JP6677360B2 - Epoxy resin composition and electronic device - Google Patents

Description

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

  Until now, various developments have been made on epoxy resin compositions. As this type of technology, for example, a technology described in Patent Document 1 is known. Patent Document 1 describes using an epoxy compound produced by a method that does not use epichlorohydrin (epichlorohydrin) as a raw material in order to reduce the content of hydrolyzable chlorine derived from the raw material ( Paragraph 0012 of Patent Document 1).

JP 2012-92247 A

  As a result of the study by the present inventors, it has been found that the epoxy resin composition using the epoxy compound described in Patent Document 1 has room for improvement in terms of metal adhesion.

The present inventors have further studied and found that the properties of the epoxy resin composition can be modified by appropriately controlling the state of chlorine contained in the epoxy resin composition. Further studies based on such findings have found that by including chlorine-containing particles containing an organic substance in the epoxy resin composition, it has been found that metal adhesion in the epoxy resin composition can be improved, and the present invention has been completed. Reached.
Although the detailed mechanism is unclear, the chlorine-containing particles have an oxidizing effect on a metal such as Cu, and the surface of the metal is modified by such oxidizing effect, thereby improving the affinity with the epoxy resin composition. It is considered that the metal adhesion is improved.

According to the present invention,
An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler,
Including chlorine-containing particles containing organic matter,
Obtaining a sample of 50g by using the epoxy resin composition, the number of the chlorine-containing particles in a sample of said 50g is state, and are 10 or less 1 or more,
The chlorine-containing particles are obtained by mixing the epoxy resin composition with acetone to obtain a solution, filtering the obtained solution through a filter having a mesh size of 75 μm, and being contained in a residue on the filter. ,
An epoxy resin composition is provided.

  Further, according to the present invention, there is provided an electronic device including the cured product of the epoxy resin composition.

  According to the present invention, an epoxy resin composition having excellent metal adhesion and an electronic device using the same are provided.

  The above and other objects, features and advantages will become more apparent from the preferred embodiments described below and the accompanying drawings.

FIG. 3 is a cross-sectional view illustrating an example of a semiconductor device. FIG. 3 is a cross-sectional view illustrating an example of a semiconductor device. It is sectional drawing which shows an example of a structure.

  Hereinafter, embodiments will be described with reference to the drawings as appropriate. In all the drawings, the same components are denoted by the same reference numerals, and description thereof will not be repeated.

[Epoxy resin composition]
The epoxy resin composition of the present embodiment can include an epoxy resin, a curing agent, and an inorganic filler. This epoxy resin composition contains chlorine-containing particles containing an organic substance.

According to the findings of the present inventors, the following has been found.
BACKGROUND ART Conventionally, there has been known a method of inspecting total chlorine and hydrolyzable chlorine in an epoxy resin composition using the content of the target as an index. Conventionally, hydrolyzable chlorine and free chlorine are uniformly present throughout the epoxy resin composition (for example, a sealing material).
On the other hand, a new form of chlorine, which is called chlorine-containing particles containing an organic substance (hereinafter, may be simply referred to as “chlorine-containing particles”), has been found. It has been found that the chlorine in the chlorine-containing particles has a different form from chlorine derived from hydrolyzable chlorine or free chlorine, and is present locally with respect to the epoxy resin composition. High concentration. For example, the presence of chlorine in chlorine-containing particles can be significantly confirmed by elemental mapping of energy dispersive X-ray spectroscopy (EDX).
Although the detailed mechanism is not clear, such chlorine-containing particles have an oxidizing effect on a metal such as Cu, and modify the surface of the metal by such an oxidizing effect to improve the affinity with the epoxy resin composition. It is considered that the adhesion can be improved and the metal adhesion in the epoxy resin composition can be improved.
Therefore, 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.

  In the present embodiment, the chlorine-containing particles are obtained by mixing the epoxy resin composition with acetone to obtain a solution, filtering the obtained solution through a filter having a mesh size of 75 μm, and being contained in a residue on the filter. Things.

In the present embodiment, the chlorine-containing particles can be detected by the following inspection method (hereinafter, also referred to as a chlorine-containing particle inspection method).
(1) As a sample (sample), an epoxy resin composition or a raw material component (for example, an epoxy resin, a curing agent, an inorganic filler, or the like) constituting the epoxy resin composition is prepared. As the epoxy resin composition, one obtained by mixing and kneading the respective raw material components and cooling the obtained kneaded material (B-stage epoxy resin composition) is used.
(2) 50 g of the sample of (1) was put into a 1000 ml container of washed polypropylene, 300 ml of acetone was added, the container was capped, and then room temperature of 25 ° C., using a shaker, at 300 reciprocations / minute. Shake (mix) for 50 minutes. The acetone used is filtered through a filter having a mesh size of 12 μm.
(3) The filter washed with acetone is placed in a funnel set (filtration device). The filter used is a nylon filter having a mesh size of 75 μm, which is subjected to ultrasonic cleaning.
(4) The container shaken in (2) was allowed to stand, and then the solution in the container was poured from above the funnel in (3) and suction-filtered through a filter. When the particle size of the filler such as the inorganic filler contained in the sample is larger than the size of the opening of the filter, the supernatant in the solution may be filtered with a filter.
(5) Remove the funnel and dry the residue on the filter with suction.
(6) The adhesive surface of the measurement sheet is attached to the filter surface of (5), and the residue is collected on the adhesive surface of the measurement sheet.
(7) The measurement sheet of (6) is peeled off from the filter, and a composite photograph is created for the entire surface of the adhesive surface using a digital microscope. After adjusting the field magnification to 50 times, the entire surface is observed, and the position where the residue exists is recorded and printed.
(8) While confirming the position of the residue in the printed matter of (7), the composition of the residue is analyzed using a scanning electron microscope (SEM) / energy dispersive X-ray analyzer (EDS).
(9) The number of chlorine-containing particles contained in the epoxy resin composition or the raw material components constituting the epoxy resin composition is counted from the result of the composition analysis of the residue based on the energy dispersive X-ray spectroscopy (EDX) of (8). At the same time, the element components in the chlorine-containing particles are specified. If necessary, various analyzes may be performed on the chlorine-containing particles.

The conventional method for measuring the total chlorine amount is intended for hydrolyzable chlorine such as inorganic chlorine, and raw materials of epoxy resin, so that the above chlorine-containing particles cannot be measured. Was.
On the other hand, the method for testing chlorine-containing particles is a method for stably detecting chlorine-containing particles contained in an epoxy resin composition or a raw material component thereof and chlorine contained in the particles. This is a newly established method.

The organic substance in the chlorine-containing particles contained in the epoxy resin can include at least one selected from the group consisting of a carbonate, an amide compound, and a silicate. These organic substances may be a mixture with an epoxy resin.
The organic substance in the chlorine-containing particles contained in the epoxy resin composition may include at least one selected from the group consisting of cellulose, polyethylene terephthalate, polypropylene, silk, silicone compounds, and amide compounds. These may be used alone or in combination of two or more. Or a mixture thereof may be used.
The chlorine-containing particles may contain organic substances other than these. An organic substance can be identified from a spectrum result of chlorine-containing particles using FT-IR (Fourier transform infrared spectroscopy).

The lower limit of the chlorine concentration in the chlorine-containing particles is, for example, 0.01 Atm% or more, 0.5 Atm% or more, or 0.1 Atm% or more. Thereby, 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. Thereby, the reliability can be improved.
When a plurality of chlorine-containing particles are present, 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. This makes it possible to stably fix chlorine in the chlorine-containing particles. On the other hand, the upper limit of the carbon concentration in the chlorine-containing particles may be appropriately changed depending on other constituents, and is not particularly limited. For example, the upper limit may be 99 Atm% or less, 90 Atm% or less, or 85 Atm% or less. It may be lower than 70 Atm%.

  The chlorine-containing particles may contain an oxygen component. In this case, the oxygen concentration in the chlorine-containing particles may be, for example, 1 Atm% to 50 Atm% or less, 2 Atm% to 35 Atm%, 3 Atm% to 30 Atm%, or 3 Atm% to 28 Atm% (hereinafter, referred to as “Atm% to 28 Atm%”). "-" Means including the upper limit and the lower limit unless otherwise specified).

The chlorine-containing particles contain at least one selected from the group consisting of Al, Mg, Si, Fe, Zn, Ti, Ca, Na, K, S, and carbonate compounds. be able to. These may be used alone or in combination of two or more.
In this case, the Al concentration in the chlorine-containing particles may be from 0.1 Atm% to 4 Atm%, or from 0.1 Atm% to 1.0 Atm%.
The Mg concentration in the chlorine-containing particles may be from 0.1 Atm% to 0.5 Atm%, or from 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 Zn concentration in the chlorine-containing particles may be from 0.1 Atm% to 5 Atm%, or from 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 from 0.01 Atm% to 5 Atm%, or from 0.1 Atm% to 1.0 Atm%.
The S concentration in the chlorine-containing particles may be 0.01 Atm% to 2 Atm%, or may be 0.02 Atm% to 1.0 Atm%.
As the element component in the chlorine-containing particles, one or more, two or more, or five or more other elements may be contained in addition to the chlorine element and the carbon element.

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

In the present embodiment, the number of chlorine-containing particles in the epoxy resin composition or the number of chlorine-containing particles in the epoxy resin can be measured by using the above-described <test method for chlorine-containing particles>.
The number of chlorine-containing particles in the 50 g of the epoxy resin composition can be one or more. Thereby, when the epoxy resin composition is used as a sealing material (encapsulating epoxy resin composition) for sealing an electronic component, adhesion to a metal member such as a metal circuit, a metal pad, and a metal wire is improved. be able to. In particular, the adhesion to a metal member such as Cu can be improved. Further, 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. Thereby, when the epoxy resin composition is used as a sealing material for sealing the electronic component, the reliability can be improved.
Regarding each component used in the epoxy resin composition, for example, in 50 g of epoxy resin, the number of chlorine-containing particles may be 1 to 5 or less, 1 to 3 or less, or 1 to 2 or less. , May be one.

  In the present embodiment, for example, the type, blending amount, production method (production method or purification method after production) of each component contained in the thermosetting resin composition, the preparation method of the thermosetting resin composition, and the like are appropriately determined. By selection, the amount of the chlorine-containing particles can be controlled. Among them, for example, for each component such as an epoxy resin and a curing agent, a liquid material such as a solution dissolved in an organic solvent is filtered through a filter, in which case, the filter having a small opening size is used, In addition, centrifuging the liquid material to remove the lower layer containing foreign substances, using only the upper layer, and thoroughly removing HCL generated during the reaction to eradicate the chlorine source. For example, reducing the size of the assurance sieve for the inorganic filler, selecting an appropriate one from a plurality of lots, and the like are factors for setting the amount of the chlorine-containing particles in 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 an epoxy resin.
The epoxy resin includes 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 or crystalline epoxy resins such as biphenyl type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, stilbene type epoxy resin, hydroquinone type epoxy resin; cresol novolak type epoxy resin Novolak type epoxy resins such as phenol novolak type epoxy resin and naphthol novolak type epoxy resin; phenol aralkyl type epoxy resins such as phenylene skeleton containing phenol aralkyl type epoxy resin, biphenylene skeleton containing phenol aralkyl type epoxy resin and phenylene skeleton containing naphthol aralkyl type epoxy resin. Epoxy resin; trifunctional epoxy resin such as triphenolmethane epoxy resin and alkyl-modified triphenolmethane epoxy resin Dicyclopentadiene-modified phenol type epoxy resins, modified phenol type epoxy resins such as terpene-modified phenol type epoxy resins; heterocycle-containing epoxy resins such as triazine nucleus-containing epoxy resins. These may 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 is, for example, preferably 8% by mass or more, more preferably 10% by mass or more, based on the total solid content of the epoxy resin composition. , 12% by mass or more is particularly preferable. By setting the content of the epoxy resin to the above lower limit or more, the flowability 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, for example, preferably 30% by mass or less, more preferably 20% by mass or less, based on the total solid content of the epoxy resin composition. When the content of the epoxy resin is equal to or less than the above upper limit, the moisture resistance reliability, reflow resistance, and temperature cycle resistance of the semiconductor device and other structures including the cured product formed using the epoxy resin composition are improved. Can be improved.

  In the present specification, the total solid content of the epoxy resin composition refers to a non-volatile content in the epoxy resin composition, and refers to a residue excluding volatile components such as water and a solvent. In the present embodiment, the content in the entire epoxy resin composition, when including a solvent, refers to the content in the entire solid content excluding the solvent in the resin composition.

[Curing agent]
The epoxy resin composition can include a curing agent.
The curing agent is not particularly limited as long as it is generally used in an epoxy resin composition. Examples thereof include a phenol resin-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, and a mercaptan-based curing agent. , And the like. Among these, a phenolic resin-based curing agent is preferred from the viewpoint of the balance among flame resistance, moisture resistance, electrical properties, curability, storage stability, and the like.

<Phenolic resin-based curing agent>
The phenolic resin-based curing agent is not particularly limited as long as it is generally used in an epoxy resin composition.Examples include phenol novolak resins, phenols including cresol novolak resins, cresol, resorcinol, catechol, Novolak resin obtained by condensing or co-condensing phenols such as bisphenol A, bisphenol F, phenylphenol, aminophenol, α-naphthol, β-naphthol, dihydroxynaphthalene and formaldehyde or ketone under an acidic catalyst, as described above. Phenol aralkyl resins having a phenylene skeleton and phenol aralkyl resins having a biphenylene skeleton synthesized from phenols and dimethoxyparaxylene or bis (methoxymethyl) biphenyl And a phenol resin having a trisphenylmethane skeleton. These may be used alone or in combination of two or more.

<Amine-based curing agent>
Examples of the amine-based curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and meta-xylylenediamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diaminodiphenylsulfone. In addition to aromatic polyamines such as (DDS), polyamine compounds including dicyandiamide (DICY) and organic acid dihydralazide, and the like may be used, and these may be used alone or in combination of two or more.

<Acid anhydride curing agent>
Examples of the acid anhydride-based curing agent include alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA), methyltetrahydrophthalic anhydride (MTHPA), and maleic anhydride; trimellitic anhydride (TMA); Examples include acids (PMDA), benzophenonetetracarboxylic acids (BTDA), and aromatic acid anhydrides such as phthalic anhydride. These may be used alone or in combination of two or more.

<Mercaptan-based curing agent>
Examples of the mercaptan-based curing agent include trimethylolpropane tris (3-mercaptobutyrate) and trimethylolethanetris (3-mercaptobutyrate). These may be used alone or in combination of two or more. You may.

<Other curing agents>
Examples of other curing agents include isocyanate compounds such as isocyanate prepolymers and blocked isocyanates, and organic acids such as carboxylic acid-containing polyester resins, and these may be used alone or in combination of two or more. .
Further, two or more of the different types of curing agents may be used in combination.

  When the curing agent is a phenolic resin-based curing agent, the equivalent ratio between the epoxy resin and the curing agent, that is, the ratio of the number of moles of epoxy groups in the epoxy resin / the number of moles of phenolic hydroxyl groups in the phenolic resin-based curing agent is particularly Although there is no limitation, in order to obtain an epoxy resin composition having excellent moldability and reliability, for example, the range is preferably 0.5 or more and 2 or less, more preferably 0.6 or more and 1.8 or less, and 0.8 or less. The most preferable range is 1.5 or less.

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

  The lower limit of the average particle size (D50) of the inorganic filler may be, for example, 0.01 μm or more, 1 μm or more, or 5 μm or more. This makes it possible to improve the flowability of the epoxy resin composition and more effectively improve the moldability. The upper limit of the average particle size (D50) of the inorganic filler is, for example, 50 μm or less, and preferably 40 μm or less. Thereby, occurrence of unfilling or the like can be reliably suppressed. Further, 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. Thereby, the fluidity can be further improved.

  The average particle size (D50) of the inorganic filler is determined by measuring the particle size distribution of the particles on a volume basis using a commercially available laser diffraction particle size distribution analyzer (for example, SALD-7000, manufactured by Shimadzu Corporation), and determining the median value. The diameter (D50) can be an average particle diameter.

Further, as 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 more effectively improved. In addition, in the present embodiment, a filler containing an average particle size 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, improves the filling property of the epoxy resin composition. Therefore, it may be used as an example.
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, a first filler having an average particle diameter of 0.01 μm or more and 1 μm or less, and an average particle diameter of 1 μm A second filler having a size of 15 μm or less and a third filler having a mean particle size of 15 μm or more and 50 μm or less may be included.

  The lower limit of the content of the inorganic filler is, for example, preferably 70% by mass or more, more preferably 73% by mass or more, and preferably 75% by mass, based on the total solid content of the epoxy resin composition. The above is particularly preferred. Thereby, low hygroscopicity and low thermal expansion can be improved, and the temperature cycle resistance and the reflow resistance of the semiconductor device and other structures can be more effectively improved. On the other hand, the upper limit of the content of the inorganic filler is preferably, for example, 95% by mass or less, more preferably 93% by mass or less, based on the total solid content of the epoxy resin composition, and 90% or less. It is particularly preferable that the content is not more than mass%. This makes it possible to more effectively improve the fluidity and the filling property during molding of the epoxy resin composition.

[Curing accelerator]
The epoxy resin composition may further include a curing accelerator, if necessary.
The curing accelerator may be any one that promotes a cross-linking reaction between the epoxy resin and the curing agent, and may be any of those used in general epoxy resin compositions.

  Examples of the curing accelerator include diazabicycloalkenes such as 1,8-diazabicyclo (5,4,0) undecene-7 and derivatives thereof; organic phosphines such as triphenylphosphine and methyldiphenylphosphine; Imidazole compounds such as imidazole (imidazole-based curing accelerators); and tetra-substituted phosphonium and tetra-substituted borates such as tetraphenylphosphonium and tetraphenylborate. These may be used alone or in combination of two or more.

  Examples of the imidazole-based curing accelerator include, for example, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 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- Amino-6- [2′-methylimidazolyl (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-undecylimidazolyl (1 ′)]-ethyl-s-triazine, , 4-Diamino-6- [2′-ethyl-4-methylimidazolyl (1 ′)]-ethyl-s-triazine, 2,4-diamino-6- [2′-methylimidazolyl (1 ′)]-ethyl -S-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxydimethylimidazole, 2-phenyl-4-methyl- 5-hydroxymethylimidazole and the like. These may be used alone or in combination of two or more.

  The lower limit of the content of the curing accelerator is, for example, preferably 0.20% by mass or more, more preferably 0.40% by mass or more, based on the total solid content of the epoxy resin composition. It is particularly preferred that the content be 0.70% by mass or more. By setting the content of the curing accelerator to the above lower limit or more, the curability at the time of molding can be effectively improved. On the other hand, the upper limit of the content of the curing accelerator is, for example, preferably 3.0% by mass or less, and more preferably 2.0% by mass or less based on the total solid content of the epoxy resin composition. preferable. By setting the content of the curing accelerator to be equal to or less than the upper limit, fluidity during molding can be improved.

[Coupling agent]
The epoxy resin composition can include a coupling agent, if necessary.
Examples of the coupling agent include known silane compounds such as epoxy silane, mercapto silane, amino silane, alkyl silane, ureido silane, vinyl silane, and methacryl silane; titanium compounds; aluminum chelates; and aluminum / zirconium compounds. Coupling agents can be used. Examples thereof include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane , Vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, -[Bis (β-hydroxyethyl)] aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, phenylaminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N- (Dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysila , Hexamethyldisilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl Butyl coupling agent such as hydrolyzate of (butylidene) propylamine, isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis (ditriethyl) (Decyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxya Tet titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tricumyl Titanate-based coupling agents such as phenyl titanate and tetraisopropylbis (dioctylphosphite) titanate are exemplified. These may be used alone or in combination of two or more. Among them, silane compounds of epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane or vinylsilane are more preferable. From the viewpoint of more effectively improving the filling property and the moldability, it is particularly preferable to use a secondary aminosilane represented by phenylaminopropyltrimethoxysilane.

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

Further, the epoxy resin composition may include a low-stress agent as needed.
Examples of the low stress agent include silicone oil, silicone rubber, polyisoprene, polybutadiene such as 1,2-polybutadiene and 1,4-polybutadiene, styrene-butadiene rubber, acrylonitrile-butadiene rubber, polychloroprene, poly (oxypropylene), It may contain one or more selected from thermoplastic elastomers such as poly (oxytetramethylene) glycol, polyolefin glycol, poly-ε-caprolactone, polysulfide rubber, and fluorine rubber. Among these, it is possible to include at least one of silicone rubber, silicone oil, and acrylonitrile-butadiene rubber, by controlling the elastic modulus to a desired range, and to obtain a semiconductor package and other structures having a temperature cycle resistance. From the viewpoint of improving the reflow resistance, it can be selected as a particularly preferred embodiment.

  When the above low stress agent is used, the content of the entire low stress agent is preferably 0.05% by mass or more, and more preferably 0.10% by mass, based on the total solid content of the epoxy resin composition. More preferred. On the other hand, the content of the low stress agent is preferably 2% by mass or less, and more preferably 1% by mass or less, based on the total solid content of the epoxy resin composition. By controlling the content of the low stress agent in such a range, the temperature cycle resistance and the reflow resistance of the obtained semiconductor package and other structures can be more reliably improved.

[Other ingredients]
The epoxy resin composition of the present embodiment may further include other components as necessary. Other components include, for example, ion scavengers such as hydrotalcite and aluminum-magnesium inorganic ion exchangers; coloring agents such as carbon black and red iron oxide; natural waxes such as carnauba wax; montanic acid ester waxes; diethanolamine dimontanic acid Synthetic waxes such as esters and tolylene diisocyanate-modified oxidized waxes; higher fatty acids such as zinc stearate; release agents such as metal salts thereof and paraffin; and various additives such as antioxidants. These additives may be appropriately blended.

[Production method of epoxy resin composition]
The method for producing the epoxy resin composition of the present embodiment will be described.
The method for producing the epoxy resin composition can include a lot selection step and a mixing step. First, a plurality of epoxy resins a of different lots are prepared, and the number of chlorine-containing particles of the prepared epoxy resin a is measured by using the above-described method of inspecting chlorine-containing particles. An epoxy resin a containing chlorine-containing particles is selected from a plurality of lots based on the obtained measurement results, and used as a raw material component (epoxy resin A) of the epoxy resin composition (lot sorting step). By mixing other raw material components with the epoxy resin A (mixing step), an epoxy resin composition can be obtained.
Also, for other components (for example, curing agent b and inorganic filler c), lot selection is performed in the same manner as for epoxy resin a, and curing agent b and inorganic filler c containing chlorine-containing particles are converted into raw materials. It may be used as a component (curing agent B or inorganic filler C). Further, a method for controlling the amount of the chlorine-containing particles described above can be appropriately added.

  Further, in the mixing step, a mixture is obtained by mixing by a known means. Furthermore, a kneaded material is obtained by melt-kneading the mixture. As the kneading method, for example, an extrusion kneader such as a single-screw kneading extruder, a twin-screw kneading extruder, or a roll-type kneader such as a mixing roll can be used, but a twin-screw kneading extruder is used. Is preferred. After cooling, the kneaded product can be in the form of powder, granules, tablets, or sheets.

  As a method for obtaining a powdery resin composition, for example, a method in which a kneaded material is pulverized by a pulverizer is used. The kneaded material formed into a sheet may be pulverized. As the pulverizer, for example, a hammer mill, a stone mill type grinder, a roll crusher, or the like can be used.

  As a method for obtaining a granular or powdery resin composition, for example, a die having a small diameter is installed at an outlet of a kneading device, and a kneaded material in a molten state discharged from the die is cut to a predetermined length by a cutter or the like. A granulation method represented by a hot cut method of cutting into pieces can also be used. In this case, it is preferable that after the granular or powdery resin composition is obtained by a granulation method such as a hot cut method, the degassing is performed before the temperature of the resin composition drops so much.

  The epoxy resin composition of the present embodiment can be used for various applications. For example, the epoxy resin composition of the present embodiment can be used for a sealing resin composition or a fixing resin composition. The encapsulating resin composition (encapsulating resin composition for encapsulating electronic components) according to the present embodiment can seal electronic components such as semiconductor chips and is used in the semiconductor package. Resin composition for semiconductor encapsulation, resin composition for in-vehicle electronic control unit encapsulating a substrate on which electronic components, etc. are mounted, or sensor, sensor module, camera, camera module, module with display It is applicable to resin compositions for encapsulating modules with dry batteries and coin batteries. The fixing resin composition according to the present embodiment can also be used for fixing motor components, and can be applied to, for example, a resin composition for fixing a rotor core magnet and a stator.

  The structure (for example, an electronic device) of the present embodiment includes a cured product of the epoxy resin composition. Examples of the structure include an electronic control unit that seals a substrate on which a semiconductor package, electronic components, and the like are mounted, a sensor, a sensor module, a camera, a camera module, a module with a display, a module with a dry battery and a coin battery, a motor, and the like. Is mentioned.

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

  FIG. 2 is a diagram showing a cross-sectional structure of an example of a single-sided sealing type semiconductor device using the epoxy resin composition of the present embodiment. The semiconductor element 1 is fixed via the cured die-bonding material 2 on the solder resist 7 of the laminate in which the layer of the solder resist 7 is formed on the surface of the substrate 8. In order to establish conduction between the semiconductor element 1 and the substrate 8, the solder resist 7 on the electrode pads is removed by a developing method so that the electrode pads of the substrate 8 are exposed. The electrode pads of the semiconductor element 1 and the electrode pads of the substrate 8 are connected by bonding wires 4. Only one side of the substrate 8 on which the semiconductor element 1 is mounted is sealed by the cured body 6 of the epoxy resin composition of the present embodiment. The electrode pads on the substrate 8 are internally bonded to the solder balls 9 on the non-sealing surface side of the substrate 8.

The epoxy resin composition of the present 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 illustrating an example of the structural body (vehicle-mounted electronic control unit 10) of the present embodiment.
The on-vehicle electronic control unit 10 is used for controlling an engine, various on-vehicle devices, and the like. As shown in FIG. 3, the on-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 for sealing the substrate 12 and the electronic component 16. Have. The substrate 12 has, on at least one side, connection terminals 18 for connection to the outside. The vehicle-mounted electronic control unit 10 according to an example of the present embodiment is electrically connected to the counterpart connector via the connection terminal 18 by fitting the connection terminal 18 to the counterpart connector.

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

  In the present embodiment, the substrate 12 may be provided with a through hole 120 that penetrates through the substrate 12, for example, and connects one surface to the other surface. In this case, the wiring provided on one surface of the substrate 12 and the wiring provided on the other surface are electrically connected via a conductor 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 in a cylindrical shape. In the through hole 120 after the sealing step, the void formed by the inner wall surface of the conductive pattern is filled with the cured product (the sealing resin layer 14) of the epoxy resin composition of the present embodiment.

  On one or both of one surface and the other surface of the substrate 12, for example, an electronic component 16 is mounted. The electronic component 16 is not particularly limited as long as it can be mounted on the in-vehicle electronic control unit, and includes, for example, a microcomputer.

  In the in-vehicle electronic control unit 10 according to the present embodiment, the board 12 may be mounted on, for example, a metal base. The metal base can function as a heat sink for dissipating heat generated from the electronic component 16, for example. In the present embodiment, for example, the vehicle-mounted electronic control unit 10 can be formed by integrally sealingly molding a metal base and the substrate 12 mounted on the metal base with an epoxy resin composition. The metal material forming the metal base is not particularly limited, but may include, for example, iron, copper, and aluminum, and alloys containing one or more of these. Note that the on-vehicle electronic control unit 10 need not have a metal base.

As described above, the present invention has been described based on the embodiment. However, the present invention is not limited to the above embodiment, and the configuration thereof can be changed without changing the gist of the present invention.
Hereinafter, examples of the reference embodiment will be additionally described.
1. An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler,
An epoxy resin composition containing chlorine-containing particles containing an organic substance.
2. 1. The epoxy resin composition according to the,
An epoxy resin composition, wherein the chlorine concentration in the chlorine-containing particles measured based on energy dispersive X-ray spectroscopy (EDX) is from 0.01 Atm% to 20 Atm%.
3. 1. Or 2. The epoxy resin composition according to the,
The chlorine-containing particles contain at least one selected from the group consisting of Al, Mg, Si, Fe, Zn, Ti, Ca, Na, K, S, and carbonate compounds. , Epoxy resin composition.
4. 1. From 3. The epoxy resin composition according to any one of the above,
An epoxy resin composition, wherein a carbon concentration in the chlorine-containing particles measured based on energy dispersive X-ray spectroscopy (EDX) is from 40 Atm% to 99 Atm%.
5. 1. From 4. The epoxy resin composition according to any one of the above,
An epoxy resin composition, wherein the oxygen concentration in the chlorine-containing particles measured based on energy dispersive X-ray spectroscopy (EDX) is 1 Atm% or more and 50 Atm% or less.
6. 1. To 5. The epoxy resin composition according to any one of the above,
An epoxy resin composition, wherein the organic substance contains at least one selected from the group consisting of a carbonate, an amide compound, and a silicate.
7. 1. From 6. The epoxy resin composition according to any one of the above,
The chlorine-containing particles are obtained by mixing the epoxy resin composition with acetone to obtain a solution, filtering the obtained solution through a filter having a mesh size of 75 μm, and being contained in a residue on the filter. , Epoxy resin composition.
8. 1. To 7. The epoxy resin composition according to any one of the above,
An epoxy resin composition, wherein a 50 g sample is obtained using the epoxy resin composition, and the number of the chlorine-containing particles in the 50 g sample is 1 or more and 10 or less.
9. 1. From 8. The epoxy resin composition according to any one of the above,
An epoxy resin composition used for a sealing resin composition for sealing an electronic component.
10. 1. To 9. The epoxy resin composition according to any one of the above,
An epoxy resin composition used for a sealing resin composition for sealing a vehicle-mounted electronic control unit.
11. 1. To 10. An electronic device comprising a cured product of the epoxy resin composition according to any one of the above .

  Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the descriptions of these Examples.

  The raw material components used in each of the examples and comparative examples are shown below.

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

［硬化促進剤１の合成方法］
メタノール１８００ｇを入れたフラスコに、フェニルトリメトキシシラン２４９．５ｇ、２，３−ジヒドロキシナフタレン３８４．０ｇを加えて溶かし、次に室温攪拌下２８％ナトリウムメトキシド−メタノール溶液２３１．５ｇを滴下した。さらにそこへ予め用意したテトラフェニルホスホニウムブロマイド５０３．０ｇをメタノール６００ｇに溶かした溶液を室温攪拌下滴下すると結晶が析出した。析出した結晶を濾過、水洗、真空乾燥し、桃白色結晶の上記硬化促進剤１を得た。(Curing accelerator)
Curing accelerator 1: Curing accelerator 1 represented by the following formula

[Synthesis method of curing 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 231.5 g of a 28% sodium methoxide-methanol solution was added dropwise with stirring at room temperature. Further, a solution prepared by dissolving 503.0 g of tetraphenylphosphonium bromide prepared in advance in 600 g of methanol was added dropwise thereto with stirring at room temperature to precipitate crystals. The precipitated crystals were filtered, washed with water, and dried under vacuum to obtain the above-mentioned curing accelerator 1 as pink white crystals.

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

[Synthesis method of curing accelerator 2]
12.81 g (0.080 mol) of 2,3-dihydroxynaphthalene, 16.77 g (0.040 mol) of tetraphenylphosphonium bromide, and 100 ml of methanol were charged into a separable flask equipped with a cooling tube and a stirrer, and uniformly dissolved. Was. When a sodium hydroxide solution in which 1.60 g (0.04 ml) of sodium hydroxide was previously dissolved in 10 ml of methanol was gradually dropped into the flask, crystals were precipitated. The precipitated crystals were filtered, washed with water, and dried under vacuum to obtain a curing accelerator 2 represented by the above formula.

(Coupling agent)
Coupling agent 1: N-phenyl-3-aminopropyltrimethoxysilane (CF-4083, manufactured by Dow Corning Toray)
Coupling agent 2: 3-mercaptopropyltrimethoxysilane (S810, manufactured by Chisso)

(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 using epichlorohydrin (glycidyl ether type liquid epoxy resin, EPICLON EXA-4880 manufactured by DIC, total chlorine: 0 ppm)
Epoxy resin 5: Epoxy resin synthesized without using epichlorohydrin (alicyclic epoxy resin, EHPE3150 manufactured by Daizel, total chlorine: 0 ppm)

(Inorganic filler C)
Inorganic filler c1: fused spherical silica (FB-100XFC, manufactured by Denka Corporation, average particle size 13 μm)
Inorganic filler c2: fused spherical silica (MSV-SC3, manufactured by Tatsumori, average particle size 19 μm)
Inorganic filler c3: spherical silica (SD2500-SQ, manufactured by Admatechs, average particle size 0.5 μm)
Inorganic filler c4: spherical silica (SC-2500-SQ, manufactured by Admatechs, average particle size 0.5 μm)
Inorganic filler c5: fused spherical silica (FB-950FC, manufactured by Denka, average particle size 22 μm)

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

(Curing agent B)
Curing agent b1: Biphenylene skeleton-containing phenol aralkyl resin (MEH-7851SS, manufactured by Meiwa Kasei Co., Ltd.)
Curing agent b2: Novolak type phenol resin (PR-HF-3, manufactured by Sumitomo Bakelite Co., Ltd.)

(Ion scavenger)
Ion scavenger 1: Hydrotalcite (DHT-4H, manufactured by Kyowa Chemical Industry Co., Ltd.)
Ion scavenger 2: Aluminum-magnesium inorganic ion exchanger (IXE-700F, manufactured by Toagosei Co., Ltd.)

低応力剤３：アルキル基含有シリコーン（シルソフト０３４、モメンティブ社製）(Low stress agent)
Low stress agent 1: acrylonitrile-butadiene copolymer compound (CTBN1008SP, manufactured by PTI Japan)
Low stress agent 2: Molten reactant A (silicone) obtained by the following synthesis method
[Method of synthesizing molten reactant A]
66.1 parts by weight of a bisphenol A type epoxy resin (manufactured by Java Epoxy Resin Co., Ltd., jER (registered trademark) YL6810, softening point 45 ° C, epoxy equivalent 172) represented by the following formula (8) was heated and melted at 140 ° C. Then, 33.1 parts by weight of an organopolysiloxane 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: alkyl group-containing silicone (Silsoft 034, manufactured by Momentive)

(Release agent)
Release agent 1: montanic acid ester wax (WE-4, manufactured by Clariant Japan)
Release agent 2: diethanolamine dimontanate (NC-133, manufactured by Ito Oil Co., Ltd.)
Release agent 3: Tolylene diisocyanate-modified oxidized wax (NPS-6010, manufactured by Nippon Seiro)
Release agent 4: Stearic acid (SR-Sakura, manufactured by NOF CORPORATION)

<Preparation of epoxy resin composition>
[Example 1]
A plurality of epoxy resins a1 of different lots were prepared, and the number of chlorine-containing particles of the prepared epoxy resin a1 was measured by using a chlorine-containing particle inspection method described below. Based on the measurement results obtained, an epoxy resin a1 containing chlorine-containing particles in the number shown in Table 2 was selected from a plurality of lots and used as a raw material component (epoxy resin A) of the epoxy resin composition. . As the curing agent B, the curing agent b1 was used, and as the inorganic filler C, the inorganic fillers c1 and c3 were used.
Subsequently, using the other raw material components shown in Table 1 together with the above-mentioned epoxy resin A, curing agent B, and inorganic filler C, and mixing them at room temperature using a mixer based on the mixing ratio shown in Table 1 And roll kneading at 70 to 90 ° C. Next, after cooling the obtained kneaded material, it was pulverized to obtain an epoxy resin composition.
For the obtained epoxy resin composition, the number of chlorine-containing particles was measured using the following method for inspecting chlorine-containing particles. Table 2 shows the results.

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

[Example 3]
An epoxy resin composition was obtained in the same manner as in Example 1, except that the inorganic fillers C2 and c3 were used as the inorganic filler C.

[Example 4]
A curing agent b1 of the same lot as in Example 1 was dissolved in an organic solvent, and a solution obtained by filtering the solution with a 1 μm filter was used in the same manner as in Example 1 except that a raw material component (curing agent B) was used. Thus, an epoxy resin composition was obtained.

[Example 5]
A plurality of epoxy resins a3 of different lots 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 measurement results obtained, an epoxy resin a3 containing chlorine-containing particles in the number shown in Table 2 was selected from a plurality of lots and used as a raw material component (epoxy resin A) of the epoxy resin composition. . As the curing agent B, a curing agent b1 was used, and as the inorganic filler C, inorganic fillers c4 and c5 were used.
Subsequently, using the other raw material components shown in Table 1 together with the above-mentioned epoxy resin A, curing agent B, and inorganic filler C, and mixing them at room temperature using a mixer based on the mixing ratio shown in Table 1 And roll kneading at 70 to 90 ° C. Next, after cooling the obtained kneaded material, it was pulverized to obtain an epoxy resin composition.
For the obtained epoxy resin composition, the number of chlorine-containing particles was measured using the following method for inspecting chlorine-containing particles. Table 2 shows the results.

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

[Example 7]
With respect to the epoxy resin a3 of a lot different from that of Example 5, the solution obtained by dissolving the same in an organic solvent was filtered through a 1 μm filter, and the number of chlorine particles shown in Table 2 was measured using the following method for inspecting chlorine-containing particles. An epoxy resin composition was obtained in the same manner as in Example 5, except that the epoxy resin a3 containing the containing 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]
With respect to the epoxy resin a2 of a lot different from that of Example 2, the solution obtained by dissolving the resin in an organic solvent was filtered through a 1 μm filter, and the number of chlorine-containing particles measured by the following method for examining chlorine-containing particles was 0. An epoxy resin composition was obtained in the same manner as in Example 2, except that the individual epoxy resin a2 was used as a raw material component (epoxy resin A).

(Inspection method for chlorine-containing particles)
(1) As a sample, an epoxy resin composition or a raw material component constituting the epoxy resin composition was prepared. As the epoxy resin composition, one obtained by mixing and kneading the respective raw material components and cooling the obtained kneaded material was used.
(2) 50 g of the sample of (1) was put into a 1000 ml container of washed polypropylene, 300 ml of acetone was added, the container was capped, and then, using a shaker, at room temperature of 25 ° C. and 300 reciprocations / minute. Shake (mix) for 50 minutes. The acetone used was filtered through a filter having a mesh size of 12 μm.
(3) The filter washed with acetone was placed in a funnel set (filtration device). The filter used was a nylon filter having a mesh size of 75 μm, which was subjected to ultrasonic cleaning.
(4) The container shaken in (2) was allowed to stand, and then the solution in the container was poured from above the funnel in (3) and suction-filtered through a filter.
(5) The funnel was removed, and the residue on the filter was dried with suction.
(6) The adhesive surface of the measurement sheet was attached to the filter surface of (5), and the residue was collected on the adhesive surface of the measurement sheet.
(7) The measurement sheet of (6) was peeled off from the filter, and a composite photograph was created using a digital microscope on the entire surface of the adhesive surface. After adjusting the visual field magnification to 50 times, the entire surface was observed, and the position where the residue was present was recorded and printed.
(8) The position of the residue was confirmed in the printed matter of (7), and the residue was subjected to composition analysis using a scanning electron microscope (SEM) / energy dispersive X-ray analyzer (EDS). As a result of SEM image observation, it was confirmed that a particulate residue was present.
(9) From the result of the composition analysis of the residue based on the energy dispersive X-ray spectroscopy (EDX) of (8), the number of chlorine-containing particles contained in the epoxy resin composition or the raw material component constituting the epoxy resin composition Was measured (counted).

  Further, with respect to the chlorine-containing particles detected in the epoxy resin or the epoxy resin composition, organic substances in the chlorine-containing particles were identified from the spectrum results using FT-IR (Fourier transform infrared spectroscopy). Table 2 shows the evaluation results.

  In Table 2, the organic substance of the chlorine-containing particles 1A-1 is a mixture of an epoxy resin and a carbonate, the organic substance of the chlorine-containing particles 1A-2 is a carbonate, the organic substance of the chlorine-containing particles 2A-1 is an amide compound, and the chlorine-containing particles 5A- The organic matter of 1 is carbonate, the organic matter of the chlorine-containing particles 5A-2 is carbonate and silicate, the organic matter of the chlorine-containing particles 1-4 is cellulose, the organic matter of the chlorine-containing particles 2-1 is cellulose, and the chlorine-containing particles 3- Organic substance No. 4 was identified to contain cellulose.

<Evaluation>
The following evaluation was performed about the obtained epoxy resin composition. Table 2 shows the evaluation results.

(Spiral flow)
Spiral flow measurement was performed on the obtained epoxy resin composition. Spiral flow measurement was performed using a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) into a mold for spiral flow measurement according to EMMI-1-66 at a mold temperature of 175 ° C. and an injection pressure. This was performed by injecting the epoxy resin composition under the conditions of 6.9 MPa and a curing time of 120 seconds, and measuring the flow length. Table 2 shows the results.

(Gel time)
A sample composed of the obtained epoxy resin composition was placed on a hot plate at 175 ° C., and the time required for the sample to melt and harden while kneading with a spatula was measured. The unit is seconds (sec). Table 2 shows the results.

(Metal adhesion)
Using the obtained epoxy resin composition, using a low pressure transfer molding machine (“AV-600-50-TF” manufactured by Yamashiro Seiki Co., Ltd.), a mold temperature of 175 ° C., an injection pressure of 10 MPa, and a curing time of 180 seconds. Under the conditions, 10 pieces of 3.6 mmφ × 3 mm adhesion strength test pieces were formed on a 9 × 29 mm strip test copper lead frame per level. Subsequently, the die shear strength between the test piece and the frame was measured at room temperature using an automatic die shear measuring device (DAGE4000 type, manufactured by Nordson Advanced Technology). Table 2 shows the average value of the die shear strength (MPa) of the ten test pieces.

  The epoxy resin compositions of Examples 1 to 7 were found to be excellent in metal adhesion since the epoxy resin compositions of Comparative Examples 1 to 3 had improved adhesion to the Cu frame.

  This application claims priority based on Japanese Patent Application No. 2017-234008 filed on December 6, 2017, the disclosure of which is incorporated herein in its entirety.

Claims (9)

An epoxy resin composition comprising an epoxy resin, a curing agent and an inorganic filler,
Including chlorine-containing particles containing organic matter,
Obtaining a sample of 50g by using the epoxy resin composition, the number of the chlorine-containing particles in a sample of said 50g is state, and are 10 or less 1 or more,
The chlorine-containing particles are obtained by mixing the epoxy resin composition with acetone to obtain a solution, filtering the obtained solution through a filter having a mesh size of 75 μm, and being contained in a residue on the filter. ,
Epoxy resin composition. The epoxy resin composition according to claim 1,
An epoxy resin composition, wherein the chlorine concentration in the chlorine-containing particles measured based on energy dispersive X-ray spectroscopy (EDX) is from 0.01 Atm% to 20 Atm%. The epoxy resin composition according to claim 1 or 2,
The chlorine-containing particles contain at least one selected from the group consisting of Al, Mg, Si, Fe, Zn, Ti, Ca, Na, K, S, and carbonate compounds. , Epoxy resin composition. The epoxy resin composition according to any one of claims 1 to 3, wherein
An epoxy resin composition, wherein a carbon concentration in the chlorine-containing particles measured based on energy dispersive X-ray spectroscopy (EDX) is from 40 Atm% to 99 Atm%. The epoxy resin composition according to any one of claims 1 to 4, wherein
An epoxy resin composition, wherein the oxygen concentration in the chlorine-containing particles measured based on energy dispersive X-ray spectroscopy (EDX) is 1 Atm% or more and 50 Atm% or less. The epoxy resin composition according to any one of claims 1 to 5, wherein
An epoxy resin composition, wherein the organic substance contains at least one selected from the group consisting of a carbonate, an amide compound, and a silicate. The epoxy resin composition according to any one of claims 1 to 6 , wherein
An epoxy resin composition used for a sealing resin composition for sealing an electronic component. The epoxy resin composition according to any one of claims 1 to 7 , wherein
An epoxy resin composition used for a sealing resin composition for sealing a vehicle-mounted electronic control unit. Electronic device comprising a cured product of the epoxy resin composition according to any one of claims 1 to 8.

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