WO2023100572A1 - 多価ヒドロキシ樹脂、エポキシ樹脂、それらの製造方法、エポキシ樹脂組成物及びその硬化物 - Google Patents

多価ヒドロキシ樹脂、エポキシ樹脂、それらの製造方法、エポキシ樹脂組成物及びその硬化物 Download PDF

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WO2023100572A1
WO2023100572A1 PCT/JP2022/040682 JP2022040682W WO2023100572A1 WO 2023100572 A1 WO2023100572 A1 WO 2023100572A1 JP 2022040682 W JP2022040682 W JP 2022040682W WO 2023100572 A1 WO2023100572 A1 WO 2023100572A1
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formula
group
epoxy resin
resin
represented
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PCT/JP2022/040682
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English (en)
French (fr)
Japanese (ja)
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伸悟 金光
正浩 宗
起煥 柳
▲清▼來 林
海璃 尹
仲輝 池
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日鉄ケミカル＆マテリアル株式会社
株式会社国都化▲学▼
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Publication of WO2023100572A1 publication Critical patent/WO2023100572A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G59/18—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
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs

Definitions

  • the present invention relates to a polyhydric hydroxy resin or epoxy resin with excellent low viscosity and low dielectric properties, and a method for producing the same.
  • Epoxy resins are excellent in adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity, so they are used in a wide variety of applications such as paints, civil engineering adhesives, cast molding, electrical and electronic materials, and film materials. In particular, it is widely used for printed wiring boards, which is one of electrical and electronic materials, by imparting flame retardancy to epoxy resins.
  • epoxy resin compositions which are used as materials for electrical and electronic parts, are required to have low dielectric properties as substrates become thinner and more functional.
  • dicyclopentadiene phenolic resins with an aliphatic skeleton have been used to lower the dielectric constant of laminates, but they are not very effective in improving the dielectric loss tangent.
  • the low viscosity was also unsatisfactory (Patent Documents 1 and 2).
  • Dicyclopentadiene phenolic resin modified with an aromatic group has been used to improve dielectric properties, but it has not been possible to achieve both low dielectric properties and low viscosity (Patent Document 3).
  • the problem to be solved by the present invention is a polyhydric hydroxy resin that exhibits an excellent dielectric loss tangent and provides a cured product with a good low viscosity, an epoxy resin thereof, an epoxy resin composition using them, and It is to provide those manufacturing methods.
  • a dicyclopentadiene-type phenol resin is reacted with a specific ratio of dicyclopentadiene and further reacted with an aromatic vinyl compound to obtain a dicyclopentadiene-type
  • a dicyclopentadiene skeleton derived from dicyclopentadiene and an aromatic skeleton derived from an aromatic vinyl compound can be added to the phenol ring of the phenol resin, and the epoxy resin obtained by epoxidizing this phenol resin has excellent low viscosity, When cured with a curing agent, the resulting cured product has excellent low dielectric properties, and has completed the present invention.
  • the dicyclopentadiene-type phenol resin may be reacted with the aromatic vinyl compound first, and then with the dicyclopentadiene.
  • the present invention is a polyhydric hydroxy resin (A) characterized by being represented by the following general formula (1).
  • R1 independently represents a hydrocarbon group having 1 to 8 carbon atoms
  • R21 is independently a hydrogen atom, a dicyclopentenyl group represented by formula (2a) or formula (2b), a group represented by formula (3a), or a group represented by formula (3b); Of these, one is a dicyclopentenyl group represented by formula (2a) or (2b), and the other is a group represented by formula (3a) or (3b).
  • R3 independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms
  • R4 independently represents a hydrogen atom or a group represented by formula (3a).
  • A1 is a residue obtained by removing two R21 from formula (1), wherein R21 in the residue is a hydrogen atom, a dicyclopentenyl group represented by formula (2a) or formula (2b), or formula (3a ) is a group represented by Me represents a methyl group.
  • i is an integer from 0 to 2;
  • n1 indicates the number of repetitions, and its average value is a number from 0 to 5.
  • p1 indicates the number of repetitions, and its average value is a number from 0.01 to 3.
  • R1 is preferably a methyl group or a phenyl group, and the above i is preferably 1 or 2.
  • the present invention also provides a polyhydric hydroxy resin (a) represented by the following general formula (4), an aromatic vinyl compound (b) represented by the following general formula (5a) and/or general formula (5b), and a di
  • a polyhydric hydroxy resin characterized by reacting cyclopentadiene.
  • R1 independently represents a hydrocarbon group having 1 to 8 carbon atoms.
  • i is an integer from 0 to 2;
  • m indicates the number of repetitions, and its average value is a number from 0 to 5.
  • R3 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
  • the above production method is preferably carried out in the presence of an acid catalyst, and 0.05 to 2.0 mol of the aromatic vinyl compound (b ) and 0.05 to 2.0 mol of dicyclopentadiene at a reaction temperature of 50 to 200°C.
  • the present invention also provides an epoxy resin characterized by being represented by the following general formula (6).
  • R1 independently represents a hydrocarbon group having 1 to 8 carbon atoms
  • R2 is independently a hydrogen atom, a dicyclopentenyl group represented by formula (2a) or formula (2b), a group represented by formula (3a), or a group represented by formula (3c); Of these, one is a dicyclopentenyl group represented by formula (2a) or (2b), and the other is a group represented by formula (3a) or (3c).
  • R3 independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms
  • R4 independently represents a hydrogen atom or a group represented by formula (3a).
  • A is a residue obtained by removing two R2 from formula (6), and R2 in the residue is a hydrogen atom, a dicyclopentenyl group represented by formula (2a) or formula (2b), or formula (3a ) is a group represented by Me represents a methyl group.
  • i is an integer from 0 to 2;
  • n3 indicates the number of repetitions, and its average value is a number from 0 to 5.
  • p indicates the number of repetitions, and its average value is a number from 0.01 to 3.
  • the present invention also provides a method for producing an epoxy resin, characterized in that 1 to 20 mol of epihalohydrin is reacted with 1 mol of the phenolic hydroxyl group of the polyhydric hydroxy resin (A) in the presence of an alkaline compound. be.
  • the present invention also provides an epoxy resin composition containing an epoxy resin and a curing agent, wherein the epoxy resin composition essentially comprises the polyhydric hydroxy resin (A) and/or the epoxy resin. .
  • the present invention is also a cured product obtained by curing the epoxy resin composition, and is a prepreg, laminate, or printed wiring board using the epoxy resin composition.
  • a dicyclopentadiene-type phenol resin is reacted with dicyclopentadiene, and further reacted with an aromatic vinyl compound, so that dicyclopentadiene derived from dicyclopentadiene is added to the phenol ring of the dicyclopentadiene-type phenol resin.
  • groups and aromatic backbones derived from aromatic vinyl compounds can be added.
  • the cured product using the polyhydric hydroxy resin and/or epoxy resin obtained by the production method exhibits excellent dielectric properties, and has excellent copper foil peel strength and interlayer adhesion strength for use in printed wiring boards.
  • An epoxy resin composition is provided.
  • FIG. 1 is a GPC chart of a polyhydric hydroxy resin obtained in Example 1.
  • FIG. 1 is an IR chart of the polyhydric hydroxy resin obtained in Example 1.
  • FIG. 4 is a GPC chart of the epoxy resin obtained in Example 7.
  • FIG. 4 is an IR chart of the epoxy resin obtained in Example 7.
  • the polyhydric hydroxy resin (also referred to as a phenolic resin) of the present invention is a polyhydric hydroxy resin (A) represented by the following general formula (1).
  • This polyvalent hydroxy resin (A) is advantageously obtained by adding dicyclopentadiene to the dicyclopentadiene type polyhydroxy resin (a) represented by the general formula (4) in the presence of a Lewis acid. It is obtained by reacting and further reacting the aromatic vinyl compound (b) represented by the general formulas (5a) and (5b).
  • the polyhydric hydroxy resin (a) has a structure in which phenols are linked by dicyclopentadiene.
  • the polyhydric hydroxy resin (A) of the present invention is obtained by adding cyclopentadiene or an aromatic vinyl compound (b) to the phenol ring of the dicyclopentadiene type polyhydric hydroxy resin (a).
  • R1 represents a hydrocarbon group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, or allyl groups are preferred.
  • the alkyl group having 1 to 8 carbon atoms may be linear, branched or cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl and hexyl. group, cyclohexyl group, methylcyclohexyl group, and the like.
  • the aryl group having 6 to 8 carbon atoms includes phenyl group, tolyl group, xylyl group, ethylphenyl group and the like.
  • the aralkyl group having 7 to 8 carbon atoms includes benzyl group, ⁇ -methylbenzyl group and the like. Among these substituents, a phenyl group and a methyl group are preferred, and a methyl group is particularly preferred, from the viewpoints of availability and reactivity when used as a cured product.
  • the substitution position of R1 may be ortho-position, meta-position or para-position, but ortho-position is preferred.
  • R21 independently represents a hydrogen atom, a dicyclopentenyl group represented by the formula (2a) or the formula (2b), or a group represented by the formula (3a) or the formula (3b), and one of at least two is a dicyclopentenyl group represented by formula (2a) or formula (2b), and the other is a group represented by formula (3a) or formula (3b).
  • R21 does not necessarily represent only a substituent, but also represents a hydrogen atom.
  • a dicyclopentenyl group is a group derived from dicyclopentadiene and represented by the following formula (2a) or formula (2b).
  • the groups represented by formula (3a) or formula (3b) are as follows.
  • the group represented by the formula (3a) is a monovinyl compound represented by the following general formula (5a) among the raw material aromatic vinyl compounds (b) of the polyhydric hydroxy resin (A) represented by the general formula (1).
  • a group derived from a compound and represented by the formula (3b) is a group derived from a divinyl compound represented by the following general formula (5b) among the aromatic vinyl compounds (b).
  • i is the number of substituents R1 and is 0 to 2, preferably 1 or 2, more preferably 2.
  • n1 is the number of repetitions and represents a number of 0 or more, and its average value (number average) is 0 to 5, preferably 1.0 to 4.0, 1.1 to 3 0.0 is more preferred, and 1.2 to 2.5 is even more preferred.
  • R3 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Examples of the hydrocarbon group having 1 to 8 carbon atoms are the same as those for R1. Similarly to R21, unlike R1 which is a substituent, R3 does not necessarily represent only a substituent but also represents a hydrogen atom.
  • R3 is selected from factors such as availability and heat resistance of the cured product. From the viewpoint, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom and an ethyl group are particularly preferable.
  • a vinyl group may be included as R3.
  • the substitution position of R3 may be any of ortho, meta and para positions, but meta and para positions are preferred.
  • one of R3 is an ethyl group and the rest are hydrogen atoms.
  • A1 is a residue obtained by removing two R21 from general formula (1), and R21 in the residue is a hydrogen atom or a group represented by formula (3a).
  • R21 in the residue is a hydrogen atom or a group represented by formula (3a).
  • A1 is a divalent group having a structure similar to that of general formula (1), but does not contain a group represented by formula (3b).
  • R3 in formula (3b) is also synonymous with R3 in formula (3a).
  • R4 represents a hydrogen atom or a group represented by formula (3a).
  • R21 and R3 unlike R1 which is a substituent, R4 does not necessarily represent only a substituent but also represents a hydrogen atom.
  • p1 is the number of repetitions, the average value (number average) is 0.01 to 3, preferably 0.1 to 2.0, more preferably 0.2 to 1.0, 0.3 to 0 .8 is more preferred.
  • the weight average molecular weight (Mw) of the polyhydric hydroxy resin (A) of the present invention is preferably 400-2200, more preferably 500-1600. More preferably 600-1200, particularly preferably 800-1000.
  • the number average molecular weight (Mn) is preferably 300-1500, more preferably 400-1000.
  • the phenolic hydroxyl group equivalent (g/eq.) is preferably 200-500, more preferably 250-500, even more preferably 270-400.
  • the softening point is preferably 50 to 180°C, more preferably 50 to 120°C.
  • the polyhydric hydroxy resin (A) of the present invention exhibits low viscosity and a melt viscosity at 150° C. of 0.01 to 1.0 Pa ⁇ s. It is preferably 0.03 to 0.7 Pa ⁇ s, more preferably 0.05 to 0.5 Pa ⁇ s.
  • the polyhydroxy resin (A) of the present invention comprises a polyhydroxy resin (a) represented by the following general formula (4) and an aromatic resin represented by the following general formula (5a) and/or general formula (5b) It can be obtained by reacting the vinyl compound (b) with the dicyclopentadiene represented by the formula (5c).
  • R1 and i have the same definitions as in general formula (1)
  • m has the same meaning as n1 in general formula (1).
  • R3 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
  • Examples of the hydrocarbon group having 1 to 8 carbon atoms are the same as those for R1.
  • R3 is preferably a hydrogen atom, a methyl group or an ethyl group, more preferably a hydrogen atom or an ethyl group, from the viewpoint of availability and heat resistance of the cured product.
  • the substitution position of R3 may be ortho-position, meta-position or para-position, but meta-position and para-position are preferred.
  • the substitution position of the vinyl group may be any of ortho, meta, and para positions, preferably meta and para positions, and may be a mixture thereof.
  • the aromatic vinyl compound (b) used as a raw material essentially comprises a monovinyl compound (a compound represented by the general formula (5a)), and may contain a divinyl compound (a compound represented by the general formula (5b)). good.
  • the molecular weight of the polyhydric hydroxy resin (A) increases as the amount of the divinyl compound added increases. Therefore, the compounding amount may be adjusted while taking into account the molecular weight of the raw material polyhydric hydroxy resin (a) so as to obtain the desired molecular weight.
  • the monovinyl compound becomes the substituent R21 or R4 represented by the formula (3a) by an addition reaction, and exhibits the effect of reducing the dielectric properties.
  • monovinyl compounds include vinyl aromatic compounds such as styrene, vinylnaphthalene, vinylbiphenyl, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o - Nuclear alkyl-substituted vinyl aromatic compounds such as ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, ethylvinylbiphenyl and ethylvinylnaphthalene, and cyclic vinyl aromatic compounds such as indene, acenaphthylene, benzothiophene and coumarone etc. Styrene and ethylvinylbenzene are preferred. These can be used singly or in combination of two or more.
  • divinyl compounds include divinyl aromatic compounds such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl. Divinylbenzene is preferred. These can be used singly or in combination of two or more.
  • the blending amount of the monovinyl compound and the divinyl compound is preferably 15 to 50% by mass of the monovinyl compound and 50 to 85% by mass of the divinyl compound relative to the total amount of the vinyl compound.
  • the monovinyl compound is preferably 30-50% by weight, more preferably 40-50% by weight.
  • the divinyl compound is preferably 50-70% by weight, more preferably 50-60% by weight.
  • the polyhydric hydroxy resin (a) represented by the general formula (4) is obtained by reacting a phenol represented by the following general formula (9) with dicyclopentadiene in the presence of a Lewis acid.
  • R1 and i have the same definitions as in general formula (1).
  • the phenolic hydroxyl equivalent (g/eq.) of the polyhydric hydroxy resin (a) is preferably 160-220, more preferably 165-210, even more preferably 170-200.
  • Phenols represented by general formula (9) include phenol, cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, hexylphenol, cyclohexylphenol, phenylphenol, tolylphenol, benzylphenol, ⁇ -methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(t-butyl)phenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, ditolylphenol , dibenzylphenol, bis( ⁇ -methylbenzyl)phenol, methylethylphenol, methylpropylphenol, methylisopropylphenol, methylbutylphenol, methyl-t-butylphenol, methylallylphenol, tolylphenylphenol and the like. Phenol, cre
  • the catalyst used in this reaction is a Lewis acid, specifically boron trifluoride, boron trifluoride/phenol complex, boron trifluoride/ether complex, aluminum chloride, tin chloride, zinc chloride, iron chloride, and the like.
  • boron trifluoride-ether complex is preferable because of ease of handling.
  • the amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of dicyclopentadiene.
  • the amount of dicyclopentadiene used is 0.08 to 0.80 mol, preferably 0.09 to 0.60 mol, more preferably 0.10 to 0.50 mol, still more preferably 1 mol of phenols. 0.10 to 0.40 mol, particularly preferably 0.10 to 0.20 mol.
  • the phenol and the catalyst are charged in a reactor, and dicyclopentadiene is added dropwise over 0.1 to 10 hours, preferably 0.5 to 8 hours, more preferably 1 to 6 hours. .
  • the reaction temperature is preferably 50-200°C, more preferably 100-180°C, even more preferably 120-160°C.
  • the reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, even more preferably 4 to 8 hours.
  • alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide is added to deactivate the catalyst.
  • solvents such as aromatic hydrocarbons such as toluene and xylene and ketones such as methyl ethyl ketone and methyl isobutyl ketone are added to dissolve and washed with water.
  • a dicyclopentadiene phenol resin represented by formula (4) can be obtained.
  • aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethylene glycol dimethyl ether and diethylene glycol Solvents such as ethers such as dimer ether may also be used.
  • the method is a method of reacting dicyclopentadiene in a predetermined ratio with the polyhydric hydroxy resin (a) in the presence of a Lewis acid.
  • the reaction ratio is 0.05 to 2.0 mol, more preferably 0.1 to 1.0 mol, more preferably 0.15 to 0.15 to 1 mol of phenolic hydroxyl group in the polyhydric hydroxy resin (a). 0.80 mol is more preferred, and 0.20 to 0.70 mol is particularly preferred.
  • Other reaction conditions are preferably the same as those in the production method for obtaining the polyhydric hydroxy resin (a). This reaction may be continued after the synthesis of the polyhydric hydroxy resin (a) without removing the product from the reaction system.
  • Mass spectrometry and FT-IR measurement can be used as methods for confirming that a dicyclopentenyl group has been introduced into the polyhydric hydroxy resin (A).
  • the polyhydric hydroxy resin (A ) can be confirmed as a dicyclopentenyl group introduced as a substituent (R21).
  • electrospray mass spectrometry (ESI-MS), field desorption method (FD-MS), or the like can be used.
  • the introduction of a dicyclopentenyl group can be confirmed by subjecting a sample obtained by separating components having different numbers of nuclei by GPC or the like to mass spectrometry.
  • a sample dissolved in an organic solvent such as THF is applied on the KRS-5 cell, and the organic solvent is dried to obtain a sample thin film-attached cell, which is measured by FT-IR.
  • a peak derived from C—O stretching vibration in the phenol nucleus appears at around 1210 cm ⁇ 1
  • a peak derived from C—H stretching vibration of the olefin site of the dicyclopentadiene skeleton appears at 3040 cm only when a dicyclopentenyl group is introduced. It appears around -1 .
  • the dicyclopentadiene incorporated into the main chain has no olefin site, it is not detected, and only the olefin of the dicyclopentenyl group introduced as the substituent (R21) can be measured.
  • the peak (A 3040 ) near 3040 cm ⁇ 1 and 1210 cm ⁇ 1
  • the introduction amount of the dicyclopentenyl group can be quantified by the ratio (A 3040 /A 1210 ) of the nearby peak (A 1210 ).
  • a preferable ratio (A 3040 /A 1210 ) for satisfying the target physical properties is 0.01 or more, more preferably 0.05 or more, and still more preferably 0.10 or more.
  • the upper limit is preferably 0.7 or less, more preferably 0.60 or less. If this ratio is high, it means that many dicyclopentadiene substituents have been introduced.
  • the aromatic vinyl compound (b ) are reacted at a predetermined ratio.
  • the reaction ratio is 0.05 to 2.0 mol, more preferably 0.1 to 1.0 mol, of the aromatic vinyl compound (b) per 1 mol of the phenolic hydroxyl group of the polyhydric hydroxy resin (a), 0.20 to 0.80 mol is more preferred, and 0.30 to 0.70 mol is particularly preferred.
  • the catalyst used in the reaction is an acid catalyst, specifically mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid and p-toluenesulfonic acid; Examples include Lewis acids such as aluminum, iron chloride and boron trifluoride, and solid acids such as activated clay, silica-alumina and zeolite. Among them, p-toluenesulfonic acid is preferred because of ease of handling. In the case of p-toluenesulfonic acid, the amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of the polyhydric hydroxy resin (a).
  • the polyhydric hydroxy resin (a), a catalyst and a solvent are charged into a reactor and dissolved, and then the aromatic vinyl compound (b) is added for 0.1 to 10 hours, preferably 0.5 to 8 hours.
  • a system in which the solution is added dropwise over 0.5 to 5 hours is preferred.
  • the reaction temperature is preferably 50-200°C, more preferably 100-180°C, even more preferably 120-160°C.
  • the reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, even more preferably 4 to 8 hours.
  • alkali such as sodium hydroxide, potassium hydroxide, calcium hydroxide is added to deactivate the catalyst.
  • solvents such as aromatic hydrocarbons such as toluene and xylene, and ketones such as methyl ethyl ketone and methyl isobutyl ketone are added to dissolve and washed with water. resin can be obtained.
  • Solvents used in the reaction include aromatic hydrocarbons such as benzene, toluene, and xylene, ketones such as methyl ethyl ketone and methyl isobutyl ketone, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethylene glycol dimethyl ether, and diethylene glycol.
  • aromatic hydrocarbons such as benzene, toluene, and xylene
  • ketones such as methyl ethyl ketone and methyl isobutyl ketone
  • halogenated hydrocarbons such as chlorobenzene and dichlorobenzene
  • ethylene glycol dimethyl ether ethylene glycol dimethyl ether
  • diethylene glycol diethylene glycol
  • solvents such as ethers such as dimethyl ether. These solvents may be used singly or in combination of two or more.
  • Either the reaction for introducing the dicyclopentenyl group into the polyhydric hydroxy resin (a) or the reaction for introducing the aromatic skeleton structure of formula (3a) or formula (3b) may be carried out first. I do not care. From the viewpoint of ease of reaction, it is preferable to react the aromatic vinyl compound (b) after the polyhydric hydroxy resin (a) is reacted with dicyclopentadiene.
  • R22 represents a hydrogen atom or a dicyclopentenyl group represented by formula (2a) or (2b), at least one of which is a dicyclopentenyl group represented by formula (2a) or (2b).
  • k1 indicates the number of repetitions, and its average value is a number from 0 to 5.
  • the reaction intermediate before reacting dicyclopentadiene is a polyhydric hydroxy resin (a2) represented by the following general formula (11).
  • R1 and i are synonymous with the definition in General formula (1).
  • R23 represents a hydrogen atom, a group represented by formula (3a), or a group represented by formula (3d), at least one of which is a group represented by formula (3a) or (3d).
  • R3, R4 and Me have the same definitions as in formula (3b).
  • A2 is a residue obtained by removing two R23 from general formula (11), and R23 in the residue is a hydrogen atom or a group represented by formula (3a).
  • k2 indicates the number of repetitions, and its average value is a number from 0 to 5.
  • p2 indicates the number of repetitions, and its average value is a number from 0.01 to 3.
  • the epoxy resin of the present invention is represented by general formula (6).
  • This epoxy resin is obtained by reacting the polyhydric hydroxy resin (A) of the present invention with an epihalohydrin such as epichlorohydrin. This reaction is carried out according to a conventionally known method.
  • R1 and i have the same definitions as in general formula (1), and n3 has the same definition as n1 in general formula (1), but in the case of the relationship between raw materials and products, are also almost the same.
  • R2 independently represents a hydrogen atom, a dicyclopentenyl group, or a group represented by formula (3a) or formula (3c), and among at least two, one is a dicyclopentenyl group and the other is represented by the formula It is a group represented by (3a) or formula (3c).
  • R2 does not necessarily represent only a substituent, but also represents a hydrogen atom.
  • R3, R4, and Me have the same definitions as in formula (3b). Although p has the same meaning as p1 in formula (3b), it is almost the same even in the case of the relationship between raw materials and products.
  • A is a residue obtained by removing two R2 from formula (3c), and R2 in the residue is a hydrogen atom or a group represented by formula (3a). In other words, A is a divalent group having a structure similar to that of general formula (3c), but does not become a group represented by formula (3c).
  • an alkali metal hydroxide such as sodium hydroxide is added as a solid or a concentrated aqueous solution to a mixture of a phenol resin and epihalohydrin in excess moles relative to the hydroxyl groups of the phenol resin, and the C. for 0.5 to 10 hours, or a quaternary ammonium salt such as tetraethylammonium chloride is added as a catalyst to a phenolic resin and an excess molar amount of epihalohydrin at a temperature of 50 to 150.degree.
  • alkali metal hydroxide such as sodium hydroxide as a solid or concentrated aqueous solution
  • a polyhalohydrin ether obtained by reacting for a period of time and reacting at a temperature of 30 to 120° C. for 1 to 10 hours.
  • the amount of epihalohydrin used is 1 to 20 times the molar amount of the hydroxyl groups of the phenolic resin, preferably 2 to 8 times the molar amount.
  • the amount of the alkali metal hydroxide to be used is 0.85 to 1.15 times the moles of the hydroxyl groups of the phenolic resin.
  • the epoxy resin obtained by these reactions contains unreacted epihalohydrin and alkali metal halide
  • the unreacted epihalohydrin is removed from the reaction mixture by evaporation, and the alkali metal halide is extracted with water.
  • the desired epoxy resin can be obtained by removing by a method such as filtration.
  • the epoxy equivalent (g/eq.) of the epoxy resin of the present invention is preferably 200-4000, more preferably 250-2000, still more preferably 300-1000, and particularly preferably 350-500.
  • the epoxy equivalent is preferably 300 or more in order to prevent crystals of dicyandiamide from precipitating on the prepreg.
  • the total chlorine content is preferably 2000 ppm or less, more preferably 1500 ppm or less.
  • the epoxy resin of the present invention exhibits low viscosity, and has a melt viscosity of 0.01 to 1.0 Pa ⁇ s at 150°C. It is preferably 0.05 to 0.7 Pa ⁇ s, more preferably 0.1 to 0.5 Pa ⁇ s.
  • the epoxy resin composition of the present invention can be obtained by using the polyhydric hydroxy resin of the present invention and/or the epoxy resin of the present invention.
  • the epoxy resin composition of the present invention contains an epoxy resin and a curing agent as essential components.
  • part or all of the curing agent is the polyhydroxy resin of the present invention
  • part or all of the epoxy resin is the epoxy resin of the present invention
  • part or all of the curing agent is the polyhydroxy resin of the present invention.
  • part or all of the epoxy resin is the epoxy resin of the present invention.
  • At least 30% by weight of the curing agent is the polyhydric hydroxy resin of the invention or at least 30% by weight of the epoxy resin is the epoxy resin of the invention. More preferably, each content is 50% by mass or more, and still more preferably 70% by mass. If it is less than this, the dielectric properties may deteriorate.
  • the epoxy resin need not be the epoxy resin of the present invention, and the polyhydroxy resin of the present invention is less than 30% by mass of the curing agent. In the case of , it is essential that 30 mass % or more of the epoxy resin is the epoxy resin of the present invention.
  • epoxy resin used to obtain the epoxy resin composition of the present invention one or two or more of various epoxy resins may be used in combination, if necessary.
  • epoxy resins that can be used together all ordinary epoxy resins having two or more epoxy groups in the molecule can be used.
  • examples include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, tetramethylbisphenol F type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, stilbene type epoxy resin, bisphenol fluorene type epoxy resin.
  • Resins bisphenol S-type epoxy resins, bisthioether-type epoxy resins, resorcinol-type epoxy resins, biphenylaralkylphenol-type epoxy resins, naphthalene diol-type epoxy resins, phenol novolac-type epoxy resins, aromatic modified phenol novolac-type epoxy resins, cresol novolac-type epoxy resins Epoxy resins, alkyl novolak type epoxy resins, bisphenol novolac type epoxy resins, binaphthol type epoxy resins, naphthol novolac type epoxy resins, ⁇ -naphthol aralkyl type epoxy resins, dinaphthol aralkyl type epoxy resins, ⁇ -naphthol aralkyl type epoxy resins, tris trifunctional epoxy resins such as phenylmethane type epoxy resins, tetrafunctional epoxy resins such as tetrakisphenylethane type epoxy resins, dicyclopentadiene
  • Glycidylamine type epoxy resins alicyclic epoxy resins such as Celoxide 2021P (manufactured by Daicel Corporation), phosphorus-containing epoxy resins, bromine-containing epoxy resins, urethane-modified epoxy resins, oxazolidone ring-containing epoxy resins, etc., can be mentioned. It is not limited. Moreover, these epoxy resins may be used alone, or two or more of them may be used in combination.
  • epoxy resins represented by the following general formula (13), dicyclopentadiene type epoxy resins other than the present invention, naphthalenediol type epoxy resins, phenol novolak type epoxy resins, aromatic modified phenol novolak type Epoxy resins, cresol novolak type epoxy resins, ⁇ -naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, phosphorus-containing epoxy resins, and oxazolidone ring-containing epoxy resins are more preferably used.
  • R5 independently represents a hydrocarbon group having 1 to 8 carbon atoms, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, etc. and may be the same or different.
  • X represents a divalent organic group, for example, a methylene group, an ethylene group, an isopropylidene group, an isobutylene group, an alkylene group such as a hexafluoroisopropylidene group, -CO-, -O-, -S-, -SO2- , —S—S—, or an aralkylene group represented by formula (13a).
  • Each R6 independently represents a hydrogen atom or a hydrocarbon group having 1 or more carbon atoms, such as a methyl group, and may be the same or different.
  • Ar is a benzene ring or a naphthalene ring, and these benzene or naphthalene rings are alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, aryl groups having 6 to 11 carbon atoms, aryl groups having 7 to 11 carbon atoms, It may have a 12 aralkyl group, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent.
  • the curing agent in addition to the polyhydric hydroxy resin (A) of the general formula (1), various phenol resins, acid anhydrides, amines, cyanate esters, active esters, hydrazides, Commonly used curing agents such as acidic polyesters and aromatic cyanates may be used singly or in combination of two or more.
  • the content of the curing agents used in combination is preferably 70% by mass or less, more preferably 50% by mass or less, of the total curing agents. If the ratio of the curing agent used in combination is too high, the dielectric properties of the epoxy resin composition may deteriorate.
  • the molar ratio of active hydrogen groups in the curing agent is preferably 0.2 to 1.5 mol, more preferably 0.3 to 1.4 mol, per 1 mol of epoxy groups in the total epoxy resin. is more preferred, 0.5 to 1.3 mol is more preferred, and 0.8 to 1.2 mol is particularly preferred. Outside this range, curing may be incomplete and good cured physical properties may not be obtained.
  • the active hydrogen groups are blended in approximately equimolar amounts with respect to the epoxy groups.
  • an acid anhydride-based curing agent When an acid anhydride-based curing agent is used, 0.5 to 1.2 mol, preferably 0.6 to 1.0 mol, of acid anhydride group is added to 1 mol of epoxy group.
  • the phenol resin of the present invention When the phenol resin of the present invention is used alone as a curing agent, it is preferably used in the range of 0.9 to 1.1 mol per 1 mol of the epoxy resin.
  • active hydrogen group means a functional group having an active hydrogen reactive with an epoxy group (including a functional group having a latent active hydrogen that generates an active hydrogen by hydrolysis, etc., and a functional group that exhibits an equivalent curing effect). ), and specific examples include an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, and the like.
  • active hydrogen groups 1 mol of carboxyl group or phenolic hydroxyl group is calculated as 1 mol, and amino group (-NH2) is calculated as 2 mol.
  • the active hydrogen equivalent can be determined by measurement.
  • the active hydrogen equivalent of the curing agent used can be asked for.
  • triazine skeleton-containing phenolic resin aromatic modified phenol novolac resin, bisphenol A novolac resin, trishydroxyphenylmethane type novolak resin such as Resitop TPM-100 (manufactured by Gun Ei Chemical Industry Co., Ltd.), Phenols such as naphthol novolak resins and/or condensates of naphthols and/or bisphenols and aldehydes, phenols such as SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.) and/or condensates of naphthols and/or bisphenols and xylylene glycol, condensates of phenols and/or naphthols and isopropenylacetophenone, phenols and/or naphthols and/or bisphenols and dicyclo Reaction products with pentadiene, reaction products of phenols and/or naphthols
  • a novolac phenolic resin can be obtained from phenols and a cross-linking agent.
  • Phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, etc.
  • Naphthols include 1-naphthol, 2-naphthol, etc., and others. and the bisphenols mentioned above as the phenolic resin-based curing agent.
  • Aldehydes as cross-linking agents include formaldehyde, acetaldehyde, propylaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipaldehyde, and pimeline.
  • Aldehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde and the like are exemplified.
  • Biphenyl-based cross-linking agents include bis(methylol)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, bis(chloromethyl)biphenyl and the like.
  • acid anhydride curing agents include maleic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and methylbicyclo[2.2.1]heptane-2.
  • ,3-dicarboxylic anhydride bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, anhydride
  • trimellitic acid methyl nadic acid
  • copolymers of styrene monomer and maleic anhydride and copolymers of indenes and maleic anhydride.
  • amine curing agents include diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenyl ether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl ) aromatic amines such as phenol, polyether amine, biguanide compounds, dicyandiamide and anisidine, and amine compounds such as polyamidoamine which is a condensation product of acids such as dimer acid and polyamines.
  • the cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanato groups (cyanate ester groups) in one molecule.
  • novolac type cyanate ester curing agents such as phenol novolak type and alkylphenol novolak type, naphthol aralkyl type cyanate ester type curing agents, biphenylalkyl type cyanate ester type curing agents, dicyclopentadiene type cyanate ester type curing agents, bisphenol A type.
  • cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate), bis(3-methyl-4-cyanatophenyl)methane, bis(3 -ethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)-1,1-ethane, 4,4-dicyanato-diphenyl, 2,2-bis(4-cyanatophenyl)-1,1,1, 3,3,3-hexafluoropropane, 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4- cyanato)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl)methane, 1,3-
  • the active ester-based curing agent is not particularly limited, but generally contains an ester group with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more is preferably used.
  • the active ester curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound.
  • an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.
  • carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
  • Phenolic compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol , dicyclopentadienyl diphenol, dicyclopentadiene phenolic resin which is a precursor of the epoxy resin of the present invention, phenol novolac, and the like.
  • One or more active ester curing agents can be used.
  • the active ester curing agent include an active ester curing agent containing a dicyclopentadienyldiphenol structure, an active ester curing agent containing a naphthalene structure, and an active ester curing agent that is an acetylated product of phenol novolak.
  • Active ester-based curing agents that are benzoylated products of phenol novolac, etc. are preferable, and among them, active ester-based curing agents containing a dicyclopentadienyl diphenol structure containing a precursor of the epoxy resin of the present invention are preferable in that they are excellent in improving peel strength. Ester-based curing agents are more preferred.
  • curing agents include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-un imidazoles such as decylimidazole and 1-cyanoethyl-2-methylimidazole; imidazole salts that are salts of imidazoles with trimellitic acid, isocyanuric acid, or boron; quaternary ammonium salts such as trimethylammonium chloride; diazabicyclo compounds; Salts of diazabicyclo compounds and phenols or phenolic novolac resins, complex compounds of boron trifluoride and amines or ether compounds, aromatic phosphonium salts, iodonium salts and the like can be mentioned.
  • phosphine compounds such as triphenylphosphine
  • phosphonium salts such
  • a curing accelerator can be used in the epoxy resin composition as needed.
  • curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, 1, Tertiary amines such as 8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, tricyclohexylphosphine, triphenylphosphine and triphenylborane, and metal compounds such as tin octylate. mentioned.
  • the amount used is preferably 0.02 to 5 parts by mass with respect to 100 parts by mass of the epoxy resin component in the epoxy resin composition of the present invention.
  • An organic solvent or reactive diluent can be used in the epoxy resin composition for viscosity adjustment.
  • organic solvents examples include amides such as N,N-dimethylformamide and N,N-dimethylacetamide, and ethers such as ethylene glycol monomethyl ether, dimethoxydiethylene glycol, ethylene glycol diethyl ether, diethylene glycol diethyl ether, and triethylene glycol dimethyl ether.
  • ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diglycol , alcohols such as pine oil, acetic acid esters such as butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl alcohol acetate, and benzoic acid Benzoic acid esters such as methyl and ethyl benzoate, cellosolves such as methyl cellosolve, cellosolve, and butyl cellosolve, carbitols such as methyl carbitol
  • reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether and tolyl glycidyl ether, and monofunctional glycidyl esters such as glycidyl neodecanoate. etc., but not limited to these.
  • organic solvents or reactive diluents are preferably used singly or as a mixture of multiple types in the resin composition at a non-volatile content of 90% by mass or less, and the appropriate type and amount used depends on the application. Selected as appropriate.
  • a polar solvent having a boiling point of 160° C. or less such as methyl ethyl ketone, acetone, or 1-methoxy-2-propanol, is preferable, and the amount used in the resin composition is 40 to 80% by mass in nonvolatile matter. is preferred.
  • ketones for adhesive film applications, for example, it is preferable to use ketones, acetic esters, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc., and the amount used is nonvolatile is preferably 30 to 60% by mass.
  • the epoxy resin composition may be blended with other thermosetting resins and thermoplastic resins as long as the properties are not impaired.
  • phenol resin benzoxazine resin, bismaleimide resin, bismaleimide triazine resin, acrylic resin, petroleum resin, indene resin, coumarone-indene resin, phenoxy resin, polyurethane resin, polyester resin, polyamide resin, polyimide resin, polyamideimide resin , polyetherimide resin, polyphenylene ether resin, modified polyphenylene ether resin, polyether sulfone resin, polysulfone resin, polyether ether ketone resin, polyphenylene sulfide resin, polyvinyl formal resin, polysiloxane compound, reactive functional groups such as hydroxyl-containing polybutadiene Included are, but are not limited to, alkylene resins.
  • Various known flame retardants can be used in the epoxy resin composition for the purpose of improving the flame retardancy of the resulting cured product.
  • Usable flame retardants include, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. From an environmental point of view, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants may be used alone or in combination of two or more.
  • inorganic phosphorus compounds and organic phosphorus compounds can be used as phosphorus flame retardants.
  • inorganic phosphorus compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as amide phosphoric acid. be done.
  • organic phosphorus compounds include aliphatic phosphates, phosphate ester compounds, condensed phosphates such as PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), phosphazenes, phosphonic acid compounds, phosphinic acids.
  • phosphine oxide compounds examples include cyclic organic phosphorus compounds such as phosphaphenanthrene-10-oxide, and phosphorus-containing epoxy resins and phosphorus-containing curing agents which are derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.
  • the blending amount of the flame retardant is appropriately selected depending on the type of phosphorus-based flame retardant, the components of the epoxy resin composition, and the desired degree of flame retardancy.
  • the phosphorus content in the organic components (excluding the organic solvent) in the epoxy resin composition is preferably 0.2 to 4% by mass, more preferably 0.4 to 3.5% by mass, More preferably, it is 0.6 to 3% by mass. If the phosphorus content is too low, it may become difficult to ensure flame retardancy, and if it is too high, the heat resistance may be adversely affected.
  • flame retardant adjuvant such as magnesium hydroxide
  • a filler can be used in the epoxy resin composition as needed. Specifically, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, Boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, fine particle rubber, silicone rubber, thermoplastic elastomer, carbon black, pigment, etc. mentioned.
  • One of the reasons for using a filler in general is the effect of improving the impact resistance.
  • metal hydroxides such as aluminum hydroxide, boehmite and magnesium hydroxide
  • they act as flame retardant aids and have the effect of improving flame retardancy.
  • the blending amount of these fillers is preferably 1 to 150% by mass, more preferably 10 to 70% by mass, based on the entire epoxy resin composition. If the blending amount is too large, there is a risk that the adhesiveness required for use as a laminate will be lowered, and furthermore, the cured product will be brittle, and there is a risk that sufficient mechanical properties will not be obtained. On the other hand, if the blending amount is too small, there is a fear that the blending effect of the filler, such as improving the impact resistance of the cured product, may not be achieved.
  • a more preferred substrate is a glass fiber substrate in which glass fibers are woven into a mesh.
  • the epoxy resin composition further contains various additives such as silane coupling agents, antioxidants, release agents, antifoaming agents, emulsifiers, thixotropic agents, smoothing agents, flame retardants, pigments, etc. be able to.
  • the blending amount of these additives is preferably in the range of 0.01 to 20% by mass based on the epoxy resin composition.
  • the fibrous base material By impregnating the fibrous base material with the epoxy resin composition, it is possible to create a prepreg used in printed wiring boards and the like.
  • the fibrous base material inorganic fibers such as glass, and woven or non-woven fabrics of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, aromatic polyamide resin, etc. can be used, but not limited thereto. not something.
  • the method for producing a prepreg from an epoxy resin composition is not particularly limited.
  • the epoxy resin composition is immersed in a resin varnish prepared by adjusting the viscosity with an organic solvent, and then dried by heating. It is obtained by semi-curing (to B-stage) a resin component, and can be dried by heating at 100 to 200° C. for 1 to 40 minutes, for example.
  • the resin content in the prepreg is preferably 30 to 80% by mass.
  • a laminate curing method generally used when manufacturing a printed wiring board can be used, but the method is not limited to this.
  • a metal foil is arranged on one side or both sides to form a laminate, and this laminate is heated and pressed to form an integrated laminate.
  • the metal foil copper, aluminum, brass, nickel, or the like can be used alone, as an alloy, or as a composite metal foil. Then, the prepared laminate is pressurized and heated to cure the prepreg and obtain a laminate.
  • the heating temperature it is preferable to set the heating temperature to 160 to 220° C., the pressure to 5 to 50 MPa, and the heating and pressurizing time to 40 to 240 minutes, so that the desired cured product can be obtained. If the heating temperature is too low, the curing reaction will not proceed sufficiently, and if the heating temperature is too high, the epoxy resin composition may begin to decompose. In addition, if the pressure is too low, air bubbles may remain inside the resulting laminate, resulting in deterioration of the electrical properties. There is a risk that it will not be possible. Furthermore, if the heating and pressurizing time is short, the curing reaction may not proceed sufficiently, and if it is long, the epoxy resin composition in the prepreg may be thermally decomposed, which is not preferable.
  • the epoxy resin composition can be cured in the same manner as for known epoxy resin compositions to obtain a cured epoxy resin.
  • a method for obtaining a cured product the same methods as those for known epoxy resin compositions can be used, such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, resin sheets, resins, etc.
  • a method of forming a laminated plate by laminating a laminated copper foil, prepreg, or the like and curing under heat and pressure is preferably used.
  • the curing temperature at that time is usually 100 to 300° C., and the curing time is usually about 1 to 5 hours.
  • the epoxy resin cured product of the present invention can take forms such as laminates, moldings, adhesives, coatings, and films.
  • an epoxy curable resin composition that exhibits excellent low dielectric properties in the cured product.
  • dielectric properties specifically, a dielectric constant of 3.00 or less, more preferably 2.90 or less, and a dielectric loss tangent of 0.015 or less, more preferably 0.011 or less can be expressed.
  • the glass transition temperature (Tg) of the cured product is also 120° C. or higher, and may be 150° C. or higher.
  • hydroxyl equivalent The measurement was performed according to the JIS K0070 standard, and the unit was expressed as "g/eq.”.
  • the hydroxyl group equivalent of the phenolic resin means the phenolic hydroxyl group equivalent.
  • Relative permittivity and dielectric loss tangent Measured according to IPC-TM-650 2.5.5.9. Specifically, the sample was dried in an oven set at 105°C for 2 hours, allowed to cool in a desiccator, and then measured by a capacitance method using a material analyzer manufactured by AGILENT Technologies to determine the dielectric constant and dielectric loss tangent at a frequency of 1 GHz. Evaluated by asking.
  • Copper foil peel strength and interlayer adhesion It was measured according to JIS C6481, and the interlayer adhesive strength was measured by peeling off between the 7th layer and the 8th layer.
  • GPC gel permeation chromatography measurement: A column (TSKgelG4000HXL, TSKgelG3000HXL, TSKgelG2000HXL manufactured by Tosoh Corporation) in series with a main body (HLC-8220GPC manufactured by Tosoh Corporation) was used, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as an eluent at a flow rate of 1 mL/min, and a differential refractive index detector was used as a detector. As a measurement sample, 0.1 g of the sample was dissolved in 10 mL of THF and filtered through a microfilter, and 50 ⁇ L of the solution was used. For data processing, GPC-8020 model II version 6.00 manufactured by Tosoh Corporation was used.
  • THF Tetrahydrofuran
  • IR infrared absorption spectrum: A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used, sodium chloride was used for the cell, and a sample dissolved in chloroform was applied on the cell and dried. After that, the transmittance was measured at wavenumbers of 450 to 4000 cm ⁇ 1 .
  • E1 Epoxy resin obtained in Example 7
  • E2 Epoxy resin obtained in Example 8
  • E3 Epoxy resin obtained in Example 9
  • E4 Epoxy resin obtained in Example 10
  • E5 Epoxy resin obtained in Example 11
  • E6 Epoxy resin obtained in Example 12
  • EH1 Epoxy resin obtained in Comparative Example 1
  • EH2 Phenol-dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, HP-7200H, epoxy equivalent 280, softening point 83 ° C., 150 Melt viscosity at ° C. 0.40 Pa s)
  • Synthesis example 1 500 parts of 2,6-xylenol (structural formula below) was added to a reaction apparatus consisting of a glass separable flask equipped with a stirrer, thermometer, nitrogen blowing tube, dropping funnel, and cooling tube. 7.1 parts of 47% BF3 ether complex was charged and heated to 100°C while stirring. 60.1 parts of dicyclopentadiene (structural formula below) (0.11 times moles relative to 2,6-xylenol) while maintaining the same temperature was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 115-125° C. for 4 hours. 560 parts of MIBK were then added to dissolve the product.
  • Synthesis example 2 500 parts of the polyhydric hydroxy resin (PH1) obtained in Synthesis Example 1 and 125 parts of MIBK were charged into the same reactor as in Synthesis Example 1 and heated to 100° C. while stirring. 5.0 parts of 47% BF3 ether complex was charged, and while maintaining the same temperature, 75.0 parts of dicyclopentadiene (the following structural formula) (0.22 times mol relative to the hydroxyl group of the polyhydric hydroxy resin (PH1)). was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 115-125° C. for 4 hours. 669 parts of MIBK were then added to dissolve the product. 13.3 parts of sodium bicarbonate was added, and 521 parts of hot water at 80° C.
  • the hydroxyl equivalent was 234, and the resin had a softening point of 86°C.
  • the melt viscosity at 150°C was 0.15 Pa ⁇ s.
  • Synthesis example 3 In the same reactor as in Synthesis Example 1, 500 parts of 2,6-xylenol and 7.3 parts of 47% BF3 ether complex (0.1 times the moles of the initially added dicyclopentadiene) were charged and stirred. Warmed to 100°C. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12-fold mol with respect to 2,6-xylenol) was added dropwise over 1 hour. Furthermore, the reaction was carried out at a temperature of 115-125° C. for 4 hours. Thereafter, the mixture was heated to 200° C. under a reduced pressure of 5 mmHg to evaporate off unreacted raw materials, and 46.7 parts of MIBK was added to dissolve the product.
  • the melt viscosity at 150°C was 0.41 Pa ⁇ s.
  • Synthesis example 4 In the same reaction apparatus as in Synthesis Example 1, ortho-cresol (the following structural formula) 361 parts, 5.9 parts of 47% BF3 ether complex was charged and heated to 100°C while stirring. While maintaining the same temperature, 55.2 parts of dicyclopentadiene (the following structural formula) (0.13 times moles relative to ortho-cresol) was added dropwise in 1 hour. Further, the mixture was reacted at a temperature of 115 to 125° C. for 4 hours, and 9 parts of calcium hydroxide was added. An additional 16 parts of a 10% aqueous oxalic acid solution was added. Then, after heating to 160° C. for dehydration, the mixture was heated to 200° C.
  • ortho-cresol the following structural formula
  • the melt viscosity at 150°C was 0.07 Pa ⁇ s.
  • Synthesis example 5 250 parts of the polyhydric hydroxy resin (PH1) obtained in Synthesis Example 1, 2.5 parts of p-toluenesulfonic acid monohydrate, and 62.5 parts of MIBK were charged in the same reactor as in Synthesis Example 1 and stirred. It was heated to 120° C. while Divinylbenzene (mixture of the following structural formula) (manufactured by Aldrich Co., Ltd., 80% divinylbenzene, 20% ethylvinylbenzene) 150 parts (0.90 times moles relative to the hydroxyl group of pH 1) while maintaining the same temperature was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 120-130° C. for 4 hours.
  • Divinylbenzene mixture of the following structural formula
  • Example 1 In the same reactor as in Synthesis Example 1, 100 parts of the polyhydroxy resin (PH2) obtained in Synthesis Example 2, 1.0 parts of paratoluenesulfonic acid monohydrate, and 25 parts of MIBK were charged and stirred to 120 parts. It was warmed to °C. Divinylbenzene (mixture of the following structural formula) (manufactured by Aldrich Co., Ltd., 55% divinylbenzene, 45% ethylvinylbenzene) 20 parts (0.36 times moles relative to the hydroxyl group of PH2) while maintaining the same temperature was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 120-130° C. for 4 hours.
  • Divinylbenzene mixture of the following structural formula
  • a GPC chart and an IR chart of the obtained polyhydric hydroxy resin (P1) are shown in FIG. 1 and FIG. 2, respectively.
  • the melt viscosity at 150°C was 0.11 Pa ⁇ s.
  • Example 2 In the same reactor as in Synthesis Example 1, 100 parts of the polyhydroxy resin (PH2) obtained in Synthesis Example 2, 1.0 parts of paratoluenesulfonic acid monohydrate, and 25 parts of MIBK were charged and stirred to 120 parts. It was warmed to °C. Divinylbenzene (mixture of the following structural formula) (manufactured by Aldrich Co., Ltd., 55% divinylbenzene, 45% ethylvinylbenzene) 30 parts (0.54 times moles relative to the hydroxyl group of PH2) while maintaining the same temperature was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 120-130° C. for 4 hours.
  • Divinylbenzene mixture of the following structural formula
  • Example 3 In the same reactor as in Synthesis Example 1, 90 parts of the polyhydroxy resin (PH1) obtained in Synthesis Example 1, 1.0 parts of paratoluenesulfonic acid monohydrate, and 25 parts of MIBK were charged, and stirred to 120 parts. It was warmed to °C. Divinylbenzene (mixture of the following structural formula) (manufactured by Aldrich Co., Ltd., 55% divinylbenzene, 45% ethylvinylbenzene) 40 parts (0.67 times moles relative to the hydroxyl group of pH 1) while maintaining the same temperature was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 120-130° C. for 4 hours.
  • Divinylbenzene mixture of the following structural formula
  • Example 4 In the same reactor as in Synthesis Example 1, 100 parts of the polyhydroxy resin (PH2) obtained in Synthesis Example 2, 1.0 parts of paratoluenesulfonic acid monohydrate, and 25 parts of MIBK were charged and stirred to 120 parts. It was warmed to °C. Divinylbenzene (mixture of the following structural formula) (manufactured by Aldrich Co., Ltd., 80% divinylbenzene, 20% ethylvinylbenzene) 30 parts (0.54 times moles relative to the hydroxyl group of PH2) while maintaining the same temperature was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 120-130° C. for 4 hours.
  • Divinylbenzene mixture of the following structural formula
  • Example 5 In the same reactor as in Synthesis Example 1, 100 parts of the polyhydroxy resin (PH3) obtained in Synthesis Example 3, 1.0 parts of paratoluenesulfonic acid monohydrate, and 25 parts of MIBK were charged and stirred to 120 parts. It was warmed to °C. Divinylbenzene (mixture of the following structural formula) (manufactured by Aldrich Co., Ltd., 55% divinylbenzene, 45% ethylvinylbenzene) 20 parts (0.42 times moles relative to the hydroxyl group of pH 3) while maintaining the same temperature was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 120-130° C. for 4 hours.
  • Divinylbenzene mixture of the following structural formula
  • Example 6 500 parts of the polyhydric hydroxy resin (PH4) obtained in Synthesis Example 4 and 125 parts of MIBK were charged into the same reactor as in Synthesis Example 1 and heated to 100° C. while stirring. 5.0 parts of 47% BF3 ether complex was charged, and while maintaining the same temperature, 75.0 parts of dicyclopentadiene (the following structural formula) (0.21 times mol with respect to the hydroxyl group of PH4) was added dropwise in 1 hour. Furthermore, the reaction was carried out at a temperature of 115-125° C. for 4 hours. 669 parts of MIBK were then added to dissolve the product. 13.3 parts of sodium bicarbonate was added, and 521 parts of hot water at 80° C.
  • M- 347, 479, 587, 611, 719 was confirmed, the polyhydroxy resin of formula (1), a dicyclopentenyl group represented by formula (2a) or formula (2b), and formula ( It was confirmed that each of the structures had a group derived from divinylbenzene represented by 3a) or formula (3b) as a substituent.
  • the melt viscosity at 150°C was 0.20 Pa ⁇ s.
  • Example 7 100 parts of the polyhydric hydroxy resin (P1) obtained in Example 1 and 170.1 parts of epichlorohydrin (structural formula below) were added to a reactor equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a cooling tube. and 25.5 parts of diethylene glycol dimethyl ether were added and heated to 65°C. Under a reduced pressure of 125 mmHg, 25.5 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C. During this time, epichlorohydrin was azeotropically distilled with water, and the outflowing water was sequentially removed out of the system.
  • Mass spectrum measurement by ESI-MS (negative) confirmed M- 487, 619, 797.
  • the melt viscosity at 150°C was 0.15 Pa ⁇ s.
  • Example 8 100 parts of the polyhydric hydroxy resin (P2) obtained in Example 2, 152.8 parts of epichlorohydrin and 22.9 parts of diethylene glycol dimethyl ether were added to the same reactor as in Example 7 and heated to 65°C. Under a reduced pressure of 125 mmHg, 24.0 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C. During this time, epichlorohydrin was azeotropically distilled with water, and the outflowing water was sequentially removed out of the system. After completion of the reaction, epichlorohydrin was recovered under conditions of 5 mmHg and 180° C., and 276 parts of MIBK was added to dissolve the product.
  • the melt viscosity at 150°C was 0.30 Pa ⁇ s.
  • Example 9 100 parts of the polyhydric hydroxy resin (P3) obtained in Example 3, 141.4 parts of epichlorohydrin and 21.2 parts of diethylene glycol dimethyl ether were added to the same reactor as in Example 7 and heated to 65°C. Under a reduced pressure of 125 mmHg, 22.0 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C. During this time, epichlorohydrin was azeotropically distilled with water, and the outflowing water was sequentially removed out of the system. After completion of the reaction, epichlorohydrin was recovered under conditions of 5 mmHg and 180° C., and 273 parts of MIBK was added to dissolve the product.
  • P3 polyhydric hydroxy resin obtained in Example 3
  • 22.0 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C.
  • epichlorohydrin was azeo
  • the melt viscosity at 150°C was 0.23 Pa ⁇ s.
  • Example 10 100 parts of the polyhydric hydroxy resin (P4) obtained in Example 4, 150.6 parts of epichlorohydrin and 22.6 parts of diethylene glycol dimethyl ether were added to the same reactor as in Example 7 and heated to 65°C. Under a reduced pressure of 125 mmHg, 23.6 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C. During this time, epichlorohydrin was azeotropically distilled with water, and the outflowing water was sequentially removed out of the system. After completion of the reaction, epichlorohydrin was recovered under conditions of 5 mmHg and 180° C., and 276 parts of MIBK was added to dissolve the product.
  • P4 polyhydric hydroxy resin obtained in Example 4
  • 23.6 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C.
  • epichlorohydrin was azeo
  • the melt viscosity at 150°C was 0.27 Pa ⁇ s.
  • Example 11 100 parts of the polyhydric hydroxy resin (P5) obtained in Example 5, 152.4 parts of epichlorohydrin and 22.9 parts of diethylene glycol dimethyl ether were added to the same reactor as in Example 7 and heated to 65°C. Under a reduced pressure of 125 mmHg, 23.8 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C. During this time, epichlorohydrin was azeotropically distilled with water, and the outflowing water was sequentially removed out of the system. After completion of the reaction, epichlorohydrin was recovered under conditions of 5 mmHg and 180° C., and 276 parts of MIBK was added to dissolve the product.
  • the melt viscosity at 150°C was 0.41 Pa ⁇ s.
  • Example 12 100 parts of the polyhydric hydroxy resin (P6) obtained in Example 6, 152.4 parts of epichlorohydrin and 22.9 parts of diethylene glycol dimethyl ether were added to the same reactor as in Example 7 and heated to 65°C. Under a reduced pressure of 125 mmHg, 23.8 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C. During this time, epichlorohydrin was azeotropically distilled with water, and the outflowing water was sequentially removed out of the system. After completion of the reaction, epichlorohydrin was recovered under conditions of 5 mmHg and 180° C., and 276 parts of MIBK was added to dissolve the product.
  • Comparative example 1 100 parts of the polyhydric hydroxy resin (PH1) obtained in Synthesis Example 1, 237.2 parts of epichlorohydrin and 35.6 parts of diethylene glycol dimethyl ether were added to the same reactor as in Example 7 and heated to 65°C. Under a reduced pressure of 125 mmHg, 38.1 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C. During this time, epichlorohydrin was azeotropically distilled with water, and the outflowing water was sequentially removed out of the system. After completion of the reaction, epichlorohydrin was recovered under conditions of 5 mmHg and 180° C., and 300 parts of MIBK was added to dissolve the product.
  • PH1 polyhydric hydroxy resin obtained in Synthesis Example 1
  • 38.1 parts of a 49% sodium hydroxide aqueous solution was added dropwise over 3 hours while maintaining the temperature at 63-67°C.
  • Example 13 100 parts of an epoxy resin (E1) as an epoxy resin, 29.7 parts of a phenol novolac resin (PH6) as a curing agent, and 0.40 parts of C1 as a curing accelerator are blended, and MEK, propylene glycol monomethyl ether, N, An epoxy resin composition varnish was obtained by dissolving in a mixed solvent prepared with N-dimethylformamide. A glass cloth (WEA 7628 XS13, manufactured by Nitto Boseki Co., Ltd., 0.18 mm thick) was impregnated with the obtained epoxy resin composition varnish. The impregnated glass cloth was dried in a hot air circulating oven at 150° C. for 9 minutes to obtain a prepreg.
  • E1 an epoxy resin
  • PH6 phenol novolac resin
  • C1 curing accelerator
  • the obtained prepreg was loosened and passed through a sieve to obtain powdery prepreg powder that passed 100 mesh.
  • the obtained prepreg powder was placed in a fluororesin mold and vacuum pressed at 2 MPa under temperature conditions of 130° C. ⁇ 15 minutes+190° C. ⁇ 80 minutes to obtain a test piece of 50 mm square ⁇ 2 mm thickness.
  • Table 1 shows the dielectric constant and dielectric loss tangent results of the test piece.
  • the obtained 8 sheets of prepreg and copper foil (manufactured by Mitsui Kinzoku Mining Co., Ltd., 3EC-III, thickness 35 ⁇ m) are stacked on top and bottom, and a vacuum press of 2 MPa is performed under the temperature conditions of 130 ° C. x 15 minutes + 190 ° C. x 80 minutes. was performed to obtain a laminate having a thickness of 1.6 mm.
  • Table 1 shows the results of copper foil peel strength and interlayer adhesion of the laminate.
  • Examples 14-42 and Comparative Examples 2-12 The amounts (parts) shown in Tables 1 to 4 were blended, and the same operation as in Example 13 was performed to obtain a laminate and a test piece.
  • the curing accelerator was used in such an amount that the varnish gel time could be adjusted to about 300 seconds.
  • the same test as in Example 13 was conducted, and the results are shown in Tables 1-4.
  • the polyhydric hydroxy resins and epoxy resins obtained in the examples exhibit very good low viscosity, and the resin compositions containing them have practically no problem in terms of adhesiveness of 1.0 kN. /m or more, it is possible to provide a resin cured product exhibiting very good low dielectric properties.
  • the polyhydric hydroxy resin, epoxy resin, or resin composition of the present invention can be applied to various fields such as paints, civil engineering adhesion, casting, electrical and electronic materials, and film materials.
  • it is useful as a printed wiring board, which is one of electrical and electronic materials.

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Publication number Priority date Publication date Assignee Title
WO2024004618A1 (ja) * 2022-06-30 2024-01-04 日鉄ケミカル＆マテリアル株式会社 多官能ビニル樹脂及びその製造方法
WO2024024525A1 (ja) * 2022-07-26 2024-02-01 日鉄ケミカル＆マテリアル株式会社 エポキシ樹脂、その樹脂組成物、及びその硬化物、並びにエポキシ樹脂の製造方法

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JPH06116345A (ja) * 1992-10-02 1994-04-26 Dainippon Ink & Chem Inc 合成樹脂組成物及びそれを硬化した成形品
CN103665331A (zh) * 2013-12-16 2014-03-26 北京彤程创展科技有限公司 一种提高橡胶抗撕裂性能的树脂及其制备方法
JP2016069524A (ja) * 2014-09-30 2016-05-09 新日鉄住金化学株式会社 変性多価ヒドロキシ樹脂、エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
WO2022124252A1 (ja) * 2020-12-07 2022-06-16 日鉄ケミカル＆マテリアル株式会社 多価ヒドロキシ樹脂、エポキシ樹脂、それらの製造方法、エポキシ樹脂組成物及びその硬化物

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Publication number Priority date Publication date Assignee Title
JPH06116345A (ja) * 1992-10-02 1994-04-26 Dainippon Ink & Chem Inc 合成樹脂組成物及びそれを硬化した成形品
CN103665331A (zh) * 2013-12-16 2014-03-26 北京彤程创展科技有限公司 一种提高橡胶抗撕裂性能的树脂及其制备方法
JP2016069524A (ja) * 2014-09-30 2016-05-09 新日鉄住金化学株式会社 変性多価ヒドロキシ樹脂、エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
WO2022124252A1 (ja) * 2020-12-07 2022-06-16 日鉄ケミカル＆マテリアル株式会社 多価ヒドロキシ樹脂、エポキシ樹脂、それらの製造方法、エポキシ樹脂組成物及びその硬化物

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Publication number Priority date Publication date Assignee Title
WO2024004618A1 (ja) * 2022-06-30 2024-01-04 日鉄ケミカル＆マテリアル株式会社 多官能ビニル樹脂及びその製造方法
WO2024024525A1 (ja) * 2022-07-26 2024-02-01 日鉄ケミカル＆マテリアル株式会社 エポキシ樹脂、その樹脂組成物、及びその硬化物、並びにエポキシ樹脂の製造方法

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