JP2018203916A - Epoxy resin composition - Google Patents

Abstract

To provide an epoxy resin composition which is excellent in fluidity when being filled into a mold and has excellent curability, while not deteriorating the electrical reliability.SOLUTION: An epoxy resin composition contains: an epoxy resin (E); a compound (P) having 2 or more phenolic hydroxyl groups in each molecule; and a curing accelerator (Q). The curing accelerator (Q) contains a quaternized amidine salt (S) comprising a cyclic cation (A) having an amidine group and an anion (B) represented by a formula (7).SELECTED DRAWING: None

Description

  The present invention relates to an epoxy resin composition. More specifically, the present invention relates to an epoxy resin composition containing an epoxy resin curing accelerator composed of a salt having an amidine group, which is suitable for producing an epoxy resin-based encapsulant for electronic parts such as semiconductors.

Conventionally, an epoxy resin is excellent in moldability and electrical properties of a cured product, and is used, for example, as a sealing material for electronic parts such as a semiconductor sealing material. As the sealing material resin, epoxy resins using phenol novolacs as a curing agent and blending a large amount of fillers are widely used. In recent years, there has been a strong demand for improving the moldability of a sealing material and the reliability of a sealed semiconductor, as the semiconductor is highly integrated, thinned, or improved in mounting method. In response to this demand, the role of a curing accelerator, which is a component of a sealing material, is also increasing.
As a curing accelerator for these epoxy resins, an amine compound and triphenylphosphine are generally used. There is a problem that the fluidity and storage stability of the blend are poor.

As an improvement of this problem, for example, quaternized phosphonium salts and quaternary amine salts of TPP (see Patent Documents 1 and 2) have been proposed.

However, in a sealing material composition containing an inorganic filler at a high concentration, when the quaternary salt is used as a curing accelerator, the viscosity of the liquid mixture obtained by heating and melting a mixture of an epoxy resin, a curing agent, and a curing accelerator is Therefore, when the mold is filled, the wiring of the semiconductor chip is washed away, the viscosity increases before the composition reaches every corner, and unfilled parts are formed.

On the other hand, there is concern that quaternized phosphonium salts and quaternary amine salts remain in the cured resin as ionic components, which adversely affects electrical reliability.

JP 2004-256663 A JP 2005-162944 A

  Then, it aims at providing the epoxy resin composition which is excellent in fluidity | liquidity at the time of mold filling, is high in catalyst activity, is excellent in curability, and does not make electric reliability worse.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention includes an epoxy resin (E), a compound (P) having two or more phenolic hydroxyl groups in one molecule, and a curing accelerator (Q). A cyclic cation (A) having an amidine group represented by general formula (1), (2), (3) or (4) and an anion represented by the following general formula (5), (6) or (7) An epoxy resin composition comprising a quaternized amidine salt (S) comprising (B).

[In Formula (1), R1 represents a C1-C16 substituted or unsubstituted alkyl group, or a benzyl group. ]

[In Formula (2), R2 represents a C1-C16 substituted or unsubstituted alkyl group, or a benzyl group. ]

[In Formula (3), R3 and R5 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms or a benzyl group, and R4 represents hydrogen, a substituted or unsubstituted group having 1 to 16 carbon atoms, or An unsubstituted alkyl group or a phenyl group is represented, and R6 and R7 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a hydroxyl group, hydrogen, a hydroxymethyl group, or a hydroxyethyl group. ]

[In Formula (4), R8 and R10 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms or a benzyl group, and R9 represents hydrogen, a substituted or unsubstituted group having 1 to 16 carbon atoms, or It represents an unsubstituted alkyl group or a phenyl group, and R11 and R12 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a hydroxyl group, hydrogen, a hydroxymethyl group, or a hydroxyethyl group. ]

[In the formula (5), R13 and R15 are groups formed by proton-donating substituents releasing protons, and they may be the same or different from each other. It binds to a silicon atom to form a chelate structure. R14 is an organic group that binds to R13 and R15. R17 and R19 are groups formed by proton-donating substituents releasing protons, and R17 and R19 in the same molecule are combined with a silicon atom to form a chelate structure. R18 is an organic group that binds to R17 and R19. R14 and R18 may be the same or different from each other, and R13, R15, R17 and R19 may be the same or different from each other. R16 represents an organic group having a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

[In the formula (6), R20 and R22 are groups formed by proton-donating substituents releasing protons, and they may be the same or different from each other. It binds to a silicon atom to form a chelate structure. R21 is an organic group that binds to R20 and R22. R23 and R25 are groups formed by proton-donating substituents releasing protons, and R23 and R25 in the same molecule bind to a silicon atom to form a chelate structure. R24 is an organic group that binds to R23 and R25. R26 and R28 are groups formed by proton-donating substituents releasing protons, and R26 and R28 in the same molecule bind to a silicon atom to form a chelate structure. R27 is an organic group that binds to R26 and R28. R21, R24, and R27 may be the same as or different from each other, and R20, R22, R23, R25, R26, and R28 may be the same as or different from each other. ]

[In the formula (7), R29 and R31 are groups formed by proton-donating substituents releasing protons, and they may be the same or different, and R29 and R31 in the same molecule are It combines with a boron atom to form a chelate structure. R30 is an organic group that binds to R29 and R31. R32 and R34 are groups formed by proton-donating substituents releasing protons, and R32 and R34 in the same molecule are combined with a boron atom to form a chelate structure. R33 is an organic group that binds to R32 and R34. R30 and R33 may be the same as or different from each other, and R29, R31, R32, and R34 may be the same as or different from each other. ]

Since the epoxy resin composition of the present invention has the curing accelerator (Q), the ionic bond between the cyclic cation (A) having the amidine group and the anion is strong, whereby the epoxy resin, the curing agent and the curing accelerator At the compounding temperature at which the mixture is heated and melted, the quaternary salt (S) is difficult to dissociate, so that the curing reaction can be suppressed, and the fluidity during mold filling is excellent.

In addition, carbon between nitrogen atoms of a quaternary amidine structure is easily attacked by hydroxide ions or alkoxy group ions and loses ionicity (see the following reaction formula, reference: Sanyo Kasei News (2007), No. 442). ), A cured product with less ionicity, and electrical reliability and low water absorption are improved.

The silicate anion portion is not dissociated in a low temperature region, and the promotion of the curing reaction can be suppressed.
Furthermore, the anion part has higher thermal stability than the chelate structure, and at the compounding temperature at which the mixture of the epoxy resin, the curing agent and the curing accelerator is heated and melted, the anion part is not dissociated and does not accelerate the curing reaction. The characteristics excellent in fluidity and storage stability of the epoxy resin composition can be imparted simultaneously. Further, since the blending temperature can be set high, an epoxy resin having a high melting point and a high softening point, a curing agent, an additive, other types of resins and compounds can be blended. In the curing reaction, the chelate bond is cleaved and dissociated by heating to release an anion having high activity and promote the curing reaction, so that excellent fluidity and curability can be simultaneously imparted. (Reference: JP 2005-298794 A)

For this reason, the epoxy resin composition of the present invention is excellent in fluidity at the time of mold filling, excellent in curability, and excellent in electrical reliability of the cured product. It is suitable for manufacturing.

  Hereinafter, preferred embodiments of the epoxy resin composition of the present invention will be described.

  Hereinafter, each component in the epoxy resin composition of this invention is demonstrated one by one.

  The epoxy resin (E) used in the present invention is a monomer, oligomer or polymer in general having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, a phenol novolak type Epoxy resin, cresol novolac type epoxy resin, hydroquinone type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, triphenolmethane type epoxy resin, alkyl-modified triphenolmethane type epoxy Resin, triazine nucleus-containing epoxy resin, dicyclopentadiene modified phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, naphthol type epoxy resin, naphtha Emission type epoxy resin, naphthol aralkyl type epoxy resins. Having a phenylene and / or biphenylene skeleton, it no problem is used singly or in admixture.

As an example of an epoxy resin (E), DIC Corporation make: HP-4032, HP-4700, HP-7200, HP-820, HP-4770, HP-5000, EXA-850, EXA-830, EXA- 1514, EXA-4850 series; manufactured by Nippon Kayaku Co., Ltd .: EPPN-201L, BREN-105, EPPN-502H, EOCN-1020, NC-2000-L, XD-1000, NC-7000L, NC-7300L, EPPN -501H, NC-3000; Mitsubishi Chemical Corporation: XY-4000 and the like.

  The compound (P) having two or more phenolic hydroxyl groups in one molecule used in the present invention is a monomer, oligomer or polymer in general having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are particularly Without limitation, for example, phenol novolak resin, cresol novolak resin, triphenolmethane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin having phenylene and / or biphenylene skeleton, phenylene and Examples thereof include a naphthol aralkyl resin having a biphenylene skeleton and a bisphenol compound, and these may be used alone or in combination.

Examples of the compound (P) having two or more phenolic hydroxyl groups include: HF series, MEH-7500 series, MEH-7800 series, MEH-7801 series, MEH-7600 series, MEH-8000 manufactured by Meiwa Kasei Co., Ltd. Series; manufactured by Honshu Chemical Industry Co., Ltd .: TriP-PA, BisP-TMC, BisP-AP, OC-BP, TekP-4HBPA, CyRS-PRD4, and the like.

The curing accelerator (Q) used in the present invention is characterized by containing a quaternary salt (S) composed of a cyclic cation (A) having an amidine group and a chelate anion (B).

The cyclic cation (A) having an amidine group is an essential component for promoting the reaction between the epoxy resin and the curing agent, and is represented by the following general formulas (1), (2), (3), or (4). Is done.

[In Formula (1), R1 represents a C1-C16 substituted or unsubstituted alkyl group, or a benzyl group. ]

Examples of the alkyl group having 1 to 16 carbon atoms constituting R1 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n- Examples include heptyl group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, dodecyl group, hexadecyl group and the like.

Examples of the substituent include a carboxylic acid group, a phenol group, an amino group, an amide group, an ester group, and a hydroxy group.

  R1 is preferably an alkyl group having 1 to 4 carbon atoms and a benzyl group, more preferably a methyl group or an ethyl group, from the viewpoint of curability and the ease of synthesis.

[In Formula (2), R2 represents a C1-C16 substituted or unsubstituted alkyl group, or a benzyl group. ]

Examples of the alkyl group having 1 to 16 carbon atoms constituting R2 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n- Examples include heptyl group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, dodecyl group, hexadecyl group and the like.

Examples of the substituent include a carboxylic acid group, a phenol group, an amino group, an amide group, an ester group, and a hydroxy group.

  R2 is preferably an alkyl group having 1 to 4 carbon atoms and a benzyl group, more preferably a methyl group or an ethyl group, from the viewpoint of curability and the ease of synthesis.

[In Formula (3), R3 and R5 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms or a benzyl group, and R4 represents hydrogen, a substituted or unsubstituted group having 1 to 16 carbon atoms, or Represents an unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and R6 and R7 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a hydroxyl group, hydrogen, a hydroxymethyl group, or a hydroxy group Represents an ethyl group. ]

Examples of the alkyl group having 1 to 16 carbon atoms constituting R3 or R5 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and tert-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group N-heptyl group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, dodecyl group, hexadecyl group and the like.

Examples of the alkyl group having 1 to 16 carbon atoms constituting R4 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n- Examples include heptyl group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, dodecyl group, hexadecyl group and the like.

Examples of the alkyl group having 1 to 16 carbon atoms constituting R6 or R7 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group N-heptyl group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, dodecyl group, hexadecyl group and the like.

Examples of the substituent include a carboxylic acid group, a phenol group, an amino group, an amide group, an ester group, and a hydroxy group.

[In Formula (4), R8 and R10 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms or a benzyl group, and R9 represents hydrogen, a substituted or unsubstituted group having 1 to 16 carbon atoms, or It represents an unsubstituted alkyl group or a phenyl group, and R11 and R12 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a hydroxyl group, hydrogen, a hydroxymethyl group, or a hydroxyethyl group. ]

Examples of the alkyl group having 1 to 16 carbon atoms constituting R8 or R10 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group N-heptyl group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, dodecyl group, hexadecyl group and the like.

Examples of the alkyl group having 1 to 16 carbon atoms constituting R9 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -Pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n- Examples include heptyl group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, dodecyl group, hexadecyl group and the like.

Examples of the alkyl group having 1 to 16 carbon atoms constituting R11 or R12 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl. Group, n-pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group N-heptyl group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, dodecyl group, hexadecyl group and the like.

Examples of the substituent include a carboxylic acid group, a phenol group, an amino group, an amide group, an ester group, and a hydroxy group.

The method for synthesizing the cyclic cation (A) having an amidine group is not particularly limited. For example, the reaction using the alkyl carbonate (A1) of the cyclic cation (A) having an amidine group and the ring having an amidine group. It is obtained by a reaction using a hydroxide (A2) of the formula cation (A).

The alkyl carbonate (A1) of the cyclic cation (A) having an amidine group can be obtained, for example, by reacting a corresponding cyclic compound having an amidine group with a carbonic acid diester. The production conditions are 10 to 200 hours in an autoclave at a temperature of 50 to 150 ° C., and a reaction solvent is preferably used in order to complete the reaction quickly and with a good yield. Although it does not specifically limit as a reaction solvent, Methanol, ethanol, etc. are preferable. The amount of the solvent is not particularly limited.

Examples of the cyclic compound having a corresponding amidine group include DBU compounds, imidazoline compounds, imidazole compounds, and the like. The carbonic acid diester is not particularly limited as long as it is a known one, and specifically, diethyl carbonate, dimethyl carbonate, dibutyl carbonate, diphenyl carbonate and the like are used.

  Examples of the hydroxide (A2) of the cyclic cation (A) having an amidine group include a cyclic compound having a corresponding amidine group and a halogenated (bromine or chlorine) alkyl, or a halogenated (bromine or chlorine). After reacting with toluene, it is obtained by salt exchange with an inorganic alkali. The production conditions are a temperature of −10 to 150 ° C. and a time of 1 to 20 hours, and it is preferable to use a reaction solvent in order to complete the reaction quickly with a good yield. Although it does not specifically limit as a reaction solvent, Methanol, ethanol, etc. are preferable. The amount of the solvent is not particularly limited.

Examples of the cyclic compound having a corresponding amidine group include those described above. Examples of the halogenated alkyl include ethyl bromide, butyl chloride, 2-ethylhexyl bromide, 2-butylethanol, 2-chloropropanol and the like, and examples of the halogenated toluene include brobenzyl bromide.
Examples of the inorganic alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, and aluminum hydroxide.

The anion (B) of the present invention is an essential component for improving the fluidity after melt-kneading and curing at the curing temperature after mold filling, and the following general formula (5), (6) or (7) It is represented by

[In the formula (5), R13 and R15 are groups formed by proton-donating substituents releasing protons, and they may be the same or different from each other. It binds to a silicon atom to form a chelate structure. R14 is an organic group that binds to R13 and R15. R17 and R19 are groups formed by proton-donating substituents releasing protons, and R17 and R19 in the same molecule are combined with a silicon atom to form a chelate structure. R18 is an organic group that binds to R17 and R19. R14 and R18 may be the same or different from each other, and R13, R15, R17 and R19 may be the same or different from each other. R16 represents an organic group having a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

[In the formula (6), R20 and R22 are groups formed by proton-donating substituents releasing protons, and they may be the same or different from each other. It binds to a silicon atom to form a chelate structure. R21 is an organic group that binds to R20 and R22. R23 and R25 are groups formed by proton-donating substituents releasing protons, and R23 and R25 in the same molecule bind to a silicon atom to form a chelate structure. R24 is an organic group that binds to R23 and R25. R26 and R28 are groups formed by proton-donating substituents releasing protons, and R26 and R28 in the same molecule bind to a silicon atom to form a chelate structure. R27 is an organic group that binds to R26 and R28. R21, R24, and R27 may be the same as or different from each other, and R20, R22, R23, R25, R26, and R28 may be the same as or different from each other. ]

[In the formula (7), R29 and R31 are groups formed by proton-donating substituents releasing protons, and they may be the same or different, and R29 and R31 in the same molecule are It combines with a boron atom to form a chelate structure. R30 is an organic group that binds to R29 and R31. R32 and R34 are groups formed by proton-donating substituents releasing protons, and R32 and R34 in the same molecule are combined with a boron atom to form a chelate structure. R33 is an organic group that binds to R32 and R34. R30 and R33 may be the same as or different from each other, and R29, R31, R32, and R34 may be the same as or different from each other. ]

As the proton donor of the proton donating substituents in the formulas (5) to (7), catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′- Binaphthol, pyrogallol, trihydroxybenzoic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid A phenolic compound selected from the group consisting of 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin; and urea, 1-methylurea, 1,3-dimethyl Urea, 1,3-diaminourea, 1,3-dimethylolurea, allopha Amidochio urea, 1-methyl thiourea, 1,3-dimethyl thiourea, thiosemicarbazide, thiocarbohydrazide, 4-methyl thiosemicarbazide, urea compound selected from the group of Guaniruchio urea are preferred.

As a method for synthesizing the quaternized amidine salt (S) of the present invention, for example, the cation (A) compound, alkoxysilanes (or boric acid, boric acid esters), and silicon atoms (or An example is a method in which a boron atom is reacted with the proton donor capable of forming a chelate bond at a constant ratio.

  Examples of the alkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, and hexyltriethoxysilane. , And tetraedoxysilane.

In order to facilitate mixing with the other components of the epoxy resin composition, the curing accelerator (Q) is pulverized by a method of lowering the softening point by making a master batch with a low viscosity phenol resin or a low molecular phenol compound. A method of making it into powder may be performed.
Examples of the low viscosity phenol resin include phenol novolac resin, cresol novolac resin, phenol aralkyl resin and the like. A known method can be used as a master batch method.
Examples of the low molecular weight phenol compound include bisphenol A and bisphenol F. A known method can be used as a master batch method.

The softening point of a hardening accelerator (Q) is 70-180 degreeC normally, Preferably it is 80-140 degreeC, More preferably, it is 90-130 degreeC. If the temperature is lower than 70 ° C., it is not preferable because fusion during pulverization or blocking during storage of the powdered accelerator is likely to occur, and if it exceeds 180 ° C., the curing accelerator is melted with the epoxy resin. This is because they cannot be mixed and become non-uniform, which tends to cause curing failure.

As a method of pulverizing into a powder, for example, a powdery curing accelerator can be obtained by pulverization with an impact pulverizer or the like. In use, the particle size of the powdery curing accelerator is preferably 100% or more (measured by an air jet sieve method or the like) 95% or more. This is because if it is less than 95%, uniform dissolution in the epoxy resin composition tends to be hindered, which causes poor curing.

The epoxy resin composition of the present invention is finally cured to obtain a cured epoxy resin. Although the compounding quantity of a hardening accelerator (Q) is adjusted according to the reactivity of an epoxy resin or a hardening | curing agent, it is 1-25 weight part normally with respect to 100 weight part of epoxy resins, Preferably it is 2-20 weight part. . What is necessary is just to set the optimal compounding quantity according to the required hardening characteristic.

The compounding ratio of the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule is not particularly limited, but the compound (E) is equivalent to 1 equivalent of the epoxy group of the epoxy resin (E). The phenolic hydroxyl group of P) is preferably used in an amount of 0.5 to 2 equivalents, and more preferably 0.7 to 1.5 equivalents. Thereby, various characteristics improve more, maintaining the balance of the various characteristics of an epoxy resin composition to a suitable thing.

The epoxy resin composition of the present invention preferably further contains an inorganic filler (H).
When the epoxy resin composition of the present invention is used for sealing electronic components such as semiconductor elements, it is blended (mixed) in the epoxy resin composition for the purpose of improving the solder resistance of the resulting semiconductor device. There is no particular limitation on the type, and those generally used for sealing materials can be used.

The content of the inorganic filler (H) is not particularly limited, but per 100 parts by weight of the total amount of the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule, It is preferably 200 to 2400 parts by weight, and more preferably 400 to 1400 parts by weight. The content of the inorganic filler (H) can be used outside the above range, but if it is less than the lower limit, the reinforcing effect by the inorganic filler (H) may not be sufficiently exhibited, while the inorganic filler ( When the content of H) exceeds the upper limit, the fluidity of the epoxy resin composition is lowered, and there is a possibility that poor filling or the like may occur when the epoxy resin composition is molded (for example, during manufacturing of a semiconductor device). is there.

The epoxy resin composition of the present invention preferably further contains another functional compound (functional additive).

Examples of functional additives include 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and phenyltrimethoxysilane. Coupling agents represented by alkoxysilanes such as alkoxysilanes, titanate esters, and aluminate esters; Colorants such as carbon black; Brominated epoxy resins, antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc oxide, and phosphorus series Flame retardants such as compounds; low stress components such as silicone oil and silicone rubber; natural waxes such as carnauba wax; synthetic waxes such as polyethylene wax; higher fatty acids such as stearic acid and zinc stearate; metal salts of the higher fatty acids; Release agents such as paraffin; various additives such as magnesium, aluminum, titanium and bismuth-based ion catchers and bismuth antioxidants; and modified compounds that increase heat resistance such as benzoxazine, cyanate ester, and bismaleimide .

The epoxy resin composition of the present invention can also contain a resin component other than the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule.
Other resin components include epoxy resins using acid anhydrides, polyimide resin components, nanocomposite components, cyanate ester resin components, and the like.

Other functional compounds include “Review Epoxy Resin Vol. 1”, “Review Epoxy Resin Vol. 1”, Epoxy Resin Technology Association, 2003; Journal of Ectronics Packaging Society, 14, 204, 2011; journal of Applied Polymer Science. 109, 2023-2028, 2008; Polymer Preprints, Japan, 60, 1K19, 2011; Neckwork Polymers, 33, 130, 2012; Int. 54, 1103-1109, 2005; Journal of Applied Polymer Science, 92, 2375-2386, 2004; Neckwork Polymer, 29, 175, 2008; Polymer Papers, 65, 562, 2008; Polymer Papers, 66 ( 6), 217, 2009, and the like.

The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components and, if necessary, other additives using a mixer, and further mixing at room temperature with a roll, a kneader, and a kneader. It can also be obtained by heating and kneading using a kneader such as a twin screw extruder, followed by cooling and pulverization. Moreover, when the epoxy resin composition obtained above is a powder, it can be used as a pressure tablet by a press or the like in order to improve workability in use.

As the method of using the epoxy resin composition of the present invention, for example, when various kinds of electronic components such as semiconductor elements are sealed and a semiconductor device is manufactured, conventional methods such as transfer molding, compression molding and injection molding are used. Curing molding may be performed by a molding method.

Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.
In addition, it shows below about the content of the hardening accelerator used by the Example and the comparative example.

Hereinafter, production of a quaternary salt base of a curing accelerator having an amidine structure will be described.

<Method for producing quaternary salt base (A-Be1)>
In a stirring autoclave, 180 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol as a solvent are charged, and 152 parts of DBU (manufactured by San Apro Co., Ltd.) are charged therein at a reaction temperature of 125 ° C. The reaction was performed for 80 hours. After removing the solvent under reduced pressure, it was dissolved again in methanol to obtain a quaternary salt base (A-Be1, solid concentration 50%).

<Method for producing quaternary salt base (A-Be2)>
A stirred autoclave is charged with 240 parts of diethyl carbonate (Tokyo Chemical Industry Co., Ltd.) and 500 parts of ethanol as a solvent, and 124 parts of DBN (San Apro Co., Ltd.) is charged therein at a reaction temperature of 125 ° C. The reaction was performed for 80 hours. After removing the solvent under reduced pressure, it was dissolved again in methanol to obtain a quaternary salt base (A-Be2, solid concentration 50%).

<Method for producing quaternary salt base (A-Be3)>
In a stirring type autoclave, 220 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol as a solvent are charged, and 84 parts of 2-methyl-2-imidazoline (manufactured by Tokyo Chemical Industry Co., Ltd.) are added therein. The reaction was performed at a reaction temperature of 125 ° C. for 80 hours. After removing the solvent under reduced pressure, it was dissolved again in methanol to obtain a quaternary salt base (A-Be3, solid content concentration 50%).

<Method for producing quaternary salt base (A-Be4)>
In a stirring type autoclave, 220 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol as a solvent are charged, and 144 parts of 2-phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) are charged therein and reacted. The reaction was performed at a temperature of 125 ° C. for 80 hours. After removing the solvent under reduced pressure, it was dissolved again in methanol to obtain a quaternary salt base (A-Be4, solid content concentration 50%).

<Method for producing quaternary salt base (A-Be5)>
A glass round bottom three-necked flask equipped with a dropping funnel and a reflux tube was charged with 152 parts of DBU and 1000 parts of acetone and dissolved uniformly, and then 175 parts of benzyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. The reaction was carried out at 2 ° C. for 2 hours. Next, 40 parts of sodium hydroxide (30% methanol solution) was added, reacted at 0 ° C. for 5 hours, and the precipitated salt was removed to obtain a quaternary salt (A-Be5, solid content concentration 25%).

<Production Example for Curing Accelerator of Comparative Example>
<Method for producing quaternary phosphonium base (A-Be'1)>
In a stirring autoclave, 180 parts of dimethyl carbonate and 224 parts of methanol as a solvent were added, and 202 parts of tributylphosphine was added dropwise thereto, and reacted at a reaction temperature of 125 ° C. for 20 hours to give a quaternary phosphonium base ( A solution of tributylmethylphosphonium monomethyl carbonate (solid content concentration 50%) was obtained as A-Be′1).

Hereinafter, the production of a curing accelerator having an amidine structure will be described.

<Curing accelerator 1>
After adding 13.6 parts of methyltrimethoxysilane, 22 parts of catechol, and 200 parts of methanol to a glass round bottom three-necked flask equipped with a dropping funnel and a reflux tube, the quaternary salt base produced in Production Example 1 ( 486 parts of A-Be1) was added dropwise to obtain a quaternized amidine salt (S1). Next, after adding 200 parts of phenol novolak resin (“H-4” manufactured by Meiwa Kasei Kogyo Co., Ltd.), the temperature was raised to 175 ° C. while distilling off the solvent (methanol), and the remaining solvent was removed under reduced pressure to cure. Accelerator (Q-1) was obtained.

<Curing accelerator 2>
Example 1 instead of methyltrimethoxysilane in Example 1, 19.8 parts of phenylmethoxysilane, 32 parts of 2,3-dihydroxy instead of catechol, and production example instead of quaternary salt base (A-Be1) in Example 1 A quaternized amidine salt (S2) and a curing accelerator (Q-2) were obtained in the same manner as in Example 1 except that the dropping of the quaternary salt base (A-Be2) produced in 2 was changed.

<Curing accelerator 3>
Instead of methyltrimethoxysilane in Example 1, 19.8 parts of phenylmethoxysilane, 368 parts of ethyl gallate instead of catechol, and in Preparation Example 2 instead of quaternary salt base (A-Be1) in Example 1 A quaternized amidine salt (S3) and a curing accelerator (Q-3) were obtained in the same manner as in Example 1 except that the dropwise addition of the manufactured quaternary salt base (A-Be3) was changed.

<Curing accelerator 4>
In Example 1, 20.8 parts of tetraethoxysilane instead of methyltrimethoxysilane, 48 parts of 2,3-dihydroxy instead of catechol, and production example instead of quaternary salt base (A-Be1) in Example 1 A quaternized amidine salt (S4) and a curing accelerator (Q-4) were obtained in the same manner as in Example 1 except that the dropping of the quaternary salt base (A-Be4) produced in 2 was changed.

<Curing accelerator 5>
In place of methyltrimethoxysilane in Example 1, 14.6 parts of triethyl borate, quaternary salt base (A-Be5) prepared in Preparation Example 2 instead of quaternary salt base (A-Be1) in Example 1 A quaternized amidine salt (S5) and a curing accelerator (Q-5) were obtained in the same manner as in Example 1 except that the dripping was changed.

<Curing accelerator 6>
Curing was carried out in the same manner as in Example 1, except that the quaternary salt base (A-Be1) in Example 1 was replaced with the quaternary phosphonium base (A-Be′1) produced in Comparative Production Example 1. An accelerator (Q′-1) was obtained.

<Curing accelerator 7>
A curing accelerator (Q′-2) was obtained in the same manner as in Example 2 except that phenyltrimethoxysilane in Example 2 was not used and 200 parts of phenol novolac resin was changed to 317 parts.

Example 1
Epoxy resin 1: Nippon Kayaku Co., Ltd., trade name NC3000 (softening point 58 ° C., epoxy equivalent 273) 100 parts; Phenol resin curing agent 1: Meiwa Kasei Co., Ltd. trade name MEH-7500 (softening point) 110 ° C., hydroxyl equivalent 97) 33 parts; 7 parts of epoxy resin curing accelerator obtained in each of the above examples; 1000 parts of fused silica powder treated with 1% by weight of silane coupling agent, 1.5 parts of carnauba wax, 4 parts of antimony trioxide and 1 part of carbon black were uniformly pulverized and mixed, then melt kneaded for 10 minutes using a 130 ° C. hot roll, cooled and pulverized to obtain a sealing material. The obtained epoxy resin composition was evaluated by the following methods. The results are shown in Table 1.

<Performance evaluation>
<Flowability (flow value)>
With respect to the obtained epoxy resin composition, the flow value (unit: cm) of spiral flow at 175 ° C. (70 kg / cm 2) was measured according to the method of EMMI 1-66 and used as an index of fluidity.

<Geltime>
Each of the above epoxy resins was measured under the conditions of a temperature of 175 ° C., a resin die P-200, and an amplitude angle of ± 1/4 ° using a curast meter type 7 (manufactured by A & D Co., Ltd., trade name). The curing torque of the composition was measured, and the point at which the curing torque rises was defined as gel time (unit: seconds).

<Curing property (curing torque)>
In the measurement with the above curast meter, the value of the curing torque (unit: kgf · cm) after 300 seconds from the start of measurement was used as an index of curability (strength and hardness during demolding).

Examples 2-8, Comparative Examples 1-2
According to the composition of Table 1, an epoxy resin composition was obtained in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The results are shown in Table 1.
The raw materials used other than Example 1 are shown below.

Epoxy resin 2: manufactured by Mitsubishi Chemical Corporation, trade name XY-4000H (softening point 80 ° C., epoxy equivalent 192)

Phenol resin curing agent 2: manufactured by Meiwa Kasei Co., Ltd., trade name MEH-7851SS (softening point 67 ° C., hydroxyl group equivalent 203)

As is apparent from Table 1, the epoxy resin compositions of Examples 1 to 8 of the present invention have a high flow value of the sealant after melt-kneading and excellent fluidity, and also have high curing torque and high curability. It turns out that it is excellent.
On the other hand, in Comparative Example 1 using a curing accelerator composed of a tetraalkylphosphonium cation, the flow value of the sealant after melt-mixing is lower than that of the phosphonium cation because the stability of the phosphonium cation is low. Recognize.
Further, it can be seen that Comparative Example 2 containing no silicate anion exhibits activity at the time of blending, so that the reaction during melt kneading cannot be suppressed and the flow value is lowered.

Since the epoxy resin composition of the present invention is excellent in fluidity when filled with a mold and has high catalytic activity and excellent curability, it is suitable for producing an epoxy resin-based sealing material for electronic parts such as semiconductors.

Claims (6)

The epoxy resin (E), a compound (P) having two or more phenolic hydroxyl groups in one molecule, and a curing accelerator (Q), the curing accelerator (Q) is represented by the following general formula (1), Four comprising the cyclic cation (A) having an amidine group represented by (2), (3) or (4) and the anion (B) represented by the following general formula (5), (6) or (7) An epoxy resin composition comprising a graded amidine salt (S).

[In Formula (1), R1 represents a C1-C16 substituted or unsubstituted alkyl group, or a benzyl group. ]

[In Formula (2), R2 represents a C1-C16 substituted or unsubstituted alkyl group, or a benzyl group. ]

[In Formula (3), R3 and R5 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms or a benzyl group, and R4 represents hydrogen, a substituted or unsubstituted group having 1 to 16 carbon atoms, or Represents an unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and R6 and R7 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a hydroxyl group, hydrogen, a hydroxymethyl group, or a hydroxy group Represents an ethyl group. ]

[In Formula (4), R8 and R10 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms or a benzyl group, and R9 represents hydrogen, a substituted or unsubstituted group having 1 to 16 carbon atoms, or Represents an unsubstituted alkyl group, or a substituted or unsubstituted phenyl group, and R11 and R12 are the same or different and each represents a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a hydroxyl group, hydrogen, a hydroxymethyl group, or a hydroxy group Represents an ethyl group. ]

[In the formula (5), R13 and R15 are groups formed by proton-donating substituents releasing protons, and they may be the same or different from each other. It binds to a silicon atom to form a chelate structure. R14 is an organic group that binds to R13 and R15. R17 and R19 are groups formed by proton-donating substituents releasing protons, and R17 and R19 in the same molecule are combined with a silicon atom to form a chelate structure. R18 is an organic group that binds to R17 and R19. R14 and R18 may be the same or different from each other, and R13, R15, R17 and R19 may be the same or different from each other. R16 represents an organic group having a substituted or unsubstituted aromatic ring or a substituted or unsubstituted heterocyclic ring, or a substituted or unsubstituted aliphatic group. ]

[In the formula (6), R20 and R22 are groups formed by proton-donating substituents releasing protons, and they may be the same or different from each other. It binds to a silicon atom to form a chelate structure. R21 is an organic group that binds to R20 and R22. R23 and R25 are groups formed by proton-donating substituents releasing protons, and R23 and R25 in the same molecule bind to a silicon atom to form a chelate structure. R24 is an organic group that binds to R23 and R25. R26 and R28 are groups formed by proton-donating substituents releasing protons, and R26 and R28 in the same molecule bind to a silicon atom to form a chelate structure. R27 is an organic group that binds to R26 and R28. R21, R24, and R27 may be the same as or different from each other, and R20, R22, R23, R25, R26, and R28 may be the same as or different from each other. ]

[In the formula (7), R29 and R31 are groups formed by proton-donating substituents releasing protons, and they may be the same or different, and R29 and R31 in the same molecule are It combines with a boron atom to form a chelate structure. R30 is an organic group that binds to R29 and R31. R32 and R34 are groups formed by proton-donating substituents releasing protons, and R32 and R34 in the same molecule are combined with a boron atom to form a chelate structure. R33 is an organic group that binds to R32 and R34. R30 and R33 may be the same as or different from each other, and R29, R31, R32, and R34 may be the same as or different from each other. ] The proton donors of the proton donating substituents in the formulas (5) to (7) are catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol. , Pyrogallol, trihydroxybenzoic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, tannic acid Phenolic compound selected; alcoholic compound selected from the group of 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, glycerin; or urea, 1-methylurea, 1,3-dimethylurea 1,3-diaminourea, 1,3-dimethylolurea, allophane ami Thiourea, 1-methyl thiourea, 1,3-dimethyl thiourea, thiosemicarbazide, thiocarbohydrazide, 4-methyl thiosemicarbazide, epoxy resin composition according to claim 1 is a urea-based compound selected from the group of Guaniruchio urea. Furthermore, the epoxy resin composition of Claim 1 or 2 containing an inorganic filler. Furthermore, the epoxy resin composition in any one of Claims 1-3 containing another functional compound.   Hardened | cured material formed by hardening | curing the epoxy resin composition in any one of Claims 1-4. A semiconductor device formed by sealing an electronic component with the cured product according to claim 5.