JP2017160306A - Epoxy resin composition, epoxy resin semi-cured composition, semiconductor device, and composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition which makes it possible to obtain a cured product having excellent flowability and a high thermal conductivity, a semi-cured composition thereof, and a semiconductor device and a composite material prepared therewith.SOLUTION: The present invention provides an epoxy resin composition that has an epoxy resin having a predetermined structure with a melting point of 110°C or less, a curing agent, and α-alumina.SELECTED DRAWING: None

Description

  The present invention relates to an epoxy resin composition, an epoxy resin semi-cured composition, a semiconductor device, and a composite material.

Conventionally, epoxy resins have been widely used as insulating materials for electrical and electronic parts such as diodes, transistors and integrated circuits, and semiconductor devices.
In recent years, since the amount of heat generation has increased with the miniaturization of these devices, it has become an important issue to increase the heat dissipation of the insulating material, that is, to increase the thermal conductivity.
In general, epoxy resins have a lower thermal conductivity than inorganic materials, so in order to improve thermal conductivity, inorganic fillers such as crystalline silica, silicon nitride, aluminum nitride, and spherical alumina powder with high thermal conductivity are used. Techniques such as inclusion in an epoxy resin are disclosed (see, for example, Patent Documents 1 and 2).

However, when the content of the inorganic filler with respect to the epoxy resin is increased, the viscosity increases at the time of molding, and at the same time, the fluidity is lowered and the moldability is impaired.
Therefore, attempts have been made to use liquid crystalline epoxy resins having high thermal conductivity, and it has been reported that high thermal conductivity is exhibited when α-alumina is used as an inorganic filler (for example, Patent Documents). 3 and 4).
This is due to a mechanism in which the molecular skeleton of the liquid crystalline epoxy resin is highly oriented on the surface of the α-alumina as a result of the interaction between the surface of the α-alumina and the liquid crystalline epoxy resin (for example, Patent Document 4). reference).
However, since the liquid crystalline epoxy resin generally has a high melting point, it needs to be blended with the inorganic filler under high temperature conditions where the epoxy group curing reaction proceeds. Therefore, the epoxy resin is cured at the blending stage of the inorganic filler. Therefore, there is a problem that a uniform cured product cannot be obtained. Even when a macroscopically uniform cured product is obtained, the viscosity at the time of melting is high and the fluidity is poor, so the interface with the inorganic filler does not adhere sufficiently, or it cures at high temperatures. Therefore, the molecular motion of the epoxy resin at the curing stage is intense, and the effect of promoting the molecular arrangement by the inorganic filler is not sufficiently exhibited. As a result, there is a problem that sufficient high thermal conductivity is not achieved.
On the other hand, when an inorganic filler is blended at a mild temperature at which the curing reaction of the epoxy group of the liquid crystalline epoxy resin does not proceed, the liquid crystalline epoxy resin is solidified or crystallized, and the fluidity decreases and is used industrially. The problem of being unable to do so.
Also disclosed is a technique for obtaining a cured epoxy resin having high thermal conductivity by reducing the viscosity of the epoxy resin composition by adding an organic solvent to the epoxy resin composition or by curing at a low temperature. (For example, see Patent Document 4).

JP-A-11-147936 JP 2002-309067 A JP 2008-13759 A International Publication No. 2013-65159

  However, in general, liquid crystalline epoxy resins tend to have low solubility in organic solvents, and the solvents that can be used are limited or their solubility tends to be low. Is not obtained.

  Therefore, in the present invention, in view of the above-described problems of the prior art, the liquid crystal epoxy resin having a low melting point and high solubility in an organic solvent and α-alumina are included, and the interaction between the epoxy resin and α-alumina is An epoxy resin composition, a semi-cured composition thereof, a semiconductor device using the same, and a composite material, which are obtained more prominently, have a high fluidity, excellent workability, and obtain a cured product with high thermal conductivity. The purpose is to provide.

As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy resin composition containing an epoxy resin having a predetermined structure, a curing agent, and α-alumina is the conventional technology described above. The present inventors have found that the above problem can be solved, and have completed the present invention.
That is, the present invention is as follows.

[1]
An epoxy resin represented by the following general formula (1) and having a melting point of 110 ° C. or lower;
A curing agent;
α-alumina,
Containing
Epoxy resin composition.

(In general formula (1), MS represents the following general formula (2).
Each G independently represents a monovalent organic group represented by the following general formula (5).
SP1 and SP2 each independently represent a divalent organic group represented by the following general formula (3) or general formula (4). )

(In general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

(In general formula (3), p is an integer of 1 or more and 10 or less.)

(In general formula (4), each R ₃ independently represents a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms, and q is an integer of 1 to 10)

(In the general formula (5), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.)

[2]
The specific surface area of the α-alumina particles is 0.1 m ² / g or more and 3.0 m ² / g or less, and the average particle diameter (D50) is 0.1 μm to 100 μm.
The epoxy resin composition according to [1].
[3]
The epoxy resin composition according to [1] or [2], wherein the epoxy resin is a compound represented by the following formula (6).

[4]
The curing agent is an amine compound;
The epoxy resin composition according to any one of [1] to [3].
[5]
The curing agent is a phenolic curing agent having an adjacent hydroxyl group,
The epoxy resin composition according to any one of [1] to [3].
[6]
In the epoxy resin semi-cured composition in which the epoxy group in the epoxy resin and the functional group of the curing agent are reacted by 5% to 80% based on the epoxy group,
The α-alumina is blended,
The epoxy resin composition according to [1].
[7]
The epoxy resin semi-cured composition in which the epoxy resin and the curing agent in the epoxy resin composition according to any one of [1] to [5] are reacted by 5% to 80% based on an epoxy group. .
[8]
The semiconductor device sealed with the epoxy resin composition as described in any one of said [1] thru | or [6], or the epoxy resin semi-hardened composition as described in said [7].
[9]
A composite material in which a fibrous base material is impregnated with the epoxy resin composition according to any one of [1] to [6] or the epoxy resin semi-cured composition according to [7].

  According to the present invention, it is possible to provide an epoxy resin composition, a semi-cured composition thereof, a semiconductor device using these, and a composite material, which can obtain a cured product having excellent fluidity and high thermal conductivity.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist.

[Epoxy resin composition]
The epoxy resin composition of this embodiment is
An epoxy resin represented by the following general formula (1) and having a melting point of 110 ° C. or lower;
A curing agent;
α-alumina,
Containing
It is an epoxy resin composition.

In general formula (1), MS represents the following general formula (2).
Each G independently represents a monovalent organic group represented by the following general formula (5).
SP1 and SP2 each independently represent a divalent organic group represented by the following general formula (3) or general formula (4). )

In General Formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.

  In general formula (3), p is an integer of 1 or more and 10 or less.

In general formula (4), each R ₃ independently represents a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms, and q is an integer of 1 to 10 inclusive.

In general formula (5), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.

R ₁ and R ₂ in the general formula (2) each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
R ₁ and R ₂ tend to increase the regularity of the molecular chain constituting the cured product of the epoxy resin used in the present embodiment as the number of carbon atoms is smaller. As a result, a cured product having a high thermal conductivity is obtained. Hydrogen is most preferred.

P in the general formula (3) is an integer of 1 or more and 10 or less.
When the value of p is 10 or less, the arrangement of the molecular chains constituting the cured product of the epoxy resin composition of the present embodiment and the regularity of the arrangement of the methylstilbene skeleton tend to be high, and sufficient heat conduction is achieved. A cured product having a high rate is obtained.
When p is 1 or more, an increase in melting point can be suppressed, and good processability can be obtained in the epoxy resin composition of the present embodiment.
From such a viewpoint, p is preferably 1 or more and 5 or less, more preferably 1.

R ₃ in the general formula (4) independently represents a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.
When the carbon number of R ₃ is 4 or less, the arrangement of the molecular chains constituting the cured product of the cured product of the epoxy resin composition of the present embodiment and the regularity of the arrangement of the methylstilbene skeleton tend to increase. A cured product having high thermal conductivity is obtained.
Q in the general formula (4) is an integer of 1 or more and 10 or less.
When the value of q is 10 or less, the arrangement of the molecular chains constituting the cured product of the epoxy resin composition of the present embodiment tends to increase.
When q is 1 or more, an increase in melting point can be suppressed, and an excellent workability epoxy resin composition can be obtained. From such a viewpoint, q is preferably 1 or more and 3 or less, more preferably 1.

R ₄ in the general formula (5) represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.
When R ₄ is a hydrocarbon group, the greater the carbon number of the hydrocarbon group, the better the water resistance of the cured product obtained by curing the epoxy resin composition of the present embodiment. It tends to rise relatively.
From such a viewpoint, R ₄ in the formula (5) is preferably a hydrogen atom or a hydrocarbon group having 1 carbon atom, more preferably a hydrogen atom.

(Melting point)
The epoxy resin used in the epoxy resin composition of the present embodiment has a melting point of 110 ° C. or lower.
The lower the melting point of the epoxy resin, the higher the temperature and orientation of the molecular chain during the reaction, and the higher the orientation and regularity of the molecular chain during the reaction, the more the epoxy resin and α-alumina can be mixed. When mixed, the surface of α-alumina is sufficiently wetted, which is preferable.
From such a viewpoint, the melting point of the epoxy resin used in the epoxy resin composition of the present embodiment is preferably 100 ° C. or lower, more preferably 80 ° C. or lower.
Melting | fusing point of the epoxy resin used for the epoxy resin composition of this embodiment can be measured by the method as described in the below-mentioned Example.
From the above viewpoint, an epoxy resin represented by the following formula (6) is preferable.

(Α-alumina)
The α-alumina used in the epoxy resin composition of the present embodiment preferably has a specific surface area of 0.1 m ² / g or more and 3.0 m ² / g or less.
When the specific surface area of α-alumina is 0.1 m ² / g or more, the orientation and regularity of the molecular chain in the epoxy resin are sufficiently enhanced, and when it is 3.0 m ² / g or less, the epoxy resin composition The viscosity does not become too high, and good processability tends to be obtained.
From such a viewpoint, the more preferable specific surface area of α-alumina is 0.4 m ² / g or more and 2.0 m ² / g or less, more preferably 1.0 m ² / g or more and 1.5 m ² / g or less. It is.
In addition, the α-alumina used in the epoxy resin composition of the present embodiment is an average corresponding to a cumulative 50% from the small particle size side of the weight cumulative distribution in the particle size distribution measured using a laser diffraction method. The particle diameter (D50) is preferably 0.1 μm to 100 μm.
When the average particle diameter (D50) is 0.1 μm or more, the viscosity of the epoxy resin composition of the present embodiment can be suppressed from increasing, and good workability tends to be obtained, and is 100 μm or less. The epoxy resin composition sufficiently permeates the base material sealed with the epoxy resin composition of the present embodiment.
From such a viewpoint, D50 of more preferable α-alumina is 1.0 μm to 50 μm, and more preferably 10 μm to 20 μm.

(Curing agent)
The curing agent used in the epoxy resin composition of the present embodiment is not limited to the following, but, for example, an amine curing agent, a phenol curing agent, an acid anhydride curing agent, a catalyst curing agent, and a photocatalyst. System curing agent and the like.

<Amine-based curing agent>
As the amine curing agent, an amine compound is preferable.
Examples of the amine compound include, but are not limited to, aliphatic amines and aromatic amines.
Aromatic amines are more preferred because they have a rigid phenyl group, and therefore tend to have low network molecular chain mobility and high heat resistance.
Examples of the aromatic amine include, but are not limited to, o-xylenediamine, m-xylenediamine, p-xylenediamine, 2,4-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4, Examples include 4'-diaminodiphenylethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ester, monoallyldiaminodiphenylmethane, diallyldiaminodiphenylmethane, sulfanilamide, and the like.
Among these, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, and p-xylylenediamine are preferable because they are highly compatible with the above-described epoxy resin, and a uniform cured product can be obtained. In particular, 4,4′-diaminodiphenylethane is more preferable because two phenyl groups are substantially planar, and a cured product with higher orientation and higher thermal conductivity and heat resistance tends to be obtained.

Since aliphatic amines tend to have low viscosity, α-alumina has a tendency to increase the filling rate, and because it tends to be highly reactive and hardened at low temperature, a cured product with high orientation can be obtained. preferable.
Examples of the aliphatic amine include, but are not limited to, ethylenediamine, diaminopropane, diaminobutane, diaminopentane, hexamethylenediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, and 1,4. -Cyclohexanediamine, triethylenetetramine, o-xylylenediamine, m-xylylenediamine, p-xylylenediamine and the like.
As the aliphatic amine, diaminopropane, 1,4-cyclohexanediamine, hexamethylenediamine, and p-xylylenediamine are preferable because they are highly compatible with the above-described epoxy resin and give a uniform cured product. In particular, diaminopropane and 1,4-cyclohexanediamine are preferable because they have high orientation strength, and as a result, a cured product having high mechanical strength and high thermal conductivity can be obtained.
In the epoxy resin composition of the present embodiment, the content of the above-described amine-based curing agent is not particularly limited, but the ratio of active hydrogen bonded to a nitrogen atom with respect to 1 mol of the epoxy group in the epoxy resin is 0.7 to The amount is preferably 1.5 mol, more preferably 0.9 to 1.2 mol.

<Phenolic curing agent>
Examples of the phenolic curing agent include, but are not limited to, phenol novolak, cresol novolak, catechol novolak, resorcinol novolak, pyrogallol, and pyrogallol derivatives.
As the phenolic curing agent, a phenolic curing agent having a hydroxyl group adjacent to the ortho position or the meta position is preferable.
Examples of the phenolic curing agent having a hydroxyl group adjacent to the ortho-position or meta-position include catechol novolak, resorcinol novolak, pyrogallol, and pyrogallol derivatives. Resorcinol novolak is excellent in handleability because it tends to have a low softening point. It is preferable because it tends to be a cured product having a higher degree of orientation and thermal conductivity.
In the epoxy resin composition of the present embodiment, the phenolic curing agent is blended in such an amount that the phenolic hydroxyl group is 0 with respect to 1 mol of the epoxy group in the epoxy resin from the viewpoint of high heat resistance and low water absorption. It is preferable that it is 0.8-1.3 mol, More preferably, it is 0.9-1.2 mol, More preferably, it is 1.0-1.1 mol.

<Acid anhydride curing agent>
Examples of the acid anhydride curing agent include, but are not limited to, methyl tetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Can be mentioned.
As the acid anhydride-based curing agent, methyltetrahydrophthalic anhydride is particularly preferable from the viewpoint of obtaining a cured product having low viscosity and high heat resistance.
In the epoxy resin composition of the present embodiment, the amount of the acid anhydride-based curing agent is 0% of acid anhydride with respect to 1 mol of epoxy groups in the epoxy resin from the viewpoint of high heat resistance and low water absorption. It is preferable that it is 0.7-1.2 mol, More preferably, it is 0.75-1.1 mol, More preferably, it is 0.8-1.0 mol.

<Catalytic curing agent>
Examples of the catalyst curing agent include, but are not limited to, cationic systems such as boron trifluoride, boron trifluoride-amine complex, aromatic sulfonium salt, diazonium salt, aromatic iodonium salt, and the like. Curing catalyst: Imidazole catalysts such as 1-methylimidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole; diazabicycloundecene (DBU), diazabicyclooctane (DABCO), quinuclidine, tributylamine, benzyl Tertiary amine compounds such as dimethylamine and dimethylaminopyridine can be mentioned.
In the epoxy resin composition of the present embodiment, the content of these catalyst-based curing agents is preferably 0.0001 to 10 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the epoxy resin. More preferably.

[Epoxy resin semi-cured composition]
In the epoxy resin semi-cured composition of the present embodiment, the epoxy resin reacts with the curing agent by 5% to 80% based on the epoxy group.
The epoxy resin semi-cured composition of the present embodiment is obtained by reacting the above-described epoxy resin and curing agent in the presence or absence of an organic solvent described later in an amount of 5% to 80% based on the epoxy group.
The epoxy resin composition of this embodiment can also be obtained by blending α-alumina into the epoxy resin semi-cured composition.

The epoxy resin and the curing agent constituting the epoxy resin composition of the present embodiment usually form a uniform composition before and after the reaction and in the course of the reaction, but the intermediate formed in the reaction process is crystallized. May be non-uniform. In such a case, an epoxy resin composition substantially free of an organic solvent is obtained by diluting with a solvent as necessary, and then reacting and partially curing an epoxy group to remove the organic solvent. Can be prepared.
From such a point of view, the epoxy resin composition of the present embodiment has an epoxy resin and a curing agent diluted with an organic solvent as necessary, and then 5% to 80%, preferably 10% to epoxy group basis. After reacting 60%, more preferably 20% to 50%, the organic solvent is removed by evaporation or the like, and then further cured, whereby a cured product having higher thermal conductivity tends to be formed.
In addition, from the viewpoint described above, after reacting the epoxy resin and the curing agent in the presence of an organic solvent in an amount of 5% to 80%, preferably 10% to 60%, more preferably 20% to 50% based on the epoxy group, By removing the organic solvent by evaporation or the like, blending α-alumina, and then curing, a cured product having higher thermal conductivity tends to be formed.

In addition, an epoxy resin, a curing agent, and α-alumina are diluted with a solvent as necessary, and then applied or impregnated on a predetermined fibrous base material, and then the coated or impregnated base material is heated. By semi-curing, a composite material such as a prepreg in which the fibrous base material is impregnated with the epoxy resin composition or the epoxy resin semi-cured composition of the present embodiment can be produced.
Examples of the fibrous base material include woven fabrics of inorganic fibers such as glass fiber woven fabrics, nonwoven fabrics, woven fabrics of organic fibers such as polyester, and nonwoven fabrics.
By using such a composite material such as prepreg, a laminated plate or the like can be easily produced by a usual method.

The organic solvent used in the semi-curing process is not particularly limited as long as it does not inhibit the curing reaction of the epoxy resin composition. For example, hydrocarbons such as benzene, toluene, xylene, etc. Solvents: methanol, ethanol, propanol, butanol, ethylene glycol, propylene glycol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 2-octanol 4-decanol, 2-dodecanol, 3-methyl-2-butanol, 3,3-dimethyl-2-butanol, 3-methyl-2-pentanol, 5-methyl-2-hexanol, 4-methyl-3- Heptanol, 2-methyl-2-propanol, 2-methyl-2-butanol, 2,3-dimethyl-2-butanol, 2-methyl-2-pentanol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, 2,3-dimethyl-3-pentanol, 3- Alcohol solvents such as ethyl-2,2-dimethyl-3-pentanol, 2-methyl-2-hexanol and 3,7-dimethyl-3-octanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and pentanone; N , N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, acetonitrile, benzonitrile, dimethyl sulfoxide, and other aprotic polar solvents; diethyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, 1 , 4-dioxane, tetrahydrofuran, anisole, etc. Le solvents.
Among these organic solvents, methyl ethyl ketone, methyl isobutyl ketone, and N, N-dimethylformamide are particularly preferable because they have a remarkable effect of suppressing the precipitation of crystalline intermediates and can be easily removed by evaporation.

[Other materials]
<Additives>
The epoxy resin composition of the present embodiment may further contain a predetermined additive as long as the object of the present invention is not impaired.
Examples of additives include curing accelerators, inorganic fillers different from α-alumina, coupling agents, colorants, silicone oils, silicone rubbers, natural waxes, synthetic waxes, higher fatty acids or metal salts thereof, mold release agents, An antioxidant etc. are mentioned.
Examples of the curing accelerator include, but are not limited to, for example, compounds exemplified above as a catalyst curing agent; phosphines such as triphenylphosphine, tributylphosphine, triethylphosphine; n-butyltriphenylphosphonium bromide And phosphonium salts.
Moreover, in the epoxy resin composition of this embodiment, it is preferable that content of a hardening accelerator is 0.01-10 mass parts with respect to 100 mass parts of epoxy resins, and is 0.05-6 mass parts. It is more preferable.
Examples of inorganic fillers different from α-alumina include, but are not limited to, for example, spherical or crushed fused silica, silica powder such as crystalline silica, mica, talc, calcium carbonate, aluminum, alumina, water Japanese alumina, asbestos, magnesium oxide, diatomaceous earth, graphite, boron nitride, aluminum nitride, silicon carbide, silicon nitride and the like can be mentioned.

<Other epoxy resins>
The epoxy resin composition of the present embodiment may contain an epoxy resin other than the epoxy resin represented by the above general formula (1) or an epoxy compound as necessary within a range that does not impair the purpose. it can.
Examples of the epoxy resin or epoxy compound other than the epoxy group represented by the general formula (1) include, but are not limited to, for example, bisphenol A, bisphenol S, bisphenol F, hydroquinone, and resorcinol. Dihydric phenols such as tris- (4-hydroxyphenyl) ethane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol novolac, o-cresol novolac and the like. Halogenated bisphenols such as tetrabromobisphenol A, glycidyl ethers derived from divalent or trivalent or higher phenols; alicyclic diepoxy carboxylates, alicyclic diepoxy acetals, alicyclic diepoxy adipates ,vinyl Black such as hexene diepoxides alicyclic epoxy resins; polyglycidyl compound of glycerol, aliphatic epoxy compound of polyglycidyl compounds such as trimethylol propane.
Furthermore, monoglycidyl compounds such as phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenol glycidyl ether, o-tert-butylphenol glycidyl ether, m-tert-butylphenol glycidyl ether, o-bromophenyl glycidyl ether and the like can be mentioned. .

[Method for producing epoxy resin composition]
The epoxy resin composition of the present embodiment is prepared by mixing and kneading the above-described epoxy resin, curing agent, α-alumina, predetermined additives as necessary, and other epoxy resins according to a conventional method. Thereafter, it can be produced by degassing under reduced pressure.
In the method for producing an epoxy resin composition of the present embodiment, the mixing and kneading method is not particularly limited, and examples thereof include a reactor with a stirring blade, a planetary mixer, a kneader, a roll, a homodisper, and an extruder. In particular, a method using 2 to 3 rolls, a homodisper, or the like is preferable from the viewpoint of obtaining an epoxy resin composition having a uniform composition.
In addition, the epoxy resin composition of this embodiment is obtained by making an epoxy resin and a hardening | curing agent react as mentioned above, obtaining an epoxy resin semi-hardened composition, and mix | blending (alpha) -alumina with this. You can also

[Epoxy resin cured product]
A cured product is obtained by curing the epoxy resin composition or the epoxy resin semi-cured composition of the present embodiment.

Moreover, the hardened | cured material of the epoxy resin composition of this embodiment has the characteristics that it is highly oriented.

[Use]
The epoxy resin composition of the present embodiment can be suitably used for a solid or liquid semiconductor device sealing material, a resin sheet, a composite material such as a prepreg, a laminated board, a metal substrate, and a printed wiring board.
That is, the semiconductor device is sealed with the epoxy resin composition or the epoxy resin semi-cured composition of the present embodiment, and the sealing material has high fluidity and excellent workability, and has a thermal conductivity. It has the feature of being high.

  Hereinafter, although a specific Example and a comparative example are given and this embodiment is described in detail, this embodiment is not limited to the following examples.

“%” In Examples and Comparative Examples is based on mass unless otherwise specified.
Moreover, evaluation of various physical properties in each Example and Comparative Example was carried out by the following methods.

((1) Epoxy value of epoxy resin)
An epoxy resin (sample) was dissolved in benzyl alcohol and 1-propanol to obtain a solution.
After adding an aqueous potassium iodide solution and a bromophenol blue indicator to this solution, the solution was titrated with 1 N hydrochloric acid.
The point where the reaction system in the solution turned from blue to yellow was defined as the equivalent point.
From this equivalent point, the epoxy value of the epoxy resin was calculated according to the following formula.
Epoxy value (equivalent / 100 g) = (V × N × F) / (10 × W)
W: Weight of sample (g)
V: titration to the equivalent point (mL)
N: Normality of hydrochloric acid used for titration (N)
F: Factor of hydrochloric acid used for titration

((2) Melting point of epoxy resin)
The melting point of the epoxy resin was measured using a differential scanning calorimeter (7020 manufactured by SII NanoTechnology Co., Ltd.) at a temperature rising rate of 5 ° C./min.
In this measurement, the peak temperature of the endothermic peak was taken as the melting point, and when there were a plurality of endothermic peaks, the endothermic peak temperature in the highest temperature region was taken as the melting point.

((3) α-alumina specific surface area)
The specific surface area of the α-alumina particles was determined by the BET method according to JISZ8830.

((4) α-alumina average particle diameter)
The average particle size of α-alumina particles is measured by a dry method using a laser diffraction particle size distribution measuring device HELOS / BF-M manufactured by Japan Laser Co., Ltd., and accumulated from the small particle size side of the weight cumulative distribution. The average particle size (D50) corresponding to 50% was determined.

((5) Curing reaction rate of epoxy resin)
The curing reaction rate of the epoxy resin was calculated using the ratio of the peak height attributed to the epoxy group of 915 cm ⁻¹ with the peak attributed to the benzene ring of 1510 cm ⁻¹ in the FT-IR measurement as the internal standard.

((6) Thermal conductivity of cured product of epoxy resin composition)
The thermal conductivity of the cured product of the epoxy resin composition was calculated from the values of thermal diffusivity, specific heat and density measured as follows.
<Thermal diffusivity>
The thermal diffusivity of the cured product was measured by the xenon flash method according to ASTM E1461.
A flash method thermal constant measurement device (xenon flash method thermal constant measurement device (LFA447 NanoFlash, manufactured by NETZSCH)) was used for the measurement of the thermal diffusivity.
The measurement conditions were as follows.
[Measurement condition]
Sample size: disk shape with a diameter of 10 mm and a thickness of 0.5 mm Laser irradiation wavelength: 694.3 nm
Pulse width: 1ms
Measurement temperature: normal temperature <specific heat>
Specific heat was measured with a differential scanning calorimeter (DSC).
<Density>
The density was measured according to JISK7112.
<Thermal conductivity>
The thermal conductivity was determined by the following formula.
λ = α ・ Cp ・ ρ
(Λ: thermal conductivity (W / m · K), α: thermal diffusivity (cm ² / s), Cp: specific heat (J / g · K), ρ: density (g · cm ³ ))

((7) Calculation of thermal conductivity of matrix portion from thermal conductivity of cured product of epoxy resin composition containing α-alumina)
From the thermal conductivity of the cured product of the epoxy resin composition containing α-alumina, the thermal conductivity of the thermal conductivity of the matrix portion was calculated using the following formula.
1−φ = (λc−λf) / (λm−λf) × (λm / λc) ^(1/3)
φ: Volume filling factor of filler λc: Thermal conductivity of compound (W / mK)
λf: filler thermal conductivity (W / mK)
λm: Matrix thermal conductivity (W / mK)
Thermal conductivity of α-alumina: 30 (W / mK)

((8) Volume filling rate)
The volume filling rate, that is, the filling rate of α-alumina was determined by thermogravimetric measurement (TG / DTA6200 Seiko Denshi Kogyo Co., Ltd.) of the cured product of the epoxy resin composition.
10.0 mg of a cured product of an epoxy resin composition containing α-alumina in powder form was used as a measurement sample.
The measurement region was 30 ° C. to 700 ° C. and the heating rate was 10 ° C./min.
From the remaining amount of 700 ° C., a specific gravity of α- alumina and the matrix, respectively 3.9 g / cm ^3, as 1.2 g / cm ^3, was determined volume fraction of α- alumina.

((9) Dynamic viscoelasticity measurement and glass transition temperature (Tg) measurement)
The glass transition temperature of the cured product of the epoxy resin composition was measured by dynamic viscoelasticity measurement under the following conditions.
The measurement was performed in a tensile mode using a non-resonant forced vibration type viscoelasticity measurement analyzer (Rheogel-E4000, manufactured by UBM).
In this measurement, the peak temperature of tan δ was defined as the glass transition temperature (Tg) of the cured product.
〔Measurement condition〕
Sample size: 30mm x 4.0mm x 0.4mm
Waveform: Sine wave Frequency: 10Hz
Displacement amplitude: 5 μm
Measurement temperature: -150 ° C to 250 ° C
Temperature increase rate: 2 ° C / min

〔material〕
Hereinafter, the material used for manufacture of an epoxy resin composition is shown.
(Epoxy resin)

<Epoxy resin A (see Japanese Patent Application Laid-Open No. 2014-122337)>
As the epoxy resin A, the one represented by the following formula was used.

Epoxy resin A had an epoxy value of 0.457 [equivalent / 100 g] and a melting point of 72 ° C.
Epoxy resin A was completely dissolved in the same amount of methyl ethyl ketone at 80 ° C. to form a 50 mass% solution.
Moreover, the solubility with respect to the methyl isobutyl ketone in 65 degreeC of the epoxy resin A was 50%.

<Epoxy resin B>

  Epoxy resin B had an epoxy value of 0.540 [equivalent / 100 g] and a melting point of 128 ° C.

(Α-alumina)
As α-alumina, AS-400 (specific surface area 1.2 m ² / g average particle size (D50) 13 μm, Showa Denko KK) was used.

[Example 1]
100 parts by mass of epoxy resin A, 24 parts by mass of 4,4′-diaminodiphenylethane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing agent, and 400 parts by mass of α-alumina powder were mixed at 80 ° C. with a revolving mixer. An epoxy resin composition containing α-alumina was prepared.
A butyl rubber (30 mm × 70 mm × 1 mm) with a 10 mm diameter hole as a spacer is placed on a 30 mm × 70 mm × 2 mm steel plate, and the epoxy resin containing α-alumina is placed in the 10 mm diameter butyl rubber hole. The composition was loaded.
Furthermore, when a steel plate of the same size as described above was placed and sandwiched between W clips, it was confirmed that the epoxy resin composition had fluidity and could be compressed.
In an oven, heat treatment was performed at 90 ° C. for 4 hours, and then at 170 ° C. for 30 minutes, and cured to obtain a cured product of an epoxy resin composition containing α-alumina.
The α-alumina filling rate of the cured product of the obtained epoxy resin composition containing α-alumina was 0.56.
Moreover, it was 3.1 W / (m * K) when the heat conductivity was measured.
From this result, the thermal conductivity of the matrix portion in the cured product was calculated to be 0.35 W / (m · K).
Moreover, Tg was 110 degreeC.
On the other hand, as [Reference Example 1], 100 parts by mass of epoxy resin A and 24 parts by mass of 4,4′-diaminodiphenylethane were added to a test tube and heated in an oil bath at 90 ° C. for 4 hours and then at 170 ° C. for 30 minutes. Cured.
It was 0.24 W / (m * K) when the heat conductivity of the hardened | cured material of the obtained epoxy resin composition was measured.
Therefore, by adding α-alumina to the liquid crystalline epoxy resin composition, the thermal conductivity of the matrix portion is from 0.24 W / (m · K) when α-alumina is not added to 0 of the α-alumina composite material. It increased to about 35 times / .35W / (m · K).
This is because the melting point of the epoxy resin is low, the contact time with the α-alumina surface is long at low temperatures, and the molecular mobility during the curing process is low, so the interaction with the α-alumina surface is effectively expressed. As a result, the orientation of the network molecular chain and the ordering of the methylstilbene skeleton are increased.
When a solvent is used, α-alumina and the matrix component can be brought into contact with each other at a relatively low temperature in a state where molecular motion is suppressed, so that the thermal conductivity of the matrix component can be improved. When an epoxy resin having a low melting point is used, the thermal conductivity of the matrix portion can be increased without using a solvent as in [Example 1].

[Example 2]
100 parts by mass of epoxy resin A, 24 parts by mass of 4,4′-diaminodiphenylethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 100 parts by mass of methyl ethyl ketone were added to a sample container, reacted at 70 ° C. for 6 hours, and then reduced in pressure. Methyl ethyl ketone was distilled off to obtain an epoxy resin semi-cured composition.
The curing reaction rate at this point was 33%.
Next, 400 parts by mass of α-alumina powder is added to 124 parts by mass of the obtained epoxy resin semi-cured composition, and the mixture is mixed at 80 ° C. with a rotation and revolution mixer to prepare an epoxy resin composition containing α-alumina. Obtained.
A butyl rubber (30 mm × 70 mm × 1 mm) with a 10 mm diameter hole as a spacer is placed on a 30 mm × 70 mm × 2 mm steel plate, and the epoxy resin containing α-alumina is placed in the 10 mm diameter butyl rubber hole. The composition was loaded.
Furthermore, when a steel plate having the same size as described above was placed and sandwiched between W clips, it was confirmed that the epoxy resin composition had fluidity and could be compressed.
Then, it hardened | cured at 70 degreeC for 12 hours, and also it heat-processed at 170 degreeC for 30 minutes, and it was made to harden | cure, and the hardened | cured material of the epoxy resin composition containing alpha alumina was obtained.
The cured α-alumina-containing cured product of the obtained α-alumina had an α-alumina filling rate of 0.52, and its thermal conductivity was measured to be 3.7 W / (m · K).
From this result, the thermal conductivity of the matrix portion in the cured product was calculated to be 0.56 W / (m · K).
When the dynamic viscoelasticity of the cured product of the epoxy resin composition containing this α-alumina was measured, it showed a broad peak near 115 ° C.
Moreover, as [Reference Example 2], a cured product of the epoxy resin composition was produced in the same manner as described above except that α-alumina was not blended, and its thermal conductivity was measured to find 0.28 W / ( m · K).
Therefore, by blending α-alumina and a solvent into the liquid crystalline epoxy resin composition, the thermal conductivity of the matrix portion is from 0.28 W / (m · K) in the case of no α-alumina compounding, to 0 of the alumina composite material. It was about doubled to .56W / (m · K).
This is because the epoxy resin has high solubility in a solvent having a low boiling point, can contact the α-alumina surface at a low temperature, and has low molecular mobility during the curing process. This is because the action is effectively expressed, and as a result, the orientation of the network molecular chain and the order of the methylstilbene skeleton are increased. Accordingly, [Example 2] can further increase the thermal conductivity of the matrix portion as compared to the case of using no solvent as in [Example 1].

Example 3
100 parts by weight of epoxy resin A, 24 parts by weight of 4,4′-diaminodiphenylethane (manufactured by Tokyo Chemical Industry Co., Ltd.), 1240 parts by weight of α-alumina powder, and 100 parts by weight of methyl ethyl ketone are added to a sample container, and then at 60 ° C. for 30 minutes. Stir.
Then, methyl ethyl ketone was distilled off under reduced pressure at 80 ° C. to obtain an epoxy resin semi-cured composition.
The composition at that time was uniform and transparent, and the reaction rate based on epoxy groups was 10%.
Then, the hardened | cured material of the epoxy resin composition containing (alpha) -alumina was obtained like [Example 1] mentioned above.
The cured α-alumina-containing cured product of the obtained α-alumina had an α-alumina filling rate of 0.76, and its thermal conductivity was measured to be 11.2 W / (m · K). .
From this result, the thermal conductivity of the matrix portion in the cured product was calculated and found to be 0.58 W / (m · K).
When the dynamic viscoelasticity of this α-alumina-containing cured product was measured, no clear Tg was shown.
Further, as [Reference Example 3], a cured product of the epoxy resin composition was produced in the same manner as described above except that α-alumina was not blended, and its thermal conductivity was measured to find 0.25 W / ( m · K).
Therefore, by adding α-alumina and a solvent to the liquid crystalline epoxy resin composition, the thermal conductivity of the matrix portion is reduced from 0.25 W / (m · K) when α-alumina is not added to 0 of the alumina composite material. It increased by about 2.3 times to .58 W / (m · K).
This is because the epoxy resin has a high solubility in a solvent having a low boiling point, can be brought into contact with the α-alumina surface at a low temperature, and can be molded because the melt viscosity of the epoxy resin is low. This is due to the fact that the interaction with the α-alumina surface is effectively expressed due to the low mobility of the molecule, and as a result, the orientation of the network molecular chain and the order of the methylstilbene skeleton are enhanced.
Therefore, [Example 3] can further increase the thermal conductivity of the matrix portion as compared with the case of using no solvent as in [Example 1].

Example 4
A cured product of the epoxy resin composition containing α-alumina was used in the same manner as in [Example 2] described above, except that 124 parts by mass of the epoxy resin semi-cured composition was changed to 300 parts by mass of α-alumina powder. Obtained.
The α-alumina filling rate of the cured product of the obtained epoxy resin composition containing α-alumina was 0.43, and its thermal conductivity was measured to be 2.3 W / (m · K).
From this result, the thermal conductivity of the matrix portion in the cured product was calculated to be 0.53 W / (m · K).
Moreover, as [Reference Example 4], a cured product of the epoxy resin composition was produced in the same manner as described above except that α-alumina was not blended, and its thermal conductivity was measured to find 0.28 W / ( m · K).
Therefore, by blending α-alumina and a solvent into the liquid crystalline epoxy resin composition, the thermal conductivity of the matrix portion is from 0.28 W / (m · K) in the case of no α-alumina compounding, to 0 of the alumina composite material. It was about doubled to .53 W / (m · K).
This is because the epoxy resin has high solubility in a solvent having a low boiling point, can contact the α-alumina surface at a low temperature, and has low molecular mobility during the curing process. This is because the action is effectively expressed, and as a result, the orientation of the network molecular chain and the order of the methylstilbene skeleton are increased.

[Comparative Example 1]
100 parts by weight of epoxy resin B, 28 parts by weight of 4,4′-diaminodiphenylethane as a curing agent, and 420 parts by weight of α-alumina powder were mixed at 150 ° C. to prepare an epoxy resin composition containing alumina. .
A butyl rubber (30 mm × 70 mm × 1 mm) with a 10 mm diameter hole as a spacer is placed on a 30 mm × 70 mm × 2 mm steel plate, and the epoxy resin containing α-alumina is placed in the 10 mm diameter butyl rubber hole. The composition was loaded.
Furthermore, when a steel plate of the same size as described above was placed and sandwiched between W clips, it was confirmed that the flowability of the epoxy resin composition was low and the epoxy resin composition could not be sufficiently compressed.
Heat treatment was performed in an oven at 150 ° C. for 4 hours, and then at 180 ° C. for 1 hour, followed by curing to obtain a cured product of an epoxy resin composition containing α-alumina.
The obtained cured product of the epoxy resin composition containing α-alumina contained voids and had a non-uniform appearance.
The α-alumina filling rate was 0.49, and the thermal conductivity measured was 2.0 W / (m · K).
From this result, the thermal conductivity of the matrix portion in the cured product was calculated to be 0.32 W / (m · K).
On the other hand, as [Comparative Reference Example 1], 100 parts by mass of epoxy resin B and 28 parts by mass of 4,4′-diaminodiphenylethane were added to a test tube, and the oil bath was 150 ° C. for 4 hours, and then 180 ° C. for 1 hour. Then, heat treatment was performed and cured to produce a cured product of the epoxy resin composition.
It was 0.30 W / (m * K) when the heat conductivity of the obtained hardened | cured material was measured.
In [Comparative Example 1], the thermal conductivity of the matrix portion is increased by adding α-alumina to the liquid crystalline epoxy resin composition, but the ratio is 0.30 W / in the case where α-alumina is not added. It was about 1.1 times lower from (m · K) to 0.32 W / (m · K) of the alumina composite material.
This is because the melting point of the stilbene type epoxy resin is high, the curing agent and α-alumina must be mixed at a high temperature, and as a result, the curing reaction proceeds before the α-alumina surface and the matrix are sufficiently wetted, Since it has become a composite material containing voids, and since the interaction between the α-alumina surface and the matrix cannot be effectively acted, the orientation of the network molecular chain and the order of the methylstilbene skeleton are It shows that it did not increase effectively.

[Comparative Example 2]
100 parts by weight of epoxy resin B, 28 parts by weight of 4,4′-diaminodiphenylethane (manufactured by Tokyo Chemical Industry Co., Ltd.), 1250 parts by weight of α-alumina powder and 100 parts by weight of methyl ethyl ketone are added to the sample container, and stirred at 60 ° C. for 30 minutes. did.
Then, methyl ethyl ketone was distilled off under reduced pressure at 80 ° C. to obtain an epoxy resin semi-cured composition.
At that time, the composition was opaque and the reaction rate based on epoxy groups was 10%.
A butyl rubber (30 mm × 70 mm × 1 mm) having a 10 mm diameter hole as a spacer is placed on a 30 mm × 70 mm × 2 mm steel plate, and the epoxy resin half containing the α-alumina is placed in the 10 mm diameter butyl rubber hole. The cured composition was loaded.
Furthermore, when a steel plate of the same size as described above was placed and sandwiched between W clips, it was confirmed that the epoxy resin semi-cured composition had no fluidity and could not be compressed.
It was cured by heating in an oven at 150 ° C. for 4 hours and then at 180 ° C. for 1 hour.
The resulting cured product of the epoxy resin composition containing α-alumina contained voids and was visually non-uniform.
The α-alumina filling rate was 0.72, and the thermal conductivity measured was 9.0 W / (m · K).
From this result, the thermal conductivity of the matrix portion in the cured product was calculated to be 0.35 W / (m · K).
Moreover, as [Comparative Reference Example 2], a cured product of the epoxy resin composition was produced in the same manner as above except that α-alumina was not blended.
It was 0.30 W / (m * K) when the heat conductivity of the obtained hardened | cured material was measured.
In [Comparative Example 2], the thermal conductivity of the matrix portion is increased by blending α-alumina with the liquid crystalline epoxy resin composition, but the ratio is 0.30 W in the case where α-alumina is not blended. It was as low as about 1.2 times from / (m · K) to 0.35 W / (m · K) of the alumina composite material.
This is because the melting point of the stilbene type epoxy resin is high and the solubility in the solvent is low, so that the viscosity of the α-alumina-containing composition at the time of removing the solvent is high and the fluidity is low, so that the composite material containing voids In addition, since the interaction between the α-alumina surface and the matrix cannot be made to act effectively, the orientation of the network molecular chain and the order of the methylstilbene skeleton were not effectively increased. Show.

  The epoxy resin composition of the present invention includes insulating materials such as electric and electronic parts typified by semiconductor elements, conductive materials, sealing materials or casting materials, laminated materials, various heat dissipation materials, organic EL sealing materials, various types There is industrial applicability as materials such as paints and adhesives.

Claims (9)

An epoxy resin represented by the following general formula (1) and having a melting point of 110 ° C. or lower;
A curing agent;
α-alumina,
Containing
Epoxy resin composition.

(In general formula (1), MS represents the following general formula (2).
Each G independently represents a monovalent organic group represented by the following general formula (5).
SP1 and SP2 each independently represent a divalent organic group represented by the following general formula (3) or general formula (4). )

(In general formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms.)

(In general formula (3), p is an integer of 1 or more and 10 or less.)

(In general formula (4), each R ₃ independently represents a saturated or unsaturated hydrocarbon group having 1 to 4 carbon atoms, and q is an integer of 1 to 10)

(In the general formula (5), R ₄ represents a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms.) The specific surface area of the α-alumina particles is 0.1 m ² / g or more and 3.0 m ² / g or less, and the average particle diameter (D50) is 0.1 μm to 100 μm.
The epoxy resin composition according to claim 1. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin is a compound represented by the following formula (6).

The curing agent is an amine compound;
The epoxy resin composition according to any one of claims 1 to 3. The curing agent is a phenolic curing agent having an adjacent hydroxyl group,
The epoxy resin composition according to any one of claims 1 to 3. In the epoxy resin semi-cured composition in which the epoxy group in the epoxy resin and the functional group of the curing agent are reacted by 5% to 80% based on the epoxy group,
The α-alumina is blended,
The epoxy resin composition according to claim 1. The epoxy resin and the curing agent in the epoxy resin composition according to any one of claims 1 to 5,
An epoxy resin semi-cured composition that reacts 5% to 80% based on the epoxy group.   The semiconductor device sealed with the epoxy resin composition as described in any one of Claims 1 thru | or 6, or the epoxy resin semi-hardened composition as described in Claim 7.   A composite material in which the fibrous base material is impregnated with the epoxy resin composition according to any one of claims 1 to 6 or the epoxy resin semi-cured composition according to claim 7.