TW202012374A - Epoxy resin curing accelerator and epoxy resin composition - Google Patents

Abstract

To provide an epoxy curing accelerator which has extremely high and stable heat resistance, and in which acceleration of a curing reaction can be suppressed; and to provide an epoxy resin composition which increases the reliability of a semiconductor device and has good curing properties through use of the epoxy curing accelerator, the epoxy resin composition has good fluidity and thoroughly fills the inside of a package, and voids are not prone to occur in the epoxy resin composition. The present invention is an epoxy resin curing accelerator (Q) characterized by including an imidazolium salt (S) comprising: an imidazolium cation (A) represented by general formula (1); and an anion (B) represented by general formula (2), (3), or (4); the melting point of the imidazolium salt (S) being 170 DEG C or lower.

Description

Epoxy resin hardening accelerator and epoxy resin composition

The invention relates to an epoxy resin hardening accelerator and an epoxy resin composition. More specifically, it relates to an epoxy resin hardening accelerator suitable for manufacturing an epoxy resin-based sealant for electronic components such as semiconductor elements and an epoxy resin composition containing the epoxy resin hardening accelerator.

As a sealing method for semiconductor elements such as integrated circuits (ICs), the transfer molding cost of epoxy resin compositions is low, and mass production is excellent. However, in order to miniaturize and reduce the weight of electronic devices, semiconductors have become highly integrated, and in the process of surface mounting, epoxy resin compositions for semiconductor encapsulants have also accompanied these requirements for reliability Became very strong. Therefore, by increasing the ratio of the filler of the inorganic material in the epoxy resin composition, the characteristics of low moisture absorption, high strength, and low thermal expansion of the epoxy resin are exerted, thereby ensuring reliability.

Disadvantages of increasing the ratio of the filler of the inorganic material include two aspects, that is, insufficient hardenability at the time of molding the epoxy resin composition and that the viscosity becomes high. If the curability is poor, the reliability of the semiconductor device will be impaired. In addition, if the viscosity becomes high and the fluidity is poor, the epoxy resin composition may not be sufficiently filled into the package and there may be a void. Although those with good curability of the epoxy resin composition (for example, Patent Document 1) and those with good fluidity (for example, Patent Document 2) have been proposed, both cannot be sufficiently satisfied. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2007-119598 [Patent Document 2] Japanese Patent Laid-Open No. 2018-104559

[Problems to be solved by the invention] Therefore, an object of the present invention is to provide an epoxy resin composition: by using a specific epoxy hardening accelerator, the epoxy resin composition has good curability and improves the reliability of a semiconductor device, and also has good fluidity and environmental protection. The oxygen resin composition is sufficiently filled into the package body, and there is no fear of voids. [Means to solve the problem]

The inventors of the present invention conducted studies to achieve the above-mentioned object, and as a result, the present invention has been achieved. That is, the present invention is an epoxy resin hardening accelerator (Q) characterized by containing an imidazolium salt (S) containing the imidazolium cation (A) represented by the general formula (1) , And the anion (B) represented by the general formula (2), (3) or (4), the melting point of the imidazolium salt (S) is 170°C or lower; and an epoxy resin composition containing the Epoxy resin hardening accelerator (Q), epoxy resin (E), and compound (P) having two or more phenolic hydroxyl groups in one molecule.

[Chemical 1]

[In formula (1), R1 represents a hydrogen atom, methyl, ethyl, propyl or butyl, R2 and R3 are the same or different, and represent methyl, ethyl, propyl or butyl, R4 and R5 are the same or different , Representing a hydrogen atom, methyl or ethyl]

[Chem 2]

[In formula (2), the radicals represented by -R6-R7-R8- and -R10-R11-R12- are composed of radicals formed by the release of two protons from a proton donor of at least two valences. The radicals may be the same as or different from each other. R9 represents an aromatic hydrocarbon group which may have a substituent or an aliphatic hydrocarbon group which may have a substituent]

[Chemical 3]

[In formula (3), the groups represented by -R13-R14-R15-, -R16-R17-R18-, and -R19-R20-R21- are formed by the release of two protons from a proton donor of more than two valences. The bases of the bases may be the same as or different from each other]

[Chemical 4]

[In formula (4), the groups represented by -R22-R23-R24- and -R25-R26-R27- are composed of groups derived from two protons released by a proton donor of more than two valences. The bases may be the same as or different from each other] [Effect of invention]

In the epoxy resin hardening accelerator (Q) of the present invention, the imidazolium cation (A) has extremely high heat resistance and is stable. Therefore, even at the blending temperature of heating and melting, the salt can be combined with the anion (B) represented by the general formula (2), (3), or (4), and the acceleration of the hardening reaction can be suppressed. Furthermore, since the anion portion forms a chelate structure, the thermal stability is good, and the curing reaction will not be promoted even at the temperature at which the mixture of the epoxy resin, the curing agent, and the curing accelerator is heated and melted. On the other hand, at a curing temperature where the temperature rises, it decomposes rapidly, and the reaction between the epoxy resin and the hardener can be promoted. Therefore, the curability of the epoxy resin composition is good, and the reliability of the semiconductor device can be improved.

Furthermore, the epoxy resin hardening accelerator (Q) has an imidazolium cation (A), and therefore has a low melting point. That is, the blending temperature of heating and melting is close to or below the melting point. According to this, an epoxy resin composition with good fluidity can be designed. That is, it becomes an epoxy resin composition: by using an epoxy resin hardening accelerator (Q), the epoxy resin composition has good curability and improves the reliability of the semiconductor device, the fluidity is good, and the epoxy resin composition is sufficient Filled into the package, there is no fear of voids, and it is suitable for the production of epoxy resin sealing materials for electronic components such as semiconductors.

Hereinafter, the epoxy resin hardening accelerator (Q) and the epoxy resin composition of the present invention will be described. The epoxy resin hardening accelerator (Q) of the present invention is characterized by containing an imidazolium salt (S) containing the imidazolium cation (A) represented by the general formula (1) and the general formula Anions (B) represented by (2), (3) or (4).

The imidazolium cation (A) is represented by the general formula (1). In the formula (1), R1 represents a hydrogen atom, methyl, ethyl, propyl or butyl, and R2 and R3 are the same or different, and represent methyl, Ethyl, propyl or butyl, R4 and R5 are the same or different, and represent a hydrogen atom, methyl or ethyl.

[Chem 5]

Regarding the imidazolium cation (A), from the viewpoint of the curability of the epoxy resin composition, R1 is preferably a hydrogen atom. The reason is that the imidazolium becomes a carbene compound during the curing process of the epoxy resin composition. Furthermore, from the viewpoint of fluidity, R4 and R5 are preferably hydrogen atoms.

Specific examples of the imidazolium cation (A) include 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium Onium cation, 1-butyl-2,3-dimethylimidazolium cation, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1,2,3-trimethyl Imidazolium cation, 1,2,3,4-tetramethylimidazolium cation, 1,3,4-trimethyl-2-ethylimidazolium cation, 1,3-dimethyl-2,4-bis Ethylimidazolium cation, 1,2-dimethyl-3,4-diethylimidazolium cation, 1-methyl-2,3,4-triethylimidazolium cation, 1,2,3,4 -Tetraethylimidazolium cation, 1,3-dimethyl-2-ethylimidazolium cation, 1-ethyl-2,3-dimethylimidazolium cation and 1,2,3-triethylimidazolium Onium cation, etc.

The imidazolium cation (A) can be obtained, for example, by a reaction using an alkyl carbonate of a quaternized amine cation, a reaction using a hydroxide of a quaternized amine cation, or the like.

The anion (B) is represented by the general formula (2), (3) or (4).

[化6]

[In formula (2), the radicals represented by -R6-R7-R8- and -R10-R11-R12- are composed of radicals formed by the release of two protons from a proton donor of at least two valences. The radicals may be the same as or different from each other. R9 represents an aromatic hydrocarbon group which may have a substituent or an aliphatic hydrocarbon group which may have a substituent]

[化7]

[In formula (3), the groups represented by -R13-R14-R15-, -R16-R17-R18-, and -R19-R20-R21- are formed by the release of two protons from a proton donor of more than two valences. The bases of the bases may be the same as or different from each other]

[Chem 8]

[In formula (4), the groups represented by -R22-R23-R24- and -R25-R26-R27- are composed of groups derived from two protons released by a proton donor of more than two valences. The bases may be the same as or different from each other]

Examples of the proton donor of the proton-donating substituent in Formula (2) to Formula (4) include: selected from catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and 2,2 '-Biphenol, 2,2'-binaphthol, gallaphenol, trihydroxybenzoic acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, salicylic acid, 1-hydroxy-2 -Phenolic compounds in the group of naphthoic acid, 3-hydroxy-2-naphthoic acid, chlororanic acid, and tannic acid; Alcohol compounds selected from the group of 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin; And selected from urea, 1-methylurea, 1,3-dimethylurea, 1,3-diaminourea, 1,3-dimethylolurea, Allophanamide thiourea, 1- Urea compounds in the group of methylthiourea, 1,3-dimethylthiourea, thiosemicarbazide, thiocarbohydrazide (Thiocarbohydrazide), 4-methylthiosemicarbazide, and Guanamthiourea (Guanylthiourea). The phenolic compound is preferred.

In the general formula (2), R9 represents an aromatic hydrocarbon group which may have a substituent, or an aliphatic hydrocarbon group which may have a substituent. Examples of aromatic hydrocarbon groups include phenyl, naphthyl, and anthracenyl. Examples of the substituent include an alkyl group having 1 to 18 carbon atoms and a halogen atom. Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 18 carbon atoms. Examples of the substituent include halogen atoms.

As a method for synthesizing the imidazolium salt (S), for example, the imidazolium cation (A) can be chelated with alkoxysilanes (or boric acid, borate esters) and silicon atoms (or boron atoms). A method in which the bonded proton donors react at a certain ratio.

Examples of alkoxysilanes include phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyl Triethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, tetraethoxysilane, etc.

The melting point of the imidazolium salt (S) of the present invention is 170°C or lower, preferably 120°C or lower. From the viewpoint of ease of handling, the lower limit is preferably -50°C or higher. A more preferable melting point is -30°C to 120°C, further preferably -20°C to 100°C, and most preferably 0°C to 70°C. If it exceeds 170°C, the viscosity increases and the fluidity deteriorates.

The epoxy resin composition of the present invention contains an epoxy resin (E), a compound (P) having two or more phenolic hydroxyl groups in one molecule, and the epoxy resin hardening accelerator (Q).

The epoxy resin (E) is all oligomers and polymers having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited, and examples include phenol novolac epoxy resins and Phenolic novolac epoxy resin, hydroquinone epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, biphenyl epoxy resin, stilbene epoxy resin, triphenol Methane epoxy resin, alkyl modified triphenol methane epoxy resin, epoxy resin containing triazine core, dicyclopentadiene modified phenol epoxy resin, with phenylene and/or biphenylene Skeletal phenol aralkyl type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, naphthol aralkyl type epoxy resin having phenylene and/or biphenylene skeleton, etc. It can be used alone or mixed.

Examples of the epoxy resin (E) include: manufactured by DIC Corporation: 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; manufactured by Mitsubishi Chemical Corporation: XY-4000, etc.

The compound (P) having two or more phenolic hydroxyl groups in one molecule is all monomers, oligomers, and polymers having two or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. For example, phenol novolak resin, cresol novolak resin, triphenol methane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, having phenylene and/or biphenylene The skeleton phenol aralkyl resin, naphthol aralkyl resin having a phenylene and/or biphenylene skeleton, a bisphenol compound, etc., 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-7851 series, MEH-7600 series, manufactured by Minghe Chemical Industry Co., Ltd. MEH-8000 series; manufactured by Honshu Chemical Industry Co., Ltd.: TriP-PA, BisP-TMC, BisP-AP, OC-BP, TekP-4HBPA, CyRS-PRD4, etc.

By curing the epoxy resin composition of the present invention, a cured epoxy resin is finally obtained. The blending amount of the epoxy resin hardening accelerator (Q) is adjusted according to the reactivity of the epoxy resin or hardener, but it is usually 1 to 25 parts by weight, preferably 2 parts by weight relative to 100 parts by weight of the epoxy resin Parts ~ 20 parts by weight.

The mixing ratio of the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule is also not particularly limited, and it is preferably 1 equivalent to the epoxy group of the epoxy resin (E). The phenolic hydroxyl group of the compound (P) is used in a range of 0.5 to 2 equivalents, and more preferably in a range of 0.7 to 1.5 equivalents.

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, etc., it is formulated in an epoxy resin composition for the purpose of improving solder resistance of the obtained semiconductor device, etc. The type is not particularly limited, and those commonly used in sealing materials can be used.

In addition, the content of the inorganic filler (H) is not particularly limited, and is preferably 100 parts by weight relative to the total amount of 100 parts by weight of the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule. 200 parts by weight to 2400 parts by weight, more preferably 400 parts by weight to 1400 parts by weight.

The epoxy resin composition of the present invention preferably further contains other functional compounds (functional additives).

Examples of functional additives include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureido Coupling agents represented by alkoxysilanes such as propyltriethoxysilane and phenyltrimethoxysilane or titanates and aluminates; colorants such as carbon black; brominated epoxy resin, antimony oxide , Aluminum hydroxide, magnesium hydroxide, zinc oxide and phosphorus compounds and other flame retardants; silicone oil and silicone rubber and other low-stress components; carnauba wax and other natural waxes, polyethylene wax and other synthetic wax; stearic acid or stearic acid Higher fatty acids such as zinc, metal salts of the higher fatty acids, and mold release agents such as paraffin wax; magnesium, aluminum, titanium, and bismuth-based ion trapping agents, bismuth antioxidants and other additives; benzoxazine, cyanate, bismaleic Modified compounds that improve heat resistance (UP) such as amide imine.

The epoxy resin composition of the present invention may contain resins other than the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule. Examples of other resins include epoxy resins using acid anhydrides, polyimide-based resins, nano-composite-based resins, and cyanate-based resins.

Other functional compounds are described in "Review of Epoxy Resin Volume 1", Epoxy Resin Technology Association, 2003; "Journal of Electronic Installation Society", 14, 204, 2011; "journal of Applied Polymer" Science”, 109, 2023-2028, 2008; “Polymer Preprints”, Japan, 60, 1K19, 2011; “Reticulated Polymers”, 33, 130, 2012; “International Polymer (Polym .Int.)" 54, 1103-1109, 2005; "Journal of Applied Polymer Science", 92, 2375-2386, 2004; "Reticulated Polymer", 29, 175, 2008; " "Proceedings of Polymer", 65, 562, 2008; "Proceedings of Polymer", 66(6), 217, 2009, etc.

The epoxy resin composition of the present invention is obtained by using a mixer to uniformly mix the above-mentioned components, other additives as needed, and the like, and can further be used by using a roller, a kneader, a compound motion kneader (ko-kneader) and a biaxial extrusion A kneader such as a machine is obtained by heating and kneading those obtained by mixing at room temperature, and then cooling and pulverizing. In addition, in the case where the epoxy resin composition obtained as described above is a powder, in order to improve workability at the time of use, it may be used after being compressed into tablets by pressing or the like.

As a method of using the epoxy resin composition of the present invention, for example, in the case of manufacturing a semiconductor device by sealing various electronic components such as semiconductor elements, hardening molding can be performed by a conventional molding method such as a transfer mold, a compression mold, and an injection mold. [Example]

Hereinafter, the present invention will be further described by Examples and Comparative Examples, but the present invention is not limited to these Examples. Hereinafter, unless otherwise specified,% means weight%, and parts means parts by weight. In addition, the content of the epoxy resin hardening accelerator (henceforth a hardening accelerator) used in the Example and the comparative example is as follows.

<Production method of imidazolium salt (S-1)> In a stirred autoclave, 141 parts of diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of ethanol were added, to which 82 parts of 1-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The reaction temperature was 135 degreeC and it was made to react for 80 hours, whereby the ethanol solution of 1-ethyl-3-methylimidazolium ethyl carbonate (S-1-1) was obtained. In a glass round bottom three-necked flask equipped with a dropping funnel and a reflux tube, 240 parts of triethoxyphenyl silane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2,3-dihydroxynaphthalene (Tokyo Chemical Industry Co., Ltd.) 320 parts) and 30 parts of sodium methoxide 28% methanol solution (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to 900 parts of methanol, and 1-ethyl-3-methylimidazolium ethyl carbonate was added dropwise ( S-1-1) in an ethanol solution to obtain an imidazolium salt represented by the following formula (s1). It is filtered, washed with methanol several times, and dried for purification to obtain an imidazolium salt (S-1) [represented as (s1) in the chemical formula, the same is true for other imidazolium salts].

[化9]

<Production method of imidazolium salt (S-2)> By using 1,2-dimethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 96 parts instead of 1-methylimidazole in the manufacturing method of the imidazolium salt (S-1), the following formula (s2) was obtained Represented imidazolium salt (S-2).

[化10]

<Production method of imidazolium salt (S-3)> By using 104 parts of tetraethoxysilane and 165 parts of catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the production method of imidazolium salt (S-1), triethoxyphenylsilane, 2,3- Dihydroxynaphthalene to obtain an imidazolium salt (S-3) represented by the following formula (s3).

[Chem 11]

<Production method of imidazolium salt (S-4)> By using 146 parts of triethylboronic acid ester (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of imidazolium salt (S-1) production method of triethoxyphenyl silane, the following formula (s4) was obtained Represented imidazolium salt (S-4).

[化12]

<Production method of imidazolium salt (S-5)> By using 220 parts of catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2,3-dihydroxynaphthalene in the manufacturing method of imidazolium salt (S-1), imidazole represented by the following formula (s5) was obtained Onium salt (S-5).

[Chem 13]

<Production method of imidazolium salt (S-6)> By using 252 parts of gallnut (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2,3-dihydroxynaphthalene in the manufacturing method of the imidazolium salt (S-1), the solvent was removed by an evaporator instead of filtration to obtain the following The imidazolium salt (S-6) represented by the formula (s6). Furthermore, a 28% methanol solution of sodium methoxide was not used.

[化14]

<Production method of imidazolium salt (S-7)> By using gallic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 252 parts of 2,3-dihydroxynaphthalene instead of the manufacturing method of imidazolium salt (S-1), using trimethoxyhexyl silane (Tokyo Chemical Industry Co., Ltd.) (Production) 206 parts instead of triethoxyphenyl silane, the solvent was removed by an evaporator instead of filtration, and an imidazolium salt (S-7) represented by the following formula (s7) was obtained. Furthermore, a 28% methanol solution of sodium methoxide was not used.

[化15]

<Production Example of Salt (S'-1) used in Comparative Example>

<Manufacturing method of salt (S'-1)> In a stirred autoclave, 108 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol were added, and 1,8-diazabicyclo[5.4.0]11-7- 152 parts of carbene (1,8-Diazabicyclo[5.4.0]undec-7-ene, DBU) (made by San-Apro Co., Ltd.), which were reacted at a reaction temperature of 125°C for 80 hours. This obtains the methyl carbonate (S'-1-1) of the DBU derivative of the intermediate. Thereafter, the salt (S'-1) represented by the following formula (s'1) is obtained by performing the same method as the production method of the imidazolium salt (S-1).

[Chem 16]

<Manufacturing method of salt (S'-2)> In a stirred autoclave, 216 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol in solvent were added, and 2-methyl-2-imidazoline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to it. 84 parts were allowed to react at a reaction temperature of 125°C for 80 hours, thereby obtaining an intermediate imidazolium methyl carbonate (S'-2-1). Thereafter, the salt (S'-2) represented by the following formula (s'2) was obtained by performing the same method as the production method of the imidazolium salt (S-1).

[化17]

<Manufacturing method of salt (S'-3)> By using 419 parts of tetraphenylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of the production method of 1-ethyl-3-methylimidazolium ethyl carbonate instead of the imidazolium salt (S-1) ( S-1-1) to obtain the salt (S'-3) represented by the following formula (s'3).

[Chemical 18]

The melting points of imidazolium salt (S-1) to imidazolium salt (S-7) and salt (S'-1) to salt (S'-3) were measured by the following method. The results are shown in Table 1. <melting point> Place the sample on a test stand made of SUS, slowly raise the temperature, and read the dissolution temperature by visual observation.

[Table 1]

Example 1 Epoxy resin 1: manufactured by Nippon Kayaku Co., Ltd., trade name NC3000 (softening point 58°C, epoxy equivalent 273) 100 parts; phenol resin-based hardener 1: manufactured by Meiwa Chemical Co., Ltd., trade name MEH-7500 ( Softening point 110℃, hydroxyl equivalent 97) 33 parts; epoxy resin hardening accelerator [imidazolium salt (S-1)] 7 parts; 1000 parts of molten silica powder treated with 1% by weight of silane coupling agent, Brazil After 1.5 parts of carnauba wax, 4 parts of antimony trioxide, and 1 part of carbon black were uniformly pulverized and mixed, they were melt-kneaded with a hot roll at 130°C for 10 minutes, cooled, and pulverized to obtain a sealing material. The obtained epoxy resin composition was evaluated by the following method. The results are shown in Table 2.

<Performance evaluation><Flowability (flow value)> For the epoxy resin composition obtained above, the flow value of spiral flow at 175°C (70 kg/cm ² ) was measured according to the method of EMMI 1-66 (unit: cm) as an indicator of liquidity. The larger the flow value, the better the liquidity.

<gel time> Using a curelastometer type 7 (manufactured by A&D Co., Ltd., trade name), under the conditions of a temperature of 175°C, a mold for resin P-200 and an amplitude angle of ±1/4°, each epoxy The hardening torque of the resin composition was measured, and the rising point of the hardening torque was taken as the gel time (in seconds).

<Curability (hardening torque)> In the measurement using the vulcanization testing machine, the value of the hardening torque (in kgf·cm) 300 seconds after the start of the measurement is used as an index of hardenability (strength and hardness at the time of demolding).

Example 2 to Example 8, Comparative Example 1 to Comparative Example 3 According to the formulation in Table 2, 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 2. The raw materials used other than Example 1 are as follows.

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

Phenolic resin hardener 2: Manufactured by Meiwa Chemical Co., Ltd., trade name MEH-7851SS (softening point 67°C, hydroxyl equivalent 203)

It is clear from Table 2 that the epoxy resin compositions of Examples 1 to 8 of the present invention have a larger flow value of the sealant after melt-kneading than the comparative example, excellent fluidity, and high curing torque. Excellent hardenability.

On the other hand, Comparative Example 1 and Comparative Example 2 use a hardening accelerator with a low melting point. Therefore, although the flow value showing fluidity is large, the curing torque showing curability is low. Comparative Example 3 is in contrast thereto. As in Comparative Examples, for example, it cannot have both fluidity and hardenability.

[產業上之可利用性][Table 2]

[Industry availability]

Regarding the epoxy resin hardening accelerator (Q) of the present invention, it becomes an epoxy resin composition in which the epoxy resin composition has good curability and improves the reliability of the semiconductor device, the fluidity is good, and the epoxy resin composition is sufficiently filled There is no fear of voids in the package, and it is suitable for the production of epoxy resin sealing materials for electronic components such as semiconductors.

Claims (6)

An epoxy resin hardening accelerator (Q) characterized by containing an imidazolium salt (S) containing the imidazolium cation (A) represented by the general formula (1) and the general formula ( 2) The anion (B) represented by (3) or (4), the melting point of the imidazolium salt (S) is 170°C or lower;

[In formula (1), R1 represents a hydrogen atom, methyl, ethyl, propyl or butyl, R2 and R3 are the same or different, and represent methyl, ethyl, propyl or butyl, R4 and R5 are the same or different , Representing a hydrogen atom, methyl or ethyl]

[In formula (2), the groups represented by -R6-R7-R8- and -R10-R11-R12- are composed of groups derived from two protons released by a proton donor of more than two valences. The groups may be the same as or different from each other; R9 represents an aromatic hydrocarbon group which may have a substituent or an aliphatic hydrocarbon group which may have a substituent]

[In formula (3), the groups represented by -R13-R14-R15-, -R16-R17-R18- and -R19-R20-R21- are formed by the release of two protons from a proton donor of at least two valences The bases of the bases may be the same or different from each other]

[In formula (4), the groups represented by -R22-R23-R24- and -R25-R26-R27- are composed of groups derived from two protons released by a proton donor of more than two valences. The radicals may be the same as or different from each other]. The epoxy resin hardening accelerator (Q) as described in item 1 of the patent application, wherein the proton donor in the general formula (2) to the general formula (4) is selected from catechol and 1,2-dihydroxy Naphthalene, 2,3-dihydroxynaphthalene, 2,2'-biphenol, 2,2'-binaphthol, gallnut, trihydroxybenzoic acid, gallate, 2,3,4-trihydroxydi Phenolic compounds in the group of benzophenone, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chlororanic acid, and tannic acid. The epoxy resin hardening accelerator (Q) as described in item 1 or item 2 of the patent application scope, wherein the melting point of the imidazolium salt (S) is 120°C or lower. The epoxy resin hardening accelerator (Q) as described in any one of items 1 to 3 of the patent application range, wherein R1 in the general formula (1) is a hydrogen atom. An epoxy resin composition containing the epoxy resin hardening accelerator (Q), epoxy resin (E) as described in any one of the patent application items 1 to 4, and having two in one molecule More than one phenolic hydroxyl compound (P). A hardened product is obtained by hardening the epoxy resin composition as described in any one of claims 1 to 5.