JP2013006972A - Epoxy resin composition, and cured material obtained by curing the same - Google Patents

Abstract

【選択図】なしAn epoxy resin composition having high thermal conductivity while satisfying the manufacturing process suitability of a three-dimensional stacked semiconductor device is provided.
An epoxy resin composition comprising an epoxy resin having a phenol skeleton and an epoxy resin having a structure represented by the following formula (4).

[Selection figure] None

Description

  The present invention relates to an epoxy resin composition having film formability applicable to processes such as film forming and coating, excellent moldability, moisture resistance, and heat resistance, and also excellent thermal conductivity. The present invention also relates to a cured product obtained by curing the epoxy resin composition.

  Epoxy resins are excellent in heat resistance, adhesiveness, water resistance, mechanical strength, and electrical properties, so they are used in various fields such as adhesives, paints, materials for civil engineering and construction, and insulating materials for electrical and electronic parts. in use. In particular, in the electric / electronic field, it is widely used in insulating casting, laminated materials, sealing materials and the like. In recent years, in these applications, in addition to the basic physical property requirements of materials, there is an increasing demand for heat dissipation.

For example, multilayer circuit boards used in electrical and electronic equipment are becoming smaller, lighter, and more functional, and are becoming more multilayered, denser, thinner, lighter, more reliable, Improvements in molding processability are required.
In connection with this, characteristics, such as the moldability of the material used, moisture resistance, heat resistance, an electrical property, and heat dissipation, have become a problem.

In particular, with regard to heat dissipation, improvement of the thermal conductivity of the epoxy resin composition has been demanded for further densification.
High thermal conductivity materials composed of epoxy resin compositions so far are mostly related to compositions containing inorganic fillers with high thermal conductivity, and epoxy resin and higher thermal conductivity than the thermal conductivity of the epoxy resin itself as a matrix. There were many things regarding the epoxy resin composition which compounded these inorganic fillers.

  In such an epoxy resin composition, the inorganic filler is responsible for heat conduction, but in order to further improve the thermal conductivity of the high thermal conductivity material in order to satisfy the above requirements, it exists between the inorganic fillers. It is important to improve the thermal conductivity of the epoxy resin itself. On the other hand, if the thermal conductivity of the resin can be improved, the filler content to be introduced in order to achieve the desired thermal conductivity can be reduced, and the degree of freedom in material design can be increased accordingly. . Therefore, improvement in the thermal conductivity of the epoxy resin itself that is a matrix has been demanded.

As an invention for improving the thermal conductivity of the epoxy resin itself, a method for introducing a mesogenic skeleton into the epoxy resin is disclosed.
For example, Non-Patent Document 1 describes the improvement of thermal conductivity of epoxy resins by introducing various mesogenic skeletons. Although improvement in thermal conductivity is observed, cost, process compatibility, water resistance Considering the balance of decomposability and thermal stability, it is not practical.

Patent Document 1 discloses an epoxy resin having good thermal conductivity using only a biphenyl skeleton, but only an extremely low molecular weight epoxy resin is synthesized and lacks film-forming properties. It is difficult to use as a thin film.
Epoxy resins having a mesogenic skeleton are often solid at room temperature, and after curing, often have a hard structure with high orientation, and in addition to the basic physical properties of the material, a balance between thermal conductivity and low stress is required. It has been.

JP 2010-001427 A

Latest technology of epoxy resin for electronic parts (CMC Publishing, 2006, Chapter 1 P24-31, Chapter 5 P114-121)

Thus, the epoxy resin composition which is excellent in process applicability as a film and process applicability such as coating and having high thermal conductivity has not yet been provided.
Under such circumstances, an object of the present invention is an epoxy resin composition that has film formability applicable to processes such as film molding and coating, and has excellent moldability, moisture resistance, heat resistance, and thermal conductivity. Is to provide things.

As a result of intensive studies to solve the above problems, the present inventor has found that the following inventions meet the above object, and have reached the present invention.
That is, the present invention relates to the following inventions.
[1]
An epoxy resin (A) having a structure represented by the following formula (1) and having an epoxy equivalent of 2500 g / equivalent or more and an epoxy resin (B) represented by the following formula (4) Epoxy resin composition.

(In the formula (1), A is a biphenyl skeleton represented by the following formula (2), B is a hydrogen atom or the following formula (3), n is the number of repetitions, and the average value is 10 <n <50. .)

(In the formula (2), R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, may be the same or different from each other.)

Wherein _(4), R 2 to R ₅ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, _{Z 1} and _{Z 2} are groups of formula (5) or (6)

(Wherein R _{6 to} R ₉ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and n represents a number of 0 to 6. ]
[2]
The epoxy resin composition according to [1], wherein the ratio of the epoxy resin (A) to the total epoxy resin is 5% by weight or more and 95% by weight or less.
[3]
The epoxy resin composition according to [1] or [2], containing the inorganic filler (C) in an amount of 5 parts by weight to 1900 parts by weight with respect to 100 parts by weight of the total epoxy resin.
[4]
The epoxy resin composition according to any one of [1] to [3], wherein the curing agent (D) is contained in an amount of 0.01 to 200 parts by weight per 100 parts by weight of the total epoxy resin.
[1]
Hardened | cured material formed by hardening | curing the epoxy resin composition as described in any one of [1] to [4].
[6]
A prepreg obtained from the epoxy resin composition according to any one of [1] to [4].
[7]
Interlayer filler composition for a three-dimensional stacked semiconductor device obtained from the epoxy resin composition according to any one of [1] to [4] [8]
A three-dimensional stacked semiconductor device using the epoxy resin composition according to any one of [1] to [4] between layers.
[9]
A method for producing a three-dimensional stacked semiconductor device, wherein the epoxy resin composition according to any one of [1] to [4] is filled between layers.

  According to the present invention, an epoxy resin composition having film formability applicable to a process such as film molding / coating, excellent moldability, moisture resistance, heat resistance, electrical properties, and excellent thermal conductivity. Is provided.

DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example of the embodiments of the present invention, and the present invention is described below unless the gist of the present invention is exceeded. It is not limited to.
The epoxy resin composition of the present invention has a structure represented by the following formula (1), and an epoxy resin (A) having an epoxy equivalent of 2500 g / equivalent or more and represented by the following formula (4). It contains an epoxy resin (B).

(In the formula (1), A is a biphenyl skeleton represented by the following formula (2), B is a hydrogen atom or the following formula (3), n is the number of repetitions, and the average value is 10 <n <50. .)

[Epoxy resin composition]
[Epoxy resin (A)]
The epoxy resin (A) contained in the epoxy resin composition of the present invention is an epoxy resin having a structure represented by the following formula (1) and having an epoxy equivalent of 2500 g / equivalent or more.

(In the formula (1), A is a biphenyl skeleton represented by the following formula (2), B is a hydrogen atom or the following formula (3), n is the number of repetitions, and the average value is 10 <n <50. .)

(In the formula (2), R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, may be the same or different from each other.)

The epoxy resin (A) according to the present invention is an epoxy resin having sufficient elongation and excellent balance between thermal conductivity and heat resistance.
Almost all conventional high thermal conductivity epoxy resins are epoxy resins designed to increase thermal conductivity, and there are many limitations in the curing process including curing conditions, and the degree of freedom of selection is low. It was. For this reason, when trying to apply conventional high thermal conductivity epoxy resin to products such as members, sealants and adhesives, it is very difficult to achieve both the required physical properties of the product including cost and high thermal conductivity. there were.

On the other hand, the epoxy resin (A) itself is excellent in thermal conductivity, and the thermal conductivity of the cured product can be increased by adding a desired amount as an epoxy resin component. Since the low stress property can be imparted to the material due to the extensibility, the epoxy resin composition of the present invention capable of satisfying both the required physical properties of the product and the high thermal conductivity can be provided.
Although the details of the reason why the epoxy resin (A) is excellent in elongation are not clear, it has a molecular chain length that can withstand stretching when subjected to tensile stress, and in order to relieve the stress, overlapping biphenyl This is presumably because the skeletons can “slide”. In addition, at this time, if the crystallinity is too high, it is brittle and breaks without elongation. Therefore, it is important to have an appropriate amorphous portion. In the epoxy resin of the present invention, the biphenyl skeleton is substituted. By having a group, the crystallinity can be reduced moderately, which is considered to lead to the expression of elongation. Therefore, from the viewpoint of elongation, it is preferable that all R ¹ in the formula (2) is not a hydrogen atom but one or more R ¹ is a hydrocarbon group or a halogen atom.

Thermal conduction is governed by phonons and conduction electrons, and when there are free electrons like metal, the contribution of conduction electrons is large, but epoxy resin is generally an insulator, and phonons are the main heat conduction in insulators. Is a factor. Since heat conduction by phonons is propagation of vibration energy, vibrations are less likely to attenuate, and the harder the material, the better the heat conductivity.
The details of the reason why the epoxy resin (A) is excellent in thermal conductivity are not clear, but since all the skeletons are biphenyl skeletons, the degree of freedom of the structure is small, vibration energy is difficult to attenuate, and the biphenyl skeleton is flat. It is presumed that this is due to the good overlap between molecules and the ability to restrain molecular motion more.

Epoxy resins generally tend to have better heat resistance when crystallinity is better, and if the epoxy resin has the same structure, the higher the molecular weight or epoxy equivalent of the resin, the better the heat resistance. The epoxy resin (A) is excellent in heat resistance by having appropriate crystallinity and a high epoxy equivalent.
In said Formula (1), n is a repeating number and is an average value. The range of the value is 10 <n <50, but the range of n is preferably 15 <n <50, especially 20 <n <50, from the balance of both elongation and resin handling. It is preferable. If n in formula (1) is 10 or less, the elongation property of the epoxy resin composition of the present invention becomes insufficient, and if it is 50 or more, the viscosity of the epoxy resin composition of the present invention including the epoxy resin (A) is It tends to be high and difficult to handle.

In the formula (1), A is a biphenyl skeleton represented by the formula (2). In the formula (2), R ¹ may be the same or different from each other, and may be a hydrogen atom, carbon Represents a hydrocarbon group having 1 to 10 carbon atoms or a halogen atom, but one epoxy resin includes both a hydrogen atom and a hydrocarbon group having 1 to 10 carbon atoms as R ¹ It is preferable from the viewpoint of the whole crystallinity and handling. When R ¹ is the same, the crystallinity becomes high and the thermal conductivity can be increased. However, when the crystallinity is too high, the elongation when the epoxy resin composition is formed into a film tends to be small.

When R ¹ in the formula (2) is a hydrocarbon group having 1 to 10 carbon atoms, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group.
The hydrocarbon group for R ¹ may have a substituent, and the substituent is not particularly limited, but has a molecular weight of 200 or less.
Further, the halogen atom of R ^1, a fluorine atom, a chlorine atom, refers to bromine atom, it may include a plurality of kinds in only one kind.

The biphenyl skeleton of A is 2,2′-biphenyl skeleton, 2,3′-biphenyl skeleton, 2,4′-biphenyl skeleton, 3,3-biphenyl skeleton, 3,4′-biphenyl skeleton, 4,4′- Any of the biphenyl skeletons may be used, but a 4,4′-biphenyl skeleton is preferred.
R ¹ preferably has a hydrogen atom at the 2-position and / or 6-position, and preferably has a hydrocarbon group at the 3-position and / or 5-position.

The epoxy equivalent of the epoxy resin (A) used in the present invention is 2,500 g / equivalent or more, but when it is less than 2,500 g / equivalent, the epoxy resin composition of the present invention has sufficient elongation. Therefore, it becomes difficult to apply to processes such as film forming and coating.
From the viewpoint of extensibility, the epoxy equivalent of the epoxy resin (A) is preferably 3,000 g.
/ Equivalent or more, more preferably 4,000 g / equivalent or more.

On the other hand, the upper limit value of the epoxy equivalent is not particularly limited, but is preferably 15,000 g / equivalent or less, more preferably 10,000 g / equivalent or less in terms of handling and workability. The epoxy equivalent of an epoxy resin (A) is calculated | required by the method described in the term of the below-mentioned Example.
The weight average molecular weight Mw of the epoxy resin (A) is preferably 10,000 or more and 200,000 or less. If the weight average molecular weight is lower than 10,000, the elongation tends to be low, and if it is higher than 200,000, the resin tends to be difficult to handle. The weight average molecular weight of an epoxy resin (A) is calculated | required by the method described in the term of the below-mentioned Example.

  The epoxy resin (A) is excellent in heat resistance, and can be achieved at 80 ° C. or higher and 220 ° C. or lower when evaluated by the glass transition temperature Tg shown in the Examples section below. The Tg of the epoxy resin is preferably higher in applications using the epoxy resin of the present invention described later, preferably 85 ° C. or higher, more preferably 90 ° C. or higher, further preferably 95 ° C. or higher, but Tg is too high. And the curing reaction does not proceed sufficiently at the heating temperature used in the processing process, the quality may not be stable, and the required physical properties may not be exhibited. It is preferable that

Hereinafter, the manufacturing method of an epoxy resin (A) is demonstrated.
The epoxy resin (A) can be obtained, for example, by a two-stage method in which a bifunctional epoxy resin (X) having a biphenyl skeleton and a biphenol compound (Y) are reacted. It can also be obtained by a one-step method in which one or more biphenol compounds (Y) and epichlorohydrin are directly reacted. However, since the biphenol compound (Y) is not good in solvent solubility, a solvent generally used in the one-step method may not be applied as it is, and therefore, the two-step method is preferably used.

  The bifunctional epoxy resin (X) used for the production of the epoxy resin (A) is a compound having a biphenyl skeleton and having two epoxy groups in the molecule, and represented by the following formula (4) And an epoxy resin obtained by condensing with an epihalohydrin.

(In formula (4), R ² has the same meaning as R ¹ in formula (2).)
Examples of the biphenol compound represented by the formula (4) include 2,2′-biphenol, 2,3′-biphenol, 2,4′-biphenol, 3,3′-biphenol, and 3,4′-biphenol. 4,4′-biphenol, 2-methyl-4,4′-biphenol, 3-methyl-4,4′-biphenol, 2,2′-dimethyl-4,4′-biphenol, 3,3′-dimethyl -4,4'-biphenol, 3,3 ', 5,5'-tetramethyl-4,4'-biphenol, 2,2', 3,3 ', 5,5'-hexamethyl-4,4'- Biphenol, 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octamethyl-4,4′-biphenol and the like can be mentioned. Among these, 4,4′-biphenol, 3,3 are preferable.
'-Dimethyl-4,4'-biphenol, 3,3', 5,5'-tetramethyl-4,4'-biphenol. In conducting the condensation reaction with epihalohydrin, these biphenol compounds may be used alone or in combination of two or more. Moreover, bifunctional epoxy resin (X) obtained by condensing such a biphenol compound and epihalohydrin can also be used together.

  As the bifunctional epoxy resin (X), a bifunctional epoxy resin (X) having a hydrolyzable chlorine concentration of 200 ppm or less and an α glycol group concentration of 100 meq / kg or less is used as a raw material. It is preferable to do. When the hydrolyzable chlorine concentration is higher than 200 ppm or when the α glycol group concentration is higher than 100 meq / kg, it is not preferable because the molecular weight is not sufficiently increased.

  On the other hand, the biphenol compound (Y) is a compound in which two hydroxyl groups are bonded to the biphenyl skeleton, and is represented by the formula (4). As the biphenol compound (Y), as described above, for example, 2,2′-biphenol, 2,3′-biphenol, 2,4′-biphenol, 3,3′-biphenol, 3,4′-biphenol, 4 , 4′-biphenol, 2-methyl-4,4′-biphenol, 3-methyl-4,4′-biphenol, 2,2′-dimethyl-4,4′-biphenol, 3,3′-dimethyl-4 , 4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol, 2,2 ′, 3,3 ′, 5,5′-hexamethyl-4,4′-biphenol, 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octamethyl-4,4′-biphenol and the like. Among these, 4,4′-biphenol, 3,3′-dimethyl-4,4′-biphenol, 3,3 ′, 5,5′-tetramethyl-4,4′-biphenol are preferable. . These biphenol compounds can be used in combination.

The biphenyl skeleton contained in the bifunctional epoxy resin (X) and the biphenol compound (Y) is preferably not unsubstituted at the same time, and preferably has one or more substituents in one molecule. When all are unsubstituted biphenyl skeletons, the resulting epoxy resin (A) has high crystallinity and tends to have poor elongation.
In the production of the epoxy resin (A), the amount of the bifunctional epoxy resin (X) and the biphenol compound (Y) used is the compounding equivalent ratio, epoxy group: phenolic hydroxyl group = 1: 0.90-1. 10 is preferable. When the equivalent ratio is within the above range, a sufficiently high molecular weight proceeds.

  A catalyst may be used for the synthesis of the epoxy resin (A), and any catalyst may be used as long as it has a catalytic ability to promote a reaction between an epoxy group and a phenolic hydroxyl group, an alcoholic hydroxyl group or a carboxyl group. Something like that. For example, alkali metal compounds, organic phosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like can be mentioned. These catalysts can be used alone or in combination of two or more.

  Specific examples of the alkali metal compound include alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide, alkali metal salts such as sodium carbonate, sodium bicarbonate, sodium chloride, lithium chloride and potassium chloride, sodium Examples include alkali metal alkoxides such as methoxide and sodium ethoxide, alkali metal phenoxides, alkali metal hydrides such as sodium hydride and lithium hydride, and alkali metal salts of organic acids such as sodium acetate and sodium stearate.

Specific examples of the organic phosphorus compound include tri-n-propylphosphine, tri-n-butylphosphine, triphenylphosphine, tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetramethylphosphonium hydroxide, Trimethylcyclohexylphosphonium chloride, trimethylcyclohexylphosphonium bromide, trimethylbenzylphosphonium chloride, trimethylbenzylphosphonium bromide, tetraphenylphosphonium bromide, triphenylmethylphosphonium bromide, triphenylmethylphosphonium iodide, triphenylethylphosphonium chloride, triphenylethylphosphonium bromide, Triphenylethylphosphonium iodai , Triphenyl benzyl phosphonium chloride, triphenyl benzyl phosphonium bromide and the like.

Specific examples of the tertiary amine include triethylamine, tri-n-propylamine, tri-n-butylamine, triethanolamine, benzyldimethylamine and the like.
Specific examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium hydroxide, triethylmethylammonium chloride, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium bromide, Tetrapropylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium hydroxide, benzyltributylammonium chloride Id, and a phenyl trimethyl ammonium chloride.

Specific examples of cyclic amines include 1,8-diazabicyclo (5,4,0) undecene-7,1,5-diazabicyclo (4,3,0) nonene-5.
Specific examples of imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole and the like.
The usage-amount of a catalyst is 0.001-1 weight% normally in reaction solid content. In addition, when an alkali metal compound is used as a catalyst, an alkali metal component remains in the epoxy resin (A) obtained, and the epoxy resin composition of the present invention containing the epoxy resin (A) as a component is used for a printed wiring board. In this case, since the insulating properties of the used printed wiring board tend to be deteriorated, the total content of Li, Na and K in the epoxy resin needs to be 60 ppm or less, preferably 50 ppm or less.

  In addition, when organophosphorus compounds, tertiary amines, quaternary ammonium salts, cyclic amines, imidazoles and the like are used as catalysts, these remain as catalyst residues in the resulting epoxy resin (A), and alkali Since the insulating properties of the printed wiring board are deteriorated as well as the residual metal content, the content of nitrogen in the epoxy resin (A) is 300 ppm or less, and the content of phosphorus in the epoxy resin (A) is 300 ppm or less. There must be. More preferably, the content of nitrogen in the epoxy resin (A) is 200 ppm or less, and the content of phosphorus in the epoxy resin (A) is 200 ppm or less.

As for the epoxy resin (A) of the present invention, an organic solvent may be used as a solvent in the step of the synthesis reaction at the time of production, and any organic solvent can be used as long as it dissolves the epoxy resin (A). It may be anything. For example, aromatic solvents, ketone solvents, amide solvents, glycol ether solvents and the like can be mentioned.
Specific examples of the aromatic solvent include benzene, toluene, xylene and the like.

Specific examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, 2-octanone, cyclohexanone, acetylacetone, and dioxane.
Specific examples of the amide solvent include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N-methylpyrrolidone and the like.

  Specific examples of glycol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Examples thereof include mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono-n-butyl ether, propylene glycol monomethyl ether acetate.

These organic solvents may be used alone or in combination of two or more.
The solid concentration in the synthesis reaction during production of the epoxy resin (A) is preferably 35 to 95% by weight. In addition, when a highly viscous product is produced during the reaction, the reaction can be continued by additionally adding a solvent (organic solvent). After completion of the reaction, the solvent (organic solvent) can be removed or further added as necessary.

  In the production of the epoxy resin (A), the polymerization reaction between the bifunctional epoxy resin (X) and the biphenol compound (Y) is carried out at a reaction temperature at which the used catalyst is not decomposed. If the reaction temperature is too high, the produced epoxy resin may be deteriorated. Conversely, if the temperature is too low, the reaction may not proceed sufficiently. For these reasons, the reaction temperature is preferably 50 to 230 ° C, more preferably 120 to 200 ° C. Moreover, reaction time is 1 to 12 hours normally, Preferably it is 3 to 10 hours. When using a low boiling point solvent such as acetone or methyl ethyl ketone, the reaction temperature can be ensured by carrying out the reaction under high pressure using an autoclave.

[Epoxy resin (B)]
The epoxy resin (B) is an epoxy resin represented by the following formula (4).

Here, in the formula _(4), R 2 to R ₅ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, _{Z 1} and _{Z 2} represents a group of formula (5) or (6).

_R 6 to R ₉ in the formula (5) and the formula (6) represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is a number of 0 to 6. When R _{2 to} R ₉ are alkyl groups, the number of carbon atoms is 1 to 6, more preferably 1 to 3 carbon atoms, and particularly preferably a methyl group.
N in the formula (4) is a number from 0 to 6, but the epoxy resin (B) may be a mixture of different n, and in the case of a mixture of different n, the average value is within the scope of the present invention. If it is. N in Formula (4) becomes like this. Preferably it is 0-5, More preferably, it is 0-3. By doing in this way, it is preferable at the surface that the melt viscosity of the epoxy resin obtained falls and hardening reaction with a hardening | curing agent becomes favorable. Since the obtained epoxy resin is liquid at 25 ° C. or has a melting point of 80 ° C. or less, it is excellent in handleability when blended with an epoxy resin curing agent.

Z ₁ and Z ₂ represent the group of the formula (5) or (6), but the ratio of the structures of the formula (5) and the formula (6) in the epoxy resin (B) of the present invention is the formula ( If the content of the aromatic epoxy compound represented by 5) is 1 to 70% and the content of the epoxy compound represented by the formula (6) is 30 to 99%, it is an epoxy resin having a low softening point. It can be used for the epoxy resin composition.

As a method for producing the epoxy resin (B), specifically, for example, an epoxy resin in which the cyclohexane ring portion of the structure represented by the formula (4) is an aromatic ring is selected by a known method in the presence of a catalyst. In particular, there is a method of hydrogenating an aromatic ring. Among these, a more preferred hydrogenation reaction method is to dissolve an epoxy resin in which the cyclohexane ring portion of the structure represented by the general formula (4) is an aromatic ring in an ether-based organic solvent such as tetrahydrofuran or dioxane, and then rhodium or ruthenium. There is a method of selectively hydrogenating an aromatic ring in the presence of a catalyst in which is supported on graphite. It is preferable to use a support having a surface area of 10 m ² / g or more and 400 m ² / g or less for the graphite. The reaction is preferably performed within a range of pressure, 1 to 30 MPa, temperature 30 to 150 ° C., and time 0.5 to 20 hours. After completion of the reaction, the catalyst is removed by filtration, and the ether organic solvent is distilled off under reduced pressure until it substantially disappears to obtain a hydrogenated epoxy resin.

As a specific example of a biphenol compound used for producing an aromatic epoxy resin, which is a raw material in producing the epoxy resin (B) used in the epoxy resin composition of the present invention by such a method, Biphenol, 3,3′-dimethylbiphenyl-4,4′-diol, 3,3′-ditert-butylbiphenyl-4,4′-diol, 3,3 ′, 5,5′-tetramethylbiphenyl-4 , 4′-diol, 2,2′-ditert-butyl-5,5′-dimethylbiphenyl-4,4′-diol, 3,3′-ditert-butyl-5,5′-dimethylbiphenyl-4 , 4′-diol, 3,3 ′, 5,5′-tetra tert-butylbiphenyl-4,4′-diol, 2,2 ′, 3,3 ′, 5,5′-
Examples include hexamethylbiphenyl-4,4′-diol, 2,2 ′, 3,3 ′, 5,5 ′, 6,6′-octamethylbiphenyl-4,4′-diol. Among them, a biphenol compound in which R ₂ , R ₃ , R ₈ and R ₉ are hydrogen atoms or methyl groups and R ₄ , R ₅ , R ₆ and R ₇ are hydrogen atoms is easy to obtain raw materials and heat resistant. Is preferable in that a cured product can be obtained.

  The epoxy resin composition of the present invention contains an epoxy resin (B) together with the epoxy resin (A), whereby a resin composition excellent in handleability can be obtained, and sufficient cured material properties and thermal conductivity can be obtained. A cured product having can be obtained. The reason why the thermal conductivity of the epoxy resin composition of the present invention is improved is not clear, but it is presumed that the epoxy resin (A) and the epoxy resin (B) are excellent in compatibility, so that the self-orientation is improved during curing. The

In addition, the epoxy resin composition of the present invention may contain an epoxy resin other than the epoxy resin (A) and the epoxy resin (B) (hereinafter referred to as “other epoxy resin”) as long as the purpose is not impaired. . The content of the other epoxy resin is usually 70% by weight or less, preferably 60% by weight or less based on the total of all epoxy resins including the epoxy resin (A) and the epoxy resin (B).
Examples of other epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, triphenyl type Various epoxy resins such as phenylmethane type epoxy resin, dicyclopentadiene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, polyfunctional phenol type epoxy resin and the like can be mentioned. These may mix | blend 1 type and may mix 2 or more types.

  In the epoxy resin composition of the present invention, the ratio of the epoxy resin (A) in the total epoxy resin including the epoxy resin (A) and the epoxy resin (B) is 1 to 99% by weight, with the total as 100% by weight, Preferably it is 5-95 weight%. The "all epoxy resins including epoxy resin (A) and epoxy resin (B)" means that the epoxy resin contained in the epoxy resin composition of the present invention is only an epoxy resin (A) and an epoxy resin (B). In the case, it means the sum of the epoxy resin (A) and the epoxy resin (B), and when it contains other epoxy resins, the sum of the epoxy resin (A), the epoxy resin (B) and the other epoxy resins. Means.

When the ratio of the epoxy resin (A) is 5% by weight or more, it is possible to impart film formability to the epoxy resin composition, and to sufficiently obtain the effect of improving the thermal conductivity by the blending of (A), Desired high thermal conductivity can be obtained.
When the epoxy resin composition of the present invention is used in a three-dimensional stacked semiconductor device, the melt viscosity at 100 ° C. to 200 ° C. is preferably 0.1 Pa · s or more and 8 Pa · s or less, more preferably 5 Pa · s or more and 5 Pa · s or less.
[Inorganic filler (C)]
In the epoxy resin composition of the present invention, the inorganic filler (C) is added for the purpose of improving thermal conductivity and strength, and the main purpose is to improve the thermal conductivity.

Therefore, the inorganic filler (C) used in the present invention preferably has a high thermal conductivity, and the inorganic filler has a thermal conductivity of 1 W / m · K or higher, preferably 2 W / m · K or higher. Fillers are preferred.
Examples of the inorganic filler (C) include alumina (Al ₂ O ₃ ), aluminum nitride (AlN), boron nitride (BN), silicon nitride (Si ₃ N ₄ ), silica (SiO ₂ ), etc. Al ₂ O ₃ , AlN, BN, and SiO ₂ are preferable, and Al ₂ O ₃ , BN, and SiO ₂ are particularly preferable. These inorganic fillers may be used alone or in a combination of two or more in any combination and ratio.

If the inorganic filler (C) is too large, voids are likely to remain in the cured product, and if it is too small, it tends to aggregate and deteriorate dispersibility. It is preferable to use those having an average particle size of about 0.05 to 1000 μm.
Moreover, if it is an agglomerated inorganic filler, it is preferable to use one having an average crystal diameter of 0.01 μm to 5 μm and an average aggregate diameter of 1 to 1000 μm.

  The content of the inorganic filler (C) in the epoxy resin composition of the present invention is preferably 5 parts by weight or more and 1900 parts by weight or less per 100 parts by weight of the total epoxy resin including the epoxy resin (A) and the epoxy resin (B). 10 parts by weight or more and 1800 parts by weight or less are more preferable. When the content of the inorganic filler (C) is less than 5 parts by weight per 100 parts by weight of the total epoxy resin, the effect of adding the inorganic filler (C) is reduced, and the intended thermal conductivity may not be obtained. If it exceeds 1900 parts by weight, the curability and physical properties of the cured product may be insufficient.

[Curing agent (D)]
The hardening | curing agent (D) used by this invention shows the substance which contributes to the crosslinking reaction between the epoxy groups of an epoxy resin.
There is no restriction | limiting in particular as a hardening | curing agent (D), and what is generally known as an epoxy resin hardening | curing agent can be used. For example, phenolic curing agents, aliphatic amines, polyether amines, alicyclic amines, aromatic amines and other amine curing agents, acid anhydride curing agents, amide curing agents, tertiary amines, imidazoles and the like Derivatives, organic phosphines, phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, boron halide amine complexes, polymercaptan curing agents, isocyanate curing agents, blocked isocyanate curing agents, and the like.

  Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3-bis. (4-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p-cle All novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2 , 4-Benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2, -Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, etc. The

Specific examples of the amine curing agent include aliphatic diamines such as ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, Examples include diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine, and the like. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, polyoxypropylene triamines, and the like. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (m-aminophenyl) ethylamine, α- (p-aminophenyl) ethylamine Diaminodiethyldi Examples thereof include methyldiphenylmethane and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene.

  Specific examples of acid anhydride curing agents include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid) Anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Hexahydrophthalic anhydride, Methylhymic anhydride, Tetrahydrophthalic anhydride, Trialkyltetrahydrophthalic anhydride, Methylcyclohexene dicarboxylic anhydride, Methylcyclohexene tetracarboxylic Acid anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitic dianhydride, het anhydride, nadic anhydride, methyl nadic anhydride, 5- ( 2, -Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene-2-succinic acid Examples of the anhydride include 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride.

Examples of the amide type curing agent include dicyandiamide and polyamide resin.
Examples of the tertiary amine include 1,8-diazabicyclo (5,4,0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol. .
Examples of imidazole and derivatives thereof include 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole, 2-ethyl-4 (5) -methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazo Lithium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methyl Imidazolyl- (1 ′)]-ethyl-s-triazine, 2,4-diamino 6- [2′-Methylimidazolyl- (1 ′)]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl- 4
Examples include -methyl-5-hydroxymethylimidazole and adducts of an epoxy resin and the above imidazoles.

  Examples of organic phosphines include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like, and phosphonium salts include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, Examples include tetrabutylphosphonium / tetrabutylborate, and examples of the tetraphenylboron salt include 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, and the like.

Moreover, these hardening | curing agents may be used individually by 1 type, and 2 or more types may be mixed and used for them in arbitrary combinations and ratios.
The content of the curing agent (D) in the epoxy resin composition of the present invention is 0.01 parts by weight or more and 200 parts by weight or less per 100 parts by weight of the total epoxy resin including the epoxy resin (A) and the epoxy resin (B). Preferably, it is 0.05 to 180 parts by weight, more preferably 0.1 to 150 parts by weight.

If the content of the curing agent (D) is less than 0.01 parts by weight, curing may be insufficient, and if it exceeds 200 parts by weight, thermal conductivity derived from the components (A) to (C), Physical properties such as curability may not be obtained.
The epoxy resin composition of the present invention may contain various additives within the range that does not impair the effects of the present invention for the purpose of further improving the functionality.

The epoxy resin composition of the present invention is mainly composed of the above-mentioned epoxy resin (A), epoxy resin (B), inorganic filler (C) and curing agent (D), and other additive components. Is preferably 10% by weight or less, more preferably 5% by weight or less, based on the total amount of the epoxy resin composition.
As the additive component, as an additive component for improving the adhesion to the substrate and the adhesion between the matrix resin and the inorganic filler, a coupling agent such as a silane coupling agent or a titanate coupling agent, storage stability Anti-ultraviolet agents, antioxidants, plasticizers, fluxes for removing solder oxide film, flame retardants, colorants, dispersants, fluidity improvers, adhesion improvers with substrates, etc. Can be mentioned.

Any of these may be used alone or in a combination of two or more in any combination and ratio. There is no restriction | limiting in particular in the compounding quantity of another additive component, It is used with the compounding quantity of a normal resin composition to such an extent that required functionality is obtained.
Among the additives, it is preferable to include a coupling agent from the viewpoint of improving the adhesion between the epoxy resin component and the inorganic filler (C).

Here, as the silane coupling agent, epoxy silane such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ, -Aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltri Aminosilane such as ethoxysilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysila And vinyl silanes such as γ-methacryloxypropyltrimethoxysilane, and epoxy, amino and vinyl polymer type silanes.

  On the other hand, titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate It is done.

  In addition, it is preferable that the addition amount of a coupling agent shall be about 0.1 to 2.0 weight% with respect to the total solid in an epoxy resin composition among other additives. If the amount of the coupling agent is small, the effect of improving the adhesion between the matrix resin and the inorganic filler due to the incorporation of the coupling agent cannot be obtained sufficiently. There is a problem that the agent bleeds out.

  In addition, thermoplastic oligomers can be added to the epoxy resin composition of the present invention from the viewpoint of improving the fluidity during molding and improving the adhesion to the substrate. Thermoplastic oligomers include C5 and C9 petroleum resins, styrene resins, indene resins, indene / styrene copolymer resins, indene / styrene / phenol copolymer resins, indene / coumarone copolymer resins, indene / benzothiophene. Examples thereof include copolymer resins. As addition amount, it is the range of 2-30 weight part normally with respect to 100 weight part of epoxy resins.

<Manufacture of epoxy resin composition>
The epoxy resin composition of the present invention is produced by uniformly mixing an epoxy resin, an inorganic filler, a curing agent and other components with a mixer or the like and then kneading them with a heating roll, a kneader or the like. There is no restriction | limiting in particular in the mixing | blending order of these components. Further, after kneading, the melt-kneaded material can be pulverized to be powdered or tableted.

The epoxy resin composition of the present invention comprises an epoxy resin (A), an epoxy resin (B), an inorganic filler (C), a curing agent (D), and, if necessary, the above-mentioned other additives, an organic solvent (E ) To form a coating solution.
[Organic solvent (E)]
Examples of the organic solvent (E) used in the coating solution of the present invention include acetone, methyl ethyl ketone (MEK), ketones such as methyl isobutyl ketone, methyl amyl ketone, and cyclohexanone, esters such as ethyl acetate, ethylene glycol monomethyl ether, and the like. Examples include ethers, amides such as N, N-dimethylformamide and N, N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene.

Of these, taking into consideration the solubility of the resin and the boiling point of the solvent, ketones such as methyl ethyl ketone and cyclohexanone, esters and ethers are preferred, and in particular, ketones of methyl ethyl ketone and cyclohexanone are particularly preferred.
These organic solvents may be used alone or in a combination of two or more in any combination and ratio.

In the coating liquid of the present invention, the mixing ratio of the organic solvent (E) to other components is not particularly limited, but is preferably 20% by weight or more and 70% by weight or less, particularly preferably 30% by weight with respect to the other composition. % To 60% by weight. By setting it as such a mixing ratio, a favorable coating film can be formed by arbitrary coating methods by using the coating liquid of this invention.

If the mixing ratio of the organic solvent (E) is less than 20% by weight, the viscosity of the composition may increase and a good coating film may not be obtained, or if it exceeds 70% by weight, a predetermined film thickness may not be obtained. May come up with problems.
The coating liquid of the present invention may contain various additives.
Examples of such additives include surfactants, emulsifiers, low elasticity agents, diluents, antifoaming agents, ion trapping agents, and the like that improve the dispersibility of each component in the coating solution in addition to the additives described above. Is mentioned.

Here, as the surfactant, any of conventionally known anionic surfactants, nonionic surfactants, and cationic surfactants can be used.
For example, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl Examples include sulfonates, sulfosuccinate esters, alkylbetaines, amino acids, and the like.

The addition amount of the surfactant is preferably about 0.001 to 5% by weight with respect to the total solid content in the epoxy resin composition. If it is less than 0.001% by weight, the predetermined film thickness uniformity may not be obtained, and if it exceeds 5% by weight, phase separation from the epoxy resin component may be caused.
The manufacturing method of the coating liquid of this invention is not specifically limited, What is necessary is just to follow a conventionally well-known method, and can manufacture by mixing the structural component of a coating liquid. At that time, for the purpose of improving the uniformity of the composition, defoaming, etc., it may be mixed using a paint shaker, bead mill, planetary mixer, stirring type disperser, self-revolving stirring mixer, three rolls, etc. preferable.

The mixing order is arbitrary as long as there is no particular problem such as reaction or precipitation. Among the components of the coating liquid, any two components or three or more components are blended in advance, and then the remaining components are mixed. You may mix all at once.
<Use of epoxy resin composition>
The epoxy resin composition of the present invention has sufficient elongation to be applied to processes such as film molding and coating, and is excellent in balance between thermal conductivity and heat resistance, and has excellent cured properties. It can be applied to various fields such as adhesives, paints, materials for civil engineering and construction, insulating materials for electrical and electronic parts, and is particularly useful as insulating casting, laminating materials, sealing materials, etc. in the electrical and electronic fields. is there.

Examples of uses of the epoxy resin composition of the present invention include multilayer printed wiring boards, film adhesives, liquid adhesives, semiconductor sealing materials, underfill materials, and interlayer fillers for 3D stacked devices (3D-LSIs). Interchip fill), insulating sheet, prepreg, heat dissipation substrate and the like, but are not limited thereto.
<Manufacture of cured product>
Hereinafter, the cured product of the present invention will be described.

In order to obtain a cured product using the epoxy resin composition of the present invention, for example, methods such as transfer molding, press molding, cast molding, injection molding, and extrusion molding are applied.
In the case of an adhesive, after adhering the substrate using the adhesive, it is allowed to stand for 5 minutes to 1 week in an environment of 15 to 200 ° C. to be cured. The cured encapsulant can be obtained by molding the composition using a casting, transfer molding machine, injection molding machine or the like, and further heating at 80 to 200 ° C. for 2 to 10 hours. it can.

The method for producing an adhesive film for buildup from the epoxy resin composition of the present invention is, for example, applied to the support film by forming the epoxy resin composition of the present invention on a support film to form a resin composition layer. The method of setting it as an adhesive film is mentioned.
A method for producing a prepreg for an interlayer insulating layer of a multilayer printed wiring board by impregnating the epoxy resin composition of the present invention into a sheet-like reinforcing substrate made of fiber, for example, the epoxy resin composition of the present invention from fiber The sheet-like reinforcing base material is impregnated by a hot melt method or a solvent method, and semi-cured by heating. Examples of the sheet-like reinforcing substrate made of fibers that can be used here include glass cloth and aramid fibers.

  Next, a method for producing a multilayer printed wiring board using the above prepreg is, for example, by stacking one or several prepregs on a circuit board, sandwiching a metal plate through a release film, and pressing under pressure and heating conditions. The method of laminating is mentioned. Specifically, the pressure condition is preferably 0.5 to 4 MPa, and the temperature is preferably 120 to 200 ° C. and 20 to 100 minutes. Moreover, it can also be manufactured by laminating on a circuit board by a vacuum laminating method as in the case of an adhesive film, and then curing by heating. Then, a multilayer printed wiring board can be manufactured by forming a conductor layer by plating.

Hereinafter, the case where the hardened | cured material of this invention is obtained from the coating liquid containing an epoxy resin composition is explained in full detail.
When obtaining a cured product from the coating liquid of the present invention, the epoxy resin composition of the present invention is applied on a substrate, the solvent is removed from the coating film to form a B-stage film, and pressure is applied as necessary. Can be cured. The B-stage thin film refers to a thin film in which the coating film does not flow even when the coating film is tilted so that the film surface is in the vertical direction.

Although there is no restriction | limiting in particular as the coating method of the coating liquid of this invention, Since a uniform thin film can be formed easily, spin coating, dip coating, spray coating, flow coating, doctor blade method, screen printing method, inkjet It is preferable to adopt a method or the like.
The removal of the solvent when removing the solvent from the formed coating film to obtain a B stage film can be performed by evaporating the solvent at room temperature or under heating. At this time, the pressure can be reduced as necessary. It is important for removing the solvent to obtain adhesiveness to be performed at a temperature lower than the curing temperature of the epoxy resin composition.

Here, the curing temperature of the epoxy resin composition is the gel point temperature. The treatment temperature at the time of solvent removal is preferably about 50 to 200 ° C. lower than the curing temperature of the epoxy resin composition.
The B stage film thus obtained is cured by heating to a temperature equal to or higher than the curing temperature of the epoxy resin composition, for example, 5 to 50 ° C. higher than the curing temperature of the epoxy resin composition.

Instead of distilling off the solvent after obtaining the coating film, first, after obtaining a solid obtained by distilling off the solvent from the coating solution, it can be cast by the above-mentioned method and then cured by heating. .
When applying the coating liquid of this invention to manufacture of a three-dimensional laminated semiconductor device and obtaining hardened | cured material, it carries out in the following procedures. The epoxy resin composition of the present invention is applied onto a wafer substrate, the solvent is removed from the coating film to form a B stage film, and then a semiconductor chip is cut out from the wafer. The cut-out chip is placed on the substrate, and after positioning and pressurizing and heating to temporarily bond, the semiconductor chip-substrate is pressed and heated to the melting temperature of the solder for bonding. Thereafter, the bonded semiconductor chip-substrate can be heated and cured in an oven or the like. The B-stage thin film refers to a thin film in which the coating film does not flow even when the coating film is tilted so that the film surface is in the vertical direction.

Although there is no restriction | limiting in particular as the coating method of the coating liquid of this invention, Since a uniform thin film can be formed easily, spin coating, dip coating, spray coating, flow coating, doctor blade method, screen printing method, inkjet It is preferable to adopt a method or the like.
The removal of the solvent when removing the solvent from the formed coating film to obtain a B stage film can be performed by evaporating the solvent at room temperature or under heating. At this time, the pressure can be reduced as necessary. It is important for removing the solvent to obtain adhesiveness to be performed at a temperature lower than the curing temperature of the epoxy resin composition.

Here, the curing temperature of the epoxy resin composition is the gel point temperature. The treatment temperature at the time of removing the solvent is preferably a temperature lower by about 10 to 100 ° C. than the curing temperature of the epoxy resin composition.
Instead of obtaining a B-stage film on the wafer substrate as described above, first, after obtaining a solid obtained by distilling off the solvent from the coating solution, it is molded into a film using a press or a roll, and then the semiconductor. It can also be cured by being sandwiched between the chip and the substrate, soldered by pressing and heating, and then heated.

The three-dimensional stacked semiconductor device using the cured interlayer filler of the present invention has high thermal conductivity, and is expected to contribute to higher speed and higher capacity of semiconductor devices.
<Use of cured product>
The cured product of the present invention is obtained by curing the above-described epoxy resin composition of the present invention, and is excellent in moisture resistance, heat resistance, low stress, thermal conductivity, and exhibits excellent cured properties. Used as intermediate and final product in various applications described in Applications of Epoxy Compositions of the Invention.

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
In addition, the following measurement methods for various physical properties and characteristics are as follows.
The epoxy resin (A) used in the examples of the present invention was evaluated by the following method.
<Molecular weight>
Using “HLC-8120GPC device” manufactured by Tosoh Corporation, and under the following measurement conditions, as standard polystyrene, TSK Standard Polystyrene: F-128 (Mw1,090,000, Mn1,030,000), F-10 ( Mw 106,000, Mn 103,000), F-4 (Mw 43,000, Mn 42,700), F-2 (Mw 17,200, Mn 16,900), A-5000 (Mw 6,400, Mn 6,100), A- Calibration curves using 2500 (Mw 2,800, Mn 2,700) and A-300 (Mw 453, Mn 387) were prepared, and the weight average molecular weight and number average molecular weight were measured as polystyrene conversion values.

Column: “TSKGEL SuperHM-H + H5000 + H4000 + H3000 + H2000” manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran Flow rate: 0.6 ml / min
Detection: UV (wavelength 254 nm)
Temperature: 40 ° C
Sample concentration: 0.1% by weight
Injection volume: 10μL
<N number>
The value of n and the average value in the formula (1) were calculated from the number average molecular weight determined above.

<Epoxy equivalent>
Measured according to JIS K 7236 and expressed as a solid content converted value.
<Glass transition temperature Tg>
The epoxy resin from which the solvent was removed by drying was measured by increasing the temperature from 30 to 200 ° C. at 10 ° C./min using “DSC7020” manufactured by SII Nanotechnology.

<Elongation>
The epoxy resin solution was applied to a separator (silicone-treated polyethylene terephthalate film, thickness: 100 μm) with an applicator, dried at 60 ° C. for 1 hour, then at 150 ° C. for 1 hour, and further at 200 ° C. for 1 hour, and a thickness of about 50 μm. An epoxy resin film was obtained. This was cut into a width of 1 cm, and an average value measured three times at 5 mm / min using an autograph (INSTRON 5582) was shown.

<Melt viscosity>
The melt viscosity of the epoxy resin composition of the present invention is a parallel plate dynamic viscosity measured using a viscoelasticity measuring device Physica MCR301 manufactured by Anton Paar Japan. The measuring method is as follows. First, the solvent is distilled off from the epoxy resin composition of the present invention to obtain a solid, and then the solid is sandwiched between two separators and subjected to hot press molding and then allowed to cool to room temperature. A 1 mm plate sample was obtained. This sample was placed between a parallel plate dish and a parallel plate (25 mmφ), and the parallel plate dynamic viscosity was measured. The measurement conditions were that 20% sinusoidal distortion was applied to the sample, the angular frequency of the distortion was 10 rad / sec, and the viscosity was measured from 40 ° C. to 200 ° C. in the process of raising the temperature at a rate of 3 ° C. per minute. .

(1) Epoxy resin (A)
1) The epoxy resin (A) used in the examples was produced by the following method.
The raw materials, catalysts, and solvents used are shown below.
-Compound (X): Mitsubishi Chemical Corporation product name "YL6121H"(4,4'-biphenol type epoxy resin and 3,3 ', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin 1: 1 mixture, epoxy equivalent 171 g / equivalent)
Compound (Y): 3,3′-dimethyl-4,4′-biphenol (OH equivalent 107 g / equivalent, Honshu Chemical Co., Ltd.)
-Catalyst: 27 wt% tetramethylammonium hydroxide aqueous solution-Solvent Solvent 1: Cyclohexanone Solvent 2: Methyl ethyl ketone Compound (X) 210 parts by weight, Compound (Y) 127.6 parts by weight, Catalyst 0.78 parts by weight, and Solvent 1 181.8 parts by weight of (cyclohexanone) was placed in a pressure-resistant reaction vessel equipped with a stirrer, and reacted at 180 ° C. for 5 hours in a nitrogen gas atmosphere.

Thereafter, 212.1 parts by weight of solvent 1 (cyclohexanone) and 393.8 parts by weight of solvent 2 (methyl ethyl ketone) were added to the pressure-resistant reaction vessel to adjust the solid content concentration. The results of analyzing the epoxy resin (A) obtained after removing the solvent from the reaction product by a conventional method are shown below.
Epoxy resin (A)
Weight average molecular weight (Mw): 26425
Number average molecular weight (Mn): 8129
N number in Formula (1): 29
Epoxy equivalent: 4586 (g / equivalent)
Tg: 103 (° C.)
Elongation: 10 (%)
(2) The epoxy resin (B), the other epoxy resin 1, the other epoxy resin 2, and the solvent (E) which were used for manufacture of the epoxy resin composition of an Example are shown below.
1) Epoxy resin (B)
・ Epoxy resin (B): Bisphenol A type liquid epoxy resin manufactured by Mitsubishi Chemical Corporation “YL6800”
-Other epoxy resins 1: Trisphenol methane type polyfunctional epoxy resin manufactured by Mitsubishi Chemical Co., Ltd. Trade name "1032H60" (80% by weight methyl ethyl ketone solution is prepared)
-Other epoxy resin 2: bisphenol A type solid epoxy resin manufactured by Mitsubishi Chemical Co., Ltd. Trade name "1001" (80% by weight methyl ethyl ketone solution is prepared)
2) Solvent (E): Methyl ethyl ketone [Examples 1 to 6, Comparative Example 1]
The said epoxy resin (A), the epoxy resin (B), the other epoxy resin 1, and the other epoxy resin 2 were mixed with the autorotation revolution mixer as a compounding weight ratio shown in Table 1. For each sample, the properties of the B-staged film after removing the solvent, the adhesiveness at 80 ° C., and the melt viscosity at 150 ° C. were evaluated, and the results are summarized in Table 1.

  In all cases, the materials of the examples satisfied the suitability for the stacking process of the three-dimensional stacked semiconductor device. Moreover, in all the samples, the high thermal conductivity resulting from the orientation of the mesogenic sites contained in the epoxy resin (A) and the epoxy resin (B) is exhibited after curing.

  The present invention provides an interlayer filler composition that is excellent in adaptability to a manufacturing process of a three-dimensional stacked semiconductor device and excellent in performance balance such as thermal conductivity and heat resistance. Since the three-dimensional stacked semiconductor device using the interlayer filler composition of the present invention is excellent in thermal conductivity and heat resistance, it is expected to contribute to higher speed and higher capacity of semiconductor devices.

Claims (9)

An epoxy resin (A) having a structure represented by the following formula (1) and having an epoxy equivalent of 2500 g / equivalent or more and an epoxy resin (B) represented by the following formula (4) Epoxy resin composition.

(In the formula (1), A is a biphenyl skeleton represented by the following formula (2), B is a hydrogen atom or the following formula (3), n is the number of repetitions, and the average value is 10 <n <50. .)

(In the formula (2), R ¹ is a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a halogen atom, may be the same or different from each other.)

Wherein _(4), R 2 to R ₅ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, _{Z 1} and _{Z 2} are groups of formula (5) or (6)

(Wherein R _{6 to} R ₉ represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and n represents a number of 0 to 6. ]   The epoxy resin composition of Claim 1 whose ratio with respect to all the epoxy resins of an epoxy resin (A) is 5 to 95 weight%.   The epoxy resin composition of Claim 1 or Claim 2 which contains an inorganic filler (C) 5 to 1900 weight part with respect to 100 weight part of all the epoxy resins.   The epoxy resin composition according to any one of claims 1 to 3, wherein the curing agent (D) is contained in an amount of 0.01 to 200 parts by weight per 100 parts by weight of the total epoxy resin.   Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claims 1-4.   A prepreg obtained from the epoxy resin composition according to any one of claims 1 to 4.   An interlayer filler composition for a three-dimensional stacked semiconductor device obtained from the epoxy resin composition according to any one of claims 1 to 4.   A three-dimensional stacked semiconductor device using the epoxy resin composition according to any one of claims 1 to 4 between layers.   A method for manufacturing a three-dimensional stacked semiconductor device, wherein the epoxy resin composition according to claim 1 is filled between layers.