WO2010052877A1 - Mélange de résines phénoliques, mélange de résines époxydes, composition de résine époxyde et article durci - Google Patents

Mélange de résines phénoliques, mélange de résines époxydes, composition de résine époxyde et article durci Download PDF

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Publication number
WO2010052877A1
WO2010052877A1 PCT/JP2009/005783 JP2009005783W WO2010052877A1 WO 2010052877 A1 WO2010052877 A1 WO 2010052877A1 JP 2009005783 W JP2009005783 W JP 2009005783W WO 2010052877 A1 WO2010052877 A1 WO 2010052877A1
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Prior art keywords
epoxy resin
resin mixture
biphenyl
phenol
reaction
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PCT/JP2009/005783
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English (en)
Japanese (ja)
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一光 白井
押見克彦
田中栄一
須永高男
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日本化薬株式会社
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Priority to JP2010536675A priority Critical patent/JP5486505B2/ja
Priority to CN200980144467.0A priority patent/CN102209742B/zh
Publication of WO2010052877A1 publication Critical patent/WO2010052877A1/fr

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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
    • 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
    • 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
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • 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
    • C08G59/621—Phenols
    • 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

Definitions

  • the present invention relates to a novel phenol resin mixture, an epoxy resin mixture, an epoxy resin composition, and a cured product.
  • Epoxy resin composition has excellent workability and excellent electrical properties, heat resistance, chemical resistance, mechanical strength, adhesion, moisture resistance (water resistance), dimensional stability, optical characteristics, etc. Utilized in a wide range of fields such as electrical / electronic component materials, reinforced fiber composite materials, resist materials, optical materials, liquid crystal sealing materials, overcoat materials, prepregs, molding materials, adhesives, adhesives, paints, etc. Yes.
  • electrical / electronic component materials (1) semiconductor sealing materials, specifically (a) potting, dipping, transfer mold sealing, flip-flops for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc. Underfill for chips, etc.
  • optical material examples include lens materials.
  • electrical / electronic component materials As electrical / electronic equipment has become more sophisticated, electrical / electronic components have become increasingly dense and highly integrated, Due to the expansion of fields of application to high-temperature environments, outdoor environments, the vicinity of the human body, etc., and the shift to environmentally friendly technologies, the required characteristics have become widespread and sophisticated. For example, in the fields of semiconductor sealing materials and substrates, epoxy resins are required to have flame resistance and solder crack resistance in addition to heat resistance, water absorption, electrical insulation, low thermal expansion coefficient, and the like.
  • solder crack resistance changes in the mounting process have an effect.
  • the surface mounting method has become common, and the semiconductor package is often directly exposed to high temperatures during solder reflow, and when the semiconductor is mounted as the awareness of environmental problems in recent years has increased.
  • lead-free solder Since lead-free solder has a melting temperature about 20 ° C. higher than that of conventional solder (about 260 ° C.), the possibility of package cracks during solder reflow is much higher than before.
  • the plating thickness is reduced, cracks may occur during thermal shock, and the wiring board is required to have high solder crack resistance.
  • the epoxy resin composition used for electrical and electronic materials around semiconductors such as semiconductor encapsulating materials and printed wiring boards is hardened by lead-free solder, which has a higher temperature than conventional solder.
  • lead-free solder which has a higher temperature than conventional solder.
  • This crack is caused by the stress generated in the cured product when subjected to the thermal shock of lead-free solder.
  • a storage elastic modulus by a dynamic viscoelasticity test can be used.
  • the storage elastic modulus at a high temperature is preferably lower if the storage elastic modulus at 160 ° C. is 100 MPa or more (Patent Document 3).
  • the storage elastic modulus at high temperature should be higher than a certain level even above the glass transition temperature.
  • An epoxy resin composition having a storage elastic modulus at 220 ° C. of 0.5 GPa to 0.9 GPa is disclosed as a highly reliable resin that does not cause cracks in a test (Patent Document 4). Therefore, an appropriate storage elastic modulus at a high temperature is considered to be very important in order to suppress the occurrence of cracks due to thermal shock.
  • a phenol-biphenyl aralkyl type epoxy resin excellent in flame retardancy for example, NC-3000 series manufactured by Nippon Kayaku Co., Ltd. is known as a commercial product.
  • This epoxy resin can be produced by reacting 4,4'-dimethylolbiphenyl with phenol, isolating the resulting bisphenol compound, and then epoxidizing the isolated bisphenol compound with epichlorohydrin or the like.
  • Patent Document 5 a method using 4,4′-bis (chloromethyl) -biphenyl instead of the above 4,4′-dimethylolbiphenyl is also known (Patent Document 6).
  • Patent Document 7 phenol resins in which biphenyl derivatives such as 4,4′-bis (chloromethyl) -biphenyl have been previously oligomerized and condensed with phenols have been proposed.
  • Patent Document 7 a method for synthesizing 4,4′-bis (chloromethyl) -biphenyl which is the above raw material by bischloromethylation of biphenyl is generally known.
  • biphenyl, paraformaldehyde and chlorinated in a cyclohexane solvent 4,4'-bis (chloromethyl) -biphenyl can be obtained by introducing hydrogen chloride gas and reacting with vigorous stirring of zinc (Patent Document 8, page 10, columns 19 to 20).
  • An object of the present invention is to provide an epoxy resin cured product having flame retardancy equivalent to or higher than that of a cured product using a phenol-biphenylaralkyl type epoxy resin excellent in flame retardancy, and having a more optimal storage elastic modulus.
  • the present inventors surprisingly include bishalomethylbiphenyl as a main component, a certain amount of tri- and tetrahalomethylbiphenyl as side reaction products, and the balance.
  • a phenol resin mixture obtained by reacting a reaction product (mixture) obtained by halomethylation of biphenyl containing a small amount of monohalomethylbiphenyl and bisbiphenylylmethane compound with phenol without isolation and purification is The present invention was completed by finding that it is very suitable as a raw material for an epoxy resin mixture satisfying the above required performance.
  • Bi (halomethyl) biphenyl obtained by halomethylation reaction of biphenyl and in a ratio (GC area ratio) to the total reaction product by GC-MS of bishalomethylbiphenyl is 60% or more and less than 80%.
  • a phenol resin mixture obtained by a methylene crosslinking reaction of phenol with a reaction product containing a total of 15 to 30% of tetra (halomethyl) biphenyl and the balance of other by-products (2)
  • the above (1) having a softening point of 65 to 85 ° C., a number average molecular weight by GPC (gel permeation chromatography) of 350 to 1200, a weight average molecular weight of 400 to 2000, and an OH equivalent of 160 to 250 g / eq.
  • a phenolic resin mixture according to (3) An epoxy resin mixture obtained by epoxidizing the phenol resin mixture according to (1) or (2) above, (4) Softening point 50 to 75 ° C., ICI viscosity 0.02 to 0.50 Pa ⁇ s, number average molecular weight 400 to 1200 and weight average molecular weight 800 to 2000 by GPC (gel permeation chromatography), epoxy The epoxy resin mixture according to the above (3), wherein the equivalent is 200 to 360 g / eq, (5) An epoxy resin composition containing the epoxy resin mixture and a curing agent according to (3) above, (6) The epoxy resin composition according to the above (5), wherein the content of the curing agent is 0.7 to 1.2 equivalents with respect to 1 equivalent of the epoxy group of the epoxy resin mixture, (7) The epoxy resin composition according to the above (6), further comprising 50 to 90% by weight of a filler based on the total amount of the epoxy resin composition,
  • Epoxy resin mixture obtained by epoxidizing the phenol resin mixture described in (1) above, and 0.7 to 1.2 equivalents of curing agent with respect to 1 equivalent of epoxy groups of the epoxy resin mixture A cured product obtained by curing an epoxy resin composition containing (9) An epoxy resin mixture obtained by epoxidizing the phenol resin mixture described in (1) above, 0.7 to 1.2 equivalents of a curing agent with respect to 1 equivalent of epoxy groups of the epoxy resin mixture, and A cured product obtained by curing an epoxy resin composition containing 50 to 90% by weight of an inorganic filler with respect to the total amount of the epoxy resin composition; (10) In the presence of zinc halide, 2 to 8 equivalents of formaldehyde and hydrogen halide are reacted in the presence of an excess amount of hydrogen halide with respect to 1 mol of biphenyl and biphenyl, and halomethyl of biphenyl is reacted.
  • the ratio of GC-MS to the total reaction product was 60% or more and less than 80% of bishalomethylbiphenyl, and totaled tri (halomethyl) biphenyl and tetra (halomethyl) biphenyl.
  • a reaction product containing 15 to 30% and other by-products, and reacting with phenol without purifying the reaction product
  • (11) An epoxy resin mixture characterized by reacting the phenol resin mixture obtained by the production method of (10) with 0.8 to 12 equivalents of epihalohydrin with respect to 1 equivalent of a hydroxyl group of the phenol resin mixture.
  • Production method (12) An epoxy resin composition containing the phenol resin mixture according to (1) or (2) as a curing agent, About.
  • the phenol resin mixture obtained by the present invention is useful as a raw material for an epoxy resin mixture or an epoxy resin composition that gives a cured product having excellent flame retardancy and moderate storage elastic modulus, and is easy to produce. It is. Moreover, when the epoxy resin mixture or epoxy resin composition of this invention hardens
  • the halomethylation reaction of biphenyl is a reaction for obtaining a halomethylated product of biphenyl using biphenyl, formaldehydes or equivalent acetals (hereinafter collectively referred to as carbon source), hydrogen halide, catalyst and solvent.
  • carbon source biphenyl, formaldehydes or equivalent acetals
  • the halomethylated product of biphenyl may further react to produce diarylmethane.
  • Patent Document 8 Japanese Patent Publication No. 54-929
  • 4,4′-bis (chloromethyl) is obtained in a chloromethylation reaction using biphenyl, paraformaldehyde, hydrogen chloride gas, zinc chloride, and cyclohexane.
  • -1,1′-biphenyl can be produced.
  • the methods described in JP-A-9-208506, JP-A-10-139699, and Japanese Patent No. 3784865 can be mentioned.
  • the halomethylation reaction in the present invention comprises the above composition, that is, 60 to 80% by weight of bishalomethylbiphenyl, 15 to 30% in total of tri (halomethyl) biphenyl and tetra (halomethyl) biphenyl, and the remaining other by-products. Any method described above may be used as long as the reaction product can be obtained.
  • the halomethylation reaction in the present invention will be described with reference to the reaction example of Patent Document 8, which is the most typical example.
  • methyl group carbon source in the halomethylation include formaldehyde such as formalin, paraformaldehyde, methylal, and trioxane, with paraformaldehyde being preferred.
  • the charge equivalent of the carbon source (for example, formaldehyde in the reaction example of Patent Document 8) varies depending on the halomethylation rate relative to biphenyl (the number of halomethyl groups per molecule), but is 1 equivalent to 15 to 1 mole of biphenyl. Equivalents are preferred, 1.5 to 10 equivalents are more preferred, and 2 to 8 equivalents are even more preferred. If the amount is less than 1 equivalent, the reaction point with biphenyl having a phenolic hydroxyl group may be insufficient. If the amount exceeds 15 equivalents, the reaction point / cross-linking point is too much and the molecular weight becomes too large, or the solid content concentration is increased and stirred. The condition may worsen.
  • any of hydrogen halide and any one that generates hydrogen halide by reaction can be used.
  • hydrogen halide is most commonly used.
  • Preferred examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, and hydrogen iodide, with hydrogen chloride being preferred.
  • These hydrogen halides can be used in the form of a gas.
  • the reaction can be carried out by directly blowing a raw material mixture other than hydrogen halide.
  • the hydrogen halide can also be dissolved in water, acetic acid or other organic solvents and used as a hydrogen halide solution, but the method using hydrogen chloride in the form of gas is most preferred.
  • preferred catalysts include sulfuric acid, thionyl chloride, orthophosphoric acid, zinc chloride, aluminum chloride, iron chloride, tin chloride and other Friedel-Crafts type reaction catalysts, tetrabutylammonium bromide, trimethylbenzyl chloride, chloride Quaternary ammonium salts such as cetylpyridinium can be mentioned.
  • zinc chloride, aluminum chloride, iron chloride, tin chloride, tetrabutylammonium bromide, trimethylbenzyl chloride, and cetylpyridinium chloride are more preferable, and zinc chloride is particularly preferable because it is inexpensive and easy to handle.
  • These catalysts may be used alone or in combination of two or more.
  • the amount of the catalyst used is not particularly limited, but is preferably in the range of 0.01 mol to 3 mol with respect to biphenyl. 0.1 mol to 1 mol is more preferable.
  • the solvent used in the reaction is not particularly limited as long as it is a non-reactive solvent.
  • Preferred solvents include aliphatic hydrocarbon solvents (for example, chain alkanes such as hexane and heptane, cyclic alkanes such as cyclopentane and cyclohexane, and kerosene), aliphatic carboxylic acid solvents (for example, formic acid, acetic acid, propionic acid, etc.
  • Aromatic hydrocarbon solvents with low electron density of aromatic rings eg chlorobenzene, nitrobenzene, orthodichlorobenzene, trichlorobenzene, etc.
  • aliphatic halogenated hydrocarbon solvents eg chloroform, dichloromethane, dichloroethane, tetrachloroethane, etc. organic solvents
  • solvents may be used alone or in combination of two or more.
  • Preferred examples of the solvent include C5-C6 cyclic alkanes, and the most preferred examples include cyclohexane which is inexpensive and has a low boiling point and can be easily removed.
  • an aliphatic alcohol such as 1-pentanol or 1-hexanol, or water may be added in an amount equivalent to the catalyst. These additions are known to increase the solubility of the catalyst and improve the reaction activity in some cases (Bull. Chem. Soc. Jpn. 66, 3520 (1993)). In the present invention, it may not be added in particular.
  • the amount of the solvent used is not particularly limited, but it is preferably about 1 ⁇ 2 to 10 parts by weight of solid content, more preferably 8 parts by weight or less.
  • the reaction temperature is not particularly limited as long as it is within an acceptable temperature range for the solvent used. Usually, it is 0 to 100 ° C., preferably about 15 to 60 ° C. When the reaction proceeds at around room temperature, around room temperature is preferred. In general, methylene-bridged diarylmethane, which is observed as a by-product in the chloromethylation reaction, is known to be preferentially produced when the reaction temperature is high. Therefore, it is preferable to lower the reaction temperature.
  • the reaction time is not particularly limited. Usually, it can be performed in about 6 to 36 hours.
  • the charging method is not particularly limited.
  • raw materials other than hydrogen halide are charged first, and hydrogen halide gas is blown into the system so as to maintain an excessive amount of hydrohalic acid in the system during the reaction.
  • hydrogen halide hydrogen chloride is preferred.
  • the composition of the reaction product obtained above is the same as the ratio (GC area ratio) to the total reaction product (total amount) in GC-MS (Gas Chromatograph / Mass Spectrometry), unless otherwise specified.
  • a bishalomethylbiphenyl preferably bischloromethylbiphenyl
  • tri (halomethyl) biphenyl preferably tri (chloromethyl) biphenyl
  • tetra (halomethyl) biphenyl preferably Is preferably a mixture of 15% to 30% of the total content of tetra (chloromethyl) biphenyl
  • the remainder of other by-products hereinafter also referred to as a mixture of biphenyl compounds having a halomethyl group.
  • the total of the three of bishalomethylbiphenyl, tri (halomethyl) biphenyl and tetra (halomethyl) biphenyl is preferably 75% to 97%, more preferably 80% to 95%.
  • the main component, bishalomethylbiphenyl is composed of 4,4'-bishalomethylbiphenyl and its positional isomers.
  • 4,4'-bishalomethylbiphenyl is about 50-98%. Preferably, it accounts for about 60 to 95%, and the balance is considered to be the isomer.
  • the main compounds contained in the reaction product are represented by the formulas of the compounds in the case where the halomethyl group is a chloromethyl group.
  • the “chloromethyl” group in Table A and the “chloromethyl” in the following description can be read as “halomethyl” in the present invention.
  • 4,4′-bischloromethyl-biphenyl represented by formula 1-3 is a main component in bischloromethylbiphenyl, and accounts for about 50 to 98%, preferably about 60 to 98% of bischloromethylbiphenyl. Conceivable.
  • bischloromethylbiphenyl the remainder other than 4,4′-bischloromethyl-biphenyl is considered to be a positional isomer such as 2,4′-bischloromethyl-biphenyl represented by Formula 1-4.
  • Tri (chloromethyl) biphenyl and tetra (chloromethyl) biphenyl are considered to be composed of, for example, compounds represented by formula 1-5 to formula 1-8 and isomers thereof (substitution isomers).
  • Other by-products include, for example, monochloromethylbiphenyl (eg, compounds represented by Formula 1-1 and Formula 1-2), bisbiphenylylmethane (Formula 1-9), monochloromethyl-bisbiphenylylmethane ( A compound represented by formula 1-10), bischloromethyl-bisbiphenylylmethane (a compound represented by formula 1-11), and the like.
  • the content of bischloromethylbiphenyl with respect to the total amount of the reaction product is 60% or more, less than 80%, and more preferably 65 to 75%.
  • the total content of tri (chloromethyl) biphenyl and tetra (chloromethyl) biphenyl with respect to the total amount of the reaction product is about 15 to 30%, preferably about 15 to 25%.
  • the proportions of tri (chloromethyl) biphenyl and tetra (chloromethyl) biphenyl vary depending on the reaction conditions and cannot be generally stated. However, the content of trichloromethylbiphenyl with respect to the total amount of the reaction product is about 5% to 25%. 10% to 20% is preferable.
  • the content of tetra (chloromethyl) biphenyl with respect to the total amount of the reaction product is preferably 1% to 15%, more preferably 2% to 10%.
  • monochloromethylbiphenyl is usually the most abundant, and the ratio (GC area ratio) to the total reaction product in GC-MS (hereinafter the same unless otherwise specified) is about 1% to 10%. It is.
  • the reaction of the reaction product obtained above with phenol also referred to as methylene crosslinking reaction
  • the methylene crosslinking reaction is a condensation reaction
  • the reaction product (mixture of biphenyl compounds having a halomethyl group) obtained as described above is condensed with phenol.
  • the methylene crosslinking reaction is preferably carried out under acidic conditions, for example, at a pH of about 1 to 4.
  • the reaction can generally refer to the 5th edition, Experimental Chemistry Course 26 (2) p142 (2005).
  • the halomethylation reaction product of biphenyl is a mixture, and in the present invention, the mixture is used as it is for a methylene crosslinking reaction with phenol. Therefore, usually, the reaction solution obtained by the halomethylation reaction can be used as it is. If necessary, the reaction solution can be used as a raw material for the reaction with phenol after being subjected to treatments such as concentration, dilution, degassing, washing with water, neutralization and filtration. Even in that case, it is preferable that it is substantially within the range of the composition of the reaction product. Usually, it is preferable to use the reaction liquid of the halomethylation reaction of biphenyl as it is for the next methylene crosslinking reaction with phenol.
  • an acid catalyst can be added as necessary, and it is usually preferable to carry out in the presence of an acid catalyst.
  • Various acid catalysts can be used.
  • organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid, oxalic acid, methanesulfonic acid, trifluoromethanesulfonic acid, zinc chloride, aluminum chloride, iron chloride, chloride Friedel-Crafts type Lewis acid catalyst such as tin.
  • the amount of the acid catalyst used varies depending on the type of the catalyst, but it can be added within a range of 0.001 to 10 times in molar ratio to phenol. Preferably, the amount is about 0.05 to 3 moles.
  • the reaction solution of the halomethylation reaction is used as it is, and then the condensation reaction is performed. Therefore, the acid catalyst used in the halomethylation reaction can be used as it is, and there is no need to add an acid catalyst again. .
  • Biphenyl halomethylation reaction product and phenol can be reacted in any proportion. Usually, it is preferable to use 1.5 mol to 40 mol of phenol with respect to 1 mol of halomethyl group in the halomethylation reaction product of biphenyl, more preferably 2 mol to 10 mol. If the amount is 1.5 mol or less, there is a concern that the molecular weight will increase, and if it exceeds 40 mol, the pot efficiency will deteriorate.
  • the amount of phenol added is roughly 0.3 to 2 times (by weight) the total amount of biphenyl, carbon source and acid catalyst added for halomethylation of biphenyl, preferably The amount is 0.5 to 1.5 times.
  • the total amount of saponifiable chlorine can be applied according to the description of JIS K7246.
  • it can also be traced by performing a pretreatment for reacting a dye or the like as a marker to the halomethyl group of the reactive mixture.
  • the methylene crosslinking reaction can be performed in the absence of a solvent or in the presence of a solvent.
  • the reaction solution of the halomethylation reaction is preferably used as it is, and the organic solvent mentioned in the section of the halomethylation reaction can be used as it is.
  • the preferred solvent can similarly include C5-C6 cyclic alkanes, and most preferred is cyclohexane.
  • the amount of the solvent used is usually 5 to 300% by weight, preferably 10 to 200% by weight, based on the total weight of the halomethylation reaction product of biphenyl and phenol.
  • the reaction temperature of the methylene crosslinking reaction is usually about 0 to 120 ° C, preferably about 15 to 100 ° C.
  • the reaction time is usually 1 to 10 hours.
  • the reaction solution of the halomethylation reaction can be added to phenol (and optionally a mixture of an acid catalyst and a solvent). Further, if necessary, operations such as dilution, degassing, washing with water and neutralization can be performed before and after the reaction product composition within a range in which the composition of the reaction product is not significantly changed.
  • the acid catalyst is removed by neutralization, washing with water, etc., and then the solvent used under heating under reduced pressure is removed to take out the desired phenol resin mixture. It is desirable to remove unreacted phenol together with the solvent used under heating and reduced pressure.
  • the phenol resin mixture obtained by removing the solvent and unreacted phenol after removing the acid catalyst by neutralization, washing with water, etc. after completion of the methylene crosslinking reaction usually without recrystallization treatment. It is preferable to take it to the next epoxidation reaction.
  • the reaction solution after completion of the methylene crosslinking reaction can be continued to the next epoxidation step without removing the solvent and unreacted phenol, but in this case, the hydrogen halide and acid catalyst used in the reaction are used in the middle.
  • an operation of treating an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide with a base is required.
  • unreacted phenol reacts with epoxidized epichlorohydrin and the like, it cannot be said that it is very preferable.
  • the phenol resin mixture of the present invention obtained as described above is a phenol resin mixture in which phenol and biphenyl are linked by a methylene crosslinking group (partially biphenyls are linked by methylene crosslinking, and further, phenol is mixed with biphenyl. (Including phenol resins linked by methylene crosslinking), and is useful as a raw material for the epoxy resin mixture of the present invention, and can be used as an epoxy resin mixture through the following epoxidation reaction.
  • the phenol resin mixture of the present invention obtained as described above has a softening point of 65 to 85 ° C. and a number average molecular weight of about 350 to 1,200, preferably about 400 to 1,000, more preferably by GPC (gel permeation chromatography). Is about 450 to 950, most preferably about 500 to 900, and the weight average molecular weight is about 400 to 2000, preferably about 500 to 1700, more preferably about 550 to 1600, and most preferably about 600 to 1000.
  • the OH equivalent is about 160 to 250 g / eq, preferably about 170 to 240 g / eq, and most preferably about 180 to 230 g / eq.
  • the chemical structure of a typical compound of the phenol resin mixture of the present invention is considered to be F2-1 to F2-6 and the like exemplified below from the analysis result of the reaction product of the halomethylation reaction.
  • N in the formula is about 1 to 10.
  • the phenol resin mixture of the present invention is, for example, a mixture of linear molecules or branched molecules as is apparent from the following examples.
  • the epoxy resin mixture of the present invention is an epoxidized product of the phenol resin mixture of the present invention obtained above, and can be obtained by epoxidizing the phenol resin mixture by a reaction with epihalohydrin by a conventional method. More specifically, the following method is mentioned.
  • a method of epoxidation a method of reacting the phenol resin mixture of the present invention with an epihalohydrin in the presence or absence of a solvent in the presence of an alkali metal hydroxide to glycidyl ether can be mentioned.
  • the reaction temperature is usually about 10 to 100 ° C., preferably about 30 to 90 ° C.
  • the alkali metal hydroxide may use an aqueous solution thereof.
  • the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, followed by liquid separation to remove the water and remove the epihalohydrin. May be a method of continuously returning to the reaction system.
  • the catalyst used up to the previous step since the catalyst used up to the previous step remains without being removed unless specially operated, an operation of neutralizing the alkali metal hydroxide by adding it more than usual. By doing this, the reaction can proceed smoothly. Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added as a catalyst to the mixture of the phenol resin mixture of the present invention and epihalohydrin, and 0.5 to 50 ° C to 150 ° C.
  • a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added as a catalyst to the mixture of the phenol resin mixture of the present invention and epihalohydrin, and 0.5 to 50 ° C to 150 ° C.
  • epihalohydrin examples include epichlorohydrin, epibromohydrin, epiiodohydrin, ⁇ -methylepichlorohydrin, ⁇ -methylepichlorohydrin, and ⁇ -methylepichlorohydrin.
  • epichlorohydrin is preferable.
  • the amount of epihalohydrin used for the epoxidation reaction is usually 0.8 equivalents to 12 equivalents, preferably 0.9 equivalents to 11 equivalents, relative to 1 equivalent of the hydroxyl group of the phenol resin of the present invention.
  • a polar solvent preferably an alcohol (eg, a C1-C4 alcohol such as methanol or ethanol) or an aprotic polar solvent (eg, dimethylsulfone, dimethylsulfoxide, etc.) is used. It is preferable to add and perform the reaction.
  • the amount of the polar solvent used may be appropriately selected from 2% to 150% by weight based on the amount of epihalohydrin, depending on the type of solvent and the like. For example, when alcohols are used, the amount used is usually 2 to 20% by weight, preferably 4 to 15% by weight, based on the amount of epihalohydrin.
  • an aprotic polar solvent it is usually 5% to 150% by weight, preferably 10% to 140% by weight, based on the amount of epihalohydrin.
  • alkali metal hydroxide examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, and cesium hydroxide, and sodium hydroxide and potassium hydroxide are preferable.
  • the epoxy resin mixture of the present invention can be obtained by removing the epihalohydrin, the solvent, and the like after the epoxidation reaction is washed with water or without washing with water under reduced pressure. Further, in order to obtain an epoxy resin mixture with less hydrolyzable halogen, the recovered epoxy resin mixture is dissolved in a solvent such as toluene, methyl isobutyl ketone, etc., and alkali metal water such as sodium hydroxide or potassium hydroxide is dissolved therein. It is preferable to add an aqueous solution of an oxide and react with the hydrolyzable halogen contained in the reaction product to remove the hydrolyzable halogen. This post-treatment can also secure the epoxy ring.
  • a solvent such as toluene, methyl isobutyl ketone, etc.
  • alkali metal water such as sodium hydroxide or potassium hydroxide
  • the amount of alkali metal hydroxide used in this post-treatment is usually 0.01 equivalent to 0.3 equivalent, preferably 0.05 equivalent to 0.2 equivalent, relative to 1 equivalent of epoxy group in the reaction product.
  • the post-treatment temperature is usually 50 ° C. to 120 ° C., and the reaction time is usually 0.5 hours to 2 hours.
  • the produced salt is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin mixture of the present invention.
  • the epoxy resin mixture of the present invention obtained as described above has a softening point of 50 to 75 ° C, preferably 52 to 65 ° C, more preferably 54 to 60 ° C, and an ICI viscosity of 0.02 to 0.50 Pa ⁇ s. , Preferably 0.04 to 0.40 Pa ⁇ s, more preferably 0.06 to 0.20 Pa ⁇ s, number average molecular weight by GPC (gel permeation chromatography) of about 400 to 1200, preferably about 500 to 1000, More preferably, it is about 600 to 900, most preferably about 600 to 850, and the weight average molecular weight is about 800 to 2000, preferably about 900 to 1800, more preferably about 1000 to 1600, and most preferably about 1000 to 1500. is there.
  • GPC gel permeation chromatography
  • the epoxy equivalent is about 200 to 360 g / eq, preferably about 230 to 340 g / eq, and most preferably about 250 to 310 g / eq.
  • Typical chemical structures of the epoxy resin mixture in the present invention are exemplified in the following F3-1 to F3-6. Since the epoxy resin mixture of the present invention is a reaction product of the phenol resin mixture of the present invention and epihalohydrin, it becomes a mixture of linear molecules or branched molecules as will be apparent from the following examples. Note that n in the formula is the same as in F2-1 to F2-6.
  • the epoxy resin composition of the present invention contains the epoxy resin mixture and hardening
  • the epoxy resin composition of the present invention in addition to the epoxy resin mixture of the present invention, another epoxy resin can be used in combination as one of optional components.
  • the proportion of the epoxy resin mixture of the present invention in the total epoxy resin is preferably 30% by weight or more and 100% by weight or less, more preferably 40% by weight or more and 100% by weight or less, and still more preferably 50%. % By weight or more and 100% by weight or less.
  • the epoxy resin mixture of the invention is preferably 60% by weight or more, more preferably 70% by weight. Or more, more preferably 80% by weight or more, and most preferably 90% by weight or more.
  • the upper limit is up to 100% by weight.
  • Examples of other epoxy resins that can be used in combination with the epoxy resin mixture of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, and triphenylmethane type epoxy resins.
  • a glycidyl etherified product of an aromatic compound having 2 to 4 hydroxyl groups for example, bisphenol A, bisphenol F, bisphenol S, fluorenylidene diphenol, 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-hydroxy) ethane ⁇ ; or phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy
  • the phenol resin mixture of the present invention can be used as a curing agent alone or in combination with other curing agents.
  • the proportion of the phenol resin mixture of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more.
  • the upper limit is 100% by weight.
  • the curing agent used in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds.
  • amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, trifluoroborane-amine complex; dicyandiamide, dimer of linolenic acid and polyamide resin synthesized from ethylenediamine, etc.
  • Amide compounds phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.
  • Acid anhydride compounds phenols having 2 to 4 hydroxyl groups ⁇ bisphenol A, bisphenol F, bisphenol S, fluorenylidene diphenol, terpene diphenol, 4,4'-bif Enol, 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.
  • Benzene or naphthalene having a hydroxyl group which may have an alkyl substitution, and the alkyl group is preferably C1-C4 alkyl
  • an aldehyde or ketone (formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p -
  • phenol compound or an amine compound is preferable, and a phenol compound, further a phenol aralkyl resin, or a phenol resin mixture of the present invention is preferable. Most preferred is phenol aralkyl resin.
  • the amount of the curing agent used is the equivalent of the active group that reacts with the epoxy of the curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin (hydroxyl equivalent in the phenol compound, amino group in the amine compound). Equivalents), preferably 0.7 equivalents to 1.2 equivalents.
  • the active group equivalent of the curing agent is less than 0.7 equivalent to 1 equivalent of epoxy group, or exceeds 1.2 equivalent, there is a possibility that curing will be incomplete and good cured properties will not be obtained. is there.
  • a curing accelerator may be used.
  • curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole; 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo Tertiary amines such as (5,4,0) undecene-7; phosphines such as triphenylphosphine; metal compounds such as tin octylate.
  • a curing accelerator may not be used, but when used, 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the epoxy resin can be appropriately used as necessary.
  • An inorganic filler (also referred to as filler) can be added to the epoxy resin composition of the present invention as necessary.
  • Inorganic fillers include powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, etc. Examples thereof include, but are not limited to, spherical beads. These may be used alone or in combination of two or more.
  • the content of these inorganic fillers is 0 to 95% by weight, preferably 20% to 95% by weight, more preferably 50% to 95% by weight, still more preferably 70% by weight, based on the total amount of the epoxy resin composition. % To 95% by weight, most preferably 70% to 90% by weight.
  • a release agent such as silane coupling agent, stearic acid, palmitic acid, zinc stearate, calcium stearate; coloring of carbon black, phthalocyanine blue, phthalocyanine green, etc.
  • Agent Polybutadiene and its modified products, modified products of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compound, cyanate resin (or prepolymer thereof), silicone gel, silicone oil and other resins Etc. Additives such as may be added.
  • the preferred epoxy resin composition of the present invention is as follows.
  • (1) The epoxy resin mixture of the present invention and a curing agent, and 0.7 to 1.2 equivalent of a curing agent in terms of an active group that reacts with the epoxy group of the curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin
  • An epoxy resin composition comprising 4 wt% to 80 wt% of the epoxy resin mixture of the present invention with respect to the total amount of the epoxy resin composition, the balance being optional addition components.
  • the epoxy resin mixture of the present invention has a softening point of 52 to 65 ° C., an ICI viscosity of 0.04 to 0.40 Pa ⁇ s, a number average molecular weight of 400 to 1200 by GPC (gel permeation chromatography) and a weight.
  • the epoxy resin mixture of the present invention is obtained by a halomethylation reaction of biphenyl, and is a ratio (GC area ratio) to the total reaction product in GC-MS.
  • a phenol resin mixture obtained by methylene cross-linking reaction of phenol with a reaction product containing less 15 to 30% total of tri (halomethyl) biphenyl and tetra (halomethyl) biphenyl and the balance of other by-products,
  • the epoxy resin composition according to any one of (1) to (5) above, which is an epoxy resin mixture obtained by epoxidation.
  • the phenol resin mixture has a softening point of 65 to 85 ° C., a GPC (gel permeation chromatography) number average molecular weight of 350 to 1200, a weight average molecular weight of 400 to 2000, and an OH equivalent of 160 to 250 g / eq.
  • the epoxy resin composition of the present invention can be obtained by uniformly mixing the epoxy resin mixture of the present invention, a curing agent, and optional additive components.
  • the epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. More specifically, first, for example, selected from the group consisting of the epoxy resin mixture of the present invention and a curing agent, and if necessary, optional additional components (for example, a curing accelerator, an inorganic filler, a coupling agent, and a release agent). And the like are sufficiently mixed until they become uniform using, for example, an extruder, a kneader, a roll or the like to obtain the epoxy resin composition of the present invention.
  • the obtained epoxy resin composition is melted and then molded by using a casting or transfer molding machine, an injection molding machine, a casting machine, or the like, and more preferably at 80 to 200 ° C. for 2 to
  • the cured product of the epoxy resin composition of the present invention can be obtained by heating for 16 hours.
  • the viscosity of the epoxy resin composition of the present invention is lowered by heating or melting, or the viscosity is lowered by mixing a solvent with the epoxy resin composition, and the resulting mixture is made of glass fiber, carbon fiber, polyester fiber, polyamide. It is also possible to obtain a cured product by hot press molding a prepreg obtained by impregnating a substrate such as fiber, alumina fiber or paper and heating and semi-drying.
  • the solvent examples include aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethylimidazolide Amide solvents such as non; Sulfone solvents such as dimethyl sulfoxide and tetramethylene sulfone; Lactam solvents such as N-methylpyrrolidone; Lactone solvents such as ⁇ -butyrolactone; Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, Examples of the solvent include ether solvents such as propylene glycol monomethyl ether monoacetate and propylene glycol monobutyl ether.
  • aromatic solvents such as toluene and xylene
  • ketone solvents such as acetone, methyl e
  • the solvent used above may be a single solvent or a mixed solvent of two or more.
  • the amount occupying usually 10 wt% to 70 wt%, preferably 15 wt% to 70 wt%, with respect to the total amount of the epoxy resin composition of the present invention and the solvent mixture.
  • the above-mentioned prepreg is cut into a desired shape, and if necessary, laminated with a copper foil or the like, and then cured by heating under pressure by a method such as a press molding method, an autoclave molding method, or a sheet winding molding method, Or it can be set as the laminated board which has this hardened
  • a circuit is formed on a laminated plate made by stacking copper foil on the surface, and the prepreg and copper foil are stacked thereon, or a copper foil having the prepreg is stacked to form a circuit, and necessary Accordingly, the operation can be repeated to obtain a multilayer circuit board.
  • a semiconductor device that can be manufactured by sealing a semiconductor element (semiconductor chip) with the epoxy resin composition of the present invention
  • DIP dual inline package
  • QFP quad flat package
  • BGA ball grid array
  • CSP chip size package
  • SOP small outline package
  • TSOP thin small outline package
  • TQFP think quad flat package
  • encapsulated optical semiconductor elements such as light emitting diodes (LEDs), phototransistors, CCDs (charge coupled devices), EPROMs such as UV-EPROMs.
  • the epoxy resin composition of the present invention can be used as a photo-thermosetting resin composition by mixing with a compound having an ethylenically unsaturated group.
  • the composition further comprises a compound having an ethylenically unsaturated group, preferably a crosslinker (B), photopolymerization, in addition to the alkaline aqueous solution-soluble resin (A), as an optional additive component.
  • a crosslinker B
  • photopolymerization in addition to the alkaline aqueous solution-soluble resin (A), as an optional additive component.
  • the content of the epoxy resin mixture of the present invention is usually 1% to 50% by weight, preferably 2% to 30% by weight.
  • Each component of the photocurable resin composition containing the epoxy resin mixture of the present invention will be described more specifically below.
  • An aqueous alkali solution-soluble resin (A) for example, an epoxycarboxylate compound obtained by reacting an epoxy compound having two or more epoxy groups in a molecule with a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule; Reaction products with polybasic acid anhydrides, such as KAYARAD CCR-1159H, KAYARAD PCR-1169H, KAYARAD TCR-1310H, KAYARAD ZFR-1401H, KAYARAD ZAR-1395H (all Nippon Kayaku Co., Ltd.) Manufactured) and the like.
  • polybasic acid anhydrides such as KAYARAD CCR-1159H, KAYARAD PCR-1169H, KAYARAD TCR-1310H, KAYARAD ZFR-1401H, KAYARAD ZAR-1395H (all Nippon Kayaku Co., Ltd.) Manufactured) and the like.
  • Crosslinking agent (B) compounds having an ethylenically unsaturated group, such as acrylates and methacrylate compounds, and specific examples include KAYARAD HX-220, KAYARAD HX-620, KAYARAD DPHA, KAYARAD DPCA-60 (all Nippon Kayaku Co., Ltd.).
  • Photopolymerization initiator (C) for example, benzoins, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, phosphine oxides, etc.
  • benzoins for example, benzoins, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, phosphine oxides, etc.
  • KAYACURE DETX-S manufactured by Nippon Kayaku Co., Ltd.
  • Irgacure 907 Ciba Specialty Chemical
  • additives for example, fillers such as talc, barium sulfate, aluminum hydroxide, aluminum oxide, silica, clay; thixotropic agents such as aerosil; coloring of phthalocyanine blue, phthalocyanine green, titanium oxide, etc. Agents; silicones, fluorine-based leveling agents and antifoaming agents; polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be added for the purpose of enhancing various performances of the composition.
  • fillers such as talc, barium sulfate, aluminum hydroxide, aluminum oxide, silica, clay
  • thixotropic agents such as aerosil
  • silicones silicones, fluorine-based leveling agents and antifoaming agents
  • polymerization inhibitors such as hydroquinone and hydroquinone monomethyl ether can be added for the purpose of enhancing various performances of the composition.
  • the photocurable resin composition can contain a solvent as necessary.
  • solvents include, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene, and tetramethylbenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, Glycol ethers such as dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, glutar Dialkyl acid, dialkyl succinate, dialkyl adipate, etc.
  • Esters ; cyclic esters such as ⁇ -butyrolactone; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, solvent naphtha, etc., but these may be used alone or in combination of two or more. May be.
  • the photo-curable resin composition containing the epoxy resin mixture of the present invention is useful as a resist material such as an insulating material between electronic component layers, an optical waveguide connecting optical components, a solder resist for printed circuit boards, and a coverlay. Besides, it can also be used as a color filter, printing ink, sealant, paint, coating agent, adhesive.
  • the photocurable resin composition containing the epoxy resin mixture of the present invention can be cured by irradiation with energy rays such as ultraviolet rays. Curing by irradiation with energy rays such as ultraviolet rays can be performed by a conventional method.
  • an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser (such as an excimer laser) may be used.
  • the photocurable resin composition containing the epoxy resin mixture of the present invention includes, for example, a resist film, an interlayer insulating material for a build-up method and an optical waveguide as a printed board, an electric / electronic / optical substrate such as an optoelectronic board and an optical board. Used for materials. Specific articles using these include, for example, computers, home appliances, portable devices, and the like. Specifically, for example, when manufacturing a printed wiring board constituting a printed circuit board, when using a liquid resin composition, first, a screen printing method, a spray method, a roll coating method, an electrostatic coating method, a curtain is applied to the printed wiring board.
  • the photocurable resin composition containing the epoxy resin of the present invention is applied with a film thickness of 5 to 160 ⁇ m by a coating method or the like, and the coating film is usually dried at 50 to 110 ° C., preferably 60 to 100 ° C. As a result, a coating film is formed. Thereafter, the coating film is directly or indirectly irradiated with high-energy rays such as ultraviolet rays with an intensity of about 10 to 2000 mJ / cm 2 through a photomask having an exposure pattern such as a negative film, and the unexposed portion is developed later. Using the liquid, development is performed, for example, by spraying, rocking dipping, brushing, scrubbing, or the like.
  • Examples of the developer include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate, potassium phosphate, and other inorganic alkaline aqueous solutions, tetramethyl ammonium hydroxide, tetraethyl Organic alkaline aqueous solutions such as ammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used.
  • Ion source EI ⁇ Measurement model of SEM-EDS (Scanning Electron Microscopy-Energy Disperse Spectroscopy): JED-2140 (manufactured by JEOL) Acceleration voltage: 20 kV Working distance: 10mm Measurement of number average molecular weight and weight average molecular weight by GPC (gel permeation chromatography) Column: Shodex KF-801, KF-802, KF-802.5, KF-803 manufactured by Showa Denko KK Column temperature: 40 ° C Injection volume: 0.02 mL Liquid feeding amount: 1.0 mL / min Detector: RI Solvent: Tetrahydrofuran Viscosity measurement: Measured at 150 ° C.
  • OH equivalent measurement average mass number of compounds per OH group, according to JIS K-0070 Measured by acetylation method according to the same method.
  • Measurement of epoxy equivalent Average mass number of the compound per epoxy group. Measured according to JIS K-7236.
  • DMA (dynamic viscoelasticity measurement) analysis DMA 2980 manufactured by TA Instruments (Dynamic viscoelasticity measuring machine) Tg and the storage elastic modulus at 250 ° C. were measured using a frequency of 10 Hz.
  • Example 1 Chloromethylation reaction of biphenyl Cyclohexane 200 mL, biphenyl 77.05 g, paraformaldehyde 33.55 g, and zinc chloride 46.38 g were charged into a glass 300 mL flask equipped with a stirrer, a thermometer, and a condenser. While vigorously stirring them, hydrogen chloride gas was blown into them vigorously and reacted until a homogeneous solution was obtained. Meanwhile, the liquid temperature was kept at 50 ° C. The liquid temperature was further lowered by 30 ° C., hydrogen chloride gas was blown in for 24 hours, and the reaction was continued to obtain a reaction liquid.
  • the composition of the phenol resin mixture is 72% of bischloromethylbiphenyl-derived component (F2-1) and trichloromethylbiphenyl-derived component (previously described) than the composition of the biphenyl chloromethylation reaction product obtained in (1) above.
  • F2-2 is estimated to be 15%, tetrachloromethylbiphenyl-derived component (said F2-3) 6%, and other components (said F2-4, F2-5, F2-6, etc.) 7%.
  • Example 2 Synthesis of epoxy resin mixture
  • a glass 300 mL flask equipped with a stirrer, a thermometer, and a condenser 26.3 g of the phenol resin mixture of the present invention obtained in Example 1, 52.0 g of epichlorohydrin, 8.6 g of dimethyl sulfoxide, 12.3 g of 30% by weight aqueous sodium hydroxide solution was added and mixed with stirring at 45 ° C. for 1 hour. Next, 3.95 g of flaky sodium hydroxide was added in portions, and the mixture was stirred at 45 ° C. for 2 hours and at 70 ° C. for 1 hour.
  • Methyl isobutyl ketone was added to the obtained reaction solution for dilution, and then water was added to perform water washing by liquid / liquid separation.
  • To the obtained organic layer 0.93 g of a 30 wt% aqueous sodium hydroxide solution was added and stirred at 70 ° C. for 1 hour. Again, water washing by liquid / liquid separation was performed in the same manner as described above.
  • the obtained reaction solution was concentrated to obtain 20.5 g of the epoxy resin mixture of the present invention.
  • the obtained resin mixture had a softening point of 57.6 ° C., an ICI viscosity of 0.11 Pa ⁇ s, an epoxy equivalent of 292 g / eq, a number average molecular weight of 668 by GPC (gel permeation chromatography), and a weight average molecular weight of 1187.
  • the composition of the epoxy resin mixture is 72% bischloromethylbiphenyl-derived component (F3-1) and trichloromethylbiphenyl-derived component (F3-F3) based on the composition of the biphenyl chloromethylation reaction product obtained in (1) above. 2) Estimated to be 15%, tetrachloromethylbiphenyl-derived component (F3-3) 6%, and other components (F3-4, F3-5, F3-6, etc.) 7%.
  • Example 3 and Comparative Example 1 Preparation of Flame Retardant Resin Composition and Evaluation of Cured Product
  • the cured product was obtained by molding at 175 ° C. using a transfer molding machine.
  • Example 3 Comparative Example 1 Epoxy resin (epoxy resin mixture of Example 2) (NC-3000) 6.17g 6.17g Curing agent (XLC-3L) 3.6 g 3.8 g Curing catalyst (TPP) 0.105 g 0.105 g Filler (MSR-2212) 50.2g 51.2g Mold release agent (Carnauba No. 1) 0.18 g 0.19 g Coupling agent (KBM-303) 0.20g 0.20g
  • XLC-3L Phenol aralkyl resin, TPP manufactured by Mitsui Chemicals Co., Ltd .
  • Triphenylphosphine MSR-2212 Kicross MSR-2212 Carnauba No. 1 manufactured by Tatsumori Co., Ltd. Coupling agent Shin-Etsu Chemical Co., Ltd.
  • Table 2 shows the results of evaluating the flame retardancy and the storage elastic modulus at 250 ° C. of the cured product thus obtained based on the following method.
  • Measurement of flame retardancy In the flame retardancy test, the total burning time (time until self-digestion) was measured for a test piece (cured product) having a thickness of 0.8 mm in accordance with UL-94.
  • Measurement of storage elastic modulus at 250 ° C . Tg and storage elastic modulus at 250 ° C. were measured using DMA 2980 (dynamic viscoelasticity measuring machine) manufactured by TA Instruments using a frequency of 10 Hz.
  • the epoxy resin composition containing the epoxy resin mixture of the present invention is excellent in flame retardancy, with the same or higher flame retardance as NC-3000, which is widely used as an excellent flame retardant resin,
  • the storage elastic modulus at a high temperature of 250 ° C., which is higher than the glass transition point, is within the range of 500 to 1000 MPa, which is considered preferable for solder crack resistance, compared to the value of NC-3000 of 2000 MPa or more. It can be seen that this also has excellent properties.
  • the epoxy resin mixture of the present invention has excellent properties as described above, can be produced consistently from biphenyl, and is easy to produce.
  • Example 4 Chloromethylation reaction of biphenyl Cyclohexane 200 mL, biphenyl 154 g, paraformaldehyde 66 g, and zinc chloride 93 g were charged into a glass 1000 mL flask equipped with a stirrer, a thermometer, and a condenser. While stirring them, hydrogen chloride gas was strongly blown into them and reacted until a uniform solution was obtained. Meanwhile, the temperature was maintained at 30 ° C. Thereafter, hydrogen chloride gas was further blown for 10 hours at 50 ° C., and the reaction was continued to obtain a reaction solution. A part of the reaction solution was taken and subjected to LC measurement as an N, N′-dimethylformamide solution.
  • the resin mixture had a softening point of 79.6 ° C., a number average molecular weight of 855 by GPC (gel permeation chromatography), a weight average molecular weight of 1332, and an OH equivalent of 196 g / eq.
  • the composition of the phenol resin mixture was 8% monochloromethylbiphenyl, 68% bischloromethylbiphenyl-derived component (F2-1) and tri (chloro) from the composition of the chloromethylation reaction product obtained in (1) above. It is estimated that 18% is included in total of the component derived from methyl) biphenyl (F2-2) and the component derived from tetra (chloromethyl) biphenyl (F2-3 etc.).
  • Example 5 Synthesis of Epoxy Resin Mixture
  • Methyl isobutyl ketone was added thereto for dilution, and then 13.3 g of a 30 wt% aqueous sodium hydroxide solution was added and stirred at 70 ° C. for 1 hour. Water was added thereto, followed by washing with liquid / liquid separation. The reaction solution after washing with water was concentrated to obtain 215 g of the epoxy resin mixture of the present invention.
  • the epoxy mixture had a softening point of 56.5 ° C., an ICI viscosity of 0.11 Pa ⁇ s, an epoxy equivalent of 264 g / eq, a number average molecular weight of 803 by GPC (gel permeation chromatography), and a weight average molecular weight of 1419.
  • the composition of the epoxy resin mixture was 8% monochloromethylbiphenyl-derived component and bischloromethylbiphenyl-derived component (structural formula: F3-1) based on the composition of the chloromethylation reaction product obtained in Example 4 (1) above. Etc.) and 68% of total components derived from tri (chloromethyl) biphenyl (structural formula: F3-3 etc.) and tetra (chloromethyl) biphenyl derived components (structural formula: F3-3 etc.) Is done.
  • Example 6 In the same manner as in Example 3, the epoxy resin mixture of the present invention obtained in Example 5 was prepared into a flame retardant resin composition having the composition shown in Table 3 below, and molded with a transfer molding machine to obtain a cured product. It was.
  • Example 7 500 g of the phenol resin mixture of the present invention obtained in the same manner as in Example 4 was dissolved in 1000 ml of methyl isobutyl ketone, the insoluble matter was filtered, water was added thereto, and water washing was performed by liquid / liquid separation. It was. As a result, a phenol resin mixture (referred to as EX7PhnolMix) having a hydroxyl group (OH) equivalent of 204 g / eq was obtained. The obtained phenol resin mixture is used as a curing agent, and the epoxy resin of the present invention having the composition shown in Table 5 below is used as the epoxy resin, using the above-mentioned Nippon Kayaku Co., Ltd. phenol-biphenyl aralkyl epoxy resin NC-3000. A composition was prepared and molded with a transfer molding machine to obtain a cured product.
  • EX7PhnolMix a phenol resin mixture having a hydroxyl group (OH) equivalent of 204 g
  • Example 8 and Comparative Example 2 Using the phenol resin mixture of the present invention obtained in Example 7 (EX7PhnolMix) as a curing agent and using the above-mentioned phenol-biphenylaralkyl type epoxy resin NC-3000 manufactured by Nippon Kayaku Co., Ltd. as Table 7
  • the epoxy resin composition (EX8 EPOXY COM) of the present invention having the composition shown in FIG.
  • Comparative Example 2 as a curing agent, instead of the phenol resin mixture (EX7PhnolMix) of the present invention, a phenol-biphenylaralkyl type phenol resin GPH-65 (OH equivalent 199 g / eq, softening point 65. 1 ° C) was used to prepare a comparative epoxy resin composition (Comparative Example 2) (CPA2 EPOXY COM) shown in Table 7 below.
  • the epoxy resin composition prepared above was roll-kneaded to obtain an epoxy resin composition for evaluation.
  • the epoxy resin composition of Example 8 is the epoxy resin of Comparative Example 2. It shows that the composition is excellent in fluidity.
  • the cured product of the epoxy resin composition containing the epoxy resin mixture of the present invention is not only excellent in flame retardancy, but also has a storage elastic modulus at 250 ° C. within a certain range as compared with the conventional flame retardant epoxy resin cured product, Since it is reduced, it also has excellent resistance to solder cracks, and the epoxy resin mixture of the present invention and the epoxy resin composition containing it are suitable as electrical and electronic materials around semiconductors such as semiconductor sealing materials and printed wiring boards. ing.
  • the phenol resin mixture of the present invention is an intermediate raw material for the epoxy resin mixture of the present invention having the above-mentioned excellent properties, and can be produced without isolating and purifying the intermediate halomethylbiphenyl. It is easy to manufacture and has high industrial utility.

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  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)

Abstract

L'invention porte sur un mélange de résines phénoliques qui est produit par l'opération consistant à soumettre un produit réactionnel contenant un sous-produit produit par l'halométhylation d'un biphényle à la réaction de réticulation du méthylène avec du phénol. L'invention porte également sur un mélange de résines époxydes produit par époxydation du mélange de résines phénoliques. L'invention porte en outre sur une composition de résine époxyde contenant le mélange de résines époxydes. Un produit durci du mélange de résines époxydes ou de la composition de résine époxyde contenant le mélange de résines époxydes présente un excellent caractère ignifuge et un module de conservation qui est inférieur à celui de produits en résine époxyde durcis ignifuges classiques, d'une valeur s'inscrivant dans une plage spécifique à 250 °C. Par conséquent, le mélange de résines époxydes ou la composition de résine époxyde contenant le mélange de résines époxydes est utile en tant que matière d'enrobage de semi-conducteur qui doit présenter un caractère ignifuge élevé et une excellente résistance à la soudure sans plomb.
PCT/JP2009/005783 2008-11-06 2009-10-30 Mélange de résines phénoliques, mélange de résines époxydes, composition de résine époxyde et article durci WO2010052877A1 (fr)

Priority Applications (2)

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JP2010536675A JP5486505B2 (ja) 2008-11-06 2009-10-30 フェノール樹脂混合物、エポキシ樹脂混合物、エポキシ樹脂組成物、及び硬化物
CN200980144467.0A CN102209742B (zh) 2008-11-06 2009-10-30 酚醛树脂混合物、环氧树脂混合物、环氧树脂组合物及固化物

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JP2008-285856 2008-11-06
JP2008285856 2008-11-06

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WO2010052877A1 true WO2010052877A1 (fr) 2010-05-14

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JP (1) JP5486505B2 (fr)
KR (1) KR101564957B1 (fr)
CN (1) CN102209742B (fr)
MY (1) MY153048A (fr)
TW (1) TWI530511B (fr)
WO (1) WO2010052877A1 (fr)

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JP2010138311A (ja) * 2008-12-12 2010-06-24 Jfe Chemical Corp ４，４’−ビフェニルジイルメチレン−フェノール樹脂の製造方法
JP2013237715A (ja) * 2012-05-11 2013-11-28 Sumitomo Bakelite Co Ltd 樹脂組成物、プリプレグ、回路基板および半導体装置
JP2019048998A (ja) * 2018-11-14 2019-03-28 日立化成株式会社 モールドアンダーフィル用樹脂組成物及び電子部品装置

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TWI666307B (zh) * 2015-06-04 2019-07-21 日商住友電木股份有限公司 密封用樹脂組成物、半導體裝置、及構造體

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JPH08143648A (ja) * 1994-09-20 1996-06-04 Meiwa Kasei Kk 新規フェノールノボラック縮合体
JPH1180047A (ja) * 1997-09-12 1999-03-23 Ube Ind Ltd ４，４’−ビスクロロメチルビフェニルの製造法
JPH11130706A (ja) * 1997-10-31 1999-05-18 Ube Ind Ltd ４，４’−ビスクロロメチルビフェニルの製造方法
JP2001040053A (ja) * 1999-07-26 2001-02-13 Nippon Kayaku Co Ltd ４，４’−ビフェニルジイルジメチレン−フェノール樹脂及びその製造法
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WO2006090662A1 (fr) * 2005-02-25 2006-08-31 Nippon Kayaku Kabushiki Kaisha Resine epoxy, composition de resine durcissable la contenant et son utilisation
WO2007063894A1 (fr) * 2005-11-30 2007-06-07 Nippon Kayaku Kabushiki Kaisha Resine phenolique, son procede de fabrication, resine epoxy et son utilisation

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010138311A (ja) * 2008-12-12 2010-06-24 Jfe Chemical Corp ４，４’−ビフェニルジイルメチレン−フェノール樹脂の製造方法
JP2013237715A (ja) * 2012-05-11 2013-11-28 Sumitomo Bakelite Co Ltd 樹脂組成物、プリプレグ、回路基板および半導体装置
JP2019048998A (ja) * 2018-11-14 2019-03-28 日立化成株式会社 モールドアンダーフィル用樹脂組成物及び電子部品装置

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TW201026737A (en) 2010-07-16
JPWO2010052877A1 (ja) 2012-04-05
KR20110094278A (ko) 2011-08-23
JP5486505B2 (ja) 2014-05-07
CN102209742B (zh) 2013-03-27
CN102209742A (zh) 2011-10-05
KR101564957B1 (ko) 2015-11-13
TWI530511B (zh) 2016-04-21
MY153048A (en) 2014-12-31

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