Polyhydric hydroxyl resin, epoxy resin, method for producing the same, epoxy resin composition, and use of the epoxy resin composition

Abstract

The present invention provides an epoxy resin composition exhibiting excellent low dielectric properties, a polyhydric hydroxyl resin and an epoxy resin for providing the epoxy resin composition, a method for producing these, and an application of the epoxy resin composition. A polyhydric hydroxyl resin, wherein represented by the following general formula (1).

Description

Technical Field

[0001] This invention relates to a polyhydroxy resin or epoxy resin with excellent low viscosity and low dielectric properties, and a method for manufacturing the same. Background Technology

[0002] Epoxy resins are widely used in coatings, civil engineering adhesives, injection molding, electrical and electronic materials, and membrane materials due to their excellent adhesion, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity. They are particularly prevalent in printed circuit boards, a type of electrical and electronic material, where flame-retardant properties are imparted to the epoxy resin.

[0003] In recent years, the miniaturization and high performance of information devices have been developing rapidly. Along with this, the requirements for materials used in the field of semiconductors or electronic components are higher than ever before. In particular, epoxy resin compositions used as materials for electrical and electronic components require low dielectric properties that are accompanied by thinner substrates and higher functionality.

[0004] To date, in reducing the dielectric constant for laminate applications, dicyclopentadienol resins with an aliphatic backbone have been used. However, their effectiveness in improving the dielectric loss tangent is insufficient, and their low viscosity, which is important for increasing filler content, is also unsatisfactory (Patent Document 1, Patent Document 2). Furthermore, while aromatically modified dicyclopentadienol resins have improved dielectric properties, they do not simultaneously achieve both low dielectric properties and low viscosity (Patent Document 3).

[0005] Existing technical documents

[0006] Patent documents

[0007] Patent Document 1: Japanese Patent Application Publication No. 2001-240654

[0008] Patent Document 2: Japanese Patent Application Publication No. 5-339341

[0009] Patent Document 3: Japanese Patent Application Publication No. 2016-69524 Summary of the Invention

[0010] Therefore, the problem to be solved by the present invention is to provide a polyhydroxy resin and epoxy resin thereof that can produce a cured product exhibiting excellent dielectric loss tangent and good low viscosity, epoxy resin compositions using these, and methods for manufacturing the above.

[0011] To solve the aforementioned problem, the inventors conducted various studies and discovered that by reacting a dicyclopentadiene-type phenolic resin with an aromatic vinyl compound in a specific ratio, an aromatic skeleton derived from the aromatic vinyl compound can be added to the phenol ring of the dicyclopentadiene-type phenolic resin. The epoxy resin obtained by epoxidizing the phenolic resin exhibits excellent low viscosity, and the cured product obtained by curing with a curing agent exhibits excellent low dielectric properties, thus completing the present invention.

[0012] That is, the present invention is a polyhydroxy resin (A), wherein it is represented by the following general formula (1).

[0013] [Chemistry 1]

[0014]

[0015] Here, R 1 Independently representing hydrocarbon groups having 1 to 8 carbon atoms, R 2 Independently representing a hydrogen atom, a base represented by formula (2), or a base represented by formula (3), with at least one being formula (2) or formula (3). R 3 Independently representing a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 4 Independently represent a hydrogen atom or a base represented by formula (2). A is the result of removing two R atoms from formula (1). 2 The residues formed at this time, R 2 is a hydrogen atom or a group represented by formula (2); Me represents a methyl group. i is an integer from 0 to 2. n1 represents the number of repetitions, with an average value of 0 to 5. p represents the number of repetitions, with an average value of 0.01 to 3.

[0016] The R 1 Preferably methyl or phenyl, and i is preferably 1 or 2.

[0017] In addition, the present invention is a method for manufacturing a polyhydroxy resin, wherein a polyhydroxy resin (a) represented by the following general formula (4) is reacted with an aromatic vinyl compound (b) represented by the following general formula (5a) and / or general formula (5b).

[0018] [Chemistry 2]

[0019]

[0020] Here, R 1 Independently represent hydrocarbon groups with 1 to 8 carbon atoms. i is an integer from 0 to 2. m represents the repetition number, with an average value of 0 to 5.

[0021] [Chemistry 3]

[0022]

[0023] Here, R 3 It represents a hydrogen atom or a hydrocarbon group with 1 to 8 carbon atoms.

[0024] The manufacturing method is preferably carried out in the presence of an acid catalyst, and preferably, 0.05 to 2.0 moles of the aromatic vinyl compound (b) are reacted at a reaction temperature of 50°C to 200°C relative to 1 mole of the phenolic hydroxyl groups of the polyhydroxy resin (a).

[0025] In addition, the present invention is an epoxy resin, wherein it is represented by the following general formula (6).

[0026] [Chemistry 4]

[0027]

[0028] Here, R 1 Independently representing hydrocarbon groups having 1 to 8 carbon atoms, R 2 Independently representing a hydrogen atom, a base represented by formula (2), or a base represented by formula (3), with at least one being formula (2) or formula (3). R 3 Independently representing a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 4 Independently represent a hydrogen atom or a base represented by equation (2). A is the result of removing two R atoms from equation (6). 2 The residues formed at this time, R 2 is a hydrogen atom or a group represented by formula (2). Me represents a methyl group. i is an integer from 0 to 2. n3 represents the number of repetitions, with an average value of 0 to 5. p represents the number of repetitions, with an average value of 0.01 to 3.

[0029] In addition, the present invention is a method for manufacturing an epoxy resin, wherein, relative to 1 mole of phenolic hydroxyl groups in the polyhydroxy resin (A), 1 to 20 moles of epihaloalcohol are reacted in the presence of an alkali metal hydroxide.

[0030] In addition, the present invention is an epoxy resin composition containing epoxy resin and a curing agent, wherein the polyhydroxy resin (A) and / or epoxy resin are essential components.

[0031] In addition, the present invention is a cured product formed by curing the epoxy resin composition, and is a prepreg, laminate or printed wiring board using the epoxy resin composition.

[0032] The manufacturing method of the present invention readily adds an aromatic backbone derived from aromatic vinyl compounds to the phenol ring of a dicyclopentadiene-type polyhydroxy resin. Furthermore, the cured product of the polyhydroxy resin and / or epoxy resin obtained by the manufacturing method can provide an epoxy resin composition exhibiting excellent dielectric loss tangent, and consequently excellent copper foil peel strength and interlayer adhesion strength in printed circuit board applications. Attached Figure Description

[0033] Figure 1 This is a gel permeation chromatography (GPC) chromatogram of the phenolic resin obtained in Example 1.

[0034] Figure 2 This is the GPC diagram of the epoxy resin obtained in Example 6. Detailed Implementation

[0035] The embodiments of the present invention will now be described in detail.

[0036] The polyhydroxy resin (also known as phenolic resin) of the present invention is a polyhydroxy resin (A) represented by the general formula (1). The resin is obtained, for example, by reacting an aromatic vinyl compound (b) represented by general formula (5a) and / or general formula (5b) with a dicyclopentadiene type polyhydroxy resin (a) represented by general formula (4) in the presence of a Lewis acid.

[0037] Here, the polyhydroxy resin (a) has a structure in which phenols are linked by dicyclopentadiene. The polyhydroxy resin (A) of the present invention is a polyhydroxy resin (A) formed by adding an aromatic skeleton represented by the formula (2) to the phenol ring in the dicyclopentadiene type polyhydroxy resin (a).

[0038] In general formula (1), R 1 This refers to a hydrocarbon group having 1 to 8 carbon atoms. Preferably, it is 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 an allyl group. As an alkyl group having 1 to 8 carbon atoms, it can be linear, branched, or cyclic, and examples include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, hexyl, cyclohexyl, methylcyclohexyl, etc., but it is not limited to these. As an aryl group having 6 to 8 carbon atoms, examples include phenyl, tolyl, xylyl, ethylphenyl, etc., but it is not limited to these. As an aralkyl group having 7 to 8 carbon atoms, examples include benzyl, α-methylbenzyl, etc., but it is not limited to these. Among these substituents, from the viewpoint of ease of acquisition and reactivity when preparing a cured product, phenyl and methyl are preferred, and methyl is particularly preferred. R 1 The substitution position can be any of the adjacent, intermediate, or antiparallel positions, but the adjacent position is preferred.

[0039] R 2 Represents a hydrogen atom, or a base represented by formula (2) or formula (3), and at least one of formula (2) or formula (3). R 2 With R as a substituent 1 The difference does not necessarily refer only to substituents, but also to hydrogen atoms.

[0040] The group represented by formula (2) is derived from the monovinyl group represented by formula (5a) in aromatic vinyl compounds (b), and the group represented by formula (3) is derived from the divinyl group represented by formula (5b) in aromatic vinyl compounds (b).

[0041] i represents the substituent R 1 The number of elements is 0 to 2, preferably 1 or 2, and more preferably 2.

[0042] n1 is a repeating number and represents a number greater than or equal to 0. Its average value (quantity average) is 0 to 5, preferably 1.0 to 4.0, more preferably 1.1 to 3.0, and even more preferably 1.2 to 2.5.

[0043] In equation (2), R 3 This represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Examples of hydrocarbon groups having 1 to 8 carbon atoms include those with R. 1 The same hydrocarbon group. R 3 Also with R 2 Similarly, with R as a substituent 1 The difference does not necessarily refer only to substituents, but also to hydrogen atoms.

[0044] When using the monovinyl compound represented by formula (5a) as a raw material, as R 3 From the viewpoint of ease of acquisition and heat resistance of the cured product, hydrogen atoms, methyl groups, and ethyl groups are preferred, with hydrogen atoms and ethyl groups being particularly preferred. When using a divinyl compound represented by formula (5b) as a raw material, as R... 3 It may also contain vinyl. Additionally, R 3 The substitution position can be any of the adjacent, intermediate, or anti-position, but intermediate and anti-position are preferred.

[0045] R is preferred 3 One of them is an ethyl group, and the rest are hydrogen atoms.

[0046] In equation (3), A is the result of removing two R values ​​from equation (1). 2 The residues formed at this time, R 2 It is a hydrogen atom or a base represented by formula (2). In other words, A does not contain a base represented by formula (3).

[0047] R in equation (3) 3 Also with R in equation (2)3 Synonyms.

[0048] R 4 Represents a hydrogen atom or the radical represented by formula (2). R 4 Also with R 2 or R 3 Similarly, with R as a substituent 1 The difference does not necessarily refer only to substituents, but also to hydrogen atoms.

[0049] p is a repetition number and represents a number greater than 0. Its average value (quantity average) is 0.01 to 3, preferably 0.1 to 2.0, more preferably 0.2 to 1.0, and even more preferably 0.3 to 0.8.

[0050] The weight average molecular weight (Mw) of the phenolic resin of the present invention is preferably 400 to 2000, more preferably 500 to 1500. The number average molecular weight (Mn) is preferably 350 to 1500, more preferably 400 to 1000.

[0051] The phenolic hydroxyl equivalent (g / eq.) is preferably 190 to 500, more preferably 200 to 500, and even more preferably 220 to 400.

[0052] As for the content obtained by GPC, the molecular weight distribution of the polyhydroxy resin (a) as raw material is kept roughly the same. In general formula (1), it is preferably in the range of n1=0 with a volume of 10 area% or less, n1=1 with a volume of 50 area% to 90 area%, and n1=2 or more with a volume of 0 area% to 50 area%.

[0053] The softening point is preferably 50℃~180℃, more preferably 50℃~120℃.

[0054] The phenolic resin of the present invention exhibits low viscosity, with a melt viscosity of 0.01 Pa·s to 1.0 Pa·s at 150°C. Preferably, it is 0.03 Pa·s to 0.5 Pa·s, and more preferably, it is 0.05 to 0.4 Pa·s.

[0055] In general formula (4), R 1 i is synonymous with the definition in general formula (1), and m is synonymous with n1 in general formula (1).

[0056] In general formula (5a), R 3 This represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Examples of hydrocarbon groups having 1 to 8 carbon atoms include those with R. 1 The same hydrocarbon group. As R 3 From the viewpoint of ease of acquisition and heat resistance of the hardened material, hydrogen atoms, methyl groups, and ethyl groups are preferred, with hydrogen atoms and ethyl groups being particularly preferred. 3The substitution position can be any of the adjacent, intermediate, or anti-position, but intermediate and anti-position are preferred.

[0057] In general formula (5b), the vinyl group can be substituted at any of the ortho, meta, or para positions, but is preferably meta or para, or a mixture thereof.

[0058] The aromatic vinyl compound (b) represented by general formula (5) requires a monovinyl compound (the compound represented by general formula (5a)) as an essential component, and may also include a divinyl compound (the compound represented by general formula (5b)). The more divinyl compound is added, the higher the molecular weight of the polyhydroxy resin (A). Therefore, the amount of the compound can be adjusted while considering the molecular weight of the polyhydroxy resin (a) in order to achieve the target molecular weight. The monovinyl compound becomes the substituent R represented by formula (2) through an addition reaction. 2 Or R 4 This demonstrates the effect of reducing dielectric properties.

[0059] Examples of monovinyl compounds include vinyl aromatic compounds such as styrene, vinylnaphthalene, vinyl biphenyl, and α-methylstyrene; nucleoalkyl-substituted vinyl aromatic compounds such as o-methylstyrene, m-methylstyrene, p-methylstyrene, o-dimethylstyrene, p-dimethylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene, ethylvinyl biphenyl, and ethylvinylnaphthalene; and cyclic vinyl aromatic compounds such as indene, acenaphthene, benzothiophene, and coumarone. Styrene and ethylvinylbenzene are preferred.

[0060] These can be used individually or in combination of two or more.

[0061] Examples of divinyl compounds include divinylbenzene, divinylnaphthalene, divinylbiphenyl, and other divinyl aromatic compounds. Divinylbenzene is preferred.

[0062] These can be used individually or in combination of two or more.

[0063] Regarding the proportions of the monovinyl compound and the divinyl compound, relative to the total amount of the vinyl compound, the monovinyl compound may be 15% to 50% by mass and the divinyl compound may be 50% to 85% by mass. The monovinyl compound is preferably 30% to 50% by mass, more preferably 40% to 50% by mass. The divinyl compound is preferably 50% to 70% by mass, more preferably 50% to 60% by mass.

[0064] The polyhydroxy resin (a) is obtained by reacting dicyclopentadiene with a phenol represented by the following general formula (7) in the presence of a Lewis acid.

[0065] [Chemistry 5]

[0066]

[0067] Here, R 1 And i is synonymous with the definition in general formula (1).

[0068] The phenolic hydroxyl equivalent (g / eq.) of the polyhydroxy resin (a) is preferably 160-220, more preferably 165-210, and even more preferably 170-200.

[0069] The content obtained by GPC is preferably in the range of 10 area% or less for m=0, 50 area% to 90 area% for m=1, and 0 area% to 50 area% for m=2 or more.

[0070] Examples of phenols represented by the general formula (7) include: phenol, cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, tert-butylphenol, hexylphenol, cyclohexylphenol, phenylphenol, tolylphenol, benzylphenol, α-methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(tert-butyl)phenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, xylylphenol, dibenzylphenol, bis(α-methylbenzyl)phenol, methylethylphenol, methylpropylphenol, methyl isopropylphenol, methylbutylphenol, methyl tert-butylphenol, methyl allylphenol, tolylphenylphenol, etc. From the viewpoint of ease of acquisition and reactivity when forming a hardened product, phenol, cresol, phenylphenol, dimethylphenol, and diphenylphenol are preferred, with cresol and dimethylphenol being particularly preferred.

[0071] The catalyst used in the reaction is a Lewis acid, specifically boron trifluoride, boron trifluoride-phenol complex, boron trifluoride-ether complex, aluminum chloride, tin chloride, zinc chloride, ferric chloride, etc., among which, in terms of ease of operation, boron trifluoride-ether complex is preferred. In the case of boron trifluoride-ether complex, the amount of catalyst used is 0.001 to 20 parts by mass relative to 100 parts by mass of dicyclopentadiene, preferably 0.5 to 10 parts by mass.

[0072] Regarding the ratio of phenol to dicyclopentadiene in the reaction, the ratio of dicyclopentadiene to phenol is 0.08 to 0.80 mol, preferably 0.09 to 0.60 mol, more preferably 0.10 to 0.50 mol, even more preferably 0.10 to 0.40 mol, and particularly preferably 0.10 to 0.20 mol.

[0073] The reaction is preferably carried out by loading phenols and catalysts into a reactor and adding dicyclopentadiene dropwise over a period of 0.1 to 10 hours, preferably 0.5 to 8 hours, and more preferably 1 to 6 hours.

[0074] The reaction temperature is preferably 50℃ to 200℃, more preferably 100℃ to 180℃, and even more preferably 120℃ to 160℃. The reaction time is preferably 1 hour to 10 hours, more preferably 3 hours to 10 hours, and even more preferably 4 hours to 8 hours.

[0075] After the reaction is complete, alkalis such as sodium hydroxide, potassium hydroxide, and calcium hydroxide are added to deactivate the catalyst. Then, solvents such as toluene, xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone are added to dissolve the catalyst. After washing with water, the solvent is recovered under reduced pressure, thereby obtaining the dicyclopentadiene phenol resin represented by the target general formula (3). Furthermore, it is preferable to react as completely as possible with the dicyclopentadiene and recover the unreacted phenolic raw material under reduced pressure.

[0076] During the reaction, solvents such as 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, or ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether can also be used as needed.

[0077] As a reaction method for introducing the aromatic skeleton structure of formula (2) or formula (3) into a polyhydroxy resin (a), it is a method of reacting an aromatic vinyl compound (b) with the polyhydroxy resin (a) at a predetermined ratio. Regarding the reaction ratio, the amount of aromatic vinyl compound (b) relative to 1 mole of phenolic hydroxyl groups in the polyhydroxy resin (a) is 0.05 to 2.0 moles, more preferably 0.1 to 1.0 moles, further preferably 0.15 to 0.80 moles, and particularly preferably 0.30 to 0.70 moles.

[0078] The catalyst used in the reaction is an acid catalyst. Specifically, examples include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, and p-toluenesulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride; and solid acids such as activated clay, silica-alumina, and zeolite. Among these, p-toluenesulfonic acid is preferred for ease of operation. In the case of p-toluenesulfonic acid, the amount of catalyst used is 0.001 to 20 parts by weight relative to 100 parts by weight of the polyhydroxy resin (a), preferably 0.5 to 10 parts by weight.

[0079] The reaction is preferably carried out by loading the polyhydroxy resin (a), catalyst and solvent into a reactor, dissolving them, and then adding the aromatic vinyl compound (b) dropwise over a period of 0.1 hours to 10 hours, preferably 0.5 hours to 8 hours, and more preferably 0.5 hours to 5 hours.

[0080] The reaction temperature is preferably 50℃ to 200℃, more preferably 100℃ to 180℃, and even more preferably 120℃ to 160℃. The reaction time is preferably 1 hour to 10 hours, more preferably 3 hours to 10 hours, and even more preferably 4 hours to 8 hours.

[0081] After the reaction is complete, alkalis such as sodium hydroxide, potassium hydroxide, and calcium hydroxide are added to deactivate the catalyst. Then, solvents such as toluene, xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone are added to dissolve the catalyst. After washing with water, the solvent is recovered under reduced pressure, thereby obtaining the target phenolic resin.

[0082] Solvents used in the reaction may 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; or ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether. These solvents may be used alone or in combination of two or more.

[0083] The epoxy resin of the present invention is represented by general formula (6). The epoxy resin is obtained by reacting epichlorohydrin or other epihaloalcohols with the polyhydroxy resin (A) of the present invention. The reaction is carried out according to existing known methods.

[0084] In general formula (6), R 1 R 2 The definitions of 、 and i are synonyms with those in general formula (1), and n3 is synonym of n1 in general formula (1).

[0085] As a method of epoxidation, it can be obtained, for example, by adding an alkali metal hydroxide such as sodium hydroxide in the form of a solid or viscous aqueous solution to a mixture of phenolic resin and an excess molar amount of epihalohydrin relative to the hydroxyl groups of the phenolic resin, and reacting it at a reaction temperature of 30°C to 120°C for 0.5 hours to 10 hours; or by adding a quaternary ammonium salt such as tetraethylammonium chloride as a catalyst to the phenolic resin and an excess molar amount of epihalohydrin, reacting it at a temperature of 50°C to 150°C for 1 hour to 5 hours, and then adding an alkali metal hydroxide such as sodium hydroxide in the form of a solid or viscous aqueous solution to the resulting polyhalohydrin ether, and reacting it at a temperature of 30°C to 120°C for 1 hour to 10 hours.

[0086] In the reaction, the amount of epihaloalcohol used relative to the hydroxyl groups of the phenolic resin is 1 to 20 moles, preferably 2 to 8 moles. Additionally, the amount of alkali metal hydroxide used relative to the hydroxyl groups of the phenolic resin is 0.85 to 1.15 moles.

[0087] Since the epoxy resin obtained in these reactions contains unreacted epihalools and alkali metal halides, the unreacted epihalools can be removed by evaporation from the reaction mixture, and the alkali metal halides can be removed by extraction with water, filtration, etc., thereby obtaining the target epoxy resin.

[0088] The epoxy equivalent (g / eq.) of the epoxy resin of the present invention is preferably 200 to 4000, more preferably 220 to 2000, and even more preferably 250 to 700. In particular, when dicyandiamide is used as a curing agent, the epoxy equivalent is preferably 300 or more in order to prevent the crystallization of dicyandiamide on the prepreg.

[0089] As the content obtained by GPC, the molecular weight distribution of the polyhydroxy resin (a) or phenolic resin used as raw material is kept roughly the same. In general formula (6), it is preferably in the range of n3=0 with a volume of 10 area% or less, n3=1 with a volume of 40 area% to 90 area%, and n3=2 or more with a volume of 0 area% to 60 area%.

[0090] The total chlorine content is preferably below 2000 ppm, and more preferably below 1500 ppm.

[0091] The epoxy resin of the present invention exhibits low viscosity, with a melt viscosity of 0.01 Pa·s to 1.0 Pa·s at 150°C. Preferably, it is 0.05 Pa·s to 0.7 Pa·s, more preferably 0.1 Pa·s to 0.5 Pa·s.

[0092] The epoxy resin composition of the present invention can be obtained by using the polyhydroxy resin of the present invention and / or the epoxy resin of the present invention. The epoxy resin composition of the present invention uses epoxy resin and a curing agent as essential components. As an embodiment, 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, or part or all of the curing agent is the polyhydroxy resin of the present invention, and part or all of the epoxy resin is the epoxy resin of the present invention.

[0093] Preferably, at least 30% by mass of the curing agent is the polyhydroxy resin of the present invention, or at least 30% by mass of the epoxy resin is the epoxy resin of the present invention. More preferably, it contains 50% by mass or more, and even more preferably 70% by mass. With less than that, there is a risk of deterioration in dielectric properties.

[0094] In other words, if the curing agent is 30% or more of the polyhydroxy resin of the present invention, the epoxy resin need not be the epoxy resin of the present invention; if the polyhydroxy resin of the present invention is less than 30% by mass of the curing agent, then the epoxy resin must be 30% or more of the epoxy resin of the present invention.

[0095] As the epoxy resin used to obtain the epoxy resin composition of the present invention, one or more of various epoxy resins may be used in combination as needed.

[0096] As compatible epoxy resins, any common epoxy resin having two or more epoxy groups in its 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, bisphenol S type epoxy resin, disulfide type epoxy resin, resorcinol type epoxy resin, biphenyl arylalkylphenol type epoxy resin, naphthol type epoxy resin, phenolic varnish type epoxy resin, and aromatic modified epoxy resins. Trifunctional epoxy resins such as phenolic varnish epoxy resins, cresol phenolic varnish epoxy resins, alkylphenolic varnish epoxy resins, bisphenolic varnish epoxy resins, binatol type epoxy resins, naphthol phenolic varnish epoxy resins, β-naphthol aralkyl type epoxy resins, dinaphthol aralkyl type epoxy resins, α-naphthol aralkyl type epoxy resins, triphenylmethane type epoxy resins, and tetrafunctional epoxy resins such as tetraphenylethane type epoxy resins, and other epoxy resins not included in this invention. Cyclopentadiene-type epoxy resins, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolethane polyglycidyl ether, pentaerythritol polyglycidyl ether and other polyol polyglycidyl ethers, propylene glycol diglycidyl ether and other alkyldiol-type epoxy resins, cyclohexanediol diglycidyl ether and other aliphatic cyclic epoxy resins, dimer acid polyglycidyl esters and other glycidyl esters. The range of epoxy resins includes, but is not limited to, glycidylamine-type epoxy resins such as phenyl diglycidylamine, tri-diglycidylamine, diaminodiphenylmethane tetraglycidylamine, and aminophenol-type epoxy resins; alicyclic epoxy resins such as Celloxide 2021P (manufactured by Daicel Co., Ltd.); phosphorus-containing epoxy resins; bromine-containing epoxy resins; urethane-modified epoxy resins; and epoxy resins containing oxazolidinone rings. Furthermore, these epoxy resins can be used alone or in combination of two or more. From the viewpoint of ease of acquisition, it is preferable to use epoxy resin represented by the following general formula (8), or dicyclopentadiene type epoxy resin, naphthol type epoxy resin, phenolic varnish type epoxy resin, aromatic modified phenolic varnish type epoxy resin, cresol varnish type epoxy resin, α-naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, phosphorus-containing epoxy resin, or epoxy resin containing an oxazolidinone ring.

[0097] [Chemistry 6]

[0098]

[0099] Here, R 5 Alkyl groups that independently represent hydrocarbon groups having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl, etc., which may be the same as or different from each other.

[0100] X represents a divalent organic group, such as alkylene such as methylene, ethylene, isopropylene, isobutylene, hexafluoroisopropylene, -CO-, -O-, -S-, -SO2-, -SS-, or alkylene represented by formula (8a).

[0101] R 6 Independently representing hydrogen atoms or hydrocarbon groups with one or more carbon atoms, such as methyl, which may be the same or different from each other.

[0102] Ar is a benzene ring or a naphthalene ring, which may have alkyl, alkoxy, aryl, aralkyl, aryl, or aralkyloxy groups having 1 to 10 carbon atoms as substituents.

[0103] As a curing agent, in addition to the polyhydroxy resin (A) of general formula (1), one or more commonly used curing agents such as various phenolic resins, acid anhydrides, amines, cyanate esters, reactive esters, hydrazides, acid polyesters, and aromatic cyanate esters may be used as needed. When using these curing agents, the amount of curing agent used is preferably 70% or less by mass of the total curing agent, more preferably 50% or less by mass. If the proportion of the curing agent used is too high, there is a risk of deterioration of the dielectric properties of the epoxy resin composition.

[0104] In the epoxy resin composition of the present invention, the molar ratio of active hydrogen groups of the curing agent to 1 mole of epoxy groups in the total epoxy resin is preferably 0.2 mol to 1.5 mol, more preferably 0.3 mol to 1.4 mol, further preferably 0.5 mol to 1.3 mol, and particularly preferably 0.8 mol to 1.2 mol. Outside of these ranges, there is a risk of incomplete curing and failure to obtain good cured properties. For example, when using phenolic resin-based or amine-based curing agents, approximately equimolar amounts of active hydrogen groups are prepared relative to the epoxy groups. When using anhydride-based curing agents, 0.5 mol to 1.2 mol, preferably 0.6 mol to 1.0 mol, of anhydride groups are prepared relative to 1 mole of epoxy groups. When using the phenolic resin of the present invention alone as a curing agent, it is ideally used in the range of 0.9 mol to 1.1 mol relative to 1 mole of epoxy resin.

[0105] In this invention, the term "active hydrogen group" refers to a functional group possessing active hydrogen that reacts with epoxy groups (including functional groups possessing potential active hydrogen that can generate active hydrogen through hydrolysis, etc., or functional groups exhibiting equivalent curing effects). Specifically, examples include anhydride groups, carboxyl groups, amino groups, and phenolic hydroxyl groups. Furthermore, regarding active hydrogen groups, 1 mole of carboxyl or phenolic hydroxyl group is counted as 1 mole, and amino (NH2) groups are counted as 2 moles. Additionally, when the active hydrogen group is not clearly defined, the active hydrogen equivalent can be determined by measurement. For example, a monoepoxy resin such as phenyl glycidyl ether with a known epoxy equivalent can be reacted with a curing agent with an unknown active hydrogen equivalent, and the amount of monoepoxy resin consumed can be measured to determine the active hydrogen equivalent of the curing agent used.

[0106] Specific examples of phenolic resin-based curing agents that can be used in the epoxy resin compositions of the present invention include: bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, tetrabromobisphenol A, dihydroxydiphenyl sulfide, 4,4'-thiobis(3-methyl-6-tert-butylphenol), and other bisphenols, or catechol, resorcinol, methylresorcinol, hydroquinone, etc. Dihydroxybenzenes such as monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, and di-tert-butylhydroquinone; or hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, and trihydroxynaphthalene; or phosphorus-containing phenolic hardeners such as LC-950PM60 (manufactured by Shin-AT&C); or Shonol BRG-555 (manufactured by Aica Industries). Kogyo Co., Ltd. manufactures phenolic varnish resins such as phenolic resin and cresol phenolic resin, DC-5 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.), phenolic resins containing a triazine skeleton, aromatic modified phenolic varnish resins, bisphenol A phenolic varnish resins, Resitop TPM-100 (manufactured by Kunei Chemical Industry Co., Ltd.), trihydroxyphenylmethane type phenolic varnish resins, naphthol phenolic varnish resins, and other condensates of phenols, naphthols, and / or bisphenols with aldehydes, SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.). This includes phenolic compounds such as phenolic resins (manufactured by the company), condensates of phenols and / or naphthols and / or bisphenols with xylene diol, condensates of phenols and / or naphthols with isopropenyl acetophenone, reaction products of phenols and / or naphthols and / or bisphenols with dicyclopentadiene, reaction products of phenols and / or naphthols and / or bisphenols with divinylbenzene, reaction products of phenols and / or naphthols and / or bisphenols with terpenes, and condensates of phenols and / or naphthols and / or bisphenols with biphenyl crosslinking agents, as well as polybutadiene-modified phenolic resins and spirocyclic phenolic resins. From the viewpoint of ease of acquisition, phenolic resins, dicyclopentadiene phenolic resins, trihydroxyphenylmethane-type phenolic resins, and aromatic-modified phenolic resins are preferred.

[0107] Phenolic resins for varnishes can be obtained from phenols and crosslinking agents. Examples of phenols include phenol, cresol, xylenol, butylphenol, pentylphenol, nonylphenol, butylmethylphenol, trimethylphenol, and phenylphenol. Examples of naphthols include 1-naphthol and 2-naphthol. Bisphenols, which are used as curing agents in the phenolic resin system, can also be listed. Examples of aldehydes used as crosslinking agents include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, pentanal, hexanal, benzaldehyde, chloral, bromoal, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, hexadialdehyde, heptadialdehyde, sebacaldehyde, acrolein, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, and hydroxybenzaldehyde. Examples of biphenyl-based crosslinking agents include bis(hydroxymethyl)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, and bis(chloromethyl)biphenyl.

[0108] Specifically, examples of anhydride-based curing agents include: maleic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, 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, trimellitic anhydride, methylnadic anhydride, copolymers of styrene monomer and maleic anhydride, copolymers of indene and maleic anhydride, etc.

[0109] Specifically, examples of amine-based curing agents include: diethylenetriamine, triethylenetetramine, m-phenylenediamine, isophorone diamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, polyetheramines, biguanide compounds, dicyandiamine, anisidine and other aromatic amines, as well as amine compounds such as polyamide amines, which are condensations of dimer acids and polyamines.

[0110] As a cyanate ester compound, there is no particular limitation as long as it is a compound having two or more cyanate groups (cyanate ester groups) in one molecule. Examples include: phenolic varnish type cyanate ester curing agents such as phenolic varnish type and alkylphenolic varnish type; naphthol aralkyl type cyanate ester curing agents; biphenyl alkyl type cyanate ester curing agents; dicyclopentadiene type cyanate ester curing agents; bisphenol type cyanate ester curing agents such as bisphenol A type, bisphenol F type, bisphenol E type, tetramethylbisphenol F type, and bisphenol S type; and some of these triazine-modified prepolymers, etc. Specific examples of cyanate-based curing agents include: bisphenol A dicyanate, polyphenol cyanates (oligomeric (3-methylene-1,5-phenylene cyanate), bis(3-methyl-4-cyanate phenyl)methane, bis(3-ethyl-4-cyanate phenyl)methane, bis(4-cyanate phenyl)-1,1-ethane, 4,4-dicyanate-diphenyl ester, 2,2-bis(4-cyanate phenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis( Difunctional cyanate resins such as 4-cyanoester phenylmethane, bis(4-cyanoester-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanoester phenyl-1-(methylethylidene))benzene, bis(4-cyanoester phenyl) sulfide, and bis(4-cyanoester phenyl) ether; cyanates of triphenols such as tri(4-cyanoester phenyl)-1,1,1-ethane and bis(3,5-dimethyl-4-cyanoester phenyl)-4-cyanoester phenyl-1,1,1-ethane; polyfunctional cyanate resins derived from phenolic varnishes, cresol varnishes, and phenolic resins containing a dicyclopentadiene structure; and triazine-modified prepolymers of some of these cyanate resins. One or more of these may be used.

[0111] There are no particular limitations on the active ester-based curing agent, but compounds with two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxyl compounds, are generally preferred. The active ester-based curing agent is preferably obtained through a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxyl compound and / or a thiol compound. Particularly from the viewpoint of improving heat resistance, active ester-based curing agents obtained from carboxylic acid compounds and hydroxyl compounds are preferred, and more preferably active ester-based curing agents obtained from carboxylic acid compounds and phenolic compounds and / or naphthol compounds. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenolic or naphthol compounds include: hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 2,6-dihydroxynaphthol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, pyroglucinol, dicyclopentadienyldiphenol, dicyclopentadienylphenol resin (as a precursor of the epoxy resin of this invention), phenolic varnish, etc. One or more reactive ester-based curing agents may be used. As an active ester curing agent, the preferred active ester curing agents are those containing a dicyclopentadienyl diphenol structure, those containing a naphthalene structure, those that are acetylated derivatives of phenolic varnishes, and those that are benzoyl derivatives of phenolic varnishes. Among these, the active ester curing agent containing a dicyclopentadienyl diphenol structure and which is a precursor of the epoxy resin of the present invention is more preferably an active ester curing agent containing a dicyclopentadienyl diphenol structure and which is a precursor of the epoxy resin of the present invention.

[0112] Other hardeners include, specifically: phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, imidazoles such as 2-methylimidazolium, 2-phenylimidazolium, 2-ethyl-4-methylimidazolium, 2-undecylimidazolium, and 1-cyanoethyl-2-methylimidazolium, imidazole salts that are salts of imidazoles with trimellitic acid, isocyanuric acid, or boron, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclic compounds, salts of diazabicyclic compounds with phenols or phenolic varnishes and resins, complexes of boron trifluoride with amines or ethers, aromatic phosphonium salts, or aromatic iodonium salts.

[0113] Curing accelerators may be used in the epoxy resin composition as needed. Examples of usable curing accelerators include: imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, and 1,8-diaza-bicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane; and metal compounds such as tin octoate. When using a curing accelerator, the amount of curing accelerator used is preferably 0.02 to 5 parts by weight relative to 100 parts by weight of the epoxy resin component in the epoxy resin composition of the present invention. By using a curing accelerator, the curing temperature can be reduced or the curing time can be shortened.

[0114] Organic solvents or reactive diluents can be used in epoxy resin compositions to adjust viscosity.

[0115] Examples of organic solvents include: amides such as N,N-dimethylformamide and N,N-dimethylacetamide; 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, and cyclohexanone; alcohols such as methanol, ethanol, 1-methoxy-2-propanol, 2-ethyl-1-hexanol, benzyl alcohol, ethylene glycol, propylene glycol, butyl diethylene glycol, and pine oil; and butyl acetate and methoxybutyl acetate. Acetates such as esters, methyl cellulose acetate, ethyl cellulose acetate, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl alcohol acetate, etc.; or benzoate esters such as methyl benzoate, ethyl benzoate, butyl cellulose acetate, etc.; or carbitols such as methyl carbitol, ethyl carbitol, butyl carbitol, etc.; or aromatic hydrocarbons such as benzene, toluene, xylene; or dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone, etc., but not limited to these.

[0116] Examples of reactive diluents include: allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, tolyl glycidyl ether and other monofunctional glycidyl ethers, or neodecanoic acid glycidyl esters and other monofunctional glycidyl esters, but are not limited to these.

[0117] These organic solvents or reactive diluents are preferably used alone or in mixtures in the resin composition at a non-volatile content of 90% or less. The appropriate type or amount can be selected according to the application. For example, in printed circuit board applications, polar solvents with boiling points below 160°C, such as methyl ethyl ketone, acetone, and 1-methoxy-2-propanol, are preferred, and the amount used in the resin composition, based on the non-volatile content, is preferably 40% to 80% by mass. Furthermore, in adhesive film applications, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred, and the amount used, based on the non-volatile content, is preferably 30% to 60% by mass.

[0118] Epoxy resin compositions may also be formulated with other thermosetting resins and thermoplastic resins without impairing their properties. Examples include: phenolic resins, benzoxazine resins, bismaleimide resins, bismaleimide triazine resins, acrylic resins, petroleum resins, indene resins, coumarone indene resins, phenoxy resins, polyurethane resins, polyester resins, polyamide resins, polyimide resins, polyamide-imide resins, polyetherimide resins, polyphenylene ether resins, modified polyphenylene ether resins, polyethersulfone resins, polysulfone resins, polyetheretherketone resins, polyphenylene sulfide resins, polyvinyl formal resins, polysiloxane compounds, alkylene resins containing reactive functional groups such as hydroxyl-containing polybutadiene, but are not limited to these.

[0119] To improve the flame retardancy of the resulting cured product, various known flame retardants can be used in the epoxy resin composition. Examples of usable flame retardants include halogen-based, phosphorus-based, nitrogen-based, silicone-based, inorganic, and organometallic salt-based flame retardants. From an environmental perspective, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants can be used alone or in combination of two or more.

[0120] Phosphorus-based flame retardants can be any type of inorganic phosphorus compound or organic phosphorus compound. Examples of inorganic phosphorus compounds include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, as well as inorganic nitrogen- and phosphorus-containing compounds such as phosphoramides. Examples of organophosphorus compounds include aliphatic phosphate esters, phosphate ester compounds, condensed phosphate esters such as PX-200 (manufactured by Daihachi Chemical Co., Ltd.), polyphosphazenes, phosphonic acid compounds, hypophosphonic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen- and phosphorus-containing compounds, and other general organophosphorus compounds, or metal salts of hypophosphonic acids. In addition, examples include cyclic organophosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, or phosphorus-containing epoxy resins or phosphorus-containing curing agents as derivatives obtained by reacting these compounds with compounds such as epoxy resins or phenolic resins.

[0121] The amount of flame retardant used can be appropriately selected based on the type of phosphorus-based flame retardant, the composition of the epoxy resin composition, and the desired degree of flame retardancy. For example, the phosphorus content in the organic components (excluding organic solvents) of the epoxy resin composition is preferably 0.2% to 4% by mass, more preferably 0.4% to 3.5% by mass, and even more preferably 0.6% to 3% by mass. If the phosphorus content is too low, it may be difficult to ensure flame retardancy; if it is too high, it may adversely affect heat resistance. In addition, when using phosphorus-based flame retardants, flame retardant additives such as magnesium hydroxide may also be used in combination.

[0122] Fillers may be used in epoxy resin compositions as needed. Specifically, examples include: 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, microparticle rubber, silicone rubber, thermoplastic elastomers, carbon black, pigments, etc. One reason for using fillers is generally to improve impact resistance. Furthermore, when using metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide, they act as flame retardant additives, thus improving flame retardancy. The preferred amount of these fillers relative to the overall epoxy resin composition is 1% to 150% by mass, more preferably 10% to 70% by mass. If the amount of filler is too large, there is a risk of reduced adhesion required for use in laminates, which in turn may cause the hardened material to become brittle and fail to achieve sufficient mechanical properties. On the other hand, if the amount of filler is too small, there is a risk that the effects of the filler, such as improving the impact resistance of the hardened material, may not be realized.

[0123] When epoxy resin compositions are made into plate-shaped substrates, fibrous fillers are preferred in terms of dimensional stability and flexural strength. Glass fiber substrates woven into a mesh are more preferred.

[0124] The epoxy resin composition can be further formulated with various additives such as silane coupling agents, antioxidants, release agents, defoamers, emulsifiers, thixotropic agents, smoothers, flame retardants, and pigments as needed. The preferred amount of these additives relative to the epoxy resin composition is in the range of 0.01% to 20% by mass.

[0125] Epoxy resin compositions can be impregnated into fibrous substrates to produce prepregs used in printed wiring boards and the like. The fibrous substrate can be inorganic fibers such as glass, or woven or non-woven fabrics made of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, or aromatic polyamide resin, but is not limited to these. The method for manufacturing the prepreg from the epoxy resin composition is not particularly limited; for example, after impregnating and containing the epoxy resin composition in a resin varnish prepared by adjusting the viscosity with an organic solvent, the resin component is heated and dried to semi-harden (B-stage curing) to obtain the prepreg. For example, it can be heated and dried at 100°C to 200°C for 1 minute to 40 minutes. Here, the resin content in the prepreg is preferably 30% to 80% by mass.

[0126] Furthermore, to harden the prepreg, a hardening method commonly used in the manufacture of printed circuit boards (PCBs) can be used, but it is not limited to this. For example, when forming a PCB using a prepreg, one or more prepreg sheets are stacked, and metal foil is placed on one or both sides to form a laminate. The laminate is then heated and pressurized to make it integrally laminated. Here, copper, aluminum, brass, nickel, etc., can be used as the metal foil, and alloy or composite metal foils can also be used. Moreover, the prepreg can be hardened by pressurizing and heating the prepared laminate to obtain a PCB. In this case, it is preferable to set the heating temperature to 160°C to 220°C, the pressurization pressure to 5 MPa to 50 MPa, and the heating and pressurization time to 40 minutes to 240 minutes to obtain the desired hardened product. If the heating temperature is too low, the hardening reaction will not proceed sufficiently; if the heating temperature is too high, there is a risk that the epoxy resin composition will begin to decompose. Furthermore, if the pressure is too low, air bubbles may remain inside the resulting laminate, reducing its electrical properties. If the pressure is too high, the resin may flow before curing, making it impossible to obtain the desired thickness of the cured material. Moreover, if the heating and pressurizing time is too short, the curing reaction may not be sufficient. If the heating and pressurizing time is too long, thermal decomposition of the epoxy resin composition in the prepreg may occur, which is undesirable.

[0127] Epoxy resin compositions can be cured to obtain cured epoxy resin products using the same methods as known epoxy resin compositions. As for the method of obtaining the cured product, the same methods as known epoxy resin compositions can be used, such as injection molding, injection, potting, impregnation, drip coating, transfer molding, compression molding, etc., or by laminating resin sheets, resin-coated copper foil, prepregs, etc., and then heating and pressurizing to produce laminates. The curing temperature is typically 100°C to 300°C, and the curing time is typically about 1 hour to 5 hours.

[0128] The epoxy resin cured product of the present invention can take the form of a laminate, a molded product, an adhesive, a coating, a film, etc.

[0129] An epoxy resin composition was prepared, and the laminate and cured product were evaluated by heat curing. The result was an epoxy-curable resin composition exhibiting excellent low dielectric properties in the cured product. Specifically, the dielectric properties exhibited a relative permittivity of 3.00 or less, more preferably 2.90 or less, and a dielectric loss tangent of 0.015 or less, more preferably 0.010 or less. Furthermore, the glass transition temperature (Tg) of the cured product was 120°C or more, and could also be 150°C or more.

[0130] Example

[0131] The present invention has been specifically described by way of examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" means parts by mass, "%" means % by mass, and "ppm" means ppm by mass. In addition, the determination methods are performed by the following methods respectively.

[0132] • Hydroxyl equivalent:

[0133] The measurement is conducted according to Japanese Industrial Standards (JIS) K 0070, and the unit is expressed as "g / eq." Furthermore, unless otherwise specified, the hydroxyl equivalent of phenolic resin refers to the phenolic hydroxyl equivalent.

[0134] • Softening point:

[0135] The determination was performed according to JIS K 7234 standard using the ring and ball method. Specifically, an automatic softening point device (manufactured by Meitec Corporation, ASP-MG4) was used.

[0136] • Epoxy equivalent:

[0137] The determination was performed according to JIS K 7236 standard, and the unit is expressed as "g / eq.". Specifically, an automatic potentiometric titration apparatus (manufactured by Hiranuma Sangyo Co., Ltd., COM-1600ST) was used, with chloroform as the solvent, and tetraethylammonium bromide acetic acid solution was added. Titration was performed using a 0.1 mol / L perchloric acid-acetic acid solution.

[0138] Total chlorine content:

[0139] The determination was performed according to JIS K 7243-3 standard, and the unit is expressed in "ppm". Specifically, diethylene glycol monobutyl ether was used as the solvent, and after heating with 1 mol / L potassium hydroxide 1,2-propanediol solution, titration was performed using an automatic potentiometric titration apparatus (manufactured by Hiranuma Sangyo Co., Ltd., COM-1700) with 0.01 mol / L silver nitrate solution.

[0140] Melt viscosity:

[0141] The melt viscosity at 150°C was measured using an ICI viscosity measuring device (manufactured by Dong-A Industrial Co., Ltd., CV-1S).

[0142] • Relative permittivity and dielectric loss tangent:

[0143] The measurements were performed according to Institute of Printed Circuits (IPC) TM-650 2.5.5.9. Specifically, the samples were dried in an oven set to 105°C for 2 hours, cooled in a desiccant, and then evaluated using a material analyzer manufactured by Agilent Technologies. The relative permittivity and dielectric loss tangent at a frequency of 1 GHz were determined by capacitance method.

[0144] • Copper foil peel strength and interlayer adhesion:

[0145] According to JIS C 6481, the interlayer adhesion was measured between the seventh and eighth layers.

[0146] • GPC (Gel Permeation Chromatography) determination:

[0147] The apparatus used consisted of columns (TSKgel G4000HXL, TSKgel G3000HXL, and TSKgel G2000HXL, all manufactured by Tosoh Corporation) arranged in series within the main body (HLC-8220GPC, manufactured by Tosoh Corporation), with the column temperature set to 40°C. Tetrahydrofuran (THF) was used as the eluent, with a flow rate of 1 mL / min, and a differential refractive index detector was used. The sample was prepared by dissolving 0.1 g of the sample in 10 mL of THF and filtering it using a microfilter. Data processing was performed using a GPC-8020 model II version 6.00 manufactured by Tosoh Corporation.

[0148] ESI-MS:

[0149] The mass analysis was performed using a mass analyzer (manufactured by Shimadzu Corporation, LCMS-2020) with acetonitrile and water as the mobile phase, and the sample dissolved in acetonitrile was measured.

[0150] The abbreviations used in the examples and comparative examples are as follows.

[0151] [Epoxy Resin]

[0152] E1: Epoxy resin obtained in Example 6

[0153] E2: The epoxy resin obtained in Example 7

[0154] E3: The epoxy resin obtained in Example 8

[0155] E4: Epoxy resin obtained in Example 9

[0156] E5: The epoxy resin obtained in Example 10

[0157] EH1: The epoxy resin obtained in Synthesis Example 4

[0158] EH2: Phenol-dicyclopentadiene type epoxy resin (manufactured by DIC Corporation, HP-7200H, epoxy equivalent 280, softening point 83℃, melt viscosity at 150℃ 0.40 Pa·s)

[0159] [hardener]

[0160] P1: Phenolic resin obtained in Example 1

[0161] P2: Phenolic resin obtained in Example 2

[0162] P3: Phenolic resin obtained in Example 3

[0163] P4: Phenolic resin obtained in Example 4

[0164] P5: Phenolic resin obtained in Example 5

[0165] PH1: The phenolic resin obtained in Synthesis Example 1

[0166] PH2: The phenolic resin obtained in Synthesis Example 2

[0167] PH3: Aromatic modified phenolic resin obtained in Synthesis Example 3

[0168] PH4: Phenolic varnish resin (manufactured by Aike Industrial Co., Ltd., Shonol BRG-557, hydroxyl equivalent 105, softening point 80℃, melt viscosity at 150℃ 0.30 Pa·s)

[0169] [Hardening Accelerator]

[0170] C1: 2E4MZ: 2-Ethyl-4-methylimidazol (manufactured by Shikoku Chemical Industry Co., Ltd., Curezol 2E4MZ)

[0171] Synthesis example 1

[0172] 500 parts of 2,6-xylenol and 7.3 parts of 47% BF3 ether complex were charged into a reaction apparatus including a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and cooling tube, containing a separable glass flask. The mixture was heated to 100°C while stirring. While maintaining the same temperature, 67.6 parts of dicyclopentadiene (0.12 molar ratio relative to 2,6-xylenol) were added dropwise over 1 hour. The reaction was then carried out at 115°C–125°C for 4 hours, followed by the addition of 11 parts of calcium hydroxide. Then, 19 parts of a 10% oxalic acid aqueous solution were added. After dehydration at 160°C, the mixture was heated to 200°C under reduced pressure (5 mmHg) to evaporate unreacted reactants. 1320 parts of MIBK were added to dissolve the product, followed by washing with 400 parts of warm water (80°C) to separate and remove the lower aqueous layer. Subsequently, under reduced pressure of 5 mmHg, the MIBK was evaporated and removed by heating to 160 °C, yielding 164 parts of a reddish-brown phenolic resin (PH1). The hydroxyl equivalent was 195, and the softening point was 73 °C. The GPC contained 470 Mw, 440 Mn, 2.8% by area of ​​m=0 bulk, 86.2% by area of ​​m=1 bulk, and 11.0% by area of ​​bulks greater than m=2. The melt viscosity at 150 °C was 0.05 Pa·s.

[0173] Synthesis example 2

[0174] 361 parts of o-cresol and 5.9 parts of 47% BF3 ether complex were charged into the same reaction apparatus as in Synthesis Example 1, and the mixture was heated to 100°C with stirring. While maintaining the same temperature, 55.2 parts of dicyclopentadiene (0.13 molar ratio relative to o-cresol) were added dropwise over 1 hour. The reaction was then carried out at 115°C–125°C for 4 hours, and 9 parts of calcium hydroxide were added. Then, 16 parts of a 10% oxalic acid aqueous solution were added. Subsequently, the mixture was heated to 160°C for dehydration, and unreacted raw materials were evaporated by heating to 200°C under reduced pressure of 5 mmHg. 970 parts of MIBK were added to dissolve the product, and 290 parts of warm water at 80°C were added for washing, separating and removing the lower aqueous layer. Subsequently, MIBK was evaporated by heating to 160°C under reduced pressure of 5 mmHg to obtain 137 parts of a reddish-brown phenolic resin (PH2). The hydroxyl equivalent is 184, and the softening point is 78℃. In GPC, Mw is 460, Mn is 410, the m=0 volume content is 0.8% by area, the m=1 volume content is 75.5% by area, and the content of m=2 and above is 23.7% by area. The melt viscosity at 150℃ is 0.07 Pa·s.

[0175] Synthesis example 3

[0176] 105 parts of phenolic varnish resin (hydroxyl equivalent 105, softening point 130°C) and 0.1 parts of p-toluenesulfonic acid were charged into the same reaction apparatus as in Synthesis Example 1, and the temperature was raised to 150°C. While maintaining the same temperature, 94 parts of styrene were added dropwise over 3 hours, and stirring was continued for another hour at the same temperature. Subsequently, it was dissolved in 500 parts of MIBK and washed five times with water at 80°C. Then, MIBK was removed by vacuum distillation to obtain aromatic modified phenolic varnish resin (PH3). The hydroxyl equivalent was 199, and the softening point was 110°C. The melt viscosity at 150°C was 0.18 Pa·s.

[0177] Example 1

[0178] 100 parts of the phenolic resin (PH1) obtained in Synthesis Example 1, 1.0 part of p-toluenesulfonic acid / monohydrate, and 25 parts of MIBK were charged into the same reaction apparatus as in Synthesis Example 1, and the mixture was heated to 120°C while stirring. While maintaining the same temperature, 30 parts of divinylbenzene (manufactured by Aldrich, 55% divinylbenzene, 45% ethylvinylbenzene) (0.45 molar ratio relative to the phenolic resin) were added dropwise over 1 hour. The reaction was then carried out at 120°C–130°C for 4 hours. 280 parts of MIBK were added to dissolve the product, neutralized with 1.3 parts of sodium bicarbonate, and washed with 90 parts of warm water at 80°C to separate and remove the lower aqueous layer. Subsequently, the MIBK was evaporated by heating to 180°C under reduced pressure of 5 mmHg to obtain 123 parts of a reddish-brown phenolic resin (P1). The hydroxyl equivalent was 250, and the softening point was 81°C. The mass spectra obtained by electrospray ionization mass spectrometry (ESI-MS) (negative) were determined, and the results were confirmed to M- = 375, 507, 629, 639, 761. The GPC of the obtained phenolic resin (P1) is shown in the figure. Figure 1 In GPC, Mw is 740, Mn is 540, n=0 volume content is 4.9% by area, n=1 volume content is 53.3% by area, and n=2 or more volume content is 41.8% by area. The melt viscosity at 150℃ is 0.13 Pa·s.

[0179] Example 2

[0180] 100 parts of the phenolic resin (PH1) obtained in Synthesis Example 1, 1.0 part of p-toluenesulfonic acid / monohydrate, and 25 parts of MIBK were charged into the same reaction apparatus as in Synthesis Example 1, and the mixture was heated to 120°C while stirring. While maintaining the same temperature, 45 parts of divinylbenzene (manufactured by Aldrich, 55% divinylbenzene, 45% ethylvinylbenzene) (0.67 molar ratio relative to the phenolic resin) were added dropwise over 1 hour. The reaction was then carried out at 120°C–130°C for 4 hours. 310 parts of MIBK were added to dissolve the product, neutralized with 1.3 parts of sodium bicarbonate, and washed with 100 parts of warm water at 80°C to separate and remove the lower aqueous layer. Subsequently, the MIBK was evaporated by heating to 180°C under reduced pressure of 5 mmHg to obtain 139 parts of a reddish-brown phenolic resin (P2). The hydroxyl equivalent was 276, and the softening point was 71°C. The mass spectra obtained by ESI-MS (negative) were determined, and the results confirmed M- = 375, 507, 629, 639, 761. In the GPC, Mw was 800, Mn was 540, the content of n=0 was 6.5% by area, the content of n=1 was 51.1% by area, and the content of n=2 and above was 42.4% by area. The melt viscosity at 150℃ was 0.09 Pa·s.

[0181] Example 3

[0182] 80 parts of the phenolic resin (PH1) obtained in Synthesis Example 1, 0.8 parts of p-toluenesulfonic acid / monohydrate, and 20 parts of MIBK were charged into the same reaction apparatus as in Synthesis Example 1, and the mixture was heated to 120°C while stirring. While maintaining the same temperature, 48 parts of divinylbenzene (manufactured by Aldrich, 55% divinylbenzene, 45% ethylvinylbenzene) (0.90 molar ratio relative to the phenolic resin) were added dropwise over 1 hour. The reaction was then carried out at 120°C–130°C for 4 hours. 280 parts of MIBK were added to dissolve the product, neutralized with 1.1 parts of sodium bicarbonate, and washed with 90 parts of warm water at 80°C to separate and remove the lower aqueous layer. Subsequently, the MIBK was evaporated by heating to 180°C under reduced pressure of 5 mmHg to obtain 120 parts of a reddish-brown phenolic resin (P3). The hydroxyl equivalent was 306, and the softening point was 68°C. The mass spectra obtained by ESI-MS (negative) were determined, and the results confirmed M- = 375, 507, 629, 639, 761. The Mw in the GPC was 910, the Mn was 550, the n=0 volume content was 7.5% by area, the n=1 volume content was 48.9% by area, and the content of n=2 and above was 43.6% by area. The melt viscosity at 150℃ was 0.08 Pa·s.

[0183] Example 4

[0184] 93 parts of the phenolic resin (PH1) obtained in Synthesis Example 1, 0.9 parts of p-toluenesulfonic acid / monohydrate, and 23 parts of MIBK were charged into the same reaction apparatus as in Synthesis Example 1, and the mixture was heated to 120°C with stirring. While maintaining the same temperature, 41.8 parts of divinylbenzene (manufactured by Aldrich, 80% divinylbenzene, 20% ethylvinylbenzene) (0.90 molar ratio relative to the phenolic resin) were added dropwise over 1 hour. The reaction was then carried out at 120°C–130°C for 4 hours. 290 parts of MIBK were added to dissolve the product, neutralized with 1.2 parts of sodium bicarbonate, and washed with 90 parts of warm water at 80°C to separate and remove the lower aqueous layer. Subsequently, the MIBK was evaporated by heating to 180°C under reduced pressure of 5 mmHg to obtain 128 parts of a reddish-brown phenolic resin (P4). The hydroxyl equivalent was 281, and the softening point was 88°C. The mass spectra obtained by ESI-MS (negative) were determined, and the results confirmed M- = 375, 507, 629, 639, 761. The Mw in the GPC was 1400, the Mn was 650, the n=0 volume content was 3.1% by area, the n=1 volume content was 43.3% by area, and the content of n=2 and above was 53.6% by area. The melt viscosity at 150℃ was 0.33 Pa·s.

[0185] Example 5

[0186] 100 parts of the phenolic resin (PH2) obtained in Synthesis Example 2, 1.0 part of p-toluenesulfonic acid / monohydrate, and 25 parts of MIBK were charged into the same reaction apparatus as in Synthesis Example 1, and the mixture was heated to 120°C with stirring. While maintaining the same temperature, 45 parts of divinylbenzene (manufactured by Aldrich, 55% divinylbenzene and 45% ethylvinylbenzene) (0.45 molar ratio relative to the phenolic resin) were added dropwise over 1 hour. The reaction was then carried out at 120°C to 130°C for 4 hours. 310 parts of MIBK were added to dissolve the product, neutralized with 1.3 parts of sodium bicarbonate, and washed with 100 parts of warm water at 80°C to separate and remove the lower aqueous layer. Subsequently, the MIBK was evaporated by heating to 180°C under reduced pressure of 5 mmHg to obtain 140 parts of a reddish-brown phenolic resin (P5). The hydroxyl equivalent was 255, and the softening point was 77°C. The mass spectra obtained by ESI-MS (negative) were determined, and the results confirmed M- = 347, 479, 587, 611, 719. In GPC, Mw was 780, Mn was 500, the content of n=0 was 3.0% by area, the content of n=1 was 45.1% by area, and the content of n=2 and above was 51.9% by area. The melt viscosity at 150℃ was 0.20 Pa·s.

[0187] Example 6

[0188] 100 parts of the phenolic resin (P1) obtained in Example 1, 185 parts of epichlorohydrin, and 55 parts of diethylene glycol dimethyl ether were added to a reaction apparatus including a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and cooling tube, and the mixture was heated to 65°C. Under reduced pressure of 125 mmHg, while maintaining a temperature of 63°C–67°C, 35.9 parts of a 49% sodium hydroxide aqueous solution were added dropwise over 4 hours. During this period, the epichlorohydrin was azeotropically reacted with water, and the outflowing water was sequentially removed from the system. After the reaction was completed, the epichlorohydrin was recovered at 5 mmHg and 180°C, and 290 parts of MIBK were added to dissolve the product. Subsequently, 90 parts of water were added to dissolve the byproduct salt, and the mixture was allowed to stand to separate and remove the lower layer of brine. After neutralization with a phosphoric acid aqueous solution, the resin solution was washed with water and filtered until the washing liquid became neutral. Under reduced pressure of 5 mmHg, the mixture was heated to 180 °C, and MIBK was removed by distillation to obtain 117 parts of a reddish-brown epoxy resin (E1). This resin had an epoxy equivalent of 315, a total chlorine content of 590 ppm, and a softening point of 62 °C. The GPC of the obtained epoxy resin (E1) is shown in [Figure / Table / Issue]. Figure 2 In GPC, Mw is 890, Mn is 580, the content of k=0 is 3.8% by area, the content of k=1 is 50.7% by area, and the content of k=2 and above is 45.5% by area. The melt viscosity at 150℃ is 0.18 Pa·s.

[0189] Example 7

[0190] 102 parts of the phenolic resin (P2) obtained in Example 2, 171 parts of epichlorohydrin, and 51 parts of diethylene glycol dimethyl ether were added to a reaction apparatus including a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and cooling tube, and the mixture was heated to 65°C. Under reduced pressure of 125 mmHg, while maintaining a temperature of 63°C–67°C, 33.3 parts of a 49% sodium hydroxide aqueous solution were added dropwise over 4 hours. During this period, the epichlorohydrin was azeotropically reacted with water, and the outflowing water was sequentially removed from the system. After the reaction was completed, the epichlorohydrin was recovered at 180°C and 5 mmHg, and 290 parts of MIBK were added to dissolve the product. Subsequently, 90 parts of water were added to dissolve the byproduct salt, and the mixture was allowed to stand to separate and remove the lower layer of brine. After neutralization with a phosphoric acid aqueous solution, the resin solution was washed with water and filtered until the washing liquid became neutral. Under reduced pressure of 5 mmHg, the mixture was heated to 180 °C, and MIBK was removed by distillation to obtain 118 parts of a reddish-brown epoxy resin (E2). This resin had an epoxy equivalent of 345, a total chlorine content of 510 ppm, and a softening point of 57 °C. In the GPC, Mw was 1180, Mn was 590, the k=0 bulk content was 5.5% by area, the k=1 bulk content was 48.0% by area, and the content of k=2 and above was 46.5% by area. The melt viscosity at 150 °C was 0.14 Pa·s.

[0191] Example 8

[0192] 101 parts of the phenolic resin (P3) obtained in Example 3, 153 parts of epichlorohydrin, and 46 parts of diethylene glycol dimethyl ether were added to a reaction apparatus including a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and cooling tube, and the mixture was heated to 65°C. Under reduced pressure of 125 mmHg, while maintaining a temperature of 63°C–67°C, 29.7 parts of a 49% sodium hydroxide aqueous solution were added dropwise over 4 hours. During this period, the epichlorohydrin was azeotropically reacted with water, and the outflowing water was sequentially removed from the system. After the reaction was completed, the epichlorohydrin was recovered at 5 mmHg and 180°C, and 280 parts of MIBK were added to dissolve the product. Subsequently, 80 parts of water were added to dissolve the byproduct salt, and the mixture was allowed to stand to separate and remove the lower layer of brine. After neutralization with a phosphoric acid aqueous solution, the resin solution was washed with water and filtered until the washing liquid became neutral. Under reduced pressure of 5 mmHg, the mixture was heated to 180 °C, and MIBK was removed by distillation to obtain 113 parts of a reddish-brown epoxy resin (E3). It was a resin with an epoxy equivalent of 373, a total chlorine content of 530 ppm, and a semi-solid state at room temperature. In the GPC, Mw was 1670, Mn was 610, the k=0 bulk content was 6.1% by area, the k=1 bulk content was 45.5% by area, and the content of k=2 and above was 48.4% by area. The melt viscosity at 150 °C was 0.15 Pa·s.

[0193] Example 9

[0194] 101 parts of the phenolic resin (P4) obtained in Example 4, 166 parts of epichlorohydrin, and 50 parts of diethylene glycol dimethyl ether were added to a reaction apparatus including a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and cooling tube, and the mixture was heated to 65°C. Under reduced pressure of 125 mmHg, while maintaining a temperature of 63°C–67°C, 32.3 parts of a 49% sodium hydroxide aqueous solution were added dropwise over 4 hours. During this period, the epichlorohydrin was azeotropically reacted with water, and the outflowing water was sequentially removed from the system. After the reaction was completed, the epichlorohydrin was recovered at 5 mmHg and 180°C, and 280 parts of MIBK were added to dissolve the product. Subsequently, 90 parts of water were added to dissolve the byproduct salt, and the mixture was allowed to stand to separate and remove the lower layer of brine. After neutralization with a phosphoric acid aqueous solution, the resin solution was washed with water and filtered until the washing liquid became neutral. Under reduced pressure of 5 mmHg, the mixture was heated to 180 °C, and MIBK was removed by distillation to obtain 118 parts of a reddish-brown epoxy resin (E4). This resin had an epoxy equivalent of 351, a total chlorine content of 550 ppm, and a softening point of 77 °C. In the GPC, Mw was 2080, Mn was 690, the k=0 bulk content was 2.6% by area, the k=1 bulk content was 40.0% by area, and the content of k=2 and above was 57.4% by area. The melt viscosity at 150 °C was 0.44 Pa·s.

[0195] Example 10

[0196] 100 parts of the phenolic resin (P5) obtained in Example 5, 181 parts of epichlorohydrin, and 54 parts of diethylene glycol dimethyl ether were added to a reaction apparatus including a stirrer, thermometer, nitrogen inlet tube, dropping funnel, and cooling tube, and the mixture was heated to 65°C. Under reduced pressure of 125 mmHg, while maintaining a temperature of 63°C–67°C, 35.2 parts of a 49% sodium hydroxide aqueous solution were added dropwise over 4 hours. During this period, the epichlorohydrin was azeotropically reacted with water, and the outflowing water was sequentially removed from the system. After the reaction was complete, the epichlorohydrin was recovered at 5 mmHg and 180°C, and 290 parts of MIBK were added to dissolve the product. Subsequently, 90 parts of water were added to dissolve the byproduct salt, and the mixture was allowed to stand to separate and remove the lower layer of brine. After neutralization with a phosphoric acid aqueous solution, the resin solution was washed with water and filtered until the washing liquid became neutral. Under reduced pressure of 5 mmHg, the mixture was heated to 180 °C, and MIBK was removed by distillation to obtain 116 parts of a reddish-brown epoxy resin (E5). This resin had an epoxy equivalent of 323, a total chlorine content of 580 ppm, and a softening point of 70 °C. In the GPC, Mw was 1200, Mn was 550, the k=0 bulk content was 2.5% by area, the k=1 bulk content was 42.0% by area, and the content of k=2 and above was 55.5% by area. The melt viscosity at 150 °C was 0.32 Pa·s.

[0197] Synthesis example 4

[0198] 150 parts of the phenolic resin (P1) obtained in Synthesis Example 1, 356 parts of epichlorohydrin, and 107 parts of diethylene glycol dimethyl ether were added to the same reaction apparatus as in Example 6, and the mixture was heated to 65°C. Under reduced pressure of 125 mmHg, while maintaining a temperature of 63°C–67°C, 69.1 parts of a 49% sodium hydroxide aqueous solution were added dropwise over 4 hours. During this period, the epichlorohydrin was azeotropically reacted with water, and the outflowing water was sequentially removed from the system. After the reaction was completed, the epichlorohydrin was recovered at 5 mmHg and 180°C, and 450 parts of MIBK were added to dissolve the product. Subsequently, 140 parts of water were added to dissolve the byproduct salt, and the mixture was allowed to stand to separate and remove the lower layer of brine. After neutralization with an aqueous phosphoric acid solution, the resin solution was washed with water and filtered until the washing liquid became neutral. Under reduced pressure of 5 mmHg, the resin was heated to 180 °C, and MIBK was removed by distillation to obtain 183 parts of a reddish-brown dicyclopentadiene-type epoxy resin (EH1). It has an epoxy equivalent of 261, a total chlorine content of 710 ppm, and a softening point of 55 °C. In the GPC, Mw is 670, Mn is 570, the content of k=0 is 2.3% by area, the content of k=1 is 73.1% by area, and the content of k=2 and above is 24.6% by area. The melt viscosity at 150 °C is 0.10 Pa·s.

[0199] Example 11

[0200] 100 parts of epoxy resin (E1) as epoxy resin, 33 parts of phenolic resin (PH4) as curing agent, and 0.40 parts of C1 as curing accelerator were dissolved in a mixed solvent adjusted with methyl ethyl ketone (MEK), propylene glycol monomethyl ether, and N,N-dimethylformamide to obtain an epoxy resin composition varnish. The obtained epoxy resin composition varnish was impregnated with glass cloth (manufactured by Nitto Spinning Co., Ltd., WEA 7628XS13, 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulating oven at 150°C for 9 minutes to obtain a prepreg. Eight sheets of the obtained prepreg were stacked on top of copper foil (manufactured by Mitsui Metals & Mining Co., Ltd., 3EC-III, 35 μm thick) and vacuum-pressed at 2 MPa under temperature conditions of 130°C × 15 min + 190°C × 80 min to obtain a laminate with a thickness of 1.6 mm. The results of copper foil peel strength and interlayer stress of the laminate are shown in Table 1.

[0201] In addition, the obtained prepreg was disassembled and made into a powder that passed through a 100-mesh sieve. The obtained prepreg powder was placed in a fluororesin mold and vacuum-pressed at 2 MPa under temperature conditions of 130℃×15 min + 190℃×80 min to obtain a test piece with a surface area of ​​50 mm square × 2 mm thickness. The results of the relative permittivity and dielectric loss tangent of the test piece are shown in Table 1.

[0202] Examples 12 to 32 and Comparative Examples 1 to 8

[0203] Prepare the mixture according to the proportions (parts) in Tables 1 to 4, and perform the same operation as in Example 11 to obtain laminated boards and test pieces. The amount of curing accelerator used is set to adjust the varnish gel time to approximately 300 seconds. Perform the same tests as in Example 11, and the results are shown in Tables 1 to 4.

[0204]

[0205]

[0206]

[0207]

[0208] As can be seen from these results, the polyhydroxy resins and epoxy resins obtained in the examples exhibit very good low viscosity, and the resin compositions containing these can provide resin curings that maintain adhesion of more than 1.0 kN / m without practical problems and exhibit very good low dielectric properties.

[0209] Industrial applications

[0210] The polyhydroxy resin, epoxy resin, or epoxy resin composition of the present invention can be used in coatings, civil bonding, injection molding, electrical and electronic materials, membrane materials, etc., and is particularly useful in printed circuit board applications as one of the electrical and electronic materials.

Claims

1. A polyhydroxy resin, characterized in that, It is represented by the following general formula (1), Here, R 1 Independently representing hydrocarbon groups having 1 to 8 carbon atoms, R 2 Independently representing a hydrogen atom, a base represented by formula (2), or a base represented by formula (3), with at least one being a base represented by formula (2) and a base represented by formula (3); R 3 Independently representing a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 4 Independently represent a hydrogen atom or the base represented by formula (2); A is the result of removing two R atoms from formula (1). 2 The residues formed at this time, R 2 is a hydrogen atom or a group represented by formula (2); Me represents a methyl group; i is an integer from 0 to 2; n1 represents the number of repetitions and represents a number greater than 0 with an average value of 1.0 to 4.0; p represents the number of repetitions with an average value of 0.01 to 3.

2. The polyhydroxy resin according to claim 1, wherein R 1 It is methyl or phenyl, and i is 1 or 2.

3. A method for manufacturing a polyhydroxy resin, characterized in that, The polyhydroxy resin (a) represented by general formula (4) below is reacted with the aromatic vinyl compound (b) represented by general formulas (5a) and (5b) below. Here, R 1 Independently represent hydrocarbon groups with 1 to 8 carbon atoms; i is an integer from 0 to 2; m represents the repetition number, and represents numbers greater than 0, with an average value of 1.0 to 4.

0. Here, R 3 It represents a hydrogen atom or a hydrocarbon group with 1 to 8 carbon atoms.

4. The method for manufacturing a polyhydroxy resin according to claim 3, characterized in that... In the presence of an acid catalyst, 0.05 to 2.0 moles of the aromatic vinyl compound (b) are reacted at a reaction temperature of 50°C to 200°C relative to 1 mole of the phenolic hydroxyl groups of the polyhydroxy resin (a).

5. An epoxy resin, characterized in that, It is represented by the following general formula (6), Here, R 1 Independently representing hydrocarbon groups having 1 to 8 carbon atoms, R 2 Independently representing a hydrogen atom, a base represented by formula (2), or a base represented by formula (3), with at least one being a base represented by formula (2) and a base represented by formula (3); R 3 Independently representing a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R 4 Independently represent a hydrogen atom or the base represented by formula (2); A is the result of removing two R atoms from formula (6). 2 The residues formed at this time, R 2 is a hydrogen atom or the base represented by formula (2); i is an integer from 0 to 2; n3 represents the number of repetitions and represents a number greater than 0 with an average value of 1.0 to 4.0; p represents the number of repetitions with an average value of 0.01 to 3.

6. A method for manufacturing an epoxy resin, characterized in that, One to 20 moles of epihaloalcohol are reacted in the presence of an alkali metal hydroxide relative to 1 mole of the phenolic hydroxyl group of the polyhydroxy resin represented by formula (1) as described in claim 1.

7. An epoxy resin composition comprising an epoxy resin and a curing agent, characterized in that, The polyhydroxy resin as described in claim 1 and / or the epoxy resin as described in claim 5 are essential components.

8. A prepreg, characterized in that, Use the epoxy resin composition as described in claim 7.

9. A laminated plate, characterized in that, Use the epoxy resin composition as described in claim 7.

10. A printed wiring board, characterized in that, Use the epoxy resin composition as described in claim 7.

11. A cured material formed by curing the epoxy resin composition as described in claim 7.

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