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WO2015053299A1 - Procédé pour produire une résine phénolique, résine phénolique, résine époxy et composition de résine époxy - Google Patents

Procédé pour produire une résine phénolique, résine phénolique, résine époxy et composition de résine époxy Download PDF

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Publication number
WO2015053299A1
WO2015053299A1 PCT/JP2014/076880 JP2014076880W WO2015053299A1 WO 2015053299 A1 WO2015053299 A1 WO 2015053299A1 JP 2014076880 W JP2014076880 W JP 2014076880W WO 2015053299 A1 WO2015053299 A1 WO 2015053299A1
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Prior art keywords
epoxy resin
phenol
phenol resin
carbon atoms
alkyl group
Prior art date
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Ceased
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PCT/JP2014/076880
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English (en)
Japanese (ja)
Inventor
昌照 木村
政隆 中西
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Priority to JP2015541605A priority Critical patent/JP6359024B2/ja
Publication of WO2015053299A1 publication Critical patent/WO2015053299A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/02—Condensation polymers of aldehydes or ketones with phenols only of ketones
    • 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
    • C08G59/08—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols from phenol-aldehyde condensates
    • 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
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates

Definitions

  • the present invention relates to a phenol resin production method, a phenol resin, an epoxy resin, and an epoxy resin composition containing them, which can be used for an epoxy resin composition suitable for electrical and electronic material applications requiring heat resistance.
  • Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.
  • Non-Patent Documents 1 and 2 materials that are lightweight and have excellent mechanical properties are required for aerospace materials and leisure / sports equipment applications.
  • semiconductor encapsulation and substrates substrate itself or its peripheral materials
  • the semiconductor transitions it becomes increasingly complex with thinning, stacking, systematization, and three-dimensionalization. Required characteristics such as heat resistance and high fluidity are required.
  • heat resistance of 150 ° C. or higher has been required due to an increase in semiconductor driving temperature.
  • an epoxy resin tends to have high heat resistance when the softening point is high, but on the other hand, it tends to increase in viscosity, making it difficult to use it as a sealing material.
  • the fall of a thermal decomposition temperature and a flame retardance become a subject.
  • Patent Document 1 has a xanthene derivative having a phenolic hydroxyl group introduced in the main chain structure, which facilitates epoxidation, chemical modification, reaction with an epoxy resin, etc. by reaction with epichlorohydrin and the like, and fluidity. It is possible to synthesize from a low molecular weight product rich in high to a high softening point, and when this phenol resin is used as a curing agent such as an epoxy resin, a cured product having a high Tg can be obtained without impairing the adhesiveness. A phenolic resin that can be used is described.
  • Non-Patent Document 3 As an epoxy resin having good heat resistance, an epoxy resin having a dibenzoxanthene structure as shown in Non-Patent Document 3 has been developed. However, the epoxy resin has many steps in the synthesis process for obtaining the raw material phenol compound, and further uses harmful sodium dichromate. In the European market, the use of chromium compounds in electrical and electronic products on the market is generally prohibited (Non-Patent Document 4). In addition, since there is a possibility that the cyclic skeleton may be cleaved during the synthesis, it is possible to find a method for producing an epoxy resin having a dibenzoxanthene structure that is less likely to be produced, can be produced safely, and has a high yield and low production cost. It was requested.
  • the present invention relates to the following (1) to (10).
  • each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Indicates an integer of 4.
  • An epoxy resin composition comprising the epoxy resin according to (4) above and a curing agent and / or a curing accelerator.
  • each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Indicates an integer of 4.
  • each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and k represents an integer of 1 to 4.
  • each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Indicates an integer of 4.
  • a phenol resin or an epoxy resin having a benzoxanthene structure can be obtained by a safe and simple method by using an organic acid catalyst. Moreover, since there are few reaction steps at the time of synthesis
  • dihydroxynaphthalenes (a) and ketones (b) are reacted in an aprotic polar solvent under an organic acid catalyst.
  • dihydroxynaphthalene (a) is demonstrated.
  • Dihydroxynaphthalene (a) is a compound represented by the following formula (2).
  • each R 2 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and k represents an integer of 1 to 4.
  • alkyl group having 1 to 6 carbon atoms include butyl, pentyl, hexyl and the like in addition to the above.
  • Specific examples of the compound represented by the formula (2) include 1,4-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxy-5-alkyl-naphthalene, 1,4-dihydroxy-6, for example.
  • Ketones are compounds represented by the following formula (3).
  • each R 1 independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, propyl and the like.
  • examples of such ketone compounds include acetone, cyclohexanone, bicyclohexanone, acetophenone, hydroxyacetophenone, formaldehyde, hydroxybenzaldehyde, acetaldehyde, benzaldehyde, furfural, and formaldehyde is preferred.
  • Formaldehyde is a concept including synthetic equivalents of formaldehyde such as paraformaldehyde and formalin.
  • the method for producing a phenol resin of the present invention is a condensation reaction between one or more compounds represented by formula (2) and a compound represented by formula (3) under acidic conditions.
  • the compound represented by the formula (3) is usually used in an amount of 0.25 to 5.0 mol, preferably 0.3 to 2.5 mol based on 1 mol of the compound represented by the formula (2).
  • the acidic catalyst that can be used is an organic acid catalyst, and examples thereof include toluenesulfonic acid, xylenesulfonic acid, and oxalic acid. These may be used alone or in combination of a plurality of types.
  • the amount of the acidic catalyst to be used is generally 0.001 to 15 mol, preferably 0.002 to 10 mol, per 1 mol of the compound represented by the formula (3).
  • a solvent may be used as necessary.
  • the solvent that can be used is not particularly limited as long as it is not reactive with the compound represented by the formula (2) such as ketones, but the compound represented by the formula (2) as a raw material can be easily used. It is preferable to use alcohols as the solvent in terms of dissolution in the solvent.
  • solvents that can be used include alcohols such as methanol, ethanol, isopropyl alcohol, aprotic polar solvents such as methyl ethyl ketone, methyl isobutyl ketone, dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran, dioxane, methyl ethyl ketone, and methyl isobutyl ketone.
  • Etc The amount used in the case of using a solvent is not particularly limited. For example, it can be used in an amount of 100 to 500 parts by weight per 1 mol of the compound represented by the formula (2).
  • the reaction temperature is usually 10 to 150 ° C, preferably 50 to 140 ° C.
  • the reaction time is usually 0.5 to 20 hours, but is not limited to this because the reactivity varies depending on the type of raw material compound.
  • the phenol resin thus obtained is represented by the following formula (1).
  • R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • k represents 1 to 4
  • examples of the alkyl group having 1 to 3 carbon atoms include methyl, ethyl, propyl and the like, and examples of the alkyl group having 1 to 6 carbon atoms include butyl, pentyl, hexyl and the like.
  • the phenol compound represented by the above formula (2) may remain.
  • a mixture of the phenol compound of the above formula (1) and the phenol compound of the above formula (2) is obtained.
  • the phenol compound represented by the above formula (2) is calculated by measurement of gel permeation chromatography (GPC).
  • the content ratio is preferably 1 to 20 area%, more preferably 1 to 15 area%.
  • the phrase “substantially containing no heavy metal component” means that the heavy metal component is 500 ppm or less, and more preferably 100 ppm or less.
  • the hydroxyl equivalent is preferably 100 to 500 g / eq, and particularly preferably 120 to 450 g / eq.
  • the softening point is preferably 30 to 300 ° C, particularly preferably 70 to 250 ° C.
  • the phenol resin described in the above formula (1) can be obtained in one step. Therefore, the objective phenol resin can be obtained by a simple method with low production cost and high yield. it can. Moreover, since the obtained phenol resin does not contain heavy metal components such as chromium, it is environmentally friendly.
  • the epoxy resin of this invention is demonstrated.
  • the epoxy resin of the present invention is obtained by reacting a phenol resin obtained by the above production method (hereinafter, also simply referred to as “phenol resin (A)” or “phenol resin of the present invention”) with epihalohydrin in a solvent, and epoxidizing.
  • phenol resin (A) also simply referred to as “phenol resin (A)” or “phenol resin of the present invention”
  • a phenol compound other than the phenol resin (A) may be used in combination with the phenol resin (A).
  • a phenol compound other than the phenol resin (A) that can be used in combination any phenol compound that is usually used as a raw material for an epoxy resin can be used without particular limitation.
  • the epoxy resin of the present invention a cured product having an excellent melting point and high heat resistance can be obtained.
  • epichlorohydrin, ⁇ -methylepichlorohydrin, ⁇ -methylepichlorohydrin, epibromohydrin and the like can be used as the epihalohydrin, and epichlorohydrin which is easily available industrially is preferable.
  • the amount of epihalohydrin used is usually 2 to 20 mol, preferably 2 to 15 mol, particularly preferably 2 to 8 mol, per mol of the hydroxyl group of the phenol resin (A).
  • the epoxy resin is obtained by a reaction in which a phenol compound and an epihalohydrin are added in the presence of an alkali metal oxide, and then the resulting 1,2-halohydrin ether group is opened to epoxidize.
  • the molecular weight of the epoxy resin can be increased and the molecular weight distribution can be broadened.
  • the resulting epoxy resin can be removed from the system as a resinous material having a relatively low softening point, and exhibits excellent solvent solubility.
  • an alcohol such as methanol, ethanol or isopropyl alcohol, or an aprotic polar solvent such as dimethyl sulfone, dimethyl sulfoxide, tetrahydrofuran or dioxane.
  • alcohols are preferable, and the ionic reaction during epoxidation can be efficiently advanced depending on the polarity of the alcohol solvent, and an epoxy resin can be obtained with high purity.
  • the alcohol solvent that can be used methanol, ethanol, and isopropyl alcohol are preferable. Among these, it is particularly preferable to use methanol from the viewpoint of compatibility with the epoxy resin.
  • the amount used is usually 2 to 50% by mass, preferably 4 to 35% by mass, based on the amount of epihalohydrin used.
  • an aprotic polar solvent is used, it is usually 5 to 100% by mass, preferably 10 to 80% by mass, based on the amount of epihalohydrin used.
  • Alkali metal hydroxides can be used in the epoxidation reaction.
  • Examples of the alkali metal hydroxide that can be used for the epoxidation reaction include sodium hydroxide, potassium hydroxide, and the like, and these may be used as they are, or an aqueous solution thereof may be used.
  • an aqueous solution the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and separated from a mixture of water and epihalohydrin distilled continuously under reduced pressure or normal pressure. Alternatively, water may be removed and only the epihalohydrin is continuously returned to the reaction system.
  • the amount of the alkali metal hydroxide used is usually 0.9 to 3.0 mol, preferably 1.0 to 2.5 mol, more preferably 1.0 to 2.5 mol per mol of the hydroxyl group of the phenol resin of the present invention.
  • the amount is 2.0 mol, particularly preferably 1.0 to 1.3 mol.
  • the flaky sodium hydroxide is preferably added in portions in the reaction system. By performing divided addition, it is possible to prevent a rapid decrease in the reaction temperature, thereby preventing the formation of impurities such as 1,3-halohydrin and halomethylene.
  • a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst.
  • the amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol resin (A).
  • the reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C.
  • the reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.
  • an alcohol solvent it is preferably 50 ° C. to 90 ° C., more preferably 60 to 85 ° C., and particularly preferably 70 to 80 ° C.
  • the recovered epoxy resin of the present invention is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal such as sodium hydroxide or potassium hydroxide.
  • the reaction can be carried out by adding an aqueous solution of hydroxide to ensure ring closure.
  • the amount of alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, per mol of the hydroxyl group of the phenol resin (A).
  • the reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.
  • the produced salt is removed by filtration, washing with water, and the like, and the solvent is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.
  • the epoxy resin of this invention precipitates as a crystal
  • generated in a lot of water you may collect the crystal
  • a glycidylated product of the phenol compound represented by the above formula (1) is obtained.
  • the phenol compound represented by the above formula (2) is added to the phenol resin used as a raw material. When it is contained, a glycidylated product of the phenol compound represented by the above formula (2) is also obtained.
  • the content ratio of the glycidylated product of the phenol compound represented by the above formula (2) in the resin calculated by gel permeation chromatography (GPC) is 1 to 25. Area% is preferable, and 1 to 20 area% is more preferable.
  • the total halogen content of the epoxy resin of the present invention obtained by using flaky sodium hydroxide is usually 1800 ppm or less, preferably 1600 ppm or less, more preferably 1300 ppm or less. If the total halogen content is too large, the cured product properties of the cured product will be adversely affected, and it will remain as uncrosslinked terminals, so the orientation of molecules in the molten state during curing will not progress and the cured product properties will deteriorate. Leads to.
  • the epoxy resin composition of the present invention contains at least one of the epoxy resin of the present invention and the phenol resin of the present invention as an essential component.
  • the epoxy resin of the present invention when the epoxy resin of the present invention is contained as an essential component, the epoxy resin of the present invention can be used alone or in combination with other epoxy resins.
  • epoxy resins include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, bisphenol I, etc.) and phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted) Naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene and dihydroxynaphthalene) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Of polycondensates with benzene, aromatic compounds such as xylene and formaldehy
  • the proportion of the epoxy resin of the present invention in the total epoxy resin component in the epoxy resin composition of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, and 70% by mass. The above is more preferable, and 100% by mass (when no other epoxy resin is used in combination) is particularly preferable.
  • the epoxy resin of the present invention is used as a modifier for the epoxy resin composition, it is added in a proportion of 1 to 30% by mass in the total epoxy resin.
  • the epoxy resin composition of the present invention contains the epoxy resin of the present invention as an essential component, it is preferable to use a curing agent.
  • the curing agent that can be used may be the above-described phenolic resin of the present invention or other curing agent.
  • other curing agents include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples of these other curing agents are shown in the following (a) to (e).
  • Phenol compounds Polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,3 ', 5, 5′-tetramethyl- (1,1′-biphenyl) -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane and 1,1,2,2-tetrakis (4 -Hydroxyphenyl) ethane, etc .; phenols (eg, phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene and dihydroxynaphthalene) and aldehydes (formaldehyde, acetaldehyde, benzaldehyde, p
  • active hydrogen such as amine compounds such as diaminodiphenylmethane, diaminodiphenylsulfone and naphthalenediamine, and condensates of catechol with aldehydes, ketones, dienes, substituted biphenyls or substituted phenyls.
  • a curing agent having a structure in which groups are adjacent is preferable because it contributes to the arrangement of the epoxy resin.
  • Other curing agents may be used alone or in combination.
  • the phenol resin of the present invention when used as a curing agent, other curing agents may be used in combination with the phenol resin of the present invention.
  • the curing agent used in combination include the same amine compounds, acid anhydride compounds, amide compounds, and phenol compounds as described above.
  • the proportion of the phenolic resin of the present invention in the total curing agent component in the epoxy resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and 70% by mass. The above is more preferable, and 100% by mass (when no other curing agent is used in combination) is particularly preferable.
  • the use amount of the total curing agent containing the phenol resin of the present invention is preferably 0.5 to 2.0 equivalents relative to 1 equivalent of the epoxy groups of all epoxy resins, 0.6 to 1.5 equivalents are particularly preferred.
  • a curing accelerator may be added to the epoxy resin composition of the present invention.
  • the curing accelerator include phosphines such as triphenylphosphine and bis (methoxyphenyl) phenylphosphine, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethylimidazole and 4-methylimidazole, Tertiary amines such as 2- (dimethylaminomethyl) phenol, trisdimethylaminomethylphenol, diazabicycloundecene, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc.
  • Quaternary phosphonium salts such as quaternary ammonium salts, triphenylbenzyl phosphonium salts, triphenylethyl phosphonium salts, tetrabutyl phosphonium salts (the counter ions of quaternary salts are halogens)
  • Organic acid ions hydroxide ions, such as, but not particularly specified, in particular an organic acid ion, a hydroxide ion.), Metal compounds such as tin octylate and the like.
  • the amount of the curing accelerator used is usually 0.2 to 5.0 parts by weight, preferably 0.2 to 4.0 parts by weight per 100 parts by weight of the epoxy resin.
  • the epoxy resin composition of the present invention (hereinafter also referred to as a curable resin composition) can contain an inorganic filler as necessary. If the inorganic filler which the epoxy resin composition of this invention contains is a well-known thing, there will be no restriction
  • the shape of these inorganic fillers may be any of powder (lump shape, spherical shape), single fiber, long fiber and the like.
  • the amount of the inorganic filler used in the epoxy resin composition of the present invention is usually 2 to 1000 parts by mass with respect to 100 parts by mass of the resin component in the epoxy resin composition.
  • These inorganic fillers may be used alone or in combination of two or more.
  • thermosetting resins and thermoplastic resins include vinyl ester resins, unsaturated polyester resins, maleimide resins, cyanate resins, isocyanate compounds, benzoxazine compounds, vinyl benzyl ether compounds, polybutadiene and its modified products, and acrylonitrile.
  • thermosetting resin or thermoplastic resin is used in an amount occupying 60% by mass or less in the epoxy resin composition of the present invention.
  • the epoxy resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components, and preferred applications thereof include semiconductor encapsulants and printed wiring boards.
  • the epoxy resin composition of the present invention can be easily made into a cured product by the same method as conventionally known.
  • the epoxy resin composition of the present invention obtained by sufficiently mixing until uniform using a kneader or a roll is molded by a melt casting method, a transfer molding method, an injection molding method, a compression molding method, etc.
  • a cured product of the epoxy resin composition of the present invention can be obtained by heating at the melting point or higher for 2 to 10 hours.
  • the epoxy resin composition of the present invention can be used for semiconductor sealing applications.
  • the epoxy resin composition of this invention can also be made into the varnish containing a solvent.
  • the varnish includes, for example, an epoxy resin of the present invention or a phenol resin of the present invention in at least one of an epoxy resin and a curing agent, and if necessary, an inorganic filler having a thermal conductivity of 20 W / m ⁇ K or more.
  • the prepreg of the present invention can be obtained by mixing with organic solvents such as petroleum solvents such as cyclic esters, petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha.
  • the amount of the solvent is usually 10 to 95% by mass, preferably 15 to 85% by mass, based on the entire varnish.
  • the varnish obtained as described above is impregnated into a fiber substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber and paper, and then the solvent is removed by heating, and the epoxy resin composition of the present invention By making a semi-cured state, the prepreg of the present invention can be obtained.
  • the “semi-cured state” means a state in which an epoxy group which is a reactive functional group partially remains unreacted.
  • the prepreg can be hot press molded to obtain a cured product.
  • the epoxy resin (EP1) or the comparative epoxy resin (EP2) obtained above was used as the curing agent (P1), filler (inorganic filler), wax, coupling agent, and curing accelerator (C1) as shown in Table 1. It mix
  • the curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation. Using this test specimen for evaluation, heat resistance and flame retardancy were measured and evaluated in the following manner. The test results are shown in Table 1.
  • EP2 Nippon Kayaku NC3000 P1: Millex XLC-3L manufactured by Mitsui Chemicals Fused silica: MSR-2212 manufactured by Kashimori Kogyo Co.
  • Wax Carnauba No. 1 C1: Triphenylphosphine (TPP manufactured by Hokuko Chemical) Coupling agent: KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.
  • Inorganic filler fused silica MSR-2122 made by Ashimori 83 wt% resin
  • Curing accelerator usage The sample used for evaluation of heat resistance was 1% based on the weight of the epoxy resin, and the sample used for evaluation of flame retardancy was 2% based on the weight of the epoxy resin.
  • Wax amount used 0.3% by weight
  • Composition coupling agent amount used 0.4% by weight
  • Filler epoxy resin / curing agent ratio 1.0 equivalent
  • the comparative example 1 had the same flame retardancy as compared with the epoxy resin excellent in flame retardancy. Furthermore, since the high heat resistance is hold
  • Example 2 and Comparative Example 2 Using the phenol resin (PH1) obtained above or the phenol resin for comparison (PH7) as a curing agent, the epoxy resin (EP2), filler, wax, coupling agent, and curing accelerator (C1) in the proportions shown in Table 2 ( Equivalent) and uniformly mixed and kneaded using a mixing roll to obtain a curable resin composition.
  • the curable resin composition was pulverized with a mixer and further tableted with a tablet machine. This tableted curable resin composition was transfer molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation. Using this test specimen for evaluation, heat resistance, fracture toughness, water absorption, and dielectric loss tangent were measured and evaluated. The test results are also shown in Table 2. The physical property values were measured by the following methods.
  • EP2 Nippon Kayaku Co., Ltd. NC3000 PH7: Phenol novolak wax manufactured by Meiwa Kasei Kogyo Co., Ltd .: Carnauba No. 1 C1: Triphenylphosphine (TPP manufactured by Hokuko Chemical Co., Ltd.) Coupling agent: KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd. Inorganic filler: fused silica MSR-2122 made by Ashimori 83 wt% resin Curing accelerator usage: It was 1% with respect to the weight of the epoxy resin. Wax amount used: 0.3% by weight Composition coupling agent amount used: 0.4% by weight Filler epoxy resin / curing agent ratio: 1.0 equivalent
  • the cured epoxy resin of the present invention has excellent heat resistance as compared with a cured cured epoxy resin. Further, it is clear that the comparative example 2 is excellent in toughness, hygroscopicity and dielectric properties while having high heat resistance.
  • the phenol resin produced by the method of the present invention can be used for an epoxy resin composition, and the cured product of the epoxy resin composition exhibits excellent heat resistance and flame retardancy. It is useful when used for various composite materials including adhesives, adhesives, paints and the like.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Epoxy Resins (AREA)
  • Phenolic Resins Or Amino Resins (AREA)

Abstract

　L'invention concerne un procédé pour produire une résine phénolique qui permet de produire, facilement et à un bon rendement, une résine époxy présentant une structure benzoxanthène par un procédé sûr, une résine phénolique, une résine époxy et une composition de résine époxy les contenant. On fait réagir des dihydroxynaphtalènes et des cétones en présence d'un catalyseur acide organique et une résine phénolique représentée par la formule (1) est produite. (Dans la formule, R1 et R2 représentent des atomes d'hydrogène ou analogues et k représente un entier de 1-4.)
PCT/JP2014/076880 2013-10-11 2014-10-08 Procédé pour produire une résine phénolique, résine phénolique, résine époxy et composition de résine époxy Ceased WO2015053299A1 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107699581A (zh) * 2017-08-21 2018-02-16 上海交通大学 3，7‑二羟基卓酚酮生物合成基因簇及其应用
WO2018101463A1 (fr) * 2016-12-02 2018-06-07 三菱瓦斯化学株式会社 Composé, résine, compositions, procédé de formation de motif, et procédé de purification
JP2018154600A (ja) * 2017-03-21 2018-10-04 三菱瓦斯化学株式会社 化合物、樹脂、組成物、パターン形成方法及び精製方法
CN116478177A (zh) * 2023-03-30 2023-07-25 陕西泰合利华工业有限公司 一种制备9,9-双(三氟甲基)氧杂蒽四甲酸二酐的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3137835B2 (ja) 1994-06-15 2001-02-26 ダイハツ工業株式会社 ピストン突出し量測定装置

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0586171A (ja) * 1991-09-27 1993-04-06 Yuka Shell Epoxy Kk 半導体封止用のエポキシ樹脂組成物
JPH06107772A (ja) * 1992-09-28 1994-04-19 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物
WO1998055523A1 (fr) * 1997-06-03 1998-12-10 Hitachi Chemical Company, Ltd. Resine phenolique, composition a base de cette resine, materiau de moulage pour encapsulation et dispositif a composants electroniques
JPH11166036A (ja) * 1997-10-03 1999-06-22 Hitachi Chem Co Ltd 半導体封止用エポキシ樹脂組成物及びそれを用いた半導体装置
JP2001506769A (ja) * 1996-12-18 2001-05-22 クラリアント インターナショナル リミテッド 重合体添加剤を含有するフォトレジスト組成物
JP2013151605A (ja) * 2012-01-25 2013-08-08 Sumitomo Chemical Co Ltd レゾルシンとアセトンとの縮合物の製造方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01283280A (ja) * 1988-05-06 1989-11-14 Asahi Denka Kogyo Kk 新規エポキシ化合物及びその製造方法
JP3095317B2 (ja) * 1992-11-10 2000-10-03 信越化学工業株式会社 重合体スケール付着防止剤及びそれを使用する重合体製造方法
JP5776580B2 (ja) * 2011-02-25 2015-09-09 信越化学工業株式会社 ポジ型レジスト材料及びこれを用いたパターン形成方法
EP2743769B1 (fr) * 2011-08-12 2017-03-22 Mitsubishi Gas Chemical Company, Inc. Composition de réserve, procédé de formation de motif de réserve, composé polyphénol mis en uvre dans ce procédé, et composé alcool obtenu par dérivation de ce composé polyphénol
US10377734B2 (en) * 2013-02-08 2019-08-13 Mitsubishi Gas Chemical Company, Inc. Resist composition, method for forming resist pattern, polyphenol derivative for use in the composition

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0586171A (ja) * 1991-09-27 1993-04-06 Yuka Shell Epoxy Kk 半導体封止用のエポキシ樹脂組成物
JPH06107772A (ja) * 1992-09-28 1994-04-19 Sumitomo Bakelite Co Ltd エポキシ樹脂組成物
JP2001506769A (ja) * 1996-12-18 2001-05-22 クラリアント インターナショナル リミテッド 重合体添加剤を含有するフォトレジスト組成物
WO1998055523A1 (fr) * 1997-06-03 1998-12-10 Hitachi Chemical Company, Ltd. Resine phenolique, composition a base de cette resine, materiau de moulage pour encapsulation et dispositif a composants electroniques
JPH11166036A (ja) * 1997-10-03 1999-06-22 Hitachi Chem Co Ltd 半導体封止用エポキシ樹脂組成物及びそれを用いた半導体装置
JP2013151605A (ja) * 2012-01-25 2013-08-08 Sumitomo Chemical Co Ltd レゾルシンとアセトンとの縮合物の製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018101463A1 (fr) * 2016-12-02 2018-06-07 三菱瓦斯化学株式会社 Composé, résine, compositions, procédé de formation de motif, et procédé de purification
JPWO2018101463A1 (ja) * 2016-12-02 2019-10-24 三菱瓦斯化学株式会社 化合物、樹脂、組成物、パターン形成方法及び精製方法
JP7090843B2 (ja) 2016-12-02 2022-06-27 三菱瓦斯化学株式会社 化合物、樹脂、組成物、パターン形成方法及び精製方法
JP2018154600A (ja) * 2017-03-21 2018-10-04 三菱瓦斯化学株式会社 化合物、樹脂、組成物、パターン形成方法及び精製方法
CN107699581A (zh) * 2017-08-21 2018-02-16 上海交通大学 3，7‑二羟基卓酚酮生物合成基因簇及其应用
CN107699581B (zh) * 2017-08-21 2020-12-29 上海交通大学 3，7-二羟基卓酚酮生物合成基因簇及其应用
CN116478177A (zh) * 2023-03-30 2023-07-25 陕西泰合利华工业有限公司 一种制备9,9-双(三氟甲基)氧杂蒽四甲酸二酐的方法

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