Classifications

• • 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
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
• • 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
  • C08G59/50—Amines
• • 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
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/24—Acids; Salts thereof
  • C08K3/26—Carbonates; Bicarbonates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
  • H01L23/293—Organic, e.g. plastic
  • H01L23/295—Organic, e.g. plastic containing a filler
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L23/00—Details of semiconductor or other solid state devices
  • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
  • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape

Definitions

• the present invention relates to an epoxy resin composition, an epoxy resin composition molded article, a cured product, and a semiconductor device suitable for electrical and electronic material applications that require heat resistance, flame retardancy, and low water absorption.
• Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.
• the resin composition has high purity, moisture resistance, adhesion, dielectric properties, low viscosity for high filling with filler (inorganic or organic filler), and reactivity for shortening the molding cycle. Further improvement of various characteristics such as up is required (Non-Patent Document 1).
• a material that is lightweight and has excellent mechanical properties is required for aerospace materials, leisure / sports equipment applications, and the like.
• Non-patent Document 2 Especially in the field of semiconductor encapsulating materials and substrates (substrate itself or its peripheral materials), as the semiconductor transitions, it becomes increasingly complex with thinning, stacking, systematization, and three-dimensionalization. Characteristics such as heat resistance and high fluidity are required. Furthermore, with the expansion of plastic packages to in-vehicle applications, heat resistance requirements are becoming more severe, and it is necessary to cope with solder reflow with high Tg and low linear expansion resin. At the same time, reduction or maintenance of water absorption is required (Non-patent Document 2).
• heat resistance One of the characteristics particularly required for high functionality is heat resistance.
• communication devices typified by smartphones
• heat resistance is required to improve dimensional stability as a method for reducing warpage.
• dielectric properties at higher frequencies are required, and not only heat resistance but also electrical reliability is very important.
• the heat resistance is increased, the dielectric properties are deteriorated, and thus the electrical reliability is lowered in exchange for the heat resistance. Therefore, it is strongly desired to maintain higher heat resistance and electrical characteristics.
• a method using an amine-based curing agent with a high crosslinking density can be considered.
• solid sealing materials do not use an amine-based curing agent, but are cured with a phenol resin. Is common. These amine-based compounds were used for sealing materials several decades ago, but the chemical resistance and hygroscopic / water-absorbing and dielectric properties deteriorated. Residual organic bond chlorine (generally expressed as hydrolyzable chlorine, etc.) is extracted by the nucleophilicity of amines, and there is a problem of deteriorating electrical reliability, and current high functionality and high reliability are required. As a generation, it is only used for liquid sealing that is difficult to replace by others, and there is an environment in which liquid phenolic resin is required in order to improve reliability even in its use ( Patent Document 1).
• the present invention (1) a bifunctional or higher functional epoxy resin (component A), an aniline resin (component B) having a biphenylene novolak structure, and an inorganic filler containing at least one selected from silica gel and alumina, An epoxy resin composition having a content of 50 to 95% by weight of the total amount of the three components A to C; (2) The epoxy resin composition according to item (1), wherein the aniline resin has a structure represented by the following formula (1) and a softening point is 50 to 180 ° C.
• a plurality of R's each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• N is an integer, and the average value (A) of n represents 1 ⁇ A ⁇ 5.
• the epoxy resin composition of the present invention and the molded body thereof have an insulating material for electrical and electronic parts and a laminate (printed wiring) because the cured product has excellent heat resistance, water absorption characteristics, electrical reliability, and flame retardancy. Plate, build-up substrate, etc.) and various composite materials including CFRP, adhesives, paints, etc., and particularly useful as a semiconductor sealing material.
• the epoxy resin composition of the present invention comprises a bifunctional or higher functional epoxy resin (component A), an aniline resin (component B) having a biphenylene novolak structure, and an inorganic filler (component C) containing at least one selected from silica gel and alumina.
• Bifunctional or higher functional epoxy resins (component A) used in the present invention include bisphenol type epoxy resins (bisphenol A, bisphenol F, bisphenol C, bisphenol E, bisphenol TMC, bisphenol Z, etc.), biphenyl type epoxy resins (tetramethylbiphenyl).
• Cycloaliphatic epoxy resins such as 4-ether-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, tetraglycidyldiaminodiphenylmethane (TGDDM)
• glycidylamine-based epoxy resins such as triglycidyl-p-aminophenol, glycidyl ester-based epoxy resins, and the like, but are not limited thereto as long as they are usually used epoxy resins. These may be used alone or in combination of two or more.
• biphenyl type epoxy resins such as tetramethylbiphenyl diglycidyl ether and bisglycidyloxybiphenyl, tetramethylbis F type epoxy, crystalline bisphenol A type epoxy resin, tetrahydroanthracene type epoxy resin, dihydroxynaphthalene type epoxy resin, Those having a bifunctional and solid shape such as a funolphthalein type epoxy resin, a phenolphthalimide type epoxy resin, a bisphenolfluorene type epoxy resin (softening point or melting point of 50 ° C. or higher and lower than 200 ° C., more preferably 50 ° C.
• heat resistance is increased by introducing an alicyclic epoxy resin or the like, but in the present invention, since an amine-based curing agent is used, the reactivity with the alicyclic epoxy resin may be deteriorated.
• the use of bifunctional or polyfunctional glycidyl ether epoxy resins as preferred above is preferred.
• the bifunctional or higher functional epoxy resin used in the present invention preferably has a total chlorine content and hydrolyzable chlorine content of 1000 ppm or less.
• the total amount of chlorine and the total amount of hydrolyzable chlorine in the mixture are preferably 1000 ppm or less. Particularly preferably, it is 700 ppm or less.
• amine-based compounds may extract chlorine at the time of curing, and the total chlorine of the epoxy resin used is preferably as low as possible, and a large amount is not preferable because it may lead to deterioration of electrical reliability.
• the aniline resin (component B) having a biphenyllene novolak structure used in the present invention is a resin in which aromatic amines (anilines) are connected by bisalkylene biphenyl to have a molecular weight distribution in a novolak form.
• anilines aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 2-ethylaniline, 3-ethylaniline, 4-ethylaniline, 2,3-dimethylaniline, 2,4 -Dimethylaniline, 2,5-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline, 3,5-dimethylaniline, 2-propylaniline, 3-propylaniline, 4-propylaniline, 2-isopropyl Aniline, 3-isopropylaniline, 4-isopropylaniline, 2-ethyl-6-methylaniline, 2-sec-butylaniline, 2-tert-butylaniline, 4-butylaniline, 4-sec-butylaniline, 4-tert -Butylaniline, 2,3-diethylaniline, 2,4-diethi Aniline, 2,5-diethylaniline, 2,6-diethylaniline, 2-isopropyl-6
• aniline, 2-methylaniline, and 2,6-dimethylaniline are preferable, and aniline is particularly preferable from the viewpoint that a cured product having more excellent heat resistance, impact resistance, and flame retardancy can be obtained as the epoxy resin composition. preferable.
• Disubstituted methylbiphenyls that can be used include 4,4'-bis (chloromethyl) biphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-dimethoxymethylbiphenyl, 4,4'-bis (phenylaminomethyl) biphenyl Is mentioned. These may be used alone or in combination of two or more.
• the amount of disubstituted methylbiphenyls used is usually 0.05 to 0.8 mol, preferably 0.1 to 0.6 mol, relative to 1 mol of the anilines used.
• an acidic catalyst can be used as necessary.
• the acidic catalyst that can be used include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid and the like. These may be used alone or in combination of two or more.
• the amount of the catalyst used is 0.1 to 0.8 mol, preferably 0.5 to 0.7 mol, based on 1 mol of the aniline used. If the amount is too large, the viscosity of the reaction solution is too high and stirring is performed. If the amount is too small, the progress of the reaction may be slow.
• aniline, disubstituted methylbiphenyl, and a catalyst / solvent aromatic or alicyclic hydrocarbons such as toluene, xylene, cyclohexane, etc. are preferable
• a catalyst / solvent aromatic or alicyclic hydrocarbons such as toluene, xylene, cyclohexane, etc. are preferable
• acidic catalyst for example, in the case of the aforementioned 4,4′-bischloromethylbiphenyl, the following procedure can be mentioned. After adding the acidic catalyst to the mixed solution of the aniline derivative and the solvent, when the catalyst contains water, the water is removed from the system by azeotropic distillation.
• 4,4′-bischloromethylbiphenyl is usually added at 40 to 100 ° C., preferably 50 to 80 ° C. over 1 to 5 hours, preferably 2 to 4 hours, and then the solvent is removed from the system.
• the temperature is further raised, and the reaction is carried out at a temperature of usually 180 to 240 ° C., preferably 190 to 220 ° C. for 5 to 30 hours, preferably 10 to 20 hours.
• neutralize the acidic catalyst with an aqueous alkaline solution add a water-insoluble organic solvent to the oil layer and repeat washing with water until the wastewater becomes neutral, and then distill off excess aniline derivative and organic solvent under heating and reduced pressure.
• an aniline resin is obtained.
• a specific structural formula of the aniline resin obtained by the method is an aniline resin as described in the following formula (1).
• a plurality of R's each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• N is an integer, and the average value (A) of n represents 1 ⁇ A ⁇ 5.
• the amine equivalent of the aniline resin (aromatic amine resin) used in the present invention is 180 to 300 g / eq. Is preferred, 190 to 250 g / eq. Is particularly preferred.
• the softening point of the aniline resin (aromatic amine resin) used in the present invention is preferably 50 ° C. or higher and lower than 180 ° C., more preferably 150 ° C. or lower, from the viewpoint of moldability.
• the melt viscosity is preferably 0.005 to 1.5 Pa ⁇ s, and particularly preferably 0.01 to 1.0 Pa ⁇ s.
• the extraction is below 10 ppm, preferably below 5 ppm.
• the amount of the aniline resin used is preferably 0.30 to 0.50 equivalent (amine equivalent) relative to the epoxy equivalent of epoxy resin (average epoxy equivalent when mixed).
• a curing catalyst (curing accelerator) can be used in combination.
• the curing catalyst include pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, imidazole, triazole, tetrazole 2-methylimidazole, 2-phenylimidazole.
• Salts polyvalent carboxylic acids or salts with phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, trimethylethylammonium hydroxide, trimethylpropylammonium hydroxide , Trimethylbutylammonium hydroxide, trimethylcetylammonium hydroxide, trioctylmethylammonium hydroxide, tetramethylammonium chloride, tetramethylammonium Ammonium salts such as monium bromide, tetramethylammonium iodide, tetramethylammonium acetate, trioctylmethylammonium acetate, phosphines such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide,
• phosphonium salts, ammonium salts, and metal compounds are particularly preferable from the viewpoint of coloring during curing and changes thereof.
• a salt with a halogen leaves the cured product with a halogen, which is not preferable from the viewpoint of electrical reliability and environmental problems.
• the used amount of the curing catalyst is 0.01 to 5.0 parts by weight with respect to the epoxy resin 100 as required.
• a phenol resin is preferable from the viewpoint of electrical reliability.
• the phenol resin include bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1, 1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols ( Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldeh
• the epoxy resin composition of the present invention contains at least one inorganic filler (inorganic filler) (component C) selected from silica gel and alumina.
• inorganic fillers may be used in combination.
• Other inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, etc.
• beads obtained by spheroidizing these may be used, but the present invention is not limited thereto.
• These inorganic fillers may be used alone or in combination of two or more.
• the content of these inorganic fillers is used within the range of 50 to 95% by weight of the total amount of the three components A to C in the epoxy resin composition of the present invention.
• silica gels such as crystals, melting and crushing, and aluminas are preferable, and the particle size is preferably 50 microns or less from the viewpoint of line width.
• the epoxy resin composition of the present invention includes an antioxidant, a light stabilizer, a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate, calcium stearate, carnauba wax, carbon black, pigment, etc.
• the various compounding agents and various thermosetting resins can be added. Especially about a coupling agent, addition of the coupling agent which has an epoxy group is preferable.
• the epoxy resin composition of the present invention contains an inorganic filler containing at least one selected from a bifunctional or higher functional epoxy resin and an aniline resin having a biphenylene novolac structure, silica gel, and alumina, and a curing accelerator as necessary. It can be obtained by uniformly mixing the above-described additive components. As a uniform mixing method, mixing is performed by kneading using a device such as a kneader, a roll, or a planetary mixer at a temperature in the range of 50 to 110 ° C. to obtain a uniform epoxy resin composition.
• the obtained epoxy resin composition is pulverized and then molded into a cylindrical tablet by a molding machine such as a tablet machine, or a granular powder, or a powdery molded body, or these compositions are formed on a surface support. And then molded into a sheet having a thickness of 0.05 mm to 10 mm to obtain a molded product of the epoxy resin composition of the present invention.
• the resulting molded product becomes a non-sticky molded product at 0 to 20 ° C., and even when stored at ⁇ 25 to 0 ° C. for 1 week or longer, the fluidity and curability are hardly deteriorated.
• the molded epoxy resin composition of the present invention preferably has a pigment or carbon black added at the stage of the composition, and is preferably colored at the stage of molding.
• the obtained molded body is molded into a cured product using a transfer molding machine or a compression molding machine.
• the molding temperature is 100 to 300 ° C, particularly preferably 130 to 255 ° C.
• the cured product thus molded exhibits a heat resistance (Tg) of 100 ° C. or higher. Especially preferably, it is 150 degreeC or more.
• the epoxy resin composition of the present invention or a molded product thereof can be used as a semiconductor element sealing material (a semiconductor package material that protects a semiconductor by curing around a semiconductor element such as silicon, silicon carbide, or gallium nitride).
• a semiconductor element sealing material a semiconductor package material that protects a semiconductor by curing around a semiconductor element such as silicon, silicon carbide, or gallium nitride.
• the semiconductor device of the invention is obtained.
• the flow rate is 0.5 ml / min.
• Column temperature is 40 ° C
• Dynamic viscoelasticity measuring instrument manufactured by TA-instruments, DMA-2980 Measurement temperature range: -30 ° C to 280 ° C Temperature rate: 2 ° C./min
• Test piece size 5 mm ⁇ 50 mm cut out (thickness is about 800 ⁇ m).
• aromatic amine resin (A) was obtained by distilling off excess aniline and toluene from the oil layer with a rotary evaporator under heating and reduced pressure (200 ° C., 0.6 KPa). The obtained resin was again dripped little by little on the rotary evaporator under heating and reduced pressure (200 ° C., 4 KPa) instead of steam blowing. As a result, 166 parts of aromatic amine resin (A1) was obtained.
• the aromatic amine resin (A1) obtained had a softening point of 56 ° C., a melt viscosity of 0.035 Pa ⁇ s, and diphenylamine of 0.1% or less.
• the amine equivalent was 195 g / eq. Met.
• Example 1 Comparative Examples 1 and 2 Epoxy resin 1 (Nippon Kayaku NC-3000 Epoxy equivalent 277 g / eq. Softening point 57.5 ° C. or lower and referred to as “EP1”), aromatic amine resin (A1) obtained in Synthesis Example 1 as a curing agent, comparison Trisphenol methane type phenol resin (P-1 KAYAHARD KTG-105 hydroxyl equivalent 104 g / eq.), Phenol novolak (P-2 Meiwa Kasei H-1, hydroxyl equivalent 106 g / eq.
• the epoxy resin composition of the present invention can be tableted in the same manner as a normal epoxy resin composition without stickiness at the stage of the epoxy resin composition molding, and the cured product has high heat resistance and high water resistance. It was found to have High water resistance contributes to electrical reliability because ion migration is reduced. Moreover, when the flame retardance was confirmed, it confirmed that it had high flame retardance.
• a silane coupling agent (trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.) was used as an additive, and the ratio (part by weight) shown in Table 2 was used.
• the mixture was uniformly mixed and kneaded using a mixing roll to obtain an epoxy resin composition.
• the epoxy resin composition was pulverized and tableted with a tablet machine. Using the tableted epoxy resin composition molding, the maximum torque (hereinafter referred to as MH) and gel time were measured with a curastometer.
• Curing meter V-type manufactured by Nichigo Shoji Co., Ltd., trade name
• Curing meter V-type is used to set the curing torque for each of the above sealants under the conditions of a temperature of 175 ° C., a resin die P-200 and an amplitude angle of ⁇ 1 °.
• the point at which the curing torque rises is defined as the gel time (unit: second), and the value of the curing torque (unit: N ⁇ m) in seconds shown in Table 2 from the start of measurement is set as the curability (strength and hardness at demolding). ).
• the epoxy resin composition of the present invention has a higher maximum torque value and excellent demoldability compared to an epoxy resin composition using a phenol resin as a curing agent with a combined gel time. It was confirmed that it was effective for productivity when used as a semiconductor encapsulant.
• silica gel inorganic filler
• silica MSR-2212 manufactured by Tatsumori
• carnauba wax manufactured by Celerica Noda
• silane coupling agent trade name: KBM-303, manufactured by Shin-Etsu Chemical Co., Ltd.
• the epoxy resin composition was pulverized and tableted with a tablet machine. This tableted epoxy resin composition molded body is transfer molded (175 ° C. for 60 seconds to 15 minutes), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation. It was.
• Examples 5 and 6 have a long gel time, they have high heat resistance and low water absorption characteristics, respectively, and are found to be effective in heat resistance and electrical reliability.
• Synthesis example 2 A phenol resin produced in accordance with International Publication No. 2007/007827 while performing nitrogen purging on a flask equipped with a stirrer, a reflux condenser, and a stirrer (the following formula (2)
• Example 7 Comparative Example 5 Epoxy resins “EP1” and “EP3” Aromatic amine resin (A1) obtained in Synthesis Example 1 as a curing agent, phenolic resin “P4” As curing accelerators, salicylic acid (C-1), triphenylphosphine (C— 2) Silica gel (fused silica MSR-2212, manufactured by Tatsumori) as an inorganic filler, carnauba wax (manufactured by Celerica Noda) as a release agent, and a silane coupling agent (trade name: KBM-303, manufactured by Shin-Etsu Chemical) as an additive Were mixed in the proportions (parts by weight) shown in Table 4, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition.
• phenolic resin “P4” As curing accelerators, salicylic acid (C-1), triphenylphosphine (C— 2) Silica gel (fused silica MSR-2212, manufactured by Tatsumori) as an
• the epoxy resin composition was pulverized and tableted with a tablet machine. This tableted epoxy resin composition molded body was transfer molded (175 ° C. for 60 to 15 minutes), and after demolding, cured under conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation. .
• the epoxy resin composition of the present invention was confirmed to have high heat resistance, low hygroscopicity and flame retardancy even when compared to the case of using a polyfunctional phenol resin having a similar skeleton.
• Example 8 Test Examples 1 and 2 Using the following cured product, after pulverizing with a cyclomill, 20 parts of Millipore water is used for 1 part of the pulverized sample, and extraction is performed at 121 ° C. for 24 hours with a PCT extraction device, and chlorine ions contained in water are ion chromatographed. The chlorine ion content extracted under high temperature conditions was measured.
• Example 8 Cured product of Example 1 Test example 1: Cured product of Comparative Example 2 Test example 2: After pulverizing the composition used in Comparative Example 3, it was tableted on a tablet machine, and this tableted epoxy resin was used. A cured product obtained by transfer molding (175 ° C.
• Example 8 0.5 ppm Test Example 1: 0.9 ppm Test example 2: 0.4 ppm

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