WO2020054356A1 - Epoxy resin curing accelerator and epoxy resin composition - Google Patents
Epoxy resin curing accelerator and epoxy resin composition Download PDFInfo
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- WO2020054356A1 WO2020054356A1 PCT/JP2019/032967 JP2019032967W WO2020054356A1 WO 2020054356 A1 WO2020054356 A1 WO 2020054356A1 JP 2019032967 W JP2019032967 W JP 2019032967W WO 2020054356 A1 WO2020054356 A1 WO 2020054356A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/70—Chelates
Definitions
- the present invention relates to an epoxy resin curing accelerator and an epoxy resin composition. More specifically, the present invention relates to an epoxy resin curing accelerator suitable for producing an epoxy resin-based encapsulant for electronic components such as semiconductor elements, and an epoxy resin composition containing the same.
- the curability of the epoxy resin composition is good and the reliability of the semiconductor device is improved, and the flowability is good and the epoxy resin composition is sufficiently filled in the package, and the void is improved. It is an object of the present invention to provide an epoxy resin composition which is free from the possibility of occurrence of a resin.
- the present invention provides an imidazolium salt (S) comprising an imidazolium cation (A) represented by the general formula (1) and an anion (B) represented by the general formula (2), (3) or (4).
- the melting point of the imidazolium salt (S) is 170 ° C. or less; an epoxy resin curing accelerator (Q); and the epoxy resin curing accelerator (Q), an epoxy resin (E), And an epoxy resin composition containing a compound (P) having two or more phenolic hydroxyl groups in one molecule.
- R1 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group
- R2 and R3 are the same or different and represent a methyl group, an ethyl group, a propyl group or a butyl group
- R4 and R5 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
- the group represented by -R6-R7-R8- and -R10-R11-R12- is a group formed by a divalent or higher proton donor releasing two protons. And these groups may be the same 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.
- the group represented by -R13-R14-R15-, -R16-R17-R18- and -R19-R20-R21- is a group in which a divalent or higher-valent proton donor has two protons. These groups are constituted by groups that are released, and these groups may be the same or different from each other. ]
- the group represented by -R22-R23-R24- and -R25-R26-R27- is a group formed by a divalent or higher proton donor releasing two protons. And these groups may be the same or different from each other. ]
- the epoxy resin curing accelerator (Q) of the present invention has extremely high heat resistance of the imidazolium cation (A) and is stable. Therefore, the salt can be combined with the anion (B) represented by the general formula (2), (3) or (4) even at the compounding temperature at which the composition is heated and melted, and the acceleration of the curing reaction can be suppressed. Furthermore, since the anion portion forms a chelate structure, it has good thermal stability, and does not accelerate the curing reaction even at the compounding 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 an even higher curing temperature, the epoxy resin composition can be quickly decomposed, and the reaction between the epoxy resin and the curing agent can be promoted. Therefore, the curability of the epoxy resin composition is good and the reliability of the semiconductor device can be improved.
- the epoxy resin curing accelerator (Q) has an imidazolium cation (A) and therefore has a relatively low melting point. That is, the melting point is close to or lower than the compounding temperature at which the mixture is heated and melted. From this, an epoxy resin composition having good fluidity can be designed. That is, by using the epoxy resin curing accelerator (Q), the curability of the epoxy resin composition is improved, the reliability of the semiconductor device is improved, the fluidity is improved, the epoxy resin composition is sufficiently filled in the package, and voids are formed. It is an epoxy resin composition that is unlikely to be produced, and is suitable for producing an epoxy resin-based sealing material for electronic components such as semiconductors.
- the epoxy resin curing accelerator (Q) of the present invention comprises an imidazolium cation (A) represented by the general formula (1) and an anion (B) represented by the general formula (2), (3) or (4). Characterized by containing an imidazolium salt (S).
- the imidazolium cation (A) is represented by the general formula (1), wherein R1 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, and R2 and R3 are the same or different. Differently represents a methyl group, an ethyl group, a propyl group or a butyl group, and R4 and R5 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
- R1 is preferably a hydrogen atom from the viewpoint of curability of the epoxy resin composition. This is because imidazolium becomes a carbene compound in the process of curing the epoxy resin composition. Further, from the viewpoint of fluidity, R4 and R5 are preferably a hydrogen atom.
- imidazolium cation (A) examples include 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-butyl-2 1,3-dimethylimidazolium cation, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1,2,3-trimethylimidazolium cation, 1,2,3,4-tetramethylimidazolium cation 1,3,4-trimethyl-2-ethylimidazolium cation, 1,3-dimethyl-2,4-diethylimidazolium cation, 1,2-dimethyl-3,4-diethylimidazolium cation, 1-methyl- 2,3,4-triethylimidazolium cation, 1,2,3,4-te La ethyl imidazolium cation,
- the imidazolium cation (A) can be produced, 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).
- the group represented by -R6-R7-R8- and -R10-R11-R12- is a group formed by a divalent or higher proton donor releasing two protons. And these groups may be the same 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.
- the group represented by -R13-R14-R15-, -R16-R17-R18- and -R19-R20-R21- is a group in which a divalent or higher-valent proton donor has two protons. These groups are constituted by groups that are released, and these groups may be the same or different from each other. ]
- the group represented by -R22-R23-R24- and -R25-R26-R27- is a group formed by a divalent or higher proton donor releasing two protons. And these groups may be the same 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.
- the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group.
- the substituent include an alkyl group having 1 to 18 carbon atoms and a halogen atom.
- the aliphatic hydrocarbon group include an alkyl group having 1 to 18 carbon atoms.
- the substituent include a halogen atom.
- the above-mentioned imidazolium cation (A), a chelate bond with an alkoxysilane (or boric acid, borate), and a silicon atom (or boron atom) are used.
- a method of reacting the proton donor that can be formed with the proton donor at a fixed ratio may be used.
- alkoxysilanes include, for example, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and tetra Ethoxysilane and the like can be mentioned.
- the melting point of the imidazolium salt (S) of the present invention is 170 ° C. or lower, preferably 120 ° C. or lower.
- the lower limit is preferably ⁇ 50 ° C. or higher from the viewpoint of ease of handling.
- the more preferable melting point is from -30 ° C to 120 ° C, more preferably from -20 ° C to 100 ° C, and most preferably from 0 ° C to 70 ° C. If the temperature 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 curing accelerator (Q).
- the epoxy resin (E) is generally an oligomer or polymer having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Examples thereof include a phenol novolak type epoxy resin and a cresol novolak 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, epoxy containing triazine nucleus Resin, dicyclopentadiene-modified phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, naphthol type epoxy resin, naphthalene type epoxy resin, resin Ylene and / or naphthol aralkyl type epoxy resins. Having a biphenylene skeleton, it no problem is used singly or in admixture.
- Examples of the epoxy resin (E) include those 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.
- the compound (P) having two or more phenolic hydroxyl groups in one molecule includes all monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure are not particularly limited.
- a naphthol aralkyl resin and a bisphenol compound which may be used singly or as a mixture.
- 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, MEH-8000 manufactured by Meiwa Kasei Corporation. Series: TriP-PA, BisP-TMC, BisP-AP, OC-BP, TekP-4HBPA, CyRS-PRD4, etc., manufactured by Honshu Chemical Industry Co., Ltd.
- the amount of the epoxy resin curing accelerator (Q) is adjusted according to the reactivity of the epoxy resin and the curing agent, and is usually 1 to 25 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the epoxy resin. It is.
- the mixing ratio of the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule is not particularly limited, either, but the compound ( The phenolic hydroxyl group of P) is preferably used in an amount of 0.5 to 2 equivalents, more preferably 0.7 to 1.5 equivalents.
- the epoxy resin composition of the present invention preferably further contains an inorganic filler (H).
- an inorganic filler H
- the epoxy resin composition of the present invention is used for sealing electronic components such as semiconductor elements, for the purpose of improving the solder resistance of the obtained semiconductor device, the epoxy resin composition is incorporated into the epoxy resin composition.
- the type is not particularly limited, and those generally used for a sealing material can be used.
- the content of the inorganic filler (H) is not particularly limited, the total amount of the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule per 100 parts by weight is as follows: It is preferably from 200 to 2400 parts by weight, more preferably from 400 to 1400 parts by weight.
- the epoxy resin composition of the present invention further contains another functional compound (functional additive).
- Functional additives include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and phenyltrimethoxysilane Coupling agents represented by alkoxysilanes, titanate esters, and aluminate esters; and coloring agents such as carbon black; brominated epoxy resins, antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc oxide, and phosphorus.
- Flame retardants such as system 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 and paraffin; various additives such as magnesium, aluminum, titanium and bismuth-based ion catchers and bismuth antioxidants; and heat-resistant UP-modified compounds such as benzoxazine, cyanate ester and bismaleimide.
- 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 and paraffin
- various additives such as magnesium, aluminum, titanium and bismuth-based ion catchers and bismuth antioxidants
- the epoxy resin composition of the present invention may contain a resin other than the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule.
- Other resins include an epoxy resin using an acid anhydride, a polyimide resin, a nanocomposite resin, a cyanate ester resin, and the like.
- the epoxy resin composition of the present invention is obtained by uniformly mixing the above components and, if necessary, other additives and the like using a mixer, and further, a mixture obtained at room temperature, roll, kneader, co-kneader And kneading by heating using a kneader such as a twin screw extruder, and then cooling and pulverizing.
- a kneader such as a twin screw extruder
- the epoxy resin composition obtained above is a powder, it can be used in the form of a pressurized tablet by a press or the like in order to improve workability in use.
- Examples of the use of the epoxy resin composition of the present invention include, for example, encapsulating various electronic components such as a semiconductor element, and when manufacturing a semiconductor device, a conventional method such as a transfer mold, a compression mold, and an injection mold. Curing molding can be performed by a molding method.
- curing accelerators epoxy resin curing accelerators
- ⁇ Method for producing imidazolium salt (S-7) 252 parts of pyrogallol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of 2,3-dihydroxynaphthalene in the method for producing the imidazolium salt (S-1), and trimethoxyhexylsilane (in place of triethoxyphenylsilane) was used.
- the imidazolium salt (S-7) represented by the following formula (s7) was obtained by using 206 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) and removing the solvent with an evaporator instead of filtration. Note that a 28% methanol solution of sodium methoxide was not used.
- the melting points of the imidazolium salts (S-1) to (S-7) and the salts (S'-1) to (S'-3) were measured by the following method. Table 1 shows the results. ⁇ Melting point> The sample was placed on a SUS test table, the temperature was gradually raised, and the melting temperature was read visually.
- Epoxy resin 1 100 parts, manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000 (softening point: 58 ° C., epoxy equivalent: 273); Phenolic resin-based curing agent: manufactured by Meiwa Kasei Co., Ltd., trade name: MEH-7500 (softening point) 33 parts of 110 ° C., hydroxyl equivalent 97); 7 parts of epoxy resin curing accelerator [imidazolium salt (S-1)]; 1000 parts of fused silica powder treated with 1% by weight of a silane coupling agent, 1.5 parts of carnauba wax Parts, 4 parts of antimony trioxide and 1 part of carbon black were uniformly pulverized and mixed, then melt-kneaded using 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. Table 2 shows the results.
- Examples 2 to 8 Comparative Examples 1 to 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. Table 2 shows the results. The raw materials used in other than Example 1 are shown below.
- Epoxy resin 2 XY-4000H (manufactured by Mitsubishi Chemical Corporation) (softening point 80 ° C, epoxy equivalent 192)
- Phenolic resin-based curing agent 2 MEH-7851SS (trade name: softening point 67 ° C, hydroxyl equivalent 203, manufactured by Meiwa Kasei Co., Ltd.)
- the epoxy resin compositions of Examples 1 to 8 of the present invention have a large flow value of the sealant after melt-kneading, are excellent in fluidity, and are hardened, as compared with Comparative Examples. It can be seen that the torque is high and the curability is excellent.
- Comparative Examples 1 and 2 use a curing accelerator having a low melting point, so that the flow value indicating fluidity is relatively large, but the curing torque indicating curability is low. Comparative Example 3 is the opposite, and Comparative Example does not have both fluidity and curability as in the example.
- the epoxy resin curing accelerator (Q) of the present invention has good curability of the epoxy resin composition, enhances reliability of the semiconductor device, has good fluidity, sufficiently fills the package with the epoxy resin composition, and generates voids. It is an epoxy resin composition that does not have a risk of becoming, and is suitable for producing an epoxy resin-based sealing material for electronic components such as semiconductors.
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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°C or lower.
Description
本発明は、エポキシ樹脂硬化促進剤及びエポキシ樹脂組成物に関する。さらに詳しくは、半導体素子などの電子部品用のエポキシ樹脂系封止剤の製造に適したエポキシ樹脂硬化促進剤及びそれを含有するエポキシ樹脂組成物に関する。
The present invention relates to an epoxy resin curing accelerator and an epoxy resin composition. More specifically, the present invention relates to an epoxy resin curing accelerator suitable for producing an epoxy resin-based encapsulant for electronic components such as semiconductor elements, and an epoxy resin composition containing the same.
ＩＣ等の半導体素子の封止方法として、エポキシ樹脂組成物のトランスファー成形が低コスト、大量生産に優れている。しかし、電子機器の小型化、軽量化のために半導体の高集積化が進んでおり、また表面実装も進んでいる中で半導体封止剤用エポキシ樹脂組成物もそれらにつれて、信頼性の要求が非常に強くなってきた。このため、エポキシ樹脂組成物の中に無機材料の充填剤の比率を多くすることで、エポキシ樹脂の低吸湿性、高強度、低熱膨張化という特性を出すことで、信頼性を担保してきた。
(2) As a method for encapsulating a semiconductor element such as an IC, transfer molding of an epoxy resin composition is excellent in low cost and mass production. However, as semiconductors are becoming more highly integrated in order to reduce the size and weight of electronic devices, and as surface mounting is progressing, epoxy resin compositions for semiconductor encapsulants are also required to have higher reliability. It has become very strong. For this reason, reliability has been ensured by increasing the ratio of the filler of the inorganic material in the epoxy resin composition to provide the epoxy resin with characteristics of low hygroscopicity, high strength, and low thermal expansion.
無機材料の充填剤の比率を多くした場合の弊害は、エポキシ樹脂組成物の成型時の硬化性が不十分になる点と高粘度になる点の２つである。硬化性が悪いと、半導体装置の信頼性を損ねることとなり、また高粘度となり流動性が悪いと、エポキシ樹脂組成物がパッケージ内に十分に充填されず、空隙が生じてしまう恐れがある。エポキシ樹脂組成物の硬化性が良いもの（例えば、特許文献１）や流動性が良いもの（例えば、特許文献２）が提案されているが、両方を十分に満足できるものはなかった。
(4) When the ratio of the filler of the inorganic material is increased, there are two problems that the curability during molding of the epoxy resin composition becomes insufficient and that the viscosity becomes high. If the curability is poor, the reliability of the semiconductor device is impaired. If the viscosity is high and the fluidity is poor, the epoxy resin composition may not be sufficiently filled in the package, and voids may be generated. An epoxy resin composition having good curability (for example, Patent Document 1) and a resin having good fluidity (for example, Patent Document 2) have been proposed, but none of them can sufficiently satisfy both.
そこで、特定のエポキシ硬化促進剤を用いることで、エポキシ樹脂組成物の硬化性が良く半導体装置の信頼性を高め、また、流動性が良くエポキシ樹脂組成物がパッケージ内に十分に充填され、空隙が生じてしまう恐れのないエポキシ樹脂組成物を提供することを目的とする。
Therefore, by using a specific epoxy curing accelerator, the curability of the epoxy resin composition is good and the reliability of the semiconductor device is improved, and the flowability is good and the epoxy resin composition is sufficiently filled in the package, and the void is improved. It is an object of the present invention to provide an epoxy resin composition which is free from the possibility of occurrence of a resin.
本発明者らは、上記の目的を達成するべく検討を行った結果、本発明に到達した。
すなわち、本発明は、一般式（１）で示されるイミダゾリウムカチオン（Ａ）と、一般式（２）、（３）又は（４）で示されるアニオン（Ｂ）からなるイミダゾリウム塩（Ｓ）を含み、そのイミダゾリウム塩（Ｓ）の融点が１７０℃以下であることを特徴とするエポキシ樹脂硬化促進剤（Ｑ）；並びに、該エポキシ樹脂硬化促進剤（Ｑ）、エポキシ樹脂（Ｅ）、及び１分子内にフェノール性水酸基を２個以上有する化合物（Ｐ）を含有するエポキシ樹脂組成物である。 The present inventors have studied to achieve the above object, and as a result, have reached the present invention.
That is, the present invention provides an imidazolium salt (S) comprising an imidazolium cation (A) represented by the general formula (1) and an anion (B) represented by the general formula (2), (3) or (4). Wherein the melting point of the imidazolium salt (S) is 170 ° C. or less; an epoxy resin curing accelerator (Q); and the epoxy resin curing accelerator (Q), an epoxy resin (E), And an epoxy resin composition containing a compound (P) having two or more phenolic hydroxyl groups in one molecule.
すなわち、本発明は、一般式（１）で示されるイミダゾリウムカチオン（Ａ）と、一般式（２）、（３）又は（４）で示されるアニオン（Ｂ）からなるイミダゾリウム塩（Ｓ）を含み、そのイミダゾリウム塩（Ｓ）の融点が１７０℃以下であることを特徴とするエポキシ樹脂硬化促進剤（Ｑ）；並びに、該エポキシ樹脂硬化促進剤（Ｑ）、エポキシ樹脂（Ｅ）、及び１分子内にフェノール性水酸基を２個以上有する化合物（Ｐ）を含有するエポキシ樹脂組成物である。 The present inventors have studied to achieve the above object, and as a result, have reached the present invention.
That is, the present invention provides an imidazolium salt (S) comprising an imidazolium cation (A) represented by the general formula (1) and an anion (B) represented by the general formula (2), (3) or (4). Wherein the melting point of the imidazolium salt (S) is 170 ° C. or less; an epoxy resin curing accelerator (Q); and the epoxy resin curing accelerator (Q), an epoxy resin (E), And an epoxy resin composition containing a compound (P) having two or more phenolic hydroxyl groups in one molecule.
［式（１）中、Ｒ１は、水素原子、メチル基、エチル基、プロピル基又はブチル基を表し、Ｒ２及びＲ３は、同一または異なって、メチル基、エチル基、プロピル基又はブチル基を表し、Ｒ４及びＲ５は、同一または異なって、水素原子、メチル基又はエチル基を表す。］
[In the formula (1), R1 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, and R2 and R3 are the same or different and represent a methyl group, an ethyl group, a propyl group or a butyl group. , R4 and R5 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group. ]
［式（２）中、－Ｒ６－Ｒ７－Ｒ８－及び－Ｒ１０－Ｒ１１－Ｒ１２－で表される基は、２価以上のプロトン供与体が、プロトンを２個放出してなる基で構成されるものであり、これらの基は、互いに同一であっても異なっていてもよい。Ｒ９は置換基を有していてもよい芳香族炭化水素基、又は置換基を有していてもよい脂肪族炭化水素基を表す。］
[In the formula (2), the group represented by -R6-R7-R8- and -R10-R11-R12- is a group formed by a divalent or higher proton donor releasing two protons. And these groups may be the same 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. ]
［式（３）中、－Ｒ１３－Ｒ１４－Ｒ１５－、－Ｒ１６－Ｒ１７－Ｒ１８－及び－Ｒ１９－Ｒ２０－Ｒ２１－で表される基は、２価以上のプロトン供与体が、プロトンを２個放出してなる基で構成されるものであり、これらの基は、互いに同一であっても異なっていてもよい。］
[In the formula (3), the group represented by -R13-R14-R15-, -R16-R17-R18- and -R19-R20-R21- is a group in which a divalent or higher-valent proton donor has two protons. These groups are constituted by groups that are released, and these groups may be the same or different from each other. ]
［式（４）中、－Ｒ２２－Ｒ２３－Ｒ２４－及び－Ｒ２５－Ｒ２６－Ｒ２７－で表される基は、２価以上のプロトン供与体が、プロトンを２個放出してなる基で構成されるものであり、これらの基は、互いに同一であっても異なっていてもよい。］
[In the formula (4), the group represented by -R22-R23-R24- and -R25-R26-R27- is a group formed by a divalent or higher proton donor releasing two protons. And these groups may be the same or different from each other. ]
本発明のエポキシ樹脂硬化促進剤（Ｑ）は、イミダゾリウムカチオン（Ａ）の耐熱性が極めて高く安定である。そのため、加熱溶融する配合温度でも一般式（２）、（３）又は（４）で示されるアニオン（Ｂ）と塩を組むことができ、硬化反応の促進を抑制させることが可能となる。さらに、アニオン部はキレート構造を形成するため、熱安定性がよく、エポキシ樹脂、硬化剤及び硬化促進剤の混合物を加熱溶融する配合温度でも、硬化反応を促進しない。一方、さらに温度があがった硬化温度では、すばやく分解し、エポキシ樹脂と硬化剤の反応を促進させることができるため、エポキシ樹脂組成物の硬化性が良く半導体装置の信頼性を高めることができる。
The epoxy resin curing accelerator (Q) of the present invention has extremely high heat resistance of the imidazolium cation (A) and is stable. Therefore, the salt can be combined with the anion (B) represented by the general formula (2), (3) or (4) even at the compounding temperature at which the composition is heated and melted, and the acceleration of the curing reaction can be suppressed. Furthermore, since the anion portion forms a chelate structure, it has good thermal stability, and does not accelerate the curing reaction even at the compounding 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 an even higher curing temperature, the epoxy resin composition can be quickly decomposed, and the reaction between the epoxy resin and the curing agent can be promoted. Therefore, the curability of the epoxy resin composition is good and the reliability of the semiconductor device can be improved.
さらに、エポキシ樹脂硬化促進剤（Ｑ）は、イミダゾリウムカチオン（Ａ）を有するため、比較的融点が低い。つまり、加熱溶融する配合温度と融点が近い、又はそれ以下である。このことから、流動性が良いエポキシ樹脂組成物を設計できる。つまりエポキシ樹脂硬化促進剤（Ｑ）を用いることで、エポキシ樹脂組成物の硬化性が良く半導体装置の信頼性を高め、流動性が良くエポキシ樹脂組成物がパッケージ内に十分に充填され、空隙が生じてしまう恐れのないエポキシ樹脂組成物となり、半導体などの電子部品用のエポキシ樹脂系封止材の製造に好適である。
Further, the epoxy resin curing accelerator (Q) has an imidazolium cation (A) and therefore has a relatively low melting point. That is, the melting point is close to or lower than the compounding temperature at which the mixture is heated and melted. From this, an epoxy resin composition having good fluidity can be designed. That is, by using the epoxy resin curing accelerator (Q), the curability of the epoxy resin composition is improved, the reliability of the semiconductor device is improved, the fluidity is improved, the epoxy resin composition is sufficiently filled in the package, and voids are formed. It is an epoxy resin composition that is unlikely to be produced, and is suitable for producing an epoxy resin-based sealing material for electronic components such as semiconductors.
以下、本発明のエポキシ樹脂硬化促進剤（Ｑ）及びエポキシ樹脂組成物について説明する。本発明のエポキシ樹脂硬化促進剤（Ｑ）は、一般式（１）で示されるイミダゾリウムカチオン（Ａ）と、一般式（２）、（３）又は（４）で示されるアニオン（Ｂ）からなるイミダゾリウム塩（Ｓ）を含むことを特徴とする。
Hereinafter, the epoxy resin curing accelerator (Q) and the epoxy resin composition of the present invention will be described. The epoxy resin curing accelerator (Q) of the present invention comprises an imidazolium cation (A) represented by the general formula (1) and an anion (B) represented by the general formula (2), (3) or (4). Characterized by containing an imidazolium salt (S).
イミダゾリウムカチオン（Ａ）は、一般式（１）で示され、式（１）中、Ｒ１は、水素原子、メチル基、エチル基、プロピル基又はブチル基を表し、Ｒ２及びＲ３は、同一又は異なって、メチル基、エチル基、プロピル基又はブチル基を表し、Ｒ４及びＲ５は、同一又は異なって、水素原子、メチル基又はエチル基を表す。
The imidazolium cation (A) is represented by the general formula (1), wherein R1 represents a hydrogen atom, a methyl group, an ethyl group, a propyl group or a butyl group, and R2 and R3 are the same or different. Differently represents a methyl group, an ethyl group, a propyl group or a butyl group, and R4 and R5 are the same or different and represent a hydrogen atom, a methyl group or an ethyl group.
イミダゾリウムカチオン（Ａ）は、エポキシ樹脂組成物の硬化性の観点から、Ｒ１は、好ましくは水素原子である。
これは、エポキシ樹脂組成物の硬化の過程でイミダゾリウムがカルベン化合物になる事に由来する。さらに流動性の観点から、Ｒ４及びＲ５は、好ましくは水素原子である。 In the imidazolium cation (A), R1 is preferably a hydrogen atom from the viewpoint of curability of the epoxy resin composition.
This is because imidazolium becomes a carbene compound in the process of curing the epoxy resin composition. Further, from the viewpoint of fluidity, R4 and R5 are preferably a hydrogen atom.
これは、エポキシ樹脂組成物の硬化の過程でイミダゾリウムがカルベン化合物になる事に由来する。さらに流動性の観点から、Ｒ４及びＲ５は、好ましくは水素原子である。 In the imidazolium cation (A), R1 is preferably a hydrogen atom from the viewpoint of curability of the epoxy resin composition.
This is because imidazolium becomes a carbene compound in the process of curing the epoxy resin composition. Further, from the viewpoint of fluidity, R4 and R5 are preferably a hydrogen atom.
イミダゾリウムカチオン（Ａ）の具体例としては、１－エチル－３－メチルイミダゾリウムカチオン、１－プロピル－３－メチルイミダゾリウムカチオン、１－ブチル－３－メチルイミダゾリウムカチオン、１－ブチル－２，３－ジメチルイミダゾリウムカチオン、１，３－ジメチルイミダゾリウムカチオン、１，３－ジエチルイミダゾリウムカチオン、１，２，３－トリメチルイミダゾリウムカチオン、１，２，３，４－テトラメチルイミダゾリウムカチオン、１，３，４－トリメチル－２－エチルイミダゾリウムカチオン、１，３－ジメチル－２，４－ジエチルイミダゾリウムカチオン、１，２－ジメチル－３，４－ジエチルイミダゾリウムカチオン、１－メチル－２，３，４－トリエチルイミダゾリウムカチオン、１，２，３，４－テトラエチルイミダゾリウムカチオン、１，３－ジメチル－２－エチルイミダゾリウムカチオン、１－エチル－２，３－ジメチルイミダゾリウムカチオン、及び１，２，３－トリエチルイミダゾリウムカチオン等が挙げられる。
Specific examples of the imidazolium cation (A) include 1-ethyl-3-methylimidazolium cation, 1-propyl-3-methylimidazolium cation, 1-butyl-3-methylimidazolium cation, 1-butyl-2 1,3-dimethylimidazolium cation, 1,3-dimethylimidazolium cation, 1,3-diethylimidazolium cation, 1,2,3-trimethylimidazolium cation, 1,2,3,4-tetramethylimidazolium cation 1,3,4-trimethyl-2-ethylimidazolium cation, 1,3-dimethyl-2,4-diethylimidazolium cation, 1,2-dimethyl-3,4-diethylimidazolium cation, 1-methyl- 2,3,4-triethylimidazolium cation, 1,2,3,4-te La ethyl imidazolium cation, 1,3-dimethyl-2-ethyl-imidazolium cation, 1-ethyl-2,3-dimethyl imidazolium cations, and 1,2,3-triethyl imidazolium cation and the like.
イミダゾリウムカチオン（Ａ）の製造は、例えば、四級化アミンカチオンのアルキル炭酸塩を使用する反応、及び四級化アミンカチオンの水酸化物を使用する反応等により得られる。
The imidazolium cation (A) can be produced, 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.
アニオン（Ｂ）は、一般式（２）、（３）又は（４）で示される。
The anion (B) is represented by the general formula (2), (3) or (4).
［式（２）中、－Ｒ６－Ｒ７－Ｒ８－及び－Ｒ１０－Ｒ１１－Ｒ１２－で表される基は、２価以上のプロトン供与体が、プロトンを２個放出してなる基で構成されるものであり、これらの基は、互いに同一であっても異なっていてもよい。Ｒ９は置換基を有していてもよい芳香族炭化水素基、又は置換基を有していてもよい脂肪族炭化水素基を表す。］
[In the formula (2), the group represented by -R6-R7-R8- and -R10-R11-R12- is a group formed by a divalent or higher proton donor releasing two protons. And these groups may be the same 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. ]
［式（３）中、－Ｒ１３－Ｒ１４－Ｒ１５－、－Ｒ１６－Ｒ１７－Ｒ１８－及び－Ｒ１９－Ｒ２０－Ｒ２１－で表される基は、２価以上のプロトン供与体が、プロトンを２個放出してなる基で構成されるものであり、これらの基は、互いに同一であっても異なっていてもよい。］
[In the formula (3), the group represented by -R13-R14-R15-, -R16-R17-R18- and -R19-R20-R21- is a group in which a divalent or higher-valent proton donor has two protons. These groups are constituted by groups that are released, and these groups may be the same or different from each other. ]
［式（４）中、－Ｒ２２－Ｒ２３－Ｒ２４－及び－Ｒ２５－Ｒ２６－Ｒ２７－で表される基は、２価以上のプロトン供与体が、プロトンを２個放出してなる基で構成されるものであり、これらの基は、互いに同一であっても異なっていてもよい。］
[In the formula (4), the group represented by -R22-R23-R24- and -R25-R26-R27- is a group formed by a divalent or higher proton donor releasing two protons. And these groups may be the same or different from each other. ]
式（２）～（４）中のプロトン供与性置換基のプロトン供与体としては、カテコール、１，２－ジヒドロキシナフタレン、２，３－ジヒドロキシナフタレン、２，２’－ビフェノール、２，２’－ビナフトール、ピロガロール、トリヒドロキシ安息香酸、没食子酸エステル、２，３，４－トリヒドロキシベンゾフェノン、サリチル酸、１－ヒドロキシ－２－ナフトエ酸、３－ヒドロキシ－２－ナフトエ酸、クロラニル酸、タンニン酸の群から選ばれるフェノール系化合物；
２－ヒドロキシベンジルアルコール、１，２－シクロヘキサンジオール、１，２－プロパンジオール、グリセリンの群から選ばれるアルコール系化合物；
及び、尿素、１－メチル尿素、１，３－ジメチル尿素、１，３－ジアミノ尿素、１，３－ジメチロール尿素、アロファンアミドチオ尿素、１－メチルチオ尿素、１，３－ジメチルチオ尿素、チオセミカルバジド、チオカルボヒドラジド、４－メチルチオセミカルバジド、グアニルチオ尿素の群から選ばれる尿素系化合物が挙げられる。好ましくは、上記フェノール系化合物である。 As the proton donor of the proton donating substituent in the formulas (2) to (4), catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′- Group of binaphthol, pyrogallol, trihydroxybenzoic acid, gallic 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:
Alcohol compounds selected from the group consisting of 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin;
And urea, 1-methylurea, 1,3-dimethylurea, 1,3-diaminourea, 1,3-dimethylolurea, allophanamidthiourea, 1-methylthiourea, 1,3-dimethylthiourea, thiosemicarbazide Thiocarbohydrazide, 4-methylthiosemicarbazide and guanylthiourea. Preferably, the phenolic compound is used.
２－ヒドロキシベンジルアルコール、１，２－シクロヘキサンジオール、１，２－プロパンジオール、グリセリンの群から選ばれるアルコール系化合物；
及び、尿素、１－メチル尿素、１，３－ジメチル尿素、１，３－ジアミノ尿素、１，３－ジメチロール尿素、アロファンアミドチオ尿素、１－メチルチオ尿素、１，３－ジメチルチオ尿素、チオセミカルバジド、チオカルボヒドラジド、４－メチルチオセミカルバジド、グアニルチオ尿素の群から選ばれる尿素系化合物が挙げられる。好ましくは、上記フェノール系化合物である。 As the proton donor of the proton donating substituent in the formulas (2) to (4), catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′- Group of binaphthol, pyrogallol, trihydroxybenzoic acid, gallic 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:
Alcohol compounds selected from the group consisting of 2-hydroxybenzyl alcohol, 1,2-cyclohexanediol, 1,2-propanediol, and glycerin;
And urea, 1-methylurea, 1,3-dimethylurea, 1,3-diaminourea, 1,3-dimethylolurea, allophanamidthiourea, 1-methylthiourea, 1,3-dimethylthiourea, thiosemicarbazide Thiocarbohydrazide, 4-methylthiosemicarbazide and guanylthiourea. Preferably, the phenolic compound is used.
一般式（２）中、Ｒ９は置換基を有していてもよい芳香族炭化水素基、又は置換基を有していてもよい脂肪族炭化水素基を表す。
芳香族炭化水素基としてはフェニル基、ナフチル基、アントラセニル基等が挙げられる。その置換基としては炭素数１～１８のアルキル基、ハロゲン原子が挙げられる。
脂肪族炭化水素基としては炭素数１～１８のアルキル基が挙げられる。その置換基としてはハロゲン原子が挙げられる。 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 the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group. 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 an alkyl group having 1 to 18 carbon atoms. Examples of the substituent include a halogen atom.
芳香族炭化水素基としてはフェニル基、ナフチル基、アントラセニル基等が挙げられる。その置換基としては炭素数１～１８のアルキル基、ハロゲン原子が挙げられる。
脂肪族炭化水素基としては炭素数１～１８のアルキル基が挙げられる。その置換基としてはハロゲン原子が挙げられる。 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 the aromatic hydrocarbon group include a phenyl group, a naphthyl group, and an anthracenyl group. 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 an alkyl group having 1 to 18 carbon atoms. Examples of the substituent include a halogen atom.
イミダゾリウム塩（Ｓ）の合成方法としては、例えば、前記のイミダゾリウムカチオン（Ａ）と、アルコキシシラン類（又はホウ酸、ホウ酸エステル類）、及び珪素原子（又はホウ素原子）とキレート結合を形成可能な前記プロトン供与体とを一定な比率で反応させる方法が挙げられる。
As a method for synthesizing the imidazolium salt (S), for example, the above-mentioned imidazolium cation (A), a chelate bond with an alkoxysilane (or boric acid, borate), and a silicon atom (or boron atom) are used. A method of reacting the proton donor that can be formed with the proton donor at a fixed ratio may be used.
アルコキシシラン類としては、例えば、フェニルトリメトキシシラン、フェニルトリエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ヘキシルトリメトキシシラン、ヘキシルトリエトキシシラン、及びテトラエトキシシラン等が挙げられる。
Examples of the alkoxysilanes include, for example, phenyltrimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, and tetra Ethoxysilane and the like can be mentioned.
本発明のイミダゾリウム塩（Ｓ）の融点は、１７０℃以下であり、好ましくは、１２０℃以下である。下限は扱いやすさの観点で、－５０℃以上が好ましい。より好ましい融点としては、－３０℃～１２０℃、さらに好ましくは、－２０℃～１００℃、もっとも好ましくは、０℃～７０℃である。１７０℃を超えると、粘度があがり流動性が悪くなる。
The melting point of the imidazolium salt (S) of the present invention is 170 ° C. or lower, preferably 120 ° C. or lower. The lower limit is preferably −50 ° C. or higher from the viewpoint of ease of handling. The more preferable melting point is from -30 ° C to 120 ° C, more preferably from -20 ° C to 100 ° C, and most preferably from 0 ° C to 70 ° C. If the temperature exceeds 170 ° C., the viscosity increases and the fluidity deteriorates.
本発明のエポキシ樹脂組成物は、エポキシ樹脂（Ｅ）と、１分子内にフェノール性水酸基を２個以上有する化合物（Ｐ）と、上記エポキシ樹脂硬化促進剤（Ｑ）を含有する。
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 curing accelerator (Q).
エポキシ樹脂（Ｅ）は、１分子内にエポキシ基を２個以上有するオリゴマー、ポリマー全般であり、その分子量、分子構造は特に限定するものではないが、例えば、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ハイドロキノン型エポキシ樹脂、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビフェニル型エポキシ樹脂、スチルベン型エポキシ樹脂、トリフェノールメタン型エポキシ樹脂、アルキル変性トリフェノールメタン型エポキシ樹脂、トリアジン核含有エポキシ樹脂、ジシクロペンタジエン変性フェノール型エポキシ樹脂、フェニレン及び／又はビフェニレン骨格を有するフェノールアラルキル型エポキシ樹脂、ナフトール型エポキシ樹脂、ナフタレン型エポキシ樹脂、フェニレン及び／又はビフェニレン骨格を有するナフトールアラルキル型エポキシ樹脂等が挙げられ、これらは単独でも混合して用いても差し支えない。
The epoxy resin (E) is generally an oligomer or polymer having two or more epoxy groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Examples thereof include a phenol novolak type epoxy resin and a cresol novolak 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, epoxy containing triazine nucleus Resin, dicyclopentadiene-modified phenol type epoxy resin, phenol aralkyl type epoxy resin having phenylene and / or biphenylene skeleton, naphthol type epoxy resin, naphthalene type epoxy resin, resin Ylene and / or naphthol aralkyl type epoxy resins. Having a biphenylene skeleton, it no problem is used singly or in admixture.
エポキシ樹脂（Ｅ）の例としては、ＤＩＣ株式会社製の：ＨＰ－４０３２、ＨＰ－４７００、ＨＰ－７２００、ＨＰ－８２０、ＨＰ－４７７０、ＨＰ－５０００、ＥＸＡ－８５０、ＥＸＡ－８３０、ＥＸＡ－１５１４、ＥＸＡ－４８５０シリーズ；日本化薬株式会社製の：ＥＰＰＮ－２０１Ｌ、ＢＲＥＮ－１０５、ＥＰＰＮ－５０２Ｈ、ＥＯＣＮ－１０２０、ＮＣ－２０００－Ｌ、ＸＤ－１０００、ＮＣ－７０００Ｌ、ＮＣ－７３００Ｌ、ＥＰＰＮ－５０１Ｈ、ＮＣ－３０００；三菱ケミカル株式会社製の：ＸＹ－４０００などが挙げられる。
Examples of the epoxy resin (E) include those 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.
１分子内にフェノール性水酸基を２個以上有する化合物（Ｐ）は、１分子内にフェノール性水酸基を２個以上有するモノマー、オリゴマー、ポリマー全般であり、その分子量、分子構造を特に限定するものではないが、例えば、フェノールノボラック樹脂、クレゾールノボラック樹脂、トリフェノールメタン型フェノール樹脂、テルペン変性フェノール樹脂、ジシクロペンタジエン変性フェノール樹脂、フェニレン及び／又はビフェニレン骨格を有するフェノールアラルキル樹脂、フェニレン及び／又はビフェニレン骨格を有するナフトールアラルキル樹脂、ビスフェノール化合物等が挙げられ、これらは単独でも混合して用いても差し支えない。
The compound (P) having two or more phenolic hydroxyl groups in one molecule includes all monomers, oligomers and polymers having two or more phenolic hydroxyl groups in one molecule, and the molecular weight and molecular structure are not particularly limited. However, for example, phenol novolak resin, cresol novolak resin, triphenol methane type phenol resin, terpene modified phenol resin, dicyclopentadiene modified phenol resin, phenol aralkyl resin having phenylene and / or biphenylene skeleton, phenylene and / or biphenylene skeleton And a naphthol aralkyl resin and a bisphenol compound, which may be used singly or as a mixture.
フェノール性水酸基を２個以上有する化合物（Ｐ）の例としては、明和化成株式会社製の：ＨＦシリーズ、ＭＥＨ－７５００シリーズ、ＭＥＨ－７８００シリーズ、ＭＥＨ－７８５１シリーズ、ＭＥＨ－７６００シリーズ、ＭＥＨ－８０００シリーズ；本州化学工業株式会社製の：ＴｒｉＰ－ＰＡ、ＢｉｓＰ－ＴＭＣ、ＢｉｓＰ－ＡＰ、ＯＣ－ＢＰ、ＴｅｋＰ－４ＨＢＰＡ、ＣｙＲＳ－ＰＲＤ４などが挙げられる。
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, MEH-8000 manufactured by Meiwa Kasei Corporation. Series: TriP-PA, BisP-TMC, BisP-AP, OC-BP, TekP-4HBPA, CyRS-PRD4, etc., manufactured by Honshu Chemical Industry Co., Ltd.
本発明のエポキシ樹脂組成物は、これを硬化することにより、最終的に硬化エポキシ樹脂が得られる。エポキシ樹脂硬化促進剤（Ｑ）の配合量はエポキシ樹脂や硬化剤の反応性に応じて調整されるが、エポキシ樹脂１００重量部に対して通常１～２５重量部、好ましくは２～２０重量部である。
By curing the epoxy resin composition of the present invention, a cured epoxy resin is finally obtained. The amount of the epoxy resin curing accelerator (Q) is adjusted according to the reactivity of the epoxy resin and the curing agent, and is usually 1 to 25 parts by weight, preferably 2 to 20 parts by weight, per 100 parts by weight of the epoxy resin. It is.
エポキシ樹脂（Ｅ）と、１分子内にフェノール性水酸基を２個以上有する化合物（Ｐ）との配合比率も、特に限定されないが、エポキシ樹脂（Ｅ）のエポキシ基１当量に対し、前記化合物（Ｐ）のフェノール性水酸基が０．５～２当量となるように用いるのが好ましく、０．７～１．５当量となるように用いるのが、より好ましい。
The mixing ratio of the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule is not particularly limited, either, but the compound ( The phenolic hydroxyl group of P) is preferably used in an amount of 0.5 to 2 equivalents, more preferably 0.7 to 1.5 equivalents.
本発明のエポキシ樹脂組成物は、さらに無機充填材（Ｈ）を含むことが好ましい。
本発明のエポキシ樹脂組成物を半導体素子などの電子部品の封止などに用いる場合、得られる半導体装置の耐半田性向上などを目的として、エポキシ樹脂組成物中に配合されるものであり、その種類については、特に制限はなく、一般に封止材料に用いられているものを使用することができる。 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, for the purpose of improving the solder resistance of the obtained semiconductor device, the epoxy resin composition is incorporated into the epoxy resin composition. The type is not particularly limited, and those generally used for a sealing material can be used.
本発明のエポキシ樹脂組成物を半導体素子などの電子部品の封止などに用いる場合、得られる半導体装置の耐半田性向上などを目的として、エポキシ樹脂組成物中に配合されるものであり、その種類については、特に制限はなく、一般に封止材料に用いられているものを使用することができる。 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, for the purpose of improving the solder resistance of the obtained semiconductor device, the epoxy resin composition is incorporated into the epoxy resin composition. The type is not particularly limited, and those generally used for a sealing material can be used.
また、無機充填材（Ｈ）の含有量は、特に限定されないが、エポキシ樹脂（Ｅ）と、１分子内にフェノール性水酸基を２個以上有する化合物（Ｐ）との合計量１００重量部あたり、２００～２４００重量部が好ましく、４００～１４００重量部が、より好ましい。
Although the content of the inorganic filler (H) is not particularly limited, the total amount of the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule per 100 parts by weight is as follows: It is preferably from 200 to 2400 parts by weight, more preferably from 400 to 1400 parts by weight.
本発明のエポキシ樹脂組成物は、さらに他の機能性ある化合物（機能性添加剤）を含むことが好ましい。
It is preferable that the epoxy resin composition of the present invention further contains another functional compound (functional additive).
機能性添加剤には、例えば、３－グリシジルオキシプロピルトリメトキシシラン、３－メルカプトプロピルトリメトキシシラン、Ｎ－フェニル－３－アミノプロピルトリメトキシシラン、３－ウレイドプロピルトリエトキシシラン及びフェニルトリメトキシシラン、等のアルコキシシラン類やチタネートエステル類及びアルミナートエステル類に代表されるカップリング剤；カーボンブラック等の着色剤；臭素化エポキシ樹脂、酸化アンチモン、水酸化アルミニウム、水酸化マグネシウム、酸化亜鉛及びリン系化合物等の難燃剤；シリコーンオイル及びシリコーンゴム等の低応力成分；カルナバワックス等の天然ワックス、ポリエチレンワックス等の合成ワックス；ステアリン酸やステアリン酸亜鉛等の高級脂肪酸、該高級脂肪酸の金属塩類及びパラフィン等の離型剤；マグネシウム、アルミニウム、チタン及びビスマス系等のイオンキャッチャー、ビスマス酸化防止剤等の各種添加剤；ベンゾオキサジン、シアネートエステル、ビスマレイミドのような耐熱性ＵＰさせる変性化合物が挙げられる。
Functional additives include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane and phenyltrimethoxysilane Coupling agents represented by alkoxysilanes, titanate esters, and aluminate esters; and coloring agents such as carbon black; brominated epoxy resins, antimony oxide, aluminum hydroxide, magnesium hydroxide, zinc oxide, and phosphorus. Flame retardants such as system 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 and paraffin; various additives such as magnesium, aluminum, titanium and bismuth-based ion catchers and bismuth antioxidants; and heat-resistant UP-modified compounds such as benzoxazine, cyanate ester and bismaleimide. Can be
本発明のエポキシ樹脂組成物は、エポキシ樹脂（Ｅ）と、１分子内にフェノール性水酸基を２個以上有する化合物（Ｐ）以外の樹脂を含むこともできる。
その以外の樹脂としては、酸無水物を用いるエポキシ樹脂、ポリイミド系樹脂、ナノコンポジット系樹脂、シアネートエステル系樹脂などが挙げられる。 The epoxy resin composition of the present invention may contain a resin other than the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule.
Other resins include an epoxy resin using an acid anhydride, a polyimide resin, a nanocomposite resin, a cyanate ester resin, and the like.
その以外の樹脂としては、酸無水物を用いるエポキシ樹脂、ポリイミド系樹脂、ナノコンポジット系樹脂、シアネートエステル系樹脂などが挙げられる。 The epoxy resin composition of the present invention may contain a resin other than the epoxy resin (E) and the compound (P) having two or more phenolic hydroxyl groups in one molecule.
Other resins include an epoxy resin using an acid anhydride, a polyimide resin, a nanocomposite resin, a cyanate ester resin, and the like.
他の機能性ある化合物は、「総説エポキシ樹脂第一巻」、「総説エポキシ樹脂第一巻」、エポキシ樹脂技術協会、２００３；エクトロニクス実装学会誌、１４、２０４、２０１１；ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ，１０９，２０２３－２０２８，２００８；Ｐｏｌｙｍｅｒ Ｐｒｅｐｒｉｎｔｓ，Ｊａｐａｎ，６０，１Ｋ１９，２０１１；ネックワークポリマー，３３，１３０，２０１２；Ｐｏｌｙｍ．Ｉｎｔ．５４，１１０３－１１０９，２００５；Ｊｏｕｒｎａｌ ｏｆ Ａｐｐｌｉｅｄ Ｐｏｌｙｍｅｒ Ｓｃｉｅｎｃｅ，９２，２３７５－２３８６，２００４；ネックワークポリマー，２９，１７５，２００８；高分子論文集，６５，５６２，２００８；高分子論文集，６６（６），２１７，２００９などに記載されている。
Other functional compounds are described in “Reviewed Epoxy Resin Vol. 1”, “Reviewed Epoxy Resin Vol. 1”, Epoxy Resin Technology Association, 2003; Journal of the Japan Institute of Ectronics, 14, 204, 2011; journal of Applied Polymer Polymer Science. Polymer, Preprints, Japan, 60, 1K19, 2011; Neckwork Polymer, 33, 130, 2012; Polym., 109, 2023-2028, 2008; Int. 54, 1103-1109, 2005; Journal of Applied Polymer Polymer Science, 92, 2375-2386, 2004; Neckwork Polymer, 29, 175, 2008; Collection of Polymer Papers, 65, 562, 2008; Collection of Polymer Papers, 66 ( 6), 217, 2009 and the like.
本発明のエポキシ樹脂組成物は、上記成分、必要に応じて、その他の添加剤等を、ミキサーを用いて均一混合して得られ、さらには、常温で混合したものを、ロール、ニーダー、コニーダー及び二軸押出機等の混練機を用いて、加熱混練した後、冷却、粉砕することにより得ることができる。また、上記で得たエポキシ樹脂組成物は、紛体である場合、使用にあたっての作業性を向上させるために、プレス等により加圧タブレット化して使用することもできる。
The epoxy resin composition of the present invention is obtained by uniformly mixing the above components and, if necessary, other additives and the like using a mixer, and further, a mixture obtained at room temperature, roll, kneader, co-kneader And kneading by heating using a kneader such as a twin screw extruder, and then cooling and pulverizing. In addition, when the epoxy resin composition obtained above is a powder, it can be used in the form of a pressurized tablet by a press or the like in order to improve workability in use.
本発明のエポキシ樹脂組成物の用い方としては、例えば、半導体素子等の各種の電子部品を封止し、半導体装置を製造する場合には、トランスファーモールド、コンプレッションモールド及びインジェクションモールド等の従来からの成形方法により、硬化成形することができる。
Examples of the use of the epoxy resin composition of the present invention include, for example, encapsulating various electronic components such as a semiconductor element, and when manufacturing a semiconductor device, a conventional method such as a transfer mold, a compression mold, and an injection mold. Curing molding can be performed by a molding method.
以下、実施例及び比較例により本発明をさらに説明するが、本発明はこれらに限定されるものではない。以下、特に定めない限り、％は重量％、部は重量部を示す。
なお、実施例、比較例で用いたエポキシ樹脂硬化促進剤（以下、硬化促進剤と記す。）の内容について以下に示す。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% means% by weight and part means parts by weight.
The contents of the epoxy resin curing accelerators (hereinafter, referred to as curing accelerators) used in Examples and Comparative Examples are shown below.
なお、実施例、比較例で用いたエポキシ樹脂硬化促進剤（以下、硬化促進剤と記す。）の内容について以下に示す。 Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% means% by weight and part means parts by weight.
The contents of the epoxy resin curing accelerators (hereinafter, referred to as curing accelerators) used in Examples and Comparative Examples are shown below.
＜イミダゾリウム塩（Ｓ－１）の製造方法＞
攪拌式のオートクレーブに、炭酸ジエチル（東京化成工業株式会社社製）１４１部及び溶媒のエタノール５００部を仕込み、この中に１－メチルイミダゾール（東京化成工業株式会社社製）８２部を仕込み、反応温度１３５℃にて８０時間反応させることで、１－エチル－３－メチルイミダゾリウム・エチル炭酸塩（Ｓ－１－１）のエタノール溶液を得た。滴下ロート、及び還流管を備え付けたガラス製丸底３つ口フラスコに、トリエトキシフェニルシラン（東京化成工業株式会社社製）２４０部、２，３－ジヒドロキシナフタレン（東京化成工業株式会社社製）３２０部、及びナトリウムメトキシド２８％メタノール溶液（東京化成工業株式会社社製）３０部をメタノール９００部中に投入後、１－エチル－３－メチルイミダゾリウム・エチル炭酸塩（Ｓ－１－１）のエタノール溶液を滴下し、下記式（ｓ１）で表わされるイミダゾリウム塩が得られた。ろ過しメタノールで数回洗浄し乾燥することで精製を行い、イミダゾリウム塩（Ｓ－１）［化学式では（ｓ１）と表示、その他のイミダゾリウム塩についても同様である。］とした。 <Method for producing imidazolium salt (S-1)>
A stirred autoclave was charged with 141 parts of diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of ethanol as a solvent, and 82 parts of 1-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged therein, followed by reaction. By reacting at a temperature of 135 ° C. for 80 hours, an 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 triethoxyphenylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2,3-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) After 320 parts and 30 parts of a 28% methanol solution of sodium methoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) are charged into 900 parts of methanol, 1-ethyl-3-methylimidazolium ethyl carbonate (S-1-1) is added. ) Was added dropwise to obtain an imidazolium salt represented by the following formula (s1). Purification is carried out by filtration, washing with methanol several times and drying, and the imidazolium salt (S-1) [labeled as (s1) in the chemical formula, and the same applies to other imidazolium salts. ].
攪拌式のオートクレーブに、炭酸ジエチル（東京化成工業株式会社社製）１４１部及び溶媒のエタノール５００部を仕込み、この中に１－メチルイミダゾール（東京化成工業株式会社社製）８２部を仕込み、反応温度１３５℃にて８０時間反応させることで、１－エチル－３－メチルイミダゾリウム・エチル炭酸塩（Ｓ－１－１）のエタノール溶液を得た。滴下ロート、及び還流管を備え付けたガラス製丸底３つ口フラスコに、トリエトキシフェニルシラン（東京化成工業株式会社社製）２４０部、２，３－ジヒドロキシナフタレン（東京化成工業株式会社社製）３２０部、及びナトリウムメトキシド２８％メタノール溶液（東京化成工業株式会社社製）３０部をメタノール９００部中に投入後、１－エチル－３－メチルイミダゾリウム・エチル炭酸塩（Ｓ－１－１）のエタノール溶液を滴下し、下記式（ｓ１）で表わされるイミダゾリウム塩が得られた。ろ過しメタノールで数回洗浄し乾燥することで精製を行い、イミダゾリウム塩（Ｓ－１）［化学式では（ｓ１）と表示、その他のイミダゾリウム塩についても同様である。］とした。 <Method for producing imidazolium salt (S-1)>
A stirred autoclave was charged with 141 parts of diethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of ethanol as a solvent, and 82 parts of 1-methylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was charged therein, followed by reaction. By reacting at a temperature of 135 ° C. for 80 hours, an 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 triethoxyphenylsilane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2,3-dihydroxynaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.) After 320 parts and 30 parts of a 28% methanol solution of sodium methoxide (manufactured by Tokyo Chemical Industry Co., Ltd.) are charged into 900 parts of methanol, 1-ethyl-3-methylimidazolium ethyl carbonate (S-1-1) is added. ) Was added dropwise to obtain an imidazolium salt represented by the following formula (s1). Purification is carried out by filtration, washing with methanol several times and drying, and the imidazolium salt (S-1) [labeled as (s1) in the chemical formula, and the same applies to other imidazolium salts. ].
＜イミダゾリウム塩（Ｓ－２）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法の１－メチルイミダゾールの代わりに、１，２ジメチルイミダゾール（東京化成工業株式会社社製）９６部を用いることで、下記式（ｓ２）で表わされるイミダゾリウム塩（Ｓ―２）が得られた。 <Method for producing imidazolium salt (S-2)>
By using 96 parts of 1,2-dimethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 1-methylimidazole in the method for producing imidazolium salt (S-1), imidazo represented by the following formula (s2) is obtained. Lithium salt (S-2) was obtained.
イミダゾリウム塩（Ｓ－１）の製造方法の１－メチルイミダゾールの代わりに、１，２ジメチルイミダゾール（東京化成工業株式会社社製）９６部を用いることで、下記式（ｓ２）で表わされるイミダゾリウム塩（Ｓ―２）が得られた。 <Method for producing imidazolium salt (S-2)>
By using 96 parts of 1,2-dimethylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 1-methylimidazole in the method for producing imidazolium salt (S-1), imidazo represented by the following formula (s2) is obtained. Lithium salt (S-2) was obtained.
＜イミダゾリウム塩（Ｓ－３）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法のトリエトキシフェニルシラン、２，３－ジヒドロキシナフタレンの代わりに、テトラエトキシシラン１０４部、カテコール（東京化成工業株式会社社製）１６５部を用いることで、下記式（ｓ３）で表わされるイミダゾリウム塩（Ｓ―３）が得られた。 <Method for producing imidazolium salt (S-3)>
By using 104 parts of tetraethoxysilane and 165 parts of catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of triethoxyphenylsilane and 2,3-dihydroxynaphthalene in the method for producing imidazolium salt (S-1), An imidazolium salt (S-3) represented by the following formula (s3) was obtained.
イミダゾリウム塩（Ｓ－１）の製造方法のトリエトキシフェニルシラン、２，３－ジヒドロキシナフタレンの代わりに、テトラエトキシシラン１０４部、カテコール（東京化成工業株式会社社製）１６５部を用いることで、下記式（ｓ３）で表わされるイミダゾリウム塩（Ｓ―３）が得られた。 <Method for producing imidazolium salt (S-3)>
By using 104 parts of tetraethoxysilane and 165 parts of catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of triethoxyphenylsilane and 2,3-dihydroxynaphthalene in the method for producing imidazolium salt (S-1), An imidazolium salt (S-3) represented by the following formula (s3) was obtained.
＜イミダゾリウム塩（Ｓ－４）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法のトリエトキシフェニルシランの代わりに、トリエチルボレート（東京化成工業株式会社社製）１４６部を用いることで、下記式（ｓ４）で表わされるイミダゾリウム塩（Ｓ―４）が得られた。 <Method for producing imidazolium salt (S-4)>
By using 146 parts of triethyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of triethoxyphenylsilane in the method for producing the imidazolium salt (S-1), the imidazolium salt represented by the following formula (s4) ( S-4) was obtained.
イミダゾリウム塩（Ｓ－１）の製造方法のトリエトキシフェニルシランの代わりに、トリエチルボレート（東京化成工業株式会社社製）１４６部を用いることで、下記式（ｓ４）で表わされるイミダゾリウム塩（Ｓ―４）が得られた。 <Method for producing imidazolium salt (S-4)>
By using 146 parts of triethyl borate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of triethoxyphenylsilane in the method for producing the imidazolium salt (S-1), the imidazolium salt represented by the following formula (s4) ( S-4) was obtained.
＜イミダゾリウム塩（Ｓ－５）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法の２，３－ジヒドロキシナフタレンの代わりに、カテコール（東京化成工業株式会社社製）２２０部を用いることで、下記式（ｓ５）で表わされるイミダゾリウム塩（Ｓ―５）が得られた。 <Method for producing imidazolium salt (S-5)>
By using 220 parts of catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2,3-dihydroxynaphthalene in the method for producing imidazolium salt (S-1), an imidazolium salt represented by the following formula (s5) is obtained. (S-5) was obtained.
イミダゾリウム塩（Ｓ－１）の製造方法の２，３－ジヒドロキシナフタレンの代わりに、カテコール（東京化成工業株式会社社製）２２０部を用いることで、下記式（ｓ５）で表わされるイミダゾリウム塩（Ｓ―５）が得られた。 <Method for producing imidazolium salt (S-5)>
By using 220 parts of catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of 2,3-dihydroxynaphthalene in the method for producing imidazolium salt (S-1), an imidazolium salt represented by the following formula (s5) is obtained. (S-5) was obtained.
＜イミダゾリウム塩（Ｓ－６）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法の２，３－ジヒドロキシナフタレンの代わりに、ピロガロール（東京化成工業株式会社社製）２５２部を用い、ろ過の代わりに、エバポレータで溶剤を除去することで、下記式（ｓ６）で表わされるイミダゾリウム塩（Ｓ―６）が得られた。なお、ナトリウムメトキシド２８％メタノール溶液は用いなかった。 <Method for producing imidazolium salt (S-6)>
By using 252 parts of pyrogallol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) instead of 2,3-dihydroxynaphthalene in the method for producing the imidazolium salt (S-1), the solvent was removed by an evaporator instead of filtration. Thus, an imidazolium salt (S-6) represented by the following formula (s6) was obtained. Note that a 28% methanol solution of sodium methoxide was not used.
イミダゾリウム塩（Ｓ－１）の製造方法の２，３－ジヒドロキシナフタレンの代わりに、ピロガロール（東京化成工業株式会社社製）２５２部を用い、ろ過の代わりに、エバポレータで溶剤を除去することで、下記式（ｓ６）で表わされるイミダゾリウム塩（Ｓ―６）が得られた。なお、ナトリウムメトキシド２８％メタノール溶液は用いなかった。 <Method for producing imidazolium salt (S-6)>
By using 252 parts of pyrogallol (manufactured by Tokyo Kasei Kogyo Co., Ltd.) instead of 2,3-dihydroxynaphthalene in the method for producing the imidazolium salt (S-1), the solvent was removed by an evaporator instead of filtration. Thus, an imidazolium salt (S-6) represented by the following formula (s6) was obtained. Note that a 28% methanol solution of sodium methoxide was not used.
＜イミダゾリウム塩（Ｓ－７）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法の２，３－ジヒドロキシナフタレンの代わりに、ピロガロール（東京化成工業株式会社社製）２５２部を用い、トリエトキシフェニルシランの代わりに、トリメトキシヘキシルシラン（東京化成工業株式会社社製）２０６部を用い、ろ過の代わりに、エバポレータで溶剤を除去することで、下記式（ｓ７）で表わされるイミダゾリウム塩（Ｓ―７）が得られた。なお、ナトリウムメトキシド２８％メタノール溶液は用いなかった。 <Method for producing imidazolium salt (S-7)>
252 parts of pyrogallol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of 2,3-dihydroxynaphthalene in the method for producing the imidazolium salt (S-1), and trimethoxyhexylsilane (in place of triethoxyphenylsilane) was used. The imidazolium salt (S-7) represented by the following formula (s7) was obtained by using 206 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) and removing the solvent with an evaporator instead of filtration. Note that a 28% methanol solution of sodium methoxide was not used.
イミダゾリウム塩（Ｓ－１）の製造方法の２，３－ジヒドロキシナフタレンの代わりに、ピロガロール（東京化成工業株式会社社製）２５２部を用い、トリエトキシフェニルシランの代わりに、トリメトキシヘキシルシラン（東京化成工業株式会社社製）２０６部を用い、ろ過の代わりに、エバポレータで溶剤を除去することで、下記式（ｓ７）で表わされるイミダゾリウム塩（Ｓ―７）が得られた。なお、ナトリウムメトキシド２８％メタノール溶液は用いなかった。 <Method for producing imidazolium salt (S-7)>
252 parts of pyrogallol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in place of 2,3-dihydroxynaphthalene in the method for producing the imidazolium salt (S-1), and trimethoxyhexylsilane (in place of triethoxyphenylsilane) was used. The imidazolium salt (S-7) represented by the following formula (s7) was obtained by using 206 parts (manufactured by Tokyo Chemical Industry Co., Ltd.) and removing the solvent with an evaporator instead of filtration. Note that a 28% methanol solution of sodium methoxide was not used.
＜比較例に用いる塩（Ｓ’－１）の製造例＞
<Production Example of Salt (S′-1) Used in Comparative Example>
＜塩（Ｓ’－１）の製造方法＞
攪拌式のオートクレーブに、炭酸ジメチル（東京化成工業株式会社社製）１０８部及び溶媒のメタノール５００部を仕込み、この中にＤＢＵ（サンアプロ株式会社社製）１５２部を仕込み、反応温度１２５℃にて８０時間反応させたることで、中間体のＤＢＵ誘導体のメチル炭酸塩（Ｓ’－１－１）を得た。以降は、イミダゾリウム塩（Ｓ－１）の製造方法と同様にすることで、下記式（ｓ’１）で表わされる塩（Ｓ’－１）が得られた。 <Method for producing salt (S′-1)>
In a stirred autoclave, 108 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol as a solvent were charged, and 152 parts of DBU (manufactured by San Apro Co.) were charged therein, and the reaction temperature was 125 ° C. By reacting for 80 hours, methyl carbonate (S'-1-1) of the intermediate DBU derivative was obtained. Thereafter, the salt (S′-1) represented by the following formula (s′1) was obtained in the same manner as in the method for producing the imidazolium salt (S-1).
攪拌式のオートクレーブに、炭酸ジメチル（東京化成工業株式会社社製）１０８部及び溶媒のメタノール５００部を仕込み、この中にＤＢＵ（サンアプロ株式会社社製）１５２部を仕込み、反応温度１２５℃にて８０時間反応させたることで、中間体のＤＢＵ誘導体のメチル炭酸塩（Ｓ’－１－１）を得た。以降は、イミダゾリウム塩（Ｓ－１）の製造方法と同様にすることで、下記式（ｓ’１）で表わされる塩（Ｓ’－１）が得られた。 <Method for producing salt (S′-1)>
In a stirred autoclave, 108 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol as a solvent were charged, and 152 parts of DBU (manufactured by San Apro Co.) were charged therein, and the reaction temperature was 125 ° C. By reacting for 80 hours, methyl carbonate (S'-1-1) of the intermediate DBU derivative was obtained. Thereafter, the salt (S′-1) represented by the following formula (s′1) was obtained in the same manner as in the method for producing the imidazolium salt (S-1).
＜塩（Ｓ’－２）の製造方法＞
攪拌式のオートクレーブに、炭酸ジメチル（東京化成工業株式会社社製）２１６部及び溶媒のメタノール５００部を仕込み、この中に2-メチル-2-イミダゾリン（東京化成工業株式会社社製）８４部を仕込み、反応温度１２５℃にて８０時間反応させることで、中間体のイミダゾリニウムのメチル炭酸塩（Ｓ’－２－１）を得た。以降は、イミダゾリウム塩（Ｓ－１）の製造方法と同様にすることで、下記式（ｓ’２）で表わされる塩（Ｓ’－２）が得られた。 <Method for producing salt (S′-2)>
In a stirred autoclave, 216 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol as a solvent were charged, and 84 parts of 2-methyl-2-imidazoline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto. By charging and reacting at a reaction temperature of 125 ° C. for 80 hours, an intermediate imidazolinium methyl carbonate (S′-2-1) was obtained. Thereafter, the salt (S'-2) represented by the following formula (s'2) was obtained in the same manner as in the method for producing the imidazolium salt (S-1).
攪拌式のオートクレーブに、炭酸ジメチル（東京化成工業株式会社社製）２１６部及び溶媒のメタノール５００部を仕込み、この中に2-メチル-2-イミダゾリン（東京化成工業株式会社社製）８４部を仕込み、反応温度１２５℃にて８０時間反応させることで、中間体のイミダゾリニウムのメチル炭酸塩（Ｓ’－２－１）を得た。以降は、イミダゾリウム塩（Ｓ－１）の製造方法と同様にすることで、下記式（ｓ’２）で表わされる塩（Ｓ’－２）が得られた。 <Method for producing salt (S′-2)>
In a stirred autoclave, 216 parts of dimethyl carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 500 parts of methanol as a solvent were charged, and 84 parts of 2-methyl-2-imidazoline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto. By charging and reacting at a reaction temperature of 125 ° C. for 80 hours, an intermediate imidazolinium methyl carbonate (S′-2-1) was obtained. Thereafter, the salt (S'-2) represented by the following formula (s'2) was obtained in the same manner as in the method for producing the imidazolium salt (S-1).
＜塩（Ｓ’－３）の製造方法＞
イミダゾリウム塩（Ｓ－１）の製造方法の１－エチル－３－メチルイミダゾリウムのエチル炭酸塩（Ｓ－１－１）の代わりに、テトラフェニルホスホニウムブロミド（東京化成工業株式会社社製）４１９部を用いることで、下記式（ｓ’３）で表わされる塩（Ｓ’－３）が得られた。 <Method for producing salt (S′-3)>
In place of 1-ethyl-3-methylimidazolium ethyl carbonate (S-1-1) in the method for producing imidazolium salt (S-1), tetraphenylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 419 By using the part, a salt (S′-3) represented by the following formula (s′3) was obtained.
イミダゾリウム塩（Ｓ－１）の製造方法の１－エチル－３－メチルイミダゾリウムのエチル炭酸塩（Ｓ－１－１）の代わりに、テトラフェニルホスホニウムブロミド（東京化成工業株式会社社製）４１９部を用いることで、下記式（ｓ’３）で表わされる塩（Ｓ’－３）が得られた。 <Method for producing salt (S′-3)>
In place of 1-ethyl-3-methylimidazolium ethyl carbonate (S-1-1) in the method for producing imidazolium salt (S-1), tetraphenylphosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) 419 By using the part, a salt (S′-3) represented by the following formula (s′3) was obtained.
イミダゾリウム塩（Ｓ－１）～（Ｓ－７）、塩（Ｓ’－１）～（Ｓ’－３）の融点を以下の方法で測定した。結果を表１に示す。
＜融点＞
ＳＵＳ製の試験台にサンプルを置き、徐々に昇温させ目視で溶解した温度を読み取った。 The melting points of the imidazolium salts (S-1) to (S-7) and the salts (S'-1) to (S'-3) were measured by the following method. Table 1 shows the results.
<Melting point>
The sample was placed on a SUS test table, the temperature was gradually raised, and the melting temperature was read visually.
＜融点＞
ＳＵＳ製の試験台にサンプルを置き、徐々に昇温させ目視で溶解した温度を読み取った。 The melting points of the imidazolium salts (S-1) to (S-7) and the salts (S'-1) to (S'-3) were measured by the following method. Table 1 shows the results.
<Melting point>
The sample was placed on a SUS test table, the temperature was gradually raised, and the melting temperature was read visually.
実施例１
エポキシ樹脂１：日本化薬（株）製、商品名ＮＣ３０００（軟化点５８℃、エポキシ当量２７３）１００部；フェノール樹脂系硬化剤１：明和化成（株）製、商品名ＭＥＨ－７５００（軟化点１１０℃、水酸基当量９７）３３部；エポキシ樹脂硬化促進剤［イミダゾリウム塩（Ｓ－１）］７部；１重量％のシランカップリング剤で処理した溶融シリカ粉末１０００部、カルナバワックス１．５部、三酸化アンチモン４部及びカーボンブラック１部を均一に粉砕混合後、 １３０℃の熱ロールを用いて１０分間溶融混練し、冷却後粉砕して封止材を得た。得られたエポキシ樹脂組成物を、以下の方法で評価した。結果を表２に示す。 Example 1
Epoxy resin 1: 100 parts, manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000 (softening point: 58 ° C., epoxy equivalent: 273); Phenolic resin-based curing agent: manufactured by Meiwa Kasei Co., Ltd., trade name: MEH-7500 (softening point) 33 parts of 110 ° C., hydroxyl equivalent 97); 7 parts of epoxy resin curing accelerator [imidazolium salt (S-1)]; 1000 parts of fused silica powder treated with 1% by weight of a silane coupling agent, 1.5 parts of carnauba wax Parts, 4 parts of antimony trioxide and 1 part of carbon black were uniformly pulverized and mixed, then melt-kneaded using 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. Table 2 shows the results.
エポキシ樹脂１：日本化薬（株）製、商品名ＮＣ３０００（軟化点５８℃、エポキシ当量２７３）１００部；フェノール樹脂系硬化剤１：明和化成（株）製、商品名ＭＥＨ－７５００（軟化点１１０℃、水酸基当量９７）３３部；エポキシ樹脂硬化促進剤［イミダゾリウム塩（Ｓ－１）］７部；１重量％のシランカップリング剤で処理した溶融シリカ粉末１０００部、カルナバワックス１．５部、三酸化アンチモン４部及びカーボンブラック１部を均一に粉砕混合後、 １３０℃の熱ロールを用いて１０分間溶融混練し、冷却後粉砕して封止材を得た。得られたエポキシ樹脂組成物を、以下の方法で評価した。結果を表２に示す。 Example 1
Epoxy resin 1: 100 parts, manufactured by Nippon Kayaku Co., Ltd., trade name: NC3000 (softening point: 58 ° C., epoxy equivalent: 273); Phenolic resin-based curing agent: manufactured by Meiwa Kasei Co., Ltd., trade name: MEH-7500 (softening point) 33 parts of 110 ° C., hydroxyl equivalent 97); 7 parts of epoxy resin curing accelerator [imidazolium salt (S-1)]; 1000 parts of fused silica powder treated with 1% by weight of a silane coupling agent, 1.5 parts of carnauba wax Parts, 4 parts of antimony trioxide and 1 part of carbon black were uniformly pulverized and mixed, then melt-kneaded using 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. Table 2 shows the results.
＜性能評価＞
＜流動性（フロー値）＞
前記の得られたエポキシ樹脂組成物について、ＥＭＭＩ １－６６ の方法に準じて１７５℃（７０ｋｇ/ｃｍ２）でのスパイラルフローのフロー値（単位はｃｍ）を測定し、流動性の指標とした。フロー値が大きいほど流動性が良いことを表す。 <Performance evaluation>
<Fluidity (flow value)>
With respect to the obtained epoxy resin composition, the flow value (unit: cm) of the spiral flow at 175 ° C. (70 kg / cm 2) was measured in accordance with the method of EMMI 1-66 and used as an index of fluidity. The larger the flow value, the better the fluidity.
＜流動性（フロー値）＞
前記の得られたエポキシ樹脂組成物について、ＥＭＭＩ １－６６ の方法に準じて１７５℃（７０ｋｇ/ｃｍ２）でのスパイラルフローのフロー値（単位はｃｍ）を測定し、流動性の指標とした。フロー値が大きいほど流動性が良いことを表す。 <Performance evaluation>
<Fluidity (flow value)>
With respect to the obtained epoxy resin composition, the flow value (unit: cm) of the spiral flow at 175 ° C. (70 kg / cm 2) was measured in accordance with the method of EMMI 1-66 and used as an index of fluidity. The larger the flow value, the better the fluidity.
＜ゲルタイム＞
キュラストメーター７型（株式会社エー・アンド・デイ製、商品名）を使用して、温度１７５℃、樹脂用ダイスＰ－２００及び振幅角度±１／４°の条件で、それぞれの上記エポキシ樹脂組成物について硬化トルクを測定し、硬化トルクの立ち上がる点をゲルタイム（単位は秒）とした。 <Gel time>
Each of the above epoxy resins was used at a temperature of 175 ° C., a resin die P-200, and an amplitude angle of ± 1/4 °, using a type 7 Curast Meter (trade name, manufactured by A & D Corporation). The curing torque was measured for the composition, and the point at which the curing torque rose was defined as the gel time (unit: seconds).
キュラストメーター７型（株式会社エー・アンド・デイ製、商品名）を使用して、温度１７５℃、樹脂用ダイスＰ－２００及び振幅角度±１／４°の条件で、それぞれの上記エポキシ樹脂組成物について硬化トルクを測定し、硬化トルクの立ち上がる点をゲルタイム（単位は秒）とした。 <Gel time>
Each of the above epoxy resins was used at a temperature of 175 ° C., a resin die P-200, and an amplitude angle of ± 1/4 °, using a type 7 Curast Meter (trade name, manufactured by A & D Corporation). The curing torque was measured for the composition, and the point at which the curing torque rose was defined as the gel time (unit: seconds).
＜硬化性（硬化トルク）＞
上記のキュラストメーターでの測定で、測定開始から３００秒後の硬化トルクの値（単位はｋｇｆ・ｃｍ）を硬化性（脱型時の強度及び硬度）の指標とした。 <Curability (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 the measurement was used as an index of the curability (strength and hardness at the time of demolding).
上記のキュラストメーターでの測定で、測定開始から３００秒後の硬化トルクの値（単位はｋｇｆ・ｃｍ）を硬化性（脱型時の強度及び硬度）の指標とした。 <Curability (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 the measurement was used as an index of the curability (strength and hardness at the time of demolding).
実施例２～８、比較例１～３
表２の配合に従い、実施例１と同様にしてエポキシ樹脂組成物を得て、実施例１と同様にして評価した。結果を表２に示す。
実施例１以外で用いた原材料を以下に示す。 Examples 2 to 8, Comparative Examples 1 to 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. Table 2 shows the results.
The raw materials used in other than Example 1 are shown below.
表２の配合に従い、実施例１と同様にしてエポキシ樹脂組成物を得て、実施例１と同様にして評価した。結果を表２に示す。
実施例１以外で用いた原材料を以下に示す。 Examples 2 to 8, Comparative Examples 1 to 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. Table 2 shows the results.
The raw materials used in other than Example 1 are shown below.
エポキシ樹脂２：三菱ケミカル（株）製、商品名ＸＹ－４０００Ｈ（軟化点８０℃、エポキシ当量１９２）
Epoxy resin 2: XY-4000H (manufactured by Mitsubishi Chemical Corporation) (softening point 80 ° C, epoxy equivalent 192)
フェノール樹脂系硬化剤２：明和化成（株）製、商品名ＭＥＨ－７８５１ＳＳ（軟化点６７℃、水酸基当量２０３）
Phenolic resin-based curing agent 2: MEH-7851SS (trade name: softening point 67 ° C, hydroxyl equivalent 203, manufactured by Meiwa Kasei Co., Ltd.)
表２から明らかなように、本発明の実施例１～８のエポキシ樹脂組成物は、比較例と比べて、溶融混練後の封止剤のフロー値が大きく流動性に優れており、また硬化トルクも高く硬化性に優れていることが分かる。
As is clear from Table 2, the epoxy resin compositions of Examples 1 to 8 of the present invention have a large flow value of the sealant after melt-kneading, are excellent in fluidity, and are hardened, as compared with Comparative Examples. It can be seen that the torque is high and the curability is excellent.
一方、比較例１，２は融点が低い硬化促進剤を用いているので流動性を示すフロー値が比較的大きいものの、硬化性を示す硬化トルクが低い。比較例３はその逆であり、比較例は実施例のように、流動性と硬化性の両立ができていない
On the other hand, Comparative Examples 1 and 2 use a curing accelerator having a low melting point, so that the flow value indicating fluidity is relatively large, but the curing torque indicating curability is low. Comparative Example 3 is the opposite, and Comparative Example does not have both fluidity and curability as in the example.
本発明のエポキシ樹脂硬化促進剤（Ｑ）は、エポキシ樹脂組成物の硬化性が良く半導体装置の信頼性を高め、流動性が良くエポキシ樹脂組成物がパッケージ内に十分に充填され、空隙が生じてしまう恐れのないエポキシ樹脂組成物となり、半導体などの電子部品用のエポキシ樹脂系封止材の製造に好適である。
The epoxy resin curing accelerator (Q) of the present invention has good curability of the epoxy resin composition, enhances reliability of the semiconductor device, has good fluidity, sufficiently fills the package with the epoxy resin composition, and generates voids. It is an epoxy resin composition that does not have a risk of becoming, and is suitable for producing an epoxy resin-based sealing material for electronic components such as semiconductors.
The epoxy resin curing accelerator (Q) of the present invention has good curability of the epoxy resin composition, enhances reliability of the semiconductor device, has good fluidity, sufficiently fills the package with the epoxy resin composition, and generates voids. It is an epoxy resin composition that does not have a risk of becoming, and is suitable for producing an epoxy resin-based sealing material for electronic components such as semiconductors.
Claims (6)
- 一般式（１）で示されるイミダゾリウムカチオン（Ａ）と、一般式（２）、（３）又は（４）で示されるアニオン（Ｂ）からなるイミダゾリウム塩（Ｓ）を含み、そのイミダゾリウム塩（Ｓ）の融点が１７０℃以下であることを特徴とするエポキシ樹脂硬化促進剤（Ｑ）。
- 一般式（２）～（４）中のプロトン供与体がカテコール、１，２－ジヒドロキシナフタレン、２，３－ジヒドロキシナフタレン、２，２’－ビフェノール、２，２’－ビナフトール、ピロガロール、トリヒドロキシ安息香酸、没食子酸エステル、２，３，４－トリヒドロキシベンゾフェノン、サリチル酸、１－ヒドロキシ－２－ナフトエ酸、３－ヒドロキシ－２－ナフトエ酸、クロラニル酸、タンニン酸の群から選ばれるフェノール系化合物である請求項１に記載のエポキシ樹脂硬化促進剤（Ｑ）。 The proton donor in the general formulas (2) to (4) is catechol, 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,2′-biphenol, 2,2′-binaphthol, pyrogallol, trihydroxybenzoate A phenolic compound selected from the group consisting of acid, gallic acid ester, 2,3,4-trihydroxybenzophenone, salicylic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, chloranilic acid, and tannic acid The epoxy resin curing accelerator (Q) according to claim 1.
- イミダゾリウム塩（Ｓ）の融点が１２０℃以下である請求項１又は２に記載のエポキシ樹脂硬化促進剤（Ｑ）。 The epoxy resin curing accelerator (Q) according to claim 1 or 2, wherein the melting point of the imidazolium salt (S) is 120 ° C or less.
- 一般式（１）中のＲ１が水素原子である請求項１～３のいずれかに記載のエポキシ樹脂硬化促進剤（Ｑ）。 エ ポ キ シ The epoxy resin curing accelerator (Q) according to any one of claims 1 to 3, wherein R1 in the general formula (1) is a hydrogen atom.
- 請求項１～４のいずれかに記載のエポキシ樹脂硬化促進剤（Ｑ）、エポキシ樹脂（Ｅ）、及び１分子内にフェノール性水酸基を２個以上有する化合物（Ｐ）を含有するエポキシ樹脂組成物。 An epoxy resin composition comprising the epoxy resin curing accelerator (Q) according to any one of claims 1 to 4, an epoxy resin (E), and a compound (P) having two or more phenolic hydroxyl groups in one molecule. .
- 請求項１～５のいずれかに記載のエポキシ樹脂組成物が硬化してなる硬化物。
A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 5.
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| JP2020200393A (en) * | 2019-06-10 | 2020-12-17 | サンアプロ株式会社 | Epoxy resin curing accelerator and epoxy resin composition |
| US10906921B2 (en) * | 2016-05-10 | 2021-02-02 | Toyo Gosei Co., Ltd. | Base generator, reagent, organic salt, composition, method for manufacturing device, cured film and device |
| WO2023182370A1 (en) * | 2022-03-25 | 2023-09-28 | パナソニックＩｐマネジメント株式会社 | Epoxy resin composition for sealing and electronic device |
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| JP2001253933A (en) * | 2000-03-09 | 2001-09-18 | Sumitomo Bakelite Co Ltd | Epoxy resin molding material for sealing semiconductor and semiconductor device produced by using the material |
| JP2007119598A (en) * | 2005-10-28 | 2007-05-17 | Sumitomo Bakelite Co Ltd | Semiconductor sealing epoxy resin composition and semiconductor device |
| JP2008081684A (en) * | 2006-09-28 | 2008-04-10 | Sumitomo Bakelite Co Ltd | One pack type epoxy resin composition |
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| JP2018104559A (en) * | 2016-12-27 | 2018-07-05 | サンアプロ株式会社 | Epoxy resin curing accelerator |
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| JP2001253933A (en) * | 2000-03-09 | 2001-09-18 | Sumitomo Bakelite Co Ltd | Epoxy resin molding material for sealing semiconductor and semiconductor device produced by using the material |
| JP2007119598A (en) * | 2005-10-28 | 2007-05-17 | Sumitomo Bakelite Co Ltd | Semiconductor sealing epoxy resin composition and semiconductor device |
| JP2008081684A (en) * | 2006-09-28 | 2008-04-10 | Sumitomo Bakelite Co Ltd | One pack type epoxy resin composition |
| JP2010529271A (en) * | 2007-06-11 | 2010-08-26 | ビーエーエスエフ ソシエタス・ヨーロピア | Catalyst for epoxy curing |
| JP2018104559A (en) * | 2016-12-27 | 2018-07-05 | サンアプロ株式会社 | Epoxy resin curing accelerator |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US10906921B2 (en) * | 2016-05-10 | 2021-02-02 | Toyo Gosei Co., Ltd. | Base generator, reagent, organic salt, composition, method for manufacturing device, cured film and device |
| JP2020200393A (en) * | 2019-06-10 | 2020-12-17 | サンアプロ株式会社 | Epoxy resin curing accelerator and epoxy resin composition |
| JP7283984B2 (en) | 2019-06-10 | 2023-05-30 | サンアプロ株式会社 | Epoxy resin curing accelerator and epoxy resin composition |
| WO2023182370A1 (en) * | 2022-03-25 | 2023-09-28 | パナソニックＩｐマネジメント株式会社 | Epoxy resin composition for sealing and electronic device |
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