JP6900749B2 - Carbon black dispersed phenol resin composition, epoxy resin composition and method for producing these - Google Patents

Description

The present invention relates to a carbon black dispersed phenol resin, an epoxy resin composition, and a method for producing these.

So far, various developments have been made in the epoxy resin composition from the viewpoint of the dispersibility of carbon black. As a technique of this kind, there is one described in Patent Document 1. Patent Document 1 describes that an epoxy resin composition is obtained by pre-kneading carbon black, phenol resin and silica powder and mixing the obtained pre-kneading composition with an epoxy resin and a curing accelerator. (Patent Document 1, paragraphs 0046, 0047). According to the same document, it is described that the dispersibility of carbon black in the epoxy resin composition can be improved by pre-kneading the carbon black, the phenol resin and the silica powder (Patent Document 1, paragraph 0043). ..

JP-A-2007-84624

However, as a result of studies by the present inventors, it has been found that the method for producing an epoxy resin composition described in Document 1 has room for improvement in suppressing the aggregation of carbon black.

According to the present invention
A carbon black-dispersed phenol resin composition in which carbon black is dispersed in a phenol resin.
Provided is a carbon black-dispersed phenolic resin composition having an average particle size of 80 nm or more and 400 nm or less and one peak in the particle size distribution of the carbon black as measured by a dynamic light scattering method. ..

Further, according to the present invention.
Epoxy resin and
Hardener and
Inorganic filler and, including
An epoxy resin composition is provided in which the curing agent contains the carbon black dispersed phenol resin composition.

Further, according to the present invention.
A method for producing a carbon black-dispersed phenol resin composition in which carbon black is dispersed in a phenol resin.
A step of obtaining a carbon black dispersion liquid containing a carbon black dispersant, an organic solvent, and the carbon black.
After the step of obtaining the carbon black dispersion liquid, a step of obtaining a phenol resin solution by dissolving the carbon black dispersion liquid and the phenol resin, and a step of obtaining the phenol resin solution.
The step of filtering the phenol resin solution with a filter and
Provided is a method for producing a carbon black-dispersed phenol resin composition , which comprises a step of obtaining a carbon black-dispersed phenol resin by removing the organic solvent from the phenol resin solution.

Further, according to the present invention.
A method for producing an epoxy resin composition, which comprises a step of mixing the epoxy resin, a curing agent containing the carbon black-dispersed phenol resin obtained by the method for producing the carbon black-dispersed phenol resin composition, and an inorganic filler. Provided.

According to the present invention, it is possible to provide a carbon black dispersed phenol resin in which aggregation of carbon black is suppressed and an epoxy resin composition using the same.

It is sectional drawing which shows an example of the semiconductor package which concerns on this embodiment. It is sectional drawing which shows an example of the semiconductor package which concerns on this embodiment.

Hereinafter, the present invention will be described in detail based on the embodiments.
In addition, in this specification, "~" represents the following from the above unless otherwise specified.

The outline of the method for producing the carbon black dispersed phenol resin of the present embodiment will be described.

The method for producing a carbon black-dispersed phenol resin of the present embodiment is to produce a carbon black-dispersed phenol resin in which carbon black is dispersed in the phenol resin, and a carbon black dispersant, an organic solvent, and carbon black are used. After the step of obtaining the carbon black dispersion containing, and the step of obtaining the carbon black dispersion, the step of obtaining the phenol resin solution by dissolving the carbon black dispersion and the phenol resin,
A step of obtaining a carbon black-dispersed phenol resin by removing the organic solvent from the phenol resin solution can be included.

According to the present embodiment, a carbon black dispersion in which carbon black is dispersed with a carbon black dispersant can be prepared in advance, and the carbon black can be highly dispersed in the phenol resin by using the carbon black dispersion. Therefore, it is possible to realize a carbon black-dispersed phenol resin in which the aggregation of carbon black is suppressed.

Hereinafter, the manufacturing process of the carbon black dispersed phenol resin of the present embodiment will be described in detail.

First, the step of obtaining the carbon black dispersion liquid can include a step of preparing a carbon black dispersant, an organic solvent, and carbon black and mixing them.

As the carbon black, those usually used as the carbon black contained in the epoxy resin composition can be appropriately selected and adopted. For example, acetylene black, furnace black, ketjen black, channel black, lamp black, thermal can be used. Black and the like can be mentioned. These may be used alone or in combination of two or more.

As the carbon black dispersant, resin-type dispersants such as polyamide resins, polyurethane resins, polyester resins, and acrylic resins can be used. Specifically, for example, "DISPERBYK" manufactured by Big Chemie Co., Ltd., It is possible to use "EFKA" manufactured by Ciba Specialty Chemicals, "Solspers" manufactured by Lubrizol, "Ajispar" manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

Examples of the organic solvent include alcohol solvents such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and butyl alcohol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; diethyl ether, Ether solvents such as dipropyl ether, tetrahydrofuran, phenyl methyl ether, ethylene glycol dimethyl ether; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; methyl formate, ethyl formate, acetic acid Examples thereof include ester solvents such as methyl and ethyl acetate; aromatic solvents such as benzene, toluene and xylene; halogen solvents such as chloroform. These may be used alone or in combination of two or more. Among these, methyl ethyl ketone may be used.

A carbon black dispersion liquid can be obtained by mixing the above carbon black dispersant, an organic solvent and carbon black and dispersing the carbon black in the organic solvent.

The mixing method is not particularly limited, but for example, a stirrer or a vibrating device may be used.

In the step of obtaining the present carbon black dispersion, the average particle size of the carbon black in the carbon black dispersion measured by the dynamic light scattering method can be set to, for example, 80 nm or more and 400 nm or less, and the particles of the carbon black can be set. There can be one peak in the diameter distribution.

Subsequently, the step of obtaining the phenol resin solution can include a step of dissolving the carbon black dispersion liquid and the phenol resin after the step of obtaining the carbon black dispersion liquid.

The phenol resin is a general monomer, oligomer, or polymer having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, a phenol novolac resin and a cresol novolac resin. , Novorac-type phenol resin such as naphthol novolac resin; Polyfunctional phenol resin such as triphenol methane-type phenol resin; Modified phenol resin such as terpen-modified phenol resin and dicyclopentadiene-modified phenol resin; Examples thereof include phenol aralkyl resins having an aralkyl type resin such as naphthol aralkyl resin having a phenylene and / or biphenylene skeleton; and bisphenol compounds such as bisphenol A and bisphenol F. These may be used alone or in combination of two or more.

In this step, after dissolving the phenol resin in an organic solvent, the carbon black dispersion may be added to the solution. The addition method is not particularly limited, and for example, batch addition, divided addition, or sequential addition may be used. At this time, the reaction system may be mixed using a stirrer or a vibration device. From the above, a phenol resin solution can be obtained.

Subsequently, the step of obtaining the carbon black-dispersed phenol resin can include a step of removing the organic solvent from the phenol resin solution.

In this step, a known method can be used as a method for removing the organic solvent, but for example, the organic solvent may be distilled off by heat treatment. The temperature condition of the heat treatment may be, for example, a temperature equal to or higher than the boiling point temperature of the organic solvent under normal pressure conditions.

From the above, the carbon black dispersed phenol resin of the present embodiment can be obtained.

The carbon black-dispersed phenol resin of the present embodiment obtained by the above-mentioned production method is one in which carbon black is dispersed in the phenol resin. In the carbon black dispersed phenol resin, the average particle size (average particle size D50) of carbon black measured by a dynamic light scattering method is, for example, 80 nm or more and 400 nm or less, and the peak in the particle size distribution of carbon black is one. It is one.
The lower limit of the average particle size D50 of carbon black in the carbon black dispersed phenol resin of the present embodiment is, for example, 80 nm or more, preferably 150 nm or more, and more preferably 180 nm or more. On the other hand, the upper limit of the average particle size D50 of the carbon black is, for example, 400 nm or less, preferably 350 nm or less, and more preferably 250 nm or less. By setting such a numerical range, the dispersibility of carbon black in the carbon black-dispersed phenol resin can be improved.

In the carbon black dispersed phenol resin of the present embodiment, since there is one peak in the particle size distribution of carbon black and the average particle size (average particle size D50) of carbon black is 80 nm or more and 400 nm or less, carbon black It shows that the particle size distribution is monodisperse, and the particle size of carbon black becomes very small. Therefore, it is possible to realize a carbon black-dispersed phenol resin in which the aggregation of carbon black is suppressed.

In the present embodiment, the average particle size and particle size distribution of carbon black in the carbon black dispersed phenol resin can be measured by using the dynamic light scattering method as follows.
First, the carbon black-dispersed phenol resin is redissolved in methyl ethyl ketone to prepare a liquid sample diluted so that the concentration of carbon black is 500 ppm. Using this liquid sample, using a dynamic light scattering (DLS) particle size distribution measuring device (for example, Nanotrac Wave-EX150 manufactured by Microtrac Bell) at a room temperature of 25 ° C., the average of carbon black. Measure the particle size (D50) and particle size distribution.
For this particle size distribution, data based on the volume of the filler is obtained, and the expression "D10" is used. D10 refers to the particle size when the cumulative volume distribution corresponds to 10% when the particle size distribution is measured and the horizontal axis is the particle size and the vertical axis is the cumulative volume distribution (%). For example, D50 and D90 represent the particle size when the cumulative volume distribution corresponds to 50% and 90%, respectively, and serve as an index of the particle size distribution.

Further, when D50 of carbon black in the carbon black dispersed phenol resin is X and D50 of carbon black in the carbon black dispersion is Y, the lower limit of Y / X is, for example, 0.6 or more. 0.7 or more is preferable, and 0.75 or more is more preferable. Thereby, the dispersibility of carbon black in the carbon black-dispersed phenol resin can be improved. The upper limit value of Y / X is not particularly limited, but may be, for example, 1 or less.

In the carbon black dispersed phenol resin of the present embodiment, the lower limit of D50 / D90 is, for example, 0.5 or more, preferably 0, with respect to D50 and D90 of carbon black measured by a dynamic light scattering method. It is .55 or more, more preferably 0.57 or more. As a result, the variation in the particle size distribution of carbon black in the carbon black-dispersed phenol resin can be reduced, so that the dispersibility can be improved. On the other hand, the upper limit of D50 / D90 is not particularly limited, but may be, for example, 0.9 or less.

In the carbon black dispersed phenol resin of the present embodiment, the lower limit of the peak value in the particle size distribution of carbon black measured by the dynamic light scattering method may be, for example, 180 nm or more. On the other hand, the upper limit of the peak value is, for example, 350 nm or less, preferably 300 nm or less, and more preferably 280 nm or less. Thereby, the viscosity of the carbon black dispersed phenol resin can be reduced.

In the carbon black-dispersed phenol resin of the present embodiment, the lower limit of the half-value width of the peak value may be, for example, 80 nm or more. On the other hand, the upper limit of the half width of the peak value is, for example, 200 nm or less, preferably 190 nm or less. Thereby, the dispersibility of carbon black in the carbon black-dispersed phenol resin can be improved.

The lower limit of the softening point of the carbon black-dispersed phenol resin of the present embodiment may be, for example, 50 ° C. or higher, 55 ° C. or higher, or 60 ° C. or higher. On the other hand, the upper limit of the softening point may be, for example, 100 ° C. or lower, 95 ° C. or lower, or 90 ° C. or lower. By setting such a numerical range, it is possible to improve the familiarity when kneading the carbon black dispersed phenol resin and other components.

The lower limit of the ICI viscosity of the carbon black dispersed phenol resin of the present embodiment at 150 ° C. may be, for example, 0.01 Pa · s or more. On the other hand, the upper limit of the ICI viscosity at 150 ° C. is, for example, 0.5 Pa · s or less, preferably 0.4 Pa · s or less, and more preferably 0.3 Pa · s or less. Thereby, the fluidity of the epoxy resin composition using the carbon black dispersed phenol resin can be improved.

The upper limit of the water content in the carbon black dispersed phenol resin of the present embodiment is, for example, 1% or less, preferably 0.9% or less, and more preferably 0.8% or less. Thereby, the storage stability of the carbon black dispersed phenol resin can be improved. On the other hand, the lower limit of the water content is not particularly limited, but may be, for example, 0% or more.

In the carbon black-dispersed phenol resin of the present embodiment, ^{the upper limit of the total value of the ion concentrations of Na +} and Cl ⁻ is, for example, 30 ppm or less, preferably 20 ppm or less, and more preferably 10 ppm or less. By using such a carbon black dispersed phenol resin, impurities in the epoxy resin composition can be reduced.

A method for producing the epoxy resin composition of the present embodiment will be described.

In the method for producing the epoxy resin composition of the present embodiment, the epoxy resin, the curing agent containing the carbon black-dispersed phenol resin obtained by the above-mentioned method for producing the carbon black-dispersed phenol resin, and the inorganic filler are mixed. Can include steps.

Hereinafter, the components used in the method for producing the epoxy resin composition will be described, and then the process will be described in detail.

The epoxy resin composition of the present embodiment contains an epoxy resin, a curing agent, and an inorganic filler, and the curing agent can contain the carbon black-dispersed phenol resin according to the present embodiment.

(Epoxy resin)
As the epoxy resin in the present embodiment, a monomer, an oligomer, or a polymer having two or more epoxy groups in one molecule can be used in general, and the molecular weight and molecular structure thereof are not particularly limited. In the present embodiment, it is particularly preferable to use a non-halogenated epoxy resin as the epoxy resin.

In the present embodiment, the epoxy resin is, for example, a biphenyl type epoxy resin; a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol type epoxy resin such as a tetramethyl bisphenol F type epoxy resin; a stillben type epoxy resin; a phenol novolac type epoxy. Novolak type epoxy resin such as resin, cresol novolac type epoxy resin; polyfunctional epoxy resin such as triphenol methane type epoxy resin, alkyl modified triphenol methane type epoxy resin; phenol aralkyl type epoxy resin having phenylene skeleton, having biphenylene skeleton Phenol aralkyl type epoxy resin such as phenol aralkyl type epoxy resin; naphthol type epoxy resin such as epoxy resin obtained by glycidyl etherification of dihydroxynaphthalene type epoxy resin and dihydroxynaphthalene dimer; triglycidyl isocyanurate, monoallyl diglycidyl Triazine nuclei-containing epoxy resin such as isocyanurate; one or more selected from a bridge cyclic hydrocarbon compound modified phenol type epoxy resin such as dicyclopentadiene modified phenol type epoxy resin.
Of these, from the viewpoint of improving the balance between moisture resistance reliability and moldability, among bisphenol type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, phenol aralkyl type epoxy resin, and triphenol methane type epoxy resin. It is more preferable to include at least one. Further, from the viewpoint of suppressing warpage of the semiconductor package, it is particularly preferable to contain at least one of a phenol aralkyl type epoxy resin and a novolak type epoxy resin. A biphenyl type epoxy resin is particularly preferable for further improving the fluidity, and a phenol aralkyl type epoxy resin is particularly preferable for controlling the elastic modulus at a high temperature.

Examples of the epoxy resin include an epoxy resin represented by the following formula (1), an epoxy resin represented by the following formula (2), an epoxy resin represented by the following formula (3), and a following formula (4). An epoxy resin containing at least one selected from the group consisting of an epoxy resin represented by the following formula (5) can be used.

（式（１）中、Ａｒ^１はフェニレン基またはナフチレン基を表し、Ａｒ^１がナフチレン基の場合、グリシジルエーテル基はα位、β位のいずれに結合していてもよい。Ａｒ^２はフェニレン基、ビフェニレン基またはナフチレン基のうちのいずれか１つの基を表す。Ｒ_ａおよびＲ_ｂは、それぞれ独立に炭素数１〜１０の炭化水素基を表す。ｇは０〜５の整数であり、ｈは０〜８の整数である。ｎ^３は重合度を表し、その平均値は１〜３である。）

(In the formula (1), Ar ¹ represents a phenylene group or a naphthylene group, and when Ar ¹ is a naphthylene group, the glycidyl ether group may be bonded to either the α-position or the β-position ^{. Ar 2} is a phenylene group. , A group of any one of a biphenylene group and a naphthalene group. _Ra and R _b each independently represent a hydrocarbon group having 1 to 10 carbon atoms. G is an integer of 0 to 5, and h. Is an integer from 0 to 8. n ³ represents the degree of polymerization, and the average value thereof is 1 to 3.)

（式（２）中、複数存在するＲ_ｃは、それぞれ独立に水素原子または炭素数１〜４の炭化水素基を表す。ｎ^５は重合度を表し、その平均値は０〜４である。）

(In the formula (2), a plurality of R _cs independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁵ represents the degree of polymerization, and the average value thereof is 0 to 4. )

（式（３）中、複数存在するＲ_ｄおよびＲ_ｅは、それぞれ独立に水素原子又は炭素数１〜４の炭化水素基を表す。ｎ^６は重合度を表し、その平均値は０〜４である。）

(In the formula (3), a plurality of R _d and _Re each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁶ represents the degree of polymerization, and the average value thereof is 0 to 4. Is.)

（式（４）中、複数存在するＲ_ｆは、それぞれ独立に水素原子又は炭素数１〜４の炭化水素基を表す。ｎ^７は重合度を表し、その平均値は０〜４である。）

(In the formula (4), a plurality of R _fs independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁷ represents the degree of polymerization, and the average value thereof is 0 to 4. )

（式（５）中、複数存在するＲ_ｇは、それぞれ独立に水素原子又は炭素数１〜４の炭化水素基を表す。ｎ^８は重合度を表し、その平均値は０〜４である。）

(In the formula (5), a plurality of R _g each independently represent a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. N ⁸ represents the degree of polymerization, and the average value thereof is 0 to 4. )

(Hardener)
The curing agent can contain the carbon black dispersed phenol resin according to the present embodiment. In addition to the carbon black-dispersed phenol resin, this curing agent can include, for example, a general curing agent such as a phenol-based curing agent, an amine-based curing agent, an acid anhydride-based curing agent, and a mercaptan-based curing agent. 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. These may be used alone or in combination of two or more.

(Inorganic filler)
The inorganic filler that can be used in this embodiment is not particularly limited, but for example, silica such as molten spherical silica, crystalline silica, and fine silica, alumina, silicon nitride, aluminum nitride, aluminum hydroxide, magnesium hydroxide, and zinc borate. , Zinc molybdate and the like, and any one or more of these can be used. Among these, it is more preferable to use silica from the viewpoint of excellent versatility. Further, it can be said that it is also a preferable embodiment that the inorganic filler contains a component capable of imparting flame retardancy, such as aluminum hydroxide, magnesium hydroxide, zinc borate, and zinc molybdenate.

When silica is used as the inorganic filler, for example, two or more kinds of silica having _{different average particle diameters (D 50) can be used in combination.} More specifically, the inclusion of fused spherical silica having an average particle size of 1 μm or more and fine silica having an average particle size of 1 μm or less as silica improves the filling property of the epoxy resin composition and warps of the semiconductor package. From the viewpoint of suppressing the above, it is mentioned as one of the preferable embodiments.

The epoxy resin composition of the present embodiment may contain a curing accelerator, a silane coupling agent, and other additives in addition to the epoxy resin, the curing agent, and the inorganic filler. Additives include mold release agents and other organic components.

(Curing accelerator)
The epoxy resin composition of the present embodiment can contain a curing accelerator. As the curing accelerator, those used in general epoxy resin compositions can be used.
The curing accelerator is a phosphorus atom-containing compound such as an organic phosphine, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, an adduct of a phosphonium compound and a silane compound; 5.4.0] One selected from amidin and tertiary amines such as undecene-7, benzyldimethylamine, 2-methylimidazole, and nitrogen atom-containing compounds such as the quaternary salt of amidin and amine, or Two or more types can be included. Among these, it is more preferable to contain a phosphorus atom-containing compound from the viewpoint of improving curability. Further, from the viewpoint of improving the balance between moldability and curability, it has latent properties such as a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, and an adduct of a phosphonium compound and a silane compound. It is more preferable to include one.

(Silane coupling agent)
The epoxy resin composition of the present embodiment can contain a silane coupling agent. This makes it possible to improve the adhesion between the epoxy resin and the curing agent and the inorganic filler. The silane coupling agent can include, for example, one or more selected from epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, vinylsilane, and methacrylsilane.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, and β- (3,4-epoxy). Cyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacry Loxypropyltriethoxysilane, vinyltriacetoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-anilinopropyltrimethoxysilane, γ-anilinopropylmethyldimethoxysilane, γ-[bis (bis) β-Hydroxyethyl)] Aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (Aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ- (β-aminoethyl) aminopropyldimethoxymethylsilane, N- (trimethoxysilylpropyl) ethylenediamine, N -(Dimethoxymethylsilylisopropyl) ethylenediamine, methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxy Silane, Hexamethyldisilane, Vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, 3-Ixionpropyltriethoxysilane, 3-Acryloxypropyltrimethoxysilane, 3-Triethoxysilyl-N- (1,3-dimethi) Lubutylidene) Examples thereof include a hydrolyzate of propylamine. These may be used individually by 1 type, and may be used in combination of 2 or more type.

(Release agent and other organic components)
Examples of the mold release agent that can be used in the present embodiment include natural waxes such as carnauba wax, synthetic waxes such as montanic acid ester wax, higher fatty acids such as zinc stearate, and metal salts thereof or mold release agents such as paraffin. Be done.
In addition, various additions such as known antioxidants that can be dissolved in organic solvents and known coupling agents (titanium compounds, aluminum chelates, aluminum / zirconium compounds, etc.) other than the above-mentioned silane coupling agents. The agent can be dissolved in the carbon black dispersion.

According to the present embodiment, the above components are mixed, melt-kneaded with a kneader such as a roll, kneader or extruder, cooled and then crushed, and crushed and then tablet-molded into a tablet shape. An epoxy resin composition can be obtained. Such an epoxy resin composition may be in the form of granules, tablets or sheets.

The content of the epoxy resin in the epoxy resin composition of the present embodiment is preferably 2% by mass or more, more preferably 4% by mass or more, and 6% by mass, based on the whole epoxy resin composition. The above is more preferable. By setting the content of the epoxy resin to the above lower limit value or more, the fluidity of the epoxy resin composition can be improved and the moldability can be further improved. On the other hand, the content of the epoxy resin in the epoxy resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, based on the whole epoxy resin composition. By setting the content of the epoxy resin to the above upper limit value or less, it is possible to improve the moisture resistance reliability and the reflow resistance of the semiconductor package including the sealing resin formed by using the epoxy resin composition.

The content of the curing agent in the epoxy resin composition of the present embodiment is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the total amount of the epoxy resin composition. It is more preferably 5.5% by mass or more. The content of the curing agent in the epoxy resin composition is preferably 20% by mass or less, more preferably 15% by mass or less, based on the entire epoxy resin composition.
By setting the content of the curing agent in the above range, an epoxy resin composition having excellent moldability and reflow resistance can be obtained.

Further, in the present embodiment, the content of the inorganic filler is preferably 30% by mass or more, more preferably 45% by mass or more, and 50% by mass or more with respect to the entire epoxy resin composition. It is more preferable to have. By setting the content of the inorganic filler to the above lower limit or higher, the low hygroscopicity and low thermal expansion of the sealing resin formed by using the epoxy resin composition are improved, and the moisture resistance reliability and reflow resistance are further improved. It can be effectively improved. On the other hand, the content of the inorganic filler is preferably 95% by mass or less, more preferably 93% by mass or less, and further preferably 90% by mass or less with respect to the entire epoxy resin composition. preferable. By setting the content of the inorganic filler to the above upper limit or less, it is possible to suppress the decrease in moldability due to the decrease in the fluidity of the epoxy resin composition and the flow of bonding wires due to the increase in viscosity. Become.

[Semiconductor package]

The epoxy resin composition of this embodiment can be used for various purposes. For example, the epoxy resin composition of the present embodiment can be used for a sealing epoxy resin composition or a fixing epoxy resin composition. The sealing epoxy resin composition according to the present embodiment can seal electronic parts such as semiconductor chips, and can be applied to the epoxy resin composition used for the above semiconductor package.

FIG. 1 is a diagram showing a cross-sectional structure of an example of a semiconductor package 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 pad of the semiconductor element 1 and the lead frame 5 are connected by a bonding wire 4. The semiconductor element 1 is sealed with a cured body 6 of the epoxy resin composition of the present embodiment. As the bonding wire 4, a metal wire such as a gold wire, a silver wire, or a copper wire can be used.

FIG. 2 is a diagram showing a cross-sectional structure of an example of a single-sided sealed semiconductor package using the epoxy resin composition of the present embodiment. The semiconductor element 1 is fixed on the solder resist 7 of the laminated body in which the layer of the solder resist 7 is formed on the surface of the substrate 8 via the cured die bond material 2. In order to make the semiconductor element 1 and the substrate 8 conductive, 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 pad of the semiconductor element 1 and the electrode pad of the substrate 8 are connected by a bonding wire 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 pad on the substrate 8 is internally bonded to the solder ball 9 on the non-sealing surface side on the substrate 8.

Although the embodiments of the present invention have been described above, these are examples of the present invention, and various configurations other than the above can be adopted.
Hereinafter, an example of the reference form will be added.
1. 1. It is a carbon black dispersed phenol resin in which carbon black is dispersed in the phenol resin.
A carbon black-dispersed phenolic resin having an average particle size of 80 nm or more and 400 nm or less and one peak in the particle size distribution of the carbon black as measured by a dynamic light scattering method.
2. Above 1. The carbon black dispersed phenol resin described in
A carbon black-dispersed phenol resin having a D50 / D90 of 0.5 or more and 0.9 or less with respect to the carbon blacks D50 and D90 measured by a dynamic light scattering method.
3. 3. Above 1. Or 2. The carbon black dispersed phenol resin described in
A carbon black-dispersed phenol resin having a peak value of 180 nm or more and 350 nm or less in the particle size distribution of carbon black measured by a dynamic light scattering method.
4. Above 3. The carbon black dispersed phenol resin described in
A carbon black-dispersed phenol resin having a half-value width of 80 nm or more and 200 nm or less.
5. Above 1. From 4. The carbon black dispersed phenol resin according to any one of the above.
A carbon black-dispersed phenol resin having a softening point of 50 ° C. or higher and 100 ° C. or lower.
6. Above 1. From 5. The carbon black dispersed phenol resin according to any one of the above.
A carbon black-dispersed phenol resin having an ICI viscosity at 150 ° C. of 0.01 Pa · s or more and 0.5 Pa · s or less.
7. Above 1. From 6. The carbon black dispersed phenol resin according to any one of the above.
A carbon black-dispersed phenol resin having a water content of 1% or less in the carbon black-dispersed phenol resin.
8. Above 1. From 7. The carbon black dispersed phenol resin according to any one of the above.
In the carbon black dispersion phenolic resins, Na ⁺ and Cl ^- total value of the ion concentration is at 30ppm or less, carbon black dispersed phenolic resin.
9. Epoxy resin and
Hardener and
Inorganic filler and, including
The above-mentioned curing agent is the above-mentioned 1. From 8. An epoxy resin composition containing the carbon black dispersed phenol resin according to any one of the above.
10. It is a method for producing a carbon black-dispersed phenol resin in which carbon black is dispersed in the phenol resin.
A step of obtaining a carbon black dispersion liquid containing a carbon black dispersant, an organic solvent, and the above carbon black.
After the step of obtaining the carbon black dispersion, a step of obtaining a phenol resin solution by dissolving the carbon black dispersion and the phenol resin, and
A method for producing a carbon black-dispersed phenol resin, which comprises a step of obtaining a carbon black-dispersed phenol resin by removing the organic solvent from the phenol resin solution.
11. 10. The method for producing a carbon black dispersed phenol resin described in 1.
In the step of obtaining the carbon black-dispersed phenol resin, the average particle size of the carbon black in the carbon black-dispersed phenol resin measured by a dynamic light scattering method is 80 nm or more and 400 nm or less, and the particle size distribution of the carbon black. A method for producing a carbon black dispersed phenol resin having one peak in.
12. 10. Or 11. The method for producing a carbon black dispersed phenol resin described in 1.
In the step of obtaining the carbon black dispersion, the average particle size of the carbon black in the carbon black dispersion measured by a dynamic light scattering method is 80 nm or more and 400 nm or less, and the peak in the particle size distribution of the carbon black. Is one method for producing a carbon black dispersed phenol resin.
13. 10. From 12. The method for producing a carbon black dispersed phenol resin according to any one of the above.
When the D50 of the carbon black in the carbon black dispersed phenol resin is X and the D50 of the carbon black in the carbon black dispersion is Y, the Y / X is 0.6 or more and 1 or less. A method for producing a black dispersed phenol resin.
14. Epoxy resin and 10. To 13. A method for producing an epoxy resin composition, which comprises a step of mixing a curing agent containing a carbon black-dispersed phenol resin obtained by the method for producing a carbon black-dispersed phenol resin according to any one of the above and an inorganic filler. ..

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

[Preparation of carbon black dispersed phenol resin]
(Carbon black dispersed phenol resin 1)
First, 25 parts by weight of carbon black 1 (# 5 manufactured by Mitsubishi Chemical Corporation), 3.75 parts by weight of carbon black dispersant 1 (Ajinomoto Fine-Techno Co., Ltd. Ajispar PB821), 1.75 parts by weight of carbon black dispersion Agent 2 (Solspers 5000 manufactured by Nippon Lubrizol Co., Ltd.) and 69.5 parts by weight of methyl ethyl ketone were mixed and sufficiently dispersed using a paint shaker to prepare a carbon black dispersion.
The average particle size of the obtained carbon black dispersion was measured using a Nanotrac Wave-EX150 manufactured by Microtrac Bell Co., Ltd. to measure a sample diluted with methyl ethyl ketone so that the concentration of carbon black was 500 ppm. The average particle size of D50 was 194 nm.
Subsequently, 91 parts by weight of phenol resin (KAYAHARD GHP-65 manufactured by Nippon Kayaku) was dissolved in 140 parts by weight of methyl ethyl ketone at room temperature, and then 32.8 parts by weight of the above carbon was added to the solution obtained by stirring. The black dispersion was added dropwise, and the mixture was stirred for 1 hour to obtain a phenol resin solution. The obtained phenol resin solution was filtered through a filter having a mesh size of 20 μm.
Subsequently, the obtained phenol resin solution was concentrated at atmospheric pressure at 100 to 130 ° C., and further concentrated under reduced pressure (finally 2 to 5 kPa over 4 hours), and 95.0 g of carbon black dispersed phenol resin 1 ( Solid) was obtained.
The obtained carbon black-dispersed phenol resin 1 had a softening point of 68.5 ° C., an ICI viscosity (150 ° C.) of 0.08 Pa · s, and a hydroxyl value of 222 g / eq. The water content was 0.2% ^{and the ion concentrations of Na +} and Cl ⁻ were 0.2 ppm and 1.8 ppm, respectively.
0.5 g by weight of the obtained carbon black-dispersed phenol resin was weighed and dissolved in 99.5 parts by weight of methyl ethyl ketone at room temperature. The average particle size D50 of carbon black was measured for this solution using Nanotrac Wave-EX150 manufactured by Microtrac Bell, and found to be 212 nm.
From this result, it was confirmed that the carbon black contained in the carbon black-dispersed phenol resin exists in the state of fine particles without causing aggregation in the process of producing the resin.

(Carbon black dispersed phenol resin 2)
A carbon black-dispersed phenol resin 2 (solid) was obtained in the same manner as the carbon black-dispersed phenol resin 1 except that the carbon black 1 was changed to carbon black 2 (MA-100 manufactured by Mitsubishi Chemical Corporation).
The average particle size D50 of carbon black in the obtained carbon black dispersion was 180 nm as a result of measurement by the same method.
The obtained carbon black-dispersed phenol resin 2 had a softening point of 72 ° C., an ICI viscosity (150 ° C.) of 0.10 Pa · s, and a hydroxyl value of 226 g / eq.

(Carbon black dispersed phenol resin 3)
A carbon black-dispersed phenol resin 3 (solid) was obtained in the same manner as the carbon black-dispersed phenol resin 1 except that the carbon black dispersant 1 was changed to a carbon black dispersant 3 (Ajinomoto Fine-Techno Co., Ltd. Azisper PB822). It was.
The average particle size D50 of carbon black in the obtained carbon black dispersion was 200 nm as a result of measurement by the same method.
The obtained carbon black-dispersed phenol resin 3 had a softening point of 69 ° C., an ICI viscosity (150 ° C.) of 0.08 Pa · s, and a hydroxyl value of 222 g / eq.

(Carbon black dispersed phenol resin 4)
The carbon black dispersed phenol resin 4 (solid) was obtained in the same manner as the carbon black dispersed phenol resin 1 except that the carbon black dispersant 1 was changed to the carbon black dispersant 4 (Ajinomoto Fine-Techno Co., Ltd. Azisper PB881). It was.
The average particle size D50 of carbon black in the obtained carbon black dispersion was 190 nm as a result of measurement by the same method.
The obtained carbon black-dispersed phenol resin 3 had a softening point of 68 ° C., an ICI viscosity (150 ° C.) of 0.05 Pa · s, and a hydroxyl value of 227 g / eq.

(Carbon black dispersed phenol resin 5)
The carbon black dispersed phenol resin 5 was prepared in the same manner as the carbon black dispersed phenol resin 1 except that the carbon black dispersant 1 and the carbon black dispersant 2 were not used. However, without the dispersant, a carbon black dispersed phenol resin could not be obtained.

[Preparation of epoxy resin composition]
Subsequently, each raw material blended according to Table 1 was mixed at room temperature using a mixer, and then roll-kneaded at 70 to 100 ° C. Then, the obtained kneaded product was cooled and then pulverized to obtain an epoxy resin composition. The details of each component in Table 1 are as follows.

(Inorganic filler)
Inorganic filler 1: Spherical molten silica (manufactured by Electrochemical Industry Co., Ltd., trade name "FB560", average particle size (D ₅₀ ) 30 μm).
The average particle size of the inorganic filler in this example was measured using a laser diffraction scattering type particle size distribution meter SALD-7000 manufactured by Shimadzu Corporation.

(Epoxy resin)
Epoxy resin 1: Biphenyl type epoxy resin (manufactured by Mitsubishi Chemical Corporation, YX4000K)

(Carbon black dispersed phenol resin)
Carbon black dispersed phenol resin 1: Carbon black dispersed phenol resin 1 prepared by the above method.
Carbon black dispersed phenol resin 2: Carbon black dispersed phenol resin 2 prepared by the above method.
Carbon black dispersed phenol resin 3: Carbon black dispersed phenol resin 3 prepared by the above method.
Carbon black dispersed phenol resin 4: Carbon black dispersed phenol resin 4 prepared by the above method.
Carbon black dispersed phenol resin 5: Carbon black dispersed phenol resin 5 prepared by the above method.

(Colorant)
Colorant 1: Carbon Black (Carbon # 5, Mitsubishi Chemical Corporation)

(Phenol resin)
Phenol resin 1: Phenol aralkyl resin having a biphenylene skeleton (manufactured by Nippon Kayaku Co., Ltd., GPH-65)
Phenol resin 2: Phenol novolac resin (manufactured by Sumitomo Bakelite Co., Ltd., PR-HF-3)

(Coupling agent)
Coupling Agent 1: Silane Coupling Agent (CF4083, manufactured by Toray Dow Corning)

(Curing accelerator)
Curing Accelerator 1: Addition of triphenylphosphine and p-benzoquinone (TPP-BQ, Keiai Kasei Co., Ltd.)

(Release agent)
Release agent 1: (Ricowax PED191, manufactured by Clariant Japan Co., Ltd.))

Hereinafter, the carbon black dispersed phenol resins 1 to 4 were evaluated as follows. The evaluation results are shown in Table 2.

(Average particle size of carbon black)
The obtained carbon black-dispersed phenol resin is redissolved in methyl ethyl ketone to prepare a liquid sample diluted so that the concentration of carbon black is 500 ppm. Using this liquid sample, the average particle size of carbon black was measured using a dynamic light scattering (DLS) particle size distribution measuring device (Nanotrac Wave-EX150 manufactured by Microtrac Bell) at room temperature of 25 ° C. (D50) and the particle size distribution were measured.
(Carbon black particle size distribution, peak value, half width)
The obtained carbon black dispersed phenol resin is dissolved in methyl ethyl ketone to prepare a resin solution of 0.3 to 0.7%. The particle size distribution of the solution was measured using Nanotrac Wave-EX150 manufactured by Microtrac Bell Co., Ltd. under the following conditions.
Particle permeability: Transmitted particle refractive index: 1.81
Particle shape: Non-spherical density (g / cm ³ ): 1.00
Monodisperse: Invalid Distribution display: Sedimentary solvent refractive index: 1.38
In the obtained carbon black-dispersed phenolic resins 1 to 4, there was one peak in the particle size distribution of carbon black.
(D50, D90)
D50 refers to the particle size when the cumulative volume distribution corresponds to 50% when the particle size distribution is measured and the horizontal axis is the particle size and the vertical axis is the cumulative volume distribution (%). For example, D90 represents the particle size when the cumulative volume distribution corresponds to 90%.
(ICI viscosity)
The ICI viscosity of the obtained carbon black dispersed phenol resin was measured at 150 ° C. by a method according to JIS K 7117-2. The unit is Pa · s.
(Softening point)
The obtained carbon black dispersed phenol resin was measured by a method according to JIS K-7234. The unit is ° C.
(Moisture content)
The water content of the obtained carbon black-dispersed phenol resin was measured by a method according to JIS K-0068. The unit is%.
(Na ⁺ and Cl ^- ion concentration)
Weigh 8.00 g of the sample (the obtained carbon black-dispersed phenol resin) into a 100 mL polyethylene bottle, and add 100 mL of purified water. The polyethylene bottle was placed in an oven set at 95 ° C. and extracted for 20 hours. It was taken out from the oven, allowed to cool to room temperature, sampled, filtered through a 0.45 μm filter, and then measured by ion chromatography to measure the ion concentrations of ^{Na +} and Cl ^−. The unit is ppm. As an ion chromatography measuring device, ICS-3000 manufactured by Thermo Fisher Scientific Co., Ltd. or an equivalent product was used.

Hereinafter, the epoxy resin composition was evaluated as follows. The evaluation results are shown in Table 3.

(Carbon agglutinin)
Using a low-pressure transfer molding machine (Made by Kotaki Co., Ltd., 30t press), the epoxy resin composition was injection-molded under the conditions of a mold temperature of 175 ° C., a molding pressure of 9.8 MPa, and a curing time of 120 seconds to obtain a diameter. A test piece having a thickness of 100 mm and a thickness of 2 mm was prepared. Then, after heat treatment at 175 ° C. for 4 hours, the surface of the test piece was sanded, and carbon black aggregates were observed with a microscope at a magnification of 100 times. The total number of carbon black aggregates having a major axis of 20 μm or more was measured.

(Spiral flow)
Spiral flow measurement was performed on the obtained epoxy resin composition for each Example and Comparative Example. Spiral flow measurement uses a low-pressure transfer molding machine (“KTS-15” manufactured by Kotaki Seiki Co., Ltd.) to mold for spiral flow measurement according to EMMI-1-66 with a mold temperature of 175 ° C and injection pressure. The epoxy resin composition was injected under the conditions of 6.9 MPa and a curing time of 120 seconds, and the flow length was measured. The results are shown in Table 1.

(Gel time)
The gel time was measured by measuring the time (gel time) from melting the obtained epoxy resin composition on a hot plate heated to 175 ° C. to curing while kneading with a spatula. The results are shown in Table 1.

It was found that the carbon black was not aggregated in the carbon black dispersed phenol resin and epoxy resin compositions of Examples 1 to 5. In the epoxy resin composition of Comparative Example 1, carbon black was aggregated.

1 Semiconductor element 2 Die bond material hardened body 3 Die pad 4 Bonding wire 5 Lead frame 6 Hardened body 7 Solder resist 8 Substrate 9 Solder ball

Claims (14)

A carbon black-dispersed phenol resin composition in which carbon black is dispersed in a phenol resin.
A carbon black-dispersed phenolic resin composition having an average particle size of 80 nm or more and 400 nm or less and one peak in the particle size distribution of the carbon black, as measured by a dynamic light scattering method. The carbon black dispersed phenol resin composition according to claim 1.
A carbon black-dispersed phenolic resin composition having a D50 / D90 of 0.5 or more and 0.9 or less with respect to the carbon blacks D50 and D90 measured by a dynamic light scattering method. The carbon black dispersed phenol resin composition according to claim 1 or 2.
A carbon black-dispersed phenol resin composition having a peak value of 180 nm or more and 350 nm or less in the particle size distribution of carbon black measured by a dynamic light scattering method. The carbon black dispersed phenol resin composition according to claim 3.
A carbon black-dispersed phenol resin composition in which the half width of the peak value is within the range of 80 nm or more and 200 nm or less. The carbon black-dispersed phenolic resin composition according to any one of claims 1 to 4.
A carbon black-dispersed phenolic resin composition having a softening point of the carbon black-dispersed phenolic resin of 50 ° C. or higher and 100 ° C. or lower. The carbon black dispersed phenol resin composition according to any one of claims 1 to 5.
A carbon black dispersed phenol resin composition having an ICI viscosity at 150 ° C. of the carbon black dispersed phenol resin of 0.01 Pa · s or more and 0.5 Pa · s or less. The carbon black dispersed phenol resin composition according to any one of claims 1 to 6.
A carbon black-dispersed phenol resin composition having a water content of 1% or less in the carbon black-dispersed phenol resin. The carbon black-dispersed phenolic resin composition according to any one of claims 1 to 7.
A carbon black-dispersed phenol resin composition having ^{a total value of Na +} and Cl ⁻ ion concentrations of 30 ppm or less in the carbon black-dispersed phenol resin. Epoxy resin and
Hardener and
Inorganic filler and, including
An epoxy resin composition, wherein the curing agent contains the carbon black dispersed phenol resin composition according to any one of claims 1 to 8. A method for producing a carbon black-dispersed phenol resin composition in which carbon black is dispersed in a phenol resin.
A step of obtaining a carbon black dispersion liquid containing a carbon black dispersant, an organic solvent, and the carbon black.
After the step of obtaining the carbon black dispersion liquid, a step of obtaining a phenol resin solution by dissolving the carbon black dispersion liquid and the phenol resin, and a step of obtaining the phenol resin solution.
The step of filtering the phenol resin solution with a filter and
A method for producing a carbon black-dispersed phenol resin composition , which comprises a step of obtaining a carbon black-dispersed phenol resin by removing the organic solvent from the phenol resin solution. The method for producing a carbon black dispersed phenol resin composition according to claim 10.
In the step of obtaining the carbon black dispersed phenol resin, the average particle size of the carbon black in the carbon black dispersed phenol resin measured by the dynamic light scattering method is 80 nm or more and 400 nm or less, and the particle size distribution of the carbon black. A method for producing a carbon black dispersed phenol resin composition having one peak in. The method for producing a carbon black dispersed phenol resin composition according to claim 10 or 11.
In the step of obtaining the carbon black dispersion, the average particle size of the carbon black in the carbon black dispersion measured by a dynamic light scattering method is 80 nm or more and 400 nm or less, and the peak in the particle size distribution of the carbon black. Is one method for producing a carbon black dispersed phenol resin composition. The method for producing a carbon black-dispersed phenol resin composition according to any one of claims 10 to 12.
When the D50 of the carbon black in the carbon black dispersed phenol resin is X and the D50 of the carbon black in the carbon black dispersion is Y, the Y / X is 0.6 or more and 1 or less. A method for producing a black dispersed phenol resin composition. The epoxy resin, the curing agent containing the carbon black-dispersed phenol resin obtained by the method for producing the carbon black-dispersed phenol resin composition according to any one of claims 10 to 13, and the inorganic filler are mixed. A method for producing an epoxy resin composition, which comprises a step.

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