WO2013080936A1 - Phenol novolak resin and epoxy resin composition using same - Google Patents
Phenol novolak resin and epoxy resin composition using same Download PDFInfo
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- 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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- 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
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- 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
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- 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
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- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08J2363/04—Epoxynovolacs
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- 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.
Abstract
Description
(1) 下記一般式(1)で表される化学構造によって構成されているフェノールノボラック樹脂。 The present invention relates to the following items.
(1) A phenol novolac resin constituted by a chemical structure represented by the following general formula (1).
但し、フェノールノボラック樹脂全体としては、Aは、下記一般式(2)の1価若しくは2価のユニット、及び下記一般式(3)の1価若しくは2価のユニットの両者によって構成されている。
However, as a whole phenol novolac resin, 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).
(6) The epoxy resin composition as described in 5 above, wherein the obtained cured product has a glass transition temperature of 155 ° C. or higher, preferably 170 ° C. or higher, more preferably 180 ° C. or higher.
(10) 前記項8のエポキシ樹脂組成物を用いてマトリックス樹脂を形成した積層板。 (9) A cured product obtained by curing any of the epoxy resin compositions according to the above items 5 to 8.
(10) A laminate in which a matrix resin is formed using the epoxy resin composition according to
また、本発明ではガラス転移温度の測定方法として、比較の便宜上2種の方法で測定したが、万一測定方法による差異が生じる場合には、動的粘弾性測定装置による測定方法を優先する。 Here, “independently” means that when there are a plurality of symbols representing the corresponding substituents and numbers, each symbol representing a plurality of substituents and numbers is independently a different substituent or number. Means that you can take For example, 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.
In the present invention, 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.
また、原料のフェノール類とナフトール類とのモル比[フェノール類/ナフトール類]は、好ましくは10/90~90/10、より好ましくは40/60~90/10の範囲が好適である。原料のフェノール類とナフトール類とのモル比をこの範囲内にすることによって、以下で説明するが、得られるフェノールノボラック樹脂のフェノール類に起因する一般式(2)のユニットとナフトール類に起因する一般式(3)のユニットとの割合を本発明の好ましい範囲とすることができる。すなわち、ナフトール成分が少な過ぎると、樹脂中に導入される一般式(3)のユニットが減少して十分な耐熱性を得ることが難しくなる場合がある。また、ナフトール成分が多過ぎると、樹脂中に導入される一般式(3)のユニットが増加し、一般式(4)で示されるユニットも増加することから溶剤溶解性が損なわれる原因となる。
反応は、通常、溶媒の非存在下、あるいは水及び/又は有機溶媒等の溶媒の存在下、0℃~150℃、0.5時間~10時間程度で行うことができるが、フェノールノボラック樹脂を構成する成分の割合や重合度等を調節するために、反応温度、反応時間等の反応条件などは適宜調節される。
なお、反応終了後、未反応のフェノール類やナフトール類などは、減圧下又は不活性ガスを吹き込みながら加熱して、系外へ留去することが好適である。また、酸触媒は、水洗等の洗浄により除去することができる。 In this reaction, 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. By making the molar ratio of the raw material phenols and naphthols within this range, it will be explained below, but it is caused by the unit of the general formula (2) and naphthols resulting from the phenols of the obtained phenol novolac resin. 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 may reduce, and it may become difficult to obtain sufficient heat resistance. Moreover, when there are too many 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. In order to adjust the ratio of the constituent components, the degree of polymerization, and the like, reaction conditions such as reaction temperature and reaction time are appropriately adjusted.
After the reaction, 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.
従って、一般式(1)において、一般式(5)及び一般式(6)で表されるフェノール類やナフトール類が分子末端を構成した場合は、一般式(1)中のAは一般式(2)及び一般式(3)の1価のユニットとなり、分子内に組み込まれた場合には、一般式(1)中のAは一般式(2)及び一般式(3)の2価のユニットとなる。
また、この反応においては、先ず一般式(1)のnが0の成分が生成する。次いで生成したnが0の成分の一部は、さらにビフェニル化合物或いは生成したnが0の成分と反応する。このようにして、更にnが1及び1を越える成分を順次生成する。一方、nが1及び1を越える成分を生成する反応が進んでいる間も、nが0の成分を生成する反応は継続するので、本発明のフェノールノボラック樹脂は、通常は一般式(1)のn値が異なる複数の成分の集合体である。 By this reaction, 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). To do.
Therefore, in the general formula (1), when the phenols and naphthols represented by the general formula (5) and the general formula (6) constitute the molecular end, 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.
In this reaction, first, a component in which n in general formula (1) is 0 is generated. Next, a part of the produced n = 0 component further reacts with the biphenyl compound or the produced n = 0 component. In this way, components in which n exceeds 1 and 1 are sequentially generated. On the other hand, while the reaction for generating a component in which n exceeds 1 and 1 proceeds, the reaction for generating a component in which n is 0 continues. Therefore, 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.
一般式(2)のユニットと一般式(3)のユニットとの割合が、この範囲内であることによって、本発明のエポキシ樹脂組成物からなる硬化物の耐熱性や耐燃焼性を好適に改善することができる。
樹脂中に、4,4’-体からなるビフェニル化合物と組合せて、一般式(3)で表されるユニットを導入することで、得られる樹脂の耐熱性が効率よく改良され、燃焼を効果的に抑制して耐燃焼性を改良することが可能になる。しかし、一般式(3)のユニットの割合が高くなり過ぎると、樹脂の粘度や軟化点の上昇を招いてハンドリング性を損なう場合があるし、更に、樹脂中の一般式(4)のユニットが増加して樹脂の溶解性を制御することが難しくなる。 In the present invention, 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.
When 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.
By introducing a unit represented by the general formula (3) in combination with a biphenyl compound consisting of 4,4′-form into the resin, the heat resistance of the resulting resin is efficiently improved, and combustion is effectively performed. This makes it possible to improve the combustion resistance. However, if 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. Further, the unit of the general formula (4) in the resin It increases and it becomes difficult to control the solubility of the resin.
一方、全成分中の一般式(4)で表される成分がHPLCで測定したときの面積割合で27%を越えると、有機溶媒に対する溶解性が低下して、例えばメチルエチルケトンに対して樹脂/溶媒を質量で50/50の割合では、均一に溶解するのが困難になる。
例えばメチルエチルケトンを用いて、樹脂/溶媒が質量で50/50の高濃度の割合でも均一に溶解できれば、本発明のエポキシ樹脂組成物をメチルエチルケトンに溶解してワニス化して、積層板のマトリックス材料や層間絶縁材料として用いることが容易になる。均一に溶解できなくてワニス化できない場合には、積層板のマトリックス材料や層間絶縁材料として用いることが容易ではなくなる。 In the present invention, 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. When 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. For example, the resin / It is possible to uniformly dissolve the solvent even at a ratio of 50/50 by mass.
On the other hand, when the component represented by the general formula (4) in all the components exceeds 27% in terms of the area ratio when measured by HPLC, 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.
フェノール類とナフトール類の合計に対するビフェニル化合物のモル比[(フェノール類とナフトール類)/ビフェニル化合物]は、通常よりもより小さな値(より1に近い値)にすることが、成分を全体的に高分子量化して一般式(4)の成分を減らせるので好適である。また、フェノール類とナフトール類とのモル比は、フェノール類に比べてナフトール類の反応性が高いのでナフトール類の割合を比較的高くすることが、より反応を進めて、成分を全体的に高分子量化して一般式(4)の成分を減らせるので好適であるが、一方、ナフトール類の割合が高くなりすぎると一般式(4)の成分が増えて溶解性に悪影響がある。例えば、ナフトール類100%にすると、当然一般式(4)の成分の量を減らして溶解性を高めることが著しく困難になる。
これらの割合の調節は、それらの反応性の大きさ、更に採用する反応条件等を加味して行われる。当業者にとっては、その調節方法は自明であるが、必要なら予備的実験を行うことによって簡単に見出すことができる。 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). It is preferable because the component of the general formula (4) can be reduced by increasing the molecular weight. In addition, 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. It is preferable because the component of the general formula (4) can be reduced by increasing the molecular weight. On the other hand, if 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).
These ratios are adjusted in consideration of the magnitude of their reactivity and the reaction conditions employed. For those skilled in the art, the adjustment method is self-explanatory, but can be easily found by conducting preliminary experiments if necessary.
本発明のエポキシ樹脂組成物は、一般式(1)で表される化学構造によって構成されているフェノールノボラック樹脂(A)とエポキシ樹脂(B)とを含んでなる。 Next, the epoxy resin composition of the present invention will be described.
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).
これらの中でも、ビフェニル型エポキシ樹脂、フェノールアラルキル型エポキシ樹脂、トリフェニルメタン型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂などが、耐熱性や耐燃焼性を改良する上で特に好適である。 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.
Among these, 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.
フェノールノボラック樹脂(A)以外の他の硬化剤は、特に限定はなく、組成物の使用目的に応じて種々のエポキシ樹脂硬化剤を用いることができる。例えば、アミン系硬化剤、アミド系硬化剤、酸無水物系硬化剤、一般式(1)で表される化学構造によって構成されているフェノールノボラック樹脂(A)以外のフェノール樹脂系硬化剤など、通常のエポキシ樹脂硬化剤を好適に用いることができる。
また、本発明のエポキシ樹脂組成物において、硬化剤中の一般式(1)で表される化学構造によって構成されているフェノールノボラック樹脂(A)の割合は、特に限定はないが、硬化物の耐熱性や耐燃焼性を改良するためにより高い割合が好ましく、30質量%以上、好ましくは50質量%以上、より好ましくは70質量%以上、更に好ましくは90質量%、特に好ましくは100質量%である。 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).
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. For example, an amine-based curing agent, an amide-based curing agent, an acid anhydride-based curing agent, a phenol resin-based curing agent other than the phenol novolac resin (A) configured by the chemical structure represented by the general formula (1), etc. A normal epoxy resin curing agent can be suitably used.
Moreover, in the epoxy resin composition of the present invention, 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.
得られる硬化物の耐熱性や耐燃焼性が優れるエポキシ樹脂組成物を、高濃度で均一なワニス溶液にすることができれば、積層板のマトリックス材料や層間絶縁材料として好適に用いることが可能になる。
前記溶媒(C)は、エポキシ樹脂組成物を溶解させるものであれば特に限定はないが、好ましくは通常の積層板のマトリックス材料や層間絶縁材料をワニス化する際に用いられる有機溶媒を好適に用いることができる。例えば、メチルエチルケトン、アセトン、ジエチルケトン、メチルイソブチルケトン、シクロヘキサノンなどのケトン類、プロピレングリコールモノメチルエーテルなどのエーテル類、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド類、ジメチルスルホキシドなどのスルホキシド類、γ-ブチルラクトンなどのラクトン類、N‐メチルピロリドンなどのピロリドン類、トルエン、キシレンなどの芳香族炭化水素類を好適に挙げることができる。これらの中では、メチルエチルケトン、ジメチルホルムアミドが特に好ましい。これらの溶媒は単独でも2種以上を組み合わせても使用することができる。
本発明のエポキシ樹脂組成物をワニス化した場合は、限定するものではないが、好ましくは、樹脂成分の濃度は10~90質量%程度であり、溶液粘度は30℃で1~5000cP程度である。 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). Is preferred.
If the epoxy resin composition excellent in heat resistance and combustion resistance of the resulting cured product can be made into a uniform varnish solution at a high concentration, it can be suitably used as a matrix material or an interlayer insulating material for laminates. .
The 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. For example, 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, γ-butyllactone, etc. Preferable examples include lactones, pyrrolidones such as N-methylpyrrolidone, and aromatic hydrocarbons such as toluene and xylene. Among these, methyl ethyl ketone and dimethylformamide are particularly preferable. These solvents can be used alone or in combination of two or more.
When the epoxy resin composition of the present invention is varnished, the concentration of the resin component is preferably about 10 to 90% by mass, and the solution viscosity is about 1 to 5000 cP at 30 ° C. .
例えば、エポキシ樹脂をフェノール樹脂で硬化させるための硬化促進剤を用いることができる。硬化促進剤としては、公知の、有機ホスフィン化合物及びそのボロン塩、3級アミン、4級アンモニウム塩、イミダゾール類及びのテトラフェニルボロン塩などを好適に挙げることができる。これらの中でも、硬化性や耐湿性の面からトリフェニルホスフィンが好ましい。なお、エポキシ樹脂組成物により高流動性が要求される場合には、加熱処理にて活性が発現する熱潜在性の硬化促進剤が好ましく、中でも、テトラフェニルホスフォニウム・テトラフェニルボレートなどのテトラフェニルホスフォニウム誘導体がより好ましい。硬化促進剤の添加量は公知のエポキシ樹脂組成物における割合と同様でよい。 In the epoxy resin composition of this invention, the other component used with a normal epoxy resin composition can be used suitably according to the use.
For example, 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. In addition, when high fluidity is required by the epoxy resin composition, 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.
無機充填剤の配合割合については特に制限は無いが、エポキシ樹脂組成物中の70重量%~95重量%、好ましくは75重量%~90重量%、より好ましくは80重量%~90重量%である。無機充填剤の割合が上記範囲外であるとエポキシ樹脂組成物の硬化物の吸水率が増加し好ましくない。また、無機充填剤の割合が多すぎると流動性を損なわれる恐れがある。 Furthermore, fillers such as inorganic fillers can also be suitably used. As 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. Although there is no restriction | limiting in particular as 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. . If 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 | liquidity may be impaired.
このようなエポキシ樹脂組成物は、限定するものではないが、半導体封止材料などとして好適に用いることができる。 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.
このワニス化したエポキシ樹脂(溶液)組成物は、限定するものではないが、積層板のマトリックス材料や層間絶縁材料として好適に用いることができる。 In addition, 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. , Epoxy resin (B) and, if necessary, other curing agents, curing accelerators, inorganic fillers, additives and the like, and at least phenol novolac resin (A) by heating and stirring as necessary. ) And the epoxy resin (B) can be uniformly dissolved in the solvent (C) to produce a varnish solution.
Although 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.
硬化物を得るための加熱処理条件は、硬化触媒や硬化促進剤の有無、それらの添加量などにも依存するが、通常は100~300℃程度、好ましくは120~200℃程度の温度で1分間から10時間程度加熱処理するのが好適である。 As for the epoxy resin composition of this invention, after drying a solvent as needed, a hardened | 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. For example, after a lead frame or the like on which the semiconductor element is mounted is placed in a metal cavity, 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.
以下のフェノールノボラック樹脂の調製の例で用いた材料について説明する。
(1)フェノール:和光純薬工業社製
(2)α―ナフトール(1-ナフトール):和光純薬工業社製
(3)4、4’-ビス(クロロメチル)ビフェニル:和光純薬工業社製 [1] Preparation of phenol novolac resin The materials used in the following examples of preparation of phenol novolac resin will be described.
(1) Phenol: manufactured by Wako Pure Chemical Industries, Ltd. (2) α-naphthol (1-naphthol): manufactured by Wako Pure Chemical Industries, Ltd. (3) 4, 4′-bis (chloromethyl) biphenyl: manufactured by Wako Pure Chemical Industries, Ltd.
(1)軟化点:JIS K6910に基づく環球法軟化点測定によって行った。
(2)水酸基当量: JIS K0070に準じた水酸基当量測定によって行った。
(3)一般式(2)のユニットと一般式(3)のユニットとの割合[一般式(2)のユニット/一般式(3)のユニット]の測定:フェノールノボラック樹脂の調製において、原料の仕込み量、生成したフェノールノボラック樹脂量、及び副生成物量を測定し、反応収支から未反応原料の量を算出する。ビフェニル化合物は全量反応させるので、未反応原料は、一般式(2)のユニットを構成する原料のフェノール類と一般式(3)のユニットを構成する原料のナフトール類とからなる。反応混合液中の未反応のフェノール類とナフトール類との割合を、以下に示す条件のHPLC測定によって得られるHPLCチャートから求めた。なお、割合(モル比)は面積比とした。以上のデータから下記数式によって、一般式(2)のユニットと一般式(3)のユニットとの割合[一般式(2)のユニット/一般式(3)のユニット]を算出した。 The analysis method and evaluation method used in the following examples of preparing phenol novolac resins will be described.
(1) Softening point: Performed by ring and ball method softening point measurement based on JIS K6910.
(2) Hydroxyl equivalent: The hydroxyl equivalent was measured according to JIS K0070.
(3) Measurement of ratio of unit of general formula (2) and unit of general formula (3) [unit of general formula (2) / unit of general formula (3)]: In preparation of phenol novolac resin, The amount charged, the amount of phenol novolak resin produced, and the amount of by-products are measured, and the amount of unreacted raw material is calculated from the reaction balance. Since all of the biphenyl compound is reacted, 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.
機器:島津製作所社製HPLC
カラム:STR ODS-Hカラム (信和化工社製)
カラムオーブン温度:40℃
移動層:アセトニトリル、5%リン酸溶液
移動層の濃度調節は、測定開始時はアセトニトリル/5%リン酸溶液の容積割合が20/60の混合液を用い、測定開始後10分間かけて容積割合を60/40までアセトニトリルの割合を直線的に増加させ、次いで5分間かけて容積割合を100/0まで直線的にアセトニトリルの割合を増加させ、その後はそのままの状態で測定終了までアセトニトリルを用いた。
流量:1.00mL/分
検出波長:220nm 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
HPLCの測定条件
機器:島津製作所社製HPLC
カラム:STR ODS-Hカラム (信和化工社製)
カラムオーブン温度:40℃
移動層:アセトニトリル、5%リン酸溶液
移動層の濃度調節は、測定開始時はアセトニトリル/5%リン酸溶液の容積割合が50/50の混合液を用い、測定開始後20分間かけて容積割合を75/25までアセトニトリルの割合を直線的に増加させ、次いで20分間かけて容積割合を100/0まで直線的にアセトニトリルの割合を増加させ、その後はそのままの状態で測定終了までアセトニトリルを用いた。
流量:1.00mL/分
検出波長:220nm
(5)溶解性:
以下に示す方法で溶解性試験によって評価した。
溶媒:メチルエチルケトン
溶解比率(質量):フェノールノボラック樹脂/溶媒=50/50
溶解条件:密閉容器に樹脂と溶媒を加え、60℃で攪拌溶解させた。
評価判定:溶解後と常温(23℃)で12時間静置後とを目視で観察した。樹脂が均一に溶解し且つ静置後も均一な溶液が保持されたものを○、樹脂が均一に溶解したが静置後に樹脂の一部が析出したものを△、均一な溶液を得ることができなかったものを×とした。 (4) 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.
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 50/50 volume ratio of acetonitrile / 5% phosphoric acid solution, and the volume ratio over 20 minutes after the start of measurement. The acetonitrile ratio was linearly increased to 75/25, then the acetonitrile volume was linearly increased to 100/0 over 20 minutes, and then acetonitrile was used as it was until the measurement was completed. .
Flow rate: 1.00 mL / min Detection wavelength: 220 nm
(5) Solubility:
It evaluated by the solubility test by the method shown below.
Solvent: Methyl ethyl ketone Dissolution ratio (mass): Phenol novolac resin / Solvent = 50/50
Dissolution condition: Resin and solvent were added to an airtight container and dissolved by stirring at 60 ° C.
Evaluation: Visual observation was performed after dissolution and after standing at room temperature (23 ° C.) for 12 hours. It is possible to obtain a uniform solution by ◯ when the resin is uniformly dissolved and a uniform solution is retained after standing, and when the resin is uniformly dissolved but a part of the resin is deposited after standing. What was not made was set as x.
温度計、仕込み・留出口、冷却器および攪拌機を備えた容量1000mLのガラス製フラスコにフェノール188.0g(2.0モル)、α―ナフトール123.4g(0.9モル)を加え、窒素気流下、内温60℃まで上昇させて原料を溶解させた。4、4’-ビス(クロロメチル)ビフェニル179.3g(0.7モル)を加え、内温60℃~100℃にて4時間、さらに165℃にて3時間反応させた後に、減圧-スチーミング処理にて原料の未反応成分を除去した。
得られたフェノールノボラック樹脂の軟化点は113℃、水酸基当量は263g/eq、HPLCにて測定した、一般式(2)のユニットと一般式(3)のユニットとの割合[一般式(2)のユニット/一般式(3)のユニット]は30/70、一般式(4)で表される成分の割合は15%であった。このフェノールノボラック樹脂の溶解性の評価判定は○であった。
なお、この反応の未反応原料のHPLCチャートを図1に示す。このチャートから未反応原料中のフェノール類及びナフトール類の割合を82%及び18%と算出した。この割合を用い、前記算出方法に従って、樹脂中に導入された一般式(2)のユニットと一般式(3)のユニットとの割合[一般式(2)のユニット/一般式(3)のユニット]を算出した。
また、得られたフェノールノボラック樹脂のHPLCチャートを図2に示す。このチャートの面積比より一般式(4)で表される成分(異性体があるので3ピークの合計)の割合を求めた。 [Example 1]
Add 188.0 g (2.0 mol) of phenol and 123.4 g (0.9 mol) of α-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 ○.
In addition, 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%. Using this ratio, 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.
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.
温度計、仕込み・留出口、冷却器および攪拌機を備えた容量1000mLのガラス製フラスコにフェノール84.6g(0.9モル)、α―ナフトール129.6g(0.9モル)を加え、窒素気流下、内温60℃まで上昇させて原料を溶解させた。4、4’-ビス(クロロメチル)ビフェニル180.7g(0.7モル)を加え、内温60℃~100℃にて4時間、さらに165℃にて3時間反応させた後に、減圧-スチーミング処理にて原料の未反応成分を除去した。
得られたフェノールノボラック樹脂の軟化点は131℃、水酸基当量は256g/eq、HPLCにて測定した、一般式(2)のユニットと一般式(3)のユニットとの割合[一般式(2)のユニット/一般式(3)のユニット]は20/80、一般式(4)で表される成分の割合は18%であった。このフェノールノボラック樹脂の溶解性の評価判定は○であった。
なお、この反応の未反応原料のHPLCチャートを図3に示す。このチャートから未反応原料中のフェノール類及びナフトール類の割合を76%及び24%と算出した。この割合を用い、前記算出式に従って、一般式(2)のユニットと一般式(3)のユニットとの割合[一般式(2)のユニット/一般式(3)のユニット]を算出した。
また、得られたフェノールノボラック樹脂のHPLCチャートを図4に示す。このチャートの面積比より一般式(4)で表される成分(異性体があるので3ピークの合計)の割合を求めた。 [Example 2]
Phenol 84.6 g (0.9 mol) and α-naphthol 129.6 g (0.9 mol) were added 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 180.7 g (0.7 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 of the raw material were removed by the teaming process.
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 ○.
In addition, 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%. Using this ratio, 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.
温度計、仕込み・留出口、冷却器および攪拌機を備えた容量1000mLのガラス製フラスコにフェノール94.0g(1.0モル)、α―ナフトール144.0g(1.0モル)を加え、窒素気流下、内温60℃まで上昇させて原料を溶解させた。4、4’-ビス(クロロメチル)ビフェニル161.9g(0.7モル)を加え、内温60℃~100℃にて4時間、さらに165℃にて3時間反応させた後に、減圧-スチーミング処理にて原料の未反応成分を除去した。
得られたフェノールノボラック樹脂の軟化点は117℃、水酸基当量は247g/eq、HPLCにて測定した、一般式(4)で表される成分の割合は24%であった。このフェノールノボラック樹脂の溶解性の評価判定は△であった。 Example 3
Phenol 94.0 g (1.0 mol) and α-naphthol 144.0 g (1.0 mol) were added 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 161.9 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 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 Δ.
温度計、仕込み・留出口、冷却器および攪拌機を備えた容量1000mLのガラス製フラスコにフェノール188.0g(2.0モル)、α―ナフトール123.4g(1.0モル)を加え、窒素気流下、内温60℃まで上昇させて原料を溶解させた。4、4’-ビス(クロロメチル)ビフェニル119.5g(0.5モル)を加え、内温60℃~100℃にて4時間、さらに165℃にて3時間反応させた後に、減圧-スチーミング処理にて未反応成分を除去した。
得られたフェノールノボラック樹脂の軟化点は97℃、水酸基当量は238g/eq、HPLCにて測定した一般式(4)で表される成分の割合は30%であった。このフェノールノボラック樹脂の溶解性の評価判定は×であった。 Example 4
Add 188.0 g (2.0 mol) of phenol and 123.4 g (1.0 mol) of α-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.
温度計、仕込み・留出口、冷却器および攪拌機を備えた容量1000mLのガラス製フラスコにフェノール141.0g(1.5モル)、α―ナフトール216.0g(1.5モル)を加え、窒素気流下、内温60℃まで上昇させて原料を溶解させた。4、4’-ビス(クロロメチル)ビフェニル125.5g(0.5モル)を加え、内温60℃~100℃にて4時間、さらに165℃にて3時間反応させた後に、減圧-スチーミング処理にて未反応成分を除去した。
得られたフェノールノボラック樹脂の軟化点は94℃、水酸基当量は238g/eq、HPLCにて測定した一般式(4)で表される成分の割合は49%であった。このフェノールノボラック樹脂の溶解性の評価判定は×であった。 Example 5
Phenol 141.0 g (1.5 mol) and α-naphthol 216.0 g (1.5 mol) were added to a 1000 mL glass flask equipped with a thermometer, a charging / distilling outlet, a condenser and a stirrer, and a nitrogen stream Then, the raw material was dissolved by raising the internal temperature to 60 ° C. 4,4′-bis (chloromethyl) biphenyl (125.5 g, 0.5 mol) was added, and 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 were removed by teaming treatment.
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.
以下にエポキシ樹脂組成物に係る例で用いた材料について説明する。
(1)エポキシ樹脂
オルソクレゾール型エポキシ樹脂「EOCN-1020-70」:日本化薬社製、エポキシ当量:200g/eq、軟化点:70℃
(2)硬化促進剤(硬化触媒)
トリフェニルホスフィン(TPP):北興化学社製 [2] Comparison of Preparation of Epoxy Resin Composition of the Present Invention and Patent Document 2 Materials used in the examples relating to the epoxy resin composition will be described below.
(1) Epoxy resin Orthocresol type epoxy resin “EOCN-1020-70”: manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 200 g / eq, softening point: 70 ° C.
(2) Curing accelerator (curing catalyst)
Triphenylphosphine (TPP): manufactured by Hokuko Chemical Co., Ltd.
(1)耐熱性(ガラス転移温度(Tg))
特許文献2の測定方法に準じて行った。すなわち、寸法が4mm×6mm×10mmの硬化物からなる試験片を用い、昇温速度5℃/分で昇温して、TMA法(Thermal Mechanical Analysis、熱機械分析法)によって測定した。 Below, the evaluation method which concerns on an epoxy resin composition is demonstrated.
(1) Heat resistance (glass transition temperature (Tg))
It carried out according to the measuring method of patent document 2. That is, using a test piece made of a cured product having dimensions of 4 mm × 6 mm × 10 mm, the temperature was increased at a rate of temperature increase of 5 ° C./min, and measurement was performed by the TMA method (Thermal Mechanical Analysis).
実施例1で得られたフェノールノボラック樹脂、オルソクレゾール型エポキシ樹脂のEOCN-1020-70、硬化促進剤のTPPを、表2に示す配合で加えてエポキシ樹脂組成物とし、これを150℃の条件で加熱溶融混合し、真空脱泡した後に150℃の金型(厚さ4mm)に注型し、150℃、5時間で硬化させた後、さらに180℃、8時間かけて硬化して、硬化成形体を得た。
この硬化成形体について、ガラス転移温度を測定したところ、175℃であった。 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.
以下にエポキシ樹脂組成物に係る例で用いた材料について説明する。
(1)エポキシ樹脂
ビフェニル型エポキシ樹脂「YX-4000」:三菱化学社製、エポキシ当量:187g/eq
(2)硬化促進剤(硬化触媒)
トリフェニルホスフィン(TPP):北興化学社製
(3)無機充填剤
シリカ「MSR-2212」:龍森社製
[3] Preparation of epoxy resin composition of the present invention and evaluation by EMC test piece The materials used in the examples relating to the epoxy resin composition will be described below.
(1) Epoxy resin Biphenyl type epoxy resin “YX-4000”: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 187 g / eq
(2) Curing accelerator (curing catalyst)
Triphenylphosphine (TPP): Hokuko Chemical Co., Ltd. (3) Inorganic filler Silica “MSR-2212”: Tatsumori Co., Ltd.
(1)燃焼性
UL-94に準拠して測定した。
(2)耐熱性(ガラス転移温度(Tg))
寸法が40mm×12mm×1mmのEMC試験片を用いて動的粘弾性測定装置(TAインスツルメント社製 RSA-G2)を用い昇温速度3℃/分にて測定した。
(3)機械特性:機械強度:JIS K 7171に準拠して測定した。 Below, the evaluation method which concerns on an epoxy resin composition is demonstrated.
(1) 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.
実施例1で得られたフェノールノボラック樹脂、ビフェニル型エポキシ樹脂のYX-4000、硬化促進剤のTPP、及び無機充填剤のシリカMSR-2212を、表2に示す配合で加え、これらを、80℃~100℃の条件で2本ロールを用いて混練後、粉砕し本発明のエポキシ樹脂組成物を得た。
得られたエポキシ樹脂組成物を用いてタブレットを作成し、それを低圧トランスファー成形機を用いて、金型温度175℃、注入圧力6.8MPa、保圧時間600秒の条件で金型に注入して試験片を作成し、金型から取り出した後更に180℃、8時間のポストキュアを行いエポキシ樹脂組成物の硬化物からなるEMC(Epoxy Moldering Compound)試験片を得た。
これを評価した結果を表3に示す。 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.
実施例2で得られたフェノールノボラック樹脂を用いた以外は実施例7と同様の操作を行い、エポキシ樹脂組成物の硬化物からなるEMC(Epoxy Moldering Compound)試験片を得た。
これを評価した結果を表3に示す。 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.
実施例3で得られたフェノールノボラック樹脂を用いた以外は実施例7と同様の操作を行い、エポキシ樹脂組成物の硬化物からなるのEMC(Epoxy Moldering Compound)試験片を得た。
これを評価した結果を表3に示す。 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.
実施例4で得られたフェノールノボラック樹脂を用いた以外は実施例7と同様の操作を行い、エポキシ樹脂組成物の硬化物からなるEMC(Epoxy Moldering Compound)試験片を得た。
これを評価した結果を表3に示す。 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.
これを評価した結果を表3に示す。 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.
これを評価した結果を表3に示す。 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.
温度計、仕込み・留出口、冷却器および攪拌機を備えた容量1000mLのガラス製フラスコにフェノール470.0g(5.0モル)を加え、窒素気流下、内温60℃まで上昇させて原料を溶解させた。4、4’-ビスクロロメチルビフェニル313.8g(1.3モル)を加え、内温60℃~100℃にて4時間、さらに165℃にて3時間反応させた後に、減圧-スチーミング処理にて未反応成分を除去した。得られたフェノールノボラック樹脂Eの軟化点は68℃、水酸基当量は202g/eqであった。 [Reference Example 1]
Phenol 470.0 g (5.0 mol) was added to a 1000 mL glass flask equipped with a thermometer, charging / distilling outlet, condenser and stirrer, and the temperature was raised to an internal temperature of 60 ° C. under a nitrogen stream to dissolve the raw material. I let you. After adding 313.8 g (1.3 mol) of 4,4′-bischloromethylbiphenyl and reacting at an internal temperature of 60 ° C. to 100 ° C. for 4 hours and further at 165 ° C. for 3 hours, vacuum-steaming treatment To remove unreacted components. The obtained phenol novolac resin E had a softening point of 68 ° C. and a hydroxyl group equivalent of 202 g / eq.
参考例1で得られたフェノールノボラック樹脂を用いた以外は実施例6と同様の操作を行い、エポキシ樹脂組成物の硬化物からなる寸法が40mm×12mm×1mmのEMC(Epoxy Moldering Compound)試験片を得た。
これを評価した結果を表3に示す。 [Comparative Example 1]
Except that the phenol novolac resin obtained in Reference Example 1 was used, the same operation as in Example 6 was performed, and an EMC (Epoxy Molding Compound) test piece having dimensions of 40 mm × 12 mm × 1 mm made of a cured product of the epoxy resin composition. Got.
The results of evaluating this are shown in Table 3.
以下に銅張積層板の製造に係る例で用いた材料について説明する。
(1)エポキシ樹脂
ビスフェノールA型エポキシ樹脂「828EL」:三菱化学社製、エポキシ当量:186g/eq
(2)硬化促進剤(硬化触媒)
2-エチル-4-メチルイミダゾール(2E4MZ):四国化成社製
(3)溶媒(メチルエチルケトン):和光純薬工業社製
(4)ガラスクロス(無アルカリ処理ガラスクロス)「M7628-105」:有沢製作所社製
(5)銅箔(電解銅箔)「CF-T9B-THE」:福田金属箔粉工業社製、厚さ35μ [4] Manufacture and evaluation of copper-clad laminate using the epoxy resin composition of the present invention The materials used in the examples relating to the production of copper-clad laminate are described below.
(1) Epoxy resin Bisphenol A type epoxy resin “828EL”: manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 186 g / eq
(2) Curing accelerator (curing catalyst)
2-Ethyl-4-methylimidazole (2E4MZ): Shikoku Kasei Co., Ltd. (3) Solvent (methyl ethyl ketone): Wako Pure Chemical Industries, Ltd. (4) Glass cloth (non-alkali treated glass cloth) “M7628-105”: Arisawa Manufacturing Co., Ltd. (5) Copper foil (electrolytic copper foil) “CF-T9B-THE”: manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., thickness 35 μ
(1)接着性(ピール強度)
動的粘弾性測定装置(島津製作所株式会社製「AG-5000D」)を用い、荷重:1kN/100kgf 試験速度:50mm/分にて、90°銅箔引き剥がし強度を測定した。
(2)耐熱性
動的粘弾性測定装置(TAインスツルメント社製「RSA-G2」)を用い、昇温速度3℃/分にて、ガラス転移温度(Tg)を測定した。
(3)吸水率
JIS C6481に準拠して測定した。 Below, the evaluation method which concerns on a copper clad laminated board is demonstrated.
(1) Adhesiveness (peel strength)
Using a dynamic viscoelasticity measuring device (“AG-5000D” manufactured by Shimadzu Corporation), the 90 ° copper foil peel strength was measured at a load of 1 kN / 100 kgf and a test speed of 50 mm / min.
(2) Heat resistance The glass transition temperature (Tg) was measured using a dynamic viscoelasticity measuring apparatus (“RSA-G2” manufactured by TA Instruments) at a temperature rising rate of 3 ° C./min.
(3) Water absorption Measured according to JIS C6481.
希釈溶媒のメチルエチルケトン 231.2質量部に、実施例1で得られたフェノールノボラック樹脂 131質量部、ビスフェノール型エポキシ樹脂 100質量部、硬化促進剤の2E4MZ 0.1質量部を加えてワニス化し、均一に溶解した樹脂分濃度が50質量%のワニス溶液を得た。
得られたワニス溶液をガラスクロスのM7628-105に含浸させた後に130℃、15分間の条件で乾燥させ、プリプレグを得た。このプリプレグ8枚を重ねて、その両側に銅箔のCF-T9B-THEを重ね、170℃ 、30kg/cm2で15分間プレス機を用いてプレスした。張積層体をプレス機から取り出した後、さらに200℃、5時間アフターキュアすることで両面銅張積層板を得た。
得られた銅張積層板のガラス転移温度は159℃、ピール強度は2.0 N/mm、吸水率は0.05質量%であった。結果を表4に示す。 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. and 30 kg / cm 2 for 15 minutes. After taking out the tension laminate from the press machine, it was further cured at 200 ° C. for 5 hours to obtain a double-sided copper clad laminate.
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.
温度計、仕込み・留出口、冷却器および攪拌機を備えた容量1000mLのガラス製フラスコにフェノール470.0g(5.0モル)、92%パラホルムアルデヒド110.9g(3.4モル)、シュウ酸0.3gを加え、100℃にて5時間反応させた。反応終了後、減圧-スチーミング処理にて未反応成分を除去した。得られたフェノールノボラック樹脂Eの軟化点は96℃、水酸基当量は107g/eqであった。 [Reference Example 2]
In a glass flask with a capacity of 1000 mL equipped with a thermometer, charging / distilling outlet, condenser and stirrer, phenol 470.0 g (5.0 mol), 92% paraformaldehyde 110.9 g (3.4 mol), oxalic acid 0 .3 g was added and reacted at 100 ° C. for 5 hours. After completion of the reaction, unreacted components were removed by reduced pressure-steaming treatment. The obtained phenol novolac resin E had a softening point of 96 ° C. and a hydroxyl group equivalent of 107 g / eq.
実施例1で得られたフェノールノボラック樹脂の代わりに、参考例2で調製した一般的なフェノールノボラック樹脂を用い、配合を表4のとおりにしたこと以外は、実施例9と同様にして両面銅張積層板を得た。
得られた銅張積層板のガラス転移温度は147℃、ピール強度は1.6 N/mm、吸水率は0.09質量%であった。結果を表4に示す。 [Comparative 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.
Claims (10)
- 下記一般式(1)で表される化学構造によって構成されているフェノールノボラック樹脂。
但し、フェノールノボラック樹脂全体としては、Aは、下記一般式(2)の1価若しくは2価のユニット、及び下記一般式(3)の1価若しくは2価のユニットの両者によって構成されている。
However, as a whole phenol novolac resin, 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).
- 前記一般式(2)のユニットと前記一般式(3)のユニットとの割合[一般式(2)のユニット/一般式(3)のユニット]が、10/90~90/10の範囲内であることを特徴とする請求項1に記載のフェノールノボラック樹脂。 The ratio of the unit of the general formula (2) to the unit of the general formula (3) [unit of the general formula (2) / unit of the general formula (3)] is in the range of 10/90 to 90/10. The phenol novolac resin according to claim 1, wherein the phenol novolac resin is present.
-
フェノールノボラック樹脂を構成する全成分中の下記一般式(4)で表される成分が、HPLCで測定したときの面積割合で27%以下であることを特徴とする請求項1又は2に記載のフェノールノボラック樹脂。
The component represented by the following general formula (4) in all components constituting the phenol novolac resin is 27% or less in terms of an area ratio when measured by HPLC. Phenol novolac resin.
- 下記一般式(5)で表されるフェノール類及び下記一般式(6)で表されるナフトール類を、下記一般式(7)で表されるビフェニル化合物と反応させることを特徴とするフェノールノボラック樹脂の製造方法。
- 請求項1~3のいずれか1項に記載のフェノールノボラック樹脂(A)とエポキシ樹脂(B)とを含んでなるエポキシ樹脂組成物。 An epoxy resin composition comprising the phenol novolac resin (A) according to any one of claims 1 to 3 and an epoxy resin (B).
- 得られる硬化物のガラス転移温度が155℃以上であることを特徴とする請求項5記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 5, wherein the obtained cured product has a glass transition temperature of 155 ° C. or higher.
- 得られる硬化物のUL-94による難燃性がV-0であることを特徴とする請求項5又は6に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 5 or 6, wherein the obtained cured product has flame retardancy according to UL-94 of V-0.
- 請求項1~3のいずれか1項に記載のフェノールノボラック樹脂(A)、エポキシ樹脂(B)、及び溶媒(C)を含んでなり、フェノールノボラック樹脂(A)とエポキシ樹脂(B)とが、溶媒(C)中に均一に溶解していることを特徴とするエポキシ樹脂組成物。 A phenol novolac resin (A), an epoxy resin (B), and a solvent (C) according to any one of claims 1 to 3, comprising the phenol novolac resin (A) and the epoxy resin (B). An epoxy resin composition, which is uniformly dissolved in the solvent (C).
- 請求項5~8のいずれか1項に記載のエポキシ樹脂組成物を硬化させた硬化物。 A cured product obtained by curing the epoxy resin composition according to any one of claims 5 to 8.
- 請求項8に記載のエポキシ樹脂組成物を用いてマトリックス樹脂を形成した積層板。 A laminate comprising a matrix resin formed using the epoxy resin composition according to claim 8.
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JP2015067806A (en) * | 2013-09-30 | 2015-04-13 | 日本ゼオン株式会社 | Curable composition for forming print wiring board and manufacturing method of laminate for forming print wiring board |
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JP5135973B2 (en) | 2007-09-28 | 2013-02-06 | Dic株式会社 | Epoxy resin composition and cured product thereof |
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JPH04202219A (en) * | 1990-11-29 | 1992-07-23 | Mitsui Toatsu Chem Inc | Production of phenol polymer |
JPH06100667A (en) * | 1990-12-21 | 1994-04-12 | Mitsui Toatsu Chem Inc | Production of phenol polymer |
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JPH09183829A (en) * | 1995-12-28 | 1997-07-15 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition and its hardened article |
JPH09268218A (en) * | 1996-03-29 | 1997-10-14 | Nippon Kayaku Co Ltd | Production of epoxy resin, epoxy resin composition and irs cured material |
JP2003277468A (en) * | 2002-03-22 | 2003-10-02 | Nippon Kayaku Co Ltd | Epoxy resin, epoxy resin composition and its cured product |
JP2011252037A (en) * | 2010-05-31 | 2011-12-15 | Meiwa Kasei Kk | Epoxy resin composition and semiconductor sealing material and laminated board using the same |
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JP5752574B2 (en) | 2015-07-22 |
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TW201329137A (en) | 2013-07-16 |
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