JP5558875B2 - Novel inclusion complex, epoxy resin composition and epoxy resin composition for semiconductor encapsulation - Google Patents

Description

  The present invention relates to a novel inclusion complex, an epoxy resin composition using the same, and an epoxy resin composition for semiconductor encapsulation.

  Epoxy resins are widely used in various fields because they have excellent mechanical and thermal properties. As a curing agent for curing such an epoxy resin, imidazole is used, but the epoxy resin-imidazole mixed liquid has a quick start of curing, and thickens and gels in long-term storage. Has a problem that it cannot be used.

  Therefore, as a curing agent, an imidazolic acid addition salt obtained by adding hydroxybenzoic acid to imidazole (see Patent Document 1) or a tetrakisphenol compound (for example, 1,1,2,2-tetrakis (4-hydroxyphenyl)) The use of an inclusion compound of ethane (hereinafter referred to as TEP) and imidazole has been proposed (see Patent Documents 2 and 3). The present inventors have also proposed a cured resin composition using an inclusion compound of an isophthalic acid compound and imidazole (see Patent Document 4). However, although these have certain effects, they are still not satisfactory.

  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 and LSIs, and electrical components. For the purpose of improvement, it has been proposed to use an inclusion compound containing a imidazole compound or an amine compound as a guest compound and TEP as a host as a curing accelerator (see Patent Document 5). Inclusion of an imidazole compound or an amine compound makes it possible to improve the storage stability of the encapsulant at room temperature compared to the case where these compounds are used alone or in combination, but remarkable progress has been made in recent years. It does not sufficiently satisfy the sealing material composition for the fine specifications of the semiconductor.

Japanese Patent Publication No.4-2638 JP-A-11-71449 Japanese Patent Laid-Open No. 10-324826 International Patent Publication WO2008 / 074427 Pamphlet JP 2004-307545 A

  The object of the present invention is to improve the storage stability (1 liquid stability) by suppressing the curing reaction at a low temperature, and to perform the heat treatment, the inclusion can effectively cure the resin. It is to provide a complex. Also, in order to support dense semiconductor encapsulants, the storage stability of the encapsulant is improved, the fluidity of the encapsulant during sealing is maintained, and the effective curing rate of the encapsulant by heat It aims at providing the epoxy resin composition which implement | achieves. Also provided are curable epoxy resin compositions having excellent storage stability and curing characteristics in compositions containing organic solvents that require storage stability and compositions containing liquid epoxy resins as base resins. The purpose is to do.

  As a result of diligent research to solve the above problems, the present inventors have found that a specific pyridine derivative forms an inclusion complex using the pyridine derivative as a host, and an inclusion using an imidazole compound as a guest compound When a complex is formed, it has been found that the above problem can be solved by using it as a curing agent and / or curing accelerator for an epoxy resin, and the present invention has been completed.

  That is, the present invention is [1] an inclusion complex having at least one pyridine derivative represented by the general formula (I) as a host compound,

(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. The times may be the same or different.)
[2] The inclusion complex according to [1], wherein the compound represented by the general formula (I) is a pyridine derivative represented by the general formula (II).

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and m represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.)

  [3] An inclusion complex containing at least one pyridine derivative represented by the general formula (I) and at least one nitrogen-containing heterocyclic compound,

(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. The times may be the same or different.)
[4] The inclusion complex according to [3], wherein the compound represented by the general formula (I) is a pyridine derivative represented by the general formula (II).

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and m represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.)

The present invention also provides [5] an epoxy resin composition comprising the following component (A) and component (B):
(A) an epoxy resin (B) an inclusion complex containing at least one pyridine derivative represented by the general formula (I) and at least one nitrogen-containing heterocyclic compound

(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. The times may be the same or different.)
[6] The epoxy resin composition according to [5], wherein the compound represented by the general formula (I) of the component (B) is a pyridine derivative represented by the general formula (II).

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and m represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.)

  Furthermore, the present invention provides [7] a curing agent for epoxy resin compositions comprising an inclusion complex containing at least one pyridine derivative represented by the general formula (I) and at least one nitrogen-containing heterocyclic compound, or A curing accelerator,

(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. The times may be the same or different.)
[8] The curing agent or curing accelerator for an epoxy resin composition according to [7], wherein the compound of the general formula (I) is a pyridine derivative represented by the general formula (II).

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and m represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.)

  Furthermore, the present invention is [9] an epoxy resin composition for encapsulating a semiconductor, comprising the composition described in [5] and [6] above.

  The present invention also provides [10] a host compound for inclusion complex comprising a pyridine derivative represented by the general 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. The times may be the same or different.)
[11] The inclusion complex host compound according to [10], wherein the compound represented by the general formula (I) is a pyridine derivative represented by the general formula (II),

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and m represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.)
[12] An inclusion method using a pyridine derivative represented by the general formula (I) as a host compound,

(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. The times may be the same or different.)
[13] The inclusion method according to [12], wherein the compound represented by the general formula (I) is a pyridine derivative represented by the general formula (II).

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and m represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.)

  According to the present invention, a curing agent and a curing accelerator (inclusion complex) that are excellent in storage stability of a resin composition and can effectively cure a resin can be obtained. Further, it is possible to provide an epoxy resin composition for encapsulating a semiconductor which can retain a storage stability and fluidity and has an efficient curability and can be used for a dense semiconductor circuit.

(Host compound)
The inclusion complex of the present invention is not particularly limited as long as it contains at least one pyridine derivative represented by the general formula (I) as a constituent element. Here, the “inclusion complex” refers to a compound in which two or more molecules are bonded by a bond other than a covalent bond, and more preferably, two or three or more molecules are bonded by a bond other than a covalent bond. A bonded crystalline compound. 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 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. The times may be the same or different.)

  Here, 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 aralkyl group. The alkyl group of the substituent may have a hydroxy group or a carboxyl group.

In the formula (I), the alkyl group includes methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, and n-pentyl. C1-6 alkyl groups such as a group and n-hexyl group.
Examples of the alkoxy group include C1-6 alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an s-butoxy group, an i-butoxy group, and a 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 C6-10 aryl groups such as a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
The aralkyl group is a group in which the aryl group and the alkyl group are bonded to each other. Examples include C6-10 aryl C1-6 alkyl groups such as 2-ylethyl group, 1-naphthalen-2-yl-n-propyl group, and inden-1-ylmethyl group.

Here, the pyridine derivative is a host compound, and typical examples thereof 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 are pyridine derivatives represented by the general formula (II), specifically 2,3-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3-hydroxy-2-pyridinecarboxylic acid, 2 , 6-dihydroxyisonicotinic acid.

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and n represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.)

(Guest compound)
The guest compound used in the present invention is not particularly limited as long as it can form an inclusion complex containing the pyridine derivative as a host compound. Specific examples include pyridine, pyrrole, imidazole, pyrazine, pyrazole, 1,2,4-triazole, thiazole, pyrrolidine, imidazoline, pyrroline, oxazole, piperine, pyrimidine, pyridazine, triazine, 5-chloro-2-methyl. And monocyclic nitrogen-containing heterocyclic compounds such as -4-isothiazolin-3-one (hereinafter referred to as CMI) and 1,8-diazabicyclo [5.4.0] undecene-7 (hereinafter referred to as DBU).
Of these, imidazole compounds and nitrogen-containing heterocyclic compounds such as CMI and DBU are preferred.

  In particular, an imidazole compound represented by the general formula (III) is preferable.

Wherein, _{R 2} represents a hydrogen atom, an alkyl group of C1 -C10, an aryl group, an aralkyl group or cyanoethyl _group, R 3 to R ₅ is a hydrogen atom, a nitro group, a halogen atom, an alkyl of C1~C20 A C1-C20 alkyl group, aryl group, aralkyl group or C1-C20 acyl group substituted with a group or a hydroxy group. ]

The alkyl group, aryl group, aralkyl group, and acyl group of R _{2 to} R ₅ may have a substituent, and the substituent includes an alkyl group, a hydroxy group, an alkoxy group, an aryl group, an aralkyl group, and a halogen atom. I can give you. Examples of the aryl group include a phenyl group, and examples of the aralkyl group include a benzyl group.
Methyl group of an alkyl group expressed C1~C10 of R _2, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, butyl group, isobutyl group, s- butyl, 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, hydroxymethyl group, hydroxyethyl group, etc. Is mentioned.
Examples of the C1-C20 alkyl group of R _{3 to} R ₅ 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 ₂ .
Examples of the C1-C20 alkyl group substituted with the hydroxy group of R _{3 to} R ₅ include a hydroxymethyl group or a hydroxyethyl group.
As the C1-C20 acyl group of R _{3 to} R ₅ , 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 _{3 to} R ₅ 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 C6-10 aryl groups such as a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group.
The aralkyl group of R _{3 to} R _{5 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 naphthalene- Examples include C6-10 aryl C1-6 alkyl groups such as 1-ylmethyl group, naphthalen-2-ylethyl group, 1-naphthalen-2-yl-n-propyl group, and 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- Isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4 Dimethylimidazole, 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) Methylimidazole, And the like.

  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.

(New inclusion complex)
The inclusion complex of the present invention can be obtained by directly mixing the pyridine derivative and the guest compound or by mixing them in a solvent.
In the case of using a solvent, it can be obtained by adding the pyridine derivative and guest compound to the solvent, followed by heat treatment or heat reflux treatment with stirring as necessary, followed by precipitation. In particular, a crystalline compound that can be obtained by crystallization is more preferable. The precipitated compound is not particularly limited, and may contain a third component such as a solvent. The third component is preferably 40 mol% or less, more preferably 35 mol% or less. The content is more preferably 20 mol% or less, particularly preferably 10 mol% or less, but most preferably not containing the third component.

The pyridine derivative and the guest compound are dissolved or suspended in a solvent, but it is preferable that both are dissolved in the solvent. When dissolving in a solvent, the entire amount does not need to be dissolved in the solvent, and at least a part of the amount only needs to be dissolved in the solvent. As the solvent, water, methanol, ethanol, ethyl acetate, methyl acetate, diethyl ether, dimethyl ether, acetone, methyl ethyl ketone, acetonitrile and the like can be used. In particular, it is preferable to mix the solution after dissolving the pyridine derivative and the guest compound in the solvent.
The heat treatment is not particularly limited. For example, the heat treatment can be performed within a range of 40 to 120 ° C., and preferably heating and refluxing.

  The addition ratio of the pyridine derivative and the guest compound is not particularly limited as long as an inclusion complex can be formed, but the guest compound is 0.1 to 5.0 mol with respect to 1 mol of the pyridine derivative. It is preferably 0.5 to 3.0 mol.

  The step after heating by dissolving or suspending the pyridine derivative and the guest compound in a solvent is not particularly limited as long as a solid compound containing the pyridine derivative and the guest compound as constituent elements can be obtained. The solid compound may be precipitated by stopping the heating, but it is preferable to leave it overnight at room temperature after heating. Moreover, you may make it settle by leaving still at 5 degrees C or less suitably. After precipitating the solid compound, the target compound is obtained by, for example, filtering and drying. Depending on the type, a crystalline compound can 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.

(Epoxy resin composition)
The epoxy resin composition of the present invention is
(A) an inclusion complex containing an epoxy resin and (B) at least one pyridine derivative represented by the general formula (I) and at least one nitrogen-containing heterocyclic compound

(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. The time may be the same or different.), And is not particularly limited.

  As the epoxy resin of the component (A), various conventionally known polyepoxy compounds can be used. For example, bis (4-hydroxyphenyl) propane diglycidyl ether, bis (4-hydroxy-3,5-dibromophenyl) propanedi Glycidyl ether, bis (4-hydroxyphenyl) ethane diglycidyl ether, bis (4-hydroxyphenyl) methane diglycidyl ether, resorcinol diglycidyl ether, phloroglicinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tetraglycidyl benzophenone, Bisresorcinol tetraglycidyl ether, tetramethylbisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropropane Glycidyl ether, 1,3-bis [1- (2,3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoroethyl] benzene, 1,4-bis [1- (2, 3-epoxypropoxy) -1-trifluoromethyl-2,2,2-trifluoromethyl] benzene, 4,4′-bis (2,3-epoxypropoxy) octafluorobiphenyl, phenol novolac bisepoxy compound, etc. Aromatic glycidyl ether compounds, alicyclic diepoxy acetals, alicyclic diepoxy adipates, alicyclic diepoxy carboxylates, vinylcyclohexene dioxide, and other alicyclic polyepoxy compounds, diglycidyl phthalate, diglycidyl tetrahydro Phthalate, diglycidyl hexahydro Glycidyl ester compounds such as tarate, dimethyl glycidyl phthalate, dimethyl glycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidyl cyclopentane-1,3-dicarboxylate, dimer acid glycidyl ester, diglycidyl aniline, diglycidyl toluidine, Examples thereof include glycidylamine compounds such as triglycidylaminophenol, tetraglycidyldiaminodiphenylmethane, diglycidyltribromoaniline, and heterocyclic epoxy compounds such as diglycidylhydantoin, glycidylglycidoxyalkylhydantoin, and triglycidylisocyanurate.

Component (B) is an inclusion complex containing at least one pyridine derivative and at least one nitrogen-containing heterocyclic compound, as described above.
As the pyridine derivative which is a host compound, a pyridine derivative represented by the general formula (II) is particularly preferable. Specifically, 2,3-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3-hydroxy-2- Examples thereof include pyridinecarboxylic acid and 2,6-dihydroxyisonicotinic acid.

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and n represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.)

  The guest compound is preferably a nitrogen-containing heterocyclic compound such as an imidazole compound or DBU. Among them, for semiconductor sealing use, it is selected from the group consisting of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and DBU. At least one of them is particularly preferred.

  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 depends 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 curing agent and / or curing accelerator (guest compound) 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 the epoxy group. That is, the proportion of the component (A) and the component (B) is 0.01 to 3.0% of the nitrogen-containing heterocyclic compound in the component (B) with respect to 1 mol of the epoxy ring of the epoxy resin as the component (A). It is preferable to contain by mole, more preferably from 0.1 to 1.0 mole, and still more preferably from 0.3 to 1.0 mole. (B) A component may be used individually by 1 type, or may use 2 or more types together.

  Although the average particle diameter D50 of the inclusion complex of (B) component is not specifically limited, Usually, it is about 0.01-80 micrometers, Preferably it is the range of about 0.01-30 micrometers.

  Although the epoxy resin composition of this invention can be manufactured by mixing (A) component and (B) component, it is normally heated at about 60-100 degreeC so that sufficient mixing state may be formed. Mix. In the production of an epoxy resin, the stability of one liquid at this temperature is important. The method for producing an epoxy curable resin is not particularly limited as long as it is a method of curing the epoxy resin composition by heat treatment. Usually, the heating temperature of the heat treatment is 60 to 250 ° C., Preferably it is 100-200 degreeC, and it is preferable to harden | cure at such temperature for a short time.

  In the epoxy resin composition of the present invention, the component (B) is used as a curing agent and a curing accelerator as described above.

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 and the 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, 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.

(Resin composition / additive)
In addition to the foregoing, 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 epoxy resin. Examples of other resins include polyester resins, acrylic resins, silicone resins, polyurethane resins, and the like.

  The epoxy resin composition of the present invention is used for curing an epoxy resin, for example, an epoxy resin adhesive, a semiconductor sealing material, a laminate for a printed wiring board, a varnish, a powder coating material, a casting material, an ink, etc. Can be suitably used.

  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, is the curing agent and the epoxy resin. 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.

(Epoxy resin composition for semiconductor encapsulation)
The epoxy resin composition for semiconductor encapsulation of this invention should just contain the said (A) component and (B) component which are the said epoxy resin compositions, and also in (A) component and (B) component In addition, it may be an epoxy resin composition for solid semiconductor encapsulation containing (D) an inorganic filler.

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

  The method for producing an epoxy resin composition for semiconductor encapsulation according to the present invention comprises a mixture comprising a predetermined amount of each of the above components and other additives, for example, gelation using a kneader, a roll, an extrusion molding machine or the like. It can be manufactured by melting and kneading at a temperature and time where no occurrence occurs, 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.
[Synthesis of inclusion complex]
(Synthesis method 1)
2,3-pyridinedicarboxylic acid (4 g, 23.9 mmol) and 2-methylimidazole (2MZ 1.96 g, 23.9 mmol) were mixed in 30 ml of ethyl acetate solution, stirred and heated to reflux. Thereafter, heating was stopped and cooling was performed. After allowing to cool overnight at room temperature, the precipitated crystals were filtered and dried in vacuo. The obtained 2,3-pyridinedicarboxylic acid-2MZ inclusion complex was confirmed to be an inclusion complex having an inclusion ratio of 1: 1 by ¹ H-NMR, TG-DTA, and XRD (Example 1).
In the same manner, Examples 2, 3, 4, 5, 9, 12, 13, 14, 15, 16, 17, 18, 19, 20, Comparative Example 1-1 and Comparative Example 3-1 were synthesized.

(Synthesis method 2)
Examples 10 and 11 and Comparative Example 2-1 were synthesized in the same manner as in Synthesis Method 1 except that methanol was used instead of ethyl acetate as the solvent.

(Synthesis method 3)
A suitable amount of acetone was added to 2,6-pyridinedicarboxylic acid (12.06 g, 72.2 mmol) and 2-ethyl-4-methylimidazole (2E4MZ 3.96 g, 35.9 mmol) and mixed in a mortar. The powder obtained by evaporation of acetone was vacuum dried. The obtained 2,6-pyridinedicarboxylic acid-2E4MZ inclusion complex was confirmed to be an inclusion complex having an inclusion ratio of 2: 1 by ¹ H-NMR, TG-DTA and XRD (Example 6).
Example 7 was synthesized in the same manner.

(Synthesis method 4)
1,1,2,2-Tetrakis (4-hydroxyphenyl) ethane (TEP: 66.67 g, 167 mmol) was dispersed in 1600 ml of ethyl acetate and heated to reflux. A DBU (25.42 g, 167 mmol) ethyl acetate solution was added dropwise under reflux. After completion of dropping, the mixture was stirred for 3 hours under reflux. Then, it cooled to room temperature, the deposited crystal | crystallization was filtered and vacuum-dried at 80 degreeC. The obtained TEP-DBU inclusion complex was confirmed to be an inclusion complex having an inclusion ratio of 1: 1 by ¹ H-NMR, TG-DTA, and XRD (Comparative Example 5-1). Example 8 was synthesized in the same manner except that ethyl acetate was changed to methanol.

[Manufacture of epoxy resin]
Examples 1-20 and Comparative Examples 1-1 to 5-1 were used as curing catalysts and blended with the compositions shown in Table 1, followed by heat-kneading at 100 ° C. for 5 minutes, cooling, and pulverizing. Thus, an epoxy resin composition for semiconductor encapsulation was produced. In addition, the compounding quantity of each composition in a table | surface is represented by the mass part.

(Spiral flow test)
The epoxy resin composition of each example was tableted to form a tablet. 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 168 hours at 25 ° C. were measured, and the retention rate (%) was calculated from these values.
Only in the case of Examples 9 to 12 and Comparative Examples 3-1 and 3-2, the spiral flow value after 30 hours at 30 ° C. was measured to obtain the retention rate. The results are shown in Table 1.

(Geltime)
When an appropriate amount of the epoxy resin composition of each example is placed on a hot plate at 175 ° C. with a metal spatula, and stirred with a metal spatula, the sample is no longer sticky and peels off from the hot plate, or sticky The time when the disappearance was measured.

In addition, o-cresol novolak epoxy resin is EOCN-1020-55 epoxy equivalent 191-201 (made by Nippon Kayaku Co., Ltd.), novolak phenol is PSM-4261 OH equivalent 103 (manufactured by Gunei Chemical Industry Co., Ltd.), release The mold used was TOWAX 131 (manufactured by Toa Kasei Co., Ltd.), the coupling agent was LS2940 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the silica was Denka FB-940 spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd.).
However, in Examples 9 to 12 and Comparative Examples 3-1 and 3-2, the o-cresol novolac epoxy resin was ESCN195LL epoxy equivalent 195 (manufactured by Sumitomo Chemical Co., Ltd.), and novolac phenol was PSM-4261 OH equivalent. 103 (manufactured by Gunei Chemical Industry Co., Ltd.), release agent is refined granular carnava (manufactured by Toa Kasei Co., Ltd.), coupling agent is KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.), and silica is Denka FB. -940 spherical silica (manufactured by Denki Kagaku Kogyo Co., Ltd.) was used.

  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 sealing material is heated at a constant temperature, and can be appropriately selected with respect to the curing characteristics.

  The composition of the present invention is significantly more fluid and storable than Table 1 in comparison with a composition containing no inclusion complex, and equivalent or more than a composition containing an inclusion complex hosted by TEP. At the same time, it has moderate and efficient curability.

[Solvent epoxy resin]
The concentration of imidazole dissolved in methyl ethyl ketone (MEK) of the inclusion complexes of Example 2 and Example 4 is shown in Table 2. According to this, it can be seen that the clathrate complex of the present invention has an extremely low concentration as compared with the case where TEP and the clathrate are not clathrated, and is suitable as a one-pack type epoxy resin composition that requires storage stability.
The dissolution concentration was measured as follows.
An appropriate amount of sample was added to 4 ml of MEK, shaken at 25 ° C., and the sample was added until the sample did not dissolve. The sample solution was filtered through a 0.2 μm filter, and the imidazole concentration (mg / L) in the solution was determined by HPLC. (Analytical column: Finepak SIL C18S manufactured by JASCO Corporation, mobile phase: aqueous sodium phosphate solution / methanol = 60/40)

Claims (6)

Formula (II)

( Wherein R ₁ represents a carboxyl group or a hydroxy group, and m represents an integer of 1 to 4. When R ₁ is plural, they may be the same or different.) Seeds and
Formula (III)

Wherein, _{R 2} represents a hydrogen atom, an alkyl group of C1 -C10, an aryl group, an aralkyl group or cyanoethyl _group, R 3 to R ₅ is a hydrogen atom, a nitro group, a halogen atom, an alkyl of C1~C20 A C1-C20 alkyl group, aryl group, aralkyl group or C1-C20 acyl group substituted with a group or a hydroxy group. An inclusion complex containing at least one selected from the group consisting of 1,8-diazabicyclo [5.4.0] undecene-7 (provided that the pyridine derivative is 3-hydroxy-2-pyridine) In the case of a carboxylic acid, it is limited to the combination with 1,8-diazabicyclo [5.4.0] undecene-7) . The epoxy resin composition characterized by containing the following (A) component and (B) component.
(A) Epoxy resin (B) General 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. The times may be the same or different.)
At least one and in represented by pyridine derivatives
Formula (III)

Wherein, _{R 2} represents a hydrogen atom, an alkyl group of C1 -C10, an aryl group, an aralkyl group or cyanoethyl _group, R 3 to R ₅ is a hydrogen atom, a nitro group, a halogen atom, an alkyl of C1~C20 A C1-C20 alkyl group, aryl group, aralkyl group or C1-C20 acyl group substituted with a group or a hydroxy group. And an at least one selected from the group consisting of 1,8-diazabicyclo [5.4.0] undecene-7 The epoxy resin composition according to claim 2, wherein the compound represented by the general formula (I) of the component (B) is a pyridine derivative represented by the general formula (II).

(In the formula, R ₁ represents a carboxyl group or a hydroxy group, and m represents an integer of 0 to 4. When R ₁ is plural, they may be the same or different.) 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. The times may be the same or different.)
At least one pyridine derivative represented by
Formula (III)

Wherein, _{R 2} represents a hydrogen atom, an alkyl group of C1 -C10, an aryl group, an aralkyl group or cyanoethyl _group, R 3 to R ₅ is a hydrogen atom, a nitro group, a halogen atom, an alkyl of C1~C20 A C1-C20 alkyl group, aryl group, aralkyl group or C1-C20 acyl group substituted with a group or a hydroxy group. ] The hardening | curing agent for epoxy resin compositions containing the inclusion complex containing at least 1 sort (s) chosen from the group which consists of the imidazole compound represented by this, and 1,8- diazabicyclo [5.4.0] undecene-7 , or hardening acceleration | stimulation Agent. Compounds of general formula (I) are represented by general formula (II)

(Wherein R ₁ represents a carboxyl group or a hydroxy group, m represents an integer of 0 to 4, and when R ₁ is plural, they may be the same or different). 4. Curing agent or curing accelerator for epoxy resin composition according to 4 . Semiconductor encapsulating epoxy resin composition characterized by containing the claims 2 or 3 composition.