JP2022018051A - Pasty resin composition, high heat-conductive material, and semiconductor device - Google Patents

Abstract

To provide a pasty resin composition which enables production of a material having improved electric conductivity.SOLUTION: A pasty resin composition contains silver-containing particles A, a solvent B and a thermosetting resin C, in which a difference between a Hansen solubility parameter a of the silver-containing particles A and a Hansen solubility parameter b of the solvent B, which are measured by the following method, is 4.3 or more and 9.8 or less. [Method] A method visually evaluates dispersibility after having added 2 mL of any solvent selected from solvents for evaluation such as water, methanol, toluene and propylene glycol monomethyl ether to 0.2 g of the silver-containing particles A, into a 10 ml volume glass container, and stirred the mixture by a vortex mixer for 5 seconds, in four grades. The method inputs the solvent for evaluation and the evaluation result of the dispersibility to the solvent using computer software, and calculates the Hansen solubility parameter.SELECTED DRAWING: None

Description

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

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

As a specific example of application to a semiconductor device, as in Patent Documents 1 and 2 below, a thermosetting resin composition containing metal particles is used to bond / bond a semiconductor element and a substrate (support member). The technology is known.

Patent Document 1 describes a thermosetting resin composition for semiconductor adhesion, which comprises a (meth) acrylic acid ester compound having a predetermined structure, a radical initiator, silver fine particles, silver powder, and a solvent. A semiconductor device to which is bonded is disclosed. The document states that connection reliability for post-mounting temperature cycles 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 base material are bonded to each other in the composition. The document describes 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 describes a semiconductor having a structure in which a semiconductor element and a support member for mounting a semiconductor element are bonded to each other through a silver paste composition composed of silver particles satisfying predetermined physical property values, a solvent and an additive, and the composition. The device is disclosed. This document describes an example in which dipropylene glycol methyl ether acetate and isobonylcyclohexanol are used as a solvent.

Japanese Unexamined Patent Publication No. 2014-74132 Japanese Unexamined Patent Publication No. 2000-239616 Japanese Unexamined Patent Publication No. 2014-225350

However, in the resin compositions described in Patent Documents 1 to 3, the semiconductor device in which the semiconductor element and the base material are bonded has room for improvement in electrical conductivity.

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

That is, the present invention can be shown below.
According to the present invention
Contains silver-containing particles A, solvent B, and thermosetting resin C.
Provided is a paste-like resin composition in which the difference between the Hansen solubility parameter a of the silver-containing particles A measured by the following method and the Hansen solubility parameter b of the solvent B is 4.3 or more and 9.8 or less.
[Method]
To 0.2 g of silver-containing particles A, add 2 mL of any solvent selected from the following evaluation solvents to a 10 ml glass container, and visually check the dispersibility after stirring with a Voltex mixer for 5 seconds. The evaluation is made in the following four stages. The evaluation solvent and the evaluation result of the dispersibility in the solvent are input to 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: Not dispersed.
Sedimentation is completed in less than 1:10 minutes.
The sedimentation is completed after 2:10 minutes or more and less than 1 hour.
3: The sedimentation is completed after 1 hour or more and 12 hours or less.

According to the present invention
A high thermal conductive material obtained by sintering the paste-like resin composition is provided.

According to the present invention
With the base material
A semiconductor element mounted on the base material via an adhesive layer is provided.
A semiconductor device is provided in which the adhesive layer is obtained by sintering the paste-like resin composition.

According to the present invention
The Hansen solubility parameter a of the silver-containing particles A measured by the above method, the step of measuring the Hansen solubility parameter of the solvent, and the process.
The step of selecting the solvent B in which the difference between the Hansen solubility parameter a and the Hansen solubility parameter a is 4.3 or more and 9.8 or less is selected.
A step of mixing the silver-containing particles A, the selected solvent B, and the thermosetting resin C,
A method for producing a paste-like resin composition comprising the above is provided.

According to the present invention
The step of measuring the Hansen solubility parameter of the metal particles measured by the above method, the Hansen solubility parameter of the solvent, and the process.
A step of selecting the metal particles and / or the solvent so 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.
A step of mixing the selected metal particles, the selected solvent, and a thermosetting resin.
A method for producing a resin composition including the above is provided.

According to the present invention, it is possible to provide a paste-like resin composition capable of obtaining a material having improved electrical conductivity.

It is sectional drawing which shows an example of the semiconductor device schematically. It is sectional drawing which shows an example of the semiconductor device schematically.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all drawings, similar components are designated by the same reference numerals, and the description thereof will be omitted as appropriate. In addition, "-" represents "greater than or equal to" to "less than or equal to" unless otherwise specified.

<Paste-like resin composition>
The paste-like resin composition of the present embodiment contains silver-containing particles A, a solvent B, a thermosetting resin C, and the like.
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 measured by the following method is 4.3 or more and 9.8 or less.
[Method]
To 0.2 g of silver-containing particles A, add 2 mL of any solvent selected from the following evaluation solvents to a 10 ml glass container, and visually check the dispersibility after stirring with a Voltex mixer for 5 seconds. The evaluation is made in the following four stages. The Hansen solubility parameter is calculated by inputting all the evaluation solvents and the evaluation results of the dispersibility in the solvent into the Sphere program of the computer software HSPiP (version 5.2.02).
(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: Not dispersed.
Sedimentation is completed in less than 1:10 minutes.
The sedimentation is completed after 2:10 minutes or more and less than 1 hour.
3: The sedimentation is completed after 1 hour or more and 12 hours or less.

Visually, "precipitation is completed" means that the glass container containing the evaluation solvent in which the silver-containing particles A are dispersed is observed directly under a 32 W fluorescent lamp, and the silver dispersed in the evaluation solvent is observed. It means that the contained particles A cannot be visually confirmed.

As described above, when the difference between the parameter a and the parameter b is within a predetermined value range, the balance between the dispersion and aggregation of the silver-containing particles A in the paste-like resin composition is optimized, and the silver-containing particles A come into contact with each other. Since the rate is improved, it is considered that it is possible to provide a material in which a network is formed after sintering and the thermal conductivity and the electric conductivity are improved.

From the viewpoint of the effect 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 is preferably 5.0 or more and 9.0 or less, more preferably 5.5 or more and 9. It can be less than or equal to 0.0.

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 term (δH) is 8.0 MPa ^1/2 or more and 11.0 MPa ^1/2 or less, 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 term (δH) is 4.0 MPa ^1/2 or more and 15.5 MPa ^1/2 or less, preferably 4.0 MPa ^1/2 or more and 8.0 MPa ^1/2 or less.
Within the above range, the compatibility with the silver-containing particles A is appropriate, and the solubility in the thermosetting resin C is also excellent.

The Hansen solubility parameter (HSP) is an index of the solubility of a substance in another substance. HSP represents solubility as a three-dimensional vector. This three-dimensional vector can be typically represented by a dispersion term (δD), a polarization term (δP), and a hydrogen bond term (δH). Then, it can be judged that substances having similar vectors have high solubility. It is possible to judge the similarity of the vector by the distance of the Hansen solubility parameter (ΔHSP represented by the following equation).
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 by the dispersion term (δD2) and polarization. It is expressed using the term (δP2) and the hydrogen bond term (δH2). It is judged that the smaller ΔHSP, the better the compatibility between the two substances.

This embodiment was completed by paying attention to the relationship between the Hansen solubility parameter calculated from the evaluation of the dispersibility of the insoluble silver-containing particles A in the evaluation solvent and the Hansen solubility parameter of the solvent B. That is, if the difference in these Hansen solubility parameters (ΔHSP) is within a predetermined range, the balance between the 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 optimized. It was completed by finding that a network is formed after sintering and the 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, version 5.2.02 of the Sphere program is used as the computer software HSPiP.
Here, the computer software HSPiP developed by Hansen and Abbott includes a function for calculating the HSP distance and a database describing the Hansen parameter of solvent or non-solvent. The Hansen solubility parameter (HSP) b of the solvent B can be estimated from the database or by inputting the molecular structure into the DIY (Do It Yourself) program of the computer software HSPiP in SMILE notation.

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

In particular, the paste-like resin composition contains silver-containing particles, and in particular, silver particles having a relatively small particle size and a relatively large specific surface area are contained, so that the paste-like resin composition contains silver particles at a relatively low temperature (about 180 ° C.). A sintered structure is likely to be formed even by heat treatment. The preferred particle size will be described later.

The shape of the silver-containing particles A is not particularly limited. The preferred shape is spherical, but may be non-spherical, such as ellipsoidal, flat, plate, flake, needle-like, scaly, agglomerated, and polyhedral. The silver-containing particles A can contain at least one kind of silver-containing particles having these shapes.
In the present embodiment, it is preferable to include two or more kinds selected from spherical, scaly, aggregated, and polyhedrally shaped silver-containing particles, and the spherical silver-containing particles a1 and scaly, aggregated, and polyhedral particles. It is more preferable to contain one or more kinds of silver-containing particles a2 selected from the shape. As a result, the contact rate between the silver-containing particles is further improved, so that a network is easily formed after sintering of the paste-like resin composition, and the thermal conductivity and the electric conductivity are further improved.
When the silver-containing particles A contain the silver-containing particles a2, it is possible to suppress resin cracks in the molded product obtained from the paste-like resin composition and suppress the linear expansion coefficient.

In the present embodiment, the "spherical shape" is not limited to a perfect true sphere, but also includes a shape having some irregularities on the surface.
The surface of the silver-containing particles A may be treated with a carboxylic acid, a saturated fatty acid having 4 to 30 carbon atoms, an unsaturated fatty acid having 4 to 30 monovalent carbon atoms, a long-chain alkylnitrile or the like.

The silver-containing particles A may be (i) particles substantially composed of only silver, or (ii) particles composed of silver and components other than silver. Further, (i) and (ii) may be used in combination as the metal-containing particles.

In the present embodiment, the silver-containing particles A particularly preferably contain silver-coated resin particles whose surfaces are coated with silver. This makes it possible to prepare a paste-like resin composition capable of obtaining a cured product having excellent thermal conductivity and excellent storage elastic modulus.

Since the silver-coated resin particles have a silver surface and a resin inside, they are considered to have good thermal conductivity and are softer than particles composed only of silver. Therefore, it is considered easy to design the thermal conductivity and the storage elastic modulus to appropriate values by using the silver-coated resin particles.

Usually, in order to increase the thermal conductivity, it is considered to increase the amount of silver-containing particles. However, since metals are usually "hard", if the amount of silver-containing particles is too large, the elastic modulus after sintering may become too large. Since a part or all of the silver-containing particles are silver-coated resin particles, it is possible to easily design a paste-like resin composition capable of obtaining a cured product having a desired thermal conductivity and storage elastic modulus.

In the silver-coated resin particles, the silver layer may cover at least a part of the surface of the resin particles. Of course, silver may cover the entire surface of the resin particles.

Specifically, in the silver-coated resin particles, the silver layer covers preferably 50% or more, more preferably 75% or more, still more preferably 90% or more of the surface of the resin particles. Particularly preferably, in the silver-coated resin particles, the silver layer covers substantially the entire surface of the resin particles.
As another viewpoint, when the silver-coated resin particles are cut in a certain cross section, it is preferable that a silver layer is confirmed all around the cross section.

As another viewpoint, the mass ratio of resin / 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. be.

Examples of the "resin" in the silver-coated resin particles include silicone resin, (meth) acrylic resin, phenol resin, polystyrene resin, melamine resin, polyamide resin, and polytetrafluoroethylene resin. Of course, resins other than these may be used. Further, only one kind of resin may be used, or two or more kinds of resins may be used in combination.
From the viewpoint of elastic properties 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, and dimethyldichlorosilane. Further, a silicone resin having a structure in which organopolysiloxane is further three-dimensionally crosslinked may be used as a basic skeleton.

The (meth) acrylic resin is a resin obtained by polymerizing a monomer containing a (meth) acrylic acid ester as a main component (50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more). be able to. Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and 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, At least one compound selected from the group consisting of methoxyethyl (meth) acrylate, glycidyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate and isoboronor (meth) acrylate can be mentioned. can. Further, the monomer component of the acrylic resin may contain a small amount of other monomers. Examples of such other monomer components include styrene-based monomers. For the silver-coated (meth) acrylic resin, refer to the description in JP-A-2017-126463.

Various functional groups may be introduced into the silicone resin or the (meth) acrylic resin. The functional groups that can be introduced are 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 and the like can be mentioned.

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

The shape of the portion of the resin particles in the silver-coated resin particles is not particularly limited. A combination of a spherical shape and an irregular shape other than the spherical shape, for example, a flat shape, a plate shape, a needle shape, or the like is preferable.

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. The 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 and other silver-containing particles are used in combination.

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

Incidentally, when the ratio of the 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 substantially composed of only silver.

The median diameter D ₅₀ 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 D ₅₀ to an appropriate value, it is easy to balance thermal conductivity, sinterability, heat cycle resistance, and the like. Further, by setting D50 to an appropriate value, it may be possible to improve the workability of coating / bonding.
The particle size distribution (horizontal axis: particle diameter, vertical axis: frequency) of the silver-containing particles may be monomodal or multimodal.

The median diameter D ₅₀ of the particles substantially composed of only silver is, for example, 0.8 μm or more, preferably 1.0 μm or more, and more preferably 1.2 μm or more. Thereby, the thermal conductivity can be further enhanced.

Further, the median diameter D ₅₀ of the particles substantially composed of only silver is, for example, 7.0 μm or less, preferably 5.0 μm or less, and more preferably 4.0 μm or less. As a result, it is possible to further improve the ease of sintering and improve the uniformity of sintering.

The median diameter D ₅₀ 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. This makes it easy to set the storage elastic 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 easy to sufficiently increase the thermal conductivity.

The median diameter D ₅₀ of the silver-containing particles A can be determined, 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 A can be determined by measuring the volume-based median diameter in a wet manner using this device.

The proportion of the 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 setting the ratio of the metal-containing particles to 1% by mass or more, it is easy to increase the thermal conductivity. By setting the ratio of the silver-containing particles A to 98% by mass or less, the workability of coating / bonding can be improved.

Among the silver-containing particles A, particles consisting substantially only of silver can be obtained from, for example, DOWA Hightech Co., Ltd., Fukuda Metal Leaf Powder Industry Co., Ltd., and the like. Further, the silver-coated resin particles can be obtained from, for example, Mitsubishi Materials Corporation, Sekisui Chemical Co., Ltd., Sanno Co., Ltd., and the like.

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

When the solvent B is composed of one kind of solvent, it can be used if the difference between the Hansen solubility parameter a and the Hansen solubility parameter b is within a predetermined range in relation to the silver-containing particles A, for example, tripropylene glycol mono. Examples thereof include -n-butyl ether, dimethylsulfoxide, benzyl benzoate, diacetone alcohol, triethylene glycol dimethyl ether, γ-butyrolactone, isovonylcyclohexanol, tarpineol, isovonylcyclohexanol, diethylene glycol and the like.
Of these, tripropylene glycol mono-n-butyl ether, dimethyl sulfoxide, benzyl benzoate, γ-butyrolactone, isobonylcyclohexanol, or turpineol are preferred.

When solvent B consists of two or more solvents, tripropylene glycol mono-n-butyl ether, propylene carbonate, diacetone alcohol, triethylene glycol dimethyl ether, dimethylsulfoxide, benzyl benzoate, ethylene glycol, diethylene glycol, γ-butyrolactone, Carbitol, n-dodecane, isobonylcyclohexanol, tarpineol, propylene glycol phenyl ether, ethylene glycol mono-2-ethylhexyl ether, N-methylpyrrolidone, N-ethylpyrrolidone, δ-valerolacne, butylcarbitol, phenoxypropanol, diethylene glycol From monobutyl ether acetate, ethylene glycol mono-n-butyl ether acetate, dimethylisosorbide, isophorone, butyl diglycol acetate, hexylene glycol, butyl benzoate, 2-phenoxyethanol, benzyl alcohol, dihydrorevoglucosenone, dipropylene glycol, and caprolactone. Two or more selected solvents can be mixed and used by adjusting the Hansen solubility parameter.

The boiling point of the 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 kinds of solvents are mixed and used, it is the boiling point of the mixed solvent.
When the boiling point of the solvent B is in the above range, the generation of voids can be suppressed in the material obtained by sintering the paste-like resin composition.

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

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

The thermosetting resin C usually contains a group that polymerizes / crosslinks by the action of an active chemical species such as a radical, and / or a chemical structure that reacts with the curing agent D described later. 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, an epoxy resin can be preferably mentioned.
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.

Examples of the epoxy resin include bifunctional or crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, stilben type epoxy resin, and hydroquinone type epoxy resin; cresol novolac type epoxy resin, Novolak type epoxy resin such as phenol novolac type epoxy resin, naphthol novolak type epoxy resin; phenol aralkyl type epoxy resin containing phenylene skeleton, phenol aralkyl type epoxy resin containing biphenylene skeleton, phenol aralkyl type epoxy resin such as naphthol aralkyl type epoxy resin containing phenylene skeleton Resin: Trifunctional epoxy resin such as triphenol methane type epoxy resin and alkyl modified triphenol methane type epoxy resin; Modified phenol type epoxy resin such as dicyclopentadiene modified phenol type epoxy resin and terpene modified phenol type epoxy resin; Triazine nucleus Examples thereof include a heterocycle-containing epoxy resin such as a contained epoxy resin.

Further, as the epoxy group-containing compound, a monofunctional epoxy group-containing compound such as 4-tert-butylphenylglycidyl ether, m, p-cresyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether and the like can also be included.
The paste-like resin composition of the present embodiment may contain only one type of thermosetting component, or may contain two or more types.

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

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

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 the present embodiment is, for example, 3 to 20% by mass, preferably 5 to 15% by mass, based on the total non-volatile components.

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

Examples of the curing agent D include those having a reactive group that reacts with the thermosetting resin C. The curing agent D contains, for example, a reactive group that reacts with a functional group such as an epoxy group, a maleimide group, or a hydroxy group contained in the thermosetting resin C.

The curing agent D preferably contains a phenol-based curing agent and / or an imidazole-based curing agent. These curing agents are particularly preferable when the thermosetting component contains an epoxy group.
The phenolic curing agent may be a low molecular weight compound or a high molecular weight compound (that is, a phenol resin).

Examples of the phenolic curing agent which is a low molecular weight compound include bisphenol compounds such as bisphenol A and bisphenol F (dihydroxydiphenylmethane) (phenol resins having a bisphenol F skeleton); compounds having a biphenylene skeleton such as 4,4'-biphenol. And so on.

Specifically, as the phenol resin, a novolak type phenol resin such as a phenol novolac resin, a cresol novolak resin, a bisphenol novolak resin, a phenol-biphenylnovolak resin; a polyvinylphenol; a polyfunctional phenol resin such as a triphenylmethane type phenol resin; a terpene. Modified phenol resins such as modified phenol resins and dicyclopentadiene modified phenol resins; phenol aralkyl resins having a phenylene skeleton and / or biphenylene skeleton, phenol aralkyl-type phenol resins such as naphthol aralkyl resins having phenylene and / or biphenylene skeletons, and the like. be able to.
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 the present embodiment contains the curing agent D, the amount thereof is, for example, 30 to 300 parts by mass, preferably 50 to 200 parts by mass, when the amount of the thermosetting resin C is 100 parts by mass. Is.

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

Specifically, as the curing accelerator, phosphorus atom-containing compounds such as organic phosphine, tetra-substituted phosphonium compound, phosphobetaine compound, adduct of phosphine compound and quinone compound, adduct of phosphonium compound and silane compound; dicyandiamide, 1 , 8-diazabicyclo [5.4.0] Undecene-7, amidines and tertiary amines such as benzyldimethylamine; nitrogen atom-containing compounds such as the amidine or the quaternary ammonium salt of the 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 the present embodiment contains a curing accelerator, the amount thereof is, for example, 0.1 to 10 parts by mass, preferably 0.5 when the amount of the thermosetting resin C is 100 parts by mass. ~ 5 parts by mass.

(Silane coupling agent)
The paste-like resin composition of the present embodiment can further contain a silane coupling agent. As a result, the adhesive strength can be further improved.

Examples of the silane coupling agent include known silane coupling agents, and specifically, vinylsilanes such as nyltrimethoxysilane and vinyltriethoxysilane;
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl Epoxysilanes such as methyldiethoxysilane, 3-glycidoxypropyltriethoxysilane;
Styrylsilanes such as p-styryltrimethoxysilane;
Methylsilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane;
Acrylic silanes such as 3- (trimethoxysilyl) propyl methacrylate, 3-acryloxypropyltrimethoxysilane;
N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, Aminosilanes such as 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-γ-aminopropyltrimethoxysilane;
Isocyanurate silane;
Alkylsilane;
Ureidosilanes such as 3-ureidopropyltrialkoxysilanes;
Mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
Examples thereof include isocyanatesilane such as 3-isocyanatepropyltriethoxysilane.
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 the present embodiment contains a silane coupling agent, the amount thereof is the amount of the thermosetting component (the total amount of the (meth) acrylic group-containing compound (A) and the thermosetting resin C). When it is 100 parts by mass, it is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass.

(Plasticizer)
The paste-like resin composition of the present embodiment can contain a plasticizer. The plasticizer makes it easy to design with a small storage elastic modulus. Then, it becomes easier to suppress the decrease in the adhesive force due to the heat cycle.

Specific examples of the plasticizer include a polyester compound, a silicone oil, a silicone compound such as silicone rubber, a polybutadiene compound such as a polybutadiene maleic anhydride adduct, and an acrylonitrile butadiene copolymer compound.
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 the present embodiment contains a plasticizer, the amount thereof is 100% by mass of the amount of the thermosetting component (the total amount of the (meth) acrylic group-containing compound (A) and the thermosetting resin C). When it is divided into parts, it is, for example, 5 to 50 parts by mass, preferably 10 to 30 parts by mass.

(Radical initiator)
The paste-like resin composition of the present embodiment can contain a radical initiator.
With the radical initiator, for example, it is possible to suppress insufficient curing, sufficiently proceed the curing reaction at a relatively low temperature (for example, 180 ° C.), and further improve the adhesive strength. May be created.
Examples of the radical initiator include peroxides and azo compounds.

Examples of the peroxide include organic peroxides such as diacyl peroxide, dialkyl peroxide, and peroxyketal, and more specifically, ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide; Peroxyketals such as 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (4,4-di (t-butylperoxy) cyclohexyl) propane;
Hydroperoxides such as p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, cumene hydroperoxide, t-butylhydroperoxide;
To di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t- Dialkyl peroxides such as xyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, di-t-butyl peroxide;
Diacyl peroxides such as dibenzoyl peroxide and di (4-methylbenzoyl) peroxide;
Peroxydicarbonates such as di-n-propylperoxydicarbonate and diisopropylperoxydicarbonate;
Peroxyesters such as 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t-hexylperoxybenzoate, t-butylperoxybenzoate, t-butylperoxy2-ethylhexanonate, etc. Can be mentioned.

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) and the like can be mentioned.
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 the present embodiment contains a radical initiator, the amount thereof is, for example, 0.1 to 10 parts by mass, preferably 0.5 to 10 parts by mass when the amount of the thermosetting component is 100 parts by mass. 5 parts by mass.

(Characteristics of composition)
The paste-like resin composition of the present embodiment is preferably in the form of a paste at 20 ° C. That is, the paste-like resin composition of the present embodiment can be preferably applied to a substrate or the like at 20 ° C. like glue. As a result, the paste-like resin composition of the present embodiment can be preferably used as an adhesive for semiconductor devices and 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.

<Manufacturing method of paste-like resin composition>
The method for producing the paste-like resin composition of the present embodiment is as follows.
The step 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, and the step of measuring the Hansen solubility parameter b.
The step of selecting the solvent B in which the difference between the Hansen solubility parameter a and the Hansen solubility parameter b is 4.3 or more and 9.8 or less.
It comprises 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.

<High thermal conductivity material>
A highly thermally conductive material can be obtained by sintering the paste-like resin composition of the present embodiment.
By changing the shape of the highly thermally conductive material, it can be applied to various parts that require heat dissipation in the fields of automobiles and electric appliances.

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

In other words, the semiconductor device of the present embodiment comprises, for example, a base material and a semiconductor element mounted on the base material via an adhesive layer obtained by sintering the above-mentioned paste-like resin composition by heat treatment. Be prepared.
In the semiconductor device of the present embodiment, the adhesiveness of the adhesive layer is unlikely to decrease even with a heat cycle. That is, the reliability of the semiconductor device of this embodiment is high.
Examples of the semiconductor element 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.

Hereinafter, an example of a semiconductor device will be described 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 base material 30 and a semiconductor element 20 mounted on the base material 30 via an adhesive layer 10 (diatack material) which is a heat-treated body of a paste-like resin composition.

The semiconductor element 20 and the base material 30 are electrically connected via, for example, a bonding wire 40 or the like. Further, the semiconductor element 20 is sealed with, for example, a sealing resin 50.

The thickness of the adhesive layer 10 is preferably 5 μm or more, more preferably 10 μm or more, still more preferably 20 μm or more. As a result, the stress absorption capacity 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, preferably 50 μm or less.

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

The base material 30 may be an organic substrate or a ceramic substrate. Examples of the organic substrate include those made of an epoxy resin, a cyanate resin, a maleimide resin, or the like.
The surface of the base material 30 may be coated with a metal such as silver or gold. This improves the adhesiveness between the adhesive layer 10 and the base material 30.

FIG. 2 is a cross-sectional view showing an example of a semiconductor device 100 different from that of FIG.
In the semiconductor device 100 of FIG. 2, the base material 30 is, for example, an interposer. Of the base material 30 that is an interposer, for example, a plurality of solder balls 52 are formed on the surface opposite to one 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 base material 30, and then the semiconductor element 20 is arranged on the paste-like resin composition. That is, the base material 30, the paste-like resin composition, and the semiconductor element 20 are laminated in this order.
The method of applying the paste-like resin composition is not particularly limited. Specific examples thereof include a dispensing method, a printing method, and an inkjet method.

Then, the paste-like resin composition is heat-cured. The thermosetting is preferably performed by pre-curing and post-curing. By thermosetting, the paste-like resin composition is made into a heat-treated body (cured product). By thermosetting (heat treatment), the metal-containing particles in the paste-like resin composition are aggregated, and a structure in which the interface between the plurality of metal-containing particles disappears is formed in the adhesive layer 10. As a result, the base material 30 and the semiconductor element 20 are adhered to each other via the adhesive layer 10. Next, the semiconductor element 20 and the base material 30 are electrically connected using the bonding wire 40. Next, the semiconductor element 20 is sealed with the sealing resin 50. In this way, the semiconductor device can be manufactured.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted. Further, the present invention is not limited to the above-described embodiment, and modifications, improvements, and the like to the extent that the object of the present invention can be achieved are included in the present invention.

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.

<Solvent ΔHSP for silver-containing particles>
Using the following silver-containing particles and the following solvent, the ΔHSP of the solvent with respect to the silver-containing particles was adjusted to be in five stages.
(Silver-containing particles)
-Silver filler 1: Fukuda Metal Foil Powder Industry Co., Ltd., HKD-12, median diameter D ₅₀ : 20.2 μm, D ₉₀ : 39.6 μm, aspect ratio 15.5, scaly / silver filler 2: manufactured by DOWA Electronics Co., Ltd. , AG-DSB-114, spherical, D ₅₀ : 0.7 μm
(solvent)
Solvent 1: Tripropylene glycol mono-n-butyl ether (BFTG, manufactured by Nippon Embroidery 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 parameter a of the silver-containing particles (silver filler 1, silver filler 2) was measured by the following method.
[Method]
To 0.2 g of silver-containing particles, add 2 mL of any solvent selected from the following evaluation solvents to a 10 ml glass container, and visually check the dispersibility after stirring with a Voltex mixer for 5 seconds. Evaluate in the following 4 stages. The Hansen solubility parameter is calculated by inputting all the evaluation solvents and the evaluation results of the dispersibility in the solvent into the Sphere program of the computer software HSPiP (version 5.2.02).
(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: Not dispersed.
Sedimentation is completed in less than 1:10 minutes.
The sedimentation is completed after 2:10 minutes or more and less than 1 hour.
3: The sedimentation is completed after 1 hour or more and 12 hours or less.

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

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

The Hansen solubility parameter b of the solvent of Reference Examples 1 to 9 (solvent 1 to 6 or the mixed solvent of solvent 1 and solvent 2) measured by changing the mixing ratio of the solvent as shown in Table 1 is shown below. ..
Reference Example 1: The dispersion term (δD) is 16.1 MPa ^1/2 , the polarization term (δP) is 5.2 MPa ^1/2 , and the hydrogen bond term (δH) is 7.4 MPa ^1/2 .
Reference Example 2: The dispersion term (δD) is 17.9 MPa ^1/2 , the polarization term (δP) is 11.1 MPa ^1/2 , and the hydrogen bond term (δH) is 5.9 MPa ^1/2 .
Reference Example 3: The dispersion term (δD) is 18.6 MPa ^1/2 , the polarization term (δP) is 13.5 MPa ^1/2 , and the 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 , and 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 , and 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 .

Table 1 shows the difference between the Hansen solubility parameter b of the solvent of Reference Examples 1 to 9 with respect to the Hansen solubility parameter a of the silver-containing particles.

<Preparation of paste-like resin composition>
[Examples 1 and 2, Comparative Examples 1 to 7]
First, each raw material component was mixed according to the blending amount 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 blended according to the blending amounts shown in Table 2 and kneaded at room temperature with a three-roll mill. As a result, a paste-like resin composition was prepared. The silver-containing particles and the solvent used were as 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)

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

(Curing accelerator)
-Radical polymerization initiator: Dicumyl peroxide (manufactured by Kayaku Akzo, Percadox BC)
-Imidazole-based catalyst: 2-phenyl-1H-imidazole-4,5-dimethanol (manufactured by Shikoku Chemicals Corporation, 2PHZ-PW)

<Measurement of electrical resistivity>
The obtained paste-like resin composition was applied onto a glass plate, heated from 30 ° C. to 200 ° C. over 60 minutes under a nitrogen atmosphere, and then heat-treated at 200 ° C. for 120 minutes. As a result, a heat-treated body of a paste-like resin composition having a thickness of 0.05 mm was obtained. The resistance value on the surface of the heat-treated body was measured using a DC four-electrode method using a milliome meter (manufactured by HIOKI) and electrodes having an electrode spacing of 40 mm.

From the results in Table 2, the difference between the Hansen solubility parameter a of the silver-containing particles and the Hansen solubility parameter b of the solvent is 4.3 or more and 9.8 or less, so that a material having excellent electrical conductivity can be obtained. It became clear that it could be done.

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

<Solvent ΔHSP for silver-containing particles>
Using the following silver-containing particles and the following solvent, the ΔHSP of the solvent with respect to the silver-containing particles was adjusted to be in five stages.
(Silver-containing particles)
・ Silver filler 1: Fukuda Metal Leaf Powder Industry Co., Ltd., HKD-12, median diameter D ₅₀ : 7.6 μm , scaly ・ 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, manufactured by Nippon Embroidery 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)

Claims (15)

Silver-containing particles A and
Solvent B and
Thermosetting resin C and
Including
A paste-like resin composition in which the difference between the Hansen solubility parameter a of the silver-containing particles A measured by the following method and the Hansen solubility parameter b of the solvent B is 4.3 or more and 9.8 or less.
[Method]
To 0.2 g of silver-containing particles A, add 2 mL of any solvent selected from the following evaluation solvents to a 10 ml glass container, and visually check the dispersibility after stirring with a Voltex mixer for 5 seconds. The evaluation is made in the following four stages. The Hansen solubility parameter is calculated by inputting all the evaluation solvents and the evaluation results of the dispersibility in the solvent into the Sphere program of the computer software HSPiP (version 5.2.02).
(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: Not dispersed.
Sedimentation is completed in less than 1:10 minutes.
Sedimentation is completed after 2:10 minutes or more and less than 1 hour.
3: Sedimentation is completed after 1 hour or more and 12 hours or less. The paste-like resin composition according to claim 1, wherein the silver-containing particles A contain two or more kinds selected from spherical, scaly, agglomerated, and polyhedral silver-containing particles. The paste-like resin composition according to claim 1 or 2, wherein the solvent B comprises one kind or two or more kinds of solvents. Solvent B is tripropylene glycol mono-n-butyl ether, propylene carbonate, diacetone alcohol, triethylene glycol dimethyl ether, dimethylsulfoxide, benzyl benzoate, ethylene glycol, diethylene glycol, γ-butyrolactone, carbitol, n-dodecane, isobonyl. Cyclohexanol, Tarpineol, Propylene Glycolphenyl Ether, Ethylene Glycol Mono-2-ethylhexyl Ether, N-Methylpyrrolidone, N-Ethylpyrrolidone, δ-Valeroracun, Butylcarbitol, Phenoxypropanol, Diethylene Glycol Monobutyl Ether Acetate, Ethylene Glycol Mono-n -From two or more solvents selected from butyl ether acetate, dimethylisosorbide, isophorone, butyl diglycol acetate, hexylene glycol, butyl benzoate, 2-phenoxyethanol, benzyl alcohol, dihydrorevoglucosenone, dipropylene glycol, and caprolactone. The paste-like resin composition according to any one of claims 1 to 3. The paste-like resin composition according to any one of claims 1 to 4, wherein the solvent B has a boiling point of 220 ° C. or higher and 350 ° C. or lower. The paste-like resin composition according to any one of claims 1 to 5, wherein the thermosetting resin C contains an epoxy resin. The paste-like resin composition according to any one of claims 1 to 6, 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 7. With the base material
A semiconductor element mounted on the base material via an adhesive layer is provided.
The adhesive layer is a semiconductor device obtained by sintering the paste-like resin composition according to any one of claims 1 to 7. The steps of measuring the Hansen solubility parameter a of the silver-containing particles A and measuring the Hansen solubility parameter b of the solvent by the following method, and
A step of selecting the solvent B in which the difference between the Hansen solubility parameter a and the Hansen solubility parameter b is 4.3 or more and 9.8 or less.
A step of mixing the silver-containing particles A, the selected solvent B, and the thermosetting resin C,
A method for producing a paste-like resin composition.
[Method]
To 0.2 g of silver-containing particles A, add 2 mL of any solvent selected from the following evaluation solvents to a 10 ml glass container, and visually check the dispersibility after stirring with a Voltex mixer for 5 seconds. The evaluation is made in the following four stages. The Hansen solubility parameter is calculated by inputting all the evaluation solvents and the evaluation results of the dispersibility in the solvent into the Sphere program of the computer software HSPiP (version 5.2.02).
(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: Not dispersed.
Sedimentation is completed in less than 1:10 minutes.
Sedimentation is completed after 2:10 minutes or more and less than 1 hour.
3: Sedimentation is completed after 1 hour or more and 12 hours or less. The method for producing a paste-like resin composition according to claim 10, wherein the solvent B comprises one kind or two or more kinds of solvents. Solvent B is tripropylene glycol mono-n-butyl ether, propylene carbonate, diacetone alcohol, triethylene glycol dimethyl ether, dimethylsulfoxide, benzyl benzoate, ethylene glycol, diethylene glycol, γ-butyrolactone, carbitol, n-dodecane, isobonyl. Cyclohexanol, Tarpineol, Propylene Glycolphenyl Ether, Ethylene Glycol Mono-2-ethylhexyl Ether, N-Methylpyrrolidone, N-Ethylpyrrolidone, δ-Valeroracun, Butylcarbitol, Phenoxypropanol, Diethylene Glycol Monobutyl Ether Acetate, Ethylene Glycol Mono-n -From two or more solvents selected from butyl ether acetate, dimethylisosorbide, isophorone, butyl diglycol acetate, hexylene glycol, butyl benzoate, 2-phenoxyethanol, benzyl alcohol, dihydrorevoglucosenone, dipropylene glycol, and caprolactone. The method for producing a paste-like resin composition according to claim 10 or 11. The method for producing a paste-like resin composition according to any one of claims 10 to 12, wherein the solvent B has a boiling point of 220 ° C. or higher and 350 ° C. or lower. The method for producing a paste-like resin composition according to any one of claims 10 to 13, wherein the thermosetting resin C contains an epoxy resin. The method for producing a paste-like resin composition according to any one of claims 10 to 14, further comprising a step of mixing the curing agent D in the mixing step.

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