TW201936773A - Epoxy resin composition and electronic device - Google Patents

Abstract

This epoxy resin composition contains an epoxy resin, a curing agent and an inorganic filler, while containing chlorine-containing particles that contain an organic substance.

Description

Epoxy resin composition and electronic device

The invention relates to an epoxy resin composition and an electronic device.

So far, various developments have been made on epoxy resin compositions. As such a technique, for example, the technique described in Patent Document 1 is known. Patent Document 1 describes the following: In order to reduce the content of hydrolyzable chlorine derived from raw materials, an epoxy compound produced by a method that does not use epichlorohydrin (epichlorohydrin) in the raw materials is used (Patent Document 1 of 0012).
[Prior Technical Literature]
[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2012-92247

[Problems to be solved by the invention]

As a result of research conducted by the present inventors, it was found that the epoxy resin composition using an epoxy compound described in Patent Document 1 has room for improvement in terms of metal adhesion.
[Technical means to solve the problem]

As a result of further investigations by the present inventors, it was found that by appropriately controlling the presence state of chlorine contained in the epoxy resin composition, the characteristics of the epoxy resin composition can be changed. As a result of further research based on this insight, it was found that by including chlorine-containing particles containing an organic substance in the epoxy resin composition, the metal adhesion in the epoxy resin composition can be improved, and the present invention has been completed.
Although the detailed mechanism is not yet clear, it is believed that the chlorine-containing particles have an oxidizing effect on metals such as Cu, and this type of oxidation improves the surface of the metal and improves the affinity with the epoxy resin composition, so the metal adhesion is improved .

According to the present invention, an epoxy resin composition is provided, which includes an epoxy resin, a hardener and an inorganic filler,
The epoxy resin composition includes chlorine-containing particles containing organic matter.

In addition, according to the present invention, there is provided an electronic device provided with a cured product of the epoxy resin composition.

According to the present invention, there is provided an epoxy resin composition excellent in metal adhesion and an electronic device using the epoxy resin composition.

Hereinafter, the embodiments will be described as appropriate using drawings. In addition, in all drawings, the same constituent elements are denoted by the same symbols, and descriptions are omitted as appropriate.

[Epoxy resin composition]
The epoxy resin composition of this embodiment can contain an epoxy resin, a hardener, and an inorganic filler. This epoxy resin composition includes those containing organic-containing chlorine-containing particles.

According to the inventor's opinion, the following contents were determined.
Conventionally, a method of inspecting the total chlorine and hydrolyzable chlorine in an epoxy resin composition as a target and using the target content as an index has been known. Hydrolyzable chlorine and free chlorine, which are conventional objects, exist uniformly in the entire epoxy resin composition (for example, sealing material).
In contrast to this, a new form of existence of chlorine called organic-containing chlorine-containing particles (hereinafter, sometimes simply referred to as "chlorine-containing particles") was discovered. It was found that the presence of chlorine in the chlorine-containing particles is different from chlorine derived from hydrolyzable chlorine and free chlorine, and is locally present in the epoxy resin composition and becomes a high concentration in the particles. For example, the presence of chlorine in chlorine-containing particles can be clearly confirmed by element mapping of energy dispersive X-ray spectroscopy (EDX).
Although the detailed mechanism is not clear, it is believed that the chlorine-containing particles have an oxidation effect on metals such as Cu, and the surface of the metal is modified by this oxidation, and the affinity with the epoxy resin composition is improved, so that the ring can be improved. Metal adhesion in the oxygen resin composition.
Therefore, by including chlorine-containing particles containing organic matter in the epoxy resin composition, the metal adhesion in the epoxy resin composition can be improved.

In this embodiment, it can be set as follows: a chlorine-containing particle system, this epoxy resin composition is mixed with acetone to obtain a solution, and the obtained solution is filtered using a filter with a mesh size of 75 μm, and contained in Among the residues on the filter.

In this embodiment, the chlorine-containing particles can be detected by the following inspection method (hereinafter, sometimes referred to as an inspection method for chlorine-containing particles).
(1) As a sample (sample), prepare an epoxy resin composition or a raw material component constituting the epoxy resin composition (for example, epoxy resin, hardener, inorganic filler, etc.). As the epoxy resin composition, those obtained by mixing and kneading the raw material components and cooling the obtained kneaded material (B-stage epoxy resin composition) were used.
(2) Put 50g of the sample of (1) into a cleaned polypropylene 1000ml container, add 300ml of acetone, cover the container, and use a shaker at a temperature of 300 rounds / min at room temperature 25 ° Shake (mix) for 50 minutes. The acetone used was obtained by filtering through a filter with a mesh size of 12 μm.
(3) A filter cleaned with the above acetone is installed in the funnel set (filter appliance). The filter was obtained by ultrasonic cleaning of a nylon filter with a mesh size of 75 μm.
(4) Let the container shaken in (2) stand, and then inject the solution in the container from the upper part of the funnel of (3) and filter it with suction through a filter. When the particle size of the filler such as the inorganic filler contained in the sample is larger than the particle size of the mesh of the filter, the supernatant in the solution can also be filtered using a filter.
(5) Take out the funnel and dry the residue on the filter in the state of suction.
(6) Stick the adhesive surface of the measurement sheet to the filter surface of (5), and collect the residue on the adhesive surface of the measurement sheet.
(7) Peel off the measurement sheet of (6) from the filter, and use a digital microscope to create a composite photo of the entire surface of the adhesive surface. After adjusting the field of view magnification to 50 times, observe the entire surface, record the location of the residue and print it.
(8) Confirm the position of the residue in the printed matter of (7), and use a scanning electron microscope (SEM) / energy dispersive X-ray analyzer (EDS) to conduct a composition analysis of the residue.
(9) Based on the analysis results of the residue based on the energy dispersive X-ray spectroscopy (EDX) of (8), count the chlorine-containing particles contained in the epoxy resin composition or the raw material component constituting the epoxy resin composition The number and specific element composition in chlorine-containing particles. Various analyses can also be performed on chlorine-containing particles as needed.

The conventional method for measuring the total amount of chlorine is based on inorganic chlorine and hydrolyzable chlorine derived from raw materials such as epoxy resin. Therefore, the above-mentioned chlorine-containing particles cannot be measured.
In contrast, the above-mentioned method for inspecting chlorine-containing particles is a method for stably detecting the chlorine-containing particles contained in the epoxy resin composition, its raw material components, and the chlorine contained in the particles, which is newly established by the present inventors method.

The organic substance in the chlorine-containing particles contained in the epoxy resin can include one or more kinds selected from the group consisting of carbonates, amide compounds, and silicates. The organic substance may be a mixture with epoxy resin.
The organic matter in the above-mentioned chlorine-containing particles contained in the epoxy resin composition can include one selected from the group consisting of cellulose, polyethylene terephthalate, polypropylene, silk, polysiloxane compound, and amide compound One or more. These can be used alone or in combination of two or more. Alternatively, it may be a mixture of these.
The chlorine-containing particles may contain other organic substances. FT-IR (Fourier Transform Infrared Spectroscopy) can be used to identify organic matter from the spectral results of chlorine-containing particles.

The lower limit of the chlorine concentration in the chlorine-containing particles is, for example, 0.01 Atm% or more, may be 0.5 Atm% or more, or may be 0.1 Atm% or more. With this, the metal adhesion can be improved. On the other hand, the upper limit of the chlorine concentration in the chlorine-containing particles is, for example, 20 Atm% or less, preferably 10 Atm% or less, and more preferably 7 Atm% or less. With this, reliability can be improved.
In addition, when there are a plurality of chlorine-containing particles, the reliability can be improved by reducing the maximum value of the chlorine concentration.

The lower limit of the carbon concentration in the chlorine-containing particles is, for example, 40 Atm% or more, preferably 50 Atm% or more, and more preferably 60 Atm% or more. With this, chlorine can be stably fixed in the chlorine-containing particles. On the other hand, the upper limit of the carbon concentration in the chlorine-containing particles can be appropriately changed according to other constituent components, and is not particularly limited. For example, it may be 99 Atm% or less, 90 Atm% or less, or 85 Atm% The following may also be 70 Atm% or less.

The chlorine-containing particles may contain oxygen components. In this case, the oxygen concentration in the chlorine-containing particles may be, for example, 1 Atm% to 50 Atm%, 2 Atm% to 35 Atm%, 3 Atm% to 30 Atm%, or 3 Atm% to 28 Atm% (below , As long as there is no special explanation, it means that the upper limit and lower limit are included).

The chlorine-containing particles can contain one or more selected from the group consisting of Al element, Mg element, Si element, Fe element, Zn element, Ti element, Ca element, Na element, K element, S element, and carbonic acid compound. These can be used alone or in combination of two or more.
In this case, the Al concentration in the chlorine-containing particles may be 0.1 Atm% to 4 Atm%, or may be 0.1 Atm% to 1.0 Atm%.
The Mg concentration in the chlorine-containing particles may be 0.1 Atm% to 0.5 Atm%, or may be 0.1 Atm% to 0.4 Atm%.
The Si concentration in the chlorine-containing particles may be 0.1 Atm% to 5 Atm%, 0.1 Atm% to 2.0 Atm%, or 0.1 Atm% to 1 Atm%.
The Fe concentration in the chlorine-containing particles may be 0.1 Atm% to 4 Atm% or 0.1 Atm% to 2.0 Atm%.
The concentration of Zn in the chlorine-containing particles may be 0.1 Atm% to 5 Atm%, or may be 0.1 Atm% to 1.0 Atm%.
The Ti concentration in the chlorine-containing particles may be 0.01 Atm% to 1.0 Atm%, or may be 0.04 Atm% to 0.8 Atm%.
The Ca concentration in the chlorine-containing particles may be 0.01 Atm% to 17 Atm%, 0.02 Atm% to 6 Atm%, or 0.1 Atm% to 3 Atm%.
The Na concentration in the chlorine-containing particles may be 0.01 Atm% to 2 Atm% or 0.1 Atm% to 1.5 Atm%.
The K concentration in the chlorine-containing particles may be 0.01 Atm% to 5 Atm%, or may be 0.1 Atm% to 1.0 Atm%.
The concentration of S in the chlorine-containing particles may be 0.01 Atm% to 2 Atm% or 0.02 Atm% to 1.0 Atm%.
As the element component in the chlorine-containing particles, in addition to the element chlorine and carbon, one or more elements, two or more elements, or five or more other elements may be contained.

In this embodiment, the element composition or the element concentration in the chlorine-containing particles can be measured based on energy dispersive X-ray spectroscopy (EDX).

In this embodiment, the number of chlorine-containing particles in the epoxy resin composition or chlorine-containing particles in the epoxy resin can be measured by using the above-mentioned <method for inspecting chlorine-containing particles>.
The number of chlorine-containing particles in the 50 g epoxy resin composition can be set to one or more. With this, when an epoxy resin composition is used as a sealing material (epoxy resin composition for sealing) for sealing electronic parts, the adhesion to metal parts such as metal circuits, metal pads, and metal wires can be improved. In particular, the adhesion to metal components such as Cu can be improved. In addition, the number of chlorine-containing particles in the epoxy resin composition may be, for example, 10 or less, 5 or less, 3 or less, or 2 or less. As a result, when an epoxy resin composition is used as a sealing material for sealing electronic parts, reliability can be improved.
Regarding each component used in the above epoxy resin composition, for example, in 50 g of epoxy resin, the number of chlorine-containing particles may be 1 to 5 or less, or 1 to 3 or less, or 1 ～ 2 or less, may be one.

In the present embodiment, for example, by appropriately selecting the kind, blending amount, production method (manufacturing method or purification method after production) of each component included in the thermosetting resin composition, and the production method of the thermosetting resin composition Etc. can control the amount of the chlorine-containing particles. Among these, for example, for each component such as epoxy resin and hardener, a liquid substance such as a solution dissolved in an organic solvent is filtered with a filter; in this case, the filter with a small mesh size is used; The material is centrifuged to remove the lower layer containing foreign substances, and only the upper layer is used; the chlorine source is eliminated by completely removing the HCL generated in the reaction. A suitable one is selected as an element for setting the amount of the chlorine-containing particles to a desired numerical range.

Hereinafter, each component of the epoxy resin composition in the present embodiment will be described in detail.

[Epoxy resin]
The epoxy resin composition contains epoxy resin.
As the epoxy resin, there are all monomers, oligomers, and polymers having two or more epoxy groups in one molecule, and the molecular weight and molecular structure are not particularly limited.
Examples of the epoxy resin include bifunctional epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, stilbene epoxy resins, and hydroquinone epoxy resins. Epoxy resin; cresol novolac epoxy resin, phenol novolac epoxy resin, naphthol novolac epoxy resin and other novolac epoxy resin; phenol aralkyl ring containing phenylene skeleton Oxygen resin, phenol aralkyl type epoxy resin containing biphenylene skeleton, naphthol aralkyl type epoxy resin containing phenylene skeleton etc. phenol aralkyl type epoxy resin; triphenol methane type epoxy resin Resin and alkyl modified 3-functional epoxy resins such as triphenol methane epoxy resin; modified phenol epoxy resin such as dicyclopentadiene modified phenol epoxy resin, terpene modified phenol epoxy resin Resin; epoxy resin containing three well cores and other heterocyclic epoxy resin. These can be used alone or in combination of two or more.

The lower limit of the content of the epoxy resin in the epoxy resin composition relative to the total solid content of the epoxy resin composition is, for example, preferably 8% by mass or more, more preferably 10% by mass or more, and particularly preferably 12 Mass% or more. By setting the content of the epoxy resin to the above lower limit or more, the fluidity of the epoxy resin composition can be improved, and the moldability can be further improved.
On the other hand, the upper limit of the content of the epoxy resin is preferably 30% by mass or less, and more preferably 20% by mass or less with respect to the total solid content of the epoxy resin composition. By setting the content of the epoxy resin to the upper limit value or less, it is possible to improve the humidity resistance reliability, the reflow resistance, and the resistance of semiconductor devices and other structures having a cured product formed using an epoxy resin composition Temperature cycling.

In this specification, the total solid content of the epoxy resin composition refers to the non-volatile portion in the epoxy resin composition, and refers to the remaining portion from which volatile components such as water or solvent are removed. In addition, in the present embodiment, when a solvent is contained, the content relative to the entire epoxy resin composition refers to the content relative to the entire solid component excluding the solvent in the resin composition.

[hardener]
The epoxy resin composition can contain a hardener.
The curing agent is not particularly limited as long as it is generally used in epoxy resin compositions, and examples thereof include phenol resin curing agents, amine curing agents, anhydride curing agents, and thiol curing agents. Among these, from the viewpoint of the balance of flame resistance, moisture resistance, electrical characteristics, curability, storage stability, and the like, a phenol resin-based curing agent is preferred.

<Phenolic resin hardener>
The phenolic resin-based curing agent is not particularly limited as long as it is generally used in an epoxy resin composition, and examples thereof include phenol novolak resin and cresol novolak resin. Phenol, cresol, and m-benzene Phenol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β-naphthol, dihydroxynaphthalene and other phenols and formaldehyde or ketones under acid catalyst Novolak resin obtained by condensation or co-condensation, phenol aralkyl resin with phenylene skeleton synthesized from the above phenols and dimethoxy-p-xylene or bis (methoxymethyl) biphenyl , Phenol aralkyl resins such as phenol aralkyl resins with biphenylene skeletons, phenolic resins with triphenylmethane skeletons, etc. These can be used alone or in combination of two or more.

<Amine Hardener>
Examples of the amine-based hardener include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and m-xylylenediamine (MXDA), and diaminodiphenylmethane ( DDM), m-phenylenediamine (MPDA), diaminodiphenyl sulfone (DDS) and other aromatic polyamines, and polyamine compounds such as dicyandiamine (DICY), organic acid dihydrazine, etc. These can be used alone or in combination of two or more.

<Acid anhydride hardener>
Examples of the acid anhydride-based hardener include hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), maleic anhydride and other alicyclic anhydrides, and 1,2,4-benzenetricarboxylic anhydride (TMA). , Aromatic acid anhydrides such as pyromellite dianhydride (PMDA), diphenyl ketone tetracarboxylic acid (BTDA), phthalic anhydride, etc., these can be used alone or in combination of two or more.

<Thiol-based hardener>
Examples of the thiol-based hardener include trimethylolpropane tris (3-mercaptobutyrate), trimethylolethane tris (3-mercaptobutyrate), etc. These can be used alone or in combination Use more than 2 types.

<Other hardeners>
Examples of other hardeners include isocyanate compounds such as isocyanate prepolymers and blocked isocyanates, and organic acids such as carboxylic acid-containing polyester resins. These may be used alone or in combination of two or more.
In addition, two or more kinds of hardeners of different systems may be used in combination.

When the above-mentioned hardener is a phenolic resin-based hardener, the equivalent ratio of epoxy resin to hardener, that is, the number of epoxy groups in the epoxy resin / phenolic hydroxyl mole in the phenolic resin-based hardener The number ratio is not particularly limited. In order to obtain an epoxy resin composition excellent in moldability and reliability, for example, a range of 0.5 to 2 is preferable, a range of 0.6 to 1.8 is more preferable, and a range of 0.8 to 1.5 is most preferable The following range.

[Inorganic filler]
The epoxy resin composition can contain an inorganic filler.
Examples of the inorganic filler include fused silica such as fused and crushed silica and fused spherical silica, silicon dioxide such as crystalline silica, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride. Wait. These can be used alone or in combination of two or more. Among them, silicon dioxide such as fused and crushed silicon dioxide, molten spherical silicon dioxide, and crystalline silicon dioxide is preferred, and more preferably, molten spherical silicon dioxide can be used.

The lower limit value of the average particle diameter (D50) of the inorganic filler may be, for example, 0.01 μm or more, 1 μm or more, or 5 μm or more. As a result, the fluidity of the epoxy resin composition is improved, and the moldability can be improved more effectively. In addition, the upper limit of the average particle diameter (D50) of the inorganic filler is, for example, 50 μm or less, preferably 40 μm or less. With this, unfilling and the like can be reliably suppressed. In addition, the inorganic filler of the present embodiment can include at least an inorganic filler having an average particle diameter (D50) of 1 μm or more and 50 μm or less. With this, the fluidity can be made more excellent.

The average particle size (D50) of the above inorganic filler is measured on a volume basis using a commercially available laser diffraction particle size distribution measuring device (for example, manufactured by SHIMADZU CORPORATION, SALD-7000), and the median The diameter (D50) is set as the average particle diameter.

In addition, for the inorganic filler, for example, two or more fillers having different average particle diameters (D50) may be used in combination. Thereby, the filling property of the inorganic filler with respect to the total solid content of the epoxy resin composition can be improved more effectively. In addition, in the present embodiment, from the viewpoint of improving the filling property of the epoxy resin composition, it can be used as an example: a filler including an average particle diameter of 0.01 μm or more and 1 μm or less and a filler having an average particle size of more than 1 μm and 50 μm or less. material.
In addition, as an example of the inorganic filler of the present embodiment, from the viewpoint of further improving the filling property of the epoxy resin composition, for example, the first filler having an average particle diameter of 0.01 μm or more and 1 μm or less and an average particle size of more than 1 μm In addition, the second filler material having an average particle size of 15 μm or less and the third filler material having an average particle size of more than 15 μm and 50 μm or less.

The lower limit of the content of the inorganic filler relative to the total solid content of the epoxy resin composition is preferably 70% by mass or more, more preferably 73% by mass or more, and particularly preferably 75% by mass or more. As a result, low moisture absorption and low thermal expansion can be improved, and temperature cycle resistance or reflow resistance of semiconductor devices and other structures can be more effectively improved. On the other hand, the upper limit of the content of the inorganic filler relative to the total solid content of the epoxy resin composition is, for example, preferably 95% by mass or less, more preferably 93% by mass or less, and particularly preferably 90% by mass or less . With this, the fluidity or filling property at the time of molding the epoxy resin composition can be more effectively improved.

[Hardening accelerator]
The said epoxy resin composition can further contain a hardening accelerator as needed.
The curing accelerator can be used by a general epoxy resin composition as long as it promotes the cross-linking reaction between the epoxy resin and the curing agent.

Examples of the above-mentioned hardening accelerator include diacrylic bicycloalkenes such as 1,8-diazepine (5,4,0) undecene-7 and their derivatives; triphenylphosphine, methyldiphenylphosphine, etc. Organic phosphines; imidazole compounds such as 2-methylimidazole (imidazole-based hardening accelerators); tetra-substituted phosphonium ･ tetraphenyl borate and other tetra-substituted phosphonium ･ tetra-substituted borate and so on. These can be used alone or in combination of two or more.

Examples of the imidazole-based hardening accelerator include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4. -Methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl- 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 -Cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- [2 ' -Methylimidazolyl (1 ')]-ethyl-s-three wells, 2,4-diamino-6- [2'-undecylimidazolyl (1')]-ethyl-s- Three wells, 2,4-diamino-6- [2'-ethyl-4-methylimidazolyl (1 ')]-ethyl-s-three wells, 2,4-diamino-6- [2'-Methylimidazolyl (1 ')]-ethyl-s-iso-cyanuric acid adduct of Mitsui, 2-phenylimidazole-isocyanic acid adduct, 2-methyl Isocyanuric acid adducts of imidazole, 2-phenyl-4,5-dihydroxydimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc. These can be used alone or in combination of two or more.

The lower limit of the content of the hardening accelerator is, for example, preferably 0.20% by mass or more, more preferably 0.40% by mass or more, and particularly preferably 0.70% by mass or more with respect to the total solid content of the epoxy resin composition. By setting the content of the hardening accelerator to the above lower limit or more, the hardenability during molding can be effectively improved. On the other hand, the upper limit of the content of the hardening accelerator is, for example, preferably 3.0% by mass or less, and more preferably 2.0% by mass or less with respect to the total solid content of the epoxy resin composition. By setting the content of the hardening accelerator to the upper limit value or less, it is possible to improve the fluidity during molding.

[Coupling agent]
The above epoxy resin composition may contain a coupling agent as needed.
As the coupling agent, for example, various silane-based compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, urea silane, vinyl silane, methacrylic silane, titanium compound, aluminum chelate, aluminum / Zirconium compounds and other well-known coupling agents. Examples of these include vinyl trichlorosilane, vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tri (β-methoxy ethoxy) silane, and γ-methacryl amide Propylpropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyl Triethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyl Triethoxysilane, vinyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ -Anilinopropylmethyldimethoxysilane, γ- [bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-amino Propyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldi Methoxysilane, phenylaminopropyltrimethoxysilane, γ- (β-amine Ethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (dimethoxymethylsilylisopropyl) ethylenediamine, methyl Trimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane , Γ-chloropropyltrimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3- Silane-based coupling agent such as hydrolyzate of propylene oxypropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylene) propylamine, triisostearyl acetyl group Isopropyl titanate, tris (dioctyl pyrophosphate) isopropyl titanate, tris (N-aminoethyl-aminoethyl) isopropyl titanate, tetraoctyl bis (bis (thirteen Alkyl) phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di (tridecyl)) phosphite titanate, bis (di Octyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) Ethyl titanate, isopropyl trioctyl titanate, dimethyl propenyl isostearyl isopropyl titanate, tris (dodecyl) benzenesulfonyl isopropyl titanate, isostearyl Acetyl dipropenyl isopropyl titanate, tris (dioctyl phosphate) isopropyl titanate, tricumylphenyl isopropyl titanate, tetraisopropyl bis (dioctyl phosphite ) Titanate coupling agent such as titanate. These can be used alone or in combination of two or more. Among these, silane-based compounds of epoxy silane, mercapto silane, amino silane, alkyl silane, urea silane or vinyl silane are more preferable. In addition, from the viewpoint of more effectively improving the filling property or formability, it is particularly preferable to use a second-stage aminosilane represented by phenylaminopropyltrimethoxysilane.

The lower limit of the content of the coupling agent relative to the total solid content of the epoxy resin composition is preferably 0.1% by mass or more, and more preferably 0.15% by mass or more. By setting the content of the coupling agent to the above lower limit or more, the fluidity of the epoxy resin composition can be improved. On the other hand, the upper limit of the content of the coupling agent relative to the total solid content of the epoxy resin composition is preferably 1% by mass or less, and more preferably 0.5% by mass or less. By setting the content of the coupling agent to the upper limit value or less, the mechanical strength of the cured product of the epoxy resin composition can be improved.

Moreover, the said epoxy resin composition can contain a low-stress agent as needed.
The low-stress agent can include, for example, polybutadiene and styrene selected from silicone oil, silicone rubber, polyisoprene, 1,2-polybutadiene, 1,4-polybutadiene, etc. -Butadiene rubber, acrylonitrile-butadiene rubber, polychloroprene, poly (oxypropylene), poly (oxytetramethylene) glycol, polyene glycol, poly-ε-caprolactone, etc. One or more of thermoplastic elastomer, polysulfide rubber and fluororubber. Among these, from the viewpoint of controlling the elastic modulus within a desired range, and improving the temperature cycle resistance and reflow resistance of the obtained semiconductor package and other structures, it is possible to choose to include silicone rubber , At least one of polysiloxane oil and acrylonitrile-butadiene rubber is an excellent aspect.

When the aforementioned low-stress agent is used, the content of the entire low-stress agent relative to the total solid content of the epoxy resin composition is preferably 0.05% by mass or more, and more preferably 0.10% by mass or more. On the other hand, the content of the low-stress agent relative to the total solid content of the epoxy resin composition is preferably 2% by mass or less, and more preferably 1% by mass or less. By controlling the content of the low-stress agent within this range, the temperature cycle resistance and reflow resistance of the obtained semiconductor package and other structures can be more reliably improved.

[Other ingredients]
The epoxy resin composition of this embodiment may contain other components as needed. Examples of other components include ion scavengers such as hydrotalcite and aluminum-magnesium-based inorganic ion exchangers; colorants such as carbon black and colcothar; natural waxes such as palm wax and montanic acid ester wax , Diethanolamine-dimontanate, toluene diisocyanate modified oxidized wax and other synthetic waxes, zinc stearate and other higher fatty acids and their metal salts or paraffin wax and other release agents; antioxidants and other additives. These additives can be blended appropriately.

[Manufacturing method of epoxy resin composition]
The method for producing the epoxy resin composition of this embodiment will be described.
The method for manufacturing the epoxy resin composition can include a batch selection step and a mixing step. First, prepare a plurality of epoxy resins a from different batches, and measure the number of chlorine-containing particles of the prepared epoxy resin a using the above-mentioned inspection method of the chlorine-containing particles. Based on the obtained measurement results, the epoxy resin a containing chlorine-containing particles is selected from a plurality of batches and used as the raw material component of the epoxy resin composition (epoxy resin A) (batch selection step). The other raw material components are mixed with the epoxy resin A (mixing step) to obtain an epoxy resin composition.
In addition, for other components (for example, hardener b or inorganic filler c), batch selection is also performed in the same manner as epoxy resin a, and the hardener b containing chlorine-containing particles or inorganic filler c can be used as Raw material components (hardener B or inorganic filler C). In addition, a method of controlling the amount of the chlorine-containing particles can be appropriately added.

In addition, in the above mixing step, the mixture can be obtained by mixing by a known method. Furthermore, the kneaded material is obtained by melt-kneading the mixture. As the kneading method, for example, an extrusion kneading machine such as a uniaxial kneading extruder or a biaxial kneading extruder or a roller kneading machine such as a mixing roller can be used, and a biaxial kneading extruder is preferably used. After cooling, the kneaded material can be made into powder, granule, ingot or tablet.

As a method of obtaining the powdery granular resin composition, for example, a method of pulverizing the kneaded material with a pulverizing device can be mentioned. It can also be crushed to shape the kneaded material into pieces. As the pulverizing device, for example, a hammer mill, a stone grinder, a roller crusher, or the like can be used.

As a method for obtaining a granular or powdery resin composition, for example, a granulation method such as a hot cutting method can be used. This hot cutting method is to install a mold with a small diameter at the outlet of the kneading device and discharge it from the mold. The kneaded material in the molten state is cut to a predetermined length with a cutter or the like. In this case, it is preferable to perform degassing after obtaining a granular or powdery resin composition by a granulation method such as hot-cutting, and when the temperature of the resin composition has not decreased too much.

The epoxy resin composition of this embodiment can be used for various applications. For example, the epoxy resin composition of this embodiment can be used for a sealing resin composition or a fixing resin composition. As the resin composition for sealing (resin composition for sealing electronic components) of this embodiment, it is possible to seal electronic components such as semiconductor wafers, and it can be applied to the resin composition for semiconductor sealing used in the above semiconductor package, Resin composition for sealing of vehicle-mounted electronic control unit mounted with substrates of electronic parts, etc. or for sensor, sensor module, camera, camera module, display module, dry battery button Resin composition for battery module sealing etc. The resin composition for fixing of the present embodiment can also be used for fixing motor parts. For example, it can be applied to a resin composition for fixing a rotor core magnet and a resin for fixing a stator.

The structure (for example, an electronic device) of the present embodiment is provided with a cured product of the epoxy resin composition. Examples of the above-described structure include a semiconductor package, an electronic control unit that encapsulates a substrate on which electronic parts are mounted, a sensor, a sensor module, a camera, a camera module, a module with a display, and a dry battery with a button Battery modules, motors, etc.

FIG. 1 is a diagram showing a cross-sectional structure of an example of a semiconductor device using the epoxy resin composition of this embodiment. A semiconductor element 1 is fixed on a die pad 3 via a hardened body 2 of a die bond material. The electrode pad of the semiconductor element 1 and the lead frame 5 are connected by a bonding wire 4. The semiconductor element 1 is sealed by the cured body 6 of the epoxy resin composition of this embodiment.

2 is a diagram showing a cross-sectional structure of an example of a single-sided sealed semiconductor device using the epoxy resin composition of the present embodiment. The semiconductor element 1 is fixed on the solder resist 7 of the layered body in which the layer of the solder resist 7 is formed on the surface of the substrate 8 via the cured material 2 of the die-bonding material. In order to conduct the semiconductor element 1 and the substrate 8, the solder resist 7 on the electrode pad is removed by a development method to expose the electrode pad of the substrate 8. The electrode pad of the semiconductor element 1 and the electrode pad of the substrate 8 are connected by a bonding wire 4. With the cured body 6 of the epoxy resin composition of this embodiment, only the side of the substrate 8 on which the semiconductor element 1 is mounted is sealed. The electrode pad on the substrate 8 and the solder ball 9 on the non-sealing surface side of the substrate 8 are internally joined.

The epoxy resin composition of this embodiment can be used as a sealing resin composition for sealing a vehicle-mounted electronic control unit.
FIG. 3 is a schematic cross-sectional view showing an example of the structural body (vehicle electronic control unit 10) of this embodiment.
The vehicle-mounted electronic control unit 10 is used to control the engine, various vehicle-mounted devices, and the like. As shown in FIG. 3, the in-vehicle electronic control unit 10 includes, for example, a substrate 12, an electronic component 16 mounted on the substrate 12, and a sealing resin layer 14 that seals the substrate 12 and the electronic component 16. The substrate 12 has connection terminals 18 for connecting to the outside at least on one side. The on-vehicle electronic control unit 10 of an example of the present embodiment is electrically connected to the docking connector via the connection terminal 18 by fitting the connection terminal 18 and the docking connector.

The substrate 12 is, for example, a wiring substrate provided with circuit wiring on one or both of one side and the other side opposite to the one side. As shown in FIG. 3, the substrate 12 has a flat plate shape, for example. In this embodiment, an organic substrate formed of an organic material such as polyimide can be used as the substrate 12. In addition, the thickness of the substrate 12 is not particularly limited. For example, it may be 0.1 mm or more and 5 mm or less, and preferably 0.5 mm or more and 3 mm or less.

In this embodiment, the substrate 12 may be provided with, for example, a through-hole 120 penetrating the substrate 12 to connect one side and the other side. In this case, the wiring provided on one side of the substrate 12 and the wiring provided on the other side are electrically connected via the conductive pattern provided in the through hole 120. The conductive pattern is formed along the wall surface of the through hole 120. That is, the conductive pattern in the through hole 120 is formed into a cylindrical shape. In the through-hole 120 after the sealing step, the void hole constituted by the inner wall surface of the conductive pattern is filled with the cured product (sealing resin layer 14) of the epoxy resin composition of this embodiment.

For example, electronic components 16 are mounted on one or both of one side and the other side of the substrate 12. The electronic component 16 is not particularly limited as long as it can be mounted on an in-vehicle electronic control unit. For example, a microcomputer can be mentioned.

In the vehicle-mounted electronic control unit 10 of this embodiment, the substrate 12 can be mounted on a metal chassis, for example. The metal base can function as a heat sink for dissipating heat generated from the electronic component 16, for example. In this embodiment, for example, the vehicle-mounted electronic control unit 10 can be formed by integrally sealing and molding the metal base and the substrate 12 mounted on the metal base with an epoxy resin composition. The metal material constituting the metal base is not particularly limited, and for example, it may include iron, copper, and aluminum, and one or more alloys including these. In addition, the vehicle-mounted electronic control unit 10 may not have a metal base.

The present invention has been described above based on the embodiments. However, the present invention is not limited to the above embodiments, and its configuration can be changed without changing the gist of the present invention.
[Example]

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the description of these examples.

The raw material components used in each example and each comparative example are as follows.

(Colorant)
Colorant 1: Carbon black (Carbon # 5, manufactured by Mitsubishi Chemical Corporation)

(Hardening accelerator)
Hardening accelerator 1: Hardening accelerator 1 represented by the following formula

[Synthesis method of hardening accelerator 1]
In a flask containing 1800 g of methanol, 249.5 g of phenyltrimethoxysilane and 384.0 g of 2,3-dihydroxynaphthalene were added and dissolved, and then 28% sodium methoxide-methanol was added dropwise with stirring at room temperature Solution 231.5g. If a solution prepared by dissolving 503.0 g of tetraphenylphosphonium bromide in 600 g of methanol was added dropwise under stirring at room temperature, crystals were precipitated. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain the hardening accelerator 1 of peach white crystals.

Hardening accelerator 2: Hardening accelerator 2 represented by the following formula

[Synthesis method of hardening accelerator 2]
A separable flask with a cooling tube and a stirring device was charged with 12.81g (0.080mol) of 2,3-dihydroxynaphthalene, 16.77g (0.040mol) of tetraphenylphosphonium bromide and 100ml of methanol and stirred to make Dissolves evenly. If a sodium hydroxide solution obtained by dissolving 1.60 g (0.04 ml) of sodium hydroxide in 10 ml of methanol in advance is slowly added dropwise to the flask, crystals are precipitated. The precipitated crystals were filtered, washed with water, and vacuum-dried to obtain a hardening accelerator 2 represented by the above formula.

(Coupling agent)
Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (CF-4083, manufactured by Dow Corning Toray Co., Ltd.)
Coupling agent 2: 3-mercaptopropyltrimethoxysilane (S810, manufactured by CHISSO CORPORATION)

(Epoxy resin A)
Epoxy resin a1: phenol aralkyl type epoxy resin containing biphenylene skeleton (NC3000L, manufactured by Nippon Kayaku Co., Ltd.)
Epoxy resin a2: Bisphenol A type epoxy resin (YL6810, manufactured by Mitsubishi Chemical Corporation)
Epoxy resin a3: Biphenyl type epoxy resin (YX4000K, manufactured by Mitsubishi Chemical Corporation)
Epoxy resin 4: Epoxy resin synthesized without epichlorohydrin (glycidyl ether liquid epoxy resin, EPICLON EXA-4880 manufactured by DICCorporation, total chlorine: 0 ppm)
Epoxy resin 5: Epoxy resin synthesized without using epichlorohydrin (alicyclic epoxy resin, EHPE3150 manufactured by Daicel Corporation, total chlorine: 0 ppm)

(Inorganic filler C)
Inorganic filler material c1: molten spherical silica (FB-100XFC, manufactured by Denka Company Limited, average particle size 13 μm)
Inorganic filler material c2: molten spherical silica (MSV-SC3, manufactured by TATSUMORI LTD., Average particle diameter 19 μm)
Inorganic filler c3: spherical silica (SD2500-SQ, manufactured by Admatechs Company Limited, average particle size 0.5 μm)
Inorganic filler c4: spherical silica (SC-2500-SQ, manufactured by Admatechs Company Limited, average particle diameter 0.5 μm)
Inorganic filler material c5: molten spherical silica (FB-950FC, manufactured by Denka Company Limited, average particle size 22 μm)

(Flame retardant)
Flame retardant 1: aluminum hydroxide (BE043, manufactured by Nippon Light Metal Company, Ltd.)
Flame retardant 2: aluminum hydroxide (CL-303, manufactured by Sumitomo Chemical Co., Ltd.)

(Hardener B)
Hardener b1: Phenol aralkyl resin with biphenylene skeleton (MEH-7851SS, manufactured by Meiwa Plastic Industries, Ltd.)
Hardener b2: Novolac-type phenolic resin (PR-HF-3, manufactured by Sumitomo Bakelite Co., Ltd.)

(Ion trapping agent)
Ion trap 1: hydrotalcite (DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd.)
Ion trapping agent 2: Aluminum-magnesium-based inorganic ion exchanger (IXE-700F, manufactured by TOAGOSEI CO., LTD.)

(Low stress agent)
Low stress agent 1: acrylonitrile-butadiene copolymer compound (CTBN1008SP, manufactured by POWERTECH TECHNOLOGY JAPAN LTD.)
Low stress agent 2: Molten reactant A (polysiloxane) obtained by the following synthesis method
[Synthesis method of molten reactant A]
66.1 parts by weight of bisphenol A type epoxy resin (manufactured by Japan Epoxy Resins Co., Ltd., jER (registered trademark) YL6810, softening point 45 ° C, epoxy equivalent 172) represented by the following formula (8) at 140 ° C The mixture was heated and melted, and 33.1 parts by weight of organic polysiloxane represented by the following formula (7) and 0.8 parts by weight of triphenylphosphine were added, and melt-mixed for 30 minutes to obtain a molten reactant A.


Low stress agent 3: polysiloxane containing alkyl group (Silsoft034, manufactured by Momentive)

(Release agent)
Release agent 1: montanate wax (WE-4, manufactured by Clariant Japan K.K.)
Release agent 2: Diethanolamine-dimontanate (NC-133, manufactured by ITOH OIL CHEMICALS CO., LTD.)
Release agent 3: toluene diisocyanate modified oxidized wax (NPS-6010, manufactured by NIPPON SEIRO CO., LTD.)
Release agent 4: stearic acid (SR-Sakura, manufactured by NOF CORPORATION)

<Preparation of epoxy resin composition>
[Example 1]
A plurality of epoxy resins a1 in different batches were prepared, and the number of chlorine-containing particles of the prepared epoxy resin a1 was measured using the following chlorine-containing particle inspection method. Based on the obtained measurement results, the epoxy resin a1 containing the number of chlorine-containing particles shown in Table 2 was selected from a plurality of batches and used as the raw material component of the epoxy resin composition (epoxy resin A). As the hardener B, a hardener b1 was used, and as the inorganic filler C, inorganic fillers c1 and c3 were used.
Next, the other raw material components described in Table 1 are used together with the above-mentioned epoxy resin A, hardener B, and inorganic filler C, and are mixed at room temperature using a mixer according to the blending ratio shown in Table 1, at 70 to Roll mixing was carried out at 90 ° C. Next, after cooling the obtained kneaded material, this was pulverized to obtain an epoxy resin composition.
Regarding the obtained epoxy resin composition, the number of chlorine-containing particles was measured using the following inspection method of chlorine-containing particles. The results are shown in Table 2.

[Example 2]
A plurality of epoxy resins a2 in different batches were prepared, and the number of chlorine-containing particles of the prepared epoxy resin a2 was measured using the following chlorine-containing particle inspection method. Based on the obtained measurement results, the epoxy resin a2 containing the number of chlorine-containing particles shown in Table 2 was selected from a plurality of batches to be used as the raw material component of the epoxy resin composition (epoxy resin A), Except for this, the epoxy resin composition was obtained in the same manner as in Example 1.

[Example 3]
As the inorganic filler C, the inorganic fillers c2 and c3 were used, except that the epoxy resin composition was obtained in the same manner as in Example 1.

[Example 4]
Regarding the same batch of hardener b1 as in Example 1, the solution obtained by filtering and dissolving in an organic solvent using a 1 μm filter was used as the raw material component (hardener B). 1 The epoxy resin composition was obtained in the same manner.

[Example 5]
A plurality of epoxy resins a3 in different batches were prepared, and the number of chlorine-containing particles of the prepared epoxy resin a3 was measured using the following chlorine-containing particle inspection method. Based on the obtained measurement results, an epoxy resin a3 containing the number of chlorine-containing particles shown in Table 2 was selected from a plurality of batches and used as the raw material component of the epoxy resin composition (epoxy resin A). As the hardener B, a hardener b1 was used, and as the inorganic filler C, inorganic fillers c4 and c5 were used.
Next, the other raw material components described in Table 1 are used together with the above-mentioned epoxy resin A, hardener B, and inorganic filler C, and are mixed at a normal temperature using a mixer according to the blending ratio shown in Table 1, at 70 to 90 Roll mixing was carried out at ℃. Next, after cooling the obtained kneaded material, this was pulverized to obtain an epoxy resin composition.
Regarding the obtained epoxy resin composition, the number of chlorine-containing particles was measured using the following inspection method of chlorine-containing particles. The results are shown in Table 2.

[Example 6]
The hardener b2 was used instead of the hardener b1 of Example 2. As for the hardener b2, a solution obtained by filtering and dissolving in an organic solvent using a 1 μm filter was used as a raw material component (hardener B). Except for this, an epoxy resin composition was obtained in the same manner as in Example 5.

[Example 7]
Regarding the epoxy resin a3 in a different batch from Example 5, a solution obtained by dissolving in an organic solvent was filtered using a 1 μm filter, and the number containing the number shown in Table 2 measured using the following chlorine-containing particle inspection method An epoxy resin composition was obtained in the same manner as in Example 5 except that the epoxy resin a3 containing chlorine particles was used as a raw material component (epoxy resin A).

[Comparative Example 1]
An epoxy resin composition was obtained in the same manner as in Example 1 except that epoxy resin 4 was used as epoxy resin A.
[Comparative Example 2]
An epoxy resin composition was obtained in the same manner as in Example 5 except that epoxy resin 5 was used as epoxy resin A.

[Comparative Example 3]
Regarding the epoxy resin a2 in a different batch from Example 2, the solution obtained by dissolving in an organic solvent was filtered using a 1 μm filter, and the number of chlorine-containing particles measured using the following chlorine-containing particle inspection method was 0 An epoxy resin composition was obtained in the same manner as in Example 2 except that each epoxy resin a2 was used as a raw material component (epoxy resin A).

(Inspection method of chlorine-containing particles)
(1) As a sample, an epoxy resin composition or raw material components constituting the epoxy resin composition were prepared. The epoxy resin composition was obtained by mixing and kneading the raw material components and cooling the kneaded material obtained.
(2) Put 50g of the sample of (1) into a cleaned polypropylene 1000ml container and add 300ml of acetone. After closing the container, use a shaker at 300 reciprocating / min conditions at room temperature 25 ° C Shake (mix) for 50 minutes. The acetone used was obtained by filtering through a filter with a mesh size of 12 μm.
(3) A filter cleaned with the above acetone is installed in the funnel set (filter appliance). For the filter, a nylon filter with a mesh size of 75 μm was used for ultrasonic cleaning.
(4) Let the container shaken in (2) stand, and then inject the solution in the container from the upper part of the funnel of (3) and filter it with suction through a filter.
(5) Take out the funnel and dry the residue on the filter in the state of suction.
(6) Stick the adhesive surface of the measurement sheet to the filter surface of (5), and collect the residue on the adhesive surface of the measurement sheet.
(7) The measurement sheet of (6) was peeled from the filter, and a composite photograph was produced using a digital microscope for the entire surface of the adhesive surface. After adjusting the field of view magnification to 50 times, observe the entire surface, record the location of the residue and print it.
(8) The position of the residue was confirmed in the printed matter of (7), and a composition analysis was performed on the residue using a scanning electron microscope (SEM) / energy dispersive X-ray analyzer (EDS). As a result of SEM image observation, it was confirmed that particulate residues were present.
(9) Measure (count) the content contained in the epoxy resin composition or the raw material component constituting the epoxy resin composition based on the analysis result of the residue based on the energy dispersive X-ray spectroscopy (EDX) of (8) The number of chlorine particles.

In addition, regarding the chlorine-containing particles detected in the epoxy resin or the epoxy resin composition, the organic matter in the chlorine-containing particles was identified from the results of the spectrum using FT-IR (Fourier Transform Infrared Spectroscopy). Table 2 shows the evaluation results.

[Table 1]

[Table 2]

In Table 2, it is identified that the organic matter of the chlorine-containing particles 1A-1 contains a mixture of epoxy resin and carbonate; the organic matter of the chlorine-containing particles 1A-2 contains carbonate; and the organic matter of the chlorine-containing particles 2A-1 contains an amide compound; The organic matter of the chlorine-containing particles 5A-1 contains carbonate; the organic matter of the chlorine-containing particles 5A-2 contains carbonate and silicate; the organic matter of the chlorine-containing particles 1-4 contains cellulose; the organic matter of the chlorine-containing particles 2-1 contains fibers The organic matter containing 3-4 chlorine-containing particles contains cellulose.

<Evaluation>
The obtained epoxy resin composition was evaluated as follows. Table 2 shows the evaluation results.

(Spiral flow)
The obtained epoxy resin composition was subjected to spiral flow measurement. The spiral flow measurement was performed by the following steps: using a low-pressure rotary injection molding machine ("KTS-15" manufactured by Kohtaki Precision Machine Co., Ltd.) at a mold temperature of 175 ° C, an injection pressure of 6.9 MPa, and a hardening time of 120 seconds Next, the epoxy resin composition was injected into the mold for spiral flow measurement according to EMMI-1-66, and the flow length was measured. The results are shown in Table 2.

(Gel time)
A sample composed of the obtained epoxy resin composition was placed on a hot plate set at 175 ° C. After the sample was melted, the time until hardening was measured while stirring with a spatula. The unit is seconds (sec). The results are shown in Table 2.

(Metal adhesion)
Using the obtained epoxy resin composition, and using a low-pressure rotary injection molding machine (manufactured by SANJO SEIKI CO., LTD., "AV-600-50-TF") at a mold temperature of 175 ° C, an injection pressure of 10 MPa, and a hardening time of 180 On the condition of seconds, 10 pieces of 3.6 mmφ × 3 mm adhesion strength test pieces were formed per level on a short strip-shaped copper lead frame for test of 9 × 29 mm. Next, the wafer shear strength of the test piece and the frame was measured at room temperature using an automatic wafer shear measuring device (manufactured by Nordson Advanced Technology KK, model DAGE4000). Table 2 shows the average value of the wafer shear strength (MPa) of 10 test pieces.

Compared with the epoxy resin compositions of Comparative Examples 1 to 3, the epoxy resin compositions of Examples 1 to 7 have improved adhesion to the Cu frame, and thus it was found that the metal adhesion is excellent.

This application claims priority based on Japanese Application No. 2017-234008 filed on December 6, 2017, and incorporates the entire contents of the disclosure.

1‧‧‧Semiconductor components

2‧‧‧Viscous crystal hardened body

3‧‧‧chip pad

4‧‧‧welding line

5‧‧‧Lead frame

6‧‧‧hardened body

7‧‧‧ solder resist

8‧‧‧ substrate

9‧‧‧ solder ball

10‧‧‧Vehicle electronic control unit

12‧‧‧ substrate

14‧‧‧Sealing resin layer

16‧‧‧Electronic parts

18‧‧‧Connecting terminal

120‧‧‧Through hole

The above objects and other objects, features, and advantages are made clearer by the preferred embodiments described below and the accompanying drawings.

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

2 is a cross-sectional view showing an example of a semiconductor device.

3 is a cross-sectional view showing an example of a structure.

Claims (11)

An epoxy resin composition comprising epoxy resin, hardener and inorganic filler, The epoxy resin composition includes chlorine-containing particles containing organic matter. For example, the epoxy resin composition according to item 1 of the patent application scope, in which The chlorine concentration in the chlorine-containing particles measured by energy dispersive X-ray spectroscopy, that is, EDX, is 0.01 Atm% or more and 20 Atm% or less. For example, the epoxy resin composition according to item 1 of the patent application scope, in which The chlorine-containing particles contain one or more kinds selected from the group consisting of Al element, Mg element, Si element, Fe element, Zn element, Ti element, Ca element, Na element, K element, S element, and carbonic acid compound. For example, the epoxy resin composition according to item 1 of the patent application scope, in which The carbon concentration in the chlorine-containing particles measured by energy dispersive X-ray spectroscopy, that is, EDX, is 40 Atm% or more and 99 Atm% or less. For example, the epoxy resin composition according to item 1 of the patent application scope, in which The oxygen concentration in the chlorine-containing particles measured by energy dispersive X-ray spectroscopy, that is, EDX, is 1 Atm% or more and 50 Atm% or less. For example, the epoxy resin composition according to item 1 of the patent application scope, in which The organic substance contains one or more kinds selected from the group consisting of carbonates, amide compounds, and silicates. For example, the epoxy resin composition according to item 1 of the patent application scope, in which The chlorine-containing particle system: the epoxy resin composition is mixed with acetone to obtain a solution, and the obtained solution is filtered using a filter with a mesh size of 75 μm, and is contained in the residue on the filter. For example, the epoxy resin composition according to item 1 of the patent application scope, in which Using the epoxy resin composition, a 50 g sample was obtained, and the number of the chlorine-containing particles in the 50 g sample was 1 or more and 10 or less. For example, the epoxy resin composition of claim 1 is used in a resin composition for sealing electronic parts. The epoxy resin composition according to any one of items 1 to 9 of the patent application range is used in a sealing resin composition for sealing a vehicle-mounted electronic control unit. An electronic device provided with a cured product of an epoxy resin composition according to any one of patent application items 1 to 10.