WO2020003824A1 - Composition de résine époxy et produit durci associé - Google Patents

Composition de résine époxy et produit durci associé Download PDF

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Publication number
WO2020003824A1
WO2020003824A1 PCT/JP2019/020415 JP2019020415W WO2020003824A1 WO 2020003824 A1 WO2020003824 A1 WO 2020003824A1 JP 2019020415 W JP2019020415 W JP 2019020415W WO 2020003824 A1 WO2020003824 A1 WO 2020003824A1
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Prior art keywords
epoxy resin
resin composition
group
naphthol
curing agent
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PCT/JP2019/020415
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English (en)
Japanese (ja)
Inventor
雅樹 迫
泰 佐藤
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Dic株式会社
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Priority to JP2020527287A priority Critical patent/JP7049605B2/ja
Priority to CN201980042792.XA priority patent/CN112313260A/zh
Publication of WO2020003824A1 publication Critical patent/WO2020003824A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present invention relates to an epoxy resin composition and a cured product thereof.
  • Patent Document 1 discloses an epoxy resin composition having a predetermined structure as a resin composition having high heat resistance, low water absorption, and high adhesiveness.
  • Patent Document 2 discloses an epoxy resin having a predetermined structure as a resin having excellent flame retardancy, moisture resistance, heat resistance, low thermal expansion, and excellent adhesion to a metal substrate. ing.
  • Patent Document 3 discloses an epoxy resin composition using a polycondensate of an aromatic polycarboxylic acid and an aromatic polyhydroxy compound having an aryloxycarbonyl group at a chain end as a curing agent for an epoxy resin. Proposed. This epoxy resin composition is excellent in heat resistance and can give a cured epoxy resin having a low dielectric loss tangent.
  • the present invention is a further development of the above-described technology, and provides an epoxy resin composition having excellent heat resistance and adhesion, capable of obtaining a cured product having a lower dielectric loss tangent, and a cured product thereof. Make it an issue.
  • the present invention relates to the following [1] to [8].
  • [1] An epoxy resin composition comprising an ⁇ -naphthol biphenylaralkyl type epoxy resin and a curing agent, wherein the curing agent has an active ester structure.
  • R 1 represents a hydrogen atom, a halogen atom, a glycidyloxy group, an allyl group, an alkyl group, an alkoxy group, or an aryl group.
  • N is an integer of 1 to 20.
  • the curing agent is an active ester compound or resin using a compound having two or more phenolic hydroxyl groups and an aromatic monocarboxylic acid or an acid halide thereof as an essential reaction raw material [1] or [2].
  • the epoxy resin composition according to the above. [5] The epoxy resin composition according to any one of [1] to [4], further comprising a curing accelerator.
  • [7] A printed wiring board using the epoxy resin composition according to any one of [1] to [5].
  • [8] A semiconductor sealing material using the epoxy resin composition according to any one of [1] to [5].
  • an epoxy resin composition having excellent heat resistance and adhesion and capable of obtaining a cured product having a lower dielectric loss tangent, and a cured product thereof.
  • 5 is a GPC chart of the ⁇ -naphthol biphenylaralkyl type epoxy resin (A-2) obtained in Synthesis Example 2.
  • 6 is a GPC chart of the ⁇ -naphthol aralkyl type epoxy resin (B-2) obtained in Comparative Synthesis Example 2.
  • 9 is a GPC chart of ⁇ -naphthol aralkyl epoxy resin (B-4) obtained in Comparative Synthesis Example 4.
  • 9 is a GPC chart of the methoxy-modified ⁇ -naphthol biphenylaralkyl type epoxy resin (B-6) obtained in Comparative Synthesis Example 6.
  • epoxy resin composition contains an ⁇ -naphthol biphenylaralkyl type epoxy resin and a curing agent.
  • the ⁇ -naphthol biphenyl aralkyl type epoxy resin is an epoxy resin having a functional group derived from ⁇ -naphthol and a biphenyl group in a molecular main skeleton.
  • an epoxy resin having such a molecular main skeleton and a curing agent having an active ester structure described later an epoxy that has excellent heat resistance and adhesion and provides a cured product having superior dielectric properties than conventional ones.
  • a resin composition can be obtained.
  • an epoxy resin having a structure represented by the following formula (1) can be used as the ⁇ -naphthol biphenyl aralkyl type epoxy resin.
  • R 1 represents a hydrogen atom, a halogen atom, a glycidyloxy group, an allyl group, an alkyl group, an alkoxy group, or an aryl group.
  • n is an integer of 1 to 20, preferably 1 to 15, and more preferably 1 to 12.
  • the halogen atom include a chlorine atom, a bromo atom, and an iodine atom.
  • the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms examples include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, and a cyclohexyl group.
  • alkoxy group examples include an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms.
  • alkoxy group having 1 to 6 carbon atoms examples include a methoxy group, an ethoxy group, a normal propyloxy group, an isopropyloxy group, a normal butyloxy group, a tertiary butyloxy group, a pentyloxy group, a normal hexyloxy group, and a cyclohexyl. Oxy groups and the like can be mentioned.
  • the aryl group include a phenyl group, a benzyl group, a naphthyl group, and a methoxynaphthyl group.
  • R 1 is preferably a hydrogen atom, because it has excellent balance between impregnation into a substrate such as a reinforcing fiber and heat resistance and toughness in a cured product.
  • the softening point of the ⁇ -naphthol biphenylaralkyl type epoxy resin is not particularly limited, but is preferably from 70 ° C. to 140 ° C., and preferably from 75 ° C. to 130 ° C., since the solvent solubility and the heat resistance of the cured product are improved. Is more preferable, and the temperature is more preferably from 80 ° C to 120 ° C.
  • the softening point is measured according to JIS K7234.
  • the epoxy equivalent of the ⁇ -naphthol biphenyl aralkyl type epoxy resin is preferably in the range of 280 to 450 g / equivalent, because both the heat resistance of the cured product and the impregnation property of the base material such as reinforcing fibers are excellent.
  • the method for producing the ⁇ -naphthol biphenylaralkyl-type epoxy resin is not particularly limited, and it can be obtained by subjecting a polycondensate of ⁇ -naphthol to a biphenyl compound such as bischloromethylbiphenyl to polyglycidyl ether using epichlorohydrin or the like. .
  • the curing agent has an active ester structure.
  • Active ester structure means an ester structure derived from a phenol group and an aromatic carboxylic acid group.
  • the curing agent can be composed of a compound or a resin having an active ester structure (hereinafter, also simply referred to as “active ester resin”). Specific examples of the active ester resin include compounds (a1) having one phenolic hydroxyl group, compounds (a2) having two or more phenolic hydroxyl groups, and aromatic polycarboxylic acids or their acid halides (a3).
  • An active ester resin (II) using a compound selected from an acid halide (b3) as a reaction raw material is exemplified. These may be used alone or in combination.
  • Examples of the compound (a1) having one phenolic hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenyl
  • Examples thereof include aromatic monohydroxy compounds such as phenol, 2-benzylphenol, 4-benzylphenol, 4- ( ⁇ -cumyl) phenol, ⁇ -naphthol, and ⁇ -naphthol.
  • a cured product having a lower dielectric loss tangent when the curing agent has a residue of ⁇ -naphthol, ⁇ -naphthol o-phenylphenol, and / or p-phenylphenol, a cured product having a lower dielectric loss tangent can be obtained.
  • aromatic polyhydric hydroxy compounds examples include resorcinol, hydroquinone, trimethylhydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,3-naphthalenediol, Aromatic dihydroxy compounds such as 7-naphthalenediol, 1,4-naphthalenediol, 3,3 ′, 5,5′-tetramethylbisphenol F, 3,3 ′, 5,5′-tetramethylbiphenol; 1,3 Aromatic trihydroxy compounds such as 2,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 2,4,4'-trihydroxybenzophenone and triphenolmethane; 2,2 ', 4,4'-tetra Hydroxybenzophenone, 1,1,2,2-tetraphenolethane It can be mentioned.
  • the compounds (a2) and (b1) may be compounds represented by the following formula (4).
  • n is an integer of 0 to 20
  • Ar 1 each independently represents a substituent having a phenolic hydroxyl group
  • Z is each independently an oxygen atom, a sulfur atom, a sulfonyl group, a substituted or unsubstituted carbon atom.
  • the Ar 1 is not particularly restricted but includes, for example, phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenylphenol, 2- Examples thereof include residues of aromatic monohydroxy compounds such as benzylphenol, 4-benzylphenol, 4- ( ⁇ -cumyl) phenol, ⁇ -naphthol, and ⁇ -naphthol.
  • the alkylene having 1 to 20 carbon atoms is not particularly limited, but includes methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2 -Dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, hexylene and the like.
  • the cycloalkylene having 3 to 20 carbon atoms is not particularly limited, but includes cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the following formulas (5-1) to (5) And cycloalkylene represented by -4).
  • the arylene having 6 to 20 carbon atoms is not particularly limited, and examples thereof include an arylene represented by the following formula (6-1).
  • the aralkylene having 8 to 20 carbon atoms is not particularly limited, and examples thereof include aralkylenes represented by the following formulas (7-1) to (7-5).
  • Z in the formula (4) is preferably a cycloalkylene having 3 to 20 carbon atoms, an arylene having 6 to 20 carbon atoms, or an aralkylene having 8 to 20 carbon atoms, and the formula (5- Those represented by 3), (5-4), (6-1), and (7-1) to (7-5) are more preferable from the viewpoint of adhesion and dielectric properties.
  • M in the formula (4) is 0 or an integer of 1 to 10, preferably 0 to 8, and preferably 0 to 5 from the viewpoint of solvent solubility.
  • the compounds (a2) and (b1) may have a structure represented by the following formula (8).
  • 1 is an integer of 1 or more, and R 3 represents a hydrogen atom, an alkyl group, or an aryl group.
  • l is preferably an integer of 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12.
  • the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms examples include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, and a cyclohexyl group.
  • aryl group examples include a benzyl group, a naphthyl group, and a methoxynaphthyl group.
  • the compounds represented by the formulas (4) and (8) are preferable from the viewpoint of solvent solubility and dielectric properties of the reaction product, and the compounds represented by the formula (4) Wherein Ar 1 is a residue of phenol, orthocresol, or ⁇ -naphthol or ⁇ -naphthol, and Z is a group represented by the formulas (5-3), (6-1), (7-1) to (7-1) 5) and those represented by the formula (8) are more preferable.
  • aromatic monocarboxylic acid or its acid halide (b2) examples include benzoic acid and benzoic acid chloride.
  • aromatic polycarboxylic acids or their acid halides (a3) and (b3) include, for example, aromatics such as isophthalic acid, terephthalic acid, 1,4-, 2,3- or 2,6-naphthalenedicarboxylic acid Dicarboxylic acids; aromatic tricarboxylic acids such as trimesic acid and trimellitic acid; pyromellitic acid; and acid chlorides thereof.
  • aromatics such as isophthalic acid, terephthalic acid, 1,4-, 2,3- or 2,6-naphthalenedicarboxylic acid Dicarboxylic acids
  • aromatic tricarboxylic acids such as trimesic acid and trimellitic acid
  • pyromellitic acid and acid chlorides thereof.
  • isophthalic acid or a mixture of isophthalic acid and terephthalic acid is preferred from the viewpoint that the melting point of the reactant and the solvent solubility are excellent.
  • Examples of the active ester resin having the above structure include the following active ester resins (I) and (II).
  • Examples of the active ester resin (I) include an active ester resin having a structure represented by the following formula (2).
  • X represents a compound residue containing a monovalent phenolic hydroxyl group
  • Y represents a compound residue containing a divalent phenolic hydroxyl group.
  • n is an integer of 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
  • Examples of the active ester resin (II) include an active ester resin having a structure represented by the following formula (3).
  • Y represents a compound residue having a divalent phenolic hydroxyl group
  • R 2 represents a hydrogen atom or an alkyl group.
  • n is an integer of 0 to 20, preferably 0 to 15, and more preferably 0 to 10.
  • the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms.
  • alkyl group having 1 to 6 carbon atoms examples include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a normal butyl group, a tertiary butyl group, a pentyl group, a normal hexyl group, and a cyclohexyl group.
  • the active ester resin (I) represented by the formula (2) is preferable in terms of excellent wet heat resistance.
  • the esterification equivalent of the active ester resin is preferably from 150 to 400 g / eq, more preferably from 160 to 350 g / eq, even more preferably from 170 to 300 g / eq.
  • the melt viscosity of the active ester resin is preferably from 0.01 to 500 dPa ⁇ s, more preferably from 0.01 to 400 dPa ⁇ s, as measured by an ICI viscometer at 200 ° C. More preferably, it is 300 dPa ⁇ s.
  • the softening point of the active ester resin is not particularly limited, but is preferably 200 ° C or lower, more preferably 190 ° C or lower, further preferably 170 ° C or lower from the viewpoint of solvent solubility.
  • the softening points are as described above.
  • the method for producing the active ester resin is not particularly limited, and the active ester resin can be produced by a known and commonly used synthesis method such as an acetic anhydride method, an interfacial polymerization method, and a solution method.
  • the curing agent may further contain another curing agent for epoxy resin in addition to the active ester resin.
  • the epoxy resin curing agent that can be used here include amine compounds, amide compounds, acid anhydride compounds, and phenol compounds.
  • the amount used is preferably in the range of 1% by mass to 30% by mass in the whole resin composition.
  • the amount of the ⁇ -naphthol biphenyl aralkyl type epoxy resin and the active ester resin in the resin composition is such that the aryloxycarbonyl group in the active ester resin is based on 1 mol of the epoxy group in the ⁇ -naphthol biphenyl aralkyl type epoxy resin.
  • the amount is preferably 0.15 to 5 mol, more preferably 0.9 to 2.0 mol.
  • the resin composition can contain a curing accelerator as needed.
  • the curing accelerator include a phosphorus compound, a tertiary amine, imidazole, a metal salt of an organic acid, a Lewis acid, and an amine complex.
  • dimethylaminopyridine or imidazole is preferred from the viewpoint of excellent heat resistance, dielectric properties, solder resistance, and the like.
  • triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines because of its excellent curability, heat resistance, electrical properties, and moisture resistance reliability.
  • the amount of the curing accelerator used is preferably in the range of 0.01 to 5.0 parts by mass, and more preferably 0.01 to 2.0 parts by mass, based on 100 parts by mass of the ⁇ -naphthol biphenylaralkyl type epoxy resin. More preferably, it is within the range. When the content is in the above range, a sufficient curing reaction rate can be obtained, and a resin composition that gives a cured product having more excellent heat resistance can be obtained.
  • the resin composition may further contain other resin components.
  • Other resin components include, for example, cyanate ester resin; bismaleimide resin; benzoxazine resin; allyl group-containing resin represented by diallyl bisphenol and triallyl isocyanurate; polyphosphate and phosphate-carbonate copolymer And the like. These may be used alone or in combination of two or more.
  • the mixing ratio of these other resin components is not particularly limited, and can be appropriately adjusted according to the desired cured product performance and the like. As an example of the mixing ratio, it can be in the range of 1 to 50% by mass in the whole resin composition.
  • the resin composition may contain various additives such as a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, and an emulsifier, if necessary.
  • the flame retardant include inorganic phosphorus compounds such as ammonium phosphate such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphate amides; phosphate ester compounds, phosphonic acid Compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) Cyclic organic phosphorus such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphth
  • the inorganic filler is mixed, for example, when the resin composition is used for a semiconductor sealing material.
  • the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide.
  • fused silica is preferred because it allows more inorganic filler to be blended.
  • Fused silica can be used in either crushed or spherical form.However, in order to increase the blending amount of the fused silica, and to suppress an increase in the melt viscosity of the resin composition, a spherical form is mainly used. preferable.
  • the filling rate is preferably in the range of 0.5 to 95 parts by mass with respect to 100 parts by mass of the resin component.
  • the method for producing the resin composition is not particularly limited.
  • the resin composition can be obtained by uniformly mixing the above-mentioned components at, for example, 0 ° C. to 200 ° C. using a stirrer or a three-roll mill.
  • the resin composition can be molded by heating and curing, for example, in a temperature range of about 20 to 250 ° C. by a known and commonly used thermosetting method.
  • the cured product of the resin composition according to the present embodiment has a glass transition temperature of 140 ° C. or higher, is excellent in heat resistance, and has a low dielectric loss tangent at 1 GHz of less than 2.0 ⁇ 10 ⁇ 3.
  • the adhesion is equal to or higher than that of the conventional material. From the above, it can be preferably used for electronic materials such as printed wiring boards, semiconductor encapsulation materials, and resist materials.
  • the resin composition When the resin composition is used for a printed wiring board application or a build-up adhesive film application, it is generally preferable to mix and dilute an organic solvent before use.
  • the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like.
  • the type and amount of the organic solvent can be appropriately adjusted according to the use environment of the resin composition.For example, in the case of a printed wiring board, a polar solvent having a boiling point of 160 ° C.
  • methyl ethyl ketone, acetone, and dimethylformamide may be used.
  • it is used in such a proportion that the non-volatile content is 40 to 80% by mass.
  • ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc.
  • acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc .
  • the method of manufacturing a printed wiring board using a resin composition includes, for example, a method in which a prepreg is obtained by impregnating a resin composition into a reinforcing base material and curing the resin composition, and then laminating the prepreg with a copper foil and heat-pressing. it can.
  • the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth.
  • the impregnation amount of the resin composition is not particularly limited, but usually, it is preferably prepared so that the resin content in the prepreg is 20 to 80% by mass.
  • the semiconductor encapsulating material can be prepared by mixing the compound using an extruder, a kneader, a roll, or the like, for example.
  • a method for molding a semiconductor package using the obtained semiconductor encapsulation material is, for example, casting the semiconductor encapsulation material using a transfer molding machine, an injection molding machine, or the like, and further molding the semiconductor package at a temperature of 50 to 200 ° C.
  • a method of heating under the conditions for 2 to 10 hours can be mentioned, and a semiconductor device as a molded product can be obtained by such a method.
  • the mixture was neutralized with 85% phosphoric acid until the pH became neutral, the stirring was stopped, and the lower layer was extracted. After adding 15 parts of p-toluenesulfonic acid and heating to 180 ° C. over 2 hours while distilling off volatile components, the mixture was neutralized with a 49% aqueous sodium hydroxide solution until the pH became neutral. After reducing the pressure while maintaining the temperature and distilling off the volatile components, the resulting resin was taken out to obtain ⁇ -naphthol biphenylaralkyl resin (A-1). The hydroxyl equivalent was 272 g / eq.
  • FIG. 1 shows a GPC chart of the obtained epoxy resin (A-2).
  • the active ester resin C-1 corresponds to an active ester resin having a structure in which X is an ⁇ -naphthol residue and n is 0 in the above formula (2).
  • the esterification equivalent of this active ester resin (C-2) was 223 g / eq, and the softening point was 150 ° C.
  • the melt viscosity was 100 dPa ⁇ s (200 ° C.).
  • X is an ⁇ -naphthol residue
  • n is 2 on average
  • Y is represented by the chemical formula (4)
  • Z is (5-3) It corresponds to an active ester resin having a structure in which Ar 1 is a phenol residue.
  • Example 1 ⁇ -naphthol biphenyl aralkyl type epoxy resin (A-2), active ester (C-1), and curing accelerator (N, N-dimethyl-4-aminopyridine, special grade, manufactured by Wako Pure Chemical Industries, Ltd.)
  • A-2 ⁇ -naphthol biphenyl aralkyl type epoxy resin
  • C-1 active ester
  • curing accelerator N, N-dimethyl-4-aminopyridine, special grade, manufactured by Wako Pure Chemical Industries, Ltd.
  • Example 2 The epoxy resin (A-2) and the active ester resin (C-2) were weighed according to the formulations shown in Table 2, adjusted to a nonvolatile content of 60% with methyl ethyl ketone (MEK), and dissolved using a rotation revolution mixer. . After N, N-dimethyl-4-aminopyridine as a catalyst was adjusted and blended so that the gel time was within 5 to 7 minutes, a glass cloth laminate was prepared under the following conditions. (Conditions for creating a laminate) Base material: Nitto Boseki Co., Ltd.

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Abstract

L'invention concerne une composition de résine époxy permettant d'obtenir un produit durci ayant une excellente résistance à la chaleur et une excellente adhérence, ainsi qu'une tangente de perte diélectrique inférieure, et un produit durci de la composition de résine époxy. Spécifiquement, la présente invention concerne une composition de résine époxy contenant une résine époxy de type α-naphtol-biphényl-aralkyle et un agent de durcissement, l'agent de durcissement contenant une structure ester active. La résine époxy de type α-naphtol-biphényl-aralkyle a de préférence la structure représentée par la formule (1). L'agent de durcissement a de préférence la structure représentée par la formule (2). L'agent de durcissement est de préférence une résine ou un composé ester actif ayant comme matières premières essentielles pour la réaction un composé ayant deux groupes hydroxyle phénoliques ou plus, et un acide monocarboxylique aromatique ou un halogénure d'acide de celui-ci.
PCT/JP2019/020415 2018-06-27 2019-05-23 Composition de résine époxy et produit durci associé WO2020003824A1 (fr)

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JP2020527287A JP7049605B2 (ja) 2018-06-27 2019-05-23 エポキシ樹脂組成物及びその硬化物
CN201980042792.XA CN112313260A (zh) 2018-06-27 2019-05-23 环氧树脂组合物及其固化物

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CN115466373B (zh) * 2022-10-20 2024-01-30 湖南嘉盛德材料科技股份有限公司 一种萘酚联苯芳烷基型环氧树脂的制备方法
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