Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
  • C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
  • C07C39/15—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings with all hydroxy groups on non-condensed rings, e.g. phenylphenol
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
  • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/62—Alcohols or phenols
  • C08G59/621—Phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment
  • C08G65/485—Polyphenylene oxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/50—Phosphorus bound to carbon only
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
  • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

• the present invention relates to a phenol mixture, and more particularly, a phenol mixture of raw materials for epoxy resin production limited to a specific composition in order to provide an epoxy resin having excellent heat resistance, an epoxy resin using the same, and an epoxy resin.
• the present invention relates to compositions, cured products, and electric/electronic parts.
• epoxy resin By curing epoxy resin with various curing agents, it generally becomes a cured product with excellent mechanical properties, heat resistance, electrical properties, etc., so it is used in a wide range of fields such as adhesives, paints, electrical and electronic materials. is used in In particular, in the field of electrical and electronic materials, tetramethylbiphenol-type epoxy resins are frequently used for semiconductor encapsulants because they can provide high-value-added encapsulants.
• a tetramethylbiphenol type epoxy resin can generally be obtained by a condensation reaction between raw materials biphenol and epihalohydrin.
• 5'-tetramethyl-4,4'-biphenol (hereinafter sometimes abbreviated as TMBPL) is known.
• Patent Documents 1 to 3 describe 3,3′,5,5′-tetramethyl-4,4′-biphenol in which the content of specific impurities is in a specific range and a method for producing the same. It describes that a tetramethylbiphenol type epoxy resin was produced by the reaction of TMBPL and epichlorohydrin.
• JP 2003-327554 A Japanese Patent Application Laid-Open No. 2004-2830 JP-A-61-268641
• An object of the present invention is to provide a phenol mixture that is optimal as a raw material for manufacturing epoxy resins that can achieve the high heat resistance demanded in recent years, and epoxy resins, epoxy resin compositions, cured products, and electric/electronic parts using the same. be.
• the inventors of the present invention conducted intensive studies to solve the above problems, and found that 3,3',5,5'-tetramethyl-4,4'-biphenol contains various subcomponents generated during its production process. In the past, optimization of reaction conditions and purification were performed in order to reduce these subcomponents as much as possible, but 3,3',5,5'- The inventors have found that an epoxy resin obtained using tetramethyl-4,4'-biphenol exhibits excellent heat resistance, and have completed the present invention.
• the gist of the present invention resides in the following [1] to [8].
• [1] A phenol mixture containing 3,3′,5,5′-tetramethyl-4,4′-biphenol as a main component, containing more than 0.3% by weight and less than 10.0% by weight of polyphenylene ether , a phenolic mixture.
• the phenol mixture according to [1] which further contains 1.3% to 4.0% by weight of tetramethyldiphenoquinone.
• An epoxy resin obtained by reacting the phenol mixture according to [1] or [2] with epihalohydrin.
• An epoxy resin composition containing 0.01 to 1000 parts by weight of a curing agent per 100 parts by weight of the epoxy resin described in [3].
• the curing agent is at least one selected from the group consisting of phenolic curing agents, amine curing agents, tertiary amines, acid anhydride curing agents, amide curing agents, and imidazoles. 4].
• the epoxy resin composition according to [4] or [5] further comprising an epoxy resin different from the epoxy resin in the epoxy resin composition.
• a cured product obtained by curing the epoxy resin composition according to any one of [4] to [6].
• An electric/electronic component obtained by curing the epoxy resin composition according to any one of [4] to [6].
• the present invention it is possible to obtain a cured epoxy resin having higher heat resistance than a conventional cured epoxy resin using TMBPL.
• the epoxy resin obtained using can be used as an optimum raw material for producing a tetramethylbiphenol type epoxy resin.
• epoxy resin compositions containing this epoxy resin, cured products obtained by curing these, and electrical and electronic parts such as semiconductor encapsulants containing the epoxy resin are produced at temperatures higher than those in the conventionally used temperature range. It is expected that it can be used continuously in a high temperature range.
• the phenol mixture according to the first embodiment of the present invention contains 3,3',5,5'-tetramethyl-4,4'-biphenol as a main component, and polyphenylene ether (hereinafter sometimes abbreviated as PPE) ) is more than 0.3% by weight and less than 10.0% by weight, and tetramethyldiphenoquinone (hereinafter sometimes abbreviated as DPQ) is a phenol mixture containing 1.3 to 4.0% by weight. .
• PPE polyphenylene ether
• DPQ tetramethyldiphenoquinone
• the phenol mixture of the present embodiment is called a "phenol mixture” because it contains TMBPL as a main component and a plurality of subcomponents, but TMBPL and other Those obtained as a "mixture” of components may also be included in the phenol mixture of the present invention.
• TMBPL TMBPL
• even mixtures and the like that are not single components are sometimes expressed and called simply as “phenol” or "phenol compounds", and sometimes sold.
• the reason why the epoxy resin obtained using the phenol mixture of the present embodiment exhibits excellent heat resistance is not clear, it is presumed as follows. That is, in the phenol mixture of the present embodiment, by including PPE with a relatively high molecular weight in a specific ratio, when the epoxy resin obtained using it is cured to obtain a cured product, the cured product will be cured in some way. It is presumed that it contributes to the increase in crosslink density and, as a result, affects the improvement in heat resistance. As the PPE increases, the crosslink density of the cured product increases, so the Tg and 5% weight loss temperature of the cured product tend to increase. The temperature tends to drop.
• the melting point of DPQ itself is 222 ° C., and the boiling point is also expected to be high.
• the epoxy resin is cured to produce a cured product, the Tg and the 5% weight loss temperature are sufficiently high, and the cured product is thought to have excellent heat resistance.
• the crosslink density increases, and the Tg and 5% weight loss temperature of the resulting cured product tend to improve. tend to
• the content of PPE is preferably 0.5% to 8.0% by weight, more preferably 1.0% to 7.5% by weight, and even more preferably, 1.5% to 5.0% by weight.
• the content of DPQ is preferably 1.5 wt% to 3.5 wt%, more preferably 2.0 wt% to 3.0 wt%.
• the phenol mixture of the present embodiment contains TMBPL as a main component. % or more, and more preferably 90% or more by weight.
• the phenol mixture of this embodiment may contain a plurality of other subcomponents in addition to the main components TMBPL, PPE and DPQ described above.
• Secondary components are not particularly limited, but are preferably 4-(2,6-dimethylphenoxy)-2,6-dimethylphenol (hereinafter sometimes abbreviated as ED), 2,6-xylenol (hereinafter, may be abbreviated as XNL).
• the phenol mixture contains ED
• its content is not particularly limited, but is preferably 0.2% by weight or less, more preferably 0.1% by weight or less.
• the ED having a monofunctional phenolic hydroxyl group is 0.2% by weight or less, the Tg and the 5% weight loss temperature are sufficiently high and the cured product having excellent heat resistance is obtained when the cured product of the epoxy resin is produced. so preferred.
• the phenol mixture contains XNL, its content is not particularly limited, but is preferably 0.1 to 3.4% by weight, more preferably 0.3 to 2.5% by weight, Even more preferably, it is 0.5 to 2.0% by weight.
• the composition of the phenolic mixture can be determined by the method described in the Examples section below.
• a second embodiment of the present invention is based on 3,3′,5,5′-tetramethyl-4,4′-biphenol, contains 1.3 to 4.0% by weight of DPQ, and contains XNL. It is a phenol mixture containing 0.1 to 3.4% by weight. Preferred ranges for the contents of 3,3',5,5'-tetramethyl-4,4'-biphenol, DPQ, and XNL are the same as in the above embodiments.
• a third embodiment of the present invention contains 3,3′,5,5′-tetramethyl-4,4′-biphenol as a main component, contains 0.2% by weight or less of ED, and 0.1% of XNL. It is a phenolic mixture containing ⁇ 3.4% by weight. Preferred ranges of the contents of 3,3',5,5'-tetramethyl-4,4'-biphenol, ED, and XNL are the same as in the above embodiments.
• a fourth embodiment of the present invention contains 3,3′,5,5′-tetramethyl-4,4′-biphenol as a main component, contains 0.2% by weight or less of ED, and has a DPQ of 1.3. It is a phenol mixture containing ⁇ 4.0% by weight. Preferred ranges for the contents of 3,3',5,5'-tetramethyl-4,4'-biphenol, ED, and DPQ are the same as in the above embodiments.
• the method for producing the phenol mixture of the first to fourth embodiments is not particularly limited. and a production method comprising a step of oxidative dimerization of 2,6-xylenol.
• the amount of water used as the reaction solvent is usually 0.5-10 kg, preferably 1-5 kg, per 1 kg of 2,6-xylenol.
• surfactants include fatty acid soaps, alkylsulfonates, alkylbenzenesulfonic acids, and alkylsulfates. Sodium lauryl sulfate is preferred.
• the amount of surfactant used is usually in the range of 0.01 to 50 mmol per 1 mol of 2,6-xylenol. It is preferably in the range of 0.1 to 10 mmol.
• alkaline substances include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate, hydrogen carbonates, sodium borate, boron compounds such as borax, sodium phosphate, Alkali metal phosphates such as sodium hydrogen phosphate, potassium phosphate and potassium hydrogen phosphate, and amine bases such as triethylamine and pyridine.
• alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
• alkali metal carbonates such as sodium carbonate, hydrogen carbonates, sodium borate
• boron compounds such as borax, sodium phosphate, Alkali metal phosphates such as sodium hydrogen phosphate, potassium phosphate and potassium hydrogen phosphate
• amine bases such as triethylamine and pyridine.
• boron compounds are preferred in terms of yield and selectivity.
• Borax is particularly preferred.
• the amount of the alkaline substance to be used is generally such that the pH of the reaction system is maintained within the
• a copper compound is preferably used as the metal catalyst.
• the copper compound may be either monovalent or divalent, and specific examples thereof include copper halide, copper hydroxide, copper sulfate, copper nitrate, copper carboxylate, and copper alkyl sulfate.
• the amount of metal catalyst used is 0.005 to 0.1 mmol per 1 mol of 2,6-xylenol. It is preferably 0.01 to 0.06 mmol.
• an oxygen-containing gas such as air is used.
• Oxygen is preferably used.
• the amount of the oxidizing agent used is in the range of 0.01 to 1 mol per 1 mol of 2,6-xylenol. It is preferably 0.1 to 0.6 mol.
• the ratio of 4-(2,6-dimethylphenoxy)-2,6-dimethylphenol, tetramethyldiphenoquinone, and 2,6-xylenol in the phenol mixture can be reduced by setting the amount of the oxidizing agent to a specific range. can be a specific range.
• the reaction temperature is usually 50 to 100° C.
• the reaction pressure is in the range of atmospheric pressure to 30 atm, depending on the oxygen concentration in the gas phase.
• the reaction time is usually 1 to 24 hours, preferably 5 to 15 hours.
• the following steps are preferably included. That is, the resulting reaction solution is heated while maintaining a pH of 7.5 to 9.0 to distill off water and unreacted 2,6-xylenol. In this case, it is preferable to adjust the pH after purging the inside of the reaction system with an inert gas such as nitrogen. Acids used for pH adjustment are not particularly limited, but mineral acids are generally used. Sulfuric acid or hydrochloric acid is particularly preferred. By setting the pH within the above range, the content of the polyphenylene ether and other components can be within the specified range of each embodiment.
• the reaction pressure is not particularly limited, the reaction can be carried out under normal pressure or under reduced pressure.
• an acid is added to the obtained product liquid to adjust the pH to 2 to 6.9, and then an alcohol is added and mixed and stirred to obtain a mixed liquid.
• the alcohol lower alcohols having 1 to 4 carbon atoms such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol and n-butanol are preferably used.
• the alcohol/water weight ratio is usually 1/1 to 10/1, preferably 2/1 to 5/1. Entrained water from the reaction slurry is utilized in the preparation of the mixture, but water is added when the phenol mixture is recovered as a solid.
• the concentration of the phenol mixture in the mixture is usually 5-50% by weight.
• the temperature during mixing and stirring is usually 40 to 100°C, preferably 50 to 90°C.
• the time for mixing and stirring is usually 0.1 to 5 hours, preferably 0.3 to 2 hours.
• Solid-liquid separation employs means such as filtration and centrifugation.
• the temperature of the mixed liquid during solid-liquid separation is usually 35 to 70°C, preferably 40 to 65°C.
• the phenol mixture can be recovered by heating and depressurization.
• An epoxy resin according to another aspect of the present invention is an epoxy resin obtained by reacting the phenol mixture according to any one of the first to fourth embodiments of the present invention with epihalohydrin.
• the epoxy resin of this embodiment is produced from the phenol mixture according to any one of the first to fourth embodiments of the present invention. , those that contribute to the reaction, those that remain as they are without contributing to the reaction, and those that distill out of the system during the reaction. Therefore, it is difficult to identify the presence and form of PPE and DPQ contained in the phenol mixture in the obtained epoxy resin, and to identify the structure of the epoxy resin by analysis.
• the epoxy resin of the present embodiment includes one containing a repeating structure and one having a monomolecular structure, but in the industry, any epoxy compound may be expressed as an "epoxy resin" and sold. In the industry, a mixture further containing an epoxy resin different from the epoxy resin of the present embodiment is sometimes simply referred to as "epoxy resin".
• the epoxy resin of the present embodiment has an epoxy equivalent of 186 to 189 g/equivalent (hereinafter sometimes referred to as g/eq). preferable. By setting the epoxy equivalent to the above specific range, it is believed that excellent curing properties can be obtained.
• the epoxy equivalent increases according to the amounts of epihalohydrin and alkali metal hydroxide used in the reaction.
• “epoxy equivalent” is defined as "mass of epoxy resin containing one equivalent of epoxy group” and can be measured according to JIS K7236.
• the method for producing the epoxy resin of the present embodiment is not particularly limited, but a method of reacting the phenol mixture according to any one of the first to fourth embodiments of the present invention with epihalohydrin in the presence of an alkali metal hydroxide. is mentioned.
• an epoxy resin is produced by such a method, at least the phenol mixture according to any one of the first to fourth embodiments of the present invention and epihalohydrin are used as raw materials, but a polyhydric hydroxy compound other than the phenol mixture ( hereinafter sometimes referred to as "other polyvalent hydroxy compounds”) may be used in combination to produce an epoxy resin.
• polyhydroxy compound as used herein is a general term for phenol compounds having a hydroxyl group of two or more valences.
• polyhydric hydroxy compounds include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, bisphenol AF, hydroquinone, resorcin, methylresorcin, biphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolac resin, cresol novolac.
• polyhydric phenols such as resins, phenol aralkyl resins, biphenyl aralkyl resins, naphthol aralkyl resins, terpene phenol resins, dicyclopentadiene phenol resins, bisphenol A novolac resins, naphthol novolak resins, brominated bisphenol A, brominated phenol novolac resins (excluding the phenol mixture according to any one of the first to fourth embodiments of the present invention), and various phenols and various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, glyoxal
• polyhydric phenol resins obtained by condensation reaction polyhydric phenol resins obtained by condensation reaction of xylene resin and phenols, co-condensation resins of heavy oils or pitches, phenols and formaldehydes, etc.
• Phenolic resins and the like are exemplified. Preferred among these are phenol novolac resins, phenol aralkyl resins, polyhydric phenol resins obtained by the condensation reaction of phenol and hydroxybenzaldehyde, biphenyl aralkyl resins, naphthol aralkyl resins, and the like.
• the amount of epihalohydrin used is usually 2 to 10.0 equivalents per 1 equivalent of hydroxyl groups of all polyvalent hydroxy compounds, which is the sum of the phenol mixture used as a raw material and other polyvalent hydroxy compounds used as necessary. , particularly preferably 4 to 8 equivalents.
• the amount of epihalohydrin is at least the above lower limit, it is preferable because the polymerization reaction can be easily controlled and the resulting epoxy resin can have an appropriate epoxy equivalent weight.
• the amount of epihalohydrin is equal to or less than the above upper limit, production efficiency tends to improve, which is preferable.
• epihalohydrin epichlorohydrin or epibromohydrin is usually used, but epichlorohydrin is preferred in the present embodiment.
• the amount of alkali metal hydroxide to be used is usually 0.8 to 1.6 equivalents, preferably 1.0 to 1.4 equivalents, per equivalent of hydroxyl groups in all the polyhydroxy compounds that are raw materials for the epoxy resin.
• An amount of alkali metal hydroxide corresponding to the amount used is added in the state of solid or aqueous solution and reacted.
• the amount of the alkali metal hydroxide is at least the above lower limit, the reaction between the unreacted hydroxyl groups and the produced epoxy resin is less likely to occur, and the polymerization reaction can be easily controlled, which is preferable.
• the amount of the alkali metal hydroxide is equal to or less than the above upper limit, because impurities due to side reactions are less likely to be generated.
• Alkali metal hydroxides used herein typically include sodium hydroxide or potassium hydroxide.
• This reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is preferably 20 to 150°C, more preferably 30 to 100°C.
• the reaction temperature is equal to or higher than the above lower limit, it is preferable because the reaction can be easily proceeded and the reaction can be easily controlled. Further, when the reaction temperature is equal to or lower than the above upper limit, the side reaction is less likely to proceed, and especially chlorine impurities are easily reduced, which is preferable.
• the reaction is carried out by azeotroping the reaction liquid while maintaining a predetermined temperature as necessary, cooling the volatilizing steam, separating the condensate obtained by oil/water separation, and returning the oil content after removing the water to the reaction system. It may be carried out while dehydrating depending on the method.
• the alkali metal hydroxide is added intermittently or continuously little by little over a period of preferably 0.1 to 8 hours, more preferably 0.5 to 6 hours, in order to suppress rapid reaction. If the time taken to add the alkali metal hydroxide is equal to or longer than the above lower limit, the reaction can be prevented from progressing rapidly, and the reaction temperature can be easily controlled, which is preferable.
• the time taken for addition is equal to or less than the above upper limit, chlorine impurities are less likely to be generated, which is preferable, and is also preferable from the viewpoint of economy.
• the insoluble by-product salt is removed by filtration or washed with water, and then unreacted epihalohydrin is removed by distillation under reduced pressure to obtain a crude epoxy resin.
• quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium bromide
• tertiary amines such as benzyldimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol
• 2-ethyl Catalysts such as imidazoles such as 4-methylimidazole and 2-phenylimidazole
• phosphonium salts such as ethyltriphenylphosphonium iodide
• phosphines such as triphenylphosphine
• alcohols such as ethanol and isopropanol
• ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone
• ethers such as dioxane and ethylene glycol dimethyl ether
• glycol ethers such as methoxypropanol
• Inert organic solvents such as aprotic polar solvents such as may be used.
• the epoxy resin of the present embodiment can be obtained by refining the crude epoxy resin produced as described above by reacting it again with an alkali metal hydroxide.
• the alkali treatment conditions for producing the epoxy resin of the present embodiment are described below, but since the reaction rate may change depending on the conditions, sampling is performed at an appropriate timing during the reaction and the epoxy equivalent is analyzed. A desired epoxy resin can be obtained.
• An organic solvent for dissolving the epoxy resin may be used for the reaction between the epoxy resin and the alkali metal hydroxide.
• the organic solvent used in the reaction is not particularly limited, it is preferable to use a ketone-based organic solvent from the viewpoint of production efficiency, handleability, workability, and the like.
• an aprotic polar solvent may be used from the viewpoint of lowering the amount of hydrolyzable chlorine.
• ketone-based organic solvents include ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Methyl isobutyl ketone is particularly preferred because of ease of post-treatment.
• Aprotic polar solvents include, for example, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, sulfolane, dimethylformamide, dimethylacetamide, hexamethylphosphoramide and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types. Among these aprotic polar solvents, dimethyl sulfoxide is preferred because it is readily available and tends to reduce the amount of hydrolyzable chlorine.
• the ratio of the aprotic polar solvent to the total of these is 1 to 80% by weight, preferably 5 to 30% by weight. It is preferable to use
• the amount of the solvent used is such that the concentration of the epoxy resin in the liquid to be treated with the alkali metal hydroxide is usually 1 to 90% by weight, preferably 5 to 80% by weight.
• alkali metal hydroxides solids or solutions can be used. Potassium hydroxide, sodium hydroxide and the like can be mentioned, with sodium hydroxide being preferred.
• the alkali metal hydroxide may be dissolved in an organic solvent or water.
• the alkali metal hydroxide is used as a solution dissolved in an aqueous solvent or an organic solvent.
• the amount of the alkali metal hydroxide to be used is preferably 0.1 parts by weight or more and 20 parts by weight or less based on 100 parts by weight of the epoxy resin in terms of the solid content of the alkali metal hydroxide. By setting the amount of the alkali metal hydroxide to be used within this range, it is possible to adjust the epoxy equivalent of the obtained epoxy resin.
• the reaction temperature is preferably 10 to 150°C, more preferably 20 to 90°C, and the reaction time is preferably 0.1 to 15 hours, more preferably 0.3 to 10 hours. When the reaction temperature is within the above range, it is easy to obtain the epoxy resin of the present embodiment.
• excess alkali metal hydroxide and by-product salts are removed by a method such as washing with water, and the organic solvent is removed by vacuum distillation and/or steam distillation to obtain the epoxy resin of the present embodiment. can.
• An epoxy resin composition according to another aspect of the present invention comprises at least the epoxy resin according to one embodiment of the present invention and a curing agent.
• the epoxy resin composition of the present embodiment may optionally contain other epoxy resins other than the epoxy resin of the present embodiment (hereinafter, may be simply referred to as "other epoxy resins"), curing accelerators, Agents, inorganic fillers, coupling agents and the like can be appropriately blended.
• the epoxy resin composition of the present embodiment containing the above epoxy resin provides a cured product that sufficiently satisfies physical properties required for various uses such as excellent heat resistance.
• the curing agent refers to a substance that contributes to cross-linking reaction and/or chain extension reaction between epoxy groups of epoxy resin.
• a substance is usually called a "curing accelerator"
• it is regarded as a curing agent if it is a substance that contributes to the cross-linking reaction and/or chain extension reaction between the epoxy groups of the epoxy resin. do.
• the content of the curing agent is preferably 0.1 to 1000 parts by weight with respect to 100 parts by weight of the total epoxy resin component as a solid content. Further, it is more preferably 500 parts by weight or less, and still more preferably 300 parts by weight or less.
• the term "solid content” means the components excluding the solvent, and includes not only solid epoxy resins but also semi-solid and viscous liquid substances.
• the amount of “total epoxy resin components” is the amount of epoxy resin contained in the epoxy resin composition of the present embodiment, and the epoxy resin composition of the present embodiment is the epoxy resin according to one embodiment of the present invention. If it contains only, it corresponds to the amount of the epoxy resin, and if it contains the epoxy resin according to one embodiment of the present invention and another epoxy resin, the epoxy resin according to one embodiment of the present invention and the other epoxy resin equivalent to the total amount of
• the curing agent there are no particular restrictions on the curing agent, and any one generally known as an epoxy resin curing agent can be used.
• phenol-based curing agents such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines (excluding tertiary amines), tertiary amines, acid anhydride-based curing agents curing agents, amide curing agents, imidazoles, and the like.
• the epoxy resin composition of the present embodiment can obtain excellent heat resistance, stress resistance, moisture absorption resistance, flame retardancy, and the like. It preferably contains a phenolic curing agent.
• Curing agents may be used singly or in combination of two or more. When two or more kinds of curing agents are used in combination, they may be mixed in advance to prepare a mixed curing agent before use, or each component of the curing agent may be added separately when mixing the components of the epoxy resin composition. They may be added separately and mixed together.
• phenol-based curing agents include bisphenol A, bisphenol F, bisphenol S, bisphenol AD, hydroquinone, resorcinol, methylresorcinol, biphenol, tetramethylbiphenol, dihydroxynaphthalene, dihydroxydiphenyl ether, thiodiphenols, phenol novolak resin, Cresol novolak resin, phenol aralkyl resin, biphenyl aralkyl resin, naphthol aralkyl resin, terpene phenol resin, dicyclopentadiene phenol resin, bisphenol A novolak resin, trisphenolmethane type resin, naphthol novolak resin, brominated bisphenol A, brominated phenol novolak resin
• polyhydric phenols such as resins, polyhydric phenol resins obtained by condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde,
• phenol novolak resins for example, compounds represented by the following formula (1)
• phenol aralkyl resins for example, the following formula (2)
• biphenyl aralkyl resin for example, a compound represented by the following formula (3)
• naphthol novolac resin for example, a compound represented by the following formula (4)
• naphthol aralkyl resin for example, a compound represented by the following formula (5 )
• a trisphenolmethane type resin e.g., a compound represented by the following formula (6)
• a phenol-benzaldehyde-xylylenedimethoxide polycondensate e.g., a compound represented by the following formula (7)
• a phenol-benzaldehyde-xylylene dihalide polycondensate for example, a compound represented by the following formula (7)
• phenol novolak resins for example, compounds represented by the following formula (1)
• phenol aralkyl resins for example, the following
• k 1 to k 6 each represent an integer of 0 or more.
• k 7 , k 8 , l 1 , and l 2 in the above formulas (7) and (8) each represent an integer of 1 or more.
• the amount of the phenolic curing agent is preferably 0.1 to 1000 parts by weight, more preferably 500 parts by weight or less, still more preferably 300 parts by weight, based on 100 parts by weight of the total epoxy resin components in the epoxy resin composition. parts or less, particularly preferably 100 parts by weight or less.
• amine curing agents include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines and the like.
• aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis( hexamethylene)triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra(hydroxyethyl)ethylenediamine and the like.
• polyetheramines examples include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis(propylamine), polyoxypropylene diamine, and polyoxypropylene triamines.
• Alicyclic amines include isophoronediamine, mensendiamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-amino Propyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, norbornenediamine and the like are exemplified.
• Aromatic amines include tetrachloro-p-xylylenediamine, m-xylylenediamine, p-xylylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2-(dimethylaminomethyl)phenol, triethanolamine, methylbenzylamine, ⁇ -(m-aminophenyl)ethylamine
• the above-mentioned amine-based curing agents may be used alone, or two or more of them may be used in any combination and at any blending ratio.
• the above amine-based curing agent can be used so that the equivalent ratio of the functional group in the curing agent to the epoxy groups in all the epoxy resin components contained in the epoxy resin composition is in the range of 0.8 to 1.5. preferable. Within this range, unreacted epoxy groups and functional groups of the curing agent are less likely to remain, which is preferable.
• Tertiary amines include 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol and the like. .
• the tertiary amines listed above may be used alone or in combination of two or more in an arbitrary combination and mixing ratio.
• the above tertiary amine can be used so that the equivalent ratio of the functional group in the curing agent to the epoxy group in all the epoxy resin components contained in the epoxy resin composition is in the range of 0.8 to 1.5. preferable. Within this range, unreacted epoxy groups and functional groups of the curing agent are less likely to remain, which is preferable.
• Acid anhydride-based curing agents include acid anhydrides, modified acid anhydrides, and the like.
• acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, dodecenylsuccinic anhydride, polyadipic anhydride, polyazelaic anhydride, and polysebacic acid.
• Anhydride poly(ethyloctadecanedioic anhydride), poly(phenylhexadecanedioic anhydride), tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride , methylhimic acid anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, methylcyclohexene tetracarboxylic acid anhydride, ethylene glycol bistrimellitate dianhydride, het acid anhydride, nadic acid anhydride, methyl nadic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3,4-dicarboxy-1,2, and 3,4-te
• Modified acid anhydrides include, for example, those obtained by modifying the above acid anhydrides with glycol.
• glycols that can be used for modification include alkylene glycols such as ethylene glycol, propylene glycol and neopentyl glycol, and polyether glycols such as polyethylene glycol, polypropylene glycol and polytetramethylene ether glycol. mentioned. Furthermore, two or more of these glycols and/or copolymerized polyether glycols of polyether glycols can also be used.
• the amount of modification is equal to or less than the above upper limit, the viscosity of the epoxy resin composition does not become too high, workability tends to be good, and the rate of curing reaction with the epoxy resin tends to be good.
• the acid anhydride-based curing agents listed above may be used alone or in combination of two or more in any desired combination and amount.
• an acid anhydride-based curing agent it should be used so that the equivalent ratio of the functional group in the curing agent to the epoxy groups in all the epoxy resin components in the epoxy resin composition is in the range of 0.8 to 1.5. is preferred. Within this range, unreacted epoxy groups and functional groups of the curing agent are less likely to remain, which is preferable.
• amide curing agents include dicyandiamide and derivatives thereof, and polyamide resins.
• the amide-based curing agent may be used alone, or two or more may be used in any combination and ratio.
• imidazoles examples include 2-phenylimidazole, 2-ethyl-4(5)-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1 -Cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino- 6-[2′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s -triazine, 2,4-diamino-6-[2′-methylimidazolyl-(
• imidazoles Since imidazoles have catalytic activity, they can be generally classified as curing accelerators, but in the present invention they are classified as curing agents.
• the above-mentioned imidazoles may be used singly, or two or more of them may be used in any combination and ratio.
• imidazoles it is preferable to use imidazoles in an amount of 0.1 to 20% by weight based on the sum of all epoxy resin components and imidazoles in the epoxy resin composition.
• the epoxy resin composition of this embodiment may contain other curing agents in addition to the curing agent.
• Other curing agents that can be used in the epoxy resin composition of the present embodiment are not particularly limited, and all those generally known as curing agents for epoxy resins can be used. These other curing agents may be used alone or in combination of two or more.
• the epoxy resin composition of this embodiment can further contain other epoxy resins in addition to the epoxy resin of this embodiment.
• other epoxy resins By including other epoxy resins, the heat resistance, stress resistance, moisture absorption resistance, flame retardancy, etc. of the epoxy resin composition of the present embodiment can be improved.
• Other epoxy resins that can be used in the epoxy resin composition of the present embodiment include all epoxy resins other than the epoxy resin of the present embodiment.
• bisphenol A type epoxy resin trisphenol methane type Epoxy resin, anthracene type epoxy resin, phenol-modified xylene resin type epoxy resin, bisphenol cyclododecyl type epoxy resin, bisphenol diisopropylidene resorcinol type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, hydroquinone type epoxy resin, methyl hydroquinone-type epoxy resin, dibutylhydroquinone-type epoxy resin, resorcinol-type epoxy resin, methylresorcin-type epoxy resin, biphenol-type epoxy resin, tetramethylbiphenol-type epoxy resin other than the epoxy resin of the present embodiment, tetramethylbisphenol F-type epoxy resin, Dihydroxydiphenyl ether type epoxy resin, epoxy resin derived from thiodiphenols, dihydroxynaphthalene type epoxy resin, dihydroxyanthracene type epoxy resin, dihydroxydihydroanthracene type epoxy resin, dicycl
• bisphenol A type epoxy resin Tetramethylbiphenol-type epoxy resins other than epoxy resins, 4,4'-biphenol-type epoxy resins, biphenylaralkyl-type epoxy resins, phenol aralkyl-type epoxy resins, dihydroxyanthracene-type epoxy resins, dicyclopentadiene-type epoxy resins, ortho-cresol novolac-type epoxy resins Epoxy resins and trisphenolmethane type epoxy resins are particularly preferred.
• the content thereof is preferably 0.01 to 60 parts by weight with respect to 100 parts by weight of the total epoxy resin components in the composition. , more preferably 40 parts by weight or less, still more preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, while more preferably 1 part by weight or more.
• the epoxy resin composition of the present embodiment preferably contains a curing accelerator.
• a curing accelerator By including a curing accelerator, it is possible to shorten the curing time and lower the curing temperature, and to easily obtain a desired cured product.
• the curing accelerator is not particularly limited, but specific examples thereof include organic phosphines, phosphorus compounds such as phosphonium salts, tetraphenylboron salts, organic acid dihydrazides, halogenated boron amine complexes, and the like.
• Phosphorus compounds that can be used as curing accelerators include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl/alkoxyphenyl)phosphine, tris( dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkyl Organic phosphines such as arylphosphines and alkyldiarylphosphines, complexes of these organic phosphines with organic borons, and these organic phosphine
• the curing accelerator is preferably used in an amount of 0.1 to 20 parts by weight with respect to 100 parts by weight of all epoxy resin components in the epoxy resin composition. More preferably 0.5 parts by weight or more, still more preferably 1 part by weight or more, on the other hand, more preferably 15 parts by weight or less, still more preferably 10 parts by weight or less.
• the content of the curing accelerator is at least the above lower limit value, a good curing acceleration effect can be obtained, while when it is at most the above upper limit value, desired cured physical properties are easily obtained, which is preferable.
• An inorganic filler can be added to the epoxy resin composition of the present embodiment.
• inorganic fillers include fused silica, crystalline silica, glass powder, alumina, calcium carbonate, calcium sulfate, talc, and boron nitride. These may be used alone, or two or more of them may be used in any combination and blending ratio. Among these, crushed and/or spherical fused and/or crystalline silica powder fillers are preferred when used for semiconductor encapsulation applications.
• the thermal expansion coefficient of the semiconductor encapsulating material can be brought close to that of the internal silicon chip or lead frame. Since the amount of moisture absorbed by the entire sealing material can be reduced, solder crack resistance can be improved.
• the average particle size of the inorganic filler is usually 0.01-50 ⁇ m, preferably 1-40 ⁇ m, more preferably 2-30 ⁇ m.
• the melt viscosity does not become too high and the fluidity is less likely to decrease, which is preferable. It is preferable because the material is less likely to be clogged and the fillability of the material is easily improved.
• the inorganic filler is preferably blended in an amount of 60 to 95% by weight based on the entire epoxy resin composition.
• a release agent can be added to the epoxy resin composition of the present embodiment.
• release agents include natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid and zinc stearate and their metal salts, and hydrocarbon release agents such as paraffin. can be done. These may be used alone, or two or more of them may be used in any combination and blending ratio.
• the amount of the release agent is preferably 0.1 to 5.0 parts per 100 parts by weight of all epoxy resin components in the epoxy resin composition. 0 parts by weight, more preferably 0.5 to 3.0 parts by weight. When the amount of the release agent is within the above range, it is possible to maintain the curing properties of the epoxy resin composition and exhibit good releasability, which is preferable.
• a coupling agent is preferably added to the epoxy resin composition of the present embodiment.
• the coupling agent is preferably used in combination with the inorganic filler, and the addition of the coupling agent can improve the adhesion between the matrix epoxy resin and the inorganic filler.
• Examples of coupling agents include silane coupling agents and titanate coupling agents.
• silane coupling agents include epoxysilanes such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ - aminopropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropyltrimethoxysilane, ⁇ - Aminosilanes such as ureidopropyltriethoxysilane, mercaptosilanes such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris( ⁇ -
• titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri(N-aminoethyl/aminoethyl) titanate, diisopropyl bis(dioctylphosphate) titanate, tetraisopropyl bis(dioctylphosphite) titanate, tetraoctyl bis ( ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate and the like. be done. Any one of these coupling agents may be used alone, or two or more thereof may be used in any combination and ratio.
• the compounding amount is preferably 0.1 to 3.0 parts by weight with respect to 100 parts by weight of the total epoxy resin component.
• the amount of the coupling agent is at least the above lower limit, the effect of improving the adhesion between the matrix epoxy resin and the inorganic filler tends to be enhanced. If the amount of the agent is less than the above upper limit, the coupling agent is less likely to bleed out from the resulting cured product, which is preferable.
• the epoxy resin composition of the present embodiment may contain components other than those described above (hereinafter sometimes referred to as "other compounding components").
• Other compounding components include, for example, flame retardants, plasticizers, reactive diluents, pigments, etc., and can be appropriately compounded as necessary.
• the epoxy resin composition of the present embodiment does not at all prevent blending of components other than the components listed above.
• Flame retardants that can be used in the epoxy resin composition of the present embodiment include halogen-based flame retardants such as brominated epoxy resins and brominated phenolic resins, antimony compounds such as antimony trioxide, red phosphorus, phosphate esters, and phosphines. Nitrogen flame retardants such as melamine derivatives and inorganic flame retardants such as aluminum hydroxide and magnesium hydroxide.
• a cured product having excellent heat resistance By curing the epoxy resin composition according to one embodiment of the present invention, a cured product having excellent heat resistance can be obtained. That is, another aspect of the present invention is a cured product obtained by curing the epoxy resin composition according to one embodiment of the present invention.
• the method for curing the epoxy resin composition is not particularly limited, but usually a cured product can be obtained by a thermosetting reaction by heating. During the thermosetting reaction, it is preferable to appropriately select the curing temperature depending on the type of curing agent used. For example, when a phenol-based curing agent is used, the curing temperature is usually 100-300.degree. By adding a curing accelerator to these curing agents, it is also possible to lower the curing temperature.
• the reaction time is preferably 0.01 to 20 hours, more preferably 0.1 to 10 hours.
• the reaction time is at least the above lower limit, the curing reaction tends to proceed sufficiently, which is preferable.
• the reaction time is equal to or less than the above upper limit, deterioration due to heating and energy loss during heating are easily reduced, which is preferable.
• the cured product of this embodiment has excellent heat resistance.
• the cured product has a glass transition temperature (Tg) of 130°C or higher and a 5% weight loss temperature of 390°C or higher.
• Tg glass transition temperature
• 5% weight loss temperature 390°C or higher.
• the glass transition temperature (Tg) and the 5% weight loss temperature are measured by the methods described in Examples below.
• the phenol resin composition, epoxy resin, epoxy resin composition, and cured product according to each embodiment of the present invention can be used for any application requiring these physical properties. It can also be effectively used for other purposes.
• coatings such as electrodeposition coatings for automobiles, heavy-duty anti-corrosion coatings for ships and bridges, and coatings for the inner surface of beverage cans; electrical and electronic fields such as laminates, semiconductor sealing materials, insulating powder coatings, and coil impregnation.
• electrical and electronic fields such as laminates, semiconductor sealing materials, insulating powder coatings, and coil impregnation.
• Suitable for any application such as seismic reinforcement of bridges, reinforcement of concrete, flooring of buildings, lining of water supply facilities, drainage/permeable pavement, civil engineering, construction, and adhesives for vehicles and aircraft. can be done. Among these, it is particularly useful for electric and electronic parts such as semiconductor sealing materials and laminates.
• the epoxy resin composition according to one embodiment of the present invention may be used for the above applications after curing, or may be cured during the
• Example 2 4 kg of 2,6-xylenol (XNL), 400 g of borax, 13 g of sodium lauryl sulfate, 12 kg of water, and 0.2 g of cupric acetate were charged into a 30 L stainless steel reactor equipped with baffles, and heated while stirring. . When the content temperature reached 70°C, introduction of 0.27 kg of oxygen was started. Stirring was continued while maintaining the reaction temperature at 70° C. After 12 hours, introduction of oxygen was stopped and the inside of the reaction system was purged with nitrogen. After that, 25% sulfuric acid was added to adjust the pH of the resulting slurry to 7.8, and then the temperature was gradually raised for distillation to distill water and unreacted 2,6-xylenol.
• the temperature inside the reactor was cooled to 70° C., 25% sulfuric acid was added to adjust the pH of the reaction solution to 6.5, and then 1.75 kg of water and 6.05 kg of isopropyl alcohol were added to 60° C. C. and stirred for 30 minutes. Thereafter, the temperature was maintained at 60°C, the obtained slurry was treated with a centrifuge to separate solid and liquid, and the solid in the centrifuge was rinsed with 5 kg of hot water at 60°C. The obtained solid was dried with a vacuum dryer to obtain a phenol mixture.
• Example 3 4 kg of 2,6-xylenol (XNL), 400 g of borax, 13 g of sodium lauryl sulfate, 12 kg of water, and 0.2 g of cupric acetate were charged into a 30 L stainless steel reactor equipped with baffles, and heated while stirring. . When the content temperature reached 70°C, introduction of 0.31 kg of oxygen was started. Stirring was continued while maintaining the reaction temperature at 70° C. After 12 hours, introduction of oxygen was stopped and the inside of the reaction system was purged with nitrogen. After that, 25% sulfuric acid was added to adjust the pH of the resulting slurry to 8.1, and then the temperature was gradually raised for distillation to distill water and unreacted 2,6-xylenol.
• the temperature inside the reactor was cooled to 70° C., 25% sulfuric acid was added to adjust the pH of the reaction solution to 6.5, and then 1.75 kg of water and 6.05 kg of isopropyl alcohol were added to 60° C. C. and stirred for 30 minutes. Thereafter, the temperature was maintained at 60°C, the obtained slurry was treated with a centrifuge to separate solid and liquid, and the solid in the centrifuge was rinsed with 5 kg of hot water at 60°C. The obtained solid was dried with a vacuum dryer to obtain a phenol mixture.
• Example 4 4 kg of 2,6-xylenol (XNL), 400 g of borax, 13 g of sodium lauryl sulfate, 12 kg of water, and 0.2 g of cupric acetate were charged into a 30 L stainless steel reactor equipped with baffles, and heated while stirring. . When the content temperature reached 70°C, introduction of 0.40 kg of oxygen was started. Stirring was continued while maintaining the reaction temperature at 70° C. After 12 hours, introduction of oxygen was stopped and the inside of the reaction system was purged with nitrogen. After that, 25% sulfuric acid was added to adjust the pH of the resulting slurry to 8.5, and then the temperature was gradually raised for distillation to distill water and unreacted 2,6-xylenol.
• the temperature inside the reactor was cooled to 70° C., 25% sulfuric acid was added to adjust the pH of the reaction solution to 6.5, and then 1.75 kg of water and 6.05 kg of isopropyl alcohol were added to 60° C. C. and stirred for 30 minutes. Thereafter, the temperature was maintained at 60°C, the obtained slurry was treated with a centrifuge to separate solid and liquid, and the solid in the centrifuge was rinsed with 5 kg of hot water at 60°C. The obtained solid was dried with a vacuum dryer to obtain a phenol mixture.
• Example 5 4 kg of 2,6-xylenol (XNL), 400 g of borax, 13 g of sodium lauryl sulfate, 12 kg of water, and 0.2 g of cupric acetate were charged into a 30 L stainless steel reactor equipped with baffles, and heated while stirring. . When the content temperature reached 70°C, introduction of 0.47 kg of oxygen was started. Stirring was continued while maintaining the reaction temperature at 70° C. After 12 hours, introduction of oxygen was stopped and the inside of the reaction system was purged with nitrogen. After that, 25% sulfuric acid was added to adjust the pH of the resulting slurry to 9.0, and then the temperature was gradually raised for distillation to distill water and unreacted 2,6-xylenol.
• the temperature inside the reactor was cooled to 70° C., 25% sulfuric acid was added to adjust the pH of the reaction solution to 6.5, and then 1.75 kg of water and 6.05 kg of isopropyl alcohol were added to 60° C. C. and stirred for 30 minutes. Thereafter, the temperature was maintained at 60°C, the obtained slurry was treated with a centrifuge to separate solid and liquid, and the solid in the centrifuge was rinsed with 5 kg of hot water at 60°C. The obtained solid was dried with a vacuum dryer to obtain a phenol mixture.
• the obtained solid was dried with a vacuum dryer to obtain a phenol resin.
• a phenol resin To 1 kg of the obtained phenol resin, 4.6 kg of isopropyl alcohol and 1.5 kg of water were added, charged into a stirring tank, heated to 110° C. under pressure, and stirred for 2 hours. Thereafter, the mixture was cooled to 30° C. and solid-liquid separated by a centrifugal separator. 4.1 kg of isopropyl alcohol and 1.4 kg of water were added to the obtained solid, and the mixture was purified again in the same manner to obtain a phenol mixture.
• the temperature inside the reactor was cooled to 70° C., 25% sulfuric acid was added to adjust the pH of the reaction solution to 6.5, and then 1.75 kg of water and 6.05 kg of isopropyl alcohol were added to 60° C. C. and stirred for 30 minutes. Thereafter, the temperature was maintained at 60°C, the obtained slurry was treated with a centrifuge to separate solid and liquid, and the solid in the centrifuge was rinsed with 5 kg of hot water at 60°C. The obtained solid was dried with a vacuum dryer to obtain a phenol mixture.
• Tables 1 and 2 show the composition of the phenol mixture (PPE, TMBPL, ED, DPQ, XNL proportions (% by weight)).
• Example 7 It was synthesized in the same manner as in Example 6 except that the phenol mixture obtained in Example 2 was used. Epoxy equivalent weights are shown in Table 3.
• Example 8 Synthesis was carried out in the same manner as in Example 6, except that the phenol mixture obtained in Example 3 was used. Epoxy equivalent weights are shown in Table 3.
• Example 9 Synthesis was carried out in the same manner as in Example 6 except that the phenol mixture obtained in Example 4 was used. Epoxy equivalent weights are shown in Table 3.
• Example 10 Synthesis was performed in the same manner as in Example 6 except that the phenol mixture obtained in Example 5 was used. Epoxy equivalent weights are shown in Table 3.
• epoxy resin composition and production of cured product Examples 11 to 15, Comparative Examples 11 to 15 Using the epoxy resins obtained in Examples 6-10 and Comparative Examples 6-10, epoxy resin compositions having compositions shown in Tables 4 and 5 were prepared.
• a phenol aralkyl resin represented by formula (2) (MEHC7800SS hydroxyl equivalent 174 g / eq, manufactured by Meiwa Kasei Co., Ltd.) is used, and as a curing accelerator, triphenylphosphine (Hokuko Chemical Industry Co., Ltd.) TPP) was used. These were heated in an oven at 120° C. for 2 hours and 175° C. for 6 hours to prepare cured products.
• the glass transition temperature (Tg) and 5% weight loss temperature of the cured product were measured.
• a Tg of 130° C. or higher and a 5% weight loss temperature of 390° C. or higher was rated as heat resistance ⁇ , and a Tg of 130° C. or lower or a 5% weight loss temperature of 390° C. or lower was rated as x.
• surface shows a "weight part.”
• Tg glass transition temperature

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• 2022
  • 2022-07-14 EP EP22845836.0A patent/EP4375309A4/en active Pending
  • 2022-07-14 KR KR1020247002219A patent/KR20240035472A/ko active Pending
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