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

Abstract

The present invention provides an epoxy resin composition having excellent low dielectric properties, excellent copper foil peel strength and interlayer adhesion strength in printed wiring board applications, and an active ester resin for supplying the epoxy resin composition. An active ester resin characterized by comprising a polyaryloxy unit containing a dicyclopentenyl group represented by the following formula (1) and a polyarylcarbonyl unit. Here, R 1 represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 represents a hydrogen atom, Formula (1a) or Formula (1b), R 2 At least one of them is Formula (1a) or Formula (1b). n represents the number of repetitions of 1 to 5.

Description

Technical Field

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

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

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

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

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

[0006] The active ester resins disclosed in any of the above documents cannot fully meet the performance requirements based on high functionality in recent years, and are insufficient to ensure low dielectric properties and adhesiveness.

[0007] On the other hand, Patent Document 3 discloses a 2,6-xylenol / dicyclopentadiene type epoxy resin, but does not disclose a resin in which a plurality of dicyclopentadienes are substituted on a phenol ring, and does not study active ester resins.

[0008] Prior art literature

[0009] Patent Literature

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

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

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

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

[0014] To solve the above problems, the present inventors have found that when an aromatic polyhydric hydroxy compound obtained by reacting dicyclopentadiene with 2,6-disubstituted phenols at a specific ratio is actively esterified and cured with an epoxy resin, the obtained cured product has excellent low dielectric properties and adhesion, thereby completing the present invention.

[0015] That is, the present invention is an active ester resin characterized by having a polyaryloxy unit containing a bicyclopentenyl group represented by the following formula (1) and a polyarylcarbonyl unit.

[0016]

[0017] Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a hydrogen atom, a dicyclopentenyl group represented by the following formula (1a) or (1b), R 2 At least one of them is the above-mentioned dicyclopentenyl group. n represents the number of repetitions, and its average value is a number of 1 to 5.

[0018]

[0019] As the polyaryloxy unit, it is preferred that other polyaryloxy units be included in addition to the unit represented by the above formula (1), and the other polyaryloxy unit is a unit represented by the following formula (4) and / or formula (5).

[0020]

[0021] Here, m represents the number of repetitions, and its average value is a number from 1 to 5.

[0022]

[0023] Among them, Ar 1 Each independently represents any aromatic ring group in a benzene ring or a naphthalene ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent. 3 is a direct bond or is selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO 2 - and -C(CF3 ) 2 - is a divalent group. k is 0 or 1.

[0024] It is preferred that the monoaryloxy group be present at the molecular chain terminal, and the monoaryloxy group be a group represented by the following formula (2) and / or formula (6).

[0025]

[0026] Among them, R 1 , R 2 This has the same meaning as in the above formula (1).

[0027]

[0028] Among them, Ar 2 Each independently represents any aromatic ring group in a benzene ring or a naphthalene ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent. 4 Can be directly bonded or selected from -CH 2 -、―C(CH 3 ) 2 ―、―CH(CH 3 )―, -CO-, -O-, -S-, -SO 2 - and -C(CF 3 ) 2 - is a divalent group. k is 0 or 1.

[0029] The polyarylcarbonyl unit is preferably a unit represented by the following formula (7).

[0030]

[0031] Among them, Ar 3 Each independently represents any aromatic ring group in a benzene ring or a naphthalene ring, and these aromatic rings may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent. 3 is a direct bond or is selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO 2 -, and -C(CF 3 ) 2 - is a divalent group. k is 0 or 1.

[0032] The present invention is also a method for producing an active ester resin, characterized in that the active ester resin is produced from an aromatic hydroxy compound and an aromatic polycarboxylic acid or an acid halide thereof, wherein the aromatic hydroxy compound is a dicyclopentenyl-containing aromatic hydroxy compound represented by the following formula (8).

[0033]

[0034] Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a hydrogen atom, a dicyclopentenyl group represented by the following formula (1a) or (1b), R 2 At least one of them is the above-mentioned bicyclopentenyl group. u represents the number of repetitions, including u=0 components and u≥1 components, and the average value of the u≥1 components is a number of 1 to 5.

[0035]

[0036] The present invention is a method for producing an active ester resin, characterized in that it is a method for producing the above-mentioned active ester resin, characterized in that it is a method for producing the above-mentioned active ester resin, wherein a 2,6-disubstituted phenol is reacted with dicyclopentadiene to obtain an aromatic hydroxy compound containing a dicyclopentenyl group represented by the above-mentioned formula (8), and the aromatic hydroxy compound is reacted with an aromatic polycarboxylic acid or its acid halide.

[0037] In the method for producing the active ester resin, it is preferred that 0.28 to 2 mol of dicyclopentadiene and 1 mol of 2,6-disubstituted phenol be reacted to obtain the aromatic hydroxy compound.

[0038] The present invention is an epoxy resin composition comprising the above-mentioned active ester resin and epoxy resin as essential components.

[0039] The present invention is a cured product obtained by curing the epoxy resin composition, and is a prepreg, a laminate, and a circuit board material obtained by using the epoxy resin composition.

[0040] The epoxy resin composition of the present invention provides an epoxy resin composition having excellent dielectric properties in its cured product, and further having excellent copper foil peel strength and interlayer adhesion strength in printed wiring board applications. In particular, it can be suitably used in mobile device applications and server applications that strongly require low dielectric loss tangent. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a GPC chart of the aromatic hydroxy compound obtained in Synthesis Example 1.

[0042] Figure 2 This is the IR chart of the aromatic hydroxy compound in Synthesis Example 1.

[0043] Figure 3 This is the GPC chart of the active ester resin in Example 1.

[0044] Figure 4 This is the IR chart of the active ester resin in Example 1.

[0045] Figure 5 This is a GPC chart of the aromatic hydroxy compound in Reference Example 1.

[0046] Figure 6 This is a GPC chart of the active ester resin in Reference Example 2. DETAILED DESCRIPTION

[0047] Hereinafter, embodiments of the present invention will be described in detail.

[0048] The active ester resin of the present invention is composed of a polyaryloxy unit, which is essentially a group represented by the above formula (1), and a polyarylcarbonyl unit. The polyaryloxy unit is a residue of a raw aromatic polyhydroxy compound, and the polyarylcarbonyl unit is a residue of a raw aromatic polycarboxylic acid (aromatic polycarboxylic acid halide). In addition, the molecular chain end preferably has a monoaryloxy group. The monoaryloxy group is a group derived from a raw aromatic monohydroxy compound.

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

[0050] The ester bond in the active ester resin of the present invention has a high reactivity with the epoxy group, and therefore can be used appropriately as a curing agent for epoxy resin. In addition, since the effect of not generating highly polar hydroxyl groups during curing and the substituent R derived from dicyclopentadiene are not generated, 2 The synergistic effect of the effect, the obtained cured product exhibits low dielectric loss tangent and low relative dielectric constant. In addition, since the molecular chain ends are aryloxycarbonyl groups, even if the ester bonds at the cross-linking points of the obtained cured product are hydrolyzed due to moisture absorption, the low molecular weight carboxylic acids that increase the dielectric loss tangent will not be freed, and the obtained cured product also exhibits low dielectric loss tangent under high humidity conditions. In addition, since there are many ester bonds reactive with epoxy groups inside the molecular chain, the cross-linking density of the cured product is high, and the heat resistance (glass transition temperature: Tg) becomes higher. In addition, since there are many alicyclic structures from hydrophobic dicyclopentadiene in the structure, it absorbs less water and exhibits stable dielectric properties under high humidity environments.

[0051] In the above formula (1), R 1It represents a hydrocarbon group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 8 carbon atoms, an aralkyl group having 7 to 8 carbon atoms, or an allyl group. As an alkyl group having 1 to 8 carbon atoms, it can be any of a linear, branched, or cyclic group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, a methylcyclohexyl group, etc., but not limited thereto. As an aryl group having 6 to 8 carbon atoms, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, etc., can be mentioned, but not limited thereto. As an aralkyl group having 7 to 8 carbon atoms, a benzyl group, an α-methylbenzyl group, etc. can be mentioned, but not limited thereto. Among these substituents, from the viewpoint of ease of obtaining and reactivity when a cured product is made, a phenyl group and a methyl group are preferred, and a methyl group is particularly preferred.

[0052] The above R 2 Each independently represents a hydrogen atom, the above formula (1a) or formula (1b), R 2 At least one of them is any one of formula (1a) and formula (1b). Formula (1a) and formula (1b) can be said to be a dicyclopentenyl group derived from dicyclopentadiene.

[0053] n is the number of repetitions, and represents a number greater than or equal to 1, and its average value (number average) is 1 to 5, preferably 1.1 to 4.0, more preferably 1.2 to 3.0, and further preferably 1.3 to 2.0.

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

[0055] Among them, it is preferred that the dicyclopentadienyl group-containing unit represented by the above formula (1) is present in an amount of preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably 50 mol% or more, relative to the total amount of the polyaryloxy units constituting the active ester resin of the present invention. In addition, it is preferred that the total amount of the dicyclopentadienyl group-containing unit represented by the above formula (1) and the dicyclopentadienyl group-containing unit represented by the above formula (4) is present in an amount of preferably 30 mol% or more, more preferably 50 mol% or more, relative to the total amount of the polyaryloxy units.

[0056] In the above formula (4), m represents the number of repetitions, and its average value is a number of 1 to 5.

[0057] The above formula (5) is a general formula of the units represented by the following formulae (5a) to (5e). Formulae (6) and (7) are also general formulae of the same chemical formulae.

[0058]

[0059] Among them, R 3 R 3 Same meaning. 5 It is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms. i is an integer of 0 to 4, and j is an integer of 0 to 6.

[0060] In the above formula (5), Ar 1 represents any aromatic ring group in a benzene ring or a naphthalene ring. Moreover, even if these aromatic rings are composed only of a benzene ring or a naphthalene ring, they may have a substituent R 5 Here, the substituent R 5 It is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms.

[0061] The alkyl group having 1 to 10 carbon atoms may be any of a linear, branched or cyclic group, 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 tert-butyl group, an isopentyl group, a neopentyl group, a tert-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.

[0062] The alkoxy group having 1 to 10 carbon atoms may be any of linear, branched or cyclic, and examples thereof include methoxy, ethoxy, n-propoxy, n-butoxy, n-pentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, isopropoxy, sec-butoxy, tert-butoxy, isopentyloxy, neopentyloxy, tert-pentyloxy, isohexyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, methylcyclohexyloxy, cyclooctyloxy, dimethylcyclohexyloxy, ethylcyclohexyloxy, trimethylcyclohexyloxy and cyclodecyloxy.

[0063] Examples of the aryl group or aryloxy group having 6 to 11 carbon atoms include phenyl, tolyl, ethylphenyl, xylyl, propylphenyl, mesityl, naphthyl, methylnaphthyl, phenoxy, tolyloxy, ethylphenoxy, xylyloxy, propylphenoxy, mesityloxy, naphthyloxy, and methylnaphthyloxy.

[0064] Examples of the aralkyl group or aralkyloxy group having 7 to 12 carbon atoms include benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, phenethyl, 1-phenylethyl, 2-phenylisopropyl, naphthylmethyl, benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, phenethoxy, 1-phenylethoxy, 2-phenylisopropyloxy and naphthylmethoxy.

[0065] As the above Ar 1 , preferably a phenylene group, a naphthylene group, or an aromatic ring group substituted with a methyl group or a 1-phenylethyl group.

[0066] In the above formula (5), R 3 is a direct bond or is selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO 2 - and -C(CF 3 ) 2 -The divalent group in.

[0067] Examples of the hydrocarbon group having 1 to 20 carbon atoms include -CH 2 -、-CH(CH 3 )-、-C 2 H 4 -, -C(CH 3 ) 2 -, cyclohexylene, methylcyclohexylene, dimethylcyclohexylene, methylisopropylcyclohexylene, cyclohexylcyclohexylene, cyclohexylidene, methylcyclohexylidene, dimethylcyclohexylidene, trimethylcyclohexylidene, tetramethylcyclohexylidene, ethylcyclohexylidene, isopropylcyclohexylidene, tert-butylcyclohexylidene, phenylcyclohexylidene, cyclohexylcyclohexylidene, (methylcyclohexyl)cyclohexylidene, (ethylcyclohexyl)cyclohexylidene, (phenylcyclohexyl)cyclohexylidene, Cyclododecylene, cyclopentylidene, methylcyclopentylidene, trimethylcyclopentylidene, cyclooctylidene, cyclododecylidene, 9H-fluorene-9,9-diyl, bicyclo[4.4.0]decanediyl, bicyclohexylene, phenylene, xylylene, phenylmethylene, diphenylmethylene, norbornylene, adamantylene, tetrahydrobiscyclopentadienylene, tetrahydrotricyclopentadienylene, a divalent group having a norbornane structure or a tetrahydrotricyclopentadiene structure, or the like.

[0068] Preferred R 3 For direct bonding, -CH 2 -、-CH(CH 3 )-、-C(CH 3 ) 2 -, -CO-, -O-, -S-, -SO 2 -, trimethylcyclohexylidene, cyclooctylidene, cyclododecylidene, dicyclohexanediyl, 9H-fluorene-9,9-diyl, phenylmethylene.

[0069] The active ester resin of the present invention has a monoaryloxy group at the molecular chain terminal. The monoaryloxy group is not particularly limited, but is preferably a group represented by the above formula (2) and / or formula (6), and more preferably a group represented by formula (2).

[0070] The dicyclopentadienyl group-containing group represented by the above formula (2) preferably accounts for 20 mol% or more, more preferably 50 mol% or more, based on the total amount of the monoaryloxy groups constituting the molecular chain ends.

[0071] In formula (2), R 1 and R 2 R of the above formula (1) 1 and R 2 The meanings are the same, and the preferred substituents are also the same.

[0072] In formula (6), Ar 2 is the same as Ar in the above formula (5) 1 The same aromatic ring group may have the same substituent, and the preferred substituents are also the same.

[0073] R 4 For direct bonding, selected from -CH 2 -、―C(CH 3 ) 2 ―、―CH(CH 3 )―, -CO-, -O-, -S-, -SO 2 - and -C(CF 3 ) 2 -The divalent group in.

[0074] The polyarylcarbonyl unit is not particularly limited, but a unit represented by the above formula (7) is preferred.

[0075] In formula (7), Ar 3 is the same as Ar in the above formula (5) 1 The same aromatic ring group may have the same substituent, and the preferred substituents are also the same. 3 R 3 Same meaning.

[0076] The aromatic hydroxy compound which is an essential raw material for synthesizing the above active ester resin is represented by the above formula (8) and can be obtained by reacting 2,6-disubstituted phenols and dicyclopentadiene in the presence of a Lewis acid such as a boron trifluoride / ether catalyst.

[0077] The u=0 component of the aromatic hydroxy compound is a monoaryloxy group represented by the above formula (2) at the molecular chain terminal of the active ester resin, and the u=1 or more component is a polyaryloxy unit represented by the above formula (1) of the active ester resin.

[0078] The content of the u=0 component may be 0 to 90 area %, preferably 5 to 80 area %, and more preferably 10 to 50 area %. The content of the u=1 component may be 7 to 90 area %, preferably 15 to 70 area %, and more preferably 30 to 60 area %. The total content of the components with u=2 or more may be 3 to 50 area %, preferably 5 to 35 area %, and more preferably 10 to 25 area %.

[0079] In addition, if a large amount of an aromatic hydroxy compound having an average value of u greater than 1.8 is used, gelation may occur when the active ester resin is synthesized by dissolving in a solvent. Therefore, it is preferred to use an aromatic hydroxy compound having an average value of u in the range of 0.3 to 1.8, a more preferred range is 0.5 to 1.7, and a further preferred range is 0.8 to 1.6. In addition, gelation can also be prevented by appropriately adjusting the amount used according to the average value of u and using other monovalent or divalent aromatic hydroxy compounds.

[0080] Examples of the 2,6-disubstituted phenols include 2,6-dimethylphenol, 2,6-diethylphenol, 2,6-dipropylphenol, 2,6-diisopropylphenol, 2,6-di-n-butylphenol, 2,6-di-tert-butylphenol, 2,6-dihexylphenol, 2,6-dicyclohexylphenol, 2,6-diphenylphenol, 2,6-xylenolphenol, 2,6-dibenzylphenol, 2,6-bis(α-methylbenzyl)phenol, 2-ethyl-6-methylphenol, 2-allyl-6-methylphenol, and 2-tolyl-6-phenylphenol. From the viewpoint of availability and reactivity when formed into a cured product, 2,6-diphenylphenol and 2,6-dimethylphenol are preferred, and 2,6-dimethylphenol is particularly preferred.

[0081] The catalyst used in the above reaction is a Lewis acid, specifically, boron trifluoride, boron trifluoride phenol complex, boron trifluoride ether complex, aluminum chloride, tin chloride, zinc chloride, ferric chloride, etc., wherein, from the ease of operation, boron trifluoride ether complex is preferred. The amount of the catalyst used, in the case of boron trifluoride ether complex, is 0.001 to 20 parts by mass, preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of dicyclopentadiene.

[0082] As a reaction method for introducing the dicyclopentenyl group represented by the above formula (1a) or formula (1b) into 2,6-disubstituted phenols, there is a method of reacting dicyclopentadiene with 2,6-disubstituted phenol at a predetermined ratio, or dicyclopentadiene can be reacted in two steps. In a conventional reaction, the ratio is 0.1 to 0.25 times the mole of dicyclopentadiene relative to the 2,6-disubstituted phenol, but in the present invention, it is 0.28 to 2 times the mole, preferably 0.3 to 1.5 times the mole, and more preferably 0.5 to 1.3 times the mole.

[0083] As a method for confirming that a substituent represented by the formula (1a) or (1b) has been introduced into the aromatic hydroxy compound represented by the general formula (8), mass spectrometry and FT-IR measurement can be used.

[0084] When mass spectrometry is used, electrospray mass spectrometry (ESI-MS), field desorption mass spectrometry (FD-MS), etc. can be used. By subjecting a sample obtained by separating components having different numbers of nuclei by GPC or the like and subjecting it to mass spectrometry, it can be confirmed that a substituent represented by formula (1a) or (1b) has been introduced.

[0085] In the case of FT-IR measurement, a sample dissolved in an organic solvent such as THF is applied to a KRS-5 window, and the organic solvent is dried to obtain a window with a sample film. When the window is measured by FT-IR, the sample film is measured at 1210 cm －1 The peak derived from the C—O stretching vibration of the phenol nucleus appears near 3040 cm －1 The peak of C-H stretching vibration of the olefin part of the dicyclopentadiene skeleton appears near the peak. The starting point and the end point of the target peak are connected into a straight line, and the straight line obtained is used as the baseline. The length from the peak apex to the baseline is set as the peak height. －1 Nearby peaks (A 3040 ) and 1210cm －1 Nearby peaks (A 1210 ) ratio (A 3040 / A 1210 ) to quantify the amount of the introduced compound of formula (1a) or formula (1b). It can be confirmed that the larger the ratio, the better the physical property value. The preferred ratio (A) for satisfying the target physical property is 3040 / A 1210 ) is 0.05 or more, more preferably 0.10 or more. As the upper limit, it is preferably 0.7 or less, more preferably 0.60 or less. If this ratio is high, more dicyclopentadiene substituents are introduced.

[0086] This reaction may be carried out in a manner that 2,6-disubstituted phenols and a catalyst are placed in a reactor, and dicyclopentadiene is added dropwise over 1 to 10 hours.

[0087] The reaction temperature is preferably 50 to 200° C., more preferably 100 to 180° C., and even more preferably 120 to 160° C. The reaction time is preferably 1 to 10 hours, more preferably 3 to 10 hours, and even more preferably 4 to 8 hours.

[0088] After the reaction is completed, a base such as sodium hydroxide, potassium hydroxide, or calcium hydroxide is added to deactivate the catalyst. Thereafter, a solvent such as aromatic hydrocarbons such as toluene and xylene, or ketones such as methyl ethyl ketone and methyl isobutyl ketone is added to dissolve the mixture, and after washing with water, the solvent is recovered under reduced pressure, thereby obtaining the target aromatic hydroxy compound. It should be noted that it is preferred to react the entire amount of dicyclopentadiene as much as possible, and to leave a portion of the 2,6-disubstituted phenol unreacted, preferably less than 10%, and to recover the unreacted portion under reduced pressure.

[0089] During the reaction, a solvent such as aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, or ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether may be used as necessary.

[0090] When producing the active ester resin of the present invention, an aromatic polyvalent hydroxy compound other than the aromatic hydroxy compound represented by the above formula (8) may be used in combination unless the object of the present invention is impaired.

[0091] Among them, the amount of the dicyclopentenyl group-containing aromatic hydroxy compound represented by the above formula (8) is preferably 20 mol% or more, more preferably 30 mol% or more, and further preferably 50 mol% or more, based on the total amount of the aromatic hydroxy compound used as the raw material.

[0092] The aromatic polyhydric hydroxy compound that can be used in combination is not particularly limited, but is preferably an aromatic polyhydric hydroxy compound represented by the following formula (9) and / or formula (10).

[0093]

[0094] Here, m has the same meaning as m in the above formula (4).

[0095]

[0096] Among them, Ar 1 , R 3 and k and Ar of the above formula (5) 1 , R 3 and k have the same meanings.

[0097] If the aromatic polyhydroxy compound represented by the above formula (9) is used in combination with a large amount of aromatic polyhydroxy compounds whose average value of m exceeds 1.2, gelation may occur when it is dissolved in a solvent to synthesize an active ester resin. Therefore, when the aromatic polyhydroxy compound represented by the formula (9) is used in combination, it is preferred to use an aromatic polyhydroxy compound whose average value of m is in the range of 1 to 1.2. In addition, gelation can be prevented by appropriately adjusting the amount of the aromatic polyhydroxy compound represented by the formula (9) according to the value of m. For example, when m is 2, the amount used is preferably 20 mol% or less relative to the total amount of the aromatic polyhydroxy compound used.

[0098] Examples of the aromatic dihydroxy compound represented by the formula (10) include dihydroxybenzenes such as catechol, resorcinol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone and di-tert-butylhydroquinone; naphthalene diols such as naphthalene diol, methylnaphthalene diol and methylmethoxynaphthalene diol; bisphenols such as biphenol, dimethylbiphenol and tetramethylbiphenol; bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z; dihydroxydiphenyl sulfide; 4,4′-thiobis(3-methyl-6-tert-butylphenol); bisphenol fluorene; biscresol fluorene; and 9,9-bis(3,5-dimethyl-4-hydroxyphenyl)-9H-fluorene.

[0099] Furthermore, an aromatic monohydroxy compound may be used in combination. The aromatic monohydroxy compound that can be used in combination is not particularly limited, but an aromatic monohydroxy compound represented by the following formula (11) is preferred.

[0100]

[0101] Among them, Ar 2 , R 4 and k and Ar of the above formula (6) 2 , R 4 and k have the same meanings.

[0102] Examples of the aromatic monohydroxy compound represented by the formula (11) include phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, octylphenol, α-naphthol, β-naphthol, etc. Among them, a cured product obtained by using an active ester resin obtained by using α-naphthol, β-naphthol, o-phenylphenol, p-phenylphenol, and 4-(α-cumyl)phenol as a curing agent has a particularly low dielectric loss tangent.

[0103] The active ester resin of the present invention is obtained by reacting an aromatic polyhydroxy compound with an aromatic polycarboxylic acid or its acyl halide. In this case, the aromatic hydroxy compound represented by the above formula (8) is an essential component. In addition, an aromatic monocarboxylic acid or its acyl halide may also be used in the reaction. As the halogen of the halide of the aromatic carboxylic acid used, chlorine or bromine is usually used. As the halide of the aromatic polycarboxylic acid, for example, halides of aromatic dicarboxylic acids represented by the following formula (12), halides of aromatic tricarboxylic acids such as trimesic acid and trimellitic acid, etc. may be cited.

[0104]

[0105] Among them, Ar 3 , R 3 and k and Ar of the above formula (7) 3 , R 3 and k have the same meanings.

[0106] Examples of the aromatic dicarboxylic acid represented by the formula (12) include phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, 1,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, 4,4-biphenyl dicarboxylic acid, 4,4'-methylene dibenzoic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-isopropylidene dibenzoic acid, etc. Among them, isophthaloyl chloride and terephthaloyl chloride are preferred from the viewpoint of the balance between solvent solubility and heat resistance.

[0107] Examples of the aromatic monocarboxylic acid halide include halides of aromatic monocarboxylic acids represented by the following formula (13). When an aromatic monocarboxylic acid halide is used in combination, a part of the molecular chain terminal becomes an arylcarbonyloxy group.

[0108]

[0109] Among them, Ar 2 , R 4 and k and Ar of the above formula (6) 2 , R 4 and k have the same meanings.

[0110] Examples of the aromatic monocarboxylic acid represented by the formula (13) include benzoic acid, 1-naphthoic acid, 2-naphthoic acid, and bibenzoic acid.

[0111] The method of reacting the aromatic hydroxy compound of the above formula (8) with an aromatic carboxylic acid or an acid halide thereof is specifically a method of reacting these components in the presence of a base catalyst.

[0112] Examples of the base catalyst that can be used include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, and sodium carbonate, and organic bases such as triethylamine, diisopropylethylamine, and pyridine. Among them, sodium hydroxide and potassium hydroxide are preferred because they are excellent in reactivity and cost.

[0113] The above reaction can be carried out by mixing an aromatic hydroxy compound and an aromatic carboxylic acid or its acid halide in the presence of an organic solvent and adding the above base catalyst. The amount of the base catalyst added is preferably 0.9 to 2.0 mol per 1 mol of the phenolic hydroxyl group of the aromatic hydroxy compound.

[0114] Examples of the organic solvent used in the above reaction include toluene, dichloromethane, and chloroform. Toluene is preferred from the viewpoints of price and environmental load.

[0115] After the reaction is completed, the reaction solution is neutralized and washed with water, thereby obtaining the target resin.

[0116] The active ester equivalent (g / eq.) of the active ester resin of the present invention is preferably 200 to 600, more preferably 220 to 500, and further preferably 240 to 450. If it is less than this range, the dielectric properties may be deteriorated, and if it is greater than this range, the heat resistance and adhesion may be reduced. It should be noted that the active ester group refers to the aryloxycarbonyl group in the active ester resin.

[0117] By using such an active ester resin as a curing agent, the epoxy resin composition of the present invention can be obtained.

[0118] The epoxy resin composition of the present invention includes an epoxy resin and the above-mentioned active ester resin as essential components. In this embodiment, part or all of the active ester resin is the active ester resin of the present invention, and the active ester resin represented by the above-mentioned formula (1) in all active ester resins is preferably at least 30% by mass, more preferably 50% by mass or more, and further preferably 75% by mass or more. When the above value is less than this, the dielectric properties may be deteriorated.

[0119] As the epoxy resin for obtaining the epoxy resin of the present invention, a common epoxy resin having two or more epoxy groups in all molecules can be used.

[0120] For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetramethyl bisphenol F type epoxy resin, hydroquinone type epoxy resin, biphenyl type epoxy resin, bisphenol fluorene type epoxy resin, bisphenol S type epoxy resin, disulfide type epoxy resin, resorcinol type epoxy resin, biphenyl aralkylphenol type epoxy resin, naphthalene diol type epoxy resin, phenol novolac type epoxy resin, styrenated phenol novolac type epoxy resin, cresol novolac type epoxy resin, alkyl novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol B ... Phenol novolac type epoxy resin, naphthol novolac type epoxy resin, β-naphthol aralkyl type epoxy resin, dinaphthol aralkyl type epoxy resin, α-naphthol aralkyl type epoxy resin, triphenylmethane type epoxy resin, triphenylmethane type epoxy resin, dicyclopentadiene type epoxy resin other than the present invention, alkylene glycol type epoxy resin, aliphatic cyclic epoxy resin, diaminodiphenylmethane tetraglycidylamine, aminophenol type epoxy resin, phosphorus-containing epoxy resin, polyurethane-modified epoxy resin, containing In addition, these epoxy resins may be used alone or in combination of two or more.

[0121] From the viewpoint of availability, it is preferred to use naphthalene diol type epoxy resin, phenol novolac type epoxy resin, aromatic modified phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol aralkyl type epoxy resin, dicyclopentadiene type epoxy resin, phosphorus-containing epoxy resin, Epoxy resin with oxazolidinone ring.

[0122] In addition to the active ester resin of the present invention, it is also possible to use commonly used curing agents such as various phenolic resins, anhydrides, amines, hydrazides, acidic polyesters, etc. as needed. When these curing agents are used together, the curing agent used together is preferably less than 70% by mass of all curing agents, more preferably less than 50% by mass, and further preferably less than 25% by mass. When the ratio of the curing agent used together is too much, the dielectric properties and bonding properties as the epoxy resin composition may deteriorate.

[0123] In the epoxy resin composition of the present invention, the active hydrogen group of the curing agent is preferably 0.2 to 1.5 moles, more preferably 0.3 to 1.4 moles, further preferably 0.5 to 1.3 moles, and particularly preferably 0.8 to 1.2 moles relative to 1 mole of epoxy groups of the epoxy resin. When deviating from this range, it is possible that the curing is incomplete and good curing properties cannot be obtained. For example, when a phenolic resin curing agent and an amine curing agent are used in combination, the active hydrogen group is almost equimolar relative to the epoxy group. When an anhydride curing agent is used in combination, 0.5 to 1.2 moles, preferably 0.6 to 1.0 moles of anhydride groups are used relative to 1 mole of epoxy groups. When the active ester resin of the present invention is used alone as a curing agent, it is preferably used in the range of 0.9 to 1.1 moles relative to 1 mole of the epoxy resin.

[0124] The active hydrogen group in the present invention refers to a functional group having active hydrogen that is reactive with an epoxy group (including a functional group having potential active hydrogen that generates active hydrogen by hydrolysis, etc., and a functional group that exhibits an equivalent curing effect). Specifically, an acid anhydride group, a carboxyl group, an amino group, a phenolic hydroxyl group, etc. are exemplified. It should be noted that with respect to the active hydrogen group, 1 mole of the carboxyl group and the phenolic hydroxyl group is calculated as 1 mole, and the amino group (NH 2 ) is calculated as 2 moles. In addition, when the active hydrogen group is not clear, the active hydrogen equivalent can be obtained by measurement. For example, the active hydrogen equivalent of the curing agent used can be obtained by reacting a monoepoxy resin such as phenyl glycidyl ether with a known epoxy equivalent with a curing agent with an unknown active hydrogen equivalent, and measuring the amount of the monoepoxy resin consumed.

[0125] Specific examples of the phenolic resin curing agent that can be used in combination with the epoxy resin composition of the present invention include bisphenol A, bisphenol F, bisphenol C, bisphenol K, bisphenol Z, bisphenol S, tetramethylbisphenol A, tetramethylbisphenol F, tetramethylbisphenol S, tetramethylbisphenol Z, dihydroxydiphenyl sulfide, 4,4'-thiobis (3-methyl-6-tert-butylphenol) and other bisphenols, catechol, resorcinol, methylresorcinol, hydroquinone, monomethylhydroquinone, dimethylhydroquinone, trimethylhydroquinone, mono-tert-butylhydroquinone, di-tert-butylhydroquinone and other dihydroxybenzenes, dihydroxynaphthalene, dihydroxymethylnaphthalene, dihydroxymethylnaphthalene, trihydroxynaphthalene and other hydroxynaphthalenes, phosphorus-containing phenolic curing agents such as LC-950PM60 (manufactured by Shin-AT&C Co., Ltd.), SHONOL Condensates of phenols, naphthols, and / or bisphenols with aldehydes such as BRG-555 (manufactured by AICA Industries Co., Ltd.), cresol novolac resins such as DC-5 (manufactured by Nippon Steel Chemical Materials Co., Ltd.), aromatic modified phenol novolac resins, bisphenol A novolac resins, trishydroxyphenylmethane novolac resins such as Resitop TPM-100 (manufactured by Gunei Chemical Industries Co., Ltd.), and naphthol novolac resins The condensation products of phenols, naphthols, and / or bisphenols with benzyl alcohol, condensation products of phenols, naphthols, and / or bisphenols with isopropenyl acetophenone, reaction products of phenols, naphthols, and / or bisphenols with dicyclopentadiene, condensation products of phenols, naphthols, and / or bisphenols with biphenyl crosslinking agents, and the like are phenol compounds known as novolac-type phenolic resins, etc. From the viewpoint of easy availability, phenol novolac resins, dicyclopentadiene-type phenolic resins, trihydroxyphenylmethane-type novolac resins, aromatic modified phenol novolac resins, etc. are preferred.

[0126] In the case of novolac type phenolic resin, phenols include phenol, cresol, xylenol, butylphenol, pentylphenol, nonylphenol, butylmethylphenol, trimethylphenol, phenylphenol, etc., naphthols include 1-naphthol, 2-naphthol, etc., and the above-mentioned bisphenols can be mentioned. Aldehydes include formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, hexanal, benzaldehyde, chloral, bromoaldehyde, glyoxal, malondialdehyde, succinaldehyde, glutaraldehyde, adipaldehyde, heptanedialdehyde, suberaldehyde, acrolein, crotonaldehyde, salicylaldehyde, o-phthalaldehyde, hydroxybenzaldehyde, etc. Biphenyl crosslinking agents include bis(hydroxymethyl)biphenyl, bis(methoxymethyl)biphenyl, bis(ethoxymethyl)biphenyl, bis(chloromethyl)biphenyl, etc.

[0127] Specific examples of the acid anhydride curing agent include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, phthalic anhydride, trimellitic anhydride, and methylnadic acid.

[0128] Specific examples of the amine curing agent include diethylenetriamine, triethylenetetramine, m-xylylenediamine, isophoronediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenyl ether, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, dicyandiamide, and amine compounds such as polyamide amines which are condensates of acids such as dimer acid and polyamines.

[0129] 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 such as salts of imidazoles with trimellitic acid, isocyanuric acid, or boron, quaternary ammonium salts such as trimethylammonium chloride, diazabicyclic compounds, salts of diazabicyclic compounds with phenols, phenol novolac resins, etc., complexes of boron trifluoride with amines, ether compounds, etc., aromatic phosphonium, or iodonium salts, etc.

[0130] The epoxy resin composition of the present invention may contain a known epoxy resin curing accelerator as required. Examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, and 2-undecylimidazole, tertiary amines such as 4-dimethylaminopyridine, 2-(dimethylaminomethyl)phenol, and 1,8-diaza-bicyclo(5,4,0)undecene-7, 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, phosphines such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, and triphenylphosphine triphenylborane, and metal compounds such as tin octoate. These curing accelerators may be used alone or in combination of two or more. Among them, imidazoles are preferred.

[0131] When a curing accelerator is used, its usage amount can be appropriately selected according to the purpose of use, and 0.01 to 15 parts by mass, preferably 0.02 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and further preferably 0.1 to 5 parts by mass are used as needed relative to 100 parts by mass of the epoxy resin component in the epoxy resin composition. By using a curing accelerator, the curing temperature can be lowered and the curing time can be shortened.

[0132] An organic solvent or a reactive diluent may be used in the epoxy resin composition to adjust the viscosity.

[0133] 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, butanediol, and pine oil, and butyl acetate. Acetates such as methoxybutyl acetate, methyl cellosolve acetate, cellosolve acetate, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, carbitol acetate, benzyl acetate, benzoates such as methyl benzoate and ethyl benzoate, cellosolves such as methyl cellosolve, cellosolve, and butyl cellosolve, carbitols such as methyl carbitol, carbitol, and butyl carbitol, aromatic hydrocarbons such as benzene, toluene, and xylene, dimethyl sulfoxide, acetonitrile, and N-methylpyrrolidone, but are not limited thereto.

[0134] Examples of the reactive diluent include monofunctional glycidyl ethers such as allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and cresyl glycidyl ether; difunctional glycidyl ethers such as resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, and propylene glycol diglycidyl ether; polyfunctional glycidyl ethers such as glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, trimethylolethane polyglycidyl ether, and pentaerythritol polyglycidyl ether; glycidyl esters such as neodecanoic acid glycidyl ester; and glycidyl amines such as phenyl diglycidyl amine and cresyl diglycidyl amine, but the present invention is not limited thereto.

[0135] These organic solvents or reactive diluents are preferably used alone or in a mixture of multiple types in an amount of 90% or less in terms of non-volatile components, and the appropriate type and amount used are appropriately selected according to the application. For example, in the use of printed wiring boards, polar solvents having a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, and 1-methoxy-2-propanol, are preferred, and the amount used is preferably 40 to 80% by mass in terms of non-volatile components. In addition, in the use of adhesive films, for example, ketones, acetates, carbitols, aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the amount used is preferably 30 to 60% by mass in terms of non-volatile components.

[0136] The epoxy resin composition may also be blended with other thermosetting resins or thermoplastic resins within a range that does not impair the properties. Examples include phenolic resins, acrylic resins, petroleum resins, indene resins, coumarone indene resins, phenoxy resins, polyurethane resins, polyester resins, polyamide resins, polyimide resins, polyamideimide resins, polyetherimide resins, polyphenylene ether resins, modified polyphenylene ether resins, polyether sulfone resins, polysulfone resins, polyether ether ketone resins, polyphenylene sulfide resins, and polyvinyl formal resins, but are not limited thereto.

[0137] In order to improve the flame retardancy of the obtained cured product, various known flame retardants can be used in the epoxy resin composition. As the flame retardant that can be used, for example, halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc. can be cited. From the viewpoint of coping with the environment, it is preferred that the flame retardant does not contain halogen, and phosphorus flame retardants are particularly preferred. These flame retardants can be used alone, or two or more can be used in combination.

[0138] Phosphorus flame retardants may be inorganic phosphorus compounds or organic phosphorus compounds. Examples of inorganic phosphorus compounds include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoric acid amides. Examples of the organophosphorus compound include aliphatic phosphoric acid esters, phosphoric acid ester compounds, condensed phosphoric acid esters such as PX-200 (manufactured by Daihachi Chemical Industry Co., Ltd.), general-purpose organophosphorus compounds such as phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-phosphorus compounds, metal salts of phosphinic acid, and cyclic organophosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; derivatives thereof obtained by reacting them with compounds such as epoxy resins and phenolic resins, namely phosphorus-containing epoxy resins; and phosphorus-containing curing agents.

[0139] As the amount of flame retardant, it is appropriately selected according to the type of phosphorus flame retardant, the composition of epoxy resin composition, and the degree of desired flame retardancy. For example, the phosphorus content in the organic component (excluding organic solvent) in the epoxy resin composition is preferably 0.2 to 4% by mass, more preferably 0.4 to 3.5% by mass, and further preferably 0.6 to 3% by mass. When the phosphorus content is small, it may be difficult to ensure flame retardancy, and when it is too much, it may have an adverse effect on heat resistance. In addition, when using a phosphorus flame retardant, a flame retardant auxiliary such as magnesium hydroxide may also be used in combination.

[0140] Fillers can be used as needed in the epoxy resin composition. Specifically, fused silica, crystalline silica, aluminum oxide, silicon nitride, aluminum hydroxide, boehmite, magnesium hydroxide, talc, mica, calcium carbonate, calcium silicate, calcium hydroxide, magnesium carbonate, barium carbonate, barium sulfate, boron nitride, carbon, carbon fiber, glass fiber, aluminum oxide fiber, silicon dioxide aluminum oxide fiber, silicon carbide fiber, polyester fiber, cellulose fiber, aramid fiber, ceramic fiber, micro-particle rubber, thermoplastic elastomer, pigment, etc. can be cited. Generally, as a reason for using fillers, the effect of improving impact resistance can be cited. In addition, when using metal hydroxides such as aluminum hydroxide, boehmite, and magnesium hydroxide, it plays a role as a flame retardant aid and has the effect of improving flame retardancy. The amount of these fillers relative to the entire epoxy resin composition is preferably 1 to 150% by mass, and more preferably 10 to 70% by mass. When the amount is large, it is possible to reduce the adhesion required for the laminated board use, and then the cured product is brittle, and sufficient mechanical properties may not be obtained. On the other hand, when the amount of the filler is small, there is a possibility that the filler may not have the effect of improving the impact resistance of the cured product.

[0141] The epoxy resin composition may further contain core additives such as silane coupling agents, antioxidants, mold release agents, defoamers, emulsifiers, thixotropy agents, lubricants, flame retardants, pigments, etc. The amount of these additives is preferably in the range of 0.01 to 20% by mass relative to the epoxy resin composition.

[0142] The epoxy resin composition of the present invention is obtained by uniformly mixing the above-mentioned components. The epoxy resin composition with active ester resin, epoxy resin and various materials as required can be cured by utilizing the same method as known epoxy resin composition to obtain epoxy resin cured product. As cured product, the molded cured products such as laminates, molded products, molded products, adhesive layers, insulating layers, films can be cited. As a method for obtaining a cured product, the same method as known epoxy resin composition can be adopted, molding, injection, potting, impregnation, drop coating, transfer molding, compression molding, etc. can be appropriately used, by stacking and heating and pressurizing and curing with resin sheets, copper foil with resin, prepregs, etc. to make a method for laminated boards, etc.

[0143] The curing method of the epoxy resin composition also varies according to the ingredients and the amount of the epoxy resin composition. Generally, the curing temperature is 80 to 300 ° C and the curing time is 10 to 360 minutes. The heating is preferably carried out in a two-step process of a primary heating of 10 to 90 minutes at 80 to 180 ° C and a secondary heating of 60 to 150 minutes at 120 to 200 ° C. In addition, in a system where the glass transition temperature (Tg) exceeds the temperature of the secondary heating, it is preferred to further carry out a third heating of 60 to 120 minutes at 150 to 280 ° C. By performing such secondary heating and third heating, poor curing can be reduced. When making resin semi-cured products such as resin sheets, copper foil with resin, and prepregs, the curing reaction of the epoxy resin composition is usually carried out to the extent of maintaining the shape by heating. When the epoxy resin composition contains a solvent, most of the solvent is usually removed by heating, decompression, air drying, etc., and less than 5% by mass of the solvent may remain in the resin semi-cured product.

[0144] As the use of the epoxy resin composition, it can be applied to various fields such as circuit board materials, packaging materials, molding materials, conductive pastes, adhesives, and insulating materials. In particular, it is useful as insulating molding, laminated materials, and packaging materials in the electrical and electronic fields. As an example of the use, there can be cited printed wiring boards, flexible wiring boards, laminated boards for electrical and electronic circuits such as capacitors, adhesives such as metal foils with resins, film adhesives, and liquid adhesives, semiconductor packaging materials, bottom fillers, inter-chip filling materials for 3D-LSI, insulating materials for circuit boards, insulating sheets, prepregs, heat dissipation substrates, and resist inks, but it is not limited to these.

[0145] Among these various uses, it can be used as an insulating material for a so-called electronic component built-in substrate in which passive devices such as capacitors and active devices such as IC chips are embedded in the substrate in the use of printed wiring board materials, insulating materials for circuit substrates, and adhesive films for stacking. Among them, due to the characteristics of high flame retardancy, high heat resistance, and solvent solubility, it is preferably used for printed wiring board materials, epoxy resin compositions for flexible wiring substrates, interlayer insulating materials for stacking substrates, and other circuit substrate (laminated board) materials and semiconductor packaging materials.

[0146] When the epoxy resin composition is formed into a plate form such as a laminate, the filler used is preferably a fibrous filler in terms of dimensional stability, bending strength, etc., and more preferably glass cloth, glass mat, or glass roving cloth.

[0147] The epoxy resin composition can be impregnated into a fibrous reinforcing substrate to form a prepreg used in a printed wiring board, etc. As the fibrous reinforcing substrate, for example, inorganic fibers such as glass, polyester resins, woven fabrics or nonwoven fabrics of organic fibers such as polyamine resins, polyacrylic resins, polyimide resins, and aromatic polyamide resins can be used, but it is not limited thereto.

[0148] As a method for manufacturing a prepreg from an epoxy resin composition, there is no particular limitation. For example, by making an epoxy resin composition into a resin varnish adjusted to an appropriate viscosity with an organic solvent, the resin varnish is impregnated in the above-mentioned fibrous reinforcing substrate, and then heated and dried to semi-cure (B-stage) the resin component. As the heating temperature, it 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 according to the type of organic solvent used and the curability of the prepreg, preferably 1 to 40 minutes, more preferably 3 to 20 minutes. At this time, as the mass ratio of the epoxy resin composition used and the reinforcing substrate, there is no particular limitation. Usually, it is preferably adjusted to 20 to 80% by mass of the resin component in the prepreg.

[0149] The epoxy resin composition of the present invention can be formed into a sheet or film for use. In this case, it can be formed into a sheet or film using a conventionally known method. There is no particular limitation on the method for making a resin sheet, and for example, (A) an extrusion molding method in which the epoxy resin composition is kneaded with an extruder and then extruded and molded into a sheet using a T-die, a circular mold, etc., (B) a casting molding method in which the epoxy resin composition is dissolved or dispersed in a solvent such as an organic solvent and then cast to form a sheet, (C) other conventionally known sheet molding methods, etc. In addition, the film thickness (μm) of the resin sheet is not particularly limited, and is preferably 10 to 300, more preferably 25 to 200, and further preferably 40 to 180. The film thickness of the resin sheet when used in the stacking method is particularly preferably 40 to 90 μm. If the film thickness is 10 μm or more, insulation can be obtained, and if it is 300 μm or less, the distance of the circuit between the electrodes will not be longer than required. It should be noted that the content of the solvent in the resin sheet is not particularly limited, and is preferably 0.01 to 5% by mass relative to the entire epoxy resin composition. If the content of the solvent in the film is 0.01% by mass or more relative to the entire epoxy resin composition, it is easy to obtain close adhesion and adhesiveness when laminated on a circuit board, and if it is 5% by mass or less, it is easy to obtain flatness after heat curing.

[0150] As a more specific method for manufacturing an adhesive sheet, the adhesive sheet is obtained by applying a varnish-like epoxy resin composition containing the above-mentioned organic solvent on a supporting base film that is insoluble in the organic solvent using a coating machine such as a reverse roll coater, a comma coater, a die coater, etc., and then heating and drying the resin component to stage B. In addition, as required, another supporting base film is overlapped on the coated surface (adhesive layer) as a protective film, and dried to obtain an adhesive sheet having release layers on both sides of the adhesive layer.

[0151] As the supporting base film, metal foils such as copper foil, polyolefin films such as polyethylene film and polypropylene film, polyester films such as polyethylene terephthalate film, polycarbonate film, silicone film, polyimide film, etc. can be cited. Among them, polyethylene terephthalate film is preferred because it has no defects such as bumps, excellent dimensional accuracy and excellent cost. In addition, metal foils, especially copper foils, that are easy to multilayer the laminated board are preferred. The thickness of the supporting base film is not particularly limited, but is preferably 10 to 150 μm, and more preferably 25 to 50 μm, from the perspective of having strength as a support and not easily causing poor lamination.

[0152] The thickness of the protective film is not particularly limited, but is generally 5 to 50 μm. It should be noted that in order to facilitate the peeling of the formed adhesive sheet, it is preferably surface treated with a release agent in advance. In addition, the thickness of the coated resin varnish is preferably 5 to 200 μm, more preferably 5 to 100 μm, based on the thickness after drying.

[0153] 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.

[0154] The resin sheet thus obtained is usually an insulating adhesive sheet with insulating properties, but a conductive adhesive sheet can also be obtained by mixing a conductive metal or metal-coated particles in an epoxy resin composition. It should be noted that the above-mentioned supporting base film is peeled off after being laminated on a circuit substrate or after being heated and cured to form an insulating layer. If the supporting base film is peeled off after the adhesive sheet is heated and cured, it is possible to prevent dirt from being attached during the curing process. Here, the above-mentioned insulating adhesive sheet is also an insulating sheet.

[0155] The metal foil with resin obtained from the epoxy resin composition of the present invention is described. As the metal foil, a single substance, alloy, or composite metal foil of copper, aluminum, brass, nickel, etc. can be used. Preferably, a metal foil with a thickness of 9 to 70 μm is used. There is no particular limitation on the method for manufacturing the metal foil with resin from the epoxy resin composition and metal foil of the present invention. For example, it can be obtained in the following manner, that is, after applying a resin varnish obtained by adjusting the viscosity of the above-mentioned epoxy resin composition with a solvent to one surface of the above-mentioned metal foil using a roller coater, the resin component is semi-cured (B-staged) to form a resin layer by heating and drying. When the resin component is semi-cured, for example, it can be heated and dried at 100 to 200° C. for 1 to 40 minutes. Here, the thickness of the resin portion of the metal foil with resin is preferably formed to be 5 to 110 μm.

[0156] In addition, in order to cure the prepreg and the insulating adhesive sheet, a curing method for a laminate generally used in the manufacture of a printed wiring board can be adopted, but it is not limited thereto. For example, when a laminate is formed using a prepreg, one or more prepregs can be stacked, and a metal foil can be arranged on one side or both sides to form a laminate, and the laminate can be pressurized and heated to cure and integrate the prepreg to obtain a laminate. Here, as the metal foil, a single substance, an alloy, or a composite metal foil of copper, aluminum, brass, nickel, etc. can be used.

[0157] As the condition for heating and pressurizing the laminate, it is sufficient to adjust the heating and pressurizing appropriately under the condition of curing the epoxy resin composition. However, if the pressure of the pressurization is too low, bubbles may remain inside the laminate obtained, and the electrical properties may be reduced. Therefore, it is preferred to pressurize under the condition of satisfying the moldability. The heating temperature is preferably 160 to 250°C, and more preferably 170 to 220°C. The pressurization pressure is preferably 0.5 to 10 MPa, and more preferably 1 to 5 MPa. The heating and pressurizing time is preferably 10 minutes to 4 hours, and more preferably 40 minutes to 3 hours. If the heating temperature is low, the curing reaction may not proceed sufficiently. If it is high, thermal decomposition of the cured product may occur. If the pressurization pressure is low, bubbles may remain inside the laminate obtained, and the electrical properties may be reduced. If it is high, the resin may flow before curing, and the laminate of the desired thickness may not be obtained. In addition, if the heating and pressurizing time is short, the curing reaction may not proceed sufficiently. If it is long, thermal decomposition of the cured product may occur.

[0158] The single-layer laminated board thus obtained can be further used as an inner layer material to make a multilayer board. In this case, the laminated board is first subjected to circuit formation by an additive method, a subtractive method, etc., and the formed circuit surface is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. An insulating layer is formed on one or both sides of the inner layer material by 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.

[0159] In addition, when using prepreg to form an insulating layer, the object obtained by laminating one or more prepregs is arranged on the circuit forming surface of the inner layer material, and a metal foil is further arranged on its outside to form a laminate. Then, the laminate is heated and pressurized and integrally formed, whereby the cured product of the prepreg is formed into an insulating layer, and the metal foil on its outside is formed into a conductor layer. Here, as the metal foil, the same metal foil as the metal foil used in the laminate used as the inner layer material can be used. In addition, the heating and pressing molding can be carried out under the same conditions as the molding of the inner layer material. It is possible to further utilize the addition method and the subtraction method to implement through-hole formation and circuit formation on the surface of the multi-layer laminate so molded, and to mold it into a printed wiring board. In addition, it is possible to further form a multi-layer multilayer board by using the printed wiring board as the inner layer material by repeating the above-mentioned preparation method.

[0160] For example, when forming an insulating layer with an insulating adhesive sheet, an insulating adhesive sheet is arranged on the circuit forming surface of multiple inner layer materials to form a laminate. Alternatively, an insulating adhesive sheet is arranged between the circuit forming surface of the inner layer material and the metal foil to form a laminate. Then, the laminate is heated and pressurized for integral molding, thereby forming the cured product of the insulating adhesive sheet as an insulating layer and forming a multilayer of the inner layer material. Alternatively, the cured product of the insulating adhesive sheet is formed as an insulating layer between the inner layer material and the metal foil as a conductor layer. Here, as the metal foil, the same metal foil as that used in the laminate used as the inner layer material can be used. In addition, the heating and pressurizing molding can be carried out under the same conditions as the molding of the inner layer material.

[0161] In addition, when the epoxy resin composition is applied to the laminate to form an insulating layer, the epoxy resin composition is preferably applied to a thickness of 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 casting. The thickness after drying is preferably formed to 5 to 150 μm, preferably 5 to 80 μm. It should be noted that the viscosity of the epoxy resin composition is preferably 10 to 40000 mPa·s at 25° C., and more preferably 200 to 30000 mPa·s, from the perspective of obtaining sufficient film thickness and not being prone to uneven coating and texture. The surface of the multilayer laminate formed in this way can be further subjected to through-hole formation and circuit formation by an additive method or a subtractive method to form a printed wiring board. In addition, a multilayer laminate can be formed by repeating the above-mentioned preparation method using the printed wiring board as an inner layer material.

[0162] As the encapsulation material obtained by using the epoxy resin composition of the present invention, there are tape-shaped semiconductor chips, potting liquid encapsulation, bottom filling, semiconductor interlayer insulation film, etc., which can be appropriately used in these applications. For example, as semiconductor encapsulation molding, there can be cited a method of molding the epoxy resin composition by using a molding or transfer molding machine, an injection molding machine, etc., and then heating at 50 to 200° C. for 2 to 10 hours to obtain a molded product.

[0163] When the epoxy resin composition is prepared as a semiconductor packaging material, there can be mentioned a method in which a compounding agent such as an inorganic filler, a coupling agent, a release agent and other additives are pre-mixed in the epoxy resin composition as required, and then the mixture is melt-mixed until uniform using an extruder, a kneader, a roller and the like. At this time, silicon dioxide can generally be used as an inorganic filler, and in this case, the inorganic filler is preferably mixed in the epoxy resin composition at a ratio of 70 to 95% by mass.

[0164] When the epoxy resin composition thus obtained is used as a tape-shaped packaging material, the following method can be cited: after heating it to make a semi-cured sheet, the packaging material tape is placed on the semiconductor chip, heated to 100-150° C. to soften and shape it, and completely cured at 170-250° C. In addition, when used as a potting type liquid packaging material, the obtained epoxy resin composition is dissolved in a solvent as needed, applied to a semiconductor chip or an electronic component, and cured directly.

[0165] In addition, the epoxy resin composition of the present invention can also be further used as an anti-corrosion ink. In this case, the following method can be cited: a vinyl monomer having an ethylenically unsaturated double bond and a cationic polymerization catalyst as a curing agent are added to the epoxy resin composition, and then a pigment, talc and a filler are added to prepare a composition for an anti-corrosion ink, and then the composition is applied to a printed circuit board by screen printing to prepare a cured anti-corrosion ink. The curing temperature at this time is preferably in the temperature range of about 20 to 250°C.

[0166] The epoxy resin composition was prepared, cured by heating, and then laminated boards and cured products were evaluated. As a result, an epoxy resin composition having excellent low dielectric properties in a cured product and excellent copper foil peel strength and interlayer adhesion strength in printed wiring board applications can be provided.

[0167] Example

[0168] The present invention is specifically described with reference to the Examples and Comparative Examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" means parts by mass, "%" means mass %, and "ppm" means mass ppm. In addition, the determination methods are respectively determined by the following methods.

[0169] Hydroxyl equivalent: measured in accordance with JIS K 0070, and expressed in "g / eq." Unless otherwise specified, the hydroxyl equivalent of an aromatic polyhydric hydroxy compound means a phenolic hydroxyl equivalent.

[0170] Softening point: The softening point was measured by the ring and ball method according to JIS K 7234. Specifically, an automatic softening point device (manufactured by MEITEC Co., Ltd., ASP-MG4) was used.

[0171] Copper foil peel strength and interlayer adhesive force: The interlayer adhesive force was measured in accordance with JIS C 6481, and the interlayer adhesive force was measured by peeling between the 7th layer and the 8th layer.

[0172] Relative dielectric constant and dielectric loss tangent: The relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were obtained and evaluated by a volumetric method using a material analyzer (manufactured by AGILENT Technologies) in accordance with IPC-TM-650 2.5.5.9.

[0173] GPC (gel permeation chromatography) measurement: A main body (manufactured by Tosoh Corporation, HLC-8220GPC) and a column (manufactured by Tosoh Corporation, TSKgelG4000H) were connected in series. XL ,TSKgelG3000H XL ,TSKgelG2000H XL) with a column temperature of 40°C. In addition, tetrahydrofuran (THF) was used as the eluent at a flow rate of 1 mL / min, and a differential refractive index detector was used as the detector. The measurement sample was 50 μL of a solution obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering it with a microporous filter. Data processing was performed using GPC-8020 Model II Version 6.00 manufactured by Tosoh Corporation.

[0174] IR: A Fourier transform infrared spectrophotometer (Perkin Elmer Precisely, SpectrumOne FT-IR Spectrometer 1760X) was used. A KRS-5 window was used. The sample dissolved in THF was applied to the window and dried. The wave number was measured at 650 to 4000 cm －1 The absorbance.

[0175] ESI-MS: Mass analysis was performed by using a mass spectrometer (LCMS-2020, manufactured by Shimadzu Corporation) and acetonitrile and water as mobile phases to measure a sample dissolved in acetonitrile.

[0176] The abbreviations used in Examples and Comparative Examples are as follows.

[0177] [Aromatic hydroxy compounds]

[0178] P1: Aromatic hydroxy compound obtained in Synthesis Example 1

[0179] P2: Aromatic hydroxy compound obtained in Synthesis Example 2

[0180] P3: Aromatic hydroxy compound obtained in Synthesis Example 3

[0181] P4: Aromatic hydroxy compound obtained in Synthesis Example 4

[0182] P5: Aromatic hydroxy compound obtained in Synthesis Example 5

[0183] P6: Aromatic hydroxy compound obtained in Reference Example 1

[0184] P7: 1-naphthol

[0185] [Aromatic carboxylic acid halides]

[0186] B1: Isophthaloyl chloride

[0187] B2: Terephthaloyl chloride

[0188] B3: Benzoyl chloride

[0189] [Epoxy resin]

[0190] E1: Phenol / dicyclopentadiene type epoxy resin (manufactured by Kukto Chemical Co., Ltd., KDCP-130, epoxy equivalent 254, softening point 72°C)

[0191] [Curing agent]

[0192] A1: Active ester resin obtained in Example 1

[0193] A2: Active ester resin obtained in Example 2

[0194] A3: Active ester resin obtained in Example 3

[0195] A4: Active ester resin obtained in Example 4

[0196] A5: Active ester resin obtained in Example 5

[0197] A6: Active ester resin obtained in Example 6

[0198] A7: Active ester resin obtained in Example 7

[0199] A8: Active ester resin obtained in Example 8

[0200] A9: Active ester resin obtained in Example 9

[0201] A10: Active ester resin obtained in Example 10

[0202] A11: Active ester resin obtained in Reference Example 2

[0203] P8: phenol novolac resin (manufactured by AICA Industries, Ltd., SHONOL BRG-557, hydroxyl equivalent 105, softening point 80°C)

[0204] [Curing accelerator]

[0205] C1: 4-dimethylaminopyridine (manufactured by KISHIDA Chemical Co., Ltd.)

[0206] Synthesis example 1

[0207] In a reaction apparatus consisting of a glass separable flask equipped with a stirrer, a thermometer, a nitrogen blowing ring, a dropping funnel, and a cooling tube, 95.0 parts of 2,6-xylenol and 47% BF 34.7 parts of ether complex (0.075 times the mole of dicyclopentadiene) were heated to 70°C while stirring. While maintaining this temperature, 58.8 parts of dicyclopentadiene (0.57 times the mole of 2,6-xylenol) were added dropwise over 1 hour. The mixture was reacted at a temperature of 115-125°C for 4 hours. 7.4 parts of calcium hydroxide were added. 23 parts of a 10% aqueous solution of oxalic acid were further added. After heating to 160°C for dehydration, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 360 parts of methyl isobutyl ketone (MIBK) were added to dissolve the product, 100 parts of warm water at 80°C were added for washing, and the lower water layer was separated and removed. Then, the mixture was heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, and 136 parts of a reddish brown aromatic polyhydroxy compound (P1) were obtained. The hydroxyl equivalent is 213, the softening point is 87°C, and the absorption ratio (A 3040 / A 1210 ) was 0.12. The mass spectrum was measured by ESI-MS (negative), and M-=253, 375, 507, 629 were observed. The GPC of the obtained aromatic hydroxy compound (P1) is shown in Figure 1 , FT-IR is shown in Figure 2 . Figure 1 a represents the u=1 body of formula (8) and the R-free body of formula (8) 2 The adduct is a mixture of u=1 isomers, and b represents the u=0 isomer of formula (8). The content of u=0 isomer is 10.4 area %. Figure 2 c represents a peak derived from C—H stretching vibration of the olefin portion of the dicyclopentadiene skeleton, and d represents absorption of C—O stretching vibration in the phenol core.

[0208] Synthesis example 2

[0209] In the same reaction apparatus as in Synthesis Example 1, 95.0 parts of 2,6-xylenol and 47% BF 3 3.2 parts of ether complex (0.05 times the mole of dicyclopentadiene) were heated to 70°C while stirring. While maintaining this temperature, 58.8 parts of dicyclopentadiene (0.57 times the mole of 2,6-xylenol) were added dropwise over 1 hour. The mixture was further reacted at a temperature of 115-125°C for 4 hours. 5.0 parts of calcium hydroxide were added. 15 parts of a 10% aqueous solution of oxalic acid were then added. After heating to 160°C for dehydration, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 360 parts of MIBK were added to dissolve the product, 100 parts of warm water at 80°C were added for washing, and the lower aqueous layer was separated and removed. Then, the mixture was heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, to obtain 129 parts of a reddish-brown aromatic hydroxy compound (P2). The hydroxyl equivalent is 224, the softening point is 66°C, and the absorption ratio (A3040 / A 1210 ) was 0.21. The mass spectrum was measured by ESI-MS (negative), and M-=253, 375, 507, 629 were observed. The u=0 isomer content was 27.8 area %.

[0210] Synthesis example 3

[0211] In the same reaction apparatus as in Synthesis Example 1, 95.0 parts of 2,6-xylenol and 47% BF 3 1.6 parts of ether complex (0.025 times the mole of dicyclopentadiene) were heated to 70°C while stirring. While maintaining this temperature, 58.8 parts of dicyclopentadiene (0.57 times the mole of 2,6-xylenol) were added dropwise over 1 hour. The mixture was reacted at a temperature of 115-125°C for 4 hours. 2.5 parts of calcium hydroxide were added. 8 parts of a 10% aqueous solution of oxalic acid were further added. Then, after heating to 160°C for dehydration, the mixture was heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 360 parts of MIBK were added to dissolve the product, 100 parts of hot water at 80°C were added for washing, and the lower water layer was separated and removed. Then, the mixture was heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, to obtain 113 parts of a reddish brown aromatic hydroxy compound (P3). The hydroxyl equivalent is 255, and it is a semi-solid resin at room temperature. 3040 / A 1210 ) was 0.51. The mass spectrum was measured by ESI-MS (negative), and M-=253, 375, 507, 629 were observed. The u=0 body content was 72.3 area %.

[0212] Synthesis example 4

[0213] In the same reaction apparatus as in Synthesis Example 1, 140 parts of 2,6-xylenol and 47% BF 39.3 parts of ether complex (0.1 times the mole of dicyclopentadiene initially added) were heated to 110°C while stirring. While maintaining this temperature, 86.6 parts of dicyclopentadiene (0.57 times the mole of 2,6-xylenol) were added dropwise over 1 hour. After further reacting at 110°C for 3 hours, 68 parts of dicyclopentadiene (0.44 times the mole of 2,6-xylenol) were added dropwise over 1 hour while maintaining this temperature. Further reacting at 120°C for 2 hours. 14.6 parts of calcium hydroxide were added. 45 parts of a 10% aqueous solution of oxalic acid were further added. Then, after heating to 160°C for dehydration, the unreacted raw materials were evaporated and removed by heating to 200°C under a reduced pressure of 5 mmHg. 700 parts of MIBK were added to dissolve the product, 200 parts of warm water at 80°C were added for washing, and the lower aqueous layer was separated and removed. Then, the mixture was heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, thereby obtaining 274 parts of a reddish brown aromatic hydroxy compound (P4). The resin had a hydroxyl equivalent of 299, a softening point of 97°C, and an absorption ratio (A 3040 / A 1210 ) was 0.17. The mass spectrum was measured by ESI-MS (negative), and M-=253, 375, 507, 629 were observed. The u=0 body content was 6.5 area %.

[0214] Synthesis example 5

[0215] In the same reaction apparatus as in Synthesis Example 1, 140 parts of 2,6-xylenol and 47% BF 3 9.3 parts of ether complex (0.1 times the mole of dicyclopentadiene initially added) were heated to 110°C while stirring. While maintaining this temperature, 86.6 parts of dicyclopentadiene (0.57 times the mole of 2,6-xylenol) were added dropwise over 1 hour. After further reacting at 110°C for 3 hours, 90.6 parts of dicyclopentadiene (0.60 times the mole of 2,6-xylenol) were added dropwise over 1 hour while maintaining this temperature. Further reacting at 120°C for 2 hours. 14.6 parts of calcium hydroxide were added. 45 parts of 10% oxalic acid aqueous solution were further added. Then, after heating to 160°C for dehydration, the unreacted raw materials were evaporated and removed by heating to 200°C under a reduced pressure of 5 mmHg. 740 parts of MIBK were added to dissolve the product, 200 parts of warm water at 80°C were added for washing, and the lower water layer was separated and removed. Then, the mixture was heated to 160°C under reduced pressure of 5 mm g to evaporate and remove MIBK, thereby obtaining 310 parts of a reddish brown aromatic hydroxy compound (P5). The resin had a hydroxyl equivalent of 341, a softening point of 104°C, and an absorption ratio (A 3040 / A 1210) was 0.27. The mass spectrum was measured by ESI-MS (negative), and M-=253, 375, 507, 629 were observed. The u=0 isomer content was 5.94 area %.

[0216] Reference Example 1

[0217] In the same reaction apparatus as in Synthesis Example 1, 400 parts of phenol and 47% BF 3 7.5 parts of ether complex are heated to 70°C while stirring. While maintaining this temperature, 70.2 parts of dicyclopentadiene are added dropwise over 2 hours. The mixture is further reacted at a temperature of 125-135°C for 4 hours, and 11.7 parts of calcium hydroxide are added. 35 parts of a 10% aqueous solution of oxalic acid are then added. After heating to 160°C for dehydration, the mixture is heated to 200°C under a reduced pressure of 5 mmHg to evaporate and remove the unreacted raw materials. 1097 parts of MIBK are added to dissolve the product, 108 parts of warm water at 80°C are added for washing, and the lower aqueous layer is separated and removed. Then, the mixture is heated to 160°C under a reduced pressure of 5 mmHg to evaporate and remove MIBK, to obtain 158 parts of a reddish-brown aromatic hydroxy compound (P6). The hydroxyl equivalent is 177 and the softening point is 92°C. The mass spectrum was measured by ESI-MS (negative), and M-=319, 545 were observed, but the structure after the above formula (1a) and formula (1b) were added in the form of substituents, that is, M-=225, 451 were not observed. The reaction rate of dicyclopentadiene was 100%. The GPC of the obtained aromatic polyhydroxy compound (P6) was shown in Figure 5 . It does not include u=0 bodies.

[0218] Example 1

[0219] Into a reaction apparatus equipped with a stirrer, a thermometer, a nitrogen blowing ring, a dropping funnel and a cooling tube, 100 parts of P1 as an aromatic hydroxy compound, 0.01 parts of tetra-n-butylammonium bromide (TBAB), 47.8 parts of B1 as an aromatic carboxylic acid halide and 369 parts of toluene (TL) were added, and the temperature was raised to 50°C to dissolve them. While controlling the temperature in the system to below 60°C, 94.1 parts of a 20% aqueous sodium hydroxide solution (20% NaOH) were added dropwise over 3 hours, and then stirring was continued at this temperature for another hour. The reaction mixture was allowed to stand for separation, and the water layer was removed. This operation was repeated until the pH of the water layer reached 7. Then, the water was removed by reflux dehydration to obtain 171 parts of an active ester resin (A1) in a toluene solution state with a non-volatile component of 65%. The active ester equivalent calculated from the amount of raw materials charged was 279. The GPC of the obtained active ester resin (A1) is shown at Figure 3 , FT-IR is shown in Figure 4 .

[0220] Examples 2 to 10 and Reference Example 2

[0221] The active ester resin was obtained by mixing in the same manner as in Example 1 according to the mixing amounts (parts) shown in Table 1. The results are shown in Table 1. The GPC of the active ester resin (A11) obtained in Reference Example 2 is shown in Figure 6 .

[0222] [Table 1]

[0223]

[0224] Embodiment 11

[0225] 100 parts of E1 as epoxy resin, 110 parts of A1 as curing agent, and 0.5 parts of C1 as curing accelerator were mixed in terms of solid content and dissolved in methyl ethyl ketone to obtain epoxy resin composition varnish. The obtained epoxy resin composition varnish was impregnated in glass cloth (WEA7628XS13, 0.18 mm thick, manufactured by Nitto Bosho Co., Ltd.). The impregnated glass cloth was dried in a hot air circulation oven at 150°C for 9 minutes to obtain a prepreg. 8 sheets of the obtained prepreg were overlapped with copper foil (Mitsui Mining and Smelting Co., Ltd., 3EC-III, thickness 35 μm) on the top and bottom, and vacuum pressed at 2 MPa under the temperature conditions of 130°C × 15 minutes + 210°C × 80 minutes to obtain a 1.6 mm thick laminate. The results of the copper foil peel strength and interlayer adhesion of the laminate are shown in Table 2.

[0226] In addition, the obtained prepreg was loosened and made into a 100-mesh powdered prepreg powder using a sieve. The obtained prepreg powder was placed in a fluororesin mold and vacuum-pressed at 2 MPa under the temperature conditions of 130°C × 15 minutes + 210°C × 80 minutes to obtain a 50 mm square × 2 mm thick test piece. The results of the relative dielectric constant and dielectric loss tangent of the test piece are shown in Table 2.

[0227] Examples 12 to 20 and Comparative Examples 1 to 3

[0228] The same operation as in Example 11 was carried out by blending the components in the amounts (parts) shown in Table 2 to obtain a laminate and a test piece. The results are shown in Table 2. The amounts of A1 to A11 are expressed in terms of solid content.

[0229] [Table 2]

[0230]

[0231] These results show that the active ester resins obtained in Examples and the resin compositions containing the active ester resins can provide cured resins that exhibit very good low dielectric properties and also have excellent adhesive strength.

[0232] Industrial Applicability

[0233] The epoxy resin composition of the present invention exhibits excellent dielectric properties in its cured product, and can be suitably used for printed wiring board applications, particularly mobile device applications and server applications that strongly require low dielectric loss tangent.

Claims

1. An active ester resin, characterized in that having a bicyclopentenyl group-containing polyaryloxy unit represented by the following formula (1), and a polyarylcarbonyl unit, Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a hydrogen atom, a dicyclopentenyl group represented by the following formula (1a) or a dicyclopentenyl group represented by the following formula (1b), R 2 At least one of them is the dicyclopentenyl group, n represents the number of repetitions, and the average value thereof is a number from 1 to 5, 2. The active ester resin according to claim 1, wherein As the polyaryloxy unit, other polyaryloxy units other than the unit represented by the above formula (1) are contained, and the other polyaryloxy units are units represented by the following formula (4) and / or formula (5), Among them, m represents the number of repetitions, and its average value is a number from 1 to 5. Among them, Ar 1 Each independently represents any aromatic ring group in a benzene ring or a naphthalene ring, and these aromatic rings have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent or are unsubstituted, and R 3 It is a direct bond or a divalent group selected from a hydrocarbon group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO2- and -C(CF3)2-, and k is 0 or 1.

3. The active ester resin according to claim 1, wherein There is a monoaryloxy group at the molecular chain terminal, and the monoaryloxy group is a group represented by the following formula (2) and / or formula (6), Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a hydrogen atom, a dicyclopentenyl group represented by the following formula (1a) or a dicyclopentenyl group represented by the following formula (1b), R 2 At least one of them is the dicyclopentenyl group, Among them, Ar 2 Each independently represents any aromatic ring group in a benzene ring or a naphthalene ring, and these aromatic rings have an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 11 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an aryloxy group having 6 to 11 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms as a substituent, or are unsubstituted, and R 4 It is a direct bond or a divalent group selected from -CH2-, -C(CH3)2-, -CH(CH3)-, -CO-, -O-, -S-, -SO2- and -C(CF3)2-, and k is 0 or 1.

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

5. A method for producing an active ester resin, characterized in that: The present invention relates to a method for producing an active ester resin from an aromatic hydroxy compound and an aromatic polycarboxylic acid or an acid halide thereof, wherein the aromatic hydroxy compound is an aromatic hydroxy compound containing a dicyclopentenyl group represented by the following formula (8): Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a hydrogen atom, a dicyclopentenyl group represented by the following formula (1a) or a dicyclopentenyl group represented by the following formula (1b), R 2 At least one of them is the dicyclopentenyl group, u represents the number of repetitions, and contains u=0 components and u≥1 components, and the average value of u≥1 components is a number from 1 to 5, 6. A method for producing an active ester resin, characterized in that: A 2,6-disubstituted phenol is reacted with dicyclopentadiene to obtain a dicyclopentenyl group-containing aromatic hydroxy compound represented by the following formula (8), and the aromatic hydroxy compound is reacted with an aromatic polycarboxylic acid or an acid halide thereof, Among them, R 1 Each independently represents a hydrocarbon group having 1 to 8 carbon atoms, R 2 Each independently represents a hydrogen atom, a dicyclopentenyl group represented by the following formula (1a) or a dicyclopentenyl group represented by the following formula (1b), R 2 At least one of them is the dicyclopentenyl group, u represents the number of repetitions, and contains u=0 components and u≥1 components, and the average value of u≥1 components is a number from 1 to 5, 7. The method for producing an active ester resin according to claim 5 or 6, wherein: An aromatic hydroxy compound is obtained by reacting 0.28 to 2 mol of dicyclopentadiene with 1 mol of 2,6-disubstituted phenols.

8. An epoxy resin composition comprising the active ester resin according to claim 1 and an epoxy resin as essential components.

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

10. A prepreg, characterized in that: The epoxy resin composition according to claim 8 is used.

11. A laminated plate, characterized in that: The epoxy resin composition according to claim 8 is used.

12. A material for a circuit board, characterized in that: The epoxy resin composition according to claim 8 is used.

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