JP2012067177A - Biphenyl type epoxy resin composition for sealing semiconductor containing inclusion complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin composition for sealing a semiconductor, improving storage stability, keeping flowability at a sealing time, and achieving efficient curing speed by heat.SOLUTION: This epoxy resin composition for sealing a semiconductor includes following components: (A) a biphenyl type epoxy resin; and (B) an inclusion complex containing (b1) at least one kind of compound selected from a group consisting of a carboxylic acid compound, 4,4',4''-trihydroxy triphenyl methane, tris(2-hydroxyethyl) isocyanurate, 2,2',4,4'-tetrahydroxy benzophenone and a specific pyridine derivative, and (b2) at least one kind selected from a group consisting of a specific imidazole compound and 1,8-diazabicyclo[5.4.0] undecene-7.

Description

  The present invention relates to a biphenyl type epoxy resin composition for semiconductor encapsulation using an inclusion complex as a curing agent and / or a curing accelerator.

  An epoxy resin composition containing an epoxy resin, a curing agent, a curing accelerator, and other additives is used as a sealing material for semiconductor elements such as transistors, ICs, LSIs, and electrical components. Conventionally, amine compounds and imidazole compounds have been used as curing agents and curing accelerators, but there has been a problem with the storage stability of epoxy resin compositions. In recent years, for the purpose of improving the storage stability, an inclusion complex having an imidazole compound or an amine compound as a guest compound and 1,1 ′, 2,2′-tetrakis (4-hydroxyphenyl) ethane as a host has been developed. It has been proposed to be used as a curing accelerator (see Patent Document 1). However, 1,1 ′, 2,2′-tetrakis (4-hydroxyphenyl) ethane includes imidazole compounds and amine compounds, so that the normal temperature of the sealing material is higher than when these compounds are used alone or in combination. Although it is possible to improve the storage stability, the sealing material composition for the fine specifications of semiconductors that have been making remarkable progress in recent years has not been sufficiently satisfied.

JP 2004-307545 A

  An object of the present invention is to cope with a dense semiconductor sealing material, so that the storage stability of the sealing material is improved, the fluidity of the sealing material at the time of sealing is maintained, and efficient sealing by heat is performed. The purpose is to realize the curing speed of the stop material.

  As a result of intensive studies to solve the above problems, the present inventors have determined that an inclusion complex containing a carboxylic acid compound and the like and an imidazole compound or 1,8-diazabicyclo [5.4.0] undecene-7 is a biphenyl type epoxy. It has been found that the above problems can be solved by using the resin as a curing agent and / or a curing accelerator, and the present invention has been completed.

That is, the present invention
(1) An epoxy resin composition for semiconductor encapsulation, comprising the following component (A) and component (B):
(A) biphenyl type epoxy resin,
(B)
(B1) carboxylic acid compounds, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, tris (2-hydroxyethyl) isocyanurate, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the formula (I )

(In the formula, R represents a hydroxy group, a nitro group, an alkyl group, an alkoxy group, an amino group, a sulfo group, an acetamide group, a hydrazine group, or a carboxyl group, and n represents an integer of 1 to 5. And may be the same or different.) At least one compound selected from the group consisting of pyridine derivatives represented by:
(B2) Formula (II)

[In the formula, _{R 1} represents a hydrogen atom, an alkyl group, aryl group, arylalkyl group or cyanoethyl group C1 _-C10, R 2 to R ₄ is a hydrogen atom, a nitro group, a halogen atom, a C1~C20 An alkyl group, a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C1-C20 acyl group is represented. And an at least one selected from the group consisting of 1,8-diazabicyclo [5.4.0] undecene-7,
(2) The epoxy resin composition for semiconductor encapsulation according to (1), further comprising an inorganic filler,
(3) The component (b1) is 5-tert-butylisophthalic acid, 5-nitroisophthalic acid, 5-hydroxyisophthalic acid, pyromellitic acid, trimesic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7 -Dihydroxy-2-naphthoic acid, trans-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, fumaric acid, maleic acid, malonic acid, malic acid, succinic acid, 2,6-dihydroxyisonicotinic acid, And an epoxy resin composition for semiconductor encapsulation according to (1) or (2), wherein the epoxy resin composition is one selected from the group consisting of 2,6-pyridinedicarboxylic acid.

  By using the epoxy resin composition for encapsulating a semiconductor of the present invention, the epoxy resin composition for encapsulating a semiconductor capable of supporting a dense semiconductor circuit having storage stability and fluidity and having an efficient curability. Can be provided.

  When the curing agent for epoxy resin or the curing accelerator for epoxy resin comprising the clathrate complex of the present invention is blended with an uncured epoxy resin, the thermal stability, which is extremely important in controlling the curing reaction, Compared to the case where only the guest compound (amine-based, imidazole-based, etc., curing agent or curing accelerator before inclusion) is included in the curing accelerator. In addition, a resin composition containing these inclusion complexes as a curing agent or a curing accelerator is excellent in thermal characteristics. The thermal characteristics of the resin composition are required to have three characteristics: stability at normal temperature (one-liquid stability), thermal stability during heating from normal temperature to a desired curing temperature, and curing temperature. An uncured epoxy resin containing the inclusion complex of the present invention as a curing agent and a curing accelerator is extremely stable at room temperature (1 liquid stability is good), but only heated to a certain temperature above a certain temperature. Cure to quickly give the desired cured product.

The epoxy resin composition for semiconductor encapsulation of the present invention contains at least the following component (A) and component (B).
(A) biphenyl type epoxy resin,
(B)
(B1) carboxylic acid compounds, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, tris (2-hydroxyethyl) isocyanurate, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the formula (I )

(In the formula, R represents a hydroxy group, a nitro group, an alkyl group, an alkoxy group, an amino group, a sulfo group, an acetamide group, a hydrazine group, or a carboxyl group, and n represents an integer of 1 to 5. And may be the same or different.) At least one compound selected from the group consisting of pyridine derivatives represented by:
(B2) Formula (II)

[In the formula, _{R 1} represents a hydrogen atom, an alkyl group, aryl group, arylalkyl group or cyanoethyl group C1 _-C10, R 2 to R ₄ is a hydrogen atom, a nitro group, a halogen atom, a C1~C20 An alkyl group, a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C1-C20 acyl group is represented. And an at least one selected from the group consisting of 1,8-diazabicyclo [5.4.0] undecene-7 (hereinafter referred to as DBU).

1) Epoxy Resin As the (A) component biphenyl type epoxy resin, any epoxy resin having a biphenyl skeleton can be used without particular limitation. For example, 4,4′-bis (2,3-epoxypropoxy) biphenyl or 4,4′-bis (2,3-epoxypropoxy) -3,3 ′, 5,5′-tetramethylbiphenyl is the main component. And epoxy resin obtained by reacting epichlorohydrin with 4,4′-biphenol or 4,4 ′-(3,3 ′, 5,5′-tetramethyl) biphenol. 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethylbiphenyl as the main component is preferred. As such a compound, YX-4000H (manufactured by Mitsubishi Chemical Corporation) and the like are commercially available.

2) Inclusion Complex In the present invention, the “inclusion complex” of the component (B) refers to a compound in which two or more molecules are bonded by a bond other than a covalent bond, more preferably two or three. A crystalline compound in which molecules of more than one species are bonded by a bond other than a covalent bond. A compound to be included is called a host compound, and a compound to be included is called a guest compound. A salt is also included in the inclusion complex referred to herein.
In the present invention, the compound (b1) is a host compound, and the imidazole compound and / or DBU (b2) is a guest compound. The inclusion complex of the present invention may contain a third component such as a solvent.

The ratio of the compound of (b1) to the imidazole compound and / or DBU of (b2) is not particularly limited as long as it can form an inclusion compound, but the imidazole compound and 1 mol of the compound of (b1) It is preferable that DBU is 0.1-5.0 mol, and it is more preferable that it is 0.5-4.0 mol.
When the third component is contained, the third component is preferably 40% by mole or less, more preferably 10% by mole or less, particularly preferably not containing the third component, based on the total amount of the inclusion complex. Most preferred.

(Host compound)
The host compound includes a carboxylic acid compound, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, tris (2-hydroxyethyl) isocyanurate, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the above formula It is at least one compound selected from the group consisting of pyridine derivatives represented by (I).
Examples of the carboxylic acid compound (b1) that is a host compound include aromatic carboxylic acids and aliphatic polyvalent carboxylic acids.

  Aromatic carboxylic acids include isophthalic acid and the following formula (III)

(Wherein R ₅ represents a C1-C6 alkyl group, a C1-C6 alkoxy group, a nitro group or a hydroxy group) an isophthalic acid derivative (for example, 5-t-butylisophthalic acid, 5-hydroxyisophthalic acid) , 5-nitroisophthalic acid, etc.), 3,5-dihydroxybenzoic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 3,5 -Dihydroxy-2-naphthoic acid, 3,7-dihydroxy-2-naphthoic acid, 4,4'-benzophenone dicarboxylic acid and the like can be mentioned. Preferably, it is an aromatic carboxylic acid having 2 to 4 carboxyl groups and having 6 to 20 carbon atoms (not including the carbon of the carboxyl group).

Compared with the case where o-cresol novolac type epoxy resin is used, in particular, performance such as fluidity and storage stability can be seen, and in particular, 5-t-butylisophthalic acid, 5-nitroisophthalic acid, 5-hydroxy Isophthalic acid, pyromellitic acid, trimesic acid, 3,5-dihydroxy-2-naphthoic acid, and 3,7-dihydroxy-2-naphthoic acid are preferred.
These carboxylic acid compounds may be used alone or in combination of two or more.

Examples of aliphatic polycarboxylic acids include fumaric acid, 1,3-cyclohexanedicarboxylic acid, trans-1,4-cyclohexanedicarboxylic acid, succinic acid, malonic acid, tartaric acid, maleic acid, citric acid, malic acid, adipic acid and the like. Can give. Preferably, it is an aliphatic carboxylic acid having 2 to 4 carboxyl groups and having 2 to 10 carbon atoms (not including the carbon of the carboxyl group) or a hydroxy aliphatic polycarboxylic acid.
Compared with the case where o-cresol novolac type epoxy resin is used, in particular, improved performance such as fluidity and storage stability can be seen. In particular, trans-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Fumaric acid, maleic acid, malic acid, succinic acid and malonic acid are preferred.
These carboxylic acid compounds may be used alone or in combination of two or more.

  In the pyridine derivative represented by the formula (I) of the host compound (b1), R represents a hydroxy group, a nitro group, an alkyl group, an alkoxy group, an amino group, a sulfo group, an acetamide group, a hydrazine group, or a carboxyl group. Wherein the alkyl group, alkoxy group, amino group, and acetamide group may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group, a hydroxy group, an aryl group, and an arylalkyl group. I can give you. The alkyl group of the substituent may have a hydroxy group or a carboxyl group.

Here, examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n -C1-6 alkyl groups, such as a hexyl group, are mentioned.
Examples of the alkoxy group include C1-C6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, and t-butoxy group. .
An aryl group means a monocyclic or polycyclic aryl group. Here, in the case of a polycyclic aryl group, a partially saturated group is included in addition to the fully unsaturated group. Examples thereof include C6-C10 aryl groups such as a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
The arylalkyl group is a group in which the aryl group and the alkyl group are bonded, and includes a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 1-phenyl-n-hexyl group, a naphthalen-1-ylmethyl group, Examples thereof include C6-C10 aryl C1-C6 alkyl groups such as naphthalen-2-ylethyl group, 1-naphthalen-2-yl-n-propyl group, and inden-1-ylmethyl group.

Specific examples of the pyridine derivative represented by the formula (I) include the following compounds.
2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 2,3-dihydroxypyridine, 2,4-dihydroxypyridine, 2-hydroxy-3-nitropyridine, 2-hydroxy-5-nitropyridine, 3-hydroxy 2-nitropyridine, 4-hydroxy-3-nitropyridine, 2-amino-3-hydroxypyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5-methylpyridine, 2-hydroxy-6-methylpyridine 3-hydroxy-2-methylpyridine, nicotinic acid, isonicotinic acid, 2-hydroxynicotinic acid, 3-hydroxy-2-pyridinecarboxylic acid, 6-hydroxynicotinic acid, 2,6-dihydroxyisonicotinic acid, 2, 6-dimethyl-3-hydroxypyridine, 3-hydroxy -6-methyl-2-pyridinemethanol, 2-hydroxy-6-methylnicotinic acid, 2-methoxynicotinic acid, 3-pyridinesulfonic acid, 4-hydroxy-3-pyridinesulfonic acid, 2-aminopyridine, 3-amino Pyridine, 4-aminopyridine, 2-hydrazinopyridine, 2-acetamidopyridine, 2- (2-pyridylamino) ethanol, N- (2-pyridyl) -β-alanine, 2,5-diaminopyridine, 2,6- Diaminopyridine, 3,4-diaminopyridine, 2-aminonicotinic acid, 4-aminonicotinic acid, 6-aminonicotinic acid, 6-methylnicotinic acid, 2-pyridinemethanol, 3-pyridinemethanol, 4-pyridinemethanol, 2 -Pyridinecarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid Acids, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, nicotinamide, 2-pyridineethanol and the like.

  Particularly preferred is the general formula (IV)

(Wherein R ₆ represents a carboxyl group or a hydroxy group, m represents an integer of 0 to 4, and n represents 1 or 2. When a plurality of R ₆ are present, they may be the same or different). Specific examples thereof include 2,3-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3-hydroxy-2-pyridinecarboxylic acid, and 2,6-dihydroxyisonicotinic acid. Can do.
Compared with the case where an o-cresol novolac type epoxy resin is used, in particular, 2,6-pyridinedicarboxylic acid and 2,6-dihydroxyisonicotinic acid are used in view of improvement in performance such as fluidity and storage stability. preferable.

(Guest compound)
The guest compound (b2) is an imidazole compound and / or DBU represented by the formula (II). As the imidazole compound of the formula (II),

[In the formula, _{R 1} represents a hydrogen atom, an alkyl group, aryl group, arylalkyl group or cyanoethyl group C1 _-C10, R 2 to R ₄ is a hydrogen atom, a nitro group, a halogen atom, a C1~C20 An alkyl group, a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C1-C20 acyl group is represented. If it is a compound represented by], there will be no restriction | limiting in particular.

As the C1-C10 alkyl group of R ₁ , methyl group, ethyl group, propyl group, isopropyl group, cyclopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, cyclobutyl group, cyclopropylmethyl group Pentyl group, isopentyl group, 2-methylbutyl group, neopentyl group, 1-ethylpropyl group, hexyl group, isohexyl group, 4-methylpentyl group, 3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group 3,3-dimethylbutyl group, 2,2-dimethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1 -Ethylbutyl group, 2-ethylbutyl group, octyl group, nonyl group, decyl group and the like can be mentioned.
Examples of the C1 to C20 alkyl group of R _{2 to} R ₄ include an undecyl group, a lauryl group, a palmityl group, and a stearyl group, in addition to those exemplified as the alkyl group of R ₁ .
Examples of the C1-C20 alkyl group substituted with the hydroxy group of R _{2 to} R ₄ include a hydroxymethyl group or a hydroxyethyl group.
As the C1-C20 acyl group of R _{2 to} R ₄ , formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, pivaloyl group, hexanoyl group, octanoyl group, decanoyl group, lauroyl group, myristoyl group , Palmitoyl group, stearoyl group and the like.
The aryl group of R _{2 to} R ₄ means a monocyclic or polycyclic aryl group. Here, in the case of a polycyclic aryl group, a partially saturated group is included in addition to the fully unsaturated group. Examples thereof include C6-C10 aryl groups such as a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
The arylalkyl group represented by R _{2 to} R ₄ is a group in which the aryl group and the alkyl group are bonded, and includes a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 1-phenyl-n-hexyl group, and a naphthalene. Examples include C1-C10 aryl C1-C6 alkyl groups such as a -1-ylmethyl group, a naphthalen-2-ylethyl group, a 1-naphthalen-2-yl-n-propyl group, and an inden-1-ylmethyl group.

  Specific examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4 -Ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutyl Imidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethyl Ruimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-phenylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) Methyl imidazole, etc. It is.

  Among these, at least one selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 2-phenyl-4-methyl-5-hydroxymethylimidazole. More preferred is an imidazole compound.

  The combination of the inclusion complex of the compound (b1) with the (b2) imidazole compound and / or DBU is not particularly limited as long as it is within the above range.

(Method for producing inclusion complex)
The method for producing an inclusion complex can be obtained by directly mixing the compound (b1) with the imidazole compound (b2) and / or DBU or by mixing in a solvent.
When using a solvent, after adding the said host compound and a guest compound to a solvent, stirring as needed, it can obtain by making it precipitate, after heat-processing or a heat-refluxing process.
When the imidazole compound and / or DBU of (b2) is a low boiling point substance or a substance having a high vapor pressure, the target inclusion complex is obtained by allowing the vapor of these substances to act on the compound of (b1). Obtainable. Moreover, the inclusion complex which consists of three or more components can also be obtained by making two or more types of compounds of (b2) react with the compound of (b1). Further, by first forming an inclusion complex of the compound (b1) with a certain compound (b2), and reacting this inclusion complex with another compound (b2) by the method described above. The target inclusion complex can also be obtained.

The structure of the resulting inclusion complex can be confirmed by thermal analysis (TG and DTA), infrared absorption spectrum (IR), X-ray diffraction pattern, solid NMR spectrum, and the like. The composition of the inclusion complex can be confirmed by thermal analysis, ¹ H-NMR spectrum, high performance liquid chromatography (HPLC), elemental analysis, and the like.

  The amount of the inclusion complex to be used may be the same amount as that of a normal curing agent or curing accelerator, and varies depending on the curing method. In the case of an addition type curing agent in which a curing agent molecule is always incorporated into a cured resin by reacting with an epoxy group, depending on the properties of the required resin, it is usually included in 1 mol of an epoxy group. The inclusion complex is used so that the imidazole compound (curing agent and / or curing accelerator) is about 0.1 to 1.0 mol. In addition, in the case of a polymerization type curing agent or a photoinitiated type curing agent that induces a polymerization addition reaction between oligomers without causing the curing agent molecule to be incorporated into the resin, it is also a curing accelerator. In the case of using as, for example, 1.0 mol or less of the inclusion complex is sufficient for 1 mol of epoxy group. These inclusion complexes can be used alone or in combination of two or more.

3) Other additives The epoxy resin composition of the present invention only needs to contain the component (A) and the component (B). In addition to the component (A) and the component (B), (C) inorganic The epoxy resin composition for semiconductor sealing containing a filler may be sufficient.

  The (C) inorganic filler of the epoxy resin composition for semiconductor solid encapsulation of the present invention is not particularly limited, but for example, silica glass, spherical silica obtained by flame melting, spherical silica produced by a sol-gel method, etc. , Crystalline silica, alumina, talc, ammonium nitride, silicon nitride, magnesia, magnesium silicate, and the like. These may be used alone or in combination of two or more.

(Curing agent or effect accelerator)
In the epoxy resin composition of the present invention, the component (B) is used both as a curing agent and a curing accelerator. When the component (B) is a curing agent, it may further contain a curing accelerator, and when the component (B) is a curing accelerator, it may further contain a curing agent.

  The curing agent that may be contained in addition to the component (B) is not particularly limited as long as it is a compound that reacts with the epoxy group in the epoxy resin to cure the epoxy resin. Similarly, the curing accelerator that may be contained in addition to the component (B) is not particularly limited as long as it is a compound that accelerates the curing reaction. As such a curing agent or curing accelerator, an arbitrary one can be selected from those conventionally used as curing agents or curing accelerators for conventional epoxy resins. For example, amine compounds such as aliphatic amines, alicyclic and heterocyclic amines, aromatic amines, modified amines, imidazole compounds, imidazoline compounds, amide compounds, ester compounds, phenol compounds , Alcohol compounds, thiol compounds, ether compounds, thioether compounds, urea compounds, thiourea compounds, Lewis acid compounds, phosphorus compounds, acid anhydride compounds, onium salt compounds, active silicon compounds An aluminum complex etc. are mentioned.

Specific examples of the curing agent or curing accelerator include the following compounds.
Examples of aliphatic amines include ethylenediamine, trimethylenediamine, triethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine, Trimethylhexamethylenediamine, pentanediamine, bis (2-dimethylaminoethyl) ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo (2,2,2) octane (triethylenediamine), N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylethylenediamine , N, N-dimethylcyclohexylamine, dibutylaminopropylamine, dimethylaminoethoxyethoxy, triethanolamine, dimethylaminohexanol, and the like.

  Examples of alicyclic and heterocyclic amines include piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N, N ′, N ″ -tris (dimethylaminopropyl) hexahydro-s-triazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxyspiro (5,5) undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis (4-aminocyclohexyl) methane , N, N′-dimethylpiperazine, 1,8-diazabicyclo [4.5.0] undecene-7, and the like.

Examples of aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picoline, α- And methylbenzylmethylamine.
Examples of the modified amines include epoxy compound-added polyamine, Michael addition polyamine, Mannich addition polyamine, thiourea addition polyamine, ketone-capped polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, boron trifluoride-piperidine. Complex, boron trifluoride-monoethylamine complex, etc. are mentioned.

  Examples of the imidazole compound include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1- Isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4- Methylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1H-imidazole, 4-methyl-2-phenyl-1H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl- 2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-phenylimidazole, 2-phenylimidazole isocyanuric acid adduct, 2-methylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole 1-cyanoethyl-2-phenyl-4,5-di (2-cyanoethoxy) methylimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 1-benzyl-2-phenylimidazole hydrochloride, etc. Can be mentioned.

Examples of the imidazoline-based compound include 2-methylimidazoline, 2-phenylimidazoline, and the like.
Examples of the amide compound include polyamide obtained by condensation of dimer acid and polyamine.
Examples of the ester compounds include active carbonyl compounds such as aryl and thioaryl esters of carboxylic acids.

Examples of phenol compounds, alcohol compounds, thiol compounds, ether compounds, and thioether compounds include phenol resin curing agents, aralkyl type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins, and phenol novolac resins. , Novolac type phenol resins such as cresol novolac resin, these modified resins, for example, epoxidized or butylated novolac type phenol resin, dicyclopentadiene modified phenol resin, paraxylene modified phenol resin, triphenol alkane type phenol resin, Examples thereof include functional phenol resins. In addition, polyol, polymercaptan, polysulfide, 2- (dimethylaminomethylphenol), 2,4,6-tris (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol tri-2- And ethyl hexyl hydrochloride.
Examples of the urea compound, thiourea compound, and Lewis acid compound include butylated urea, butylated melamine, butylated thiourea, boron trifluoride, and the like.

  Examples of the phosphorus compound include organic phosphine compounds, for example, alkylphosphine such as ethylphosphine and butylphosphine, first phosphine such as phenylphosphine, dialkylphosphine such as dimethylphosphine and dipropylphosphine, diphenylphosphine such as diphenylphosphine, and methylethylphosphine. 2 phosphine; tertiary phosphine such as trimethylphosphine, triethylphosphine, triphenylphosphine, and the like.

  Examples of the acid anhydride compound include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride. Acid, maleic anhydride, tetramethylene maleic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic anhydride, dodecenyl succinic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis (anhydrotrimellitate), glycerol tris (Anhydro trimellitate), methylcyclohexene tetracarboxylic acid anhydride, polyazeline acid anhydride and the like.

  Examples of onium salt compounds and active silicon compounds-aluminum complexes include aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, triphenylsilanol-aluminum complexes, triphenylmethoxysilane-aluminum complexes, and silyl peroxides. An aluminum complex, a triphenylsilanol-tris (salicylide aldehyde) aluminum complex, etc. are mentioned.

  As the curing agent or curing accelerator, it is particularly preferable to use an amine compound, an imidazole compound, or a phenol compound. Among phenolic compounds, it is more preferable to use a phenol resin curing agent.

(Other additives)
In addition to those described above, the epoxy resin composition of the present invention includes a plasticizer, an organic solvent, a reactive diluent, an extender, a filler, a reinforcing agent, a pigment, a flame retardant, a thickener and a release agent as necessary. Various additives such as molds can be blended. Other additives include vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, and γ-methacryloxy. Propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane Silane coupling agents such as N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane; Um, light calcium carbonate, natural silica, synthetic silica, fused silica, kaolin, clay, titanium oxide, barium sulfate, zinc oxide, aluminum hydroxide, magnesium hydroxide, talc, mica, wollastonite, potassium titanate, aluminum borate , Sepiolite, Zonotolite, etc .; NBR, polybutadiene, chloroprene rubber, silicone, crosslinked NBR, crosslinked BR, acrylic, core shell acrylic, urethane rubber, polyester elastomer, functional group-containing liquid NBR, liquid polybutadiene, liquid polyester, liquid polysulfide , Elastomer modifiers such as modified silicones and urethane prepolymers;

  Hexabromocyclodecane, bis (dibromopropyl) tetrabromobisphenol A, tris (dibromopropyl) isocyanurate, tris (tribromoneopentyl) phosphate, decabromodiphenyl oxide, bis (pentabromo) phenylethane, tris (tribromophenoxy) Triazine, ethylenebistetrabromophthalimide, polybromophenylindane, brominated polystyrene, tetrabromobisphenol A polycarbonate, brominated phenylene ethylene oxide, polypentabromobenzyl acrylate, triphenyl phosphate, trigresyl phosphate, trixinyl phosphate, cresyl diphenyl Phosphate, xylyldiphenyl phosphate, cresyl bis (di-2,6-xylenyl) phosphate Fate, 2-ethylhexyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, bisphenol A bis (diphenyl) phosphate, bisphenol A bis (dicresidyl) phosphate, resorcinol bis (di-2,6-xylenyl) phosphate, tris (chloroethyl) phosphate, Tris (chloropropyl) phosphate, tris (diclopropyl) phosphate, tris (tribromopropyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphonate, anionic oxalic acid treated aluminum hydroxide, nitrate treated Aluminum hydroxide, high-temperature hydrothermal treatment aluminum hydroxide, stannic acid surface treatment hydrated metal compound, nickel compound surface treatment magnesium hydroxide, silicone poly -Flame retardants such as surface treated magnesium hydroxide, procovite, multilayer surface treated hydrated metal compound, cationic polymer treated magnesium hydroxide; high density polyethylene, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, nylon 6, 6. Engineering plastics such as polyacetal, polyethersulfone, polyetherimide, polybutylene terephthalate, polyetheretherketone, polycarbonate, polysulfone; plasticizer; n-butyl glycidyl ether, phenyl glycidyl ether, styrene oxide, t-butylphenyl glycidyl Diluents such as ether, dicyclopentadiene diepoxide, phenol, cresol, t-butylphenol; extenders; reinforcing agents; colorants; thickeners; higher fatty acids, Higher fatty acid esters, higher fatty acid calcium, and the like, for example, mold release agents such as carnauba wax and polyethylene wax; The blending amount of these additives is not particularly limited, and the blending amount can be appropriately determined within the limit that the effects of the present invention can be obtained.

  Furthermore, the epoxy resin composition of the present invention may contain other resins in addition to the biphenyl type epoxy resin. Examples of other resins include epoxy resins other than biphenyl type, polyester resins, acrylic resins, silicon resins, polyurethane resins, and the like.

4) Preparation of epoxy resin composition The method for producing an epoxy resin composition for semiconductor encapsulation according to the present invention comprises a mixture of the above-mentioned components and other additives, for example, a kneader, a roll, an extrusion molding machine. Etc. can be used by melting and kneading at a temperature and time at which gelation does not occur, cooling, pulverizing and molding again. Moreover, the manufacturing method of the epoxy resin composition for semiconductor sealing may omit the melt-kneading by heating. The produced epoxy resin composition may be solid or liquid depending on its composition and production method, and is more preferably solid. When used as a solid, the content of the inorganic filler is preferably 70 to 95% with respect to the entire epoxy resin composition.

Although an Example is shown below, this invention is not restrained at all by this Example.
(Preparation of inclusion complex)
The inclusion complex in the present invention was prepared based on a conventionally known method (for example, International Publication No. 2009/037682).

(Manufacture of epoxy resin)
The inclusion complex of the present invention is 0.249 g as imidazole, 12.445 g as YX4000H (manufactured by Mitsubishi Chemical Corporation) as a biphenyl type epoxy resin, 0.249 g as TOWAX131 (manufactured by Toa Kasei Co., Ltd.) as a release agent, and FB− as a filler. 179 spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd.) 179.97 g, LS2940 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.383 g as a silane coupling agent, novolak phenol PSM-4261 OH equivalent 103 (Gunei Chemical Co., Ltd.) as a curing agent 6.701 g (manufactured by company) was heated and kneaded at 100 ° C. for 5 minutes, cooled, and pulverized to produce an epoxy resin composition for semiconductor encapsulation.

(Spiral flow test)
Each epoxy resin composition was compressed into tablets. The lengths of these tablets were injection-molded for 3 minutes under the conditions of 175 ° C. and pressure 70 kgf / cm ² using an Archimedes spiral mold and a transfer molding machine. As the spiral flow value, the initial value and the value after 7 days at 25 ° C. were measured, and the retention rate (%) was calculated from these values.

  The spiral flow test shows that the larger the value, the better the fluidity, but it can be selected as appropriate depending on the scene used. The retention rate indicates that the larger the value, the better the storage stability of the composition. The gel time is a time until the fluidity is lost when the encapsulant is heated at a constant temperature, and can be appropriately selected with respect to the curing characteristics.

(Geltime)
Place an appropriate amount of each epoxy resin composition on a hot plate at 175 ° C with a metal spatula, stir using a metal spatula, the sample is no longer sticky, and the time when it comes off from the hot plate or the stickyness is lost The time was measured.

  Table 1 shows the results when using an inclusion complex using 2-methylimidazole (2MZ) as the (b2) compound.

  Table 2 shows the results when an inclusion complex using 2-ethyl-4-methylimidazole (2E4MZ) as the (b2) compound was used.

  Table 3 shows the results when an inclusion complex using 2-phenyl-4-methyl-5-hydroxyimidazole (2P4MHZ) as the (b2) compound was used.

  Table 4 shows the results when an inclusion complex using 2-undecylimidazole (C11Im) as the (b2) compound was used.

  Table 5 shows the results when (b2) an inclusion complex using DBU as the compound was used.

  As is clear from Tables 1 to 5, the biphenyl type epoxy resin composition containing the inclusion complex of the present invention is significantly more fluid and storable than the composition containing no inclusion complex, and has a TEP. Compared to or better than a composition containing an inclusion complex as a host, it has moderate and efficient curability.

Claims (3)

The epoxy resin composition for semiconductor sealing characterized by containing the following component (A) and a component (B).
(A) biphenyl type epoxy resin,
(B)
(B1) carboxylic acid compounds, 4,4 ′, 4 ″ -trihydroxytriphenylmethane, tris (2-hydroxyethyl) isocyanurate, 2,2 ′, 4,4′-tetrahydroxybenzophenone, and the formula (I )

(In the formula, R represents a hydroxy group, a nitro group, an alkyl group, an alkoxy group, an amino group, a sulfo group, an acetamide group, a hydrazine group, or a carboxyl group, and n represents an integer of 1 to 5. And may be the same or different.) At least one compound selected from the group consisting of pyridine derivatives represented by:
(B2) Formula (II)

[In the formula, _{R 1} represents a hydrogen atom, an alkyl group, aryl group, arylalkyl group or cyanoethyl group C1 _-C10, R 2 to R ₄ is a hydrogen atom, a nitro group, a halogen atom, a C1~C20 An alkyl group, a C1-C20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C1-C20 acyl group is represented. And an at least one selected from the group consisting of 1,8-diazabicyclo [5.4.0] undecene-7.   Furthermore, an inorganic filler is contained, The epoxy resin composition for semiconductor sealing of Claim 1 characterized by the above-mentioned.   (B1) Component is 5-tert-butylisophthalic acid, 5-nitroisophthalic acid, 5-hydroxyisophthalic acid, pyromellitic acid, trimesic acid, 3,5-dihydroxy-2-naphthoic acid, 3,7-dihydroxy- 2-naphthoic acid, trans-1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, fumaric acid, maleic acid, malonic acid, malic acid, succinic acid, 2,6-dihydroxyisonicotinic acid, and 2, The epoxy resin composition for semiconductor encapsulation according to claim 1 or 2, wherein the epoxy resin composition is a member selected from the group consisting of 6-pyridinedicarboxylic acid.