-dimethylvaleronitrile).
When a radical initiator is used, only one type may be used, or two or more types may be used in combination.

When the paste-like resin composition of this embodiment contains a radical initiator, the amount of the radical initiator is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of the thermosetting component.

(Properties of the composition)
The paste-like resin composition of the present embodiment is preferably in a paste form at 20° C. That is, the paste-like resin composition of the present embodiment can be applied to a substrate or the like, preferably at 20° C. This allows the paste-like resin composition of the present embodiment to be preferably used as an adhesive for semiconductor elements, or the like.
Of course, depending on the process to be applied, the paste-like resin composition of the present embodiment may be in the form of a varnish having a relatively low viscosity.

<Method of producing paste-like resin composition>
The method for producing a paste-like resin composition of the present embodiment includes the steps of:
measuring the Hansen solubility parameter a of the silver-containing particles A and the Hansen solubility parameter b of the solvent by the above-mentioned method;
A step of selecting a solvent B such that the difference between the Hansen solubility parameter b and the Hansen solubility parameter a is 4.3 or more and 9.8 or less;
The method includes a step of mixing silver-containing particles A, a selected solvent B, a thermosetting resin C, and, if necessary, other components, by a conventionally known method.

<Highly thermal conductive materials>
A highly thermally conductive material can be obtained by sintering the paste-like resin composition of this embodiment.
By changing the shape of the highly thermally conductive material, it can be applied to a variety of parts that require heat dissipation in the automotive and electrical fields.

<Semiconductor Device>
A semiconductor device can be manufactured using the paste resin composition of the present embodiment. For example, a semiconductor device can be manufactured by using the paste resin composition of the present embodiment as an "adhesive" between a substrate and a semiconductor element.

In other words, the semiconductor device of this embodiment includes, for example, a substrate and a semiconductor element mounted on the substrate via an adhesive layer obtained by sintering the above-mentioned paste-like resin composition through a heat treatment.
In the semiconductor device of this embodiment, the adhesiveness of the adhesive layer is not easily deteriorated even by heat cycles, which means that the reliability of the semiconductor device of this embodiment is high.
Examples of semiconductor elements include ICs, LSIs, power semiconductor elements (power semiconductors), and various other elements.
Examples of the substrate include various semiconductor wafers, lead frames, BGA substrates, mounting substrates, heat spreaders, heat sinks, and the like.

An example of a semiconductor device will be described below with reference to the drawings.
FIG. 1 is a cross-sectional view showing an example of a semiconductor device.
The semiconductor device 100 includes a substrate 30 and a semiconductor element 20 mounted on the substrate 30 via an adhesive layer 10 (die attach material) that is a heat-treated paste resin composition.

The semiconductor element 20 and the substrate 30 are electrically connected, for example, via bonding wires 40. The semiconductor element 20 is also sealed, for example, with sealing resin 50.

The thickness of the adhesive layer 10 is preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 20 μm or more, so that the stress absorption ability of the paste-like resin composition can be improved, and the heat cycle resistance can be improved.
The thickness of the adhesive layer 10 is, for example, 100 μm or less, and preferably 50 μm or less.

In FIG. 1, the substrate 30 is, for example, a lead frame. In this case, the semiconductor element 20 is mounted on the die pad 32 or the substrate 30 via an adhesive layer 10. The semiconductor element 20 is also electrically connected to the outer lead 34 (substrate 30) via, for example, a bonding wire 40. The substrate 30, which is a lead frame, is made of, for example, a 42 alloy, a Cu frame, etc.

The substrate 30 may be an organic substrate or a ceramic substrate. Examples of the organic substrate include those made of epoxy resin, cyanate resin, maleimide resin, and the like.
The surface of the substrate 30 may be coated with a metal such as silver or gold, for example, to improve the adhesion between the adhesive layer 10 and the substrate 30.

FIG. 2 is a cross-sectional view showing an example of a semiconductor device 100 different from that shown in FIG.
2, the substrate 30 is, for example, an interposer. A plurality of solder balls 52, for example, are formed on the surface of the substrate 30, which is an interposer, opposite to the surface on which the semiconductor element 20 is mounted. In this case, the semiconductor device 100 is connected to another wiring board via the solder balls 52.

An example of a method for manufacturing a semiconductor device will be described.
First, the paste-like resin composition is applied onto the substrate 30, and then the semiconductor element 20 is disposed thereon. That is, the substrate 30, the paste-like resin composition, and the semiconductor element 20 are laminated in this order.
The method for applying the paste-like resin composition is not particularly limited, and specific examples thereof include dispensing, printing, and ink-jet methods.

The paste-like resin composition is then thermally cured. The thermal curing is preferably performed by pre-curing and post-curing. The paste-like resin composition is made into a heat-treated body (cured product) by thermal curing. The metal-containing particles in the paste-like resin composition are aggregated by thermal curing (heat treatment), and a structure in which the interfaces between multiple metal-containing particles disappear is formed in the adhesive layer 10. This bonds the substrate 30 and the semiconductor element 20 via the adhesive layer 10. Next, the semiconductor element 20 and the substrate 30 are electrically connected using a bonding wire 40. Next, the semiconductor element 20 is sealed with a sealing resin 50. In this manner, a semiconductor device can be manufactured.

The above describes the embodiments of the present invention, but these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements that can achieve the object of the present invention are included in the present invention.

The embodiments of the present invention will be described in detail based on examples and comparative examples. The present invention is not limited to the examples.

<ΔHSP of solvent for silver-containing particles>
The following silver-containing particles and solvents were used, and the ΔHSP of the solvent relative to the silver-containing particles was adjusted to five levels.
(Silver-containing particles)
Silver filler 1: Fukuda Metal Foil and Powder Co., Ltd., HKD-12, median diameter D ₅₀ : 7.6 μm , flake-like Silver filler 2: Dowa Electronics Co., Ltd., AG-DSB-114, spherical, D ₅₀ : 0.7 μm
(solvent)
Solvent 1: Tripropylene glycol mono-n-butyl ether (BFTG, Nippon Nyukazai Co., Ltd., boiling point 274°C)
Solvent 2: Propylene carbonate (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 242°C)
Solvent 3: Dimethyl sulfoxide (DMSO, manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 189°C)
Solvent 4: Benzyl benzoate (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 324° C.)
Solvent 5: Diacetone alcohol (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 168° C.)
Solvent 6: Triethylene glycol dimethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd., boiling point 216° C.)

First, the Hansen solubility parameters a of the silver-containing particles (silver filler 1, silver filler 2) were measured by the following method.
[method]
2 mL of any solvent selected from the evaluation solvents listed below is added to 0.2 g of silver-containing particles in a 10 mL glass container, and the mixture is stirred for 5 seconds with a vortex mixer, after which the dispersibility is visually evaluated according to the following four-point scale: All evaluation solvents and the evaluation results of dispersibility for each solvent are input into the Sphere program of the computer software HSPiP (version 5.2.02), and the Hansen solubility parameter is calculated.
(Solvent for evaluation)
Water, methanol, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, acetonitrile, ethyl acetate, methyl ethyl ketone, 1-butanol, cyclohexanol, isopropyl alcohol (Evaluation)
0: Does not disperse.
1: Settling is complete in less than 10 minutes.
2: Settling is complete after 10 minutes or more but less than 1 hour.
3: Settling is complete after 1 hour or more and 12 hours or less.

As a result of the measurement, the dispersion term (δD) of the Hansen solubility parameters of silver filler 1 (HKD-12, scaly) was 15.9 MPa ^1/2 , the polarization term (δP) was 8.9 MPa ^1/2 , and the hydrogen bond term (δH) was 9.1 MPa ^1/2 .
The dispersion term (δD) of the Hansen solubility parameters of silver filler 2 (AG-DSB-114, spherical) was 15.7 MPa ^1/2 , the polarization term (δP) was 8.1 MPa ^1/2 , and the hydrogen bond term (δH) was 10.1 MPa ^1/2 .

The Hansen solubility parameters of the solvents were obtained from the database of the computer software HSPiP or by inputting the molecular structure into the DIY program of the computer software HSPiP. For the mixed solvents, the solubility parameters were calculated using the following formula:
In the following formula, the volume ratio of solvent 1 is represented by a, the Hansen solubility parameters are represented by the dispersion term (δD1), polarization term (δP1), and hydrogen bond term (δH1), the volume ratio of solvent 2 is represented by b, and the Hansen solubility parameters are represented by the dispersion term (δD2), polarization term (δP2), and hydrogen bond term (δH2).

The Hansen solubility parameters b of the solvents of Reference Examples 1 to 9 (solvents 1 to 6, or mixed solvents of solvent 1 and solvent 2) measured by changing the mixing ratio of the solvents as shown in Table 1 are shown below.
Reference Example 1: Dispersion term (δD) is 16.1 MPa ^1/2 , polarization term (δP) is 5.2 MPa ^1/2 , hydrogen bond term (δH) is 7.4 MPa ^1/2
Reference Example 2: Dispersion term (δD) is 17.9 MPa ^1/2 , polarization term (δP) is 11.1 MPa ^1/2 , hydrogen bond term (δH) is 5.9 MPa ^1/2
Reference Example 3: Dispersion term (δD) is 18.6 MPa ^1/2 , polarization term (δP) is 13.5 MPa ^1/2 , hydrogen bond term (δH) is 5.26 MPa ^1/2
Reference Example 4: Dispersion term (δD) is 19.3 MPa ^1/2 , polarization term (δP) is 15.8 MPa ^1/2 , hydrogen bond term (δH) is 4.7 MPa ^1/2
Reference Example 5: Dispersion term (δD) is 20.0 MPa ^1/2 , polarization term (δP) is 18.0 MPa ^1/2 , and hydrogen bond term (δH) is 4.1 MPa ^1/2
Reference Example 6: Dispersion term (δD) is 18.4 MPa ^1/2 , polarization term (δP) is 16.4 MPa ^1/2 , hydrogen bond term (δH) is 10.2 MPa ^1/2
Reference Example 7: Dispersion term (δD) is 20.0 MPa ^1/2 , polarization term (δP) is 5.1 MPa ^1/2 , and hydrogen bond term (δH) is 5.2 MPa ^1/2
Reference Example 8: Dispersion term (δD) is 15.8 MPa ^1/2 , polarization term (δP) is 8.2 MPa ^1/2 , and hydrogen bond term (δH) is 10.8 MPa ^1/2
Reference Example 9: Dispersion term (δD) is 16.1 MPa ^1/2 , polarization term (δP) is 5.8 MPa ^1/2 , and hydrogen bond term (δH) is 6.8 MPa ^1/2

The difference between the Hansen solubility parameter a of the silver-containing particles and the Hansen solubility parameter b of the solvents in Reference Examples 1 to 9 is shown in Table 1.

<Preparation of Paste-like Resin Composition>
[Examples 1 to 2, Comparative Examples 1 to 7]
First, the raw material components were mixed in the amounts shown in Table 2 to obtain a varnish.
Next, the obtained varnish, the solvent having the mixing ratio shown in Table 1, and the silver-containing particles were mixed according to the mixing amounts shown in Table 2, and kneaded at room temperature with a three-roll mill. In this way, a paste-like resin composition was prepared. The silver-containing particles and the solvent used were the same as those described above.

The information on the raw material components in Table 2 is shown below.
(Thermosetting component)
Epoxy resin 1: Bisphenol F type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., RE-303S)
Acrylic monomer 1: Ethylene glycol dimethacrylate (Kyoeisha Chemical Co., Ltd., Light Ester EG)

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

(Cure Accelerator)
Radical polymerization initiator: dicumyl peroxide (Perkadox BC, manufactured by Kayaku Akzo Co., Ltd.)
Imidazole catalyst: 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by Shikoku Chemical Industry Co., Ltd., 2PHZ-PW)

<Measurement of Electrical Resistivity>
The obtained paste-like resin composition was applied onto a glass plate, and the temperature was raised from 30° C. to 200° C. over 60 minutes in a nitrogen atmosphere, followed by heat treatment at 200° C. for 120 minutes. This resulted in a heat-treated paste-like resin composition having a thickness of 0.05 mm. The resistance value of the surface of the heat-treated product was measured using a direct current four-electrode method with a milliohmmeter (manufactured by HIOKI Corporation) with electrodes spaced 40 mm apart.

The results in Table 2 reveal that a material with excellent electrical conductivity can be obtained by having the difference between the Hansen solubility parameter a of the silver-containing particles and the Hansen solubility parameter b of the solvent be 4.3 or more and 9.8 or less.

Reference Signs List 100 Semiconductor device 10 Adhesive layer 20 Semiconductor element 30 Base material 32 Die pad 34 Outer lead 40 Bonding wire 50 Sealing resin 52 Solder ball

Claims (13)

Silver-containing particles A;
Solvent B;
A thermosetting resin C;
Including,
the silver-containing particles A are at least one type selected from the group consisting of silver particles and silver-coated resin particles,
The solvent B is one solvent selected from the group consisting of tripropylene glycol mono-n-butyl ether, dimethyl sulfoxide, benzyl benzoate, diacetone alcohol, triethylene glycol dimethyl ether, γ-butyrolactone, isobornylcyclohexanol, terpineol, isobornylcyclohexanol, and diethylene glycol;
A paste-like resin composition, wherein a difference between a Hansen solubility parameter a of the silver-containing particles A and a Hansen solubility parameter b of the solvent B, as measured by the following method, is 4.3 MPa ^1/2 or more and 9.8 MPa ^1/2 or less.
[method]
2 mL of any solvent selected from the evaluation solvents listed below is added to 0.2 g of silver-containing particles A in a 10 mL glass container, and the mixture is stirred for 5 seconds with a vortex mixer, after which the dispersibility is visually evaluated according to the following four-point scale: All evaluation solvents and the evaluation results of dispersibility for each solvent are input into the Sphere program of computer software HSPiP (version 5.2.02), and the Hansen solubility parameter is calculated.
(Solvent for evaluation)
Water, methanol, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, acetonitrile, ethyl acetate, methyl ethyl ketone, 1-butanol, cyclohexanol, isopropyl alcohol (Evaluation)
0: Does not disperse.
1: Settling is complete in less than 10 minutes.
2: Settling is complete after 10 minutes or more but less than 1 hour.
3: Settling is complete after 1 hour or more and 12 hours or less. Silver-containing particles A;
Solvent B;
A thermosetting resin C;
Including,
the silver-containing particles A are at least one type selected from the group consisting of silver particles and silver-coated resin particles,
The solvent B is composed of two or more solvents selected from the group consisting of tripropylene glycol mono-n-butyl ether, propylene carbonate, diacetone alcohol, triethylene glycol dimethyl ether, dimethyl sulfoxide, benzyl benzoate, ethylene glycol, diethylene glycol, γ-butyrolactone, carbitol, n-dodecane, isobornylcyclohexanol, terpineol, propylene glycol phenyl ether, ethylene glycol mono-2-ethylhexyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, δ-valerolactone, butyl carbitol, phenoxypropanol, diethylene glycol monobutyl ether acetate, ethylene glycol mono-n-butyl ether acetate, dimethyl isosorbide, isophorone, hexylene glycol, butyl benzoate, 2-phenoxyethanol, benzyl alcohol, dihydrolevoglucosenone, dipropylene glycol, and caprolactone;
A paste-like resin composition, wherein a difference between a Hansen solubility parameter a of the silver-containing particles A and a Hansen solubility parameter b of the solvent B, as measured by the following method, is 4.3 MPa ^1/2 or more and 9.8 MPa ^1/2 or less.
[method]
2 mL of any solvent selected from the evaluation solvents listed below is added to 0.2 g of silver-containing particles A in a 10 mL glass container, and the mixture is stirred for 5 seconds with a vortex mixer, after which the dispersibility is visually evaluated according to the following four-point scale: All evaluation solvents and the evaluation results of dispersibility for each solvent are input into the Sphere program of computer software HSPiP (version 5.2.02), and the Hansen solubility parameter is calculated.
(Solvent for evaluation)
Water, methanol, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, acetonitrile, ethyl acetate, methyl ethyl ketone, 1-butanol, cyclohexanol, isopropyl alcohol (Evaluation)
0: Does not disperse.
1: Settling is complete in less than 10 minutes.
2: Settling is complete after 10 minutes or more but less than 1 hour.
3: Settling is complete after 1 hour or more and 12 hours or less. 3. The paste-like resin composition according to claim 1 , wherein the silver-containing particles A include two or more types selected from the group consisting of spherical, scaly, aggregated, and polyhedral silver-containing particles. 4. The paste-like resin composition according to claim 1 , wherein the boiling point of the solvent B is 220° C. or higher and 350° C. or lower. The paste-like resin composition according to any one of claims 1 to 4 , wherein the thermosetting resin C includes an epoxy resin. The paste-like resin composition according to any one of claims 1 to 5 , further comprising a curing agent D. A highly thermally conductive material obtained by sintering the paste-like resin composition according to any one of claims 1 to 6 . A substrate;
A semiconductor element mounted on the base material via an adhesive layer,
The adhesive layer is formed by sintering the paste-like resin composition according to any one of claims 1 to 6. A semiconductor device. measuring the Hansen solubility parameter a of the silver-containing particles A and the Hansen solubility parameter b of the solvent by the following method;
Selecting a solvent B having a difference in Hansen solubility parameter b relative to the Hansen solubility parameter a of 4.3 MPa ^1/2 or more and 9.8 MPa ^1/2 or less;
mixing the silver-containing particles A, the selected solvent B, and a thermosetting resin C;
Including ,
the silver-containing particles A are at least one type selected from the group consisting of silver particles and silver-coated resin particles,
The solvent B is one solvent selected from the group consisting of tripropylene glycol mono-n-butyl ether, dimethyl sulfoxide, benzyl benzoate, diacetone alcohol, triethylene glycol dimethyl ether, γ-butyrolactone, isobornylcyclohexanol, terpineol, isobornylcyclohexanol, and diethylene glycol.
[method]
2 mL of any solvent selected from the evaluation solvents listed below is added to 0.2 g of silver-containing particles A in a 10 mL glass container, and the mixture is stirred for 5 seconds with a vortex mixer, after which the dispersibility is visually evaluated according to the following four-point scale: All evaluation solvents and the evaluation results of dispersibility for each solvent are input into the Sphere program of computer software HSPiP (version 5.2.02), and the Hansen solubility parameter is calculated.
(Solvent for evaluation)
Water, methanol, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, acetonitrile, ethyl acetate, methyl ethyl ketone, 1-butanol, cyclohexanol, isopropyl alcohol (Evaluation)
0: Does not disperse.
1: Settling is complete in less than 10 minutes.
2: Settling is complete after 10 minutes or more but less than 1 hour.
3: Settling is complete after 1 hour or more and 12 hours or less. measuring the Hansen solubility parameter a of the silver-containing particles A and the Hansen solubility parameter b of the solvent by the following method;
Selecting a solvent B having a difference in Hansen solubility parameter b relative to the Hansen solubility parameter a of 4.3 MPa ^1/2 or more and 9.8 MPa ^1/2 or less;
mixing the silver-containing particles A, the selected solvent B, and a thermosetting resin C;
Including ,
the silver-containing particles A are at least one type selected from the group consisting of silver particles and silver-coated resin particles,
The solvent B is tripropylene glycol mono-n-butyl ether, propylene carbonate, diacetone alcohol, triethylene glycol dimethyl ether, dimethyl sulfoxide, benzyl benzoate, ethylene glycol, diethylene glycol, γ-butyrolactone, carbitol, n-dodecane, isobornylcyclohexanol, terpineol, propylene glycol phenyl ether, ethylene glycol mono-2-ethylhexyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, δ-valerolactone, butyl carbitol, phenoxypropanol, diethylene glycol monobutyl ether acetate, ethylene glycol mono-n-butyl ether acetate, dimethyl isosorbide, isophorone, hexylene glycol, butyl benzoate, 2-phenoxyethanol, benzyl alcohol, dihydrolevoglucosenone, dipropylene glycol, and caprolactone. A method for producing a paste-like resin composition comprising two or more solvents selected from the group consisting of caprolactone .
[method]
2 mL of any solvent selected from the evaluation solvents listed below is added to 0.2 g of silver-containing particles A in a 10 mL glass container, and the mixture is stirred for 5 seconds with a vortex mixer, after which the dispersibility is visually evaluated according to the following four-point scale: All evaluation solvents and the evaluation results of dispersibility for each solvent are input into the Sphere program of computer software HSPiP (version 5.2.02), and the Hansen solubility parameter is calculated.
(Solvent for evaluation)
Water, methanol, toluene, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, acetone, acetonitrile, ethyl acetate, methyl ethyl ketone, 1-butanol, cyclohexanol, isopropyl alcohol (Evaluation)
0: Does not disperse.
1: Settling is complete in less than 10 minutes.
2: Settling is complete after 10 minutes or more but less than 1 hour.
3: Settling is complete after 1 hour or more and 12 hours or less. The method for producing a paste-like resin composition according to claim 9 or 10 , wherein the boiling point of the solvent B is 220° C. or higher and 350° C. or lower. The method for producing a paste- like resin composition according to claim 9 , wherein the thermosetting resin C includes an epoxy resin. The method for producing a paste-like resin composition according to claim 9 , further comprising the step of mixing a curing agent D in the mixing step.

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