Active ester resin, thermosetting resin composition, cured product thereof, prepreg, laminate, and build-up film

Abstract

To provide a thermosetting resin composition that exhibits sufficiently low dielectric properties and offers superior heat resistance for use in printed wiring boards, and an active ester resin that yields the same.SOLUTION: Provided is an active ester resin composed of polyaryloxy units and polyarylcarbonyl units, the active ester resin having, as the polyaryloxy units, allyl group-containing units represented by the following formula, where R1 is a hydrocarbon group having 1 to 12 carbon atoms; R2 is H or a hydrocarbon group having 1 to 12 carbon atoms; X is a bonding site with a polyarylcarbonyl unit or an allyl group; 1 to 99 mol% of all X's are allyl groups; i is an integer of 0 to 3; and n is a repeating number with an average value of 0.1 to 5.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Thermosetting resins are excellent in adhesiveness, flexibility, heat resistance, chemical resistance, insulation, and curing reactivity, and are therefore used in a wide range of applications, including coatings, civil engineering adhesives, casting, electric and electronic materials, film materials, etc. In particular, thermosetting resins are widely used in printed wiring boards, which are one type of electric and electronic material, by imparting flame retardancy to them.

[0003] In recent years, information devices have been rapidly becoming smaller and more powerful, and as a result, materials used in the fields of semiconductors and electronic components are being required to have higher performance than ever before. In particular, thermosetting resin compositions, which are materials for electric and electronic components, are being required to have low dielectric properties in response to thinner substrates and higher functionality.

[0004] In order to achieve such low dielectric properties in a thermosetting resin composition, Patent Document 1 proposes an epoxy resin composition containing, as an essential component, a polyester having an arylcarbonyloxy group at the molecular chain terminal, the polyester being composed of an aromatic polycarboxylic acid residue and an aromatic polyhydroxy compound residue.

[0005] Patent Document 2 proposes an epoxy resin composition containing, as an essential component, an active ester compound obtained by reacting a specific phenol resin, an aromatic dicarboxylic acid or its halide, and an aromatic monohydroxy compound.

[0006] However, the active ester resins disclosed in these documents do not fully satisfy the performance requirements based on the recent trend toward higher functionality, and are insufficient in ensuring low dielectric properties and heat resistance.

[0007] On the other hand, Patent Document 3 proposes an epoxy resin composition containing 2,6-xylenol-dicyclopentadiene type epoxy resin as an essential component. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2004-277461 A [Patent Document 2] JP 2009-235165 A [Patent Document 3] Japanese Patent Application Publication No. 5-339341 Summary of the Invention [Problem to be solved by the invention]

[0009] Accordingly, an object of the present invention is to provide a curable resin composition which exhibits excellent dielectric properties in a cured product and further has excellent heat resistance for use in printed wiring boards. [Means for solving the problem]

[0010] In order to solve the above problems, the present inventors have discovered that an active ester resin obtained by reacting a substituted phenol with dicyclopentadiene to obtain a substituted aromatic polyhydroxy compound, converting the polyhydroxy group into an allylic ether, and further esterifying it is useful as a curing agent for thermosetting resins, and that the obtained cured product has excellent low dielectric properties and heat resistance, thereby completing the present invention.

[0011] That is, the present invention is an active ester resin comprising a polyaryloxy unit and a polyarylcarbonyl unit, characterized in that the polyaryloxy unit has an allyl group-containing unit represented by the following formula (1). [ka] Here, R 1each independently represents a hydrocarbon group having 1 to 12 carbon atoms; R 2 independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; X independently represents a bonding site with a polyarylcarbonyl unit or an allyl group, with 1 to 99 mol % of all Xs being allyl groups; i is an integer of 0 to 3; n represents the number of repetitions, the average of which is a number of 0.1 to 5.

[0012] The polyaryloxy unit contains other polyaryloxy units than the unit represented by the above formula (1), and the other polyaryloxy units are preferably units represented by the following formula (4) and / or formula (5). [ka] Here, Ar 1 are independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have, as a substituent, 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. 11 R is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by formula (4a). 11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. m represents the number of repetitions, the average value of which is a number from 1 to 5. r is 1 or 2. [ka] Here, Ar 1 are independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have, as a substituent, 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. 3is a direct bond or a divalent group selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-. k is 0 or 1.

[0013] The other polyaryloxy unit is preferably a unit represented by the following formula (4'). [ka] Here, m represents the number of repetitions, and the average value is a number from 1 to 5.

[0014] It further contains a monoaryloxy group, and the monoaryloxy group is preferably a group represented by the following formula (6). [ka] Here, Ar 2 are independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have, as a substituent, 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. 4 R is a divalent group selected from the group consisting of a direct bond, -CH2-, -C(CH3)2-, -CH(CH3)-, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-. 14 is a divalent group selected from the group consisting of a direct bond, -CH2-, -C(CH3)2-, -CH(CH3)-, and -C(CF3)2-. k is 0 or 1.

[0015] The active ester resin has a polyarylcarbonyl unit, and the polyarylcarbonyl unit is preferably a unit represented by the following formula (7). [ka] Here, Ar 3are independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have, as a substituent, 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. 5 represents 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.

[0016] The present invention also relates to a method for producing an active ester resin by reacting an aromatic hydroxy compound with an aromatic polycarboxylic acid or an acid halide thereof, the method being characterized in that the aromatic hydroxy compound contains an allyl group-containing aromatic polyhydroxy compound represented by the following formula (11): [ka] Here, R 1 each independently represents a hydrocarbon group having 1 to 12 carbon atoms; R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; 1 each independently represents a hydrogen atom or an allyl group, 1 Among them, 1 to 99 mol % are allyl groups; i is an integer of 0 to 3; n is the number of repetitions, the average of which is a number of 0.1 to 5.

[0017] The present invention also relates to a thermosetting resin composition comprising the above-mentioned active ester resin and another thermosetting resin as essential components.

[0018] The present invention also relates to a cured product obtained by curing the above-mentioned thermosetting resin composition, and to a prepreg, a resin sheet, a laminate, and a circuit board material using the above-mentioned thermosetting resin composition. Effect of the Invention

[0019] When the active ester resin of the present invention is blended with other thermosetting resins or compounds and cured, the cured product exhibits excellent dielectric properties and provides a thermosetting resin composition having excellent heat resistance for printed wiring board applications, which is particularly suitable for mobile applications and server applications where a low dielectric tangent is strongly required. [Brief description of the drawings]

[0020] [Figure 1] 1 is a GPC chart of the active ester resin obtained in Example 1. [Diagram 2] 1 is an IR chart of the active ester resin obtained in Example 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Hereinafter, an embodiment of the present invention will be described in detail.

[0022] The active ester resin of the present invention is composed of a polyaryloxy unit and a polyarylcarbonyl unit, and the polyaryloxy unit essentially contains an allyl group-containing unit represented by the above formula (1), and may contain a monoaryloxy group. In this specification, a monoaralkyloxy group is also considered as a monoaryloxy group. The polyaryloxy unit is a structural unit derived from a raw material aromatic polyhydric hydroxy compound including the aromatic polyhydric hydroxy compound represented by the above formula (11), and the polyarylcarbonyl unit is a structural unit derived from a raw material aromatic polyhydric carboxylic acid (aromatic polyhydric carboxylic acid halide). In this specification, aromatic polyhydric hydroxy compounds and aromatic monohydroxy compounds are sometimes collectively referred to simply as "aromatic hydroxy compounds". Furthermore, aromatic polyhydric carboxylic acids or their acid halides and aromatic monocarboxylic acids or their acid halides are sometimes collectively referred to simply as "aromatic carboxylic acids or their acid halides".

[0023] The ester bond in the active ester resin of the present invention has high reactivity with epoxy groups, and therefore can be suitably used as a curing agent for epoxy resins. Furthermore, due to the effect of not generating highly polar hydroxyl groups during curing, the resulting cured product exhibits low dielectric tangent and low dielectric constant. In addition, since the molecular chain also contains many ester bonds that have reactivity with epoxy groups, the cured product has high crosslink density and high heat resistance (glass transition temperature: Tg). Furthermore, since the molecule contains allyl groups, it is possible to cure with thermosetting resins having unsaturated groups such as maleimide compounds, and the heat resistance of the cured product is high.

[0024] The active ester resin of the present invention must have an allyl group-containing unit represented by formula (1) as a polyaryloxy unit. [ka]

[0025] In formula (1), R 1 represents a hydrocarbon group having 1 to 12 carbon atoms, and is preferably an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an allyl group.

[0026] The alkyl group having 1 to 12 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a t-pentyl group, a methylbutyl group, a cyclopentyl group, an n-hexyl group, a methylpentyl group, a dimethylbutyl group, a cyclohexyl group, an n-heptyl group, a methylhexyl group, a dimethylpentyl group, a trimethylbutyl group, an ethylpentyl group, a cyclopentyl group, a cyclohex ... Examples of aryl groups include, but are not limited to, cycloheptyl, methylcyclohexyl, n-octyl, isooctyl, methylheptyl, dimethylhexyl, trimethylpentyl, ethylhexyl, cyclooctyl, methylcycloheptyl, dimethylcyclohexyl, ethylhexyl, n-octyl, n-nonyl, n-decyl, n-dodecyl, methylcyclohexyl, ethylcyclohexyl, trimethylcyclohexyl, cyclodecyl, n-undecyl, and cyclododecyl.

[0027] Examples of the aryl group having 6 to 12 carbon atoms include, but are not limited to, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a styryl group, an n-propylphenyl group, an isopropylphenyl group, a mesityl group, an ethynylphenyl group, a naphthyl group, and a vinylnaphthyl group.

[0028] Examples of the aralkyl group having 7 to 12 carbon atoms include, but are not limited to, a benzyl group, an α-methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a naphthylmethyl group, a phenethyl group, and a 2-phenylisopropyl group.

[0029] Other examples include polycyclic structure groups such as an indanyl group, a dicyclopentenyl group, a norbornyl group, and a decahydronaphthyl group, but are not limited to these.

[0030] Among these substituents, from the viewpoints of availability and reactivity when formed into a cured product, methyl, phenyl, benzyl, α-methylbenzyl, and dicyclopentenyl groups are preferred, with methyl being particularly preferred. 1 The substitution position of may be any of the ortho, meta, and para positions relative to the oxy group, but the ortho position is preferred.

[0031] In formula (1), R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and preferred R 2 is a hydrogen atom or R 1 It is the same as:

[0032] In formula (1), X independently represents a bonding site with a polyarylcarbonyl unit or an allyl group represented by the following formula (2), and the allyl group accounts for 1 to 99 mol %, preferably 10 to 80 mol %, and more preferably 15 to 60 mol % of the total of X. The allyl group may also be a group represented by the following formula (2').

[0033] [ka]

[0034] In formula (2'), R 7 R is an alkyl or alkenyl group having 1 to 8 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group. Examples of the alkenyl group include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group. 7 is preferably a methyl group.

[0035] In formula (1), i is R 1 and is an integer of 0 to 3, preferably 1, 2 or 3, more preferably 1 or 2, and further preferably 2.

[0036] In formula (1), n ​​is the number of repetitions, which is a number equal to or greater than 0, and its average value (number average) is 0.1 to 5. For the purpose of improving heat resistance, trifunctional or more is preferred, so n is preferably 1.1 to 4.0, and more preferably 1.2 to 3.0. For the purpose of reducing viscosity, n is preferably 0.1 to 1, more preferably 0.1 to 0.5 or less, and even more preferably 0.1 to 0.2. When n is less than 1, i (the substituent R 1 The number of (a) must be 1 or more, and 2 is preferable.

[0037] The polyaryloxy unit may contain units other than the allyl group- and dicyclopentadienylene group-containing units represented by the above formula (1) as long as the object of the present invention is not hindered, and such units are preferably units represented by the above formula (4) and / or formula (5). However, it is desirable that the allyl group- and dicyclopentadienylene group-containing polyaryloxy units represented by the above formula (1) account for preferably 20 mol % or more, more preferably 30 mol % or more, and even more preferably 50 mol % or more of the total amount of the polyaryloxy units constituting the active ester resin of the present invention. In addition, when the dicyclopentadienylene group-containing polyaryloxy units represented by the formula (4') are contained, [ka] It is desirable that the total amount of allyl group- and dicyclopentadienylene group-containing polyaryloxy units represented by the above formula (1) and dicyclopentadienylene group-containing polyaryloxy units represented by the above formula (4') is preferably 30 mol % or more, more preferably 50 mol % or more, based on the total amount of dicyclopentadienylene group-containing polyaryloxy units.

[0038] The active ester resin of the present invention can contain, as the polyaryloxy unit, a unit represented by formula (4) in addition to the allyl group-containing unit represented by formula (1) above. [ka] In the above formula (4), Ar 1Each independently represents an aromatic ring group selected from a benzene ring, a naphthalene ring, and a biphenyl ring. Even if these aromatic rings are each composed of only a benzene ring, a naphthalene ring, or a biphenyl ring, the substituent R 6 where R 6 represents 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. Ar 11 is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by formula (4a), and represents a linking group for a novolak resin. [ka] Examples of the divalent hydrocarbon group having 1 to 10 carbon atoms include a methylene group and a dicyclopentadienylene group. m represents the number of repetitions, and its average value is from 1 to 5, preferably from 1.0 to 4.0, more preferably from 1.0 to 3.0, and even more preferably from 1.0 to 2.0. r is the number of oxy groups and is 1 or 2.

[0039] In the above formula (4a), R 11 are independently 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. Preferred are 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 preferred are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. The alkyl group having 1 to 6 carbon atoms represents a linear, branched or cyclic alkyl group. Examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, and a cyclohexyl group. Among these, a branched or cyclic alkyl group tends to provide higher heat resistance than a linear alkyl group. 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, an isopropyl group, an isobutyl group, a t-butyl group, and a cyclohexyl group are preferable, and a t-butyl group and a cyclohexyl group are more preferable. In addition, a methyl group is also preferable because it tends to improve flame retardancy.

[0040] 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(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, as a substituent, 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. The total number of carbon atoms is 6 to 50, and more preferably, the number of carbon atoms is 6 to 20. Here, Ph represents a phenylene group (-C6H4-), and Np represents a naphthylene group (-C 10 H6-), and Flu is a fluorenyl group (-C 13H8-), where Ph-Ph represents a biphenylene group. More preferred are -CH2-Ph-CH2-, -CH2-Ph-Ph-CH2-, or -CH2-Np-CH2-, which are unsubstituted, substituted with an alkyl group, substituted with an alkoxy group, or substituted with a phenyl group, and even more preferred are -CH2-Ph-CH2- or -CH2-Ph-Ph-CH2-, which are unsubstituted, substituted with an alkyl group, substituted with an alkoxy group, or substituted with a phenyl group.

[0041] The active ester resin of the present invention can contain, as the polyaryloxy unit, a unit represented by formula (5) in addition to the allyl group-containing unit represented by formula (1) above. [ka] The polyaryloxy unit represented by the above formula (5) is a generalized formula of the units represented by the following formulae (5a) to (5h).

[0042] [ka]

[0043] Similarly, the monoaryloxy group represented by formula (6) is a generalization of the monoaryloxy group (a unit having one oxy group) corresponding to formulas (5a) to (5h), and the polyarylcarbonyl unit represented by formula (7) is a generalization of the polyarylcarbonyl unit (a unit having all oxy groups replaced with carbonyl groups) corresponding to formulas (5a) to (5h).

[0044] In the formula, R 3 is R in the above formula (5). 3 Synonymous with R. 6 represents 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.

[0045] In the above formula (5), Ar1 represents an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring. Even if these aromatic rings are composed of only a benzene ring, a naphthalene ring, or a biphenyl ring, the substituent R 6 where R 6 represents 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.

[0046] The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, an isopropyl group, a sec-butyl group, a t-butyl group, an isopentyl group, a neopentyl group, a t-pentyl group, an isohexyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a methylcyclohexyl group, a cyclooctyl group, a dimethylcyclohexyl group, an ethylcyclohexyl group, a trimethylcyclohexyl group, and a cyclodecyl group.

[0047] The alkoxy group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, an n-octyloxy group, an n-nonyloxy group, an n-decyloxy group, an isopropoxy group, a sec-butoxy group, a t-butoxy group, an isopentyloxy group, a neopentyloxy group, a t-pentyloxy group, an isohexyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a methylcyclohexyloxy group, a cyclooctyloxy group, a dimethylcyclohexyloxy group, an ethylcyclohexyloxy group, a trimethylcyclohexyloxy group, and a cyclodecyloxy group.

[0048] Examples of the aryl group or aryloxy group having 6 to 11 carbon atoms include a phenyl group, a tolyl group, an ethylphenyl group, a xylyl group, a propylphenyl group, a mesityl group, a naphthyl group, a methylnaphthyl group, a phenoxy group, a tolyloxy group, an ethylphenoxy group, a xylyloxy group, a propylphenoxy group, a mesityloxy group, a naphthyloxy group, and a methylnaphthyloxy group.

[0049] Examples of the aralkyl group or aralkyloxy group having 7 to 12 carbon atoms include a benzyl group, a methylbenzyl group, a dimethylbenzyl group, a trimethylbenzyl group, a phenethyl group, a 1-phenylethyl group, a 2-phenylisopropyl group, a naphthylmethyl group, a benzyloxy group, a methylbenzyloxy group, a dimethylbenzyloxy group, a trimethylbenzyloxy group, a phenethyloxy group, a 1-phenylethyloxy group, a 2-phenylisopropyloxy group, and a naphthylmethyloxy group.

[0050] The above Ar 1 As the alkyl group, a phenylene group, a naphthylene group, or an aromatic ring group in which the phenylene group, the naphthylene group, and the naphthylene group are substituted with a methyl group or a 1-phenylethyl group are preferable.

[0051] In the above formula (5) and formulas (5a) to (5h), R 3 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-.

[0052] Examples of the hydrocarbon group having 1 to 20 carbon atoms include, for example, -CH2-, -CH(CH3)-, -C2H4-, -C(CH3)2-, a cyclohexylene group, a methylcyclohexylene group, a dimethylcyclohexylene group, a methylisopropylcyclohexylene group, a cyclohexylcyclohexylene group, a cyclohexylidene group, a methylcyclohexylidene group, a dimethylcyclohexylidene group, a trimethylcyclohexylidene group, a tetramethylcyclohexylidene group, an ethylcyclohexylidene group, an isopropylcyclohexylidene group, a t-butylcyclohexylidene group, a phenylcyclohexylidene group, a cyclohexylcyclohexylidene group, a (methylcyclohexyl)cyclohexylidene group, an (ethyl)cyclohexylidene group, an arylcyclohexyl ... Examples of such divalent groups include a (phenylcyclohexyl)cyclohexylidene group, a (phenylcyclohexyl)cyclohexylidene group, a cyclododecylene group, a cyclopentylidene group, a methylcyclopentylidene group, a trimethylcyclopentylidene group, a cyclooctylidene group, a cyclododecylidene group, a 9H-fluorene-9,9-diyl group, a bicyclo[4.4.0]decylidene group, a bicyclohexanediyl group, a phenylene group, a xylylene group, a phenylmethylene group, a diphenylmethylene group, a norbornylene group, an adamantylene group, a tetrahydrodicyclopentadienylene group, a tetrahydrotricyclopentadienylene group, a norbornane structure, a tetrahydrotricyclopentadiene structure, or the like.

[0053] Preferred R 3 is a direct bond, -CH2-, -CH(CH3)-, -C(CH3)2-, -CO-, -O-, -S-, -SO2-, a trimethylcyclohexylidene group, a cyclooctylidene group, a cyclododecylidene group, a bicyclohexanediyl group, a 9H-fluorene-9,9-diyl group, and a phenylmethylene group.

[0054] In the above formula (5), k is 0 or 1.

[0055] The active ester resin of the present invention may have a monoaryloxy group at the molecular chain terminal. The monoaryloxy group is preferably a group represented by formula (6). [ka] The amount of monoaryloxy groups used is preferably 1 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more of the aromatic monohydroxy compound, which is the raw material from which the monoaryloxy unit represented by the above formula (6) is derived, relative to the total amount of aromatic hydroxy compounds used as raw materials.

[0056] In formula (6), Ar 2 is the Ar 1 The aromatic ring group is the same as that shown in the above, and may have the same substituents, and preferable substituents are also the same. R 4 is a divalent group selected from a direct bond, -CH2-, -C(CH3)2-, -CH(CH3)-, -CO-, -O-, -S-, -SO2-, and -C(CF3)2-. R 14 is a divalent group selected from the group consisting of a direct bond, -CH2-, -C(CH3)2-, -CH(CH3)-, and -C(CF3)2-. 14 is other than a direct bond, the group represented by formula (6) is a monoaralkyloxy group but is treated as a monoaryloxy group. k is 0 or 1.

[0057] The polyarylcarbonyl unit is not particularly limited, but is preferably a unit represented by formula (7). [ka] In formula (7), Ar 3 is the Ar 1 R is an aromatic ring group similar to those of the above, and may have the same substituents, and the preferred substituents are also the same. 5 is R in Eq. (5). 3 where k is 0 or 1.

[0058] The aromatic hydroxy compound, which is an essential raw material for synthesizing the above-mentioned active ester resin, is an allyl group-containing aromatic polyhydroxy compound represented by formula (11). [ka] In formula (11), X 1 each independently represents a hydrogen atom or an allyl group, 1 In the formula (1), 1 to 99 mol % of the groups are allyl groups. R1, R2, i, and n are each defined as in the formula (1). The allyl group-containing aromatic polyhydric hydroxy compound represented by formula (11) can be obtained by reacting a phenol, preferably a substituted phenol, with dicyclopentadiene in the presence of a Lewis acid such as boron trifluoride ether catalyst to obtain an aromatic polyhydric hydroxy compound represented by the following formula (8), and then allylating 1 to 99 mol % of the hydroxyl groups with an allyl halide, allyl acetate, or the like. [ka]

[0059] In formula (8), R 1 and i is R in the above formula (1). 1 and i, respectively. u represents the number of repetitions, the average value of which is a number from 0.1 to 5. The aromatic polyhydroxy compound component with u=1 or more corresponds to the aromatic polyhydroxy compound represented by formula (14) below that may be used in combination and can be another polyaryloxy unit represented by formula (4) above. The aromatic monohydroxy compound with u=0 corresponds to the aromatic monohydroxy compound represented by formula (16) below and can be a monoaryloxy group represented by formula (6) above at the molecular chain end of the active ester resin.

[0060] Examples of the substituent-containing phenols include cresol, ethylphenol, propylphenol, isopropylphenol, n-butylphenol, t-butylphenol, pentylphenol, isopentylphenol, neopentylphenol, cyclopentylphenol, hexylphenol, (methylpentyl)phenol, (dimethylbutane)phenol, cyclohexylphenol, phenylphenol, tolylphenol, xylylphenol, benzylphenol, α-methylbenzylphenol, allylphenol, dimethylphenol, diethylphenol, dipropylphenol, diisopropylphenol, di(n-butyl)phenol, di(t-butyl)phenol, dipentylphenol, diisopentylphenol, dineopentylphenol, dicyclopentylphenol, dihexylphenol, dicyclohexylphenol, diphenylphenol, ditolylphenol, dixylylphenol, dibenzylphenol, bis(α-methylbenzyl)phenol, methylethylphenol, methyl-t-butylphenol, methylallylphenol, and tolylphenylphenol. From the viewpoints of availability and reactivity when formed into a cured product, cresol, phenylphenol, benzylphenol, dimethylphenol, diphenylphenol, and dibenzylphenol are preferred, and cresol, phenylphenol, and dimethylphenol are particularly preferred.

[0061] 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, iron chloride, etc., among which boron trifluoride ether complex is preferred due to its ease of handling. In the case of boron trifluoride ether complex, the amount of catalyst used is 0.001 to 20 parts by mass, preferably 0.1 to 15 parts by mass, and more preferably 0.1 to 12 parts by mass, relative to 100 parts by mass of dicyclopentadiene.

[0062] The method for synthesizing the aromatic hydroxy compound represented by the above formula (8) is preferably a method in which a substituted phenol is reacted with dicyclopentadiene in a predetermined ratio, and the aromatic polyhydric hydroxy compound represented by the formula (8) can be obtained by this reaction. In this reaction, in order to obtain a compound containing many components with u=1 or more, dicyclopentadiene is used in an amount of 0.08 to 0.80 moles, preferably 0.09 to 0.60 moles, more preferably 0.10 to 0.50 moles, even more preferably 0.11 to 0.40 moles, and particularly preferably 0.11 to 0.20 moles per mole of the substituted phenol. On the other hand, in order to obtain a compound containing many components with u=0, dicyclopentadiene is used in an amount of 0.28 to 2.0 moles, preferably 0.30 to 1.50 moles, and more preferably 0.50 to 1.30 moles per mole of the substituted phenol.

[0063] This reaction is preferably carried out by charging the substituted phenol and the catalyst into a reactor and then adding dicyclopentadiene dropwise over a period of 1 to 10 hours.

[0064] 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.

[0065] After the reaction is completed, an alkali 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 or xylene, or ketones such as methyl ethyl ketone or methyl isobutyl ketone is added and dissolved, and the mixture is washed with water, and the solvent is recovered under reduced pressure to obtain the desired aromatic hydroxy compound. It is preferable to react as much of the dicyclopentadiene as possible, and leave a part of the phenols containing the substituent unreacted, preferably 10% or less, and recover them under reduced pressure.

[0066] In the reaction, a solvent such as aromatic hydrocarbons such as benzene, toluene, xylene, etc., halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, etc., or ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, etc. may be used, if necessary.

[0067] The aromatic polyhydroxy compound represented by formula (11) can be obtained by allylating 1 to 99 mol %, preferably 10 to 50 mol %, and more preferably 15 to 30 mol % of the hydroxyl groups of the aromatic polyhydroxy compound represented by formula (8) thus obtained. The method for allylating the hydroxyl group is not particularly limited, but for example, a method of reacting an allyl halide such as allyl bromide or allyl chloride with a base as described in JP 2016-204647 A can be used. Also, a method of reacting allyl acetate in the presence of a transition metal catalyst such as palladium or ruthenium as described in JP 2014-240377 A can be used.

[0068] The allyl etherification method is an excellent method for obtaining the allyl group-containing aromatic polyhydroxy compound (allyl ether compound) of general formula (11). As an example of this method, a polyhydroxy resin represented by general formula (8) is reacted with a halogenated allyl compound in a solvent in the presence of an alkali compound (allyl etherification reaction). In this case, it is preferable to dissolve the polyhydroxy resin in a solvent in advance, and then add a solution of the halogenated allyl compound and a solution of the alkali compound to react with each other. This allyl etherification reaction is preferably carried out by charging the polyhydroxy resin and a solvent into a reactor, dissolving the resin, and then dropping the solution of the halogenated allyl compound and the solution of the alkali compound.

[0069] Examples of the halogenated allyl compounds used in the production of the allyl ether compound include allyl chloride, allyl bromide, methallyl chloride, and methallyl bromide. Among these, allyl bromide or allyl chloride is preferred from the viewpoint of reactivity with polyhydric hydroxy resin. In addition, allyl chloride tends to polymerize with itself to form a polymer (polyallyl chloride), but it is preferable to use an allyl chloride with a low polyallyl chloride content for the production. If the polyallyl chloride content in the allyl chloride used is high, not only will it increase the total chlorine content of the obtained allyl ether compound, but it may also contribute to an increase in the molecular weight of the allyl ether compound, causing a small amount of gelled matter to be generated in the cured product. In addition, in order to reduce this chlorine content, a considerable amount of basic substance must be added, which is not industrially preferable. The content of this polyallyl chloride can be easily confirmed by gas chromatography, etc., and the content of polyallyl chloride is preferably 1 area% or less, more preferably 0.5 area% or less, and even more preferably 0.2 area% or less, relative to the allyl chloride monomer in terms of area ratio.

[0070] The alkali compound used in the production of the allyl ether compound is preferably an alkali metal hydroxide or carbonate, and specific examples thereof include sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, with sodium hydroxide and potassium hydroxide being preferred. Such an alkali metal hydroxide may be used in the form of a solid or a solution thereof.

[0071] The solvent used in the production of the allyl ether compound preferably contains an aprotic polar solvent, and more preferably contains an aprotic polar solvent and water from the viewpoints of the solubility of the alkaline compound and the solubility of the polyhydric hydroxy resin. Examples of such a solvent include dimethyl sulfoxide, N-methylpyrrolidone, dimethylacetamide, dimethylformamide, dioxane, dimethoxyethane, cyclopentyl methyl ether, and diglyme, with cyclopentyl methyl ether and dimethyl sulfoxide being particularly preferred. The amount of the aprotic polar solvent used is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, and particularly preferably 25 to 200% by mass, based on the total mass of the polyhydric hydroxy resin. Since an aprotic polar solvent such as dimethyl sulfoxide is not useful for purification such as washing with water and has a high boiling point and is difficult to remove, it is not preferable for the amount of the aprotic polar solvent to exceed 300% by mass based on the total mass of the polyhydric hydroxy resin. In addition to the above water and aprotic polar solvent, the solvent may contain an alcohol having 1 to 5 carbon atoms, or an organic solvent (other organic solvent) such as methyl ethyl ketone, methyl isobutyl ketone, or toluene. When using a hydrophobic organic solvent such as toluene, the aqueous solution of sodium hydroxide, which is an inorganic base, may separate. Therefore, it is desirable to add a phase transfer catalyst, such as tetra-n-butylammonium bromide (TBAB), in order to rapidly react with the phenolic resin dissolved in the organic solvent.

[0072] The reaction temperature for the allyl etherification reaction of the polyhydric hydroxy resin is usually 30 to 90° C., and preferably 35 to 80° C. In order to obtain an allyl ether compound with a higher purity, it is preferable to increase the reaction temperature in two or more stages. For example, it is particularly preferable to increase the reaction temperature to 35 to 50° C. in the first stage and 45 to 70° C. in the second stage. The reaction time for the allyl etherification reaction of the polyhydric hydroxy resin is usually 0.5 to 10 hours, preferably 1 to 8 hours, and particularly preferably 1 to 5 hours. A reaction time of 0.5 hours or more allows the reaction to proceed sufficiently, while a reaction time of 10 hours or less makes it possible to keep the amount of by-products produced low.

[0073] After the reaction is completed, the solvent is distilled off under reduced pressure with heating to obtain a product. The recovered product is dissolved in a ketone compound having 4 to 7 carbon atoms (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.), an ether such as cyclopentyl methyl ether, or an aromatic solvent such as toluene, and washed with water at a temperature of 40 to 90°C, more preferably 50 to 80°C, until the aqueous layer has a pH of 5 to 8.

[0074] The allyl etherification reaction of the polyhydric hydroxy resin is usually carried out while blowing an inert gas such as nitrogen into the system (air or liquid). By blowing an inert gas into the system while carrying out the reaction, it is possible to prevent the obtained product from being colored. The amount of inert gas blown in per unit time varies depending on the volume of the vessel used in the reaction, and it is preferable to adjust the amount of inert gas blown in per unit time so that the volume of the vessel can be replaced in, for example, 0.5 to 20 hours.

[0075] The aromatic hydroxy compound used as the active ester resin raw material of the present invention preferably has a hydroxyl equivalent (g / eq.) of 150 to 400. The allyl group-containing aromatic hydroxy compound after allylation preferably has a hydroxyl equivalent of 200 to 800, and an allyl equivalent of preferably 100 to 1500, more preferably 300 to 1200. The weight average molecular weight (Mw) is preferably 280-550, and the number average molecular weight (Mn) is preferably 230-500.

[0076] When producing the active ester resin of the present invention, an aromatic polyhydric hydroxy compound other than the aromatic hydroxy compound represented by the above formula (11) may be used in combination, so long as it does not impair the object of the present invention.

[0077] The aromatic polyhydric hydroxy compound that may be used in combination with the allyl group-containing aromatic hydroxy compound represented by formula (11) is not particularly limited, but is preferably an aromatic polyhydric hydroxy compound represented by the following formula (14) and / or formula (15). [ka] In the formula, Ar 1 , Ar 11 , m and r are Ar 1 , Ar 11 , m and r, respectively. [ka] In the formula, Ar 1 , R 3 , and k is the Ar 1 , R 3 , and k, respectively.

[0078] Examples of the aromatic dihydroxy compound represented by the above formula (14) include novolak resins such as phenol novolak resins (e.g., Shownol BRG-555 (manufactured by Aica Kogyo Co., Ltd.)), cresol novolak resins (e.g., DC-5 (manufactured by Nippon Steel Chemical & Material Co., Ltd.)), xylenol novolak resins, biphenol novolak resins, aromatic modified phenol novolak resins, and naphthol novolak resins; reaction products of phenols and dicyclopentadiene (dicyclopentadiene type phenolic resins), reaction products of naphthols and dicyclopentadiene (dicyclopentadiene type naphthol resins), and reaction products of phenols and terpene (dicyclopentadiene type naphthol resins). Examples of aralkyl novolak resins include reaction products of phenols and naphthols with xylylene glycol (terpene-type phenolic resins), reaction products of naphthols and terpenes (terpene-type naphthol resins), condensates of phenols and / or naphthols with xylylene glycol (for example, SN-160, SN-395, SN-485 (all manufactured by Nippon Steel Chemical & Material Co., Ltd.)), condensates of phenols and / or naphthols with isopropenylacetophenone, reaction products of phenols and / or naphthols with divinylbenzene, and condensates of phenols and / or naphthols with a biphenyl-based crosslinking agent (for example, MEH-7851 (manufactured by UBE Corporation)).

[0079] When the aromatic polyhydric hydroxy compound represented by the above formula (14) is used in large quantities with an average value of m exceeding 1.2, gelation may occur when the compound is dissolved in a solvent to synthesize an active ester resin. Therefore, when the aromatic polyhydric hydroxy compound represented by the formula (14) is used in large quantities, it is preferable to use one with an average value of m in the range of 1 to 2. In addition, gelation can be prevented by appropriately adjusting the amount of the aromatic polyhydric hydroxy compound represented by the formula (14) used according to the value of m. For example, when m is 2, the amount used is preferably 20 mol % or less based on the total amount of the aromatic polyhydric hydroxy compound used. In particular, an aromatic polyhydric hydroxy compound represented by the following formula (14') is preferable. [ka] In the formula, m has the same meaning as m in the above formula (4).

[0080] Examples of the aromatic dihydroxy compound represented by the above formula (15) include dihydroxybenzenes such as catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-t-butylhydroquinone, and di-t-butylhydroquinone; naphthalenediols such as naphthalenediol, methylnaphthalenediol, and methylmethoxynaphthalenediol; biphenols such as biphenol, dimethylbiphenol, and tetramethylbiphenol; and bisphenols such as 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-t-butylphenol), bisphenolfluorene, biscresolfluorene, and 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)-9H-fluorene.

[0081] An aromatic monohydroxy compound may be used in combination. The aromatic monohydroxy compound that may be used in combination is not particularly limited, but is preferably an aromatic monohydroxy compound (R 14 is a direct bond) is preferred. In addition, as the aromatic monohydroxy compound, an aromatic monoalcohol compound may be used instead of an aromatic monophenol compound. The aromatic monoalcohol compound that may be used is not particularly limited, but may be an aromatic monoalcohol compound (R 14 is other than a direct bond) is preferred.

[0082] [ka] In the formula, Ar 2 , R 4 , R 14 , and k is the Ar 2 , R 4 , R 14 , and k, respectively.

[0083] Examples of aromatic monohydroxy compounds represented by the above formula (16) 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., benzyl alcohol, tolylmethanol, dimethylbenzyl alcohol, biphenylmethanol, benzylbenzyl alcohol, naphthylmethanol, etc., and α-naphthol, β-naphthol, o-phenylphenol, p-phenylphenol, 4-(α-cumyl)phenol, benzyl alcohol, biphenylmethanol, and naphthylmethanol are preferred. Among them, the cured product using the active ester resin in combination with α-naphthol, β-naphthol, o-phenylphenol, p-phenylphenol, and 4-(α-cumyl)phenol as a curing agent has a particularly low dielectric tangent.

[0084] The active ester resin of the present invention is obtained by reacting an aromatic polyhydric hydroxy compound with an aromatic polycarboxylic acid or its acid halide. In this case, the aromatic hydroxy compound represented by the above formula (11) is an essential component. In addition, an aromatic monocarboxylic acid or its acid halide may be used in combination in this reaction. Chlorine or bromine is generally used as the halogen of the aromatic carboxylic acid halide used. Examples of the aromatic polycarboxylic acid halide include halides of aromatic dicarboxylic acids represented by the following formula (17) and halides of aromatic tricarboxylic acids such as trimesic acid and trimellitic acid. [ka] In the formula, Ar 3 , R 3 , and k is the Ar 3 , R 3 , and k, respectively.

[0085] Examples of the aromatic dicarboxylic acid represented by the above formula (17) include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, 4,4'-methylenebisbenzoic acid, 4,4'-carbonylbisbenzoic acid, 4,4'-isopropylidenedibenzoic acid, etc. Among these, isophthalic acid chloride and terephthalic acid chloride are preferred from the viewpoint of the balance between solvent solubility and heat resistance.

[0086] Examples of aromatic monocarboxylic acid halides include halides of aromatic monocarboxylic acids represented by the following formula (18): When aromatic monocarboxylic acid halides are used in combination, part of the molecular chain terminals becomes an arylcarbonyloxy group. [ka] In the formula, Ar 2 , R 4, and k is the Ar 2 , R 4 , and k, respectively. Examples of the aromatic monocarboxylic acid represented by the formula (18) include benzoic acid, 1-naphthalenecarboxylic acid, 2-naphthalenecarboxylic acid, and biphenylcarboxylic acid.

[0087] The method of reacting the aromatic hydroxy compound of the above formula (11) with an aromatic carboxylic acid or an acid halide thereof is specifically a method of reacting these components in the presence of an alkali catalyst.

[0088] Examples of the alkali catalyst that can be used here include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, and organic bases such as triethylamine, diisopropylethylamine, and pyridine, and among these, sodium hydroxide and potassium hydroxide are preferred because of their excellent reactivity and cost.

[0089] The reaction can be carried out by mixing an aromatic hydroxy compound with an aromatic carboxylic acid or its acid halide in the presence of an organic solvent and adding the above-mentioned alkali catalyst. The amount of the alkali catalyst added is preferably 0.9 to 2.0 moles per mole of the phenolic hydroxyl group of the aromatic hydroxy compound.

[0090] Examples of the organic solvent used in the above reaction include ethers such as toluene, dichloromethane, chloroform, and cyclopentyl methyl ether, and esters such as ethyl acetate, propyl acetate, and butyl acetate. From the viewpoints of cost, availability, and separability, toluene, cyclopentyl methyl ether, and propyl acetate are preferred.

[0091] After the reaction is completed, the reaction solution is neutralized and washed with water to obtain the desired resin.

[0092] The active ester equivalent of the active ester resin of the present invention is preferably 200 to 1000 g / eq., more preferably 220 to 600 g / eq., and even more preferably 250 to 450 g / eq. If it is smaller than this range, the dielectric properties may deteriorate, and if it is larger, the heat resistance and adhesiveness may decrease. The active ester group refers to an aryloxycarbonyl group in the active ester resin.

[0093] The thermosetting resin composition of the present invention can be obtained by blending such an active ester resin with other thermosetting resins or compounds and using the mixture as a curing agent.

[0094] The thermosetting resin composition of the present invention contains as essential components the above-mentioned active ester resin and another thermosetting resin, preferably an epoxy resin or a maleimide compound. In the resin composition, a part or all of the active ester resin is the active ester resin of the present invention, and the active ester resin of the present invention is preferably at least 30% by mass, more preferably 50% by mass or more, and even more preferably 75% by mass or more of the total active ester resins. If it is less than this, the dielectric properties may deteriorate.

[0095] As the epoxy resin used to obtain the thermosetting resin composition of the present invention, any ordinary epoxy resin having two or more epoxy groups in the molecule can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethylbisphenol F type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol S type epoxy resin, bisthioether type epoxy resin, resorcinol type epoxy resin, biphenyl aralkylphenol type epoxy resin, naphthalenediol 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, Examples of epoxy resins that can be used include, but are not limited to, cyclopentadiene-type epoxy resins, naphthol novolac-type epoxy resins, β-naphthol aralkyl-type epoxy resins, dinaphthol aralkyl-type epoxy resins, α-naphthol aralkyl-type epoxy resins, trisphenylmethane-type epoxy resins, trisphenylmethane-type epoxy resins, dicyclopentadiene-type epoxy resins other than those of the present invention, alkylene glycol-type epoxy resins, aliphatic cyclic epoxy resins, diaminodiphenylmethane tetraglycidylamine, aminophenol-type epoxy resins, phosphorus-containing epoxy resins, urethane-modified epoxy resins, and oxazolidone ring-containing epoxy resins. These epoxy resins may be used alone or in combination of two or more.

[0096] From the viewpoint of ease of availability, it is preferable to use naphthalenediol-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.

[0097] In addition to the active ester resin of the present invention, one or more commonly used curing agents such as various phenolic resins, acid anhydrides, amines, hydrazides, and acidic polyesters may be used in combination as necessary. When these curing agents are used in combination, the amount of the curing agent used in combination is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 25% by mass or less of the total curing agent. If the ratio of the curing agent used in combination is too high, the dielectric properties of the thermosetting resin composition may deteriorate.

[0098] In the thermosetting resin composition of the present invention, the active hydrogen group of the curing agent is preferably 0.2 to 1.5 mol, more preferably 0.3 to 1.4 mol, even more preferably 0.5 to 1.3 mol, and particularly preferably 0.8 to 1.2 mol, per mol of the epoxy group of the epoxy resin. Outside this range, the curing may be incomplete and good curing properties may not be obtained. For example, when a phenol resin-based curing agent or an amine-based curing agent is used in combination, the active hydrogen group is blended in an approximately equimolar amount relative to the epoxy group. When an acid anhydride-based curing agent is used in combination, the acid anhydride group is blended in an amount of 0.5 to 1.2 mol, preferably 0.6 to 1.0 mol, per mol of the epoxy group. When the active ester resin of the present invention is used alone as a curing agent, the amount used is in the range of 0.5 to 1.5 mol, preferably 0.9 to 1.1 mol, per mol of the epoxy resin.

[0099] The active hydrogen group in the present invention refers to a functional group having active hydrogen reactive with an epoxy group (including a functional group having latent active hydrogen that generates active hydrogen by hydrolysis or the like, and a functional group exhibiting an equivalent curing action). Specific examples include ester groups, acid anhydride groups, carboxyl groups, amino groups, and phenolic hydroxyl groups. Regarding active hydrogen groups, 1 mole of carboxyl groups or phenolic hydroxyl groups is calculated as 1 mole, and an amino group (NH2) is calculated as 2 moles. In addition, when the active hydrogen group is not clear, the active hydrogen equivalent can be determined by measurement. For example, the active hydrogen equivalent of the curing agent used can be determined 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, and measuring the amount of monoepoxy resin consumed.

[0100] Specific examples of phenolic resin-based curing agents that can be used in combination with the thermosetting resin composition of the present invention include bisphenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, and 4,4'-thiobis(3-methyl-6-t-butylphenol); dihydroxybenzenes such as catechol, resorcin, methylresorcin, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-t-butylhydroquinone, and di-t-butylhydroquinone; dihydroxynaphthalene (naphthalenediol), dihydroxymethylnaphthalene (methylnaphthalenediol), dihydroxydimethylnaphthalene (dimethylnaphthalenediol), and dihydroxymethylmethoxynaphthalene (methylmethoxynaphthalenediol). Examples of the phenolic compound include phenolic compounds called novolak phenolic resins, such as condensates of phenols, naphthols, and / or bisphenols with aldehydes, such as phenol novolak resins, cresol novolak resins, aromatic modified phenol novolak resins, bisphenol A novolak resins, trishydroxyphenylmethane novolak resins such as Resitop TPM-100 (Gunei Chemical Industry Co., Ltd.), and naphthol novolak resins, condensates of phenols, naphthols, and / or bisphenols with xylylene glycol, condensates of phenols and / or naphthols with isopropenylacetophenone, reaction products of phenols, naphthols, and / or bisphenols with dicyclopentadiene, and condensates of phenols, naphthols, and / or bisphenols with biphenyl-based crosslinking agents. From the viewpoint of availability, phenol novolac resin, dicyclopentadiene type phenol resin, trishydroxyphenylmethane type novolac resin, aromatic modified phenol novolac resin, etc. are preferred.

[0101] In the case of novolac phenolic resin, examples of the phenols include phenol, cresol, xylenol, butylphenol, amylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, etc., examples of the naphthols include 1-naphthol, 2-naphthol, etc., and the above-mentioned bisphenols are also included. Examples of the aldehydes include formaldehyde, acetaldehyde, propylaldehyde, butylaldehyde, valeraldehyde, capronaldehyde, benzaldehyde, chloraldehyde, bromoaldehyde, glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, adipic aldehyde, pimeline aldehyde, sebacic aldehyde, acrolein, crotonaldehyde, salicylaldehyde, phthalaldehyde, hydroxybenzaldehyde, etc. Examples of biphenyl-based crosslinking agents include bis(methylol)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, and bis(chloromethyl)biphenyl.

[0102] Specific examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and methylnadic acid.

[0103] Specific examples of the amine-based curing agent include amine-based compounds such as diethylenetriamine, triethylenetetramine, metaxylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiphenylether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamide, and polyamidoamines which are condensates of acids such as dimer acid and polyamines.

[0104] Specific examples of other curing agents include phosphine compounds such as triphenylphosphine, phosphonium salts such as tetraphenylphosphonium bromide, imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 1-cyanoethyl-2-methylimidazole, imidazole salts which are salts of imidazoles with trimellitic acid, isocyanuric acid, boron, or the like, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclo compounds, salts of diazabicyclo compounds with phenols, phenol novolac resins, or the like, complex compounds of boron trifluoride with amines, ether compounds, or the like, aromatic phosphonium, or iodonium salts, and the like.

[0105] Examples of the curing accelerator include amines, imidazoles, organic phosphines, Lewis acids, and organic peroxides. Specific examples of the curing accelerator include tertiary amines such as 1,8-diazabicyclo(5,4,0)undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, and tris(dimethylaminomethyl)phenol; imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, and 2-undecylimidazole; tributylphosphine, methyldiphenylphosphine, and triphenyl Examples of the organic phosphines include phosphine, diphenylphosphine, phenylphosphine, tricyclohexylphosphine, triphenylphosphine triphenylborane, and other organic phosphines; addition products of organic phosphines and quinone compounds; tetra-substituted phosphonium tetra-substituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate; tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate; and organic peroxides such as ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxydicarbonates, and peroxyesters. The amount of the additive is in the range of 0.2 to 5 parts by mass per 100 parts by mass of the resin composition.

[0106] In the thermosetting resin composition of the present invention, a known and commonly used epoxy resin curing accelerator can be used as necessary. Examples of the curing accelerator that can be used include urea compounds such as 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea, and quaternary phosphonium salts such as TBP-DA, TBP-3PC, TBP-3S, and TPP-phthalic acid manufactured by Hokko Chemical Industry Co., Ltd., and metal compounds such as tin octylate. These curing accelerators may be used alone or in combination of two or more kinds. Among these, 4-dimethylaminopyridine and imidazoles are preferred.

[0107] When a curing accelerator is used, its amount may be appropriately selected depending on the purpose of use, but 0.01 to 15 parts by mass is used as necessary, preferably 0.02 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and even more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the epoxy resin component in the thermosetting resin composition. By using the curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

[0108] In the thermosetting resin composition of the present invention, a maleimide compound can be used as necessary. The maleimide compound that can be used is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. For example, N-phenylmaleimide, phenylmethanemaleimide, N-hydroxyphenylmaleimide, 4,4'-diphenylmethane bismaleimide, 4,4-diphenylether bismaleimide, polyphenylmethanemaleimide, m-phenylene bismaleimide, p-phenylene bismaleimide, 2,2'-[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis-(3-ethyl-5-methyl-4-maleimidophenyl) Examples of the maleimide compounds include methane, bis(3,5-diethyl-4-maleimidophenyl)methane, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, N,N'-ethylene dimaleimide, N,N'-hexamethylene dimaleimide, maleimide compounds represented by the following general formula (19), prepolymers of these maleimide compounds, or prepolymers of maleimide compounds and amine compounds. These maleimide compounds can be used alone or in combination of two or more. Among these, the maleimide compounds represented by the following general formula (19) are preferred. [ka] Where: R 4 each independently represents an alkyl group having 1 to 5 carbon atoms or an aromatic group. R 5 each independently represents a hydrogen atom or a methyl group. a represents an integer of 0 to 4, and is preferably 0 or 1. b represents an integer of 0 to 3, and is preferably 0 or 1. r and q are 0 or 1. m is the number of repetitions, the average value of which is from 1 to 10, preferably from 1 to 7, and more preferably from 1 to 5.

[0109] In the resin composition of the present invention, one or more of various allyl ether compounds may be used in combination as necessary. However, it is preferable that at least 30% by mass of the allyl ether compound is the active ester resin (allyl ether compound) of the present invention, and more preferably 50% by mass or more. If it is less than this, the dielectric properties may be deteriorated.

[0110] Examples of allyl ether compounds that can be used in combination with the active ester resin (allyl ether compound) of the present invention include allyl ether compounds obtained by allyl etherifying bisphenols such as bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethyl bisphenol A, tetramethyl bisphenol F, tetramethyl bisphenol S, tetramethyl bisphenol Z, dihydroxydiphenyl sulfide, and 4,4'-thiobis(3-methyl-6-t-butylphenol); allyl ether compounds obtained by allyl etherifying dihydroxybenzenes such as catechol, resorcin, methyl resorcin, hydroquinone, monomethyl hydroquinone, dimethyl hydroquinone, trimethyl hydroquinone, mono-t-butyl hydroquinone, and di-t-butyl hydroquinone; allyl ether compounds obtained by allyl etherifying hydroxynaphthalenes such as dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, and trihydroxynaphthalene; and Shounol BRG-555 (allyl ether). phenol novolac resins such as DC-5 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), cresol novolac resins such as DC-5 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), aromatic modified phenol novolac resins, bisphenol A novolac resins, trishydroxyphenylmethane novolac resins such as Resitop TPM-100 (manufactured by Gun-ei Chemical Industry Co., Ltd.), naphthol novolac resins and other condensates of phenols, naphthols and / or bisphenols with aldehydes, SN-160, SN-395, SN-485 (manufactured by Nippon Steel Chemical & Material Co., Ltd.), etc. Examples of such allyl ether compounds include allylic ether compounds obtained by allylic etherifying polyhydric hydroxyl resins, which are so-called novolak phenol resins, such as condensates of phenols, naphthols and / or bisphenols with xylylene glycol, condensates of phenols and / or naphthols with isopropenylacetophenone, reaction products of phenols, naphthols and / or bisphenols with dicyclopentadiene, and condensates of phenols, naphthols and / or bisphenols with a biphenyl-based crosslinking agent; and triallyl isocyanurate.From the viewpoints of reactivity and availability, allyl ether compounds obtained by allylic etherification of bisphenols such as bisphenol A and bisphenol F are preferred.

[0111] The thermosetting resin composition may contain an organic solvent or a reactive diluent for adjusting the viscosity.

[0112] 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 diglycol, and pine oil, and vinegar. Examples of the organic solvent include, but are not limited to, acetates such as butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and benzyl alcohol acetate; benzoate esters 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.

[0113] Examples of reactive diluents include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and tolyl glycidyl ether; bifunctional 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 diglycidyl amine and tolyl diglycidyl amine, but are not limited thereto.

[0114] These organic solvents or reactive diluents are preferably used alone or in a mixture of multiple types in an amount of 90% by mass or less as non-volatile matter, and the appropriate type and amount of use are appropriately selected depending on the application. For example, for printed wiring board applications, polar solvents with a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, and 1-methoxy-2-propanol, are preferred, and the amount of use is preferably 40 to 80% by mass in terms of non-volatile matter. For adhesive film applications, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like are preferred, and the amount of use is preferably 30 to 60% by mass in terms of non-volatile matter.

[0115] The thermosetting resin composition may contain other thermosetting resins or thermoplastic resins within the range that does not impair the properties of the composition, such as, but not limited to, 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, polyethersulfone resins, polysulfone resins, polyetheretherketone resins, polyphenylene sulfide resins, and polyvinyl formal resins.

[0116] In the thermosetting resin composition, various known flame retardants can be used to improve the flame retardancy of the resulting cured product. Examples of flame retardants that can be used include halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants. From the viewpoint of the environment, halogen-free flame retardants are preferred, and phosphorus-based flame retardants are particularly preferred. These flame retardants may be used alone or in combination of two or more.

[0117] The phosphorus-based flame retardant may be either an inorganic phosphorus-based compound or an organic phosphorus-based compound, such as red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amide. Examples of the organic phosphorus compounds include general-purpose organic phosphorus compounds such as aliphatic phosphoric acid esters, phosphoric acid ester compounds, for example, condensed phosphoric acid esters such as PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, and organic nitrogen-containing phosphorus compounds; and metal salts of phosphinic acid. In addition, cyclic organic phosphorus 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; and phosphorus-containing epoxy resins and phosphorus-containing curing agents which are derivatives obtained by reacting these compounds with compounds such as epoxy resins and phenolic resins.

[0118] The amount of the flame retardant to be added is appropriately selected depending on the type of phosphorus-based flame retardant, the components of the thermosetting resin composition, and the desired level of flame retardancy. For example, the phosphorus content in the organic components (excluding organic solvents) in the thermosetting resin composition is preferably 0.2 to 4 mass%, more preferably 0.4 to 3.5 mass%, and even more preferably 0.6 to 3 mass%. If the phosphorus content is low, it may be difficult to ensure flame retardancy, and if it is too high, it may have an adverse effect on heat resistance. In addition, when a phosphorus-based flame retardant is used, a flame retardant assistant such as magnesium hydroxide may be used in combination.

[0119] A filler can be used in the thermosetting resin composition as necessary. Specifically, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, alumina fiber, silica alumina fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, fine rubber particles, thermoplastic elastomer, pigment, etc. are mentioned. In general, the reason for using a filler is the effect of improving impact resistance. In addition, when a metal hydroxide such as aluminum hydroxide, boehmite, magnesium hydroxide is used, it acts as a flame retardant assistant and has the effect of improving flame retardancy. The amount of these fillers is preferably 1 to 150 mass%, more preferably 10 to 70 mass%, based on the entire thermosetting resin composition. If the amount is too large, the adhesiveness required for laminate use may decrease, and further, the cured product may become brittle and sufficient mechanical properties may not be obtained. Also, if the blending amount is too small, the effects of blending the filler, such as improving the impact resistance of the cured product, may not be achieved.

[0120] The thermosetting resin composition may further contain various additives, such as a silane coupling agent, an antioxidant, a release agent, an antifoaming agent, an emulsifier, a thixotropy imparting agent, a smoothing agent, a flame retardant, a pigment, etc. The amount of these additives to be added is preferably in the range of 0.01 to 20% by mass based on the thermosetting resin composition.

[0121] The thermosetting resin composition of the present invention is obtained by uniformly mixing the above-mentioned components. The thermosetting resin composition containing the active ester resin, the epoxy resin, and further various materials as necessary can be cured in the same manner as known thermosetting resin compositions to obtain a thermosetting resin cured product. Examples of the cured product include molded cured products such as laminates, cast products, molded products, adhesive layers, insulating layers, and films. The method for obtaining the cured product can be the same as that for known thermosetting resin compositions, and methods such as casting, injection, potting, dipping, drip coating, transfer molding, compression molding, etc., or laminating in the form of a resin sheet, a copper foil with resin, a prepreg, etc., and heating and pressing to cure the laminate are preferably used.

[0122] The curing method of the thermosetting resin composition varies depending on the components and amounts in the thermosetting resin composition, but usually, the curing temperature is 80 to 300°C, and the curing time is 10 to 360 minutes. This heating is preferably performed in two stages, namely, a first heating at 80 to 180°C for 10 to 90 minutes and a second heating at 120 to 200°C for 60 to 150 minutes. In addition, in a compounding system in which the glass transition temperature (Tg) exceeds the temperature of the second heating, it is preferable to perform a tertiary heating at 150 to 280°C for 60 to 120 minutes. By performing such a second heating and a tertiary heating, it is possible to reduce the curing failure. When preparing a resin sheet, a resin-attached copper foil, a prepreg, or other semi-cured resin product, the curing reaction of the thermosetting resin composition is usually advanced to a degree that the shape can be maintained by heating or the like. When the thermosetting resin composition contains a solvent, usually, most of the solvent is removed by a method such as heating, decompression, or air drying, but 5 mass% or less of the solvent may remain in the semi-cured resin product. Furthermore, an uncured sheet or a partially cured sheet of the thermosetting resin composition of the present invention can be suitably used, for example, as a build-up film, a bonding sheet, a coverlay sheet, a bump sheet for a flip chip bonder, or an insulating layer or adhesive layer for a substrate.

[0123] The thermosetting resin composition can be used in a variety of fields, including as a circuit board material, sealing material, casting material, conductive paste, adhesive, insulating material, etc., and is particularly useful as insulating casting, lamination material, sealing material, etc. in the electrical and electronic fields. Examples of applications include printed wiring boards, flexible wiring boards, laminates for electrical and electronic circuits such as capacitors, resin-attached metal foils, adhesives such as film-like adhesives and liquid adhesives, semiconductor sealing materials, underfill materials, interchip fill materials for 3D-LSI, insulating materials for circuit boards, insulating sheets, prepregs, heat dissipation substrates, and resist inks, but are not limited thereto.

[0124] Among these various applications, in applications such as printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-up, it can be used as an insulating material for so-called electronic component-embedded substrates in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Among these, it is preferable to use it as a printed wiring board material, a thermosetting resin composition for flexible wiring boards, a material for circuit boards (laminates) such as an interlayer insulating material for build-up substrates, and a semiconductor encapsulation material, because of its characteristics such as high flame retardancy, high heat resistance, and solvent solubility.

[0125] When the thermosetting resin composition is formed into a plate such as a laminate, the filler used is preferably a fibrous one in terms of dimensional stability, bending strength, etc., and more preferably a glass cloth, glass mat, or glass roving cloth.

[0126] The thermosetting resin composition can be impregnated into a fibrous reinforcing substrate to produce a prepreg for use in printed wiring boards, etc. Examples of the fibrous reinforcing substrate that can be used include, but are not limited to, inorganic fibers such as glass, and woven or nonwoven fabrics of organic fibers such as polyester resin, polyamine resin, polyacrylic resin, polyimide resin, and aromatic polyamide resin.

[0127] The method for producing a prepreg from a thermosetting resin composition is not particularly limited, and for example, the thermosetting resin composition is prepared into a resin varnish adjusted to an appropriate viscosity with an organic solvent, and the resin varnish is impregnated into the fibrous reinforcing substrate, and then the resin component is semi-cured (B-staged) by heating and drying. 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, and is preferably 1 to 40 minutes, more preferably 3 to 20 minutes. In this case, the mass ratio of the thermosetting resin composition and the reinforcing substrate used is not particularly limited, but it is usually preferable to adjust the resin content in the prepreg to 20 to 80 mass%.

[0128] The thermosetting resin composition of the present invention can be used by forming it into a sheet or film. In this case, it is possible to form it into a sheet or film using a conventionally known method. The method for producing the resin sheet is not particularly limited, but examples thereof include (a) an extrusion molding method in which the thermosetting resin composition is kneaded in an extruder, extruded, and formed into a sheet using a T-die or a circular die, (b) a casting molding method in which the thermosetting resin composition is dissolved or dispersed in a solvent such as an organic solvent, and then cast to form into a sheet, and (c) other conventionally known sheet molding methods. In addition, the thickness (μm) of the resin sheet is not particularly limited, but is preferably 10 to 300, more preferably 25 to 200, and even more preferably 40 to 180. The thickness of the resin sheet when used in the build-up method is particularly preferably 40 to 90 μm. If the 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 be longer than necessary. The content of the solvent in the resin sheet is not particularly limited, but is preferably 0.01 to 5% by mass based on the entire thermosetting resin composition. If the content of the solvent in the film is 0.01% by mass or more based on the entire thermosetting resin composition, adhesion and bonding are easily obtained when laminated on a circuit board, and if it is 5% by mass or less, flatness after heat curing is easily obtained.

[0129] A more specific method for producing an adhesive sheet is to apply the varnish-like thermosetting resin composition containing the organic solvent onto a supporting base film that is not soluble in organic solvents using a coater such as a reverse roll coater, a comma coater, or a die coater, and then heat and dry the composition to bring the resin component into the B-stage. If necessary, a separate supporting base film is placed on the coated surface (adhesive layer) as a protective film, and the resulting film is dried to obtain an adhesive sheet having release layers on both sides of the adhesive layer.

[0130] Examples of the supporting base film include 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. Among these, polyethylene terephthalate film is preferred because it is free of defects, has excellent dimensional accuracy, and is also cost-effective. In addition, metal foils, particularly copper foils, which are easy to multilayer into a laminate, are preferred. The thickness of the supporting base film is not particularly limited, but is preferably 10 to 150 μm, more preferably 25 to 50 μm, because it has strength as a support and is less likely to cause lamination defects.

[0131] The thickness of the protective film is not particularly limited, but is generally 5 to 50 μm. In addition, in order to easily peel off the molded adhesive sheet, it is preferable to perform a surface treatment with a release agent in advance. Furthermore, the thickness of the resin varnish applied after drying is preferably 5 to 200 μm, more preferably 5 to 100 μm.

[0132] The heating temperature depends on the type of organic solvent used, and is preferably 50 to 200° C., and more preferably 100 to 170° C. The heating time is adjusted depending on the type of organic solvent used and the curing property of the prepreg, and is preferably 1 to 40 minutes, and more preferably 3 to 20 minutes.

[0133] The resin sheet thus obtained is usually an insulating adhesive sheet having insulating properties, but a conductive adhesive sheet can also be obtained by mixing conductive metal or metal-coated fine particles into the thermosetting resin composition. The supporting base film is peeled off after laminating to the circuit board or after heat curing to form an insulating layer. If the supporting base film is peeled off after the adhesive sheet is heat cured, the adhesion of dust and the like during the curing process can be prevented. Here, the insulating adhesive sheet is also an insulating sheet.

[0134] In addition, 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, a resin sheet is produced by forming a multifunctional vinyl resin composition into a sheet shape on a support film by a coating method or the like, and then drying or semi-curing by heating. This resin sheet is superimposed on a substrate (first substrate), the support film is peeled off from the resin sheet, and another substrate (second substrate) is superimposed. That is, the first substrate, the resin sheet (multifunctional vinyl resin composition), and the second substrate are laminated in this order. Subsequently, the first substrate and the second substrate are bonded via the cured product of the multifunctional vinyl resin composition by heating and curing.

[0135] The resin-attached metal foil obtained by the thermosetting resin composition of the present invention will be described. As the metal foil, a single metal foil, an alloy foil, or a composite metal foil of copper, aluminum, brass, nickel, or the like can be used. It is preferable to use a metal foil having a thickness of 9 to 70 μm. The method for producing the resin-attached metal foil from the thermosetting resin composition and metal foil of the present invention is not particularly limited, and for example, the resin-attached metal foil can be obtained by applying a resin varnish obtained by adjusting the viscosity of the thermosetting resin composition with a solvent to one side of the metal foil using a roll coater or the like, and then heating and drying the resin component to semi-cure (B stage) and form a resin layer. For semi-cure of the resin component, for example, it can be heated and dried at 100 to 200° C. for 1 to 40 minutes. Here, it is preferable to form the thickness of the resin part of the resin-attached metal foil to be 5 to 110 μm.

[0136] In addition, the curing method of the laminate used in manufacturing a printed wiring board can be used to cure the prepreg or the insulating adhesive sheet, but is not limited thereto. For example, when forming a laminate using a prepreg, one or more prepregs are laminated, metal foil is placed on one or both sides to form a laminate, and the laminate is pressurized and heated to cure and integrate the prepregs, thereby obtaining a laminate. Here, the metal foil can be a single, alloy, or composite metal foil of copper, aluminum, brass, nickel, or the like.

[0137] The conditions for heating and pressing the laminate may be appropriately adjusted under the conditions under which the thermosetting resin composition cures, but if the pressure is too low, air bubbles may remain inside the resulting laminate, and the electrical properties may deteriorate, so it is preferable to pressurize under conditions that satisfy moldability. The heating temperature is preferably 160 to 250°C, more preferably 170 to 220°C. The pressure is preferably 0.5 to 10 MPa, more preferably 1 to 5 MPa. The heating and pressing time is preferably 10 minutes to 4 hours, more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently, and if the heating temperature is high, thermal decomposition of the cured product may occur. If the pressure is low, air bubbles may remain inside the resulting laminate, and the electrical properties may deteriorate, and if the pressure is high, the resin may flow before curing, and a laminate of the desired thickness may not be obtained. In addition, if the heating and pressing time is short, the curing reaction may not proceed sufficiently, and if it is long, thermal decomposition of the cured product may occur.

[0138] Furthermore, a multilayer board can be produced by using the single-layer laminate thus obtained as an inner layer material. In this case, a circuit is first formed on the laminate by an additive method, a subtractive method, or the like, and the surface of the formed circuit is blackened by treating it with an acid solution to obtain an inner layer material. An insulating layer is formed on one or both circuit-forming surfaces of this inner layer material using a prepreg, 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.

[0139] In addition, when the insulating layer is formed using a prepreg, a laminate of one or more prepregs is placed on the circuit-forming surface of the inner layer material, and a metal foil is placed on the outside of the laminate to form a laminate. Then, the laminate is heated and pressurized to be integrally molded, so that the cured prepreg is formed as an insulating layer, and the metal foil on the outside is formed as a conductor layer. Here, the metal foil can be the same as that used for the laminate used as the inner layer material. The heat and pressure molding can be performed under the same conditions as those for molding the inner layer material. The surface of the multilayer laminate thus molded can be further subjected to via hole formation and circuit formation by an additive method or a subtractive method to mold a printed wiring board. In addition, by repeating the above-mentioned process using this printed wiring board as the inner layer material, a multilayer board with more layers can be formed.

[0140] For example, when forming an insulating layer with an insulating adhesive sheet, an insulating adhesive sheet is placed on the circuit-forming surface of a plurality of inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is placed between the circuit-forming surface of the inner layer material and a metal foil to form a laminate. Then, this laminate is heated and pressurized to integrally mold the laminate, thereby forming a cured product of the insulating adhesive sheet as an insulating layer and forming a multi-layered inner layer material. Alternatively, a cured product of the insulating adhesive sheet is formed as an insulating layer between the inner layer material and the metal foil that is a conductor layer. Here, the same metal foil as that used in the laminate used as the inner layer material can be used. The heating and pressing molding can be performed under the same conditions as those for molding the inner layer material.

[0141] In addition, when forming an insulating layer by applying a thermosetting resin composition to a laminate, the thermosetting resin composition is applied to a thickness of preferably 5 to 100 μm, and then 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. It is generally formed by a method called a casting method. It is preferable to form the thickness after drying to 5 to 150 μm, preferably 5 to 80 μm. The viscosity of the thermosetting resin composition is preferably 10 to 40,000 mPa·s at 25 ° C, and more preferably 200 to 30,000 mPa·s, because a sufficient film thickness is obtained and uneven coating or streaks are unlikely to occur. A printed wiring board can be formed by further forming via holes or circuits on the surface of the multilayer laminate formed in this way by an additive method or a subtractive method. In addition, by repeating the above-mentioned process using this printed wiring board as an inner layer material, a further multilayer laminate can be formed.

[0142] The encapsulant obtained by using the thermosetting resin composition of the present invention can be suitably used for tape-shaped semiconductor chips, potting type liquid encapsulation, underfill, interlayer insulating film of semiconductors, etc. For example, in the case of semiconductor package molding, a method of molding the thermosetting resin composition by casting or using a transfer molding machine, injection molding machine, etc., and further heating at 50 to 200°C for 2 to 10 hours to obtain a molded product can be mentioned.

[0143] In order to prepare a thermosetting resin composition for use as a semiconductor encapsulation material, a method may be used in which the thermosetting resin composition is premixed with compounding agents such as an inorganic filler, and additives such as a coupling agent and a mold release agent, which are added as necessary, and then melt-mixed thoroughly until homogeneous using an extruder, kneader, roll, etc. In this case, silica is usually used as the inorganic filler, and in this case, it is preferable to mix the inorganic filler in the thermosetting resin composition in a proportion of 70 to 95 mass%.

[0144] When the thermosetting resin composition thus obtained is used as a tape-shaped sealant, it can be heated to prepare a semi-cured sheet to form a sealant tape, and then the sealant tape is placed on a semiconductor chip, softened and molded by heating to 100 to 150° C., and completely cured at 170 to 250° C. When used as a potting-type liquid sealant, the obtained thermosetting resin composition can be dissolved in a solvent as necessary, applied to a semiconductor chip or an electronic component, and directly cured.

[0145] The thermosetting resin composition of the present invention can also be used as a resist ink. In this case, a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are mixed into the thermosetting resin composition, and a pigment, talc, and a filler are further added to prepare a resist ink composition, which is then applied onto a printed circuit board by a screen printing method to form a resist ink cured product. The curing temperature at this time is preferably in the range of about 20 to 250°C.

[0146] A thermosetting resin composition was prepared, and the laminate and cured product were evaluated after heat curing. As a result, it was found that the cured product exhibited excellent low dielectric properties, and furthermore, a thermosetting resin composition having excellent heat resistance suitable for printed wiring board applications was provided. EXAMPLES

[0147] The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" refers to parts by mass, "%" refers to mass% and "ppm" refers to mass ppm. The measurement methods were as follows.

[0148] (1) Hydroxyl equivalent: The measurement was carried out in accordance with JIS K0070 standard, and the unit was expressed as "g / eq." Unless otherwise specified, the hydroxyl equivalent of an aromatic polyhydric hydroxy compound means the phenolic hydroxyl equivalent.

[0149] (2) Softening point: The softening point was measured according to the JIS K7234 standard, the ring and ball method, using an automatic softening point device (ASP-MG4, manufactured by Meitec Corporation).

[0150] (3) Dielectric constant and dielectric loss tangent: The dielectric constant and dielectric loss tangent at a frequency of 1 GHz were evaluated by the capacitance method using a material analyzer (manufactured by AGILENT Technologies) in accordance with IPC-TM-650 2.5.5.9.

[0151] (4) Glass transition temperature (Tg): In accordance with IPC-TM-650 2.4.25.c, measurements were performed using a differential scanning calorimeter (Hitachi High-Tech Science Corporation, EXSTAR6000 DSC6200) at a temperature increase rate of 20°C / min, and the temperature was expressed as DSC·Tgm (the midpoint temperature on the displacement curve for the tangent between the glassy state and the rubbery state).

[0152] (5) GPC (gel permeation chromatography) measurement: The main body (Tosoh Corporation, HLC-8220GPC) and the column (Tosoh Corporation, TSKgel G4000H XL , TSKgelG3000H XL , TSKgelG2000H XL ) in series, and the column temperature was set to 40°C. Tetrahydrofuran (THF) was used as the eluent, with a flow rate of 1 mL / min, and a differential refractive index detector was used as the detector. 0.1 g of sample was dissolved in 10 mL of THF and filtered through a microfilter, and 50 μL of the sample was used. Mw and Mn were calculated from the calibration curve obtained from standard polystyrene (PStQuick Kit-H, manufactured by Tosoh Corporation). Data processing was performed using GPC-8020 model II version 6.00 manufactured by Tosoh Corporation.

[0153] (6)IR: A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used with a diamond ATR, and the wavenumber was 650 to 4000 cm -1 The absorbance was measured.

[0154] The abbreviations used in the examples and comparative examples are as follows. [Aromatic hydroxy compounds] PH1: Aromatic hydroxy compound obtained in Synthesis Example 1 PH2: Aromatic hydroxy compound obtained in Synthesis Example 2 PH3: Allyl group-containing aromatic hydroxy compound obtained in Synthesis Example 3 PH4: Allyl group-containing aromatic hydroxy compound obtained in Synthesis Example 4 PH5: Allyl-containing aromatic hydroxy compound obtained in Synthesis Example 5 PH6: 1-Naphthol PH7: 4,4'-(1-methylethylidene)bis(2-allylphenol) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., allyl group equivalent: 154) PH8: Biphenyl aralkyl type polyhydric hydroxyl resin (Meiwa Kasei Co., Ltd., MEH-7851, phenol hydroxyl group equivalent 223)

[0155] [Aromatic carboxylic acid halides] B1: Isophthalic acid chloride B2: Terephthalic acid chloride

[0156] [Epoxy resin] E1: Phenol-dicyclopentadiene type epoxy resin (Kokuto Chemical Co., Ltd., KDCP-130, epoxy equivalent 254, softening point 72°C)

[0157] [Maleimide compounds] M1: Phenylmethanemaleimide (manufactured by Daiwa Chemical Industry Co., Ltd., BMI-2300)

[0158] [Hardening agent] A1: Active ester resin obtained in Example 1 A2: Active ester resin obtained in Example 2 A3: Active ester resin obtained in Example 3 A4: Active ester resin obtained in Example 4 A5: Active ester resin obtained in Example 5 A6: Active ester resin obtained in Example 6 A7: Active ester resin obtained in Example 7 A8: Active ester resin obtained in Example 8 A9: Active ester resin obtained in Example 9 A10: Active ester resin obtained in Example 10 A11: Active ester resin obtained in Reference Example 1 A12: Active ester resin obtained in Reference Example 2

[0159] [Cure accelerator] C1: 4-Dimethylaminopyridine (Kishida Chemical Co., Ltd.) [others] PO: Organic peroxide (Perbutyl P, manufactured by NOF Corporation)

[0160] Synthesis Example 1 In a reaction apparatus consisting of a glass separable flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, a dropping funnel, and a cooling tube, 2,6-xylenol (structural formula below) was added. [ka] 500 parts of ethanol and 7.3 parts of 47% BF3 ether complex were charged and heated to 100°C with stirring. While maintaining the temperature, dicyclopentadiene (structural formula below) [ka] 67.6 parts (0.12 times mole relative to 2,6-xylenol) was added dropwise over 1 hour. The mixture was further reacted at a temperature of 115-125°C for 4 hours, and 11 parts of calcium hydroxide were added. 19 parts of 10% aqueous oxalic acid solution were further added. After that, the mixture was heated to 160°C for dehydration, and then heated to 200°C under a reduced pressure of 5mmHg to evaporate and remove unreacted raw materials. 1320 parts of methyl isobutyl ketone (MIBK) were added to dissolve the product, and 400 parts of 80°C hot water were added to wash the product, and the lower layer water was separated and removed. After that, the mixture was heated to 160°C under a reduced pressure of 5mmHg to evaporate and remove MIBK, and 164 parts of a reddish-brown aromatic hydroxy compound (PH1) was obtained. The aromatic hydroxy compound (PH1) thus obtained had a hydroxyl equivalent of 195 and a softening point of 73° C. The aromatic hydroxy compound represented by formula (8): [ka] R 1 was a methyl group, i was 2, Mw was 470, Mn was 440 as measured by GPC, the content of u=0 isomer was 2.8 area%, the content of u=1 isomer was 86.2 area%, and the content of u=2 or more isomers was 11.0 area%.

[0161] Synthesis Example 2 In a reaction apparatus similar to that of Synthesis Example 1, 400 parts of phenol and 7.5 parts of 47% BF3 ether complex were charged and heated to 70°C while stirring. While maintaining the same temperature, 70.2 parts of dicyclopentadiene were dropped over 2 hours. The mixture was further reacted at a temperature of 125 to 135°C for 4 hours, and 11.7 parts of calcium hydroxide were added. Furthermore, 20 parts of a 10% aqueous oxalic acid solution were added. After that, the mixture was heated to 160°C for dehydration, and then heated to 200°C under a reduced pressure of 5mmHg to evaporate and remove unreacted raw materials. 1100 parts of MIBK were added to dissolve the product, and 330 parts of 80°C hot water were added to wash the product, and the lower layer water tank was separated and removed. After that, the mixture was heated to 160°C under a reduced pressure of 5mmHg to evaporate and remove MIBK, and 158 parts of a reddish-brown aromatic hydroxy compound (PH2) was obtained. The hydroxyl equivalent was 177, and the softening point was 92°C. The aromatic hydroxy compound is represented by formula (8), in which i is 0, and the Mw and Mn measured by GPC were 460 and 394, respectively, and the content of u=0 isomer was 0 area%, the content of u=1 isomer was 66.7 area%, and the content of u=2 or more isomers was 33.3 area%.

[0162] Synthesis Example 3 In a similar apparatus to that used in Synthesis Example 1, 100 parts of aromatic hydroxy compound (PH1), 9.2 parts of 86% aqueous potassium hydroxide solution, 200 parts of cyclopentyl methyl ether (CPME) as a solvent, and 25 parts of methanol were charged and heated to 60°C to dissolve. After cooling to 20°C, 16.3 parts of allyl bromide (0.26 moles per mole of hydroxy group in PH1) were added. [ka] was added dropwise over 30 minutes, and the mixture was allowed to react at 60° C. for 3 hours. The resulting resin was dissolved in 360 parts of cyclopentyl methyl ether and washed with 100 parts of methanol water with a methanol concentration of 30%. Thereafter, the solvent was distilled off under reduced pressure at 5 mmHg and heated to 150° C. to obtain 105 parts of a solid allyl group-containing aromatic hydroxy compound (PH3). The obtained allyl group-containing aromatic hydroxy compound (PH3) had a hydroxyl equivalent of 245, an allyl equivalent of 1140, a softening point of 66°C, and a total chlorine content of 82 ppm. [ka] R 1 is a methyl group, R 2 is a hydrogen atom, i is 2, and X 1 The content of allyl groups was 17 mol %, and the remainder was hydrogen atoms. The Mw and Mn measured by GPC were 467 and 440, respectively, and the content of n=0 was 1.9 area %, the content of n=1 was 87.4 area %, and the content of n=2 or more was 10.6 area %.

[0163] Synthesis Example 4 The same procedure as in Synthesis Example 3 was carried out except that the amount of 86% potassium hydroxide aqueous solution was changed to 18.4 parts and the amount of allyl bromide was changed to 32.6 parts (0.53 moles per mole of hydroxyl groups in PH1), to obtain 110 parts of a solid allyl group-containing aromatic hydroxy compound (PH4). The obtained allyl-containing aromatic hydroxy compound (PH4) had a hydroxyl equivalent of 396, an allyl equivalent of 460, a softening point of 51°C, and a total chlorine content of 97 ppm. 1 The content of allyl groups was 46 mol %, and the remainder was hydrogen atoms. The Mw and Mn measured by GPC were 475 and 440, respectively, and the content of n=0 was 2.7 area %, the content of n=1 was 85.8 area %, and the content of n=2 or more was 11.5 area %.

[0164] Synthesis Example 5 The same procedure as in Synthesis Example 3 was carried out except that the amount of 86% potassium hydroxide aqueous solution was changed to 27.6 parts and the amount of allyl bromide was changed to 48.9 parts (0.79 moles per mole of hydroxyl groups in PH1), to obtain 115 parts of a semi-solid allyl group-containing aromatic hydroxy compound (PH5). The obtained allyl-containing aromatic hydroxy compound (PH5) had a hydroxyl equivalent of 780, an allyl equivalent of 310, and a total chlorine content of 120 ppm. 1The content of n=0 was 2.5 area %, the content of n=1 was 83.4 area %, and the content of n=2 or more was 14.1 area %.

[0165] Example 1 Into a reaction vessel equipped with a stirrer, a thermometer, a nitrogen inlet, a dropping funnel, and a cooling tube, 100 parts of the allyl group-containing aromatic hydroxy compound (PH3) obtained in Synthesis Example 3, 29.4 parts of 1-naphthol (PH6), [ka] 1.7 parts of tetra n-butylammonium bromide (TBAB), 62.2 parts of isophthalic acid chloride (B1) as an aromatic carboxylic acid halide, [ka] 479 parts of toluene (TL) were charged and heated to 50 ° C. to dissolve. While controlling the temperature in the system to 60 ° C. or less, 123 parts of 20% aqueous sodium hydroxide solution (20% NaOH) was added dropwise over 3 hours, and then stirring was continued at the same temperature for another 4 hours. The reaction mixture was allowed to stand and separated, and the water tank was removed. This operation was repeated until the pH of the water tank 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 content of 65%. The active ester equivalent calculated from the amount of raw materials charged was 277. The allyl group in the total X of general formula (1) is 17 mol %. GPC of the obtained active ester resin (A1) is shown in Figure 1, and FT-IR is shown in Figure 2.

[0166] Example 2 The same operation as in Example 1 was carried out, except that 1-naphthol (PH6) was 17.7 parts, tetra-n-butylammonium bromide (TBAB) was 1.5 parts, isophthalic acid chloride (B1) was 53.9 parts, 20% aqueous sodium hydroxide solution (20% NaOH) was 106 parts, and toluene (TL) was 430 parts, to obtain active ester resin (A2). The active ester equivalent calculated from the amount of the raw materials was 288. The allyl group in the total X of general formula (1) is 17 mol%.

[0167] Example 3 The same operation as in Example 1 was carried out, except that 5.9 parts of 1-naphthol (PH6), 1.2 parts of tetra-n-butylammonium bromide (TBAB), 45.6 parts of isophthalic acid chloride (B1), 90 parts of 20% aqueous sodium hydroxide solution (20% NaOH), and 380 parts of toluene (TL) were used, to obtain an active ester resin (A3). The active ester equivalent calculated from the amount of the raw materials was 302. The allyl group in the total X of the general formula (1) is 17 mol%.

[0168] Example 4 The same operation as in Example 1 was carried out, except that 29.4 parts of 1-naphthol (PH6), 1.7 parts of tetra-n-butylammonium bromide (TBAB), 31.1 parts of isophthalic acid chloride (B1), 31.1 parts of terephthalic acid chloride (B2), 123 parts of 20% aqueous sodium hydroxide solution (20% NaOH), and 480 parts of toluene (TL) were used, to obtain an active ester resin (A4). The active ester equivalent calculated from the amount of the raw materials charged was 277. The allyl group in the total X of the general formula (1) is 17 mol%.

[0169] Example 5 The same operation as in Example 1 was carried out to obtain an active ester resin (A5), except that the allyl group-containing aromatic hydroxy compound (PH3) obtained in Synthesis Example 3 was used in 50 parts, the aromatic hydroxy compound (PH1) in Synthesis Example 1 in 50 parts, 1-naphthol (PH6) in 33.2 parts, tetra n-butylammonium bromide (TBAB) in 1.9 parts, isophthalic acid chloride (B1) in 70.1 parts, 20% aqueous sodium hydroxide solution (20% NaOH) in 138 parts, and toluene (TL) in 510 parts were used. The active ester equivalent calculated from the amount of the raw materials was 259. The allyl group in the total X in the general formula (1) is 17 mol%.

[0170] Example 6 The same operation as in Example 1 was carried out to obtain an active ester resin (A6), except that the allyl group-containing aromatic hydroxy compound (PH3) obtained in Synthesis Example 3 was used in 50 parts, the aromatic hydroxy compound (PH2) in Synthesis Example 2 in 50 parts, 1-naphthol (PH6) in 35.1 parts, tetra n-butylammonium bromide (TBAB) in 2.0 parts, isophthalic acid chloride (B1) in 74.1 parts, 20% aqueous sodium hydroxide solution (20% NaOH) in 146 parts, and toluene (TL) in 520 parts were used. The active ester equivalent calculated from the amount of the raw materials was 251. The allyl group in the total X in the general formula (1) is 17 mol%.

[0171] Example 7 The same operation as in Example 1 was carried out to obtain an active ester resin (A7), except that the allyl group-containing aromatic hydroxy compound (PH3) obtained in Synthesis Example 3 was used in 50 parts, the aromatic hydroxy compound (PH8) in 50 parts, 1-naphthol (PH6) in 30.9 parts, tetra n-butylammonium bromide (TBAB) in 1.8 parts, isophthalic acid chloride (B1) in 65.2 parts, 20% aqueous sodium hydroxide solution (20% NaOH) in 129 parts, and toluene (TL) in 490 parts were used. The active ester equivalent calculated from the amount of the raw materials was 414. The allyl group in the total X of the general formula (1) is 17 mol%.

[0172] Example 8 The same operation as in Example 1 was carried out, except that the allyl group-containing aromatic hydroxy compound (PH4) obtained in Synthesis Example 4 was changed to 100 parts, 1-naphthol (PH6) to 18.2 parts, tetra n-butylammonium bromide (TBAB) to 1.0 parts, isophthalic acid chloride (B1) to 38.4 parts, 20% aqueous sodium hydroxide solution (20% NaOH) to 76 parts, and toluene (TL) to 390 parts, to obtain an active ester resin (A8). The active ester equivalent calculated from the amount of the raw materials was 378. The allyl group in the total X of the general formula (1) is 46 mol%.

[0173] Example 9 The same operation as in Example 1 was carried out to obtain an active ester resin (A9), except that the allyl group-containing aromatic hydroxy compound (PH5) obtained in Synthesis Example 5 was used in 100 parts, 1-naphthol (PH6) in 9.2 parts, tetra n-butylammonium bromide (TBAB) in 0.5 parts, isophthalic acid chloride (B1) in 19.5 parts, 20% aqueous sodium hydroxide solution (20% NaOH) in 38 parts, and toluene (TL) in 320 parts were used. The active ester equivalent calculated from the amount of the raw materials was 634. The allyl group in the total X of the general formula (1) is 71 mol%.

[0174] Example 10 The same operation as in Example 1 was carried out to obtain an active ester resin (A10), except that the allyl group-containing aromatic hydroxy compound (PH5) obtained in Synthesis Example 5 was changed to 100 parts, tetra n-butylammonium bromide (TBAB) to 0.4 parts, isophthalic acid chloride (B1) to 13.0 parts, 20% aqueous sodium hydroxide solution (20% NaOH) to 26 parts, and toluene (TL) to 280 parts were changed. The active ester equivalent calculated from the amount of the raw materials was 846. The allyl group in the total X of the general formula (1) is 71 mol%.

[0175] Reference example 1 The same operation as in Example 1 was carried out, except that the aromatic hydroxy compound PH1 in Synthesis Example 1 was changed to 100 parts, 1-naphthol (PH6) to 24.4 parts, tetra n-butylammonium bromide (TBAB) to 1.9 parts, isophthalic acid chloride (B1) to 69.2 parts, 20% aqueous sodium hydroxide solution (20% NaOH) to 136 parts, and toluene (TL) to 480 parts, to obtain an active ester resin (A11). The active ester equivalent calculated from the amount of the raw materials charged was 248.

[0176] Reference example 2 The same operation as in Example 1 was carried out, except that the aromatic hydroxy compound PH2 in Synthesis Example 2 was changed to 100 parts, 1-naphthol (PH6) to 26.9 parts, tetra n-butylammonium bromide (TBAB) to 2.1 parts, isophthalic acid chloride (B1) to 76.3 parts, 20% aqueous sodium hydroxide solution (20% NaOH) to 150 parts, and toluene (TL) to 510 parts, to obtain an active ester resin (A12). The active ester equivalent calculated from the amount of the raw materials was 235.

[0177] Example 11 In terms of solid content, 100 parts of the active ester resin (A1) obtained in Example 1, 67 parts of the phenol-dicyclopentadiene type epoxy resin (E1) as an epoxy resin, and 0.33 parts of C1 as a curing accelerator were mixed and dissolved in methyl ethyl ketone to obtain an epoxy resin composition varnish so that the non-volatile content was 50%. The obtained epoxy resin composition varnish was impregnated into glass cloth (manufactured by Nitto Boseki Co., Ltd., WEA 7628 XS13, 0.18 mm thick). The impregnated glass cloth was dried in a hot air circulating oven at 150°C for 5 minutes to obtain a prepreg.

[0178] The obtained prepreg was loosened and sieved to obtain prepreg powder with a 100 mesh pass. The obtained prepreg powder was placed in a fluororesin mold and vacuum pressed at 2 MPa under the temperature conditions of 130°C x 15 minutes + 210°C x 80 minutes to obtain a test piece of 50 mm square x 2 mm thick. The results of the relative dielectric constant and dielectric loss tangent of the test piece are shown in Table 1.

[0179] Examples 12 to 22, Comparative Examples 1 to 3 The blending amounts (parts) in Table 1 were used, and prepregs and test pieces were obtained by the same procedure as in Example 9. The results of the relative dielectric constant and dielectric loss tangent of the test pieces obtained are shown in Table 1. The blending amounts of A1 to A12 are shown as solid content converted values.

[0180] [Table 1]

Claims

1. An active ester resin comprising a polyaryloxy unit and a polyarylcarbonyl unit, the active ester resin having an allyl group-containing unit represented by the following formula (1) as the polyaryloxy unit: 【Chemistry 1】 Here, R １ each independently represents a hydrocarbon group having 1 to 12 carbon atoms; R ２ independently represent a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; X independently represents a bonding site with a polyarylcarbonyl unit or an allyl group, with 1 to 99 mol % of all Xs being allyl groups; i is an integer of 0 to 3; n represents the number of repetitions, the average value of which is a number of 0.1 to 5.

2. The active ester resin according to claim 1, which contains polyaryloxy units other than the unit represented by the above formula (1) as the polyaryloxy units, and the other polyaryloxy units are units represented by the following formula (4) and / or formula (5). 【Chemistry 2】 Here, Ar １ are independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have, as a substituent, 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. １１ R is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent group represented by formula (4a). １１ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. m represents the number of repetitions, the average value of which is a number from 1 to 5. r is 1 or 2. 【Chemistry 3】 Here, Ar １ are independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have, as a substituent, 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. ３ represents a direct bond or a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ２ -, and -C(CF ３ ) ２ - is a divalent group selected from the group consisting of -, and k is 0 or 1.

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

4. The active ester resin according to claim 1, further comprising a monoaryloxy group, the monoaryloxy group being a group represented by the following formula (6): 【Chemistry 5】 Here, Ar ２ are independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have, as a substituent, 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. ４ is a direct bond, -CH ２ -, -C(CH ３ ) ２ -, -CH(CH ３ )-, -CO-, -O-, -S-, -SO ２ -, and -C(CF ３ ) ２ - is a divalent group selected from the group consisting of １４ is a direct bond, -CH ２ -, -C(CH ３ ) ２ -, -CH(CH ３ )- and -C(CF ３ ) ２ - is a divalent group selected from the group consisting of -, and k is 0 or 1.

5. 2. The active ester resin according to claim 1, wherein the polyarylcarbonyl unit is a unit represented by the following formula (7): 【Chemistry 6】 Here, Ar ３ are independently an aromatic ring group of a benzene ring, a naphthalene ring, or a biphenyl ring, and these aromatic rings may have, as a substituent, 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. ５ represents a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ２ -, and -C(CF ３ ) ２ - is a divalent group selected from the group consisting of 0 and 1.

6. A method for producing an active ester resin by reacting an aromatic hydroxy compound with an aromatic polyvalent carboxylic acid or an acid halide thereof, the method being characterized in that the aromatic hydroxy compound contains an allyl group-containing aromatic polyvalent hydroxy compound represented by the following formula (11): 【Chemistry 7】 Here, R １ each independently represents a hydrocarbon group having 1 to 12 carbon atoms; R ２ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms; １ each independently represents a hydrogen atom or an allyl group, １ Among them, 1 to 99 mol % are allyl groups; i is an integer of 0 to 3; n is the number of repetitions, the average of which is a number of 0.1 to 5.

7. A thermosetting resin composition comprising the active ester resin according to any one of claims 1 to 5 and another thermosetting resin as essential components.

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

9. A prepreg comprising the thermosetting 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 thermosetting resin composition or a semi-cured product thereof according to claim 7 and a support film.

11. A laminate comprising the prepreg according to claim 9.

12. A laminate comprising the resin sheet according to claim 10.

13. A material for circuit boards, comprising the thermosetting resin composition according to claim 7.

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