WO2013080936A1 - フェノールノボラック樹脂及びそれを用いたエポキシ樹脂組成物 - Google Patents

フェノールノボラック樹脂及びそれを用いたエポキシ樹脂組成物 Download PDF

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Publication number
WO2013080936A1
WO2013080936A1 PCT/JP2012/080536 JP2012080536W WO2013080936A1 WO 2013080936 A1 WO2013080936 A1 WO 2013080936A1 JP 2012080536 W JP2012080536 W JP 2012080536W WO 2013080936 A1 WO2013080936 A1 WO 2013080936A1
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Prior art keywords
general formula
epoxy resin
integer
resin composition
carbon atoms
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English (en)
French (fr)
Japanese (ja)
Inventor
慎司 岡本
匡敏 藤永
絵梨奈 木村
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Meiwa Plastic Industries Ltd
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Meiwa Plastic Industries Ltd
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Priority to CN201280052226.5A priority Critical patent/CN103958561B/zh
Priority to KR1020147010822A priority patent/KR101889442B1/ko
Publication of WO2013080936A1 publication Critical patent/WO2013080936A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
    • C08J5/244—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/14—Layered products comprising a layer of metal next to a fibrous or filamentary layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/28—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer impregnated with or embedded in a plastic substance
    • 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
    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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    • B32B2250/05—5 or more layers
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • B32B2260/023—Two or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—Synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/206—Insulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/342—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3424—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing only carbon atoms non-conjugated, e.g. paracyclophanes or xylenes
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • C08J2363/04—Epoxynovolacs
    • 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

Definitions

  • the present invention relates to an epoxy resin composition and a phenol novolac resin suitably used for the epoxy resin composition.
  • the epoxy resin composition of the present invention is obtained by improving the heat resistance and combustion resistance of the resulting cured product. Furthermore, since the epoxy resin composition of the present invention preferably has excellent solubility of the phenol novolac resin used, it can be easily dissolved uniformly in a solvent, and is preferably used, for example, for the purpose of producing a laminate. Can do.
  • Epoxy resin composition has good workability, and its cured product has excellent electrical properties, heat resistance, adhesion, moisture resistance, etc., so electrical / electronic parts, structural materials, adhesives, paints, etc. Widely used in the field.
  • the use of lead-free solder has led to higher reflow temperatures, which means that epoxy resin compositions used in semiconductor packages such as laminates, interlayer insulation materials, and sealing materials can be compared to conventional products.
  • High heat resistance is required.
  • flame resistance flame resistance
  • the epoxy resin composition is required to be soluble in a solvent for the epoxy resin composition because the epoxy resin composition is dissolved in a solvent and used as a varnish. ing.
  • Patent Document 1 a mixture of isomers of bis (methoxymethyl) biphenyl synthesized by a dehalogenation coupling reaction of a reaction product obtained by a halogenation reaction of methoxymethylbenzene is reacted with a phenol compound.
  • a phenol novolac condensate obtained by the above-mentioned method and an epoxy resin composition containing the phenol novolac condensate and an epoxy resin are disclosed. This phenol novolac condensate is excellent in hygroscopicity, heat resistance and flexibility as an epoxy resin curing agent.
  • the phenol novolac condensate specifically disclosed herein is only one using a mixture of isomers of bis (methoxymethyl) biphenyl, and an epoxy resin containing the obtained phenol novolac condensate and an epoxy resin
  • the glass transition temperature of the cured product composed of the composition was about 140 ° C., and there was room for improvement in heat resistance.
  • Patent Document 2 discloses a phenol-naphthol novolak condensate obtained by a condensation reaction of phenols and naphthols with a biphenyl compound such as bis (methoxymethyl) biphenyl, and the phenol-naphthol novolak condensate and an epoxy resin.
  • An epoxy resin composition is disclosed.
  • the phenol-naphthol novolak condensate specifically disclosed here is also only one using a mixture of isomers of bis (methoxymethyl) biphenyl as the biphenyl compound.
  • This phenol-naphthol novolak condensate is obtained by improving low water absorption and heat resistance with respect to the phenol novolak condensate of Patent Document 1, but includes an epoxy resin containing a phenol-naphthol novolak condensate and an epoxy resin.
  • the glass transition temperature of the cured product composed of the composition was about 150 ° C., and there was room for further improvement in heat resistance.
  • Patent Documents 1 and 2 describe the use of a mixture of isomers at a specific ratio, preferably as a biphenyl compound.
  • a 4,4′-isomer such as 4,4′-bis (methoxymethyl) biphenyl is used alone as a biphenyl compound, it has any influence on heat resistance, combustion resistance, solubility, etc. There was no specific description or suggestion.
  • the present invention relates to an epoxy resin composition containing a phenol novolac resin (more specifically, a phenol-naphthol novolak resin) and an epoxy resin, and the resulting cured product has significantly improved heat resistance and combustion resistance. It is to provide an epoxy resin composition and a phenol novolac resin that can be suitably used for the epoxy resin composition. Furthermore, since the present invention preferably has excellent solubility of the phenol novolak resin used, it is easy to uniformly dissolve in a solvent, and for example, an epoxy resin composition that can be suitably used for the purpose of producing a laminated board And a phenol novolac resin that can be suitably used for the epoxy resin composition.
  • each A independently represents a monovalent or divalent unit of the following general formula (2) or a monovalent or divalent unit of the general formula (3), and n is an integer of 0 to 20 R 1 represents each independently an alkyl group having 1 to 8 carbon atoms, and p and q are each independently an integer of 0 to 2.
  • A is composed of both monovalent or divalent units of the following general formula (2) and monovalent or divalent units of the following general formula (3).
  • each R2 independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, i is an integer of 1 to 3, and j is an integer of 0 to 2) Yes, the sum of i and j is 4 or less.
  • each R3 independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, and l is an integer of 0 to 4) Yes, the sum of k and l is 6 or less.
  • R1 independently represents an alkyl group having 1 to 8 carbon atoms
  • p and q each independently represents an integer of 0 to 2
  • R3 each independently represents an integer of 1 to Represents an alkyl group of 8 or an alkoxy group of 1 to 8 carbon atoms
  • k is an integer of 1 to 3
  • l is an integer of 0 to 4
  • the sum of k and l is 6 or less.
  • each R2 independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, i is an integer of 1 to 3, and j is an integer of 0 to 2) Yes, the sum of i and j is 4 or less.
  • each R3 independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, and l is an integer of 0 to 4) Yes, the sum of k and l is 6 or less.
  • R1 independently represents an alkyl group having 1 to 8 carbon atoms, p and q each independently represents an integer of 0 to 2, and X represents an alkoxyl group having 1 to 4 carbon atoms
  • An epoxy resin composition comprising the phenol novolac resin (A) according to any one of Items 1 to 3 and an epoxy resin (B).
  • R1 in (R1) p and R1 in (R1) q in the general formula (1) may be the same alkyl group or different alkyl groups, and R1 in (R1) p is In a plurality of cases, each R1 may be the same alkyl group or may be an alkyl group having a different carbon number.
  • the glass transition temperature is measured by two methods for convenience of comparison. However, in the unlikely event that a difference due to the measurement method occurs, the measurement method by the dynamic viscoelasticity measuring device has priority.
  • an epoxy resin composition containing a phenol novolac resin (more specifically, a phenol-naphthol novolak resin) and an epoxy resin, the heat resistance and combustion resistance of the resulting cured product are remarkably improved.
  • An epoxy resin composition and a phenol novolac resin that can be suitably used for the epoxy resin composition can be provided.
  • the present invention preferably has excellent solubility of the phenol novolac resin used, and therefore can be easily dissolved in a solvent, and can be suitably used for, for example, the production of laminates and interlayer insulating materials.
  • An epoxy resin composition that can be used, and a phenol novolac resin that can be suitably used for the epoxy resin composition can be provided.
  • FIG. 2 is an HPLC chart of a reaction mixture before removal of unreacted raw material components at the end of the reaction in Example 1.
  • FIG. 2 is an HPLC chart of the phenol novolac resin obtained in Example 1.
  • FIG. 4 is an HPLC chart of a reaction mixture before removal of unreacted raw material components at the end of the reaction in Example 2.
  • FIG. 2 is an HPLC chart of a phenol novolac resin obtained in Example 2.
  • a phenol represented by the following general formula (5) and a naphthol represented by the following general formula (6) are reacted with a biphenyl compound represented by the following general formula (7). It can obtain suitably.
  • each R2 independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, i is an integer of 1 to 3, and j is an integer of 0 to 2) Yes, the sum of i and j is 4 or less.
  • each R3 independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, k is an integer of 1 to 3, and l is an integer of 0 to 4) Yes, the sum of k and l is 6 or less.
  • R1 independently represents an alkyl group having 1 to 8 carbon atoms, p and q each independently represents an integer of 0 to 2, and X represents an alkoxyl group having 1 to 4 carbon atoms
  • the phenol represented by the general formula (5) is not particularly limited as long as it is a compound having one or more hydroxyl groups on the benzene ring, and may have a substituent such as an alkyl group or an alkoxy group.
  • These phenols may be used alone or as a mixture of a plurality of them.
  • the naphthols represented by the general formula (6) are not particularly limited as long as they are compounds having one or more hydroxyl groups on the naphthalene ring, and may have a substituent such as an alkyl group or an alkoxy group.
  • ⁇ -naphthol, ⁇ -naphthol, dihydroxynaphthalene, trihydroxynaphthalene methyl naphthol, ethyl naphthol, propyl naphthol, allyl naphthol, t-butyl naphthol, octyl naphthol, methyl ethyl naphthol, methyl propyl naphthol, methyl butyl naphthol
  • Examples include methylhexyl naphthol, dimethyl naphthol, diethyl naphthol, and dibutyl naphthol, and ⁇ -naphthol is preferable.
  • These naphthols may be used alone or
  • Examples of the biphenyl compound represented by the general formula (7) include 4,4′-bis (methoxymethyl) biphenyl, 4,4′-bis (ethoxymethyl) biphenyl, 4,4′-bis (chloromethyl) biphenyl, Preferable examples include 4,4′-bis (bromomethyl) biphenyl, 4,4′-bis (fluoromethyl) biphenyl, and the like. These biphenyl compounds may have an alkyl group having 1 to 8 carbon atoms as a substituent. These biphenyl compounds may be used alone or as a mixture of a plurality of them.
  • a catalyst may not be used, but an acid catalyst is usually used.
  • an acid catalyst organic acids such as oxalic acid, formic acid and acetic acid, and Friedel-Craft type catalysts such as sulfuric acid, p-toluenesulfonic acid and diethyl sulfate are suitable.
  • the reaction can be suitably performed even in the absence of an acid catalyst.
  • the molar ratio [(phenols and naphthols) / biphenyl compound] of the raw material biphenyl compound to the total of the raw material phenols and naphthols is preferably 20 to 1.5, more preferably 6.0. A range of ⁇ 2.0 is preferred. If the molar ratio is less than 1.5, the viscosity of the resin may become too high and handling properties may be impaired. If the molar ratio exceeds 20, the cured product glass is obtained in the form of a low molecular weight product. The transition temperature becomes insufficient, and a large amount of unreacted raw material remains, making it uneconomical.
  • the molar ratio [phenols / naphthols] of the starting phenols and naphthols is preferably in the range of 10/90 to 90/10, more preferably 40/60 to 90/10.
  • the ratio with the unit of General formula (3) can be made into the preferable range of this invention. That is, when there are too few naphthol components, the unit of General formula (3) introduce
  • transduced in resin will increase, and the unit shown by General formula (4) will also increase, It will become a cause by which solvent solubility is impaired.
  • the reaction can usually be carried out in the absence of a solvent or in the presence of a solvent such as water and / or an organic solvent at 0 ° C. to 150 ° C. for about 0.5 hours to 10 hours.
  • reaction conditions such as reaction temperature and reaction time are appropriately adjusted.
  • unreacted phenols and naphthols are preferably distilled out of the system by heating under reduced pressure or blowing in an inert gas.
  • the acid catalyst can be removed by washing such as water washing.
  • a biphenyl compound forms a cross-linked structure between a plurality of units composed of phenols and / or naphthols to form a phenol novolac resin having a chemical structure represented by the general formula (1).
  • a in the general formula (1) is represented by the general formula ( 2) and a monovalent unit of the general formula (3), and when incorporated in the molecule, A in the general formula (1) is a divalent unit of the general formula (2) and the general formula (3). It becomes.
  • n in general formula (1) is 0 is generated.
  • the phenol novolac resin of the present invention is usually represented by the general formula (1). Is an aggregate of a plurality of components having different n values.
  • One of the characteristics of the phenol novolak resin of the present invention obtained by this reaction is that a phenol and a naphthol are converted into a 4,4′-form biphenyl compound such as 4,4′-bis (chloromethyl) biphenyl. It is in place to use in combination. And the hardened
  • the phenol novolac resin having the chemical structure represented by the general formula (1) is a ratio of the unit of the general formula (2) derived from phenols to the unit of the general formula (3) derived from naphthols.
  • [Unit of general formula (2) / unit of general formula (3)] is preferably in the range of 10/90 to 90/10, more preferably in the range of 10/90 to 60/40, More preferably, it is in the range of 10/90 to 50/50, and particularly preferably in the range of 10/90 to 40/60.
  • the ratio of the unit of the general formula (2) and the unit of the general formula (3) is within this range, the heat resistance and the combustion resistance of the cured product made of the epoxy resin composition of the present invention are preferably improved. can do.
  • the heat resistance of the resulting resin is efficiently improved, and combustion is effectively performed. This makes it possible to improve the combustion resistance.
  • the proportion of the unit of the general formula (3) becomes too high, the viscosity and softening point of the resin may be increased, and the handling property may be impaired.
  • the unit of the general formula (4) in the resin It increases and it becomes difficult to control the solubility of the resin.
  • the general formula (2) of the raw material is used so that the ratio of the unit of the general formula (2) to the unit of the general formula (3) is within the above range.
  • the use ratio of the phenols represented by 5) and the naphthols represented by the general formula (6) is adjusted.
  • the ratio of the raw materials used in the unit to be introduced into the phenol novolac resin is increased, but the reactivity of these phenols, naphthols, and biphenyl compounds is different.
  • the ratio is adjusted in consideration of the size, the molar ratio of the biphenyl compound to the total of phenols and naphthols [(phenols and naphthols) / biphenyl compound], the reaction conditions employed, and the like.
  • the adjustment method is self-explanatory, but can be easily found by conducting preliminary experiments if necessary.
  • one of the preferred embodiments of the phenol novolak resin is a component represented by the general formula (4) among all the components of the assembly represented by the general formula (1) constituting the phenol novolak resin. It is 27% or less, preferably 20% or less in terms of the area ratio when measured by.
  • the component represented by the general formula (4) is controlled to 27% or less by the area ratio when measured by HPLC in all the components, the solubility in an organic solvent is improved.
  • the resin / It is possible to uniformly dissolve the solvent even at a ratio of 50/50 by mass.
  • the solubility in an organic solvent is lowered, for example, a resin / solvent with respect to methyl ethyl ketone. If the ratio is 50/50 by mass, it will be difficult to dissolve uniformly. For example, using methyl ethyl ketone, if the resin / solvent can be uniformly dissolved even at a high concentration ratio of 50/50 by mass, the epoxy resin composition of the present invention is dissolved in methyl ethyl ketone to form a varnish, and the matrix material or interlayer of the laminate It becomes easy to use as an insulating material. When it cannot be dissolved uniformly and cannot be varnished, it is not easy to use it as a matrix material or an interlayer insulating material of a laminated board.
  • the amount of the component represented by the general formula (4) in the component of the phenol novolac resin is adjusted by adjusting the molar ratio of the biphenyl compound to the total of phenols and naphthols used as raw materials [(phenols and naphthols) / biphenyl.
  • Compound] and the molar ratio of phenols to naphthols [phenols / naphthols] are adjusted while taking into consideration the magnitude of their reactivity and the reaction conditions employed.
  • the molar ratio of the biphenyl compound to the sum of the phenols and naphthols [(phenols and naphthols) / biphenyl compound] should be a smaller value than normal (a value closer to 1).
  • the component of the general formula (4) can be reduced by increasing the molecular weight.
  • the molar ratio of phenols to naphthols is higher in reactivity of naphthols than phenols, so a relatively high proportion of naphthols can promote more reaction and increase the overall component.
  • the component of the general formula (4) can be reduced by increasing the molecular weight.
  • the proportion of naphthols becomes too high, the component of the general formula (4) increases and the solubility is adversely affected. For example, when the naphthols are 100%, it is naturally difficult to increase the solubility by reducing the amount of the component of the general formula (4).
  • the phenol novolac resin (A) constituted by the chemical structure represented by the general formula (1) of the present invention preferably has a softening point of 60 ° C. to 150 ° C., more preferably 70 ° C. to 140 ° C. If the softening point is less than 60 ° C., blocking or the like is likely to occur, and if it exceeds 150 ° C., there may be a problem in handling properties.
  • the weight average molecular weight of the phenol novolac resin (A) constituted by the chemical structure represented by the general formula (1) of the present invention is preferably in the range of 500 to 10,000, more preferably 500 to 5,000, More preferably, it is in the range of 500-2000.
  • the epoxy resin composition of the present invention comprises a phenol novolac resin (A) and an epoxy resin (B) that are constituted by a chemical structure represented by the general formula (1).
  • Examples of the epoxy resin (B) used in the epoxy resin composition of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol aralkyl type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, and triphenol.
  • Examples include glycidyl ether type epoxy resins such as methane type epoxy resins and biphenyl type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, halogenated epoxy resins, and other epoxy resins having two or more epoxy groups in the molecule. . These epoxy resins may be used individually by 1 type, and may use 2 or more types together.
  • a biphenyl type epoxy resin a phenol aralkyl type epoxy resin, a triphenylmethane type epoxy resin, a cresol novolac type epoxy resin, and the like are particularly suitable for improving heat resistance and combustion resistance.
  • the ratio of the hydroxyl equivalent of the curing agent to the epoxy equivalent in the epoxy resin [hydroxyl equivalent / epoxy equivalent] is 0.5 to 2.0.
  • a range of about 0.8 is preferable, and a range of about 0.8 to 1.2 is more preferable. Outside this range, the curing reaction may not proceed sufficiently, and the effects of the present invention may not be exhibited due to reasons such as unreacted curing agent or epoxy resin remaining.
  • the phenol novolac resin (A) constituted by the chemical structure represented by the general formula (1) has a role of a curing agent for the epoxy resin in the epoxy resin composition of the present invention.
  • the product may contain a curing agent other than the phenol novolac resin (A) constituted by the chemical structure represented by the general formula (1).
  • the curing agent other than the phenol novolac resin (A) there are no particular limitations on the curing agent other than the phenol novolac resin (A), and various epoxy resin curing agents can be used depending on the intended use of the composition.
  • a normal epoxy resin curing agent can be suitably used.
  • the ratio of the phenol novolac resin (A) constituted by the chemical structure represented by the general formula (1) in the curing agent is not particularly limited. In order to improve heat resistance and combustion resistance, a higher ratio is preferable, 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass, particularly preferably 100% by mass. is there.
  • the epoxy resin composition of the present invention preferably further contains a solvent (C), and the phenol novolac resin (A) and the epoxy resin (B) are uniformly dissolved in the solvent (C).
  • a solvent (C) is not particularly limited as long as it dissolves the epoxy resin composition, but is preferably an organic solvent used for varnishing a matrix material or an interlayer insulating material of a normal laminate. Can be used.
  • ketones such as methyl ethyl ketone, acetone, diethyl ketone, methyl isobutyl ketone, cyclohexanone, ethers such as propylene glycol monomethyl ether, amides such as dimethylformamide and dimethylacetamide, sulfoxides such as dimethyl sulfoxide, ⁇ -butyllactone, etc.
  • ethers such as propylene glycol monomethyl ether
  • amides such as dimethylformamide and dimethylacetamide
  • sulfoxides such as dimethyl sulfoxide, ⁇ -butyllactone
  • Preferable examples include lactones, pyrrolidones such as N-methylpyrrolidone, and aromatic hydrocarbons such as toluene and xylene.
  • methyl ethyl ketone and dimethylformamide are particularly preferable.
  • These solvents can be used alone or in combination of two or more.
  • the other component used with a normal epoxy resin composition can be used suitably according to the use.
  • a curing accelerator for curing an epoxy resin with a phenol resin can be used.
  • Preferred examples of the curing accelerator include known organic phosphine compounds and their boron salts, tertiary amines, quaternary ammonium salts, imidazoles and tetraphenylboron salts. Among these, triphenylphosphine is preferable from the viewpoints of curability and moisture resistance.
  • a heat-latent curing accelerator that exhibits activity by heat treatment is preferable, and tetraphenylphosphonium, tetraphenylborate, and the like are particularly preferable. More preferred are phenylphosphonium derivatives.
  • the addition amount of a hardening accelerator may be the same as the ratio in a well-known epoxy resin composition.
  • fillers such as inorganic fillers can also be suitably used.
  • the inorganic filler amorphous silica, crystalline silica, alumina, calcium silicate, calcium carbonate, talc, mica, barium sulfate and the like can be used, and amorphous silica and crystalline silica are more preferable.
  • a particle size of an inorganic filler When a filling rate is considered, it is desirable that it is 0.01 micrometer or more and 150 micrometers or less.
  • the blending ratio of the inorganic filler is not particularly limited, but is 70% to 95% by weight, preferably 75% to 90% by weight, more preferably 80% to 90% by weight in the epoxy resin composition.
  • the proportion of the inorganic filler is outside the above range, the water absorption rate of the cured product of the epoxy resin composition increases, which is not preferable. Moreover, when there is too much ratio of an inorganic filler, there exists a possibility that fluidity
  • the epoxy resin composition of the present invention contains a nitrogen-based flame retardant such as melamine or an isocyanuric acid compound, or a phosphorus-based flame retardant such as red phosphorus, a phosphoric acid compound or an organic phosphorus compound as a flame retardant aid. As appropriate.
  • the epoxy resin composition of the present invention uses a phenol novolak resin (A), an epoxy resin (B), a curing accelerator to be added as necessary, an inorganic filler, other additives, for example, using a mixer or the like. It can be produced by uniformly mixing, kneading in a molten state using a kneader such as a heating roll, a kneader, or an extruder, cooling, and pulverizing as necessary. Although such an epoxy resin composition is not limited, it can be suitably used as a semiconductor sealing material.
  • the epoxy resin composition of the present invention is a phenol novolac resin (A) composed of a chemical structure represented by the general formula (1) in a solvent (C) such as methyl ethyl ketone, propylene glycol monomethyl ether or dimethylformamide.
  • a solvent (C) such as methyl ethyl ketone, propylene glycol monomethyl ether or dimethylformamide.
  • the epoxy resin (B) can be uniformly dissolved in the solvent (C) to produce a varnish solution.
  • this varnished epoxy resin (solution) composition is not limited, it can be suitably used as a matrix material or an interlayer insulating material of a laminated board.
  • cured material can be obtained suitably by heat-processing.
  • the heat treatment conditions for obtaining a cured product depend on the presence or absence of a curing catalyst and a curing accelerator, the amount of addition thereof, and the like, but are usually about 100 to 300 ° C., preferably about 120 to 200 ° C.
  • the heat treatment is preferably performed for about 10 minutes to about 10 minutes.
  • the epoxy resin composition of the present invention can be suitably used as a sealing material for sealing a semiconductor element.
  • an epoxy resin composition is molded by a molding method such as transfer molding, compression molding, or injection molding, and the temperature is about 120 ° C. to 300 ° C.
  • a semiconductor device can be suitably obtained by curing the epoxy resin composition by heat treatment or the like.
  • the epoxy resin composition of the present invention is preferably uniformly dissolved in a solvent such as methyl ethyl ketone to form a varnish, and the varnish solution is applied to a porous glass substrate such as glass, glass fiber, paper, aramid fiber, etc.
  • a prepreg for a printed circuit board can be produced by impregnation and then heat treatment (semi-curing).
  • a laminated board can be manufactured by laminating a plurality of obtained prepregs for a printed circuit board and curing them by applying heat treatment while applying pressure as necessary.
  • the laminated plate or prepreg is a metal-clad laminated plate obtained by superimposing metal foils on one or both sides and performing heat treatment (eg, heat treatment at 180 ° C., 4 MPa for 60 minutes) while applying pressure as necessary. Can be obtained.
  • This metal-clad laminate can be suitably used as a printed wiring board by forming a circuit pattern by etching.
  • the epoxy resin composition of the present invention is preferably uniformly dissolved in a solvent such as methyl ethyl ketone to form a varnish, and the varnish solution is uniformly applied to a support surface such as a PET film or copper foil using a die coater or the like.
  • the laminated film having a resin layer can be suitably used as an interlayer insulating material by applying to the substrate and drying the obtained coating film by heating.
  • the unreacted raw material consists of raw material phenols constituting the unit of the general formula (2) and raw material naphthols constituting the unit of the general formula (3).
  • the ratio of unreacted phenols and naphthols in the reaction mixture was determined from an HPLC chart obtained by HPLC measurement under the following conditions. The ratio (molar ratio) was an area ratio. From the above data, the ratio of the unit of the general formula (2) and the unit of the general formula (3) [unit of the general formula (2) / unit of the general formula (3)] was calculated by the following formula.
  • HPLC measurement conditions Instrument: HPLC manufactured by Shimadzu Corporation Column: STR ODS-H column (manufactured by Shinwa Kako) Column oven temperature: 40 ° C
  • Moving layer acetonitrile, 5% phosphoric acid solution The concentration of the moving layer was adjusted at the start of measurement using a mixture of acetonitrile / 5% phosphoric acid solution with a volume ratio of 20/60. The acetonitrile ratio was linearly increased to 60/40, then the volume ratio was linearly increased to 100/0 over 5 minutes, and then acetonitrile was used as it was until the measurement was completed. .
  • Flow rate 1.00 mL / min
  • Detection wavelength 220 nm
  • Ratio of the component represented by the general formula (4) The area ratio was determined from the HPLC chart obtained by HPLC measurement under the following conditions.
  • Example 1 Add 188.0 g (2.0 mol) of phenol and 123.4 g (0.9 mol) of ⁇ -naphthol to a 1000 mL glass flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, and a nitrogen stream Then, the raw material was dissolved by raising the internal temperature to 60 ° C. After adding 179.3 g (0.7 mol) of 4,4′-bis (chloromethyl) biphenyl, the mixture was reacted at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours. Unreacted components of the raw material were removed by the teaming process.
  • the phenol novolak resin thus obtained had a softening point of 113 ° C., a hydroxyl group equivalent of 263 g / eq, and a ratio of the unit of general formula (2) and the unit of general formula (3) measured by HPLC [general formula (2) Unit / unit of general formula (3)] was 30/70, and the proportion of the component represented by general formula (4) was 15%.
  • the evaluation of solubility of this phenol novolac resin was ⁇ .
  • the HPLC chart of the unreacted raw material of this reaction is shown in FIG. From this chart, the proportions of phenols and naphthols in the unreacted raw materials were calculated as 82% and 18%.
  • the ratio of the unit of general formula (2) and the unit of general formula (3) introduced into the resin according to the calculation method [unit of general formula (2) / unit of general formula (3) ] was calculated.
  • the HPLC chart of the obtained phenol novolak resin is shown in FIG. From the area ratio of this chart, the ratio of the component represented by the general formula (4) (there is an isomer, so there are 3 peaks) was determined.
  • the obtained phenol novolac resin had a softening point of 131 ° C., a hydroxyl group equivalent of 256 g / eq, and a ratio of the unit of general formula (2) and the unit of general formula (3) measured by HPLC [general formula (2) Unit / unit of general formula (3)] was 20/80, and the proportion of the component represented by general formula (4) was 18%.
  • the evaluation of solubility of this phenol novolac resin was ⁇ .
  • the HPLC chart of the unreacted raw material of this reaction is shown in FIG. From this chart, the proportions of phenols and naphthols in the unreacted raw materials were calculated as 76% and 24%.
  • the ratio of the unit of the general formula (2) and the unit of the general formula (3) [unit of the general formula (2) / unit of the general formula (3)] was calculated according to the calculation formula. Moreover, the HPLC chart of the obtained phenol novolak resin is shown in FIG. From the area ratio of this chart, the ratio of the component represented by the general formula (4) (there is an isomer, so there are 3 peaks) was determined.
  • the obtained phenol novolac resin had a softening point of 117 ° C., a hydroxyl group equivalent of 247 g / eq, and the proportion of the component represented by the general formula (4) measured by HPLC was 24%.
  • the evaluation of solubility of this phenol novolac resin was ⁇ .
  • Example 4 Add 188.0 g (2.0 mol) of phenol and 123.4 g (1.0 mol) of ⁇ -naphthol to a 1000 mL glass flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, and a nitrogen stream Then, the raw material was dissolved by raising the internal temperature to 60 ° C. After adding 119.5 g (0.5 mol) of 4,4′-bis (chloromethyl) biphenyl and reacting at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours, Unreacted components were removed by teaming treatment.
  • the obtained phenol novolac resin had a softening point of 97 ° C., a hydroxyl group equivalent of 238 g / eq, and the proportion of the component represented by the general formula (4) measured by HPLC was 30%.
  • the evaluation of solubility of this phenol novolac resin was x.
  • the obtained phenol novolac resin had a softening point of 94 ° C., a hydroxyl group equivalent of 238 g / eq, and a proportion of the component represented by the general formula (4) measured by HPLC of 49%.
  • the evaluation of solubility of this phenol novolac resin was x.
  • the phenol novolak resins of Examples 1 to 5 are summarized in Table 1. From the solubility evaluation results in this table, in order to uniformly dissolve the epoxy resin composition using the phenol novolak resin of the present invention in a solvent, the proportion of the component represented by the general formula (4) is 27% or less, It can be seen that it is preferably 20% or less.
  • Example 6 The phenol novolak resin obtained in Example 1, orthocresol type epoxy resin EOCN-1020-70, and a curing accelerator TPP were added in the formulation shown in Table 2 to obtain an epoxy resin composition, which was subjected to the conditions at 150 ° C. The mixture is heated, melted and mixed, and vacuum degassed, then poured into a 150 ° C. mold (thickness 4 mm), cured at 150 ° C. for 5 hours, and further cured at 180 ° C. for 8 hours to cure. A molded body was obtained. With respect to this cured molded body, the glass transition temperature was measured and found to be 175 ° C.
  • Example 6 an epoxy resin composition was prepared in the same manner as in Examples 5 to 6 of Patent Document 2 except that the phenol novolac resin used was changed, and the cured product was evaluated by the same method. It is what I did.
  • the evaluation results of Example 6 are shown in Table 2 in comparison with the data of Example 7 of Patent Document 2.
  • Table 2 shows that the glass transition temperature of the cured product of the epoxy resin composition is remarkably improved by using the phenol novolac resin of the present invention.
  • Flammability Measured according to UL-94 (2) Heat resistance (glass transition temperature (Tg)) Using an EMC test piece having a size of 40 mm ⁇ 12 mm ⁇ 1 mm, a dynamic viscoelasticity measuring device (RSA-G2 manufactured by TA Instruments) was used and the temperature was increased at a rate of 3 ° C./min. (3) Mechanical properties: Mechanical strength: Measured according to JIS K 7171.
  • Example 7 The phenol novolac resin obtained in Example 1, YX-4000 of biphenyl type epoxy resin, TPP of curing accelerator, and silica MSR-2212 of inorganic filler were added in the formulation shown in Table 2, and these were added at 80 ° C. After kneading using two rolls at a temperature of ⁇ 100 ° C., the mixture was pulverized to obtain the epoxy resin composition of the present invention. A tablet is prepared using the obtained epoxy resin composition, and this is injected into a mold using a low-pressure transfer molding machine under conditions of a mold temperature of 175 ° C., an injection pressure of 6.8 MPa, and a holding time of 600 seconds. Then, after taking out from the mold and post-curing at 180 ° C. for 8 hours, an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition was obtained. The results of evaluating this are shown in Table 3.
  • Example 8 Except that the phenol novolac resin obtained in Example 2 was used, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition. The results of evaluating this are shown in Table 3.
  • Example 9 Except for using the phenol novolac resin obtained in Example 3, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition. The results of evaluating this are shown in Table 3.
  • Example 10 Except for using the phenol novolac resin obtained in Example 4, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition. The results of evaluating this are shown in Table 3.
  • Example 5 Except that the phenol novolac resin obtained in Example 5 was used, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition. The results of evaluating this are shown in Table 3.
  • Example 6 Except for using the phenol novolac resin obtained in Example 6, the same operation as in Example 7 was performed to obtain an EMC (Epoxy Molding Compound) test piece made of a cured product of the epoxy resin composition. The results of evaluating this are shown in Table 3.
  • Example 12 To 231.2 parts by mass of methyl ethyl ketone as a diluent solvent, 131 parts by mass of the phenol novolac resin obtained in Example 1, 100 parts by mass of a bisphenol type epoxy resin, and 0.1 parts by mass of 2E4MZ of a curing accelerator were added to form a varnish. A varnish solution having a resin concentration of 50% by mass dissolved in was obtained. The obtained varnish solution was impregnated with M7628-105 of glass cloth and then dried at 130 ° C. for 15 minutes to obtain a prepreg. Eight prepregs were stacked, and copper foil CF-T9B-THE was stacked on both sides of the prepregs, and pressed using a press at 170 ° C.
  • the obtained copper-clad laminate had a glass transition temperature of 159 ° C., a peel strength of 2.0 N / mm, and a water absorption of 0.05% by mass. The results are shown in Table 4.
  • Example 2 instead of the phenol novolak resin obtained in Example 1, the general phenol novolak resin prepared in Reference Example 2 was used, and the formulation was as shown in Table 4, and the double-sided copper was prepared in the same manner as in Example 9. A tension laminate was obtained.
  • the obtained copper-clad laminate had a glass transition temperature of 147 ° C., a peel strength of 1.6 N / mm, and a water absorption of 0.09% by mass. The results are shown in Table 4.
  • an epoxy resin composition containing a phenol novolac resin (more specifically, a phenol-naphthol novolak resin) and an epoxy resin, the heat resistance and combustion resistance of the resulting cured product are remarkably improved.
  • An epoxy resin composition and a phenol novolac resin that can be suitably used for the epoxy resin composition can be provided.
  • the present invention preferably has excellent solubility of the phenol novolac resin used, and therefore can be easily dissolved in a solvent, and can be suitably used for, for example, the production of laminates and interlayer insulating materials.
  • An epoxy resin composition that can be used, and a phenol novolac resin that can be suitably used for the epoxy resin composition can be provided.

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JPH09183829A (ja) * 1995-12-28 1997-07-15 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
JPH09268218A (ja) * 1996-03-29 1997-10-14 Nippon Kayaku Co Ltd エポキシ樹脂の製造方法、エポキシ樹脂組成物及びその硬化物
JP2003277468A (ja) * 2002-03-22 2003-10-02 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
JP2011252037A (ja) * 2010-05-31 2011-12-15 Meiwa Kasei Kk エポキシ樹脂組成物、該エポキシ樹脂組成物を用いた半導体封止材料及び積層板

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