JP2021113267A - Thermosetting resin composition, electronic apparatus, method for producing thermally conductive material, and method for producing thermosetting resin composition - Google Patents

Abstract

To provide a thermosetting resin composition having excellent thermal conductivity.SOLUTION: A thermosetting resin composition contains epoxy resin, and an inorganic particle surface-treated with a surface treatment agent, the surface treatment agent containing a specific phosphorus compound, the inorganic particle containing one or more selected from the group consisting of alumina, silicon carbide, boron nitride.SELECTED DRAWING: None

Description

The present invention relates to a thermosetting resin composition, an electronic device, a method for producing a heat conductive material, and a method for producing a thermosetting resin composition.

So far, various developments have been made on thermosetting resin compositions. As a technique of this kind, for example, the technique described in Patent Document 1 is known. Patent Document 1 describes a resin composition containing boron nitride and an epoxy resin (claims of Patent Document 1 and the like).

JP-A-2019-167436

However, as a result of examination by the present inventor, it has been found that the resin composition described in Patent Document 1 has room for improvement in terms of thermal conductivity.

As a result of further studies, the present inventor has found that the thermal conductivity of the cured product of the thermosetting resin composition can be controlled by appropriately selecting the surface treatment of the inorganic particles. As a result of further diligent research based on such findings, it was found that the thermal conductivity of the cured product of the thermosetting resin composition can be improved by using the inorganic particles surface-treated with a predetermined phosphoric acid compound, and the present invention has been found. Has been completed.

According to the present invention
Epoxy resin and
A thermosetting resin composition containing inorganic particles surface-treated with a surface treatment agent.
The surface treatment agent contains a phosphorus compound represented by the following general formula A and contains.
The inorganic particles contain one or more selected from the group consisting of alumina, silicon carbide, and boron nitride.
Thermosetting resin compositions are provided.
[General formula A]
XP (= O) (OR) ₂
(In the above general formula A, X is a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, and R may be the same or different from each other, and represents a hydrogen atom or an alkyl group.)

Further, according to the present invention.
With the board
Electronic components provided on the board and
A sealing material for sealing the electronic component is provided.
The sealing material is composed of a cured product of the above thermosetting resin composition.
Electronic devices are provided.

Further, according to the present invention.
A method for producing a thermally conductive material, which comprises a step of surface-treating a surface treatment agent on the surface of inorganic particles.
The surface treatment agent contains a phosphorus compound represented by the general formula A.
The inorganic particles contain one or more selected from the group consisting of alumina, silicon carbide, and boron nitride.
A method for producing a thermally conductive material is provided.

Further, according to the present invention.
Provided is a method for producing a thermosetting resin composition, which comprises a step of mixing the thermally conductive material obtained by the above-mentioned method for producing a thermally conductive material and an epoxy resin.

According to the present invention, a thermosetting resin composition, an electronic device using the same, a method for producing a thermally conductive material, and a method for producing a thermosetting resin composition are provided.

It is sectional drawing which shows an example of the structure of the electronic device which concerns on this embodiment.

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 description thereof will be omitted as appropriate. Moreover, the figure is a schematic view and does not match the actual dimensional ratio.

The thermosetting resin composition of this embodiment is outlined.

The thermosetting resin composition contains an epoxy resin and inorganic particles surface-treated with a surface treatment agent. The surface treatment agent contains a phosphorus compound represented by the following general formula A. Inorganic particles include one or more selected from the group consisting of alumina, silicon carbide, boron nitride.
[General formula A]
XP (= O) (OR) ₂
(In the above general formula A, X is a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, and R may be the same or different from each other, and represents a hydrogen atom or an alkyl group.)

According to the findings of the present inventor, it has been found that the thermal conductivity of a cured product of a thermosetting resin composition can be improved by using inorganic particles surface-treated with a predetermined phosphoric acid compound.

Although the detailed mechanism is not clear, the bonding of the phosphorus compound having an aromatic group X and the polar group OR to the particle surface enhances the familiarity of the inorganic particles with the resin and the dispersibility in the resin composition. It is considered that the effect of thermal conductivity due to the inorganic particles can be further obtained. The phosphorus compound binds to the surface of the inorganic particles by, for example, O of M (metal) -O (oxygen) of the inorganic oxide to form a bond by dehydration condensation, or dehydration condensation with a functional group such as a hydroxyl group. May form a bond by doing so.

The thermosetting resin composition of the present embodiment can be used, for example, as a heat radiating material, an insulating material, or a semiconductor encapsulating material for electrical / electronic equipment. Examples of the semiconductor encapsulating material include a thermosetting resin composition for forming a encapsulant for encapsulating an electronic component such as a semiconductor chip.

As the electric / electronic device, for example, an ordinary semiconductor device (an electronic device having a semiconductor element as an electronic component), a power module (an electronic device having a power semiconductor element as an electronic component), or the like can be used. Power semiconductor devices are made from _{wide bandgap materials such as SiC, GaN, Ga 2} O ₃ , or diamond and are designed to be used at high voltage and high currents, so they are usually silicon. Since the amount of heat generated is larger than that of a chip (semiconductor element), it operates in a higher temperature environment. Power semiconductor devices are required to be used for a long time in a high temperature operating environment such as 200 ° C. or higher or 250 ° C. or higher. Specific examples of the power semiconductor element include a rectifier diode, a power transistor, a power MOSFET, an insulated gate bipolar transistor (IGBT), a thyristor, a gate turn-off thyristor (GTO), a triac, and the like.

According to the thermosetting resin composition of the present embodiment, it is possible to provide a semiconductor encapsulating material that can be used for a power module.

Hereinafter, the thermosetting resin composition of the present embodiment will be described in detail.

The thermosetting resin composition contains an epoxy resin and aggregated boron nitride particles.

(Epoxy resin)
The epoxy resin is a compound having two or more epoxy groups in one molecule, and monomers, oligomers, and polymers in general can be used, and the molecular weight and molecular structure thereof are not particularly limited. These may be used alone or in combination of two or more.

Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, and bisphenol M type epoxy resin (4,4'-(1,3-phenylenediiso). Pridiene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4'-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4'-cyclohexy) Bisphenol type epoxy resin such as dienbisphenol type epoxy resin); phenol novolac type epoxy resin, cresol novolac type epoxy resin, trisphenol group methane type novolac type epoxy resin, tetraphenol group ethane type novolac type epoxy resin, condensed ring aromatic carbonization Novolak type epoxy resin such as novolak type epoxy resin having a hydrogen structure; biphenyl type epoxy resin; arylalkylene type epoxy resin such as xylylene type epoxy resin and biphenyl aralkyl type epoxy resin; naphthylene ether type epoxy resin, naphthol type epoxy resin, Naphthalene type epoxy resin such as naphthalenediol type epoxy resin, bifunctional to tetrafunctional epoxy type naphthalene resin, binaphthyl type epoxy resin, naphthalene aralkyl type epoxy resin; anthracene type epoxy resin; phenoxy type epoxy resin; dicyclopentadiene type epoxy resin; Norbornen type epoxy resin; Adamantane type epoxy resin; Fluorene type epoxy resin and the like can be mentioned. These may be used alone or in combination of two or more.

The lower limit of the content of the epoxy resin is, for example, preferably 0.1 part by mass or more, and more preferably 0.3 part by mass or more, based on 100 parts by mass of the solid content of the thermosetting resin composition. It is preferably 0.5 parts by mass or more, and more preferably 0.5 parts by mass or more. Thereby, the fluidity of the thermosetting resin composition at the time of molding can be appropriately controlled. On the other hand, the upper limit of the content of the epoxy resin is, for example, preferably 20 parts by mass or less, more preferably 15 parts by mass or less, based on 100 parts by mass of the solid content of the thermosetting resin composition. It is more preferably 10 parts by mass or less. Thereby, the coefficient of linear expansion of the thermosetting resin composition can be set within an appropriate range. Therefore, the high temperature storage characteristics can be improved.

In the present embodiment, the solid content of the thermosetting resin composition means the total of the components contained in the thermosetting resin composition excluding the solvent.
In the present specification, "~" means that an upper limit and a lower limit are included unless otherwise specified.

The thermosetting resin composition may or may not contain other thermosetting resins in addition to the epoxy resin.
Examples of other thermosetting resins include polyimide resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, silicone resins, bismaleimide resins, acrylic resins, and derivatives of these phenol derivatives. As these thermosetting resins, monomers, oligomers, and polymers having two or more reactive functional groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not particularly limited. These may be used alone or in combination of two or more.

(Hardener)
The thermosetting resin composition may contain a curing agent, if necessary.
The curing agent is selected according to the type of the thermosetting resin, and is not particularly limited as long as it reacts with the thermosetting resin. Specific examples of the curing agent include a polyaddition type curing agent, a catalytic type curing agent, and a condensation type curing agent.

Specific examples of the heavy addition type curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylerylene diamine (MXDA); diaminodiphenylmethane (DDM), m-phenylene. Aromatic polyamines such as diamine (MPDA) and diaminodiphenylsulfone (DDS); polyamine compounds such as diocyandiamide (DICY) and organic acid dihydralide; alicyclic such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA). Group Acid Anhydrides; Acid anhydrides such as aromatic acid anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); novolak type phenolic resin, polyvinylphenol, aralkyl Examples thereof include phenol resin-based curing agents such as type phenol resins; polyether compounds such as polysulfide, thioester and thioether; isocyanate compounds such as isocyanate prepolymer and blocked isocyanate; and organic acids such as carboxylic acid-containing polyester resin. As the heavy addition type curing agent, one or a combination of two or more of the above specific examples can be used.

Specific examples of the catalytic curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2 Examples include imidazole compounds such as −ethyl-4-methylimidazole (EMI24); Lewis acids such as the BF3 complex. As the catalyst type curing agent, one or a combination of two or more of the above specific examples can be used.

Specific examples of the condensation type curing agent include a resol type phenol resin; a urea resin such as a methylol group-containing urea resin; and a melamine resin such as a methylol group-containing melamine resin. As the condensation type curing agent, one or a combination of two or more of the above specific examples can be used.

As the curing agent, a phenol resin-based curing agent may be included in the above specific examples.
As the phenol resin-based curing agent, a phenol resin can be used, and specifically, a phenol novolac resin, a cresol novolac resin, a naphthol novolac resin, an aminotriazine novolac resin, a novolak resin, and a trisphenylmethane type phenol novolac resin. Novolac-type phenol resin such as; terpen-modified phenol resin, modified phenol resin such as dicyclopentadiene-modified phenol resin; phenol aralkyl resin having a phenylene skeleton and / or biphenylene skeleton, naphthol aralkyl resin having a phenylene skeleton and / or biphenylene skeleton, etc. Aralkyl type resin; bisphenol compound such as bisphenol A and bisphenol F; resol type phenol resin and the like can be mentioned.
These may be used alone or in combination of two or more. Among these, a novolak type phenol resin can be used from the viewpoint of improving the glass transition temperature and reducing the coefficient of linear expansion.

The content of the curing agent can be appropriately set according to the content of the epoxy resin.

(Inorganic particles)
The inorganic particles include a thermally conductive filler whose surface has been surface-treated with a surface-treating agent.
Inorganic particles include one or more selected from the group consisting of alumina, silicon carbide and boron nitride. These may be used alone or in combination of two or more.

As all of alumina, silicon carbide and boron nitride, powdery ones can be used. As the powdery inorganic particles, those in which coarse particles have been removed by a comb may be used, and for example, fine powder that has passed through a sieve, such as a 50 μm cut product or a 45 μm cut product, may be used.

The particle size d50 at which the cumulative frequency of the inorganic particles in the volume-based particle size distribution is 50% is, for example, 0.1 μm to 30 μm, preferably 0.2 μm to 28 μm, and more preferably 0.5 μm to 25 μm. By setting it to the above lower limit value or more, the melt viscosity of the resin composition can be reduced. By setting it to the above upper limit value or less, the thermal conductivity can be improved.

The particle size of the inorganic particles can be measured by using, for example, a laser diffraction / scattering type particle size distribution measuring device or the like.

A method for producing a thermally conductive material using inorganic particles will be described.
The method for producing a thermally conductive material includes a step of surface-treating a surface treatment agent on the surface of the above-mentioned inorganic particles.

The surface treatment agent contains a phosphorus compound represented by the following general formula A.
[General formula A]
XP (= O) (OR) ₂

In the above general formula A, X is a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, and R may be the same or different from each other, and represents a hydrogen atom or an alkyl group. The substituent includes, for example, a carboxyl group, an alkyl group, a hydroxy group, an amino group and the like.

In the general formula A, the aromatic group having 6 to 20 carbon atoms may be a phenyl group.
In the general formula A, the alkyl group may be a linear or branched alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or t-butyl. Group etc. can be mentioned.

It is preferable that at least one, preferably two, of R in the general formula A are hydrogen atoms in one molecule of the phosphorus compound.

The surface treatment agent preferably contains, for example, a phosphorus compound in which the aromatic group in the general formula A is a phenyl group, and more preferably contains phenylphosphonic acid.

A method for surface-treating inorganic particles using the above-mentioned surface-treating agent will be described.
First, the above phosphorus compound is mixed with a solvent to prepare a solution-like surface treatment agent.
The lower limit of the concentration of the phosphorus compound in the surface treatment agent is, for example, 0.001 mol / L or more, preferably 0.005 mol / L or more, and more preferably 0.01 mol / L or more. Thereby, the thermal conductivity can be improved. On the other hand, the upper limit of the concentration of the phosphorus compound in the surface treatment agent is, for example, 1.0 mol / L or less, preferably 0.5 mol / L or less, and more preferably 0.3 mol / L or less. As a result, it is possible to prevent the resin component from becoming unfamiliar with the resin component.

Subsequently, the inorganic particles are introduced into the solution-like surface treatment agent. The mixing ratio of the surface treatment agent and the inorganic particles can be appropriately changed, but may be, for example, 40:60 to 60:40, preferably about 50:50 in terms of volume.
In addition, powdery inorganic particles or a dispersion medium in which the inorganic particles are dispersed in a predetermined dispersion solvent may be introduced into a solution-like surface treatment agent.

Subsequently, the mixed solution of the surface treatment agent and the inorganic particles is stirred. As the stirring operation, a known method can be used, but for example, a method of rotating the container containing the mixed solution for about 2 to 20 hours may be used. The stirring may be performed at room temperature of 25 ° C., or may be heated to such an extent that the solvent does not volatilize.

The above solvent is not particularly limited as long as it dissolves a phosphorus compound, but for example, an organic solvent having a water-soluble group such as a hydroxy group may be used, and specifically, an alcohol solvent is used. You may.
Further, as the solvent, a solvent which is hard to volatilize under atmospheric pressure at 25 ° C. may be used, and for example, a solvent having a boiling point of 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher is preferable. The solvent may be a mixed solvent containing one or two or more.
Among these, 1-methoxy-2-propanol, ethanol and the like can be used from the viewpoint of solubility and non-volatility of the phosphorus compound.

If necessary, the mixed solution may be filtered, or the filtered residue after filtration may be washed. As the cleaning liquid, water, the solvent used, or the like may be used.

Then, the solvent remaining in the mixed solution or the filter residue is removed. As a method for removing the solvent, known means can be used, but vacuum drying, heat drying and the like are used.

The step of surface treatment as described above can include any of a drying treatment at room temperature, a drying treatment at room temperature and under reduced pressure, and a drying treatment at 25 ° C. to 50 ° C. and under reduced pressure.

Further, as an example of the surface treatment method, while rotating the inorganic particles in a Henshell mixer, a surface treatment agent in which a phosphorus compound is dissolved in ethanol (solvent) is gradually dropped therein to form the inorganic particles and the surface treatment agent. May be adopted, and the obtained mixture is dried in a mixer.

By the above surface treatment method, inorganic particles surface-treated with a phosphorus compound can be obtained as a heat conductive material.

Phosphorus compounds are chemically, physically, or both attached to the surface of the inorganic particles. That is, the surface-treated inorganic particles are in a state in which at least a part of the surface thereof is covered with an organic layer made of a phosphorus compound.
At this time, it is presumed that the phosphorus compound bonded to the surface has an X group such as a phenyl group on the outside and an OR group such as a hydroxy group on the inside.

According to the idea of the present inventor, the detailed mechanism is not clear, but the presence of predetermined phenyl groups and hydroxy groups in the phosphorus compound makes the balance between hydrophobicity and hydrophilicity appropriate, and thus the resin composition. It is considered that the familiarity in the inside is further improved, and the balance between the overlap of pi-electrons and the hydrogen bond is appropriate, so that the bond between the phosphoric acid compound and the inorganic particles is strengthened.

The lower limit of the content of the inorganic particles is preferably, for example, 60 parts by mass or more, more preferably 70 parts by mass or more, with respect to 100 parts by mass of the solid content of the thermosetting resin composition. It is preferably 80 parts by mass or more. Thereby, the thermal conductivity of the cured product of the thermosetting resin composition can be improved. On the other hand, the upper limit of the content of the inorganic particles is preferably less than 98 parts by mass, more preferably 95 parts by mass or less, and 93 parts by mass with respect to the solid content of the thermosetting resin composition. The following is preferable. Thereby, the viscosity of the thermosetting resin composition can be adjusted to a suitable range for performing the mixing step.

The thermosetting resin composition contains, in addition to the inorganic particles surface-treated by the above-mentioned surface treatment agent, a filler having another surface treatment such as a coupling treatment or a filler having no surface treatment. It may be.

As the filler, an inorganic filler or an organic filler is used.
Examples of the inorganic filler include fused crushed silica, molten spherical silica, crystalline silica, secondary aggregated silica, fine powder silica and other silica; alumina, silicon nitride, aluminum nitride, boron nitride, titanium oxide, silicon carbide and hydroxide. Metal compounds such as aluminum, magnesium hydroxide, titanium white; talc; clay; mica; glass fiber and the like. These may be used alone or in combination of two or more.

(Other ingredients)
The thermosetting resin composition is, if necessary, among various additives such as a coupling agent, a fluidity imparting agent, a mold release agent, an ion scavenger, a curing accelerator, a low stress agent, a coloring agent and a flame retardant. One type or two or more types can be appropriately blended.

(Coupling agent)
Specific examples of the coupling agent include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane; 2- (3,4-epylcyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3 -Epoxysilanes such as glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; styrylsilanes such as p-styryltrimethoxysilane; 3-methacryloxypropyl Methacrylic silanes such as methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane; acrylic silanes such as 3-acryloxypropyltrimethoxysilane; N -2- (Aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 Aminosilanes such as −triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, phenylaminopropyltrimethoxysilane; isocyanuratesilane; alkylsilane; 3- Ureidosilanes such as ureidopropyltrialkoxysilanes; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; isocyanatesilanes such as 3-isocyanuppropyltriethoxysilane; titanium compounds; aluminum chelates; Examples include aluminum / zirconium compounds. As the coupling agent, one or more of the above specific examples can be blended.

(Liquidity imparting agent)
The fluidity-imparting agent can suppress the reaction of a non-latent curing accelerator such as a phosphorus atom-containing curing accelerator during melt-kneading of the resin composition. Thereby, the productivity of the thermosetting resin composition can be improved.

(Release agent)
Specific examples of the release agent include natural waxes such as carnauba wax; synthetic waxes such as montanic acid ester wax and polyethylene oxide wax; higher fatty acids such as zinc stearate and metal salts thereof; paraffin; erucic acid amide and the like. Examples include carboxylic acid amide. As the release agent, one or more of the above specific examples can be blended.

(Ion scavenger)
Specific examples of the ion trapping agent include hydrotalcites such as hydrotalcites and hydrotalcite-like substances; and hydrous oxides of elements selected from magnesium, aluminum, bismuth, titanium and zirconium. As the ion scavenger, one or more of the above specific examples can be blended.

(Curing accelerator)
The curing accelerator is, for example, a phosphorus atom-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound; 1,8-diazabicyclo. [5.4.0] One selected from nitrogen atom-containing compounds such as amidine and tertiary amines such as undecene-7, benzyldimethylamine and 2-methylimidazole, and quaternary salts of the above amidine and amine. Alternatively, two or more types can be included. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving curability. Further, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. It is more preferable to include one.

(Low stress agent)
Specific examples of the low stress agent include silicone compounds such as silicone oil and silicone rubber; polybutadiene compounds; acrylonitrile-butadiene copolymer compounds such as acrylonitrile-carboxyne group-terminated butadiene copolymer compounds. As the low stress agent, one or more of the above specific examples can be blended.

(Colorant)
Specific examples of the colorant include carbon black, red iron oxide, and titanium oxide. As the colorant, one or more of the above specific examples can be blended.

(Flame retardants)
Specific examples of the flame retardant include aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene, and carbon black. As the flame retardant, one or more of the above specific examples can be blended.

The characteristics of the thermosetting resin composition of the present embodiment will be described.

The upper limit of the minimum melt viscosity of the thermosetting resin composition when measured using a cone plate viscometer at 160 ° C. and a rotation frequency of 94 rpm is, for example, 19 Pa · s or less, preferably 18 Pa · s or less. , More preferably 16 Pa · s or less. Thereby, the mold filling property of the thermosetting resin composition can be improved. On the other hand, the lower limit of the minimum melt viscosity of the thermosetting resin composition is not particularly limited, but may be, for example, 1 Pa · s or more. As a result, manufacturing stability can be improved.

A method for producing a thermosetting resin composition according to the present embodiment will be described.
The method for producing a thermosetting resin composition includes a mixing step of mixing the heat conductive material obtained by the above method for producing a heat conductive material and a raw material component such as an epoxy resin.

The mixing step is a step of mixing the raw material components to prepare a mixture. The mixing method is not limited, and a known method can be used depending on the components used.
Specifically, as the mixing step, the raw material components contained in the above-mentioned thermosetting resin composition are uniformly mixed using a mixer or the like. Then, it is melt-kneaded by a kneader such as a roll, a kneader or an extruder to prepare a mixture.

The method for producing a thermosetting resin composition may include a molding step of molding the obtained mixture.

The molding method is not limited, and a known method can be used depending on the shape of the thermosetting resin composition. The shape of the thermosetting resin composition is not limited, and examples thereof include a granule shape, a powder shape, a tablet shape, and a sheet shape. The thermosetting resin composition for encapsulating a semiconductor may be, for example, in the form of powder, granules, or tablets.

The shape of the thermosetting resin composition can be selected according to the molding method.
Examples of the molding step for producing the thermosetting resin composition in the form of granules include a step of pulverizing the cooled mixture after melt-kneading. For example, the size of the granules may be adjusted by sieving the thermosetting resin composition in the form of granules. Further, for example, the thermosetting resin composition in the form of granules may be treated by a method such as a centrifugal milling method or a hot-cut method to adjust the dispersity or fluidity.
Further, as a molding step for producing a thermosetting resin composition in the form of powder, for example, after crushing the mixture to obtain a thermosetting resin composition in the form of granules, the thermosetting resin composition in the form of granules is used. Further examples include a step of crushing.
Further, as a molding step for producing a thermosetting resin composition in the shape of a tablet, for example, after crushing the mixture into a thermosetting resin composition in the shape of granules, the thermosetting resin composition in the shape of granules is used. The step of tableting and molding can be mentioned.

Next, an electronic device using the thermosetting resin composition according to the present embodiment will be described.

The thermosetting resin composition according to this embodiment can be used to form a sealing material (sealing resin layer) for sealing electronic components.
Used for sealing resin layer. The method for forming the sealing resin layer is not limited, and examples thereof include a transfer molding method, a compression molding method, and an injection molding method. By these methods, the thermosetting resin composition can be molded and cured to form a sealing resin layer.

The electronic component is not limited, but a semiconductor element is preferable.
Examples of semiconductor devices include, but are not limited to, integrated circuits, large-scale integrated circuits, transistors, thyristors, diodes, and solid-state imaging devices.
Among these, the semiconductor element in which the thermosetting resin composition of the present embodiment is useful is a semiconductor element in which a metal portion is exposed. As a result, corrosion of the metal portion can be suppressed. A transistor is mentioned as a semiconductor element in which such a metal portion is exposed. Among the transistors, the thermosetting resin composition of the present embodiment can be effectively used for sealing the MIS transistor whose gate electrode is exposed.

Examples of the base material include, but are not limited to, a wiring board such as an interposer, a lead frame, and the like.

If an electrical connection between the electronic component and the base material is required, the connection may be made as appropriate. The method of electrically connecting is not limited, and examples thereof include wire bonding and flip-chip connection. Among these, the semiconductor element in which the thermosetting resin composition of the present embodiment is useful is a semiconductor element in which a metal portion is exposed. As a result, corrosion of the metal portion can be suppressed. Wire bonding is an example of an electrical connection method in which such a metal portion is exposed.

An electronic device can be obtained by forming a sealing resin layer for sealing an electronic component with a thermosetting resin composition. The electronic device is not limited, but a semiconductor device obtained by molding a semiconductor element is preferable.
Specific examples of the types of semiconductor devices include MAP (Mold Array Package), QFP (Quad Flat Package), SOP (Small Outline Package), CSP (Chip Size Package), and QFN (Quad Page). ), SON (Small Outline Non-led Package), BGA (Ball Grid Array), LF-BGA (Lead Frame BGA), FCBGA (Flip Chip BGA), MAPBGA (Molded ArrayBGA) ), Fan-In type eWLB, Fan-Out type eWLB and the like.

An example of an electronic device using the thermosetting resin composition according to the present embodiment will be described below.
FIG. 1 is a cross-sectional view showing an electronic device 100 according to the present embodiment.

The electronic device 100 of FIG. 1 includes a base material 30, an electronic component 20 provided on the base material 30, and a sealing material (sealing resin layer 50) for sealing the electronic component 20.
The sealing resin layer 50 is composed of a cured product of the above-mentioned thermosetting resin composition.
The electronic component 20 may be electrically connected to the outside by a bonding wire 40.

Specifically, the electronic component 20 is fixed on the base material 30 via the die attach material 10, and the electronic device 100 is connected to the electronic component 20 from an electrode pad (not shown) provided on the electronic component 20 via a bonding wire 40. Has an outer lead 34 connected to the wire. The bonding wire 40 can be set in consideration of the electronic components 20 and the like used, and for example, a Cu wire can be used.

Hereinafter, a method for manufacturing an electronic device using the thermosetting resin composition according to the present embodiment will be described.
The method for manufacturing an electronic device according to the present embodiment includes, for example, a manufacturing step for obtaining a thermosetting resin composition by the above-mentioned manufacturing method for a thermosetting resin composition, a step for mounting an electronic component on a substrate, and the like. A step of sealing the electronic component using the thermosetting resin composition is provided.

The electronic device 100 is formed, for example, by the following method.
First, electronic components are mounted on the substrate. Specifically, the electronic component 20 is fixed on the die pad 32 (board 30) using the die attach material 10, and the die pad 32 (base material 30) which is a lead frame is connected by the bonding wire 40. As a result, an object to be sealed is formed.
The electronic device 100 is manufactured by sealing the material to be sealed with a thermosetting resin composition to form a sealing resin layer 50.
The electronic device 100 in which the electronic component 20 is sealed cures the thermosetting resin composition at a temperature of about 80 ° C. to 200 ° C. for about 10 minutes to 10 hours, if necessary, and then performs electrons. It is installed in equipment.

The electronic device 100 uses the above-mentioned thermosetting resin composition as the sealing resin 50, and has sufficient adhesion between the sealing resin layer 50 and the electronic component 20, the bonding wire 40, the electrode pad 22, and the like. It also has excellent high-temperature storage characteristics. Even when a Cu wire is used as the bonding wire 40, sufficient high-temperature storage characteristics and the like can be exhibited.

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 within the range in which the object of the present invention can be achieved are included in the present invention.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the description of these Examples.
(Inorganic particles)
Alumina 1: Alumina particles (manufactured by Denka, DAB-30FC, average particle size d50: 13.2 μm)
Alumina 2: Alumina particles (manufactured by Admatex, AO-502, average particle size d50: 0.6 μm)
-Silicon Carbide 1: Silicon Carbide Particles (manufactured by Nakamura Choukousha, β-SiC, average particle size d50: 2.0 μm)
・ Boron nitride 1: Boron nitride fine powder (45 μm cut product)
_{The average particle size D 50, which} is a cumulative 50% of the volume of inorganic particles, is measured by measuring the particle size distribution of the particles using a commercially available laser diffraction type particle size distribution measuring device (SALD-7000, manufactured by Shimadzu Corporation). , The cumulative 50% particle size was determined.

-Alumina 3: Alumina 1 was surface-treated according to the following procedure.
-Alumina 4: Alumina 2 surface-treated according to the following procedure was used.
-Alumina 5: Alumina 1 surface-treated according to the following procedure was used.
-Alumina 6: Alumina 2 surface-treated according to the following procedure was used.
-Silicon carbide 2: A surface-treated silicon carbide 1 was used.
-Boron Nitride 2: A surface-treated boron nitride 1 was used.

(Surface treatment of inorganic particles)
-Surface treatment of alumina 3 and 4:
Phosphonic acid (manufactured by Nissan Chemical Industries, Ltd.) was mixed with 1-methoxy-2-propanol (manufactured by Fuji Film Co., Ltd.) to prepare a surface treatment agent having a phenylphosphonic acid concentration of 0.01 mol / L.
The obtained surface treatment agent and a mixture of the above alumina 1 and alumina 2 were placed in a bottle, and the sealed bottle was rotated at room temperature of 25 ° C. for 12 hours to mix them. The obtained mixture was filtered, washed with 1-methoxy-2-propanol, and then dried under reduced pressure for 24 hours to obtain alumina 3 and alumina 4 surface-treated with a surface treatment agent.

-Surface treatment of alumina 5 and 6:
Alumina 5 and alumina 6 surface-treated with a surface treatment agent were used in the same manner as in the above-mentioned surface treatment procedure for alumina 3 and 4, except that the concentration of phenylphosphonic acid was 0.1 mol / L.

-Surface treatment of alumina 7 and 8:
Phosphonic acid (manufactured by Nissan Chemical Industries, Ltd.) was mixed with 1-methoxy-2-propanol (manufactured by Fuji Film Co., Ltd.) to prepare a surface treatment agent having a phenylphosphonic acid concentration of 0.001 mol / L.
The obtained surface treatment agent and a mixture of the above alumina 1 and alumina 2 were placed in a bottle, and the sealed bottle was rotated at room temperature of 25 ° C. for 12 hours to mix them. After removing 1-methoxy-2-propanol from this using an evaporator, the mixture was dried under reduced pressure for 24 hours to obtain alumina 7 and alumina 8 surface-treated with a surface treatment agent.

-Silicon carbide 2 surface treatment:
Silicon carbide surface-treated with a surface treatment agent in the same manner as the surface treatment procedure for alumina 3 and 4 except that the above-mentioned silicon carbide 1 was used instead of the mixture of alumina 1 and alumina 2. 2 was used.

-Surface treatment of boron nitride 2:
Boron nitride surface-treated with a surface treatment agent in the same manner as the surface treatment procedure for alumina 3 and 4 except that the above-mentioned boron nitride 1 was used instead of the mixture of alumina 1 and alumina 2. 2 was used.

(IR spectrum)
FT-IR of surface-treated inorganic particles (alumina 1, 2, silicon carbide 1, boron nitride 1) and surface-treated inorganic particles (alumina 3 to 8, silicon carbide 2, boron nitride 2). The measurement data of (diffuse reflection method) was measured.
In the IR spectrum of the surface-treated inorganic particles, a peak derived from the benzene ring of phenylphosphonic acid, which is a surface treatment agent, was observed at a portion of ^{about 3000 cm -1, but the IR spectrum of the unsurface-treated inorganic particles was observed.} No peak was observed in the portion of about 3000 cm ^-1. Further, in the aluminas 5 and 6, a larger peak was observed in the portion of ^{about 3000 cm -1 as compared with the aluminas 3 and 4.}
Therefore, it was confirmed that phenylphosphonic acid was bound to the surface of the surface-treated inorganic particles.

(Epoxy resin)
-Epoxy resin 1: Tetramethylbiphenyl type epoxy resin (bifunctional epoxy compound, manufactured by Mitsubishi Chemical Corporation, YX-4000)

(Phenol resin)
-Phenol resin 1: Phenol novolac resin (manufactured by Sumitomo Bakelite, PR-55617)

(Curing accelerator)
-Curing accelerator 1: Curing accelerator represented by the following formula

・ Curing accelerator 1: 2,3-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Additive)
-Silane coupling agent 1: N-phenylaminopropyltrimethoxysilane (manufactured by Toray Dow Corning, CF-4083)
・ Low stress agent 1: Silicone oil (manufactured by Toray Dow Corning, FZ-3730)
-Release agent 1: Montanic acid ester wax (WE-4, manufactured by Clariant Japan)
・ Pigment 1: Carbon black (manufactured by Mitsubishi Chemical Corporation, carbon # 5))

<Preparation of thermosetting resin composition>
Each component in the blending amounts shown in Table 1 below was mixed at room temperature using a mixer, and then heated and kneaded at a temperature of about 100 to 120 ° C. using a kneader. Then, after cooling to room temperature, it was pulverized to prepare a thermosetting resin composition.

The obtained thermosetting resin composition was evaluated for the following evaluation items.

(Thermal conductivity)
-Preparation of composite molded product The obtained thermosetting resin composition was compression molded at 180 ° C. for 10 minutes, and then oven-treated at 180 ° C. for 4 hours to obtain a composite molded product.

-Specific gravity of composite molded product The specific gravity was measured in accordance with JIS K 6911 (general test method for thermosetting plastics). As the test piece, a piece cut out from the composite molded body into a length of 2 cm, a width of 2 cm, and a thickness of 2 mm was used. The unit of specific gravity (SP) is g / cm ³ .

-Specific heat of the composite molded product The specific heat (Cp) of the obtained composite molded product was measured by the DSC method.

-Measurement of thermal conductivity of the composite molded product A test piece was obtained by surface-polishing the obtained composite molded product to a diameter of 10 mm and a thickness of 0.8 mm. Next, the thermal diffusivity (α) in the thickness direction of the plate-shaped test piece was measured by the laser flash method using the Xe flash analyzer TD-1RTV manufactured by ULVAC. The measurement was carried out under the condition of 25 ° C. in the air atmosphere.
For each of the composite molded bodies, the thermal conductivity was calculated from the obtained measured values of thermal diffusivity (α), specific heat (Cp), and specific gravity (SP) based on the following formula.
Thermal conductivity [W / m · K] = α [m ² / s] x Cp [J / kg · K] x Sp [g / cm ³ ]

(Minimum melt viscosity)
The minimum melt viscosity was measured using the obtained thermosetting resin composition. Using a cone plate viscometer (CV-1 manufactured by Toa Co., Ltd.), 160 ° C., rotation speed 94 rpm, No. The minimum melt viscosity was measured using 4 cones.

(CTE: coefficient of linear expansion)
Using the obtained thermosetting resin composition, molding at 180 ° C. for 10 minutes and curing at 180 ° C. for 4 hours were carried out to prepare a test piece having a thickness of φ5 mm × 2 mm. The coefficient of linear expansion of the obtained test piece was measured. Using a TMA (Thermal Mechanical Analyzer) test device (TMA / SS6100 manufactured by Seiko Instruments), a nitrogen flow rate of 150 mL / min, a heating rate of 10 ° C./min, a load of 98 mN, a compression mode, and a measurement temperature range of 30 to 320 ° C. Thermomechanical analysis (TMA) was measured for 2 cycles under the conditions of. From the obtained results, the average value (α1) of the linear expansion coefficient in the plane direction (XY direction) from 50 ° C. to 100 ° C. and the average value (XY direction) of the linear expansion coefficient in the plane direction (XY direction) from 240 ° C. to 270 ° C. α2) was calculated. The coefficient of linear expansion (ppm / ° C.) was the value of the second cycle.

(Tg: glass transition temperature)
The obtained thermosetting resin composition was molded at 180 ° C. for 10 minutes and cured at 180 ° C. for 4 hours to prepare a test piece having a thickness of 4.5 mm 12 mm × 2 mm. The glass transition temperature (° C.) of the obtained test piece was measured by a DMS (Dynamic Mechanical Analysis) tester (DMS6100 manufactured by Seiko Instruments Inc.) at a nitrogen flow rate of 150 mL / min, a temperature rise rate of 10 ° C./min, and a frequency of 10 Hz. , The measurement temperature range was 30 to 350 ° C., and the measurement was performed in the two-handed mode.

<Manufacturing of electronic devices>
A semiconductor chip was mounted on a lead frame, and an electrode pad of the semiconductor chip and a lead frame were wire-bonded using a copper wire to obtain a structure. The obtained structure is sealed with the thermosetting resin composition of the obtained example under the conditions of a mold temperature of 175 ° C., an injection pressure of 6.9 MPa, and a curing time of 2 minutes using a transfer molding machine. It was stop-molded and then post-cured at 175 ° C. for 4 hours to obtain an electronic device (semiconductor package). It was confirmed that an electronic device having excellent heat dissipation can be obtained in practice.

The thermosetting resin compositions of Examples 1 to 7 were thermally conductive with respect to Comparative Example 1, Examples 4 and 5 with respect to Comparative Example 2, and Example 6 with respect to Comparative Example 3. The result showed that the rate improved. Further, since the thermosetting resin compositions of Examples 1 to 7 can reduce the minimum melt viscosity, low-pressure molding and high filling of the heat conductive filler are possible.
The thermosetting resin composition of such an example can be suitably used for a thermosetting resin composition for encapsulating an electronic component, whereby an electronic device having excellent heat dissipation can be obtained.

100 Electronic device 10 Diatach material 20 Electronic element 30 Base material 32 Die pad 34 Outer lead 40 Bonding wire 50 Encapsulating resin layer

Claims (14)

Epoxy resin and
A thermosetting resin composition containing inorganic particles surface-treated with a surface treatment agent.
The surface treatment agent contains a phosphorus compound represented by the following general formula A.
The inorganic particles contain one or more selected from the group consisting of alumina, silicon carbide, and boron nitride.
Thermosetting resin composition.
[General formula A]
XP (= O) (OR) ₂
(In the general formula A, X is a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, and R may be the same or different from each other, and represents a hydrogen atom or an alkyl group.) The thermosetting resin composition according to claim 1.
A thermosetting resin composition in which the surface treatment agent contains the phosphorus compound in which the aromatic group in the general formula A is a phenyl group. The thermosetting resin composition according to claim 1 or 2.
A thermosetting resin composition in which the surface treatment agent contains phenylphosphonic acid. The thermosetting resin composition according to any one of claims 1 to 3.
A thermosetting resin composition having a particle size d50 of the inorganic particles having a cumulative frequency of 50% in a volume-based particle size distribution of 0.1 μm or more and 30 μm or less. The thermosetting resin composition according to any one of claims 1 to 4.
The thermosetting resin composition contains 60% by mass or more and 98% by mass or less of the solid content of the thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 5.
A thermosetting resin composition having a minimum melt viscosity of 19 Pa · s or less when measured under the conditions of 160 ° C. and a rotation frequency: 94 rpm using a cone plate type viscometer. The thermosetting resin composition according to any one of claims 1 to 6.
A thermosetting resin composition containing a phenol resin. The thermosetting resin composition according to any one of claims 1 to 7.
A powder, granular, or tablet-like thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 8.
A thermosetting resin composition used for forming a sealing material for sealing an electronic component. With the board
Electronic components provided on the board and
A sealing material for sealing the electronic component is provided.
The sealing material is composed of a cured product of the thermosetting resin composition according to any one of claims 1 to 9.
Electronic device. A method for producing a thermally conductive material, which comprises a step of surface-treating a surface treatment agent on the surface of inorganic particles.
The surface treatment agent contains a phosphorus compound represented by the following general formula A and contains.
The inorganic particles contain one or more selected from the group consisting of alumina, silicon carbide, and boron nitride.
A method for manufacturing a thermally conductive material.
[General formula A]
XP (= O) (OR) ₂
(In the general formula A, X is a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, and R may be the same or different from each other, and represents a hydrogen atom or an alkyl group.) The method for producing a thermally conductive material according to claim 11.
A method for producing a thermally conductive material in which the surface treatment agent contains an alcohol solvent. The method for producing a thermally conductive material according to claim 11 or 12.
The surface treatment step is a method for producing a thermally conductive material, which comprises any of a drying treatment at room temperature, a drying treatment at room temperature and under reduced pressure, and a drying treatment at 25 ° C. to 50 ° C. and under reduced pressure. A method for producing a thermosetting resin composition, which comprises a step of mixing the thermally conductive material obtained by the method for producing a thermally conductive material according to any one of claims 11 to 13 and an epoxy resin. ..

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