Active ester resin, epoxy resin composition, cured product thereof, prepreg, laminate, and reduction film

Abstract

Provided are: an epoxy resin composition which exhibits excellent low dielectric properties and exhibits excellent copper foil peel strength and interlayer adhesion strength in printed wiring board applications; and an active ester resin to which the epoxy resin composition is imparted. The active ester resin is characterized by having a polyaryloxy unit represented by formula (1) and a monoaryloxy group represented by formula (2). In the formula, each R1 independently represents a hydrocarbon group having 1-8 carbon atoms, and each R2 independently represents a dicyclopentenyl group or a cyclopentenyl group. I is an integer of 1-3, j is 1 or 2, and n represents a number of repetitions, the average value of which is 1-5. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to an active ester resin having excellent dielectric properties and adhesiveness, and an epoxy resin composition, an epoxy resin cured product, a prepreg, a laminate, a printed wiring board, and a build-up film using the active ester resin. Background Art

[0002] Epoxy resins are used in many fields such as coatings, civil engineering adhesives, casting, electrical and electronic materials, and film materials because of their excellent adhesion, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity. In particular, epoxy resins are widely used in printed wiring boards, which are one of the electrical and electronic materials, by imparting flame retardancy to them.

[0003] In recent years, the miniaturization and high performance of information devices have been rapidly developing, and with this, materials used in the fields of semiconductors and electronic components are required to have higher performance than before. In particular, epoxy resin compositions that become materials for electrical and electronic components are required to have low dielectric properties that are accompanied by thinning and high functionality of substrates.

[0004] In order to achieve such low dielectric properties of epoxy resin compositions, Patent Document 1 reports that an active ester compound obtained by reacting phenols with aromatic dicarboxylic acid halides is used and cured with an epoxy resin to obtain a cured product having excellent low dielectric properties.

[0005] Patent Document 2 reports an active ester resin having improved heat resistance, low dielectric properties, and solvent solubility by reacting a dicyclopentadiene-type aromatic polyhydroxy compound and a monohydroxy compound as phenols with an aromatic dicarboxylic acid halide.

[0006] However, the active ester resins disclosed in these documents do not fully meet the performance requirements based on the recent high functionality, and are insufficient to ensure low dielectric properties and adhesiveness.

[0007] On the other hand, Patent Document 3 discloses a 2,6-xylenol-dicyclopentadiene type epoxy resin, but does not investigate an active ester resin.

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2004-277461

[0011] Patent Document 2: Japanese Patent Application Publication No. 2009-235165

[0012] Patent Document 3: Japanese Patent Application Laid-Open No. 5-339341 Summary of the invention

[0013] Therefore, an object of the present invention is to provide a curable resin composition which exhibits excellent dielectric properties in a cured product and is excellent in copper foil peel strength and interlayer adhesion strength in use for printed wiring boards.

[0014] In order to solve the above-mentioned problems, the present inventors have discovered that when an aromatic hydroxy compound including an aromatic monohydroxy compound having a substituent derived from dicyclopentadiene, obtained by reacting a phenol containing a substituent with dicyclopentadiene, is actively esterified and cured with an epoxy resin, the obtained cured product has excellent low dielectric properties and adhesion, thereby completing the present invention.

[0015] That is, the present invention is an active ester resin characterized by having a polyaryloxy unit represented by the following formula (1) and a monoaryloxy group represented by the following formula (2) at the end of the molecular chain.

[0016]

[0017] Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a dicyclopentenyl group represented by the following formula (3a) or (3b) or a cyclopentenyl group represented by the following formula (3c). i is an integer of 1 to 3, j is 1 or 2, and n represents a repeating number, the average value of which is a number of 1 to 5.

[0018]

[0019] The polyaryloxy unit includes another polyaryloxy unit other than the unit represented by the above formula (1), and the other polyaryloxy unit is preferably a unit represented by the following formula (4) and / or formula (5).

[0020]

[0021] Among them, Ar 1 Each is independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent. 11 It is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by the formula (4a). 11 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. 3It is a direct bond or a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-. m represents the number of repetitions, and its average value is a number of 1 to 5. k is 0 or 1. r is 1 or 2.

[0022] The other polyaryloxy unit is preferably a unit represented by the following formula (4').

[0023]

[0024] Here, m represents the number of repetitions, and its average value is a number from 1 to 5.

[0025] The monoaryloxy group includes another monoaryloxy group other than the group represented by the above formula (2), and the other monoaryloxy group is preferably a group represented by the following formula (6) or formula (6').

[0026]

[0027] Among them, Ar 2 Each is independently an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent. 4 R is a divalent group selected from -CH2-, -C(CH3)2-, -CH(CH3)-, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-. 14 is a divalent group selected from -CH2-, -C(CH3)2-, -CH(CH3)-, and -C(CF3)2-. k is 0 or 1.

[0028] The active ester resin preferably has a polyarylcarbonyl unit, and the polyarylcarbonyl unit is a unit represented by the following formula (7).

[0029]

[0030] Among them, Ar 3 Each is independently an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent. 5It is a direct bond or a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-. k is 0 or 1.

[0031] In addition, the present invention is a method for producing an active ester resin, which is a method for producing an active ester resin from an aromatic hydroxy compound and an aromatic polycarboxylic acid or its acid halide, characterized in that the aromatic hydroxy compound contains an aromatic polyhydroxy compound represented by the following formula (8) and an aromatic monohydroxy compound having a dicyclopentenyl group and / or a cyclopentenyl group represented by the following formula (9), and the content of the aromatic monohydroxy compound represented by the following formula (9) in the aromatic hydroxy compound measured based on GPC is 0.5 area% or more and 10 area% or less.

[0032]

[0033] Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a dicyclopentenyl group represented by the following formula (3a) or (3b) or a cyclopentenyl group represented by the following formula (3c). i is an integer of 1 to 3, j is 1 or 2, and u represents a repetition number, the average value of which is a number of 1 to 5.

[0034]

[0035] The present invention also provides an epoxy resin composition comprising the above-mentioned active ester resin and an epoxy resin as essential components.

[0036] The present invention also provides a cured product obtained by curing the epoxy resin composition, and a prepreg material, a resin sheet, a laminate, and a circuit board material using the epoxy resin composition.

[0037] The epoxy resin composition of the present invention exhibits excellent dielectric properties in its cured product, and further forms an epoxy resin composition having excellent copper foil peel strength and interlayer adhesion strength in printed wiring board applications. In particular, it can be suitably used in mobile applications and server applications that strongly require low dielectric loss tangent. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 This is the GPC chart of the active ester resin obtained in Example 1.

[0039] Figure 2 This is the IR chart of the active ester resin obtained in Example 1.

[0040] Figure 3 This is the GPC chart of the active ester resin obtained in Reference Example 1.

[0041] Figure 4This is the IR chart of the active ester resin obtained in Reference Example 1.

[0042] Figure 5 This is the GPC chart of the aromatic hydroxy compound obtained in Synthesis Example 1.

[0043] Figure 6 This is the IR chart of the aromatic hydroxy compound obtained in Synthesis Example 1.

[0044] Figure 7 This is the GPC chart of the aromatic hydroxy compound obtained in Synthesis Example 2.

[0045] Figure 8 This is the IR spectrum of the aromatic hydroxy compound obtained in Synthesis Example 2. DETAILED DESCRIPTION

[0046] Hereinafter, embodiments of the present invention will be described in detail.

[0047] The active ester resin of the present invention comprises a polyaryloxy unit and a polyarylcarbonyl unit, and has a polyaryloxy unit having a group represented by the above formula (1) as an essential part and a monoaryloxy group having a dicyclopentenyl group and / or a cyclopentenyl group represented by the above formula (2) as an essential part at the molecular chain end. In this specification, a monoaralkyloxy group is also referred to as a monoaryloxy group.

[0048] The polyaryloxy unit is a structural unit derived from a raw material aromatic polyhydroxy compound including an aromatic polyhydroxy compound represented by the above formula (8), the polyarylcarbonyl unit is a structural unit derived from a raw material aromatic polycarboxylic acid (aromatic polycarboxylic acid halide), and the monoaryloxy group present at the end of the molecular chain is a group derived from a raw material aromatic monohydroxy compound including an aromatic monohydroxy compound represented by the above formula (9).

[0049] It should be noted that in this specification, aromatic polyhydroxy compounds and aromatic monohydroxy compounds are sometimes collectively referred to as "aromatic hydroxy compounds". In addition, aromatic polycarboxylic acids or their acyl halides and aromatic monocarboxylic acids or their acyl halides are sometimes collectively referred to as "aromatic carboxylic acids or their acyl halides".

[0050] The ester bond in the active ester resin of the present invention is owing to having high reactivity for epoxy group, therefore can be suitable for being used as the curing agent of epoxy resin.And, by not producing the effect of high polar hydroxyl during solidification, thus the cured product obtained shows low dielectric loss tangent, low relative dielectric constant.And then, because the molecular chain end is aryloxycarbonyl, therefore even if the ester bond of the crosslinking point of the cured product obtained is hydrolyzed because of moisture absorption, the low molecular weight carboxylic acid that makes the dielectric loss tangent increase is not free, and the cured product obtained also shows low dielectric loss tangent under high humidity conditions.In addition, owing to also having a plurality of reactive ester bonds for epoxy group in the molecular chain interior, therefore the crosslinking density of the cured product is high, and heat resistance (glass transition temperature: Tg) raises.

[0051] In the above formula (1), R 1 It represents a hydrocarbon group having 1 to 8 carbon atoms, preferably 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 the alkyl group having 1 to 8 carbon atoms, any of linear, branched, and cyclic groups may be mentioned, for example, methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, methylpentyl, dimethylbutyl, cyclohexyl, methylcyclohexyl, etc. may be mentioned, but not limited to these. As the aryl group having 6 to 8 carbon atoms, phenyl, tolyl, xylyl, ethylphenyl, etc. may be mentioned, but not limited to these. As the aralkyl group having 7 to 8 carbon atoms, benzyl, α-methylbenzyl, etc. may be mentioned, but not limited to these. Among these substituents, from the viewpoint of ease of acquisition and reactivity when made into a cured product, phenyl and methyl are preferred, and methyl is particularly preferred. R 1 The substitution position may be any of the ortho, meta, or para position relative to the oxy group, but the ortho position is preferred.

[0052] i is the number of substitutions, and is 1 to 3, preferably 1 or 2, and more preferably 2.

[0053] n is a repetition number, which means a number of 1 or more, and its average value (number average) is 1 to 5, preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and further preferably 1.0 to 2.0.

[0054] The polyaryloxy units may contain units other than the bicyclopentadienylene group-containing units represented by the above formula (1) unless the purpose of the present invention is impaired. These units are preferably units represented by the above formula (4) and / or formula (5).

[0055] However, it is desirable to preferably have 20 mol% or more, more preferably 30 mol% or more, and still more preferably 50 mol% or more of the polyaryloxy units containing a bicyclopentadienylene group represented by the above formula (1) relative to the total amount of the polyaryloxy units constituting the active ester resin of the present invention. In addition, in the case of containing a polyaryloxy unit containing a bicyclopentadienylene group represented by the formula (4'), it is desirable to preferably have 30 mol% or more, more preferably 50 mol% or more of the total amount of the polyaryloxy units containing a bicyclopentadienylene group represented by the above formula (1) and the polyaryloxy units containing a bicyclopentadienylene group represented by the above formula (4').

[0056] In the above formula (4), Ar 1 Each independently represents an aromatic ring group of any one of a benzene ring, a naphthalene ring, or a biphenyl ring. Furthermore, these aromatic rings may only contain a benzene ring, a naphthalene ring, or a biphenyl ring, or may have a substituent R 6 Among them, the substituent R 6 It is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.

[0057] Ar 11 It is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by formula (4a), and represents a linking group of a novolac resin. Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms include a methylene group and a dicyclopentadienylene group.

[0058] m represents the number of repetitions, and its average value is a number from 1 to 5.

[0059] r is the number of the oxy groups, which is 1 or 2.

[0060] In the above formula (4a), R 11 Each independently 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 include an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 8 carbon atoms. Preferably, it is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 7 carbon atoms (more preferably 6 carbon atoms), and particularly preferably, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0061] As the alkyl group having 1 to 6 carbon atoms, a straight-chain, branched or cyclic alkyl group is represented. For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, cyclohexyl and the like can be cited. Among these, branched or cyclic alkyl groups tend to give high heat resistance compared to straight-chain ones. The number of carbon atoms is preferably 1 to 4 in the case of a chain alkyl group, and preferably 6 in the case of a cyclic alkyl group. From the viewpoint of improving heat resistance, isopropyl, isobutyl, tert-butyl and cyclohexyl are preferred, and tert-butyl and cyclohexyl are more preferred. In addition, since flame retardancy tends to improve, a methyl group is also preferred.

[0062] Examples of the divalent group represented by formula (4a) include -CH2-Ph-CH2-, -CH2-Ph-Ph-CH2-, -CH2-Ph-CH2-Ph-CH2-, -CH2-Ph-C(CH3)2-Ph-CH2-, -CH2-Ph-CH(CH3)-Ph-CH2-, -CH2-Ph-CH(C6H5)-Ph-CH2-, -CH2-Ph-Flu-Ph-CH2-, -CH2-Np-CH2-, -CH2-Np-Np-CH2-, -CH2-Np-CH2-Np-CH2-, and -CH2-Np-Flu-Np-CH2-. These aromatic rings (Ph, Np and Flu) may further have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent. The total number of carbon atoms is 6 to 50, more preferably 6 to 20. Among them, Ph represents a phenylene group (-C6H4-), and Np represents a naphthylene group (-C 10 H6-), Flu represents fluorene (-C 13 H8-), Ph-Ph represents a biphenylene group. More preferably, it is -CH2-Ph-CH2-, -CH2-Ph-Ph-CH2-, or -CH2-Np-CH2- which are unsubstituted, alkyl-substituted, alkoxy-substituted, or phenyl-substituted. Further preferably, it is -CH2-Ph-CH2- or -CH2-Ph-Ph-CH2- which are unsubstituted, alkyl-substituted, alkoxy-substituted, or phenyl-substituted.

[0063] The above formula (5) is a generalized formula of the units represented by the following formulas (5a) to (5h). Formulas (6) and (7) are also generalized formulas of the monoaryloxy or polyarylcarbonyl units corresponding to formulas (5a) to (5h).

[0064]

[0065] In the formula, R 3R 3 Synonymous. 6 It is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms. p is an integer of 0 to 4, and q is an integer of 0 to 6.

[0066] In the above formula (5), Ar 1 represents an aromatic ring group of any one of a benzene ring, a naphthalene ring, or a biphenyl ring. Moreover, these aromatic rings may only contain a benzene ring, a naphthalene ring, or a biphenyl ring, and may have a substituent R 6 Among them, the substituent R 6 It is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.

[0067] The alkyl group having 1 to 10 carbon atoms may be any of linear, branched, and cyclic groups, and examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, cyclopentyl, cyclohexyl, cycloheptyl, methylcyclohexyl, cyclooctyl, dimethylcyclohexyl, ethylcyclohexyl, trimethylcyclohexyl, and cyclodecyl.

[0068] The alkoxy group having 1 to 10 carbon atoms may be any of linear, branched or cyclic, and examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, neopentyloxy, tert-pentyloxy, isohexyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, methylcyclohexyloxy, cyclooctyloxy, dimethylcyclohexyloxy, ethylcyclohexyloxy, trimethylcyclohexyloxy and cyclodecyloxy.

[0069] Examples of the aryl group or aryloxy group having 6 to 11 carbon atoms include phenyl, tolyl, ethylphenyl, xylyl, propylphenyl, mesityl, naphthyl, methylnaphthyl, phenoxy, tolyloxy, ethylphenoxy, xylyloxy, propylphenoxy, mesityloxy, naphthyloxy, and methylnaphthyloxy.

[0070] Examples of the aralkyl or aralkyloxy group having 7 to 12 carbon atoms include benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, phenethyl, 1-phenylethyl, 2-phenylisopropyl, naphthylmethyl, benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, phenethoxy, 1-phenylethoxy, 2-phenylisopropyloxy and naphthylmethoxy.

[0071] As the above Ar 1 , preferably a phenylene group, a naphthylene group, or an aromatic ring group substituted with a methyl group or a 1-phenylethyl group.

[0072] In the above formula (5), R 3 It is a direct bond or a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-.

[0073] Examples of the hydrocarbon group having 1 to 20 carbon atoms include -CH2-, -CH(CH3)-, -C2H4-, -C(CH3)2-, cyclohexylene, methylcyclohexylene, dimethylcyclohexylene, methylisopropylcyclohexylene, cyclohexylcyclohexylene, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tetramethylcyclohexylidene, ethylcyclohexylidene, isopropylcyclohexylidene, tert-butylcyclohexylidene, phenylcyclohexylidene, cyclohexylcyclohexylidene, and (methylcyclohexyl)cyclohexylidene. , (ethylcyclohexyl)cyclohexylidene, (phenylcyclohexyl)cyclohexylidene, cyclododecylidene, cyclopentylidene, methylcyclopentylidene, trimethylcyclopentylidene, cyclooctylidene, cyclododecylidene, 9H-fluorene-9,9-diyl, bicyclo[4.4.0]decanylidene, bicyclohexanediyl, phenylene, xylylene, phenylmethylene, diphenylmethylene, norbornylene, adamantylene, tetrahydrodicyclopentadienylene, tetrahydrotricyclopentadienylene, a divalent group having a norbornane structure or a tetrahydrotricyclopentadiene structure, etc.

[0074] Preferred R 3 It is a direct bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -CO-, -O-, -S-, -SO2-, trimethylcyclohexylidene, cyclooctylidene, cyclododecylidene, bicyclohexanediyl, 9H-fluorene-9,9-diyl, and phenylmethylene.

[0075] The active ester resin of the present invention has a monoaryloxy group at the molecular chain terminal, and the monoaryloxy group is essentially a group represented by the above formula (2). The other monoaryloxy group is not particularly limited, but groups represented by formula (6) and formula (6') are preferred.

[0076] As for the amount of monoaryloxy used, it is desirable that the source material of the monoaryloxy units represented by the above formula (2), formula (6), and formula (6'), i.e., the aromatic monohydroxy compound, is preferably 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more, relative to the total amount of the aromatic hydroxy compound used as a raw material. On the other hand, the aromatic monohydroxy compound represented by formula (9), which is the source material of the monoaryloxy group represented by the above formula (2), is preferably 0.5 to 10 area%, more preferably 1 to 8 area%, and further preferably 1 to 5 area%, relative to the total amount of the aromatic hydroxy compound.

[0077] In formula (2), R 1 and i and R of the above formula (1) 1 and i have the same meanings as each other, and preferred substituents are also the same.

[0078] R 2 Each independently represents a dicyclopentenyl group represented by the following formula (3a) or formula (3b), or a cyclopentenyl group represented by formula (3c). Formula (3a), formula (3b) and formula (3c) can be said to be a group derived from dicyclopentadiene. j is a substituent R 2 The number is 1 or 2. Formula (3c) is a structure derived from the depolymerization of dicyclopentadiene and is sometimes generated during a reaction at a high temperature.

[0079]

[0080] In formula (6), Ar 2 is the same as Ar in the above formula (5) 1 The same aromatic ring group may have the same substituents, and preferred substituents are also the same.

[0081] R 4 It is a directly bonded divalent group selected from -CH2-, -C(CH3)2-, -CH(CH3)-, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-.

[0082] The polyarylcarbonyl unit is not particularly limited, but a unit represented by the above formula (7) is preferred.

[0083] In formula (7), Ar 3 is the same as Ar in the above formula (5) 1 The same aromatic ring group may have the same substituents, and the preferred substituents are also the same. 3 R 3 Synonymous.

[0084] The essential raw materials for synthesizing the above-mentioned active ester resin, namely the aromatic hydroxy compounds, are the aromatic polyhydroxy compounds represented by the above-mentioned formula (8) and the aromatic monohydroxy compounds represented by the formula (9), which can be obtained by reacting phenols containing substituents with dicyclopentadiene in the presence of a Lewis acid such as a boron trifluoride-ether catalyst.

[0085] The aromatic hydroxy compound used as the raw material of the active ester resin of the present invention preferably has a hydroxyl equivalent (g / eq.) of 180-300, a weight average molecular weight (Mw) of 280-550, and a number average molecular weight (Mn) of 230-500.

[0086] The u=1 or higher component of the aromatic polyhydroxy compound is an aromatic polyhydroxy compound represented by formula (8), which becomes a polyaryloxy unit represented by the above formula (1) of the active ester resin. The u=0 component is an aromatic monohydroxy compound represented by the above formula (9) to which a substituent derived from dicyclopentadiene is added, which can become a monoaryloxy group represented by the above formula (2) as the molecular chain terminal of the active ester resin.

[0087] The content of the aromatic monohydroxy compound represented by the formula (9) is preferably 0.5 to 10 area %, more preferably 1 to 5 area %.

[0088] The content of the aromatic polyhydroxy compound represented by the above general formula (8) is preferably 90 to 99.5 area %, more preferably 95 to 99 area %. Therefore, the content of the u=1 component can be 50 to 95 area %, preferably 60 to 93 area %, more preferably 70 to 90 area %. The total content of the components with u=2 or more can be 5 to 50 area %, preferably 5 to 35 area %, more preferably 8 to 25 area %.

[0089] In addition, if a large amount of the aromatic polyhydroxy compound is used, the compound having an average value of u greater than 1.8 may gel when dissolved in a solvent to synthesize an active ester resin. Therefore, it is preferred to use a compound having an average value of u in the range of 1 to 5, a more preferred range of 1.0 to 3.0, and a further preferred range of 1.0 to 2.0. In addition, by appropriately adjusting the amount used according to the average value of u, gelation can be prevented by using other monovalent or divalent aromatic hydroxy compounds in combination.

[0090] Examples of the phenols having a substituent include cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, tert-butylphenol, pentylphenol, isopentylphenol, neopentylphenol, cyclopentylphenol, hexylphenol, (methylpentyl)phenol, (dimethylbutane)phenol, cyclohexylphenol, phenylphenol, cresylphenol, xylenolphenol, benzylphenol, α-methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, Phenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(tert-butyl)phenol, diamylphenol, diisoamylphenol, dineopentylphenol, dicyclopentylphenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, di(tolyl)phenol, di(xylyl)phenol, dibenzylphenol, bis(α-methylbenzyl)phenol, methylethylphenol, methyltert-butylphenol, methylallylphenol, tolylphenylphenol, etc. From the viewpoint of easy availability and reactivity when made into a cured product, cresol, phenylphenol, benzylphenol, dimethylphenol, diphenylphenol, and dibenzylphenol are preferred, and cresol, phenylphenol, and dimethylphenol are particularly preferred.

[0091] The catalyst used in the above 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 them, boron trifluoride-ether complex is preferred from the perspective of ease of handling. The amount of the catalyst used is 0.001 to 20 parts by mass, preferably 0.05 to 15 parts by mass, and more preferably 0.1 to 12 parts by mass relative to 100 parts by mass of dicyclopentadiene in the case of boron trifluoride-ether complex.

[0092] As a method for synthesizing the aromatic hydroxy compounds represented by the above formula (8) and formula (9), a method of reacting dicyclopentadiene with a phenol containing a substituent at a predetermined ratio is preferred. By adopting this reaction, an aromatic polyhydroxy compound represented by formula (8) and an aromatic monohydroxy compound represented by formula (9) can be obtained simultaneously.

[0093] In this reaction, in order to obtain a large amount of compounds containing the structure of formula (8), the amount of dicyclopentadiene is 0.08 to 0.80 mol, preferably 0.09 to 0.60 mol, more preferably 0.10 to 0.50 mol, further preferably 0.11 to 0.40 mol, and particularly preferably 0.11 to 0.20 mol, relative to 1 mol of the phenol containing the substituent. On the other hand, in order to obtain a large amount of compounds containing the structure of formula (9), the amount of dicyclopentadiene is 0.28 to 2.0 times mol, preferably 0.30 to 1.50 times mol, and more preferably 0.50 to 1.30 times mol, relative to 1 mol of the phenol containing the substituent.

[0094] In addition, as the raw material of the aromatic hydroxy compound, the aromatic polyhydroxy compound represented by the formula (8) and the aromatic monohydroxy compound represented by the formula (9) are prepared separately, or a mixture thereof may be used.

[0095] As a method for confirming that the substituents represented by the formulae (3a) to (3c) are introduced into the aromatic monohydroxy compound represented by the above formula (9), mass spectrometry and FT-IR measurement can be used.

[0096] When using mass spectrometry, it is possible to use electrospray mass spectrometry (ESI-MS), field desorption mass spectrometry (FD-MS), etc. By performing mass spectrometry on a sample in which components having different numbers of nuclei are separated by GPC or the like, it is possible to confirm the introduction of substituents represented by formula (3a) to (3c).

[0097] When the FT-IR method is used, the sample is mounted on a diamond ATR and the peak derived from the CO stretching vibration of the phenol nucleus is at 1210 cm -1 Only when the groups represented by formula (3a) to (3c) are introduced, the peak derived from the CH stretching vibration of the olefin part is at 3040 cm -1 Incidentally, since the dicyclopentenylene group, which is a linking group of phenols, is not an olefin, its absorption peak does not appear.

[0098] The baseline is a line connecting the start and end of the target peak, and the length from the peak apex to the baseline is the peak height. -1 Nearby peaks (A 3040 ) and 1210cm -1 Nearby peaks (A 1210 ) ratio (A 3040 / A 1210 ), the amount of introduction of formula (3a) to formula (3c) can be quantified. The larger the ratio, the better the physical property value can be confirmed. The preferred ratio (A) for satisfying the target physical property is 3040 / A 1210 ) is 0.01 or more, more preferably 0.05 or more, and further preferably 0.10 or more. As the upper limit, it is preferably 0.7 or less, and more preferably 0.60 or less. If the ratio is high, a large amount of dicyclopentadiene substituents are introduced.

[0099] In the present reaction, a method may be adopted in which a phenol having a substituent and a catalyst are charged into a reactor, and dicyclopentadiene is added dropwise over 1 to 10 hours.

[0100] The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and further preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and further preferably 4 to 8 hours.

[0101] After the reaction is completed, a base such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst. Then, a solvent such as aromatic hydrocarbons such as toluene and xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone is added to dissolve the mixture, and after washing with water, the solvent is recovered under reduced pressure to obtain the target aromatic hydroxy compound. It should be noted that it is preferred that all of the dicyclopentadiene is reacted as much as possible, and a portion of the phenols containing substituents is left unreacted, preferably less than 10%, and the unreacted portion is recovered under reduced pressure.

[0102] During the reaction, a solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, or ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether may be used as necessary.

[0103] When producing the active ester resin of the present invention, an aromatic polyvalent hydroxy compound other than the aromatic hydroxy compounds represented by the above formula (8) and formula (9) may be used in combination unless the purpose of the present invention is impaired.

[0104] However, the aromatic hydroxy compounds represented by the above formula (8) and formula (9) are preferably used in a ratio of 50 mol % or more, more preferably 60 mol % or more, and even more preferably 80 mol % or more, based on the total amount of the aromatic hydroxy compounds used as raw materials.

[0105] It is desirable to contain the aromatic monohydroxy compound represented by the above formula (9) in an amount of preferably 0.5 mol % or more, more preferably 1 mol % or more, and further preferably 2 mol % or more, based on the total amount of the aromatic hydroxy compound.

[0106] As the aromatic polyhydric hydroxy compound which can be used in combination, any can be used without particular limitation, and an aromatic polyhydric hydroxy compound represented by the following formula (10) and / or formula (11) is preferred.

[0107]

[0108] In the formula, Ar 1 ,Ar 11 , m and r are the same as Ar in the above formula (4) 1 ,Ar 11 , m and r are synonymous.

[0109]

[0110] In the formula, Ar 1 , R 3 and k and Ar of the above formula (5)1 , R 3 and k are synonymous respectively.

[0111] Examples of the aromatic dihydroxy compound represented by the formula (10) include phenol novolac resins (e.g., Shonol BRG-555 (manufactured by Aica Industries)), cresol novolac resins (e.g., DC-5 (manufactured by Nippon Steel Chemical & Materials Co., Ltd.)), xylenol novolac resins, biphenol novolac resins, aromatic modified phenol novolac resins, naphthol novolac resins and other novolac resins, reaction products of phenols and dicyclopentadiene (dicyclopentadiene-type phenolic resins), reaction products of naphthols and dicyclopentadiene (dicyclopentadiene-type naphthol resins), reaction products of phenols and terpenes (terpene-type phenolic resins), Aralkyl-type novolac resins such as reaction products of naphthols and terpenes (terpene-type naphthol resins), condensates of phenols and / or naphthols and benzyl alcohol (e.g., SN-160, SN-395, SN-485 (all manufactured by Nippon Steel Chemical & Materials Co., Ltd.)), condensates of phenols and / or naphthols and isopropenyl acetophenone, reaction products of phenols and / or naphthols and divinylbenzene, condensates of phenols and / or naphthols and biphenyl-based crosslinking agents (e.g., MEH-7851 (manufactured by UBE Co., Ltd.)), etc.

[0112] With respect to the aromatic polyhydroxy compound represented by the above formula (10), if a large amount of an aromatic polyhydroxy compound having an average value of m greater than 1.2 is used in combination, gelation may occur when the compound is dissolved in a solvent to synthesize an active ester resin. Therefore, when the aromatic polyhydroxy compound represented by the formula (10) is used in combination, it is preferred to use an aromatic polyhydroxy compound having an average value of m in the range of 1 to 2. In addition, the amount of the aromatic polyhydroxy compound represented by the formula (10) used is appropriately adjusted according to the value of m, so that gelation can be prevented. For example, when m is 2, the amount used is preferably set to 20 mol% or less relative to the total amount of the aromatic polyhydroxy compound used. In addition, an aromatic polyhydroxy compound represented by the following formula (10') is preferred.

[0113]

[0114] In the formula, m has the same meaning as m in the above formula (4).

[0115] Examples of the aromatic dihydroxy compound represented by the formula (11) include dihydroxybenzenes such as catechol, resorcinol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone and di-tert-butylhydroquinone; dihydroxynaphthalenes such as hydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene and dihydroxymethylmethoxynaphthalene; biphenols such as biphenol, dimethylbiphenol and tetramethylbiphenol; bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z; dihydroxydiphenyl sulfide; 4,4′-thiobis(3-methyl-6-tert-butylphenol); bisphenol fluorene, biscresol fluorene and 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)-9H-fluorene.

[0116] An aromatic monohydroxy compound may be used in combination. The aromatic monohydroxy compound that can be used in combination can be used without particular limitation, and an aromatic monohydroxy compound represented by the following formula (12) is preferred.

[0117] As the aromatic monohydroxy compound, an aromatic monoalcohol compound may be used instead of an aromatic monophenol compound. The aromatic monoalcohol compound that can be used is not particularly limited, but an aromatic monoalcohol compound represented by the following formula (12') is preferred.

[0118]

[0119] In the formula, Ar 2 , R 4 , and k and Ar of the above formula (6) 2 , R 4 , and k are synonymous, R 14 R of the above formula (6') 14 Synonymous.

[0120] Examples of the aromatic monohydroxy compound represented by the formula (12) include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, octylphenol, α-naphthol, β-naphthol, etc. Among them, a cured product using an active ester resin in which α-naphthol, β-naphthol, o-phenylphenol, p-phenylphenol, and 4-(α-cumyl)phenol are used as a curing agent has a particularly low dielectric loss tangent.

[0121] Examples of the aromatic monohydroxy compound represented by the formula (12') include benzyl alcohol, tolyl carbinol, dimethyl benzyl alcohol, biphenyl carbinol, benzyl benzyl alcohol, and naphthyl carbinol. Benzyl alcohol, biphenyl carbinol, and naphthyl carbinol are preferred.

[0122] The active ester resin of the present invention is obtained by reacting an aromatic polyhydroxy compound with an aromatic polycarboxylic acid or an acyl halide thereof. In this case, the aromatic hydroxy compound represented by the above formula (8) is an essential component. In addition, in this reaction, an aromatic monocarboxylic acid or an acyl halide thereof can be used in combination. As the halogen of the halide of the aromatic carboxylic acid used, chlorine or bromine is generally used. As the halide of the aromatic polycarboxylic acid, for example, halides of aromatic dicarboxylic acids represented by the following formula (13), halides of aromatic tricarboxylic acids such as trimesic acid and trimellitic acid, etc. can be listed.

[0123]

[0124] In the formula, Ar 3 , R 3 , and k and Ar of the above formula (7) 3 , R 3 , and k are synonymous.

[0125] Examples of the aromatic dicarboxylic acid represented by the formula (13) include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, 4,4'-methylene dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-isopropylidene dibenzoic acid, etc. Among them, isophthaloyl chloride and terephthaloyl chloride are preferred from the viewpoint of the balance between solvent solubility and heat resistance.

[0126] Examples of the aromatic monocarboxylic acid halide include halides of aromatic monocarboxylic acids represented by the following formula (14). When an aromatic monocarboxylic acid halide is used in combination, a part of the molecular chain terminals becomes an arylcarbonyloxy group.

[0127]

[0128] In the formula, Ar 2 , R 4 , and k and Ar of the above formula (6) 2 , R 4 , and k are synonymous.

[0129] Examples of the aromatic monocarboxylic acid represented by the formula (14) include benzoic acid, 1-naphthoic acid, 2-naphthoic acid, and bibenzoic acid.

[0130] The method for reacting the aromatic hydroxy compound of the above formula (8) with an aromatic carboxylic acid or an acid halide thereof is specifically a method of reacting these components in the presence of a base catalyst.

[0131] Examples of the base catalyst that can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, and organic bases such as triethylamine, diisopropylethylamine, and pyridine. Among them, sodium hydroxide and potassium hydroxide are preferred because they are excellent in reactivity and cost.

[0132] The above reaction can be carried out by mixing an aromatic hydroxy compound and an aromatic carboxylic acid or an acid halide thereof in the presence of an organic solvent and adding the above base catalyst. The amount of the base catalyst added is preferably 0.9 to 2.0 mol per 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound.

[0133] Examples of the organic solvent used in the above reaction include toluene, dichloromethane, and chloroform. Toluene is preferred from the viewpoints of price and environmental load.

[0134] When a hydrophobic organic solvent such as toluene is used, the sodium hydroxide aqueous solution as an inorganic base may separate. Therefore, in order to rapidly react the aromatic compound dissolved in the organic solvent, it is preferred to add a phase transfer catalyst such as tetra-n-butylammonium bromide (TBAB).

[0135] After the reaction is completed, the reaction solution is neutralized and washed with water to obtain the target resin.

[0136] The active ester equivalent (g / eq.) of the active ester resin of the present invention is preferably 200 to 600, more preferably 220 to 500, further preferably 240 to 450, and particularly preferably 240 to 300. If it is less than this range, the dielectric properties may deteriorate, and if it is greater, the heat resistance and adhesion may decrease. It should be noted that the so-called active ester group refers to the aryloxycarbonyl group in the active ester resin.

[0137] By using such an active ester resin as a curing agent, the epoxy resin composition of the present invention can be obtained.

[0138] The epoxy resin composition of the present invention has an epoxy resin and the above-mentioned active ester resin as essential components. As this embodiment, a part or all of the active ester resin is the active ester resin of the present invention, and the active ester resin represented by the above-mentioned formula (1) in the total active ester resin is preferably at least 30% by mass, more preferably 50% by mass or more, and further preferably 75% by mass or more. If it is less than this, the dielectric properties may deteriorate.

[0139] As the epoxy resin used to obtain the epoxy resin of the present invention, any common epoxy resin having two or more epoxy groups in the molecule can be used.

[0140] For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol S type epoxy resin, bissulfide type epoxy resin, resorcinol type epoxy resin, biphenyl aralkylphenol type epoxy resin, naphthyl diol type epoxy resin, phenol novolac type epoxy resin, styrenated phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, bisphenol novolac type epoxy resin, naphthalene type epoxy resin, Phenol novolac type epoxy resin, β-naphthol aralkyl type epoxy resin, dinaphthol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, triphenylmethane type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin outside the present invention, alkylene glycol type epoxy resin, aliphatic cyclic epoxy resin, diaminodiphenylmethane tetraglycidylamine, aminophenol type epoxy resin, epoxy resin containing phosphorus, carbamate modified epoxy resin, epoxy resin containing oxazolidinone ring, but are not limited to these. In addition, these epoxy resins can be used alone, and two or more can also be used in combination.

[0141] From the viewpoint of availability, it is preferred to use naphthalene diol type epoxy resins, phenol novolac type epoxy resins, aromatic modified phenol novolac type epoxy resins, cresol novolac type epoxy resins, α-naphthol aralkyl type epoxy resins, dicyclopentadiene type epoxy resins, phosphorus-containing epoxy resins, and oxazolidone ring-containing epoxy resins.

[0142] Except active ester resin of the present invention, as required, one or more than two kinds of commonly used curing agents such as various phenolic resins, anhydrides, amines, hydrazides, acidic polyesters can be used in combination. When these curing agents are used in combination, the curing agent used is preferably less than 70% by mass in all curing agents, more preferably less than 50% by mass, and further preferably less than 25% by mass. If the ratio of the curing agent used in combination is too much, then the dielectric properties and bonding properties as epoxy resin composition may deteriorate.

[0143] In the epoxy resin composition of the present invention, the active hydrogen group of the curing agent is preferably 0.2 to 1.5 moles, more preferably 0.3 to 1.4 moles, further preferably 0.5 to 1.3 moles, and particularly preferably 0.8 to 1.2 moles relative to 1 mole of epoxy groups of the epoxy resin. Outside this range, the curing may become incomplete and good curing properties may not be obtained. For example, when a phenolic resin curing agent and an amine curing agent are used in combination, approximately equimolar active hydrogen groups are added relative to the epoxy groups. When an anhydride curing agent is used in combination, 0.5 to 1.2 moles, preferably 0.6 to 1.0 moles of anhydride groups are added relative to 1 mole of epoxy groups. The amount used when the active ester resin of the present invention is used alone as a curing agent is in the range of 0.5 to 1.5 moles, preferably 0.9 to 1.1 moles relative to 1 mole of epoxy resin.

[0144] The active hydrogen group mentioned in the present invention is a functional group having active hydrogen that is reactive with an epoxy group (including a functional group having potential active hydrogen that generates active hydrogen by hydrolysis, etc., and a functional group that shows an equivalent curing effect.), specifically, anhydride groups, carboxyl groups, amino groups, phenolic hydroxyl groups, etc. can be listed. It should be noted that with respect to active hydrogen groups, 1 mole of carboxyl groups and phenolic hydroxyl groups is calculated as 1 mole, and amino groups (NH2) are calculated as 2 moles. In addition, in the case where the active hydrogen group is unclear, the active hydrogen equivalent can be obtained by measurement. For example, by reacting a monoepoxy resin such as phenyl glycidyl ether whose epoxy equivalent is known with a curing agent whose active hydrogen equivalent is unknown, the amount of the monoepoxy resin consumed is measured, so that the active hydrogen equivalent of the curing agent used can be obtained.

[0145] Specific examples of the phenolic resin curing agent that can be used in combination with the epoxy resin composition 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, dihydroxydiphenyl sulfide, bisphenols such as 4,4'-thiobis(3-methyl-6-tert-butylphenol), catechol, resorcinol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylbenzene, dihydroxybenzenes such as methylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxydimethylnaphthalene, dihydroxymethylmethoxynaphthalene, trihydroxynaphthalene, phenol curing agents containing phosphorus such as LC-950PM60 (manufactured by Shin-AT&C Co., Ltd.), phenol novolac resins, cresol novolac resins, aromatic modified phenol novolac resins, bisphenol A novolac resins, Resitop The so-called novolac phenolic resins and so-called phenolic compounds such as trihydroxyphenylmethane novolac resins such as TPM-100 (manufactured by Gunei Chemical Industry Co., Ltd.), naphthol novolac resins, condensates of phenols, naphthols, and / or bisphenols with aldehydes, condensates of phenols, naphthols, and / or bisphenols with benzyl alcohol, condensates of phenols and / or naphthols with isopropenyl acetophenone, reactants of phenols, naphthols, and / or bisphenols with dicyclopentadiene, condensates of phenols, naphthols, and / or bisphenols with biphenyl crosslinking agents, etc. are preferred from the viewpoint of easy availability, such as phenol novolac resins, dicyclopentadiene-type phenolic resins, trihydroxyphenylmethane novolac resins, and aromatic-modified phenol novolac resins.

[0146] In the case of novolac phenolic resin, as phenols, phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, etc. can be listed, as naphthols, 1-naphthol, 2-naphthol, etc. can be listed, and the above-mentioned bisphenols can be listed. As aldehydes, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloral, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, heptanedialdehyde, decanedial, acrolein, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, hydroxybenzaldehyde, etc. can be listed. As biphenyl crosslinking agents, bis (hydroxymethyl) biphenyl, bis (methoxymethyl) biphenyl, bis (ethoxymethyl) biphenyl, bis (chloromethyl) biphenyl, etc. can be listed.

[0147] Specific examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and methylnadic acid.

[0148] Specific examples of amine curing agents include diethylenetriamine, triethylenetetramine, m-xylene diamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamide, dimer acid and other acids and polyamine condensates, i.e., polyamide amines and other amine compounds.

[0149] As other curing agents, specifically, there can be listed phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-methylimidazole, salts of imidazoles with trimellitic acid, isocyanuric acid, or boron, i.e., imidazole salts, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclic compounds, salts of diazabicyclic compounds with phenols, phenol novolac resins, etc., complexes of boron trifluoride with amines, ether compounds, etc., aromatic phosphonium, or iodonium salts, etc.

[0150] In the epoxy resin composition of the present invention, a known and commonly used epoxy resin curing accelerator can be used as needed. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, and 2-undecylimidazole, tertiary amines such as 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene-7, 3-phenyl-1,1-dimethylurea, 3-(4-methyl)-1,1-dimethylurea, and 1,8-diazabicyclo(5,4,0)undecene-7. Phosphine such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, TBP-DA, TBP-3PC, TBP-3S, TPP-phthalic acid and the like manufactured by Hokuko Chemical Industry Co., Ltd., quaternary phosphonium salts, tin octoate and the like. These curing accelerators can be used alone or in combination of two or more. Among these, 4-dimethylaminopyridine and imidazoles are preferred.

[0151] When a curing accelerator is used, its usage amount can be appropriately selected according to the purpose of use, and 0.01 to 15 parts by mass, preferably 0.02 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and further preferably 0.1 to 5 parts by mass are used as needed relative to 100 parts by mass of the epoxy resin component in the epoxy resin composition. By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

[0152] In the epoxy resin composition, an organic solvent or a reactive diluent can be used for adjusting the viscosity.

[0153] Examples of the organic solvent 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, vinegar. Acetates such as methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl acetate, benzoates such as methyl benzoate and ethyl benzoate, cellosolves such as methyl cellosolve, cellosolve, and butyl cellosolve, carbitols such as methyl carbitol, carbitol, and butyl carbitol, aromatic hydrocarbons such as benzene, toluene, and xylene, dimethyl sulfoxide, acetonitrile, and N-methylpyrrolidone, but are not limited to these.

[0154] Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether; difunctional glycidyl ethers such as resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and propylene glycol diglycidyl ether; polyfunctional glycidyl ethers such as glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolethane polyglycidyl ether, and pentaerythritol polyglycidyl ether; glycidyl esters such as neodecanoic acid glycidyl ester; and glycidyl amines such as phenyl diglycidylamine and cresyl diglycidylamine, but the present invention is not limited thereto.

[0155] As for these organic solvents or reactive diluents, it is preferred to use them alone or in a mixed form in a manner in which the non-volatile components are 90% by mass or less, and the suitable type and amount used are appropriately selected according to the purpose. For example, in the use of printed wiring boards, polar solvents having a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, are preferably used in an amount in which the non-volatile components are preferably 40 to 80% by mass. In addition, in the use of adhesive films, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used in an amount in which the non-volatile components are preferably 30 to 60% by mass.

[0156] The epoxy resin composition may be mixed with other thermosetting resins or thermoplastic resins within the range that does not impair the properties. For example, phenolic resins, acrylic resins, petroleum resins, indene resins, coumarone indene resins, phenoxy resins, polyurethane resins, polyester resins, polyamide resins, polyimide resins, polyamideimide resins, polyetherimide resins, polyphenylene ether resins, modified polyphenylene ether resins, polyether sulfone resins, polysulfone resins, polyether ether ketone resins, polyphenylene sulfide resins, polyvinyl formal resins, etc. may be cited, but the present invention is not limited to these.

[0157] In the epoxy resin composition, various known flame retardants can be used for the purpose of improving the flame retardancy of the cured product obtained. As the flame retardant that can be used, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. can be listed. From the viewpoint of the environment, halogen-free flame retardants are preferably used, and phosphorus flame retardants are particularly preferred. These flame retardants can be used alone, or two or more can be used in combination.

[0158] As phosphorus flame retardants, both inorganic phosphorus compounds and organic phosphorus compounds can be used. Examples of inorganic phosphorus compounds include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoramide. Examples of the organophosphorus compound include aliphatic phosphoric acid esters, phosphoric acid ester compounds, condensed phosphoric acid esters such as PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphacyclopentane compounds, general-purpose organophosphorus compounds such as organic nitrogen-containing phosphorus compounds, metal salts of phosphinic acid, and 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; derivatives thereof obtained by reacting compounds such as epoxy resins and phenolic resins, namely, epoxy resins containing phosphorus; and phosphorus-containing curing agents.

[0159] As the amount of flame retardant, it is appropriately selected according to the type of phosphorus flame retardant, the composition of epoxy resin composition, and the degree of flame retardancy required. For example, the phosphorus content in the organic component (excluding organic solvent) in the epoxy resin composition is preferably 0.2 to 4% by mass, more preferably 0.4 to 3.5% by mass, and further preferably 0.6 to 3% by mass. If the phosphorus content is small, it is likely to be difficult to ensure flame retardancy, and if it is too much, it is likely to have an adverse effect on heat resistance. In addition, when using a phosphorus flame retardant, a flame retardant auxiliary such as magnesium hydroxide can be used in combination.

[0160] In the epoxy resin composition, fillers can be used as needed. Specifically, fused silica, crystalline silica, aluminum oxide, 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, aluminum oxide fiber, silicon dioxide aluminum oxide fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, micro-particle rubber, thermoplastic elastomer, pigment, etc. can be listed. Generally, as a reason for using fillers, the effect of improving impact resistance can be listed. In addition, when using metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide, it acts as a flame retardant aid and has the effect of improving flame retardancy. The amount of these fillers relative to the overall epoxy resin composition is preferably 1 to 150% by mass, and more preferably 10 to 70% by mass. If the amount is large, the adhesion required for the laminated board use may be reduced, and then, it is possible that the cured product is brittle and sufficient mechanical properties cannot be obtained. On the other hand, if the amount of the filler is too small, there is a possibility that the filler's effect of improving the impact resistance of the cured product may not be achieved.

[0161] The epoxy resin composition may further contain various additives such as silane coupling agents, antioxidants, mold release agents, defoamers, emulsifiers, thixotropy imparting agents, lubricants, flame retardants, pigments, etc., as required. The amount of these additives is preferably in the range of 0.01 to 20% by mass relative to the epoxy resin composition.

[0162] Composition epoxy resin of the present invention is obtained by uniformly mixing the above-mentioned components. With regard to the composition epoxy resin obtained by coordinating active ester resin, epoxy resin, and then various materials used as required, by adopting the same method as known composition epoxy resin to solidify, thus can obtain epoxy resin cured product. As cured product, can list the molding cured products such as laminate, casting, molding, adhesive layer, insulating layer, film. As the method for obtaining cured product, the same method as known composition epoxy resin can be adopted, preferably using by casting, casting, potting, dipping, dripping, transfer molding, compression molding, etc., as resin sheet, copper foil with resin, prepreg material and other forms are stacked, heat and pressurize to solidify and make the method for laminated board etc.

[0163] The curing method of the epoxy resin composition also varies according to the ingredients and the amount of the epoxy resin composition. Generally, the curing temperature is 80 to 300 ° C and the curing time is 10 to 360 minutes. The heating is preferably carried out by a two-stage treatment of a primary heating of 10 to 90 minutes at 80 to 180 ° C and a secondary heating of 60 to 150 minutes at 120 to 200 ° C. In addition, in a system where the glass transition temperature (Tg) exceeds the temperature of the secondary heating, it is preferred to further carry out a third heating of 60 to 120 minutes at 150 to 280 ° C. By carrying out such secondary heating and third heating, poor curing can be reduced. When making resin semi-cured materials such as resin sheets, copper foil with resin, and prepreg materials, heating is usually used to carry out the curing reaction of the epoxy resin composition to the extent of maintaining the shape. When the epoxy resin composition contains a solvent, most of the solvent is usually removed by heating, decompression, air drying, etc., but less than 5% by mass of the solvent can be left in the resin semi-cured material. The uncured sheet or partially cured sheet of the epoxy resin composition of the present invention can be preferably used as, for example, a build-up film, a bonding sheet, a cover sheet, a bump sheet for a flip chip bonder, an insulating layer for a substrate, or an adhesive layer.

[0164] As the use of the epoxy resin composition, it can be applied in various fields such as circuit substrate materials, sealing materials, casting materials, conductive pastes, adhesives, and insulating materials, and in particular, it can be used as insulating castings, laminated materials, and sealing materials in the electrical-electronic field. As an example of the use, laminated boards for electrical-electronic circuits such as printed wiring substrates, flexible wiring substrates, capacitors, metal foils with resins, film adhesives, liquid adhesives, and other adhesives, semiconductor sealing materials, bottom filling materials, 3D-LSI chip inter-filling materials, circuit substrate insulating materials, insulating sheets, prepreg materials, heat dissipation substrates, and resist inks can be listed, but are not limited to these.

[0165] Among these various uses, in the use of printed wiring board materials, insulating materials for circuit substrates, and adhesive films for build-up layers, it can be used as an insulating material for so-called electronic component built-in substrates, in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Among these, it is preferably used for printed wiring board materials, epoxy resin compositions for flexible wiring substrates, interlayer insulating materials for build-up substrates, and other materials for circuit substrates (laminated boards) and semiconductor sealing materials due to its high flame retardancy, high heat resistance, and solvent solubility.

[0166] When the epoxy resin composition is formed into a plate such as a laminate, the filler used is preferably a fibrous filler in terms of dimensional stability, bending strength, etc., and more preferably glass cloth, glass mat, or glass roving cloth.

[0167] By impregnating the epoxy resin composition into a fibrous reinforcing substrate, a prepreg material used in a printed wiring board, etc. can be produced. As the fibrous reinforcing substrate, for example, inorganic fibers such as glass, polyester resins, woven or nonwoven fabrics of organic fibers such as polyamine resins, polyacrylic resins, polyimide resins, and aramid resins can be used, but the invention is not limited thereto.

[0168] There is no particular limitation on the method for manufacturing a prepreg material from an epoxy resin composition. For example, the epoxy resin composition is made into a resin varnish adjusted to an appropriate viscosity with an organic solvent, the resin varnish is impregnated into the above-mentioned fibrous reinforcing substrate, and then heated and dried to semi-cure (B-stage) the resin component. As the heating temperature, 50 to 200°C is preferred, and 100 to 170°C is more preferred, depending on the type of organic solvent used. The heating time is adjusted according to the type of organic solvent used and the curability of the prepreg material, preferably 1 to 40 minutes, and more preferably 3 to 20 minutes. At this time, the mass ratio of the epoxy resin composition used to the reinforcing substrate is not particularly limited. Generally, it is preferably adjusted in a manner that the resin component in the prepreg material becomes 20 to 80% by mass.

[0169] The epoxy resin composition of the present invention can be formed into a sheet or film for use. In this case, it can be formed into a sheet or film using a conventionally known method. There is no particular limitation on the method for manufacturing a resin sheet, and examples thereof include (1) an extrusion molding method in which the epoxy resin composition is kneaded in an extruder and then extruded, and then formed into a sheet using a T-die, a circular die, or the like; (2) a tape casting method in which the epoxy resin composition is dissolved or dispersed in a solvent such as an organic solvent and then cast into a sheet; (3) other conventionally known sheet molding methods, etc. In addition, there is no particular limitation on the film thickness (μm) of the resin sheet, and it is preferably 10 to 300, more preferably 25 to 200, and further preferably 40 to 180. The film thickness of the resin sheet used in the build-up method is particularly preferably 40 to 90 μm. If the film thickness is 10 μm or more, insulation can be obtained, and if it is 300 μm or less, the distance of the circuit between the electrodes will not become too long. It should be noted that the content of the solvent in the resin sheet is not particularly limited, but is preferably 0.01 to 5% by mass relative to the entire epoxy resin composition. If the content of the solvent in the film is 0.01% by mass or more relative to the entire epoxy resin composition, it is easy to obtain adhesion and tackiness when laminating the circuit board, and if it is 5% by mass or less, it is easy to obtain flatness after heat curing.

[0170] As a more specific method for manufacturing an adhesive sheet, a varnish-like epoxy resin composition containing the above-mentioned organic solvent is applied to a supporting base film that is insoluble in the organic solvent using a coating machine such as a reverse roll coater, a notch wheel coater, a die coater, etc., followed by heating and drying to make the resin component B-stage. In addition, as required, another supporting base film is overlapped on the coated surface (adhesive layer) as a protective film, and drying is performed to obtain an adhesive sheet having release layers on both sides of the adhesive layer.

[0171] As the supporting base film, metal foils such as copper foil, polyolefin films such as polyethylene film and polypropylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, silicone film, polyimide film, etc. can be listed. Among these, polyethylene terephthalate film is preferred because it is free of defects, has excellent dimensional accuracy, and is also excellent in cost. In addition, metal foils, especially copper foils, which are easy to multi-layer the laminated board are preferred. The thickness of the supporting base film is not particularly limited, but it is preferably 10 to 150 μm, and more preferably 25 to 50 μm, because it has strength as a support body and is unlikely to cause poor lamination.

[0172] The thickness of the protective film is not particularly limited, but is generally 5 to 50 μm. It should be noted that in order to easily peel off the molded adhesive sheet, it is preferably surface treated with a release agent in advance. In addition, the thickness of the coated resin varnish is preferably 5 to 200 μm, more preferably 5 to 100 μm, based on the thickness after drying.

[0173] The heating temperature is preferably 50 to 200° C., more preferably 100 to 170° C., depending on the type of organic solvent used. The heating time is adjusted depending on the type of organic solvent used and the curability of the prepreg material, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes.

[0174] The resin sheet obtained in this way usually becomes an insulating adhesive sheet with insulating properties, but a conductive adhesive sheet can be obtained by mixing a conductive metal or metal-coated particles in an epoxy resin composition. It should be noted that the above-mentioned supporting base film is laminated on a circuit substrate or peeled off after heat curing to form an insulating layer. If the supporting base film is peeled off after the adhesive sheet is heat cured, it is possible to prevent the attachment of garbage, etc. in the curing process. Among them, the above-mentioned insulating adhesive sheet is also an insulating sheet.

[0175] When the resin sheet of the present invention is used as a bonding sheet, for example, two substrates can be bonded with a resin sheet. Each of the two substrates is, for example, a laminate or a printed wiring board. Specifically, for example, by heating the multifunctional vinyl resin composition on a supporting film after being molded into a sheet by a coating method, it is dried or semi-cured, thereby making a resin sheet. The resin sheet is overlapped on the substrate (the first substrate), the supporting film is peeled off from the resin sheet, and another substrate (the second substrate) is overlapped. That is, the first substrate, the resin sheet (the multifunctional vinyl resin composition), and the second substrate are stacked in sequence. Then, by heat curing, the first substrate and the second substrate are bonded via the cured product of the multifunctional vinyl resin composition.

[0176] The metal foil with resin obtained by using the epoxy resin composition of the present invention is described. As the metal foil, single, alloy, or composite metal foils of copper, aluminum, brass, nickel, etc. can be used. As a thickness, a metal foil of 9 to 70 μm is preferably used. There is no particular limitation on the method for manufacturing the metal foil with resin from the epoxy resin composition and metal foil of the present invention. For example, it can be obtained by applying a resin varnish in which the viscosity of the epoxy resin composition is adjusted with a solvent on one side of the above-mentioned metal foil using a roller coater, etc., and then heating and drying to semi-cure (B-stage) the resin component to form a resin layer. When the resin component is semi-cured, it can be heated and dried at 100 to 200° C. for 1 to 40 minutes. Among them, with respect to the thickness of the resin portion of the metal foil with resin, it is preferably formed to be 5 to 110 μm.

[0177] When the prepreg material and the insulating adhesive sheet are to be cured, the curing method of the laminate used in the general manufacture of the printed wiring board can be used, but it is not limited to this. For example, when the laminate is formed using the prepreg material, one or more prepreg materials are stacked, and metal foil is arranged on one side or both sides to form a laminate. By pressurizing and heating the laminate, the prepreg material can be cured and integrated to obtain a laminate. Among them, as the metal foil, single, alloy, or composite metal foil of copper, aluminum, brass, nickel, etc. can be used.

[0178] As the conditions for heating and pressing the laminate, as long as the epoxy resin composition is properly adjusted under the conditions of curing, heating and pressing can be done. If the amount of pressing is too low, bubbles remain inside the obtained laminate, and sometimes the electrical properties are reduced. Therefore, it is preferred to press under conditions that meet the moldability. The heating temperature is preferably 160 to 250°C, and more preferably 170 to 220°C. The pressing pressure is preferably 0.5 to 10 MPa, and more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, and more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently. If it is high, thermal decomposition of the cured product may occur. If the pressing pressure is low, bubbles remain inside the obtained laminate, and sometimes the electrical properties are reduced. If it is high, the resin flows before curing, and it is possible that the laminate of the desired thickness cannot be obtained. In addition, if the heating and pressing time is short, the curing reaction may not proceed sufficiently. If it is long, thermal decomposition of the cured product may occur.

[0179] The single-layer laminated board thus obtained can be used as an inner layer material to produce a multilayer board. In this case, first, the laminated board is subjected to circuit formation by an additive method, a subtractive method, etc., and the formed circuit surface is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. On the circuit formation surface of one side or both sides of the inner layer material, an insulating layer is formed by using a prepreg material, a resin sheet, an insulating adhesive sheet, or a metal foil with a resin, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

[0180] When using prepreg material to form an insulating layer, the circuit forming surface of the inner layer material is configured with a material obtained by laminating one or more prepreg materials, and then a metal foil is configured on its outside to form a laminate. Then, the laminate is heated and pressurized to form an integral body, thereby forming a cured product of the prepreg material as an insulating layer, and simultaneously forming a metal foil on its outside as a conductor layer. Among them, as the metal foil, the same metal foil as the metal foil used in the laminate used as the inner layer material can be used. In addition, heating and pressing molding can be carried out under the same conditions as the molding of the inner layer material. On the surface of the multi-layer laminate formed in this way, through-hole formation and circuit formation are implemented by an additive method and a subtractive method, and a printed wiring board can be molded. In addition, by using the printed wiring board as the inner layer material, the above-mentioned method is repeated, so that a multi-layer multilayer board can be further formed.

[0181] For example, when an insulating adhesive sheet is used to form an insulating layer, an insulating adhesive sheet is arranged on the circuit-forming surface of multiple inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is arranged between the circuit-forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressurized to form an integral body, thereby forming a cured product of the insulating adhesive sheet as an insulating layer and forming a multilayer of the inner layer material. Alternatively, a cured product of the insulating adhesive sheet is formed between the inner layer material and the metal foil as a conductor layer as an insulating layer. Among them, as the metal foil, the same metal foil as the metal foil used in the laminate used as the inner layer material can be used. In addition, the heating and pressurizing molding can be carried out under the same conditions as the molding of the inner layer material.

[0182] In the case where the epoxy resin composition is applied to the laminate to form an insulating layer, after the epoxy resin composition is applied to a thickness of preferably 5 to 100 μm, it is heated and dried at 100 to 200° C., preferably 150 to 200° C. for 1 to 120 minutes, preferably 30 to 90 minutes, to form a sheet. Generally, a method called a casting method is used. The thickness after drying is preferably formed to 5 to 150 μm, preferably 5 to 80 μm. It should be noted that in terms of the viscosity of the epoxy resin composition, from the perspective of obtaining sufficient film thickness, uneven coating, and stripes, it is preferably 10 to 40000 mPa·s at 25° C., and more preferably 200 to 30000 mPa·s. On the surface of the multilayer laminate formed in this way, through-hole formation and circuit formation are further implemented by the additive method and the subtractive method to form a printed wiring board. In addition, by using the printed wiring board as an inner layer material and repeating the above-mentioned method, a multilayer laminate can be further formed.

[0183] The sealing material obtained by using the epoxy resin composition of the present invention can be used for tape-shaped semiconductor chips, potting-type liquid seals, bottom filling, semiconductor interlayer insulation films, etc., and can be suitably used for these purposes. For example, as semiconductor encapsulation molding, the following methods can be listed: the epoxy resin composition is cast, or it is molded using a transfer molding machine, an injection molding machine, etc., and then heated at 50 to 200° C. for 2 to 10 hours to obtain a molded product.

[0184] In order to prepare the epoxy resin composition for semiconductor sealing materials, the following method can be cited: after premixing the additives such as inorganic fillers, coupling agents, and release agents in the epoxy resin composition as required, the mixture is fully melt-mixed using an extruder, a kneader, a roller, etc. until it becomes uniform. At this time, silicon dioxide is generally used as an inorganic filler. In this case, the inorganic filler is preferably mixed in the epoxy resin composition at a ratio of 70 to 95% by mass.

[0185] When the epoxy resin composition thus obtained is used as a tape-shaped sealing material, the following method can be cited: after heating it to make a semi-cured sheet, the sealing material tape is placed on a semiconductor chip, heated to 100 to 150° C. to soften and shape it, and completely cured at 170 to 250° C. In addition, when used as a potting type liquid sealing material, the epoxy resin composition obtained can be dissolved in a solvent as needed, applied on a semiconductor chip or an electronic component, and directly cured.

[0186] The epoxy resin composition of the present invention can also be further used as an anti-etching ink. In this case, the following method can be cited: a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are mixed with the epoxy resin composition, and then a pigment, talc, and a filler are added to prepare a composition for an anti-etching ink, and then the composition is applied to a printed substrate by screen printing to prepare a cured anti-etching ink. The curing temperature at this time is preferably in the temperature range of about 20 to 250°C.

[0187] The epoxy resin composition was prepared, cured by heating, and then a laminate and a cured product were evaluated. As a result, it was found that an epoxy resin composition having excellent low dielectric properties in a cured product and excellent copper foil peel strength and interlayer adhesion strength in printed wiring board applications could be provided.

[0188] Example

[0189] Examples and comparative examples are given to specifically describe the present invention, but the present invention is not limited to these examples. Unless otherwise specified, "parts" represent parts by mass, "%" represents mass %, and "ppm" represents mass ppm. In addition, the measurement methods are measured by the following methods.

[0190] (1) Hydroxyl equivalent:

[0191] The measurement is carried out in accordance with JIS K0070, and the unit is expressed as "g / eq." It should be noted that, unless otherwise specified, the hydroxyl equivalent of the aromatic polyhydric hydroxyl compound means a phenolic hydroxyl equivalent.

[0192] (2) Softening point:

[0193] The softening point was measured by the ring and ball method according to JIS K7234. Specifically, an automatic softening point device (manufactured by Meitech Co., Ltd., ASP-MG4) was used.

[0194] (3) Copper foil peel strength and interlayer adhesion:

[0195] The interlayer adhesive strength was measured in accordance with JIS C6481 by peeling the seventh layer and the eighth layer.

[0196] (4) Relative dielectric constant and dielectric loss tangent:

[0197] The relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were determined by a volumetric method using a material analyzer (manufactured by AGILENT Technologies) in accordance with IPC-TM-650 2.5.5.9 for evaluation.

[0198] (5) Glass transition temperature (Tg):

[0199] The temperature is expressed by the DSC·Tgm (the middle temperature of the displacement curve with respect to the tangent line of the glass state and the rubber state) when measured under the condition of a temperature increase of 20°C / min using a differential scanning calorimeter (manufactured by Hitachi High-Tech Science Co., Ltd., EXSTAR6000DSC6200) in accordance with IPC-TM-6502.4.25.c.

[0200] (6) GPC (gel permeation chromatography) determination:

[0201] A column (TSKgelG4000H manufactured by Tosoh Corporation) was used in series with a main body (HLC-8220GPC manufactured by Tosoh Corporation). XL 、TSKgelG3000H XL 、TSKgelG2000H XL ) equipment, the column temperature was set to 40 ° C. In addition, tetrahydrofuran (THF) was used as an eluent, the flow rate was set to 1 mL / min, and a differential refractive index detector was used as a detector. The sample was measured using 50 μL of the substance obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering with a microfilter. Mw and Mn were calculated based on the calibration curve conversion obtained using standard polystyrene (manufactured by Tosoh Corporation, PStQuick KitH). It should be noted that data processing used GPC-8020 Model II Version 6.00 manufactured by Tosoh Corporation.

[0202] (7)IR:

[0203] A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely manufactured, SpectrumOne FT-IR Spectrometer 1760X) was used to measure the wavelength of 650 to 4000 cm using diamond ATR. -1 The absorbance.

[0204] (8) ESI-MS:

[0205] Mass analysis was performed using a mass spectrometer (LCMS-2020 manufactured by Shimadzu Corporation) and acetonitrile and water as mobile phases, and measuring a sample dissolved in acetonitrile.

[0206] The abbreviations used in Examples and Comparative Examples are as follows.

[0207] [Aromatic hydroxy compounds]

[0208] PH1: Aromatic hydroxy compound obtained in Synthesis Example 1

[0209] PH2: Aromatic hydroxy compound obtained in Synthesis Example 2

[0210] PH3: Aromatic hydroxy compound obtained in Synthesis Example 3 (Comparison)

[0211] PH4: 1-Naphthol

[0212] [Aromatic carboxylic acid halides]

[0213] B1: Isophthaloyl chloride

[0214] B2: Terephthaloyl chloride

[0215] B3: Benzoyl chloride

[0216] [Epoxy resin]

[0217] E1: Phenol-dicyclopentadiene type epoxy resin (manufactured by Kukto Chemical Co., Ltd., KDCP-130, epoxy equivalent 254, softening point 72°C)

[0218] [Curing agent]

[0219] A1: Active ester resin obtained in Example 1

[0220] A2: Active ester resin obtained in Example 2

[0221] A3: Active ester resin obtained in Example 3

[0222] A4: Active ester resin obtained in Example 4

[0223] A5: Active ester resin obtained in Example 5

[0224] A6: Active ester resin obtained in Example 6

[0225] A7: Active ester resin obtained in Example 7

[0226] A8: Active ester resin obtained in Example 8

[0227] A9: Active ester resin obtained in Example 9

[0228] A10: Active ester resin obtained in Reference Example 1

[0229] A11: Active ester resin obtained in Reference Example 2

[0230] A12: Active ester resin obtained in Reference Example 3

[0231] A13: Phenol novolac resin (manufactured by Aica Industries, Ltd., Shonol BRG-557, hydroxyl equivalent 105, softening point 80°C)

[0232] [Curing accelerator]

[0233] C1: 4-dimethylaminopyridine (manufactured by Kishida Chemical Co., Ltd.)

[0234] Synthesis example 1

[0235] In a reaction apparatus including a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a condenser, 500 parts of 2,6-xylenol (structural formula shown below) and

[0236]

[0237] 7.3 parts of 47% BF3 ether complex was heated to 100° C. with stirring. While maintaining the temperature, 67.6 parts of dicyclopentadiene (structural formula shown below) (0.12 times the mole of 2,6-dimethylphenol) was added dropwise over 1 hour.

[0238]

[0239] The mixture was reacted at a temperature of 115 to 125°C for 4 hours, and 11 parts of calcium hydroxide were added. 19 parts of a 10% aqueous solution of oxalic acid were then added. The mixture was heated to 160°C, dehydrated, and then heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 1320 parts of methyl isobutyl ketone (MIBK) were added to dissolve the product, 400 parts of warm water at 80°C were added, washed with water, and the lower aqueous layer was separated and removed. The mixture was then heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK to obtain 164 parts of a reddish brown aromatic hydroxy compound (PH1).

[0240] The obtained aromatic hydroxy compound (PH1) had a hydroxyl equivalent of 195 and a softening point of 73°C. The aromatic hydroxy compound represented by formula (8) and formula (9), R 1is methyl, i is 2, Mw obtained by GPC is 470, Mn is 440, the content of formula (8) is 97.2 area % (u=1 body content is 86.2 area %, u=2 body content or more is 11.0 area %), and the content of formula (9) is 2.8 area %. 3040 / A 1210 ) was 0.05. The mass spectrum obtained by ESI-MS (negative) was measured, and the results confirmed that M-=187, 253, 375, 629. Based on M-=187, 253, it can be confirmed that the structure has formula (3a) to formula (3c) as a substituent added, and j is 1. The GPC of the obtained aromatic hydroxy compound (PH1) is shown in Figure 5 , FT-IR is shown in Figure 6 .

[0241] Synthesis example 2

[0242] In a reaction apparatus including a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel, and a condenser, 400 parts of 2,6-xylenol and 2.7 parts of a 47% BF3 ether complex were placed, and heated to 100°C while stirring. While maintaining this temperature, 247.8 parts of dicyclopentadiene (0.57 times the mole relative to 2,6-xylenol) were added dropwise over 1 hour. The reaction was then carried out at a temperature of 115 to 125°C for 4 hours, and 4.2 parts of calcium hydroxide were added. 7.2 parts of a 10% aqueous oxalic acid solution were further added. Then, the mixture was heated to 160°C, dehydrated, and heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 1510 parts of methyl isobutyl ketone (MIBK) were added to dissolve the product, 450 parts of warm water at 80°C were added, washed with water, and the lower aqueous layer was separated and removed. Then, the mixture was heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, thereby obtaining 461 parts of a reddish brown aromatic hydroxy compound (PH2).

[0243] The obtained aromatic hydroxy compound (PH2) has a hydroxyl equivalent of 276 and is a semi-solid resin at room temperature. 1 is methyl, i is 2, Mw obtained by GPC is 300, Mn is 250, the content of formula (8) is 27.1 area % (u=1 body content is 20.1 area %, u=2 body content or more is 7.0 area %), and the content of formula (9) is 72.9 area %. Absorption ratio (A 3040 / A 1210 ) was 0.51. The mass spectrum obtained by ESI-MS (negative) was measured, and it was confirmed that M-=187, 253, 375, 629, and j was 1. The GPC of the obtained aromatic hydroxy compound (PH2) is shown in Figure 7 , FT-IR is shown in Figure 8 .

[0244] Synthesis Example 3 (Comparative)

[0245] In the same reaction apparatus as in Synthesis Example 1, 400 parts of phenol and 7.5 parts of 47% BF3 ether complex were placed and heated to 70°C while stirring. While maintaining this temperature, 70.2 parts of dicyclopentadiene were added dropwise over 2 hours. The mixture was then reacted at a temperature of 125-135°C for 4 hours, and 11.7 parts of calcium hydroxide were added. 20 parts of a 10% aqueous solution of oxalic acid were then added. The mixture was then heated to 160°C, dehydrated, and heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 1100 parts of MIBK were added to dissolve the product, 330 parts of warm water at 80°C were added, washed with water, and the lower water layer was separated and removed. The mixture was then heated to 160°C under a reduced pressure of 5 mmHg, and MIBK was evaporated to obtain 158 parts of a reddish-brown aromatic hydroxy compound (PH3). The hydroxyl equivalent was 177 and the softening point was 92°C. The mass spectrum obtained by ESI-MS (negative) confirmed M-=319, 545, but the structure in which the above formula (3a) to (3c) were added as substituents did not confirm M-=159, 225. The reaction rate of dicyclopentadiene was 100%, and no aromatic monohydroxy compound was contained.

[0246] Example 1

[0247] In a reaction apparatus equipped with a stirrer, a thermometer, a nitrogen blowing tube, a dropping funnel and a condenser, 100 parts of the compound (PH1) obtained in Synthesis Example 1 as an aromatic hydroxy compound, 24.4 parts of 1-naphthol (PH4), 1.7 parts of tetra-n-butylammonium bromide (TBAB), 69.2 parts of isophthaloyl chloride (B1) as an aromatic carboxylic acid halide, and 457 parts of toluene (TL) were charged, and the temperature was raised to 50°C to dissolve them. While controlling the temperature in the system to below 60°C, 137.1 parts of a 20% aqueous sodium hydroxide solution (20% NaOH) was dripped over 3 hours, and then stirring was continued at the same temperature for further 4 hours. The reaction mixture was allowed to stand for separation, and the water layer was removed. This operation was repeated until the pH of the water layer reached 7. Then, water was removed by reflux dehydration to obtain an active ester resin (A1) in a toluene solution state with a non-volatile component of 65%. The active ester equivalent calculated from the feed amount of the raw materials was 248. The GPC of the obtained active ester resin (A1) is shown in Figure 1 , FT-IR is shown in Figure 2 .

[0248] Examples 2 to 9 and Reference Examples 1 to 3

[0249] The active ester resin was obtained by mixing in the amounts (parts) shown in Table 1 and performing the same operation as in Example 1. The results are shown in Table 1. The GPC of the active ester resin (A10) obtained in Reference Example 1 is shown in Table 1. Figure 3 , FT-IR is shown in Figure 4 .

[0250] [Table 1]

[0251]

[0252] Example 10

[0253] 100 parts of phenol-dicyclopentadiene epoxy resin (E1) as epoxy resin in terms of solid content, 98 parts of active ester resin (A1) obtained in Example 1 as curing agent, and 0.5 parts of 4-dimethylaminopyridine (C1) as curing accelerator were mixed and dissolved in methyl ethyl ketone in a manner that the non-volatile component became 50%, thereby obtaining an epoxy resin composition varnish. The obtained epoxy resin composition varnish was impregnated in glass cloth (manufactured by Nitto Bosho Co., Ltd., WEA 7628XS13, 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulation oven at 150°C for 5 minutes to obtain a prepreg material. 8 sheets of the obtained prepreg material were overlapped with upper and lower copper foils (manufactured by Mitsui Mining and Smelting Co., Ltd., 3EC-III, 35 μm thick), and vacuum pressed at 2 MPa under the temperature conditions of 130°C × 15 minutes + 210°C × 80 minutes to obtain a 1.6 mm thick laminate. Table 2 shows the results of the copper foil peel strength and interlayer adhesive force of the laminate.

[0254] The obtained prepreg material was ground and sieved to form a 100-mesh prepreg material powder. The obtained prepreg material powder was placed in a fluororesin mold and vacuum pressed at 2MPa under the temperature conditions of 130°C×15 minutes+210°C×80 minutes to obtain a 50mm square×2mm thick test piece. The results of the relative dielectric constant and dielectric loss tangent of the test piece are shown in Table 2.

[0255] Examples 11 to 18, Comparative Examples 1 to 3 and Reference Example 4

[0256] The same operation as in Example 10 was carried out by blending the blending amounts (parts) shown in Table 2 to obtain a laminated plate and a test piece. The results are shown in Table 2. The blending amounts of A1 to A12 are expressed as solid content conversion values.

[0257] [Table 2]

[0258]

[0259] From these results, it is understood that the active ester resins obtained in Examples and the resin compositions containing them exhibit very good low dielectric properties and can provide cured resins having even better adhesive strength.

[0260] Industrial Applicability

[0261] The active ester resin of the present invention can be used for printed wiring boards, sealing materials, casting materials, etc. of electric and electronic equipment, and can be used particularly as an electric and electronic material requiring low dielectric properties in conjunction with the improvement of high performance of high-speed information equipment.

Claims

1. An active ester resin comprising polyaryloxy units and polyarylcarbonyl units, characterized in that: It has a polyaryloxy unit represented by the following formula (1) and a monoaryloxy group represented by the following formula (2) at the end of the molecular chain, Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a dicyclopentenyl group represented by the following formula (3a) or (3b) or a cyclopentenyl group represented by the following formula (3c), i is an integer of 1 to 3, j is 1 or 2, and n represents a repeating number whose average value is a number of 1 to 5, 2. The active ester resin according to claim 1, wherein As the polyaryloxy unit, another polyaryloxy unit other than the unit represented by the above formula (1) is included, and the other polyaryloxy unit is a unit represented by the following formula (4) and / or formula (5), Among them, Ar 1 Each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent, Ar 11 is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by formula (4a), R 11 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 3 It is a divalent group that is directly bonded or selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-, m represents the number of repetitions, the average value of which is 1 to 5, k is 0 or 1, and r is 1 or 2.

3. The active ester resin according to claim 2, wherein The other polyaryloxy unit is a unit represented by the following formula (4'), Here, m represents the number of repetitions, and its average value is a number between 1 and 5.

4. The active ester resin according to claim 1, wherein The monoaryloxy group includes another monoaryloxy group other than the group represented by the above formula (2), and the other monoaryloxy group is a group represented by the following formula (6) or formula (6'), Among them, Ar 2 Each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent, and R 4 is a divalent group selected from -CH2-, -C(CH3)2-, -CH(CH3)-, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-, R 14 is a divalent group selected from -CH2-, -C(CH3)2-, -CH(CH3)-, and -C(CF3)2-, and k is 0 or 1.

5. The active ester resin according to claim 1, wherein The polyarylcarbonyl unit is a unit represented by the following formula (7), Among them, Ar 3 Each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent, and R 5 It is a direct bond or a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-; k is 0 or 1.

6. A method for producing an active ester resin, which is a method for producing an active ester resin from an aromatic hydroxy compound and an aromatic polycarboxylic acid or an acid halide thereof, characterized in that: The aromatic hydroxy compound comprises an aromatic polyhydroxy compound represented by the following formula (8) and an aromatic monohydroxy compound having a dicyclopentenyl group and / or a cyclopentenyl group represented by the following formula (9), wherein the content of the aromatic monohydroxy compound represented by the following formula (9) in the aromatic hydroxy compound measured by GPC is 0.5 area % or more and 10 area % or less, Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a dicyclopentenyl group represented by the following formula (3a) or (3b) or a cyclopentenyl group represented by the following formula (3c), i is an integer of 1 to 3, j is 1 or 2, and u represents a repetition number whose average value is a number of 1 to 5.

7. An epoxy resin composition comprising the active ester resin according to any one of claims 1 to 5 and an epoxy resin as essential components.

8. A cured product obtained by curing the epoxy resin composition according to claim 7.

9. A prepreg comprising the epoxy resin composition according to claim 7 or a semi-cured product thereof, and a fibrous base material. 10 . A resin sheet comprising a resin layer of the epoxy resin composition according to claim 7 or a semi-cured product thereof, and a support film.

11. A laminated board obtained by laminating and molding the prepreg material according to claim 9 and / or the resin sheet according to claim 10.

12. A material for a circuit board, characterized in that: The epoxy resin composition according to claim 7 is used.

Images