WO2023127709A1 - Epoxy resin composition - Google Patents

Epoxy resin composition Download PDF

Info

Publication number
WO2023127709A1
WO2023127709A1 PCT/JP2022/047514 JP2022047514W WO2023127709A1 WO 2023127709 A1 WO2023127709 A1 WO 2023127709A1 JP 2022047514 W JP2022047514 W JP 2022047514W WO 2023127709 A1 WO2023127709 A1 WO 2023127709A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
formula
same
epoxy resin
represented
Prior art date
Application number
PCT/JP2022/047514
Other languages
French (fr)
Japanese (ja)
Inventor
良太 針▲崎▼
Original Assignee
住友精化株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 住友精化株式会社 filed Critical 住友精化株式会社
Publication of WO2023127709A1 publication Critical patent/WO2023127709A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate

Definitions

  • the present disclosure relates to epoxy resin compositions and the like. More particularly, the present invention relates to epoxy resin compositions containing hydroxy group-containing compounds, cured products of the epoxy resin compositions, uses thereof, and the like.
  • Epoxy resin compositions are widely used in various industrial fields, such as paints, adhesives, and electrical and electronic products, because the resulting cured products are excellent in adhesiveness, corrosion resistance, electrical properties, etc.
  • electronic materials such as semiconductors and printed wiring boards
  • it is used as a sealing material and printed circuit board material.
  • transmission loss depends on the dielectric constant and dielectric loss tangent of electronic component materials, it is effective to reduce the dielectric constant and dielectric loss tangent of these materials. low) is strongly desired.
  • Epoxy resin compositions that enable low dielectric loss tangent using epoxy resin are being developed.
  • the alicyclic epoxy group possessed by the alicyclic epoxy resin has a bulkier molecular structure than the glycidyl group. It is expected to contribute to further reduction of the dielectric loss tangent of the epoxy resin cured product.
  • activated ester curing agents are often used especially in the field of electronic materials.
  • the alicyclic epoxy resin has a problem that the reaction rate with the active ester curing agent is slow. For this reason, alicyclic epoxy resins have been difficult to use in the field of electronic materials such as semiconductors and printed wiring boards.
  • the curing conditions are 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. of heating was required.
  • a resin material containing an alicyclic epoxy resin and an active ester compound contains an epoxy resin having a glycidyl ether group as a second epoxy resin, so that the heat generated by the reaction It is disclosed that the reaction between the alicyclic epoxy resin and the active ester compound proceeds well.
  • much lower dielectric properties are required.
  • the present inventors have conducted studies to provide an alicyclic epoxy resin composition that maintains excellent dielectric properties and has a significantly improved reaction rate with an active ester curing agent compared to conventional ones. rice field.
  • the present inventors have found that an epoxy resin composition containing an alicyclic epoxy resin having no glycidyl group, an active ester curing agent, and a curing accelerator is further blended with a compound containing a hydroxy group to achieve excellent The inventors have found that it is possible to obtain an alicyclic epoxy resin composition having a markedly improved reaction rate with an active ester curing agent while maintaining dielectric properties, and made further improvements.
  • Section 1 (A) a hydroxy group-containing compound, (B) an epoxy resin, (C) a curing agent, and (D) a curing accelerator, (A) the hydroxy group-containing compound has a molecular weight of 200 or more,
  • the (B) epoxy resin comprises an alicyclic epoxy resin having no glycidyl group,
  • the (C) curing agent comprises an active ester curing agent, Epoxy resin composition.
  • An alicyclic epoxy resin having no glycidyl group is Formula (1-ia):
  • X ii is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 2 hydrogen atoms from A divalent group obtained by excluding or formula (2 g -iia):
  • R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are optionally substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms
  • R 2 is the same or different and represents an alkylene group having 1 to 18 carbon atoms, in which some carbon atoms excluding carbon atoms directly bonded to silicon atoms are selected from the group consisting of oxygen atoms and nitrogen atoms; optionally substituted with at least one
  • X iii is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 3 hydrogen atoms from A trivalent group obtained by excluding or formula (2 g -iiia):
  • X iv is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 4 hydrogen atoms from A tetravalent group obtained by excluding or formula (2 g ):
  • R IIIa are the same or different, R 1 or the following formula (3′):
  • Epoxy resin represented by and the expression:
  • the hydroxy group-containing compound has the formula:
  • R en is represented by the following formula, with * being the side bonded to O:
  • R 3 and n are the same as above.
  • R en is the same as above.
  • R en is at least one compound selected from the group consisting of compounds having a group represented by Item 4.
  • the epoxy resin composition according to item 3. Item 5.
  • a cured product obtained by curing the epoxy resin composition according to any one of Items 1 to 4.
  • Item 6. A printed circuit board material having an insulating layer containing the cured product of Item 5.
  • the epoxy resin composition of the present disclosure maintains excellent dielectric properties and cures in a short time because the reaction rate between the active ester curing agent and the alicyclic epoxy resin is significantly improved compared to conventional ones. be able to. Therefore, the epoxy resin composition of the present disclosure can be used, for example, as a semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a coverlay film, an electromagnetic wave shielding film, a printed circuit board material, a composite It can be suitably used for a wide range of applications such as materials.
  • the present disclosure preferably includes, but is not limited to, epoxy resin compositions, cured products thereof, uses thereof, and the like.
  • the present disclosure includes everything disclosed herein and recognized by a person skilled in the art. do.
  • the epoxy resin composition included in the present disclosure contains (A) a hydroxy group-containing compound, (B) an epoxy resin, (C) a curing agent, and (D) a curing accelerator. Also, (B) the epoxy resin contains an alicyclic epoxy resin having no glycidyl group, and (C) the curing agent contains an active ester curing agent.
  • the epoxy resin composition included in the present disclosure may be referred to as "the epoxy resin composition of the present disclosure”.
  • the (B) epoxy resin contained in the epoxy resin composition of the present disclosure includes an alicyclic epoxy resin having no glycidyl group.
  • the alicyclic epoxy resin is an epoxy resin having a structure in which two carbon atoms forming an epoxy group form an alicyclic ring. Only one kind of alicyclic epoxy resin may be used, or two or more kinds thereof may be used in combination. In this specification, unless otherwise specified, the alicyclic epoxy resin does not have a glycidyl group.
  • the aliphatic ring examples include monocycloalkane ring, bicycloalkane ring, tricycloalkane ring and tetracycloalkane ring. Moreover, the said aliphatic ring may have an unsaturated bond in a part of ring. From the viewpoint of further increasing the curing speed of the epoxy resin composition, the aliphatic ring preferably has at least a cyclopentane ring or a cyclohexane ring.
  • the cyclohexane ring may be a norbornane ring or a tricyclodecane ring.
  • the number of epoxy groups in the alicyclic epoxy resin is preferably 1 or more, more preferably 2 or more or 3 or more.
  • the upper limit of the number of epoxy groups is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less.
  • the alicyclic epoxy resin may be a monomer or a polymer.
  • the molecular weight of the alicyclic epoxy resin is preferably 100-1000, more preferably 130-800, still more preferably 140-700.
  • the B-stage film sini-cured film
  • the linear expansion coefficient (CTE) of the cured product can be reduced to can be lower.
  • the epoxy equivalent weight of the alicyclic epoxy resin is preferably 50-500, more preferably 65-400, still more preferably 70-350. Epoxy equivalent is measured according to JIS K7236. Epoxy equivalent weight is the mass of resin containing one equivalent of epoxy groups.
  • the alicyclic epoxy resin has formula (1):
  • the epoxy resin represented by is preferably exemplified.
  • R Xa , R Xb , R Xc , and R Xd are the same or different and are hydrogen atoms, lower alkyl groups, lower alkoxy groups, lower alkenyl groups, halogen atoms, or formula (3):
  • a lower alkyl group, a lower alkoxy group and a lower alkenyl group may be collectively referred to as a "lower carbon substituent".
  • a lower alkyl group or a lower alkoxy group is more preferred.
  • R Xa , R Xb , R Xc and R Xd is a group of formula (3).
  • R Xa , R Xb , R Xc and R Xd are three hydrogen or halogen atoms or lower carbon substituents and one is a group of formula (3), or two are hydrogen or halogen atoms or two of the lower carbon substituents are groups of formula (3), one is a hydrogen atom or halogen atom or three of the lower carbon substituents are groups of formula (3), or all are groups of formula (3) is the base.
  • R Xa , R Xb , R Xc and R Xd are hydrogen atoms, halogen atoms or lower carbon substituents, and R Xd is the formula (3), or (ii) R Xa and R Xb are hydrogen atoms or halogen atoms or lower carbon substituents and R Xc and R Xd are groups of formula (3), or (iii) R Xa is a hydrogen atom or a halogen atom or a lower carbon substituent and R Xb , R Xc and R Xd are groups of formula (3), or (iv) all of R Xa , R Xb , R Xc and R Xd can be a group of formula (3).
  • R Xa , R Xb , R Xc and R Xd those other than the group of formula (3) are more preferably hydrogen atom
  • R Xa , R Xb , R Xc and R Xd may be the same or different. Therefore, when (i) R Xa , R Xb and R Xc are hydrogen atoms, halogen atoms or lower carbon substituents and R Xd is a group of formula (3), then R Xa , R Xb and R Xc are the same or (ii) when R Xa and R Xb are hydrogen atoms or halogen atoms or lower carbon substituents and R Xc and R Xd are groups of formula (3), then R Xa and R Xb are the same or different; and R Xc and R Xd may be the same or different, and (iii) R Xa is a hydrogen atom or a halogen atom or a lower carbon substituent and R Xb , R Xc and R Xd are groups of formula (3) R Xb , R Xc and R Xd may be the same or different
  • R Xa , R Xb , R Xc and R Xd are halogen atoms or lower carbon substituents
  • these halogen atoms or lower carbon substituents may also be the same or different.
  • two or three of R Xa , R Xb , R Xc and R Xd are more preferably the same lower carbon substituent.
  • a lower carbon substituent refers to a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • Lower here means having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6).
  • lower alkyl groups or lower alkoxy groups are preferred.
  • Preferred examples of lower alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group.
  • Preferred examples of lower alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy groups.
  • a halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a fluorine atom or a bromine atom.
  • the X ring represents a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed or two are connected.
  • the saturated hydrocarbon ring is preferably a saturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8), and particularly preferably a cyclopentane ring, a cyclohexane ring, or the like.
  • the unsaturated hydrocarbon ring is preferably an unsaturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8), and particularly preferably a benzene ring.
  • the ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed includes 2, 3, saturated hydrocarbon rings and/or unsaturated hydrocarbon rings. Or a ring with 4 condensed rings is preferred, and a ring with 2 or 3 condensed rings is more preferred.
  • decahydronaphthalene ring More specifically, for example, decahydronaphthalene ring, adamantane ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, triphenylene ring, tetralin ring, 1,2,3,4,5,6,7,8- octahydronaphthalene ring, fluorene ring, norbornene ring and the like.
  • hydrocarbon rings having a structure in which 2 to 6 saturated hydrocarbon rings or unsaturated hydrocarbon rings, or saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed are collectively referred to as "hydrocarbon rings. ” is sometimes called.
  • a ring represented by is preferred.
  • Ring X 1 and ring X 2 are the same or different and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, the X 1 ring and the X 2 ring are both saturated hydrocarbon rings, both unsaturated hydrocarbon rings, or one saturated hydrocarbon ring and the other unsaturated hydrocarbon ring. It is preferred that both the X 1 ring and the X 2 ring are saturated hydrocarbon rings or both unsaturated hydrocarbon rings.
  • X 1 ring and X 2 ring are preferably both benzene rings, both cyclohexane rings, or one benzene ring and the other cyclohexane ring, more preferably both benzene rings.
  • Y is a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (-O-), a sulfur atom (-S-), -SO -, or -SO 2 -.
  • alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group and the like.
  • alkyl groups having 1 to 4 carbon atoms as substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group.
  • Preferred alkylene groups having 1 to 6 carbon atoms and substituted with alkyl groups having 1 to 4 carbon atoms include -CH(CH 3 )-, -C(CH 3 ) 2 -, and -CH 2 CH(CH 3 )CH 2- , -CH 2 C(CH 3 ) 2 CH 2 - and the like can be exemplified.
  • Y is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group, -S- or -SO 2 -, more preferably a bond, a dimethylmethylene group, an oxygen atom or -SO 2 -.
  • More specific examples of the structure represented by formula (2) include biphenyl, bicyclohexyl, phenylcyclohexane, diphenylmethane, dicyclohexylmethane, 2,2-diphenylpropane, 2,2-dicyclohexylpropane, diphenyl ether, and dicyclohexyl ether. , diphenyl sulfide, dicyclohexyl sulfide, diphenyl sulfone, dicycloexyl sulfone and the like.
  • the number of halogen atoms or lower carbon substituents are (1:0), (0:1), (2:0), (1:1), (0:2), (3:0), (2:1) , (1:2), or (0:3).
  • any one of X 1 ring and X 2 ring is two groups of formula (3) and one X 1 ring and one X 2 ring may be substituted with a group of formula (3), and one X 1 ring and X 2 ring each may be substituted with a group of formula (3) is preferably substituted with
  • the number of halogen atoms or lower carbon substituents can be (1:0), (0:1), (2:0), (1:1), or (0:2).
  • any one of X 1 ring and X 2 ring is three groups of formula (3) optionally substituted with a group of formula (3) having two X 1 rings and one X 2 ring, and having one X 1 ring and two X 2 rings of formula (3) X 1 ring is substituted with a group of formula (3 ), or X 1 ring is 1 and X 2 rings are 2
  • Formula (3) is preferably substituted with a group of In this case, when the ring represented by formula (2) is substituted with 0 or 1 halogen atoms or lower carbon substituents, the number of halogen atoms or lower carbon substituents (X 1 ring substitution number: X 2 ring number of substitutions) can be (1:0) or (0:1).
  • any one of ring X 1 and ring X 2 may be substituted with four groups of formula (3), and ring X 1 may be substituted with three groups of formula (3).
  • one X 2 ring may be substituted with one group of formula (3), one X 1 ring may be substituted with three groups of formula (3), X 1 ring may be substituted with two groups of formula (3), and preferably two rings of X 1 and X 2 are substituted with two groups of formula (3).
  • R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are It may be substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms (preferably oxygen atoms).
  • the partial carbon atoms are preferably carbon atoms that are not directly bonded to silicon atoms.
  • the partially optionally substituted carbon atoms are one or more (for example, 2, 3, 4, 5, or 6) carbon atoms, preferably one carbon atom. From the viewpoint of ease of synthesis, etc., it is preferable that the R 1s bonded to the same silicon atom are the same. It is also more preferred that all R 1s present in formula (1) are the same.
  • the alkyl group having 1 to 18 carbon atoms represented by R 1 is a linear or branched alkyl group, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n- nonyl group, n-decyl group, n-dodecyl group and the like.
  • An alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
  • the alkenyl group having 2 to 9 carbon atoms represented by R 1 is a linear or branched alkenyl group, such as vinyl group, allyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group and the like can be mentioned.
  • Alkenyl groups having 2 to 4 carbon atoms are preferred.
  • the cycloalkyl group represented by R 1 includes 3- to 8-membered cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl groups.
  • the aryl group represented by R 1 includes monocyclic or bicyclic aryl groups such as phenyl group, tolyl group, xylyl group, ethylphenyl group and naphthyl group. Among them, a phenyl group is preferred.
  • the aralkyl group represented by R 1 includes alkyl groups having 1 to 4 carbon atoms substituted with an aryl group (especially a phenyl group), such as benzyl group, ⁇ -phenethyl group, ⁇ -phenethyl group, ⁇ - A methylphenethyl group and the like can be mentioned.
  • R 1 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
  • R 2 is an alkylene group having 1 to 18 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18) indicates The alkylene group is a linear or branched alkylene group, preferably a linear alkylene group.
  • methylene group methylmethylene group, ethylmethylene group, dimethylmethylene group, diethylmethylene group, dimethylene group (--CH 2 CH 2 --), trimethylene group (--CH 2 CH 2 CH 2 --), tetramethylene group, penta methylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group and the like.
  • an alkylene group having 2 to 18 carbon atoms preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and still more preferably an alkylene group having 2 to 6 carbon atoms. and particularly preferably an alkylene group having 2 to 5 carbon atoms.
  • Part of the carbon atoms of the alkylene group having 1 to 18 carbon atoms may be substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms (preferably oxygen atoms).
  • the partial carbon atoms are preferably carbon atoms that are not directly bonded to any of silicon atoms and 3- to 8-membered rings or epoxy rings.
  • the partially optionally substituted carbon atoms are one or more (for example, 2, 3, 4, 5, or 6) carbon atoms, preferably one carbon atom.
  • Examples of such groups include (*)-C 2-9 alkylene-O-C 1-8 alkylene-, preferably (*)-C2-4 alkylene-O-C1-3 alkylene-, more preferably (*)-C2-4 alkylene-O-C1-2 alkylene-, especially (*)-C3 alkylene-O-methylene- is preferred.
  • the group of formula (4) represents any one of the following groups because only the epoxy ring remains and n is an integer of 0 to 3.
  • the epoxy resin represented by formula (1) has a glycidyl group, and therefore does not correspond to an alicyclic epoxy resin having no glycidyl group. Therefore, as described above, m is an integer of 1 to 6 as a preferred example of the alicyclic epoxy resin. Further, when m indicates 0, the epoxy resin represented by formula (1) can be said to be an example of an epoxy resin having a glycidyl group.
  • R 2 and R 3 are attached to a 3- to 8-membered ring or epoxy ring.
  • n indicates the number of R3 's bonded to the 3- to 8-membered ring or epoxy ring.
  • R 3 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are It may be substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms.
  • the partial carbon atoms are preferably carbon atoms that are not directly bonded to a 3- to 8-membered ring or epoxy ring.
  • the partially optionally substituted carbon atoms are one or more (for example, 2, 3, 4, 5, or 6) carbon atoms, preferably one carbon atom.
  • the alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 9 carbon atoms, the cycloalkyl group, the aryl group and the aralkyl group represented by R 3 are the same as the corresponding substituents represented by R 1 above . mentioned.
  • R 3 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
  • Examples of particularly preferred groups of formula (3) include R 1 , R 2 , R 3 , m, and n being the same as above, R 1 being all the same, and R 3 being (a plurality of where all are the same).
  • Particularly preferred specific examples of the group of formula (4) include groups in which R 3 is the same as above, m is 1, 2, 3 or 4, and n is 0, 1 or 2. Among them, more preferably, for example, the following groups (where R 3 is the same as above).
  • 1, 2, 3, or 4 groups of formula (4) are present in the epoxy resin represented by formula (1), and each group may be the same or different, and is preferably the same.
  • a hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting ring X and not bonded to R Xa , R Xb , R Xc and R Xd is a lower carbon substituent or It may be substituted with a halogen atom (preferably a lower carbon substituent).
  • the X ring is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, these rings are constituted a hydrogen atom bonded to a carbon atom that is a carbon atom and to which R Xa , R Xb , R Xc and R Xd are not bonded is substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent) and when the X ring is a ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are linked, these linked saturated hydrocarbon rings and/or unsaturated hydrocarbon rings A hydrogen atom bonded to a carbon atom constituting a hydrogen ring and not bonded to R Xa , R Xb , R Xc and R Xd is a lower carbon substituent or a halogen atom (preferably a lower carbon-
  • R Xa-d non-bonded a carbon atom constituting a hydrocarbon ring constituting ring X and to which R Xa , R Xb , R Xc and R Xd are not bonded.
  • only one lower carbon substituent or halogen atom which optionally replaces the hydrogen atom bonded to the R 1 Xa -d non-bonding carbon atom, is bonded to one R 1 Xa-d non-bonding carbon atom. That is, when the hydrogen atoms bonded to the R Xa-d non-bonding carbon atoms are substituted, only one of the hydrogen atoms bonded to the R Xa-d non-bonding carbon atoms is a lower carbon substituent or a halogen Atoms are preferred. Also, the number of such substitutions (ie, the sum of lower carbon substituents and halogen atoms) is preferably less than the number of R Xa-d non-bonding carbon atoms.
  • the number of such substitutions is preferably 1 to 6 (1, 2, 3, 4, 5, or 6), more preferably 1 to 4, even more preferably 1 to 2.
  • the substituted hydrogen atom is preferably a hydrogen atom bonded to a carbon atom to which Y is not bonded.
  • R Xa , R Xb , R Xc , and R Xd is a lower carbon substituent, and at least one lower carbon substituent is attached to an R Xa-d non-bonding carbon atom, all lower It is preferred that the carbon substituents are identical. That is, when lower carbon substituents are present in R Xa , R Xb , R Xc , and R Xd and there are lower carbon substituents attached to R Xa-d non-bonding carbon atoms, all lower carbon substitutions It is preferred that the groups are identical.
  • R Xa , R Xb , R Xc , and R Xd is a halogen atom, and at least one halogen atom is bonded to a non-bonding carbon atom of R Xa-d , all halogen atoms are preferably identical. That is, when halogen atoms are present in R Xa , R Xb , R Xc , and R Xd and there are halogen atoms bonded to R Xa-d non-bonding carbon atoms, all halogen atoms are the same. is preferred.
  • R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy or a lower alkenyl group
  • R Xg1 and R Xg2 are more preferably bonded to different carbon atoms on the benzene ring.
  • the epoxy resins represented by formula (1-X1) those in which R 1 Xg1 and R 1 Xg2 are hydrogen atoms are preferred.
  • formula (1-X1) is more preferable:
  • R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same as above.
  • R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same as above.
  • R 1 Xa and R 1 Xb are hydrogen atoms
  • R 1 Xc and R 1 Xd are groups of formula (3)
  • R 1 Xg1 and R 1 Xg2 are hydrogen atoms.
  • R 1 Xa and R 1 Xc are hydrogen atoms
  • R 1 Xb and R 1 Xd are groups of formula (3)
  • R 1 Xg1 and R 1 Xg2 are hydrogen atoms.
  • R 1 Xa is a hydrogen atom
  • R 1 Xb , R 1 Xc and R 1 Xd are groups of formula (3)
  • R 1 Xg1 and R 1 Xg2 are hydrogen atoms. Atoms are more preferred.
  • R Xa , R Xb , R Xc and R Xd are the same as above, R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • R Xa , R Xb , R Xc and R Xd are the same as above
  • R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower
  • R Xa , R Xc , R X11 , R X12 and R X13 are more preferably bonded to different carbon atoms
  • R Xb , R Xd , R X21 , More preferably, R X22 and R X23 are bonded to different carbon atoms.
  • none of R Xa , R Xb , R Xc , R Xd , R X11 , R X12 , R X13 , R X21 , R X22 and R X23 is bonded to the carbon atom to which Y is bonded.
  • formula (1-X2) is more preferable:
  • R Xa , R Xb , R Xc and R Xd are the same as above, R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • R Xa , R Xb , R Xc and R Xd are the same as above, R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • Y is the same as above
  • R Xa , R Xb , R Xc and R Xd are the same as above
  • R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.
  • R Xa , R Xb , R Xc and R Xd are groups of formula (3), and R X11 and R X21 are lower carbon substituents. and R X12 , R X13 , R X22 and R X23 are preferably hydrogen atoms.
  • Y is an alkylene group having 1 to 6 carbon atoms (especially —C(CH 3 ) 2 —) optionally substituted with an alkyl group having 1 to 4 carbon atoms
  • R Xa , R Xb , R Xc , and R 1 Xd are groups of formula (3)
  • R 111 and R 1 X21 are lower alkoxy groups
  • R 12 , R 13 , R 122 and R 1 X23 are hydrogen atoms.
  • the groups of formula (3) of R Xa , R Xb , R Xc and R Xd are all the same and the lower carbon substituents of R X11 and R X21 are the same.
  • R Xa and R Xb are hydrogen atoms
  • R Xc and R Xd are groups of formula (3)
  • R X11 , R X12 , R X13 , R X21 , R X22 and R X23 are preferably hydrogen atoms.
  • R 1 Xc and R 1 Xd are the same.
  • R Xa is a hydrogen atom
  • R Xb , R Xc and R Xd are groups of formula (3)
  • R X11 , R X12 , R X13 , R X21 , R X22 and R X23 are preferably hydrogen atoms.
  • R Xb , R Xc and R Xd are identical.
  • the epoxy resin represented by formula (1) has the following formula (1-iia):
  • X ii is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or the formula (2 g -iia):
  • R 1 , R 2 , R 3 , m and n are the same as above.
  • the epoxy resin represented by is preferably included.
  • R 1 , R 2 , R 3 , m, and n may be the same or different, and are preferably the same.
  • the divalent group represented by X ii preferably includes a cyclohexane-1,4-diyl group and a 1,4-phenylene group, more preferably a 1,4-phenylene group.
  • divalent groups represented by the formula (2 g -ia) preferably the formula (2 g -iia'):
  • a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — in the formula (2 g -ia′) is particularly preferred.
  • X ii preferably includes a cyclohexane-1,4-diyl group, a 1,4-phenylene group and formula (2 g -iia'), and more preferably a 1,4-phenylene group.
  • m is the same and 1, 2, 3, or 4 (particularly preferably, m is the same and 4), n is the same and 0 (i.e., the ring is substituted by R 3 ),
  • X ii is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring),
  • R 1 is the same alkyl group having 1 to 3 carbon atoms
  • R 2 are the same and each is an alkylene group having 2 to 6 carbon atoms and one carbon atom not directly bonded to a silicon atom or a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom;
  • Epoxy resins represented by the following can be more preferably used in the present invention.
  • the epoxy resin represented by formula (1) has the following formula (1-iiia):
  • X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring, or formula (2 g -iiia):
  • R 1 , R 2 , R 3 , m and n are the same as above.
  • the epoxy resin represented by is preferably included.
  • R 1 , R 2 , R 3 , m, and n may be the same or different, and are preferably the same.
  • m is the same and 1, 2, 3, or 4 (particularly preferably, m is the same and 4), n is the same and 0 (i.e., the ring is substituted by R 3
  • X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), R 1 is the same alkyl group having 1 to 3 carbon atoms, R 2 are the same and each is an alkylene group having 2 to 6 carbon atoms and one carbon atom not directly bonded to a silicon atom or a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom; Epoxy resins represented by the following can be more preferably used in the present invention.
  • X iv is a tetravalent group represented by the above (1′), and represents a group in which the hydrogen atom bonded to the R Xa-d non-bonding carbon atom in the X ring is not substituted, R 1 , R 2 , R 3 , m and n are the same as above.
  • Including the epoxy resin represented by. R 1 , R 2 , R 3 , m, and n may be the same or different, and are preferably the same.
  • X iv tetravalent group represented by X iv , preferably the following groups:
  • the tetravalent group represented by X iv is preferably a tetravalent group represented by the formula (2 g ) in which the hydrogen atom bonded to the R Xa-d non-bonding carbon atom is not substituted. is the formula (2 g ⁇ iva′):
  • m is the same and 1, 2, 3, or 4 (particularly preferably, m is the same and 4), n is the same and 0 (i.e., the ring is substituted by R 3 ),
  • X iv is a tetravalent group obtained by removing 4 hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring),
  • R 1 is the same alkyl group having 1 to 3 carbon atoms
  • R 2 are the same and each is an alkylene group having 2 to 6 carbon atoms and one carbon atom not directly bonded to a silicon atom or a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom;
  • Epoxy resins represented by the following can be more preferably used in the present invention.
  • epoxy resins represented by formula (1) more preferable ones are, for example, formula (1-IIb):
  • R 1 , R 2 , R 3 , X ii and n are the same as above.
  • the epoxy resin represented by can also be mentioned.
  • R 1 , R 2 , R 3 and n may be the same or different, and are preferably the same.
  • X ii is a 1,4-phenylene group or a group represented by formula (2 g -iia') (preferably 1,4-phenylene group), and R 1 is the same or different are (preferably the same) an alkyl group having 1 to 3 carbon atoms (especially a methyl group), both n are 0 (that is, the ring is not substituted with R 3 ), and R 2 are the same or different ( An alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: -(CH 2 ) 2 -) is more preferable.
  • R 1 , R 2 , R 3 , X iii , and n are the same as above.
  • the epoxy resin represented by can also be mentioned.
  • R 1 , R 2 , R 3 and n may be the same or different, and are preferably the same.
  • X iii is
  • R 1 is the same or different (preferably the same) alkyl group having 1 to 3 carbon atoms (especially methyl group), and n is 0 (that is, the ring is not substituted with R 3 ), and R 2 is the same or different (preferably the same) alkylene group having 2 to 6 carbon atoms (preferably dimethylene group: —(CH 2 ) 2 —) is more preferable.
  • the epoxy resin represented by formula (1) can be used alone or in combination of two or more.
  • the epoxy resin represented by formula (1) can be produced based on or according to a known method, for example, based on or according to the description in the patent document (British Patent No. 1123960). Further, for example, the epoxy resin represented by the formula (1-ia) can be produced by the reaction represented by the following reaction formula.
  • R 2A is an alkenyl group having 2 to 18 carbon atoms, in which some of the carbon atoms are substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms.
  • R 1 , R 2 , R 3 and X ii are the same as above.
  • the alkenyl group having 2 to 18 carbon atoms represented by R 2A is a linear or branched alkenyl group, preferably linear. Specific examples include vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, norbornenyl group, cyclohexenyl group and the like.
  • alkenyl group having 2 to 10 carbon atoms is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, still more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group, an allyl group, or It is a butenyl group.
  • the alkenyl group is preferably an ⁇ -alkenyl group.
  • Some of the carbon atoms in these alkenyl groups having 2 to 18 carbon atoms may be substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms (preferably oxygen atoms).
  • the partial carbon atoms are preferably carbon atoms that are not directly bonded to the epoxy ring.
  • the part of the carbon atoms that may be substituted is one or more (for example, 2, 3, 4, 5, or 6) carbon atoms, preferably one carbon atom.
  • Such groups include, for example, alkenyl-O with 2 to 9 carbon atoms-alkylene with 1 to 8 carbon atoms-, preferably alkenyl-O with 2 to 4 carbon atoms-alkylene with 1 to 3 carbon atoms-, more preferably 2 to 3 carbon atoms.
  • CH 2 ⁇ CH—O—CH 2 —, CH 2 ⁇ CH —CH 2 —O —CH 2 —, CH 2 ⁇ CH —CH 2 —O—(CH 2 ) 2 —, CH 2 CH—(CH 2 ) 3 —O—(CH 2 ) 4 — and the like, among which CH 2 ⁇ CH—CH 2 —O—CH 2 — (allyloxymethyl group) is preferred.
  • the epoxy resin represented by formula (1-ia) can be produced by hydrosilylating the compound represented by formula (5-ia) and the compound represented by formula (6).
  • the hydrosilylation reaction can generally be carried out in the presence or absence of a solvent in the presence of a catalyst.
  • Xi represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon ring
  • R 1 is the same as above.
  • the epoxy resin represented by the above formula (1-iiia) or (1-iva) or the epoxy having a structure in which one group of formula (3) is bonded to a hydrocarbon ring Resin can also be produced.
  • X i to X iv are each a monovalent group obtained by removing one hydrogen atom from the X ring, and 2 obtained by removing two hydrogen atoms from the X ring.
  • the catalyst used in the hydrosilylation reaction may be a known catalyst, for example, platinum-based catalysts such as platinum carbon, chloroplatinic acid, platinum olefin complexes, platinum alkenylsiloxane complexes, platinum carbonyl complexes; fin) Rhodium-based catalysts such as rhodium; and iridium-based catalysts such as bis(cyclooctadienyl)dichloroiridium.
  • the above catalysts may be in the form of solvates (e.g. hydrates, alcoholates, etc.), or may be used in the form of solutions by dissolving the catalysts in alcohols (e.g., ethanol, etc.). can.
  • a catalyst can be used individually or in combination of 2 or more types.
  • the amount of the catalyst used may be an effective amount as a catalyst. 0.00001 to 20 parts by mass, preferably 0.0005 to 5 parts by mass, per 100 parts by mass of the total amount of the compound represented by 6).
  • the hydrosilylation reaction proceeds without using a solvent
  • a solvent allows the reaction to be carried out under mild conditions.
  • the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as ethanol and isopropanol; These may be used alone or in combination of two or more.
  • the amount of the compound represented by formula (6) to be used is, for example, the Si- It is generally 0.5 to 2 mol, preferably 0.6 to 1.5 mol, more preferably 0.8 to 1.2 mol, per 1 mol of H group.
  • the reaction temperature is usually 0°C to 150°C, preferably 10°C to 120°C, and the reaction time is usually about 1 hour to 24 hours.
  • the epoxy resin represented by formula (1) can be obtained by using a known isolation method such as distilling off the solvent from the reaction solution.
  • the group represented by -Z I -, -(CH2) Ia -O-(CH2) Ib - or -(CH2) Ic -COO-(CH2) Id - is the side that binds to R Ia -.
  • n 0.
  • R Ia and R Ib are preferably the same.
  • -Z I - preferably represents a bond.
  • -Z I - preferably represents -(CH2) Ic -COO-(CH2) Id -, particularly preferably Ic is 0 and Id is 1.
  • R Ia and R Ib are preferably the same, and -Z I - represents a bond.
  • R IIa -Z II -R IIb (II) (Wherein, R IIa and R IIb are the same or different and represent a group of formula (3) (where m is not 0), —Z II — is a bond, —(CH 2 ) j — (j is 1, 2, 3, or 4), —CH(CH 3 )—CH 2 —, —CH 2 —CH(CH 3 )—, —C(CH 3 ) 2 —, —O—(Si( R 1 ) 2 O) IIa —, where IIa is an integer of 0 to 8 (0, 1, 2, 3, 4, 5, 6, 7, 8) and R 1 is the same as above; ) is also preferably exemplified.
  • m preferably denotes 4 in the group of formula (3).
  • R 2 is preferably an alkylene group having 1, 2, or 3 carbon atoms.
  • R 1 is preferably the same or different (preferably the same) and is a methyl group or an ethyl group.
  • R IIa and R IIb are preferably identical and both denote a group of formula (3) (m denotes 4).
  • IIa preferably represents 0-1.
  • R IIIa are the same or different, R 1 or the following formula (3′):
  • R 2 , R 3 , m, and n are the same as above, provided that at least two R IIIa represent a group of formula (3′); R 1 is the same as above and IIIc is an integer of 2-6.
  • the group of formula (3′) is the group of formula (3) from which the group —Si(R 1 ) 2 — has been removed. Except for the description of —Si(R 1 ) 2 —, it also applies to formula (3′).
  • R 1 in formula (III) is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
  • IIIc preferably represents 4, 5, or 6. Further, all of R IIIa are preferably represented by formula (3′).
  • R 1 is the same or different and is the same as above, and R IIIa is the same or different and is the same as above).
  • All of R IIIa of the epoxy resin are preferably groups of formula (3′), and it is preferred that all of the groups of formula (3′) are the same.
  • R 2 is preferably a methylene group having 1 to 4 carbon atoms, such as a methylene group, a dimethylene group (—CH 2 CH 2 —) or a trimethylene group (—CH 2 CH 2 CH 2 —) is more preferred.
  • m is four.
  • n is 0.
  • all four R 1s present in formula (III-1) are preferably the same, and more preferably a methyl group or an ethyl group.
  • the alicyclic epoxy resin has the following formula:
  • n IVa is the same or different and is an integer of 0 to 5 (0, 1, 2, 3, 4, or 5)
  • n IVb is the same or different is an integer of 0 or 1
  • n IVc is an integer of 1 to 3 (1, 2, or 3)
  • nIVb may be the same or different.
  • R 1 in formula (IV) is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
  • nIVa is preferably 0 or 1, more preferably 0.
  • nIVb is more preferably 0.
  • nIVc is preferably 1 or 2, more preferably 1.
  • the epoxy resin may include an epoxy resin having a glycidyl group.
  • the alicyclic epoxy resins include alicyclic epoxy resins also having glycidyl groups, but alicyclic epoxy resins having no glycidyl groups are preferred.
  • the epoxy resin composition of the present disclosure may further contain an epoxy resin having a glycidyl group.
  • epoxy resins having a glycidyl group include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, nitrogen-containing ring epoxy resins (e.g., triglycidyl isocyanurate , hydantoin type epoxy resin), glycidylamine type epoxy resin, aliphatic type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin An epoxy resin etc. are mentioned. Further, these resins may be halogenated or hydrogenated.
  • bisphenol A type epoxy resin bisphenol A type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, and anthracene type epoxy resin are preferable from the viewpoint of improving the dielectric properties of the cured product.
  • Only one type of epoxy resin having a glycidyl group may be used, or two or more types may be used in combination.
  • the epoxy resin has a glycidyl group. That is, the (B) epoxy resin of the present disclosure includes an alicyclic epoxy resin having no glycidyl group, and may further include an epoxy resin having a glycidyl group in which m is 0.
  • the epoxy resin composition of the present disclosure contains an alicyclic epoxy resin and an epoxy resin having a glycidyl group
  • (B) is included in the epoxy resin composition from the viewpoint of more effectively exhibiting the effects of the present invention.
  • the content of the alicyclic epoxy resin in the epoxy resin is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass. That's it.
  • it may be 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by mass or more.
  • epoxy resins may all be alicyclic epoxy resins.
  • the epoxy resin composition contains an active ester curing agent as a curing agent.
  • An active ester curing agent is a compound having an ester group (preferably an ester group with high reactivity).
  • an active ester curing agent specifically, a compound having two or more ester groups in one molecule is suitable.
  • Preferred examples of compounds having two or more ester groups in one molecule include phenol esters, naphthol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like.
  • the active ester curing agent is obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound (that is, at least one selected from the group consisting of carboxylic acid compounds and thiocarboxylic acid compounds.
  • Condensates of one and at least one selected from the group consisting of hydroxy compounds and thiol compounds) are preferred.
  • a condensate obtained from a carboxylic acid compound and a hydroxy compound is preferred, and a condensate obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred.
  • Such a condensate (active ester curing agent) can be preferably used as an epoxy resin curing agent.
  • an active ester compound disclosed in JP-A-2009-235165, JP-A-2004-277460, or WO2013/061688 can be used. It is more preferable to use the active ester compound described in JP-A-2009-235165.
  • the contents of the active ester compounds described in the specifications and/or drawings of JP-A-2009-235165, JP-A-2004-277460, and WO2013/061688 are incorporated herein by reference.
  • an ester compound containing a dicyclopentadienyldiphenol structure is preferable as the active ester curing agent.
  • R 7 is an optionally substituted phenyl group or naphthyl group, y represents an integer of 0 or 1, and z is an average of repeating units of 0.05 to 2.5.
  • R7 is preferably a naphthyl group which may have a substituent. y is preferably zero. z is preferably between 0.25 and 1.5. From the viewpoint of electrical properties and heat resistance, it is more preferable that R7 is an optionally substituted naphthyl group, y is 0, and z is 0.25 to 1.5.
  • the active ester curing agent represented by the above formula include HPC-8000-65T (manufactured by DIC, ester equivalent weight: about 223 g/eq), etc. The active ester compound may be used alone or in combination of two or more. I can.
  • a commercially available ester compound can also be used as the active ester curing agent of the present invention.
  • an ester compound containing a dicyclopentadienyldiphenol structure, an acetylated product of phenol novolak, a benzoylated product of phenol novolak, etc. are preferable, and among them, an ester containing a dicyclopentadienyldiphenol structure is preferable.
  • Compounds are more preferred.
  • ester compounds containing a dicyclopentadienyl diphenol structure include EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC, ester equivalent weight: about 223), acetylated phenol novolak DC808 (manufactured by Mitsubishi Chemical Corporation, ester equivalent of about 149), YLH1026 (manufactured by Mitsubishi Chemical Corporation, ester equivalent of about 200) as a benzoylated phenol novolak, YLH1030 (manufactured by Mitsubishi Chemical Corporation, ester equivalent of about 201), YLH1048 (Mitsubishi Chemical (Ester equivalent: about 245), etc.
  • the epoxy resin composition may contain a curing agent other than the active ester curing agent as (C) the curing agent.
  • the curing agent other than the active ester curing agent is not particularly limited as long as it has a function of curing the epoxy resin.
  • Curing agents benzoxazine-based curing agents, naphthol-based curing agents, mercaptan-based curing agents, isocyanate-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, maleimide resins, and the like. Curing agents can be selectively used according to desired properties, and may be used alone or in combination of two or more.
  • curing agents other than active ester curing agents include, more specifically, phenol, cresol, hydroquinone, resorcinol, p-propylphenol, substituted phenols such as nonylphenol, 1-naphthol, 2-naphthol, Substituted naphthols such as 1,2-naphthalenediol, 1-methyl-2-naphthol and 6-tert-butyl-2-naphthol, novolac-type phenolic resins, resol-type phenolic resins, aralkyl-type phenolic resins, dicyclopentadiene-type phenols Phenolic resins such as resins are preferred. Among them, Phenol, naphthol (1-naphthol, 2-naphthol), or formula (K):
  • k is an integer of 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), k' is 0 or 1, and R K1 is a hydrogen atom or represents a methyl group, and R K2 is
  • R K3 represents an aromatic ring or a hydrocarbon ring.
  • RK3 is an aromatic ring
  • more specific examples include a phenylene group, a naphthylene group, a biphenylene group and the like.
  • R K3 is a hydrocarbon ring, more specifically, for example, the saturated hydrocarbon ring or unsaturated hydrocarbon ring, or the saturated hydrocarbon ring and/or unsaturated ring mentioned in the description of the X ring above.
  • a ring having a structure in which 2 to 6 hydrocarbon rings are condensed can be mentioned, and more specific examples include a phenylene group, a naphthylene group, a biphenylene group and the like.
  • R K3 represents a divalent group, therefore, R K3 represents an aromatic ring or a hydrocarbon ring more specifically It can be said that the ring represents a divalent group in which two hydrogen atoms bonded to carbon atoms constituting the ring are removed.
  • the (C) curing agent contained in the epoxy resin composition contains an active ester curing agent and a curing agent other than the active ester curing agent, from the viewpoint of more effectively exhibiting the effects of the present invention, the (C) curing agent contained in the epoxy resin composition
  • the content of the active ester curing agent in (total of the active ester curing agent and other curing agents) is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. Moreover, it may be 60, 65, 70, 75, 80, 85, 90, or 95% by mass or more.
  • all of the (C) curing agents may be active ester curing agents.
  • the blending ratio of (C) the curing agent in the epoxy resin composition may be within a range where the effects of the present invention can be exhibited, and the equivalent ratio of the functional group of the curing agent to the epoxy group of the epoxy resin (ester group/epoxy group) is The ratio is preferably 0.3 to 1.5, more preferably 0.5 to 1.3, even more preferably about 0.6 to 1.2.
  • the mixing ratio of the active ester curing agent in the epoxy resin composition according to the present invention may be within a range where the effects of the present invention can be exhibited.
  • the equivalent ratio of the ester group of the active ester curing agent to the epoxy group of the active ester curing agent is preferably 0.5 to 1.5, more preferably 0.5 to 1.3. It is preferably from 0.6 to 1.2, and more preferably from 0.6 to 1.2.
  • the equivalent ratio of the functional group of the curing agent to the epoxy group of the epoxy resin is preferably from 0.5 to 1.5, more preferably from 0.5 to 1.3, even more preferably from 0.6 to 1.2.
  • Curing accelerators include, for example, 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2- imidazoles such as methylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-undecylimidazole; 2-methyl-imidazoline, imidazoline derivatives such as 2-phenylimidazoline; 2-(dimethyl aminomethyl)phenol, triethylenediamine, triethanolamine, pyridine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo(5,4,0)undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5), 1,8-bis(dimethylaminopyridine, 1,4
  • imidazoles and tertiary amines which are anionic curing accelerators, are preferable, and more preferably 1-methylimidazole, 2-ethyl-4- methylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, triethylenediamine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, 1,8 -diazabicyclo(5,4,0)undecene-7,1,5-diazabicyclo(4,3,0)-nonene-5), 1,1,3,3-tetramethylguanidine, 7-methyl-1,5 ,7-triazabicyclo[4.4.0]dec-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, more preferably 1-methylimidazole , 2-ethyl-4- methylimidazole, 2-phenylimidazole, 1,
  • the amount of the curing accelerator (D) used is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.1 part by mass, based on 100 parts by mass of the epoxy resin (B) in the resin layer. ⁇ 5 parts by mass.
  • the curing accelerator can be used singly or in combination of two or more.
  • the epoxy resin composition of the present disclosure contains a hydroxy group-containing compound, and the molecular weight of the hydroxy group-containing compound is 200 or more, preferably 200 to 5,000.
  • the lower limit of the molecular weight of the hydroxy group-containing compound is preferably 250, more preferably 300, and the upper limit of the molecular weight is preferably 4,000, more preferably 3,000, and even more preferably 2,000.
  • the handleability of the B-stage film can be improved, and the heat resistance of the cured product can be improved.
  • the hydroxy group-containing compound may contain at least one hydroxy group in the molecule, and examples thereof include cetyl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, eicosyl alcohol, isopropylidenebicyclohexanol, and biphenyldimethanol. , polyethylene glycol, polypropylene glycol, and other alcohols having 10 or more carbon atoms in one molecule. These alcohols may be primary, secondary or tertiary alcohols. It may be a linear or branched alkyl alcohol. Also, a compound having one or more epoxy groups in one molecule and a compound having one or more hydroxy groups, carboxy groups, primary or secondary amino groups, or mercapto groups in one molecule. A compound having one or more secondary hydroxy groups in one molecule obtained by the reaction can also be used as the hydroxy group-containing compound.
  • hydroxy group-containing compound has the following three formulas in its skeleton:
  • R 3 and n are the same as described above).
  • n is preferably 1 or 0, and R3 is preferably a methyl group or an ethyl group.
  • R3 is preferably a methyl group or an ethyl group.
  • the substituent represented by R3 may be bonded to any carbon atom of the naphthyl group. The same applies to the following.
  • a compound having a skeleton represented by is more preferable.
  • hydroxy group-containing compounds include compounds of the formula (A en 1):
  • the groups represented by the formula (A en 1) are the following four groups, among which the leftmost group and the rightmost group are preferred.
  • the groups represented by the formula (A en 2) are the following three groups, among which the leftmost group is preferred.
  • Compounds having a group of formula (A en 1) include, for example, formula (A en 1-1):
  • R Aen1a and R Aen1b are the same or different (preferably the same), a group represented by formula (A en 1), or a group represented by formula (A en 1-3 ):
  • R en , R 1 and R 2 are the same as above, and h represents 0 or 1).
  • R 1 may be the same or different, preferably the same.
  • R 1 is preferably a methyl group or an ethyl group
  • R 2 is a methylene group, a dimethylene group (-CH 2 CH 2 -) or a trimethylene group ( -CH 2 CH 2 CH 2 -) is preferred.
  • Z Aen1 is a bond, -O-, -COO-, -COO-CH 2 -, or -Z Aen1i (R Aen1c )(R Aen1d )-. indicates a divalent group.
  • Z Aen1 is -Z Aen1i (R Aen1c )(R Aen1d )-
  • the compound represented by formula (A en 1-1) is represented by formula (A en 1i-1):
  • R Aen1a and R Aen1b are the same as above, and R Aen1c and R Aen1d are the same or different and are a hydrogen atom or a group represented by formula (A en 1); or a group represented by formula (A en 1-3).
  • R Aen1a , R Aen1b , R Aen1c and R Aen1d preferably all represent the same group, or R Aen1a , R Aen1b and R Aen1c all represent the same group.
  • Either R Aen1d represents a hydrogen atom
  • both R Aen1a and R Aen1b represent the same group and both R Aen1c and R Aen1d represent a hydrogen atom.
  • Z Aen1i represents a tetravalent group represented by the above formula (1′) or a tetravalent group represented by the above formula (1′-1). .
  • Z Aen1i represents a tetravalent group represented by the above formula (1′) or a tetravalent group represented by the above formula (1′-1). .
  • Z Aen1i represents a tetravalent group represented by the above formula (1′) or a tetravalent group represented by the above formula (1′-1).
  • Z Aen1i is a tetravalent group represented by formula (1′) above, and R Aen1a , R Aen1b and R Aen1c all represent the same group and R Aen1d represents a hydrogen atom
  • Z Aenli is any of the following groups:
  • Z Aen1i is any of the following groups:
  • h is preferably 1 in the group represented by formula (A en 1-3).
  • R Aen1a , R Aen1b , R Aen1c and R Aen1d are preferably the same group, any is more preferably a group represented by formula (A en 1-3) and h is 0.
  • Examples of compounds having a group of formula (A en 2) include formula (A en 2-1):
  • R 1 is the same as above, q is the same or different and is an integer of 0 to 5 (0, 1, 2, 3, 4, or 5), r is the same or different and is 0 or is an integer of 1, s is an integer of 1 to 3 (1, 2, or 3), and R en is the same as above, provided that in the cyclohexane ring to which the OH group and the OR en group are bonded, r is 0 is shown.).
  • R en , r and s are the same as above. However, in the cyclohexane ring to which the OH group and the OR en group are bonded, r is 0.) is preferred. In the compound represented by formula (A en 2-1) or formula (A en 2i-1), R en may be the same or different, and are preferably the same.
  • the compound represented by the formula (A en 2-1) or the formula (A en 2i-1), wherein r is 1 in the cyclohexane ring to which the OH group and the OR en group are bonded, has the formula ( Although it is not a compound having a group of A en 2), it can be preferably used as a hydroxy group-containing compound.
  • compounds having a group of formula (A en 2) include, for example, formula (A en 2-2):
  • R en is the same as above
  • R en may be the same or different, and are preferably the same.
  • Compounds having a group of formula (A en 3) include, for example, formula (A en 3-1):
  • R X1 and ring X2 , Y, and R en and R 2 are preferred.
  • i represents 0, 1, 2, 3, or 4
  • j represents an integer from 0 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).
  • R 2 may be the same or different. Further, in the formula, as described above, when the side of R en that is bonded to O is represented by *
  • R 2 is bound to the side represented by the dashed line in the formula.
  • R en may be the same or different, and are preferably the same.
  • Compounds having a group of formula (A en 4) include, for example, formula (A en 4-1):
  • R 2 may be the same or different.
  • R en may be the same or different, and are preferably the same.
  • Y is preferably a bond.
  • both the X 1 ring and the X 2 ring are preferably benzene rings.
  • R 2 is preferably a methylene group, a dimethylene group (--CH 2 CH 2 --), or a trimethylene group (--CH 2 CH 2 CH 2 --). Also, R 2 is preferably the same.
  • j is more preferably 0-6, more preferably 0-4.
  • i is 1 or more (eg, 1 to 4)
  • j is more preferably 1 to 8, more preferably 1 to 6.
  • Examples of compounds having a group of formula (A1) include formula (A1-1):
  • R A1a and R A1b are the same or different (preferably the same), a group represented by formula (A1), or formula (A1-3):
  • R 1 and R 2 are the same as above, h represents 0 or 1, and R 3 and n are also the same as above).
  • R 1 may be the same or different, preferably the same.
  • R 1 is preferably a methyl group or an ethyl group
  • R 2 is a methylene group, a dimethylene group (--CH 2 CH 2 --) or a trimethylene group (--CH 2 CH 2 CH 2 —).
  • Z A1 is a bond, —O—, —COO—, —COO—CH 2 —, or —Z A1i (R A1c )(R A1d )—2 indicates a valence group.
  • Z A1 is -Z A1i (R A1c )(R A1d )-
  • the compound represented by formula (A1-1) is represented by formula (A1i-1):
  • R A1a and R A1b are the same as above, R A1c and R A1d are the same or different and are a hydrogen atom, a group represented by formula (A1), or a group represented by formula (A1) -3) represents a group.
  • R A1a , R A1b , R A1c and R A1d preferably all represent the same group, or R A1a , R A1b and R A1c all represent the same group and R A1d represents a hydrogen atom, or both R A1a and R A1b represent the same group and both R A1c and R A1d represent a hydrogen atom.
  • Z A1i represents a tetravalent group represented by formula (1′) above or a tetravalent group represented by formula (1′-1) above. Among them, Z A1i
  • Z A1i is a tetravalent group represented by formula (1′) above, and R A1a , R A1b and R A1c all represent the same group and R A1d represents a hydrogen atom
  • Z A1i is any of the following groups:
  • Z A1i is any of the following groups:
  • h is preferably 1 in the group represented by formula (A1-3).
  • R A1a , R A1b , R A1c and R A1d are preferably the same group, and any is more preferably a group represented by formula (A1-3) in which h is 0.
  • Examples of compounds having a group of formula (A2) include formula (A2-1):
  • r and s are the same as above. However, in the cyclohexane ring to which the OH group and the phenoxy group are bonded, r is 0.) is preferred.
  • the compound represented by formula (A2-1) or formula (A2i-1), wherein r is 1 in the cyclohexane ring to which the OH group and the phenoxy group are bonded, has the group of formula (A2) Although it is not a compound having a hydroxy group, it can be preferably used as a hydroxy group-containing compound.
  • Examples of compounds having a group of formula (A2) include formula (A2-2):
  • Examples of compounds having a group of formula (A3) include formula (A3-1):
  • X 1 ring and X 2 ring, Y and R 2 are the same as above.
  • i represents 0, 1, 2, 3, or 4
  • j represents an integer from 0 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10).
  • R 2 may be the same or different.
  • Y is preferably a bond.
  • both the X 1 ring and the X 2 ring are preferably benzene rings.
  • R 2 is preferably a methylene group, a dimethylene group (--CH 2 CH 2 --), or a trimethylene group (--CH 2 CH 2 CH 2 --). Also, R 2 is preferably the same.
  • i and j are the same as above.
  • i is 0 or 1.
  • j is more preferably 0-6, more preferably 0-4.
  • i is 1 or more (eg, 1 to 4)
  • j is more preferably 1 to 8, more preferably 1 to 6.
  • Examples of compounds having a group of formula (A4) include formula (A4-1):
  • R 2 may be the same or different.
  • Y is preferably a bond.
  • both the X 1 ring and the X 2 ring are preferably benzene rings.
  • R 2 is preferably a methylene group, a dimethylene group (--CH 2 CH 2 --), or a trimethylene group (--CH 2 CH 2 CH 2 --). Also, R 2 is preferably the same.
  • j is more preferably 0-6, more preferably 0-4.
  • i is 1 or more (eg, 1 to 4)
  • j is more preferably 1 to 8, more preferably 1 to 6.
  • hydroxy group-containing compound a compound obtained by reacting an epoxy resin and a curing agent can be used.
  • the epoxy resin for obtaining the reaction compound the epoxy resins exemplified as the (B) epoxy resin can be used.
  • the curing agent for obtaining the reaction compound the curing agent mentioned above as the curing agent (C) can be used.
  • a compound obtained by reacting the above (B) with the above (C) can also be used as the hydroxy group-containing compound.
  • a compound obtained by reacting with at least one curing agent selected from the group consisting of phenolic resins such as phenolic resins, resol phenolic resins, and aralkyl phenolic resins is preferred.
  • the curing agent ( ⁇ ) is, among others, at least one curing agent selected from the group consisting of phenol, naphthol (1-naphthol, 2-n
  • the curing agent ( ⁇ ) is expressed as R—OH.
  • the OH group of R—OH is a group substituted with a hydrogen atom of a benzene ring or a naphthalene ring.
  • the epoxy group is ring-opened to generate a new OH group.
  • the OH group of ( ⁇ ) R—OH was a group substituted with a hydrogen atom of a benzene ring or a naphthalene ring, the structure is represented by the above formula:
  • reaction compound of ( ⁇ ) the epoxy resin and ( ⁇ ) the curing agent can be preferably used as (A) the hydroxy group-containing compound.
  • the reaction between the epoxy resin ( ⁇ ) and the curing agent ( ⁇ ) can be carried out in the presence or absence of a solvent, for example, in the presence of a catalyst.
  • the catalyst used for the reaction may be a known catalyst such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl -imidazoles such as 2-methylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and 2-undecylimidazole; imidazoline derivatives such as 2-methyl-imidazoline and 2-phenylimidazoline;2 -(dimethylaminomethyl)phenol, triethylenediamine, triethanolamine, pyridine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo(5,
  • a catalyst can be used individually or in combination of 2 or more types.
  • the amount of the catalyst used may be an effective amount as a catalyst, for example, 0.01 to 20 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of ( ⁇ ) and ( ⁇ ). is.
  • the reaction temperature is generally 60° C. to 200° C., preferably 100° C. to 180° C., and the reaction time is generally about 10 minutes to 2 hours.
  • the hydroxy group-containing compound preferably has a boiling point of 180° C. or higher, more preferably 190° C. under atmospheric pressure conditions, from the viewpoint of B-stage (semi-cured state of the curable resin) and resistance to volatilization during curing. or more, and more preferably 200° C. or more.
  • the hydroxy group-containing compounds can be used singly or in combination of two or more.
  • the hydroxyl group-containing compound preferably has a hydroxyl group equivalent weight of 80 to 1,000.
  • the upper or lower limit of the range is e.g. may be The range is more preferably 100-800, more preferably 120-600.
  • the amount of (A) the hydroxy group-containing compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 parts by mass, based on 100 parts by mass of the epoxy resin (B) contained in the epoxy resin composition. to 25 parts by mass, more preferably 1.0 to 20 parts by mass.
  • the epoxy resin composition of the present disclosure may contain fillers, thermoplastic resins, additives, etc., as necessary, as long as the effects are not impaired.
  • one or more Mixtures of seeds can be used.
  • silica more specifically, crystalline silica, fused silica, spherical fused silica, etc.
  • Metals such as gold, silver, copper, aluminum, nickel, iron, zinc and stainless steel are also included.
  • minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, xonolite, verculite and sericite.
  • Other fillers include carbon compounds such as carbon black, acetylene black, ketjen black and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; various glasses such as glass beads, glass flakes and glass balloons. can be mentioned. Further, the filler may be used as a powder as it is, or may be used after being dispersed in a resin.
  • thermoplastic resin examples include polyolefin resins, acrylic resins, phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyurethane resins, polyarylate resins, polyphenylene ether resins, polyacetal resins, fluorine resins, and acid-modified resins thereof. things, etc.
  • the coating properties of the epoxy resin composition, and the dielectric properties of the cured product polyolefin resins, acrylic resins, phenoxy resins, polyarylate resins, polyphenylene ether resins, Fluororesins and acid-modified fluororesins are preferred, and among these, polyolefin resins, acid-modified polyolefin resins, phenoxy resins, polyphenylene ether resins, and fluororesins are more preferred.
  • additives examples include antioxidants, inorganic phosphors, lubricants, ultraviolet absorbers, heat and light stabilizers, antistatic agents, polymerization inhibitors, antifoaming agents, solvents, anti-aging agents, adhesion improvers, Flame retardant, surfactant, storage stability improver, antiozonant, thickener, plasticizer, radiation shielding agent, nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide decomposer, pigment , metal deactivators, physical property modifiers, and the like.
  • the epoxy resin composition of the present disclosure can be produced by mixing the above (A) to (D) and, if necessary, other components.
  • the mixing method is not particularly limited as long as it is a method that enables uniform mixing.
  • a solvent e.g., toluene, xylene, methyl ethyl ketone, acetone, cyclohexanone, methylcyclohexane, cyclohexane, etc.
  • the epoxy resin composition of the present disclosure may be made into a cured product through the process of forming a B-stage film into a film, or may be made into a cured product without going through the process of forming a B-stage film.
  • a resin varnish is prepared by dissolving the epoxy resin composition in the solvent, and this resin varnish can be applied on the release film. More specifically, on the release-treated surface of PET (polyethylene terephthalate) film, PP (polypropylene) film, PE (polyethylene) film, PEEK (polyetheretherketone) film, etc., which has been subjected to release treatment on at least one side
  • the adhesive film is dried under appropriate conditions (for example, temperature: 80 to 180 ° C., time: 2 to 10 minutes) until it reaches a semi-cured state (B stage).
  • the coating method is not particularly limited, and examples thereof include methods using a comma coater, die coater, gravure coater, and the like.
  • the thickness of the B-stage film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductors on the circuit board is usually in the range of 5-70 ⁇ m, the B-stage film preferably has a thickness of 10-300 ⁇ m.
  • the B-stage film may be peeled off from a substrate such as PET and used as a B-stage film, and includes a metal foil or a substrate film and a B-stage film laminated on the surface of the metal foil or the substrate film. It can be used in the form of a laminated film.
  • the B-stage film can be cured by further heating (for example, 150 to 300°C). Curing times are dependent on the composition and may be, for example, 2 hours or less.
  • a method of making the epoxy resin composition of the present disclosure into a cured product without going through the B-stage film process can be, for example, by heating the composition.
  • the curing temperature is, for example, 150-300.degree.
  • the curing time varies depending on the composition liquid, and can be set to, for example, 2 hours or less.
  • a laminated film can be obtained by forming the resin film on a substrate film. Also, a prepreg can be obtained by coating and impregnating a glass cloth or glass nonwoven fabric with the resin varnish, followed by heating and drying to form a B-stage. A metal foil-clad laminate can be obtained by disposing a metal foil (eg, copper foil) on one or both surfaces of this prepreg, laminating the prepreg, and heating and forming.
  • a metal foil eg, copper foil
  • a printed wiring board using the epoxy resin composition of the present disclosure includes an insulating layer and a conductor layer (eg, copper foil), wherein the insulating layer includes the resin film.
  • the metal foil-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern.
  • the epoxy resin composition of the present disclosure can be cured in a short time because the reaction rate between the active ester curing agent and the alicyclic epoxy resin is significantly improved.
  • the curability evaluation of the epoxy resin composition can be evaluated by spectral measurement using an FT-IR (infrared spectroscope). Specifically, the progress of curing can be observed from the ratio between the peak of the structure, which does not change even when the resin composition is cured and the amount is constant, and the peak of the epoxy group.
  • a benzene ring is an example of a structure that does not change and remains constant even when the resin composition is cured.
  • the epoxy resin composition of the present disclosure contains a compound having a benzene ring
  • the spectrum of the epoxy resin composition of the present disclosure is measured by FT-IR, and the benzene ring and the epoxy group in the obtained spectrum are measured in the mid-infrared range.
  • the progress of cure can be observed from the area peak ratio.
  • the benzene ring structure does not change in structure even when the resin composition is cured, and the amount is constant, whereas the epoxy group is used for polymerization and decreases in amount as it cures. Cure progress can be observed by comparing the peaks of benzene rings with those of epoxy groups whose amount decreases with cure.
  • the mid-infrared region is an infrared region with medium wavelengths, and specifically, a region with a wave number (frequency) of 500 to 4000 cm ⁇ 1 (wavelength of 20000 to 2500 nm).
  • peaks detected near 780 to 890 cm ⁇ 1 for alicyclic epoxy resins and near 900 to 920 cm ⁇ 1 for glycidyl ether type epoxy resins are used, and the peaks detected for benzene rings are can use any one of several peaks appearing in the benzene ring structure.
  • the semi-cured state of the epoxy resin composition at the initial stage of curing (the state in which the reaction between the epoxy groups has not progressed after distilling off the solvent) was measured by FT-IR.
  • the ratio to a structure (e.g., benzene ring) that is constant is defined as the degree of curing at a reaction rate of 0%, and after heating the epoxy resin composition, FT-IR is measured again. % to calculate the degree of cure at each heating time.
  • the degree of cure in a composite manner.
  • a cotton swab or Kimwipe is impregnated with an organic solvent into the heated epoxy resin composition and rubbed 10 to 30 times.
  • the epoxy resin composition is insufficiently cured, unreacted monomers and oligomer components that have not been able to build a crosslinked structure adhere.
  • the cured state can be determined based on the presence or absence of coloring.
  • the degree of cure is determined in a composite manner from FT-IR measurement and rubbing test. Specifically, when the FT-IR measurement shows that the reaction rate of the epoxy group is 90% or more and the rubbing test shows no coloration, the epoxy resin composition is judged to be cured.
  • the dielectric loss tangent of the cured product is preferably 0.015 or less, more preferably 0.012 or less or 0.01 or less, 0.008 or less, 0.01 or less. 007 or less, 0.006 or less, or 0.005 or less.
  • the dielectric loss tangent is obtained by applying an epoxy resin composition on a substrate and heating the B-stage film obtained by drying to obtain a cured product. , the test piece is measured using a network analyzer (frequency 10 GHz, 25° C.).
  • the epoxy resin composition of the present disclosure preferably has a glass transition temperature (Tg) of 110°C or higher, more preferably 120°C, 125°C, or 130°C or higher.
  • Tg glass transition temperature
  • the glass transition temperature was determined by applying the epoxy resin composition to PEEK, drying and heating the resulting cured product, cutting it into a test piece of width 3 mm ⁇ length 40 mm ⁇ thickness 100 ⁇ m, and measuring it with a thermal analyzer ( For example, TMA7100 (manufactured by Hitachi High-Tech Science Co., Ltd.) is used, and the measurement is performed in a tensile mode at 5°C/min.
  • reaction scheme (1) 4-dimethylaminopyridine is used as a curing accelerator.
  • (1-1) to (1-4) may be collectively referred to as reaction scheme (1).
  • R 1 and R 2 described in Reaction Scheme (1) only indicate that they represent different atoms or substituents, and are used with different meanings from R 1 and R 2 described above.
  • the curing accelerator (4-dimethylaminopyridine), epoxy resin, and active ester curing agent exist independently.
  • R1 represents an arbitrary organic compound and R2 represents an arbitrary resin component having an aromatic group.
  • the epoxy resin and curing The accelerator reacts to give an alkoxy group.
  • the epoxy group C—O—C three-membered ring
  • the alkoxy group reacts with the carbonyl group of the active ester curing agent and produces an aryloxy group.
  • the curing accelerator is eliminated and reacts with the aryloxy groups.
  • a three-dimensional crosslink is constructed by repeating this cycle.
  • an alicyclic epoxy resin that does not have a glycidyl group has a structure in which two carbon atoms that constitute an epoxy group are also carbon atoms that constitute an alicyclic ring. Then, in the reaction of the epoxy group represented by (1-2) in the general scheme and the anionic curing accelerator proceeding by the SN2 mechanism, in the case of an alicyclic epoxy resin, two carbon atoms constituting the epoxy group Since steric hindrance exists in the part, it is considered that the reaction becomes difficult. Moreover, it is thought that for this reason, the curing speed becomes relatively slow when using an alicyclic epoxy resin having no glycidyl group.
  • reaction scheme (1) contains a hydroxy group-containing compound, it is presumed that the reaction between the alicyclic epoxy resin and the active ester curing agent can proceed satisfactorily.
  • a reaction route different from reaction scheme (1) is that an aryloxy group is generated by transesterification of a hydroxy group-containing compound with an ester group of an active ester curing agent, and the aryloxy group reacts with an alicyclic epoxy group. This is thought to be due to the fact that this and reaction scheme (1) proceed in parallel. For this reason, it is considered possible to shorten the curing time.
  • Production Example 1 (Production of hydroxy group-containing compound A) 6.4 g of 1,2-epoxy-4-vinylcyclohexane and 2 mass% ethanol of hexachloroplatinic acid hexahydrate were placed in a 200 mL four-necked flask equipped with a stirrer, thermometer and condenser under a nitrogen atmosphere. 0.05 g of the solution and 100 g of toluene were charged, and the liquid temperature was raised to 70°C. Thereafter, 5.0 g of 1,4-bis(dimethylsilyl)benzene was added dropwise over 15 minutes, followed by stirring at 90° C. for 4 hours.
  • each component in Table 1 is as follows.
  • the numerical value of each component in Table 1 indicates parts by mass, and is the amount of solid content excluding the solvent.
  • Epoxy resin A alicyclic epoxy resin (1,4-bis[2-(3,4-epoxycyclohexyl)ethyldimethylsilyl]benzene) (epoxy equivalent weight 221 g/eq)
  • Epoxy resin B alicyclic epoxy resin (Celoxide 2021P; general name is 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate) (manufactured by Daicel, epoxy equivalent 137 g/eq)
  • Epoxy resin C alicyclic epoxy resin (1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyldisiloxane) (manufactured by Tokyo Chemical Industry, epoxy equivalent 191 g / eq) ⁇
  • Epoxy resin D alicyclic epoxy resin (THI-DE) (manufactured by ENEOS, epoxy equivalent 81 g / eq)
  • Curing agent A active ester resin EPICLON HPC-8000-65T (toluene solution, solid content concentration 65%, ester equivalent approximately 223 g/eq, manufactured by DIC); represented by the following formula.
  • Thermoplastic resin A phenoxy resin (YX7553BH30) (solid content concentration 30%, manufactured by Mitsubishi Chemical Corporation)
  • Curing accelerator A 4-dimethylaminopyridine (DMAP, manufactured by Tokyo Chemical Industry Co., Ltd.)
  • a rubbing test was performed by reciprocating a cotton swab impregnated with toluene against the heated test piece 10 times.
  • the degree of curing was evaluated by the presence or absence of coloring on the cotton swab, and the heating time at which the coloring disappeared was confirmed.
  • the curing time of the test piece in which the reaction rate of the epoxy group was 90% or more and the coloring was removed by the rubbing test was determined.
  • a test piece having a reaction rate of epoxy groups of 90% or more and having no coloration in the rubbing test was used as a cured product sample.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Provided is an alicyclic epoxy resin composition that maintains excellent dielectric properties and exhibits a remarkably improved reaction rate with an active ester curing agent as compared with conventional compositions. More specifically, provided is an epoxy resin composition comprising (A) a hydroxy group-containing compound, (B) an epoxy resin, (C) a curing agent, and (D) a curing accelerator, wherein the (A) hydroxy group-containing compound has a molecular weight of at least 200, the (B) epoxy resin includes an alicyclic epoxy resin having no glycidyl ether group, and the (C) curing agent includes an active ester curing agent.

Description

エポキシ樹脂組成物epoxy resin composition
　本開示は、エポキシ樹脂組成物等に関する。より詳細には、ヒドロキシ基含有化合物を含有するエポキシ樹脂組成物、当該エポキシ樹脂組成物の硬化物、及びそれらの用途等に関する。 The present disclosure relates to epoxy resin compositions and the like. More particularly, the present invention relates to epoxy resin compositions containing hydroxy group-containing compounds, cured products of the epoxy resin compositions, uses thereof, and the like.
　エポキシ樹脂組成物は、得られる硬化物が密着性、耐食性、電気特性等に優れることから、塗料、接着剤、電気電子など種々の産業分野で広く使用されている。これらの中でも、半導体やプリント配線基板などのエレクトロニクス材料分野においては、封止材やプリント基板材料等として用いられており、これらの分野における技術革新に伴って、高性能化への要求が高まっている。特に、通信機器では信号の高速化及び高周波化が進んでおり、伝送損失の低減が求められている。伝送損失は電子部品構成材料の比誘電率と誘電正接に依存するため、これらの低比誘電率化、低誘電正接化が有効であることから、通信部材のさらなる低誘電特性（特に誘電正接が低いこと）が強く求められている。 Epoxy resin compositions are widely used in various industrial fields, such as paints, adhesives, and electrical and electronic products, because the resulting cured products are excellent in adhesiveness, corrosion resistance, electrical properties, etc. Among these, in the field of electronic materials such as semiconductors and printed wiring boards, it is used as a sealing material and printed circuit board material. there is In particular, in communication equipment, the speed and frequency of signals are increasing, and reduction in transmission loss is required. Since transmission loss depends on the dielectric constant and dielectric loss tangent of electronic component materials, it is effective to reduce the dielectric constant and dielectric loss tangent of these materials. low) is strongly desired.
国際公開第２０１８／１３１５６９号WO2018/131569 特開第２０２１－４２２９５号公報Japanese Patent Application Laid-Open No. 2021-42295
　エポキシ樹脂を用いた低誘電正接化が可能となるエポキシ樹脂組成物の開発が行われている。エポキシ樹脂の中でも、脂環式エポキシ樹脂が有する脂環式エポキシ基は、グリシジル基と比べて、かさ高い分子構造を有するために、分子の運動が立体障害によって抑制され易いと考えられ、よって得られるエポキシ樹脂硬化物の誘電正接のさらなる低減に寄与すると期待される。 　Epoxy resin compositions that enable low dielectric loss tangent using epoxy resin are being developed. Among epoxy resins, the alicyclic epoxy group possessed by the alicyclic epoxy resin has a bulkier molecular structure than the glycidyl group. It is expected to contribute to further reduction of the dielectric loss tangent of the epoxy resin cured product.
　なお、エポキシ樹脂を硬化させる際に、エポキシ樹脂とアミン硬化剤やフェノール硬化剤とが反応する場合、エポキシ基の開環に伴う２級ヒドロキシ基が生成し、この２級ヒドロキシ基が誘電特性に悪影響を及ぼすと考えられる。一方、活性エステル硬化剤はエポキシ樹脂との反応で、２級ヒドロキシ基を発生せずに架橋構造を構築できることから、活性エステル硬化剤を含むエポキシ樹脂組成物が低誘電特性を有すると期待される。 When curing an epoxy resin, if the epoxy resin reacts with an amine curing agent or a phenol curing agent, a secondary hydroxy group is generated due to the ring opening of the epoxy group, and this secondary hydroxy group affects the dielectric properties. It is considered to have an adverse effect. On the other hand, active ester curing agents can build a crosslinked structure without generating secondary hydroxy groups by reacting with epoxy resins, so epoxy resin compositions containing active ester curing agents are expected to have low dielectric properties. .
　なお、活性化エステル硬化剤は、特にエレクトロニクス材料分野でよく用いられる。しかしながら、脂環式エポキシ樹脂は、活性エステル硬化剤とは反応速度が遅いといった問題があった。このため、脂環式エポキシ樹脂は、半導体やプリント配線基板等のエレクトロニクス材料分野には用いられにくかった。 In addition, activated ester curing agents are often used especially in the field of electronic materials. However, the alicyclic epoxy resin has a problem that the reaction rate with the active ester curing agent is slow. For this reason, alicyclic epoxy resins have been difficult to use in the field of electronic materials such as semiconductors and printed wiring boards.
　例えば、特許文献１に開示される脂環式エポキシ樹脂と活性エステル化合物を含有するエポキシ樹脂組成物では、硬化条件が１００℃で１時間、１２０℃で２時間、１５０℃で２時間と長時間の加熱が必要であった。また、特許文献２には、脂環式エポキシ樹脂と、活性エステル化合物とを含む樹脂材料が、第２のエポキシ樹脂としてグリシジルエーテル基を有するエポキシ樹脂を含むことで、その反応によって発生した熱で脂環式エポキシ樹脂と活性エステル化合物の反応が良好に進行することが開示されている。しかしながら、更なる高速通信化を達成するためにはより一層の低誘電特性が求められている。 For example, in the epoxy resin composition containing an alicyclic epoxy resin and an active ester compound disclosed in Patent Document 1, the curing conditions are 100° C. for 1 hour, 120° C. for 2 hours, and 150° C. for 2 hours. of heating was required. Further, in Patent Document 2, a resin material containing an alicyclic epoxy resin and an active ester compound contains an epoxy resin having a glycidyl ether group as a second epoxy resin, so that the heat generated by the reaction It is disclosed that the reaction between the alicyclic epoxy resin and the active ester compound proceeds well. However, in order to achieve higher speed communication, much lower dielectric properties are required.
　このため、本発明者らは、優れた誘電特性を維持しつつ、従来と比べて活性エステル硬化剤との反応速度が著しく向上した、脂環式エポキシ樹脂組成物を提供すべく、検討を進めた。 For this reason, the present inventors have conducted studies to provide an alicyclic epoxy resin composition that maintains excellent dielectric properties and has a significantly improved reaction rate with an active ester curing agent compared to conventional ones. rice field.
　本発明者らは、グリシジル基を有さない脂環式エポキシ樹脂、並びに活性エステル硬化剤及び硬化促進剤を含むエポキシ樹脂組成物に、さらにヒドロキシ基を含有する化合物を配合することによって、優れた誘電特性は維持しつつ、活性エステル硬化剤との反応速度が著しく向上した脂環式エポキシ樹脂組成物を得られうることを見いだし、さらに改良を重ねた。 The present inventors have found that an epoxy resin composition containing an alicyclic epoxy resin having no glycidyl group, an active ester curing agent, and a curing accelerator is further blended with a compound containing a hydroxy group to achieve excellent The inventors have found that it is possible to obtain an alicyclic epoxy resin composition having a markedly improved reaction rate with an active ester curing agent while maintaining dielectric properties, and made further improvements.
　本開示は例えば以下の項に記載の主題を包含する。
項１．
（Ａ）ヒドロキシ基含有化合物、（Ｂ）エポキシ樹脂、（Ｃ）硬化剤、及び（Ｄ）硬化促進剤を含み、
前記（Ａ）ヒドロキシ基含有化合物が分子量２００以上であり、
前記（Ｂ）エポキシ樹脂がグリシジル基を有さない脂環式エポキシ樹脂を含み、
前記（Ｃ）硬化剤が活性エステル硬化剤を含む、
エポキシ樹脂組成物。
項２．
グリシジル基を有さない脂環式エポキシ樹脂が、
式（１－ｉｉａ）： The disclosure includes, for example, subject matter described in the following sections.
Section 1.
(A) a hydroxy group-containing compound, (B) an epoxy resin, (C) a curing agent, and (D) a curing accelerator,
(A) the hydroxy group-containing compound has a molecular weight of 200 or more,
The (B) epoxy resin comprises an alicyclic epoxy resin having no glycidyl group,
The (C) curing agent comprises an active ester curing agent,
Epoxy resin composition.
Section 2.
An alicyclic epoxy resin having no glycidyl group is
Formula (1-ia):
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
（式中、Ｘｉｉは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から２個の水素原子を除いて得られる２価の基、あるいは式（２ｇ－ｉｉａ）： (Wherein, X ii is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 2 hydrogen atoms from A divalent group obtained by excluding or formula (2 g -iia):
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
（式中、Ｙは、結合手、炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、－ＳＯ－、又は－ＳＯ２－を示す。）で表される２価の基を示し、
Ｒ１は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
　Ｒ２は同一又は異なって、炭素数１～１８のアルキレン基を示し、この基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
　Ｒ３は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
ｍは１～６の整数を示し、
ｎは０～３の整数を示す。）
で表されるエポキシ樹脂、
式（１－ｉｉｉａ）： (Wherein, Y is a bond, an alkylene group having 1 to 6 carbon atoms optionally substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO— or —SO 2 —.) represents a divalent group represented by
R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are optionally substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms,
R 2 is the same or different and represents an alkylene group having 1 to 18 carbon atoms, in which some carbon atoms excluding carbon atoms directly bonded to silicon atoms are selected from the group consisting of oxygen atoms and nitrogen atoms; optionally substituted with at least one atom represented by
R 3 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are optionally substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms,
m represents an integer of 1 to 6,
n represents an integer of 0-3. )
Epoxy resin represented by
Formula (1-iiia):
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
（式中、Ｘｉｉｉは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から３個の水素原子を除いて得られる３価の基、又は式（２ｇ－ｉｉｉａ）： (Wherein, X iii is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 3 hydrogen atoms from A trivalent group obtained by excluding or formula (2 g -iiia):
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
（式中、Ｙは、前記に同じ。）で表される３価の基を示し、
Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。）
で表されるエポキシ樹脂、
式（１－ｉｖａ）： (Wherein, Y is the same as above.) Represents a trivalent group represented by
R 1 , R 2 , R 3 , m and n are the same as above. )
Epoxy resin represented by
Formula (1-iva):
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
（式中、Ｘｉｖは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から４個の水素原子を除いて得られる４価の基、又は式（２ｇ）： (Wherein, X iv is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 4 hydrogen atoms from A tetravalent group obtained by excluding or formula (2 g ):
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
（式中、Ｙは、前記に同じ。）で表される３価の基を示し、
Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。）
で表されるエポキシ樹脂、
式（Ｉ）：
ＲＩａ－ＺＩ－ＲＩｂ　（Ｉ）
（式中、ＲＩａ及びＲＩｂは、同一又は異なって式（４）： (Wherein, Y is the same as above.) Represents a trivalent group represented by
R 1 , R 2 , R 3 , m and n are the same as above. )
Epoxy resin represented by
Formula (I):
RIa -ZI - RIb (I)
(Wherein, R Ia and R Ib are the same or different from the formula (4):
Figure JPOXMLDOC01-appb-C000028
Figure JPOXMLDOC01-appb-C000028
（式中、Ｒ３、ｍ、及びｎは前記に同じ。）の基を示し、
－ＺＩ－は、結合手、－（ＣＨ２）Ｉａ－Ｏ－（ＣＨ２）Ｉｂ－、又は－（ＣＨ２）Ｉｃ－ＣＯＯ－（ＣＨ２）Ｉｄ－を示し、ここでＩａ及びＩｂは同一又は異なって０、１、２、３、又は４を示し、Ｉｃ及びＩｄは同一又は異なって０、１、２、３、又は４を示す。）
で表されるエポキシ樹脂、
式（ＩＩ）：
ＲＩＩａ－ＺＩＩ－ＲＩＩｂ　（ＩＩ）
（式中、ＲＩＩａ及びＲＩＩｂは、同一又は異なって式（３）の基： (Wherein, R 3 , m, and n are the same as above) represents a group,
—Z I — represents a bond, —(CH 2 ) Ia —O—(CH 2 ) Ib —, or —(CH 2 ) Ic —COO—(CH 2 ) Id —, where Ia and Ib are Ic and Id are the same or different and represent 0, 1, 2, 3 or 4; )
Epoxy resin represented by
Formula (II):
R IIa -Z II -R IIb (II)
(Wherein, R IIa and R IIb are the same or different groups of formula (3):
Figure JPOXMLDOC01-appb-C000029
Figure JPOXMLDOC01-appb-C000029
（式中、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。）の基を示し、
－ＺＩＩ－は、結合手、－（ＣＨ２）－、－（ＣＨ２）２－、－（ＣＨ２）３－、－（ＣＨ２）４－、－ＣＨ（ＣＨ３）－ＣＨ２－、－ＣＨ２－ＣＨ（ＣＨ３）－、又は－Ｃ（ＣＨ３）２－、又は－Ｏ－（Ｓｉ（Ｒ１）２Ｏ）ＩＩａ－を示す。ここで、ＩＩａは０～８の整数を示し、Ｒ１は前記に同じである。）
で表されるエポキシ樹脂、
式（ＩＩＩ）： (Wherein, R 1 , R 2 , R 3 , m, and n are the same as above) represents a group,
-Z II - is a bond, -(CH 2 )-, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -CH(CH 3 )-CH 2 - , —CH 2 —CH(CH 3 )—, —C(CH 3 ) 2 —, or —O—(Si(R 1 ) 2 O) IIa —. Here, IIa represents an integer of 0 to 8, and R 1 is the same as above. )
Epoxy resin represented by
Formula (III):
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
（式中、ＲＩＩＩａは、同一又は異なって、Ｒ１又は下記式（３’）： (Wherein, R IIIa are the same or different, R 1 or the following formula (3′):
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
（式中、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じである。）の基を示し、但し少なくとも２個以上のＲＩＩＩａが式（３’）の基を示し、
Ｒ１は前記に同じであり、ＩＩＩｃは２～６の整数を示す。）
で表されるエポキシ樹脂、
式：  (wherein R 2 , R 3 , m, and n are the same as above), provided that at least two R IIIa represent a group of formula (3′);
R 1 is the same as above and IIIc represents an integer of 2-6. )
Epoxy resin represented by
formula:
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
（式中、Ｒ１は、前記に同じであり、ｎＩＶａは同一又は異なって０～５の整数であり、ｎＩＶｂは同一又は異なって０又は１の整数であり、ｎＩＶｃは１～３の整数である。）で表されるエポキシ樹脂、
並びに
式： (wherein R 1 is the same as above, n IVa is the same or different and is an integer of 0 to 5, n IVb is the same or different and is an integer of 0 or 1, n IVc is 1 to 3 is an integer of.) Epoxy resin represented by
and the expression:
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
で表されるエポキシ樹脂
からなる群より選択される少なくとも１種のエポキシ樹脂である、
項１に記載のエポキシ樹脂組成物。
項３．
ヒドロキシ基含有化合物が、式： is at least one epoxy resin selected from the group consisting of epoxy resins represented by
Item 1. The epoxy resin composition according to item 1.
Item 3.
The hydroxy group-containing compound has the formula:
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
（式中、Ｒｅｎは、Ｏに結合している側を＊として、下記式： (Wherein, R en is represented by the following formula, with * being the side bonded to O:
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
（式中、Ｒ３及びｎは前記に同じ。）
で表される３つの基のいずれかを示す）で表される構造を有する化合物である、
項１又は２に記載のエポキシ樹脂組成物。
項４．
ヒドロキシ基含有化合物が、
式（Ａｅｎ１）： (In the formula, R 3 and n are the same as above.)
Representing any of the three groups represented by) is a compound having a structure represented by
3. The epoxy resin composition according to item 1 or 2.
Section 4.
A hydroxy group-containing compound is
Formula (A en 1):
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
（ただし、式中のシクロヘキサン環においてＯＨ基が結合する炭素原子と－Ｏ－Ｒｅｎ基が結合する炭素原子とは結合しており、Ｒｅｎは式： (However, in the cyclohexane ring in the formula, the carbon atom to which the OH group is bonded and the carbon atom to which the —O—R en group is bonded are bonded, and R en is the formula:
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
（式中、Ｒ３及びｎは前記に同じ。）
で表される３つの基のいずれかを示す。）で表される基を有する化合物、
式（Ａｅｎ２）： (In the formula, R 3 and n are the same as above.)
represents any one of the three groups represented by ) a compound having a group represented by
Formula (A en 2):
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
（ただし、式中のシクロヘキサン環においてＯＨ基が結合する炭素原子と－Ｏ－Ｒｅｎ基が結合する炭素原子とは結合しており、Ｒｅｎは前記に同じ。）で表される基を有する化合物、
式（Ａｅｎ３）： (However, in the cyclohexane ring in the formula, the carbon atom to which the OH group is bonded and the carbon atom to which the —OR en group is bonded are bonded, and R en is the same as described above.) Compound,
Formula (A en 3):
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
（式中、ＲｅｎのＯに結合している側を＊として、 (In the formula, the side bonded to O of R en is *,
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
が、下記式： is the following formula:
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
（式中、Ｒ３及びｎは前記に同じ。）
で表される３つの基のいずれかを示す。）
で表される基を有する化合物、並びに
式（Ａｅｎ４）： (In the formula, R 3 and n are the same as above.)
represents any one of the three groups represented by )
and a compound having a group represented by the formula (A en 4):
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
（式中、Ｒｅｎは前記に同じ。）
で表される基を有する化合物
からなる群より選択される少なくとも１種の化合物である、
項３に記載のエポキシ樹脂組成物。
項５．
項１～４のいずれかに記載のエポキシ樹脂組成物を硬化してなる硬化物。
項６．
項５の硬化物を含む絶縁層を有するプリント基板材料。 (In the formula, R en is the same as above.)
is at least one compound selected from the group consisting of compounds having a group represented by
Item 4. The epoxy resin composition according to item 3.
Item 5.
A cured product obtained by curing the epoxy resin composition according to any one of Items 1 to 4.
Item 6.
A printed circuit board material having an insulating layer containing the cured product of Item 5.
　本開示のエポキシ樹脂組成物は、優れた誘電特性を維持しつつ、従来と比べて、活性エステル硬化剤と脂環式エポキシ樹脂との反応速度が著しく向上しているため、短時間で硬化することができる。このため、本開示のエポキシ樹脂組成物は、例えば、半導体封止体、液状封止材、ポッティング材、シール材、層間絶縁膜、接着層、カバーレイフィルム、電磁波シールドフィルム、プリント基板材料、複合材料等の広範な用途に好適に用いることができる。 The epoxy resin composition of the present disclosure maintains excellent dielectric properties and cures in a short time because the reaction rate between the active ester curing agent and the alicyclic epoxy resin is significantly improved compared to conventional ones. be able to. Therefore, the epoxy resin composition of the present disclosure can be used, for example, as a semiconductor encapsulant, a liquid encapsulant, a potting material, a sealing material, an interlayer insulating film, an adhesive layer, a coverlay film, an electromagnetic wave shielding film, a printed circuit board material, a composite It can be suitably used for a wide range of applications such as materials.
　以下、本開示に包含される各実施形態について、さらに詳細に説明する。本開示は、エポキシ樹脂組成物、その硬化物、及びそれらの用途等を好ましく包含するが、これらに限定されるわけではなく、本開示は本明細書に開示され当業者が認識できる全てを包含する。 Each embodiment included in the present disclosure will be described in further detail below. The present disclosure preferably includes, but is not limited to, epoxy resin compositions, cured products thereof, uses thereof, and the like. The present disclosure includes everything disclosed herein and recognized by a person skilled in the art. do.
　本開示に包含されるエポキシ樹脂組成物は（Ａ）ヒドロキシ基含有化合物、（Ｂ）エポキシ樹脂、（Ｃ）硬化剤、及び（Ｄ）硬化促進剤を含む。また、（Ｂ）エポキシ樹脂はグリシジル基を有さない脂環式エポキシ樹脂を含み、（Ｃ）硬化剤は活性エステル硬化剤を含む。本開示に包含される当該エポキシ樹脂組成物を「本開示のエポキシ樹脂組成物」ということがある。 The epoxy resin composition included in the present disclosure contains (A) a hydroxy group-containing compound, (B) an epoxy resin, (C) a curing agent, and (D) a curing accelerator. Also, (B) the epoxy resin contains an alicyclic epoxy resin having no glycidyl group, and (C) the curing agent contains an active ester curing agent. The epoxy resin composition included in the present disclosure may be referred to as "the epoxy resin composition of the present disclosure".
〔（Ｂ）エポキシ樹脂〕
（脂環式エポキシ樹脂）
　本開示のエポキシ樹脂組成物に含まれる（Ｂ）エポキシ樹脂は、グリシジル基を有さない脂環式エポキシ樹脂を含む。なお、脂環式エポキシ樹脂とは、エポキシ基を構成する２個の炭素原子が脂肪族環を構成している構造を有するエポキシ樹脂である。脂環式エポキシ樹脂は、１種のみが用いられてもよく、２種以上が併用されてもよい。なお、本明細書においては、特に断らない限り、脂環式エポキシ樹脂はグリシジル基を有さないものとする。 [(B) epoxy resin]
(alicyclic epoxy resin)
The (B) epoxy resin contained in the epoxy resin composition of the present disclosure includes an alicyclic epoxy resin having no glycidyl group. The alicyclic epoxy resin is an epoxy resin having a structure in which two carbon atoms forming an epoxy group form an alicyclic ring. Only one kind of alicyclic epoxy resin may be used, or two or more kinds thereof may be used in combination. In this specification, unless otherwise specified, the alicyclic epoxy resin does not have a glycidyl group.
　前記脂肪族環としては、モノシクロアルカン環、ビシクロアルカン環、トリシクロアルカン環及びテトラシクロアルカン環等が挙げられる。また、前記脂肪族環は、環の一部に不飽和結合を有してもよい。エポキシ樹脂組成物の硬化速度を一層速める観点から、前記脂肪族環は、少なくともシクロペンタン環又はシクロヘキサン環を有することが好ましい。なお、前記シクロヘキサン環は、ノルボルナン環であってもよく、トリシクロデカン環であってもよい。 Examples of the aliphatic ring include monocycloalkane ring, bicycloalkane ring, tricycloalkane ring and tetracycloalkane ring. Moreover, the said aliphatic ring may have an unsaturated bond in a part of ring. From the viewpoint of further increasing the curing speed of the epoxy resin composition, the aliphatic ring preferably has at least a cyclopentane ring or a cyclohexane ring. The cyclohexane ring may be a norbornane ring or a tricyclodecane ring.
　前記脂環式エポキシ樹脂のエポキシ基の個数は、好ましくは１個以上であり、さらに好ましくは２個以上若しくは３個以上である。エポキシ基の個数の上限としては、好ましくは６個以下、より好ましくは５個以下、さらに好ましくは４個以下である。前記脂環式エポキシ樹脂のエポキシ基の前記下限以上及び前記上限以下であると、硬化反応をより良好に進行させることができる。 The number of epoxy groups in the alicyclic epoxy resin is preferably 1 or more, more preferably 2 or more or 3 or more. The upper limit of the number of epoxy groups is preferably 6 or less, more preferably 5 or less, still more preferably 4 or less. When the epoxy groups of the alicyclic epoxy resin are at least the lower limit and at most the upper limit, the curing reaction can proceed more favorably.
　脂環式エポキシ樹脂は、単量体または重合体であってよい。前記脂環式エポキシ樹脂の分子量は、好ましくは１００～１０００、より好ましくは１３０～８００、更に好ましくは１４０～７００である。前記脂環式エポキシ樹脂の分子量が前記の範囲内であると、Ｂステージフィルム（半硬化状態のフィルム）の取扱性を良好にすることができ、かつ、硬化物の線膨張係数（ＣＴＥ）をより低くすることができる。 The alicyclic epoxy resin may be a monomer or a polymer. The molecular weight of the alicyclic epoxy resin is preferably 100-1000, more preferably 130-800, still more preferably 140-700. When the molecular weight of the alicyclic epoxy resin is within the above range, the B-stage film (semi-cured film) can be handled well, and the linear expansion coefficient (CTE) of the cured product can be reduced to can be lower.
　前記脂環式エポキシ樹脂のエポキシ当量は、好ましくは５０～５００、より好ましくは６５～４００、更に好ましくは７０～３５０である。エポキシ当量は、ＪＩＳ　Ｋ７２３６に従って測定する。エポキシ当量は、１当量のエポキシ基を含む樹脂の質量である。 The epoxy equivalent weight of the alicyclic epoxy resin is preferably 50-500, more preferably 65-400, still more preferably 70-350. Epoxy equivalent is measured according to JIS K7236. Epoxy equivalent weight is the mass of resin containing one equivalent of epoxy groups.
　前記脂環式エポキシ樹脂としては、より具体的には、式（１）： More specifically, the alicyclic epoxy resin has formula (1):
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
で表されるエポキシ樹脂が好ましく例示される。 The epoxy resin represented by is preferably exemplified.
　ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、低級アルケニル基、ハロゲン原子、又は式（３）： R Xa , R Xb , R Xc , and R Xd are the same or different and are hydrogen atoms, lower alkyl groups, lower alkoxy groups, lower alkenyl groups, halogen atoms, or formula (3):
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
で表される基（以下「式（３）の基」ということがある）を示す。なお、以下、低級アルキル基、低級アルコキシ基、及び低級アルケニル基をまとめて、「低級炭素置換基」ということがある。本発明においては、低級炭素置換基の中でも、低級アルキル基又は低級アルコキシ基がより好ましい。 represents a group (hereinafter sometimes referred to as "group of formula (3)"). In addition, hereinafter, a lower alkyl group, a lower alkoxy group and a lower alkenyl group may be collectively referred to as a "lower carbon substituent". In the present invention, among the lower carbon substituents, a lower alkyl group or a lower alkoxy group is more preferred.
　但し、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、少なくとも１つは式（３）の基である。言い換えれば、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、３つが水素原子若しくはハロゲン原子又は低級炭素置換基で１つが式（３）の基であるか、２つが水素原子若しくはハロゲン原子又は低級炭素置換基で２つが式（３）の基であるか、１つが水素原子若しくはハロゲン原子又は低級炭素置換基で３つが式（３）の基であるか、あるいは全てが式（３）の基である。より具体的には、例えば、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、（ｉ）ＲＸａ、ＲＸｂ及びＲＸｃが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｄが式（３）の基であるか、（ｉｉ）ＲＸａ及びＲＸｂが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｃ及びＲＸｄが式（３）の基であるか、（ｉｉｉ）ＲＸａが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基であるか、あるいは（ｉｖ）ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄの全てが式（３）の基であり得る。なお、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、式（３）の基でないものは、水素原子又は低級炭素置換基であることが、より好ましい。 However, at least one of R Xa , R Xb , R Xc and R Xd is a group of formula (3). In other words, R Xa , R Xb , R Xc and R Xd are three hydrogen or halogen atoms or lower carbon substituents and one is a group of formula (3), or two are hydrogen or halogen atoms or two of the lower carbon substituents are groups of formula (3), one is a hydrogen atom or halogen atom or three of the lower carbon substituents are groups of formula (3), or all are groups of formula (3) is the base. More specifically, for example, among R Xa , R Xb , R Xc and R Xd , (i) R Xa , R Xb and R Xc are hydrogen atoms, halogen atoms or lower carbon substituents, and R Xd is the formula (3), or (ii) R Xa and R Xb are hydrogen atoms or halogen atoms or lower carbon substituents and R Xc and R Xd are groups of formula (3), or (iii) R Xa is a hydrogen atom or a halogen atom or a lower carbon substituent and R Xb , R Xc and R Xd are groups of formula (3), or (iv) all of R Xa , R Xb , R Xc and R Xd can be a group of formula (3). Among R Xa , R Xb , R Xc and R Xd , those other than the group of formula (3) are more preferably hydrogen atoms or lower carbon substituents.
　ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、同一又は異なってよい。従って、（ｉ）ＲＸａ、ＲＸｂ及びＲＸｃが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｄが式（３）の基である場合は、ＲＸａ、ＲＸｂ及びＲＸｃが同一又は異なってよく、（ｉｉ）ＲＸａ及びＲＸｂが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｃ及びＲＸｄが式（３）の基である場合は、ＲＸａ及びＲＸｂが同一又は異なってよく、ＲＸｃ及びＲＸｄも同一又は異なってよく、（ｉｉｉ）ＲＸａが水素原子若しくはハロゲン原子又は低級炭素置換基でＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基である場合は、ＲＸｂ、ＲＸｃ、及びＲＸｄが同一又は異なってよく、（ｉｖ）ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄの全てが式（３）の基である場合は、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが同一又は異なってよい。なお、これらいずれの場合においても、式（３）の基が同一であることが好ましい。 R Xa , R Xb , R Xc and R Xd may be the same or different. Therefore, when (i) R Xa , R Xb and R Xc are hydrogen atoms, halogen atoms or lower carbon substituents and R Xd is a group of formula (3), then R Xa , R Xb and R Xc are the same or (ii) when R Xa and R Xb are hydrogen atoms or halogen atoms or lower carbon substituents and R Xc and R Xd are groups of formula (3), then R Xa and R Xb are the same or different; and R Xc and R Xd may be the same or different, and (iii) R Xa is a hydrogen atom or a halogen atom or a lower carbon substituent and R Xb , R Xc and R Xd are groups of formula (3) R Xb , R Xc , and R Xd may be the same or different, and (iv) when R Xa , R Xb , R Xc , and R Xd are all groups of formula (3), then R Xa , R Xb , R Xc , and R Xd may be the same or different. In any of these cases, the groups of formula (3) are preferably the same.
　また、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、２又は３個がハロゲン原子又は低級炭素置換基である場合には、これらのハロゲン原子又は低級炭素置換基も同一又は異なってよい。この場合は、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、２又は３個が、同一の低級炭素置換基であることがさらに好ましい。 Further, when 2 or 3 of R Xa , R Xb , R Xc and R Xd are halogen atoms or lower carbon substituents, these halogen atoms or lower carbon substituents may also be the same or different. . In this case, two or three of R Xa , R Xb , R Xc and R Xd are more preferably the same lower carbon substituent.
　本明細書において、低級炭素置換基とは、低級アルキル基、低級アルコキシ基、又は低級アルケニル基をいう。ここでの低級とは、炭素数１～６（１、２、３、４、５、又は６）を意味する。低級炭素置換基のうち、好ましくは低級アルキル基又は低級アルコキシ基である。低級アルキル基としては、具体的にはメチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基等が好ましく例示できる。低級アルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、イソプロポキシ基、ブトキシ基、イソブトキシ基等が好ましく例示できる。 As used herein, a lower carbon substituent refers to a lower alkyl group, a lower alkoxy group, or a lower alkenyl group. Lower here means having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6). Among lower carbon substituents, lower alkyl groups or lower alkoxy groups are preferred. Preferred examples of lower alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. Preferred examples of lower alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, and isobutoxy groups.
　また、本明細書において、ハロゲン原子はフッ素原子、塩素原子、臭素原子、又はヨウ素原子であり、好ましくはフッ素原子、塩素原子、又は臭素原子であり、より好ましくはフッ素原子又は臭素原子である。 Also, in this specification, a halogen atom is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, preferably a fluorine atom, a chlorine atom, or a bromine atom, more preferably a fluorine atom or a bromine atom.
　Ｘ環は飽和炭化水素環又は不飽和炭化水素環、あるいは飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合又は２個連結した構造を有する環を表す。本明細書において、飽和炭化水素環としては、例えば炭素数４～８（４、５、６、７、又は８）の飽和炭化水素環が好ましく、シクロペンタン環、シクロヘキサン環等が特に好ましい。また、本明細書において、不飽和炭化水素環としては、例えば炭素数４～８（４、５、６、７、又は８）の不飽和炭化水素環が好ましく、ベンゼン環等が特に好ましい。また、本明細書において、飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環としては、飽和炭化水素環及び／又は不飽和炭化水素環が２、３、又は４個縮合した環が好ましく、２又は３個縮合した環がより好ましい。より具体的には、例えば、デカヒドロナフタレン環、アダマンタン環、ナフタレン環、フェナントレン環、アントラセン環、ピレン環、トリフェニレン環、テトラリン環、１，２，３，４，５，６，７，８－オクタヒドロナフタレン環、フルオレン環、ノルボルネン環等が挙げられる。 The X ring represents a saturated hydrocarbon ring, an unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed or two are connected. As used herein, the saturated hydrocarbon ring is preferably a saturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8), and particularly preferably a cyclopentane ring, a cyclohexane ring, or the like. In the present specification, the unsaturated hydrocarbon ring is preferably an unsaturated hydrocarbon ring having 4 to 8 carbon atoms (4, 5, 6, 7, or 8), and particularly preferably a benzene ring. Further, in the present specification, the ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed includes 2, 3, saturated hydrocarbon rings and/or unsaturated hydrocarbon rings. Or a ring with 4 condensed rings is preferred, and a ring with 2 or 3 condensed rings is more preferred. More specifically, for example, decahydronaphthalene ring, adamantane ring, naphthalene ring, phenanthrene ring, anthracene ring, pyrene ring, triphenylene ring, tetralin ring, 1,2,3,4,5,6,7,8- octahydronaphthalene ring, fluorene ring, norbornene ring and the like.
　なお、本明細書では、飽和炭化水素環又は不飽和炭化水素環、あるいは飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環を、まとめて「炭化水素環」と呼ぶことがある。 In the present specification, rings having a structure in which 2 to 6 saturated hydrocarbon rings or unsaturated hydrocarbon rings, or saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed are collectively referred to as "hydrocarbon rings. ” is sometimes called.
　飽和炭化水素環及び／又は不飽和炭化水素環が２個連結した構造を有する環としては、式（２）： As a ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are linked, the formula (2):
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
で表される環が好ましい。 A ring represented by is preferred.
　Ｘ１環及びＸ２環は、同一又は異なって、飽和炭化水素環又は不飽和炭化水素環を示す。すなわち、Ｘ１環及びＸ２環は、両方とも飽和炭化水素環であるか、両方とも不飽和炭化水素環であるか、一方が飽和炭化水素環でもう一方が不飽和炭化水素環である。Ｘ１環及びＸ２環が、両方とも飽和炭化水素環であるか、両方とも不飽和炭化水素環であることが好ましい。例えば、Ｘ１環及びＸ２環は、両方がベンゼン環、両方がシクロヘキサン環、又は一方がベンゼン環でもう一方がシクロヘキサン環、であることが好ましく、両方がベンゼン環であることがより好ましい。 Ring X 1 and ring X 2 are the same or different and represent a saturated hydrocarbon ring or an unsaturated hydrocarbon ring. That is, the X 1 ring and the X 2 ring are both saturated hydrocarbon rings, both unsaturated hydrocarbon rings, or one saturated hydrocarbon ring and the other unsaturated hydrocarbon ring. It is preferred that both the X 1 ring and the X 2 ring are saturated hydrocarbon rings or both unsaturated hydrocarbon rings. For example, X 1 ring and X 2 ring are preferably both benzene rings, both cyclohexane rings, or one benzene ring and the other cyclohexane ring, more preferably both benzene rings.
　また、Ｙは、結合手、炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、－ＳＯ－、又は－ＳＯ２－を示す。ここでの炭素数１～６のアルキレン基としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ヘキサメチレン基等が例示できる。また、置換基である炭素数１～４のアルキル基としては、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基等が例示できる。好ましい炭素数１～４のアルキル基で置換された炭素数１～６のアルキレン基としては、－ＣＨ（ＣＨ３）－、－Ｃ（ＣＨ３）２－、－ＣＨ２ＣＨ（ＣＨ３）ＣＨ２－、－ＣＨ２Ｃ（ＣＨ３）２ＣＨ２－等が例示できる。Ｙは好ましくは、結合手、酸素原子、メチレン基、ジメチルメチレン基、－Ｓ－、－ＳＯ２－であり、より好ましくは、結合手、ジメチルメチレン基、酸素原子、－ＳＯ２－である。式（２）で表される構造として、より具体例には、例えば、ビフェニル、ビシクロヘキシル、フェニルシクロヘキサン、ジフェニルメタン、ジシクロヘキシルメタン、２，２－ジフェニルプロパン、２，２－ジシクロヘキシルプロパン、ジフェニルエーテル、ジシクロヘキシルエーテル、ジフェニルスルフィド、ジシクロヘキシルスルフィド、ジフェニルスルホン、ジシクロエキシルスルホン等が挙げられる。 Y is a bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (-O-), a sulfur atom (-S-), -SO -, or -SO 2 -. Examples of the alkylene group having 1 to 6 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group and the like. Examples of alkyl groups having 1 to 4 carbon atoms as substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and isobutyl group. Preferred alkylene groups having 1 to 6 carbon atoms and substituted with alkyl groups having 1 to 4 carbon atoms include -CH(CH 3 )-, -C(CH 3 ) 2 -, and -CH 2 CH(CH 3 )CH 2- , -CH 2 C(CH 3 ) 2 CH 2 - and the like can be exemplified. Y is preferably a bond, an oxygen atom, a methylene group, a dimethylmethylene group, -S- or -SO 2 -, more preferably a bond, a dimethylmethylene group, an oxygen atom or -SO 2 -. More specific examples of the structure represented by formula (2) include biphenyl, bicyclohexyl, phenylcyclohexane, diphenylmethane, dicyclohexylmethane, 2,2-diphenylpropane, 2,2-dicyclohexylpropane, diphenyl ether, and dicyclohexyl ether. , diphenyl sulfide, dicyclohexyl sulfide, diphenyl sulfone, dicycloexyl sulfone and the like.
　式（１）において、飽和炭化水素環及び／又は不飽和炭化水素環が２個連結した構造を有する環が、式（２）で表される環である場合はＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄで置換されている。式（１）中のＸ環が式（２）であって、ＲＸａ～ＲＸｄの３つが水素原子若しくはハロゲン原子又は低級炭素置換基で１つが式（３）の基である場合、Ｘ１環及びＸ２環のいずれが式（３）の基で置換されていてもよい。この場合、式（２）で表される環は０、１、２、又は３つのハロゲン原子又は低級炭素置換基で置換されるところ、ハロゲン原子又は低級炭素置換基の（Ｘ１環の置換数：Ｘ２環の置換数）は（１：０）、（０：１）、（２：０）、（１：１）、（０：２）、（３：０）、（２：１）、（１：２）、又は（０：３）であり得る。ＲＸａ～ＲＸｄの２つが水素原子若しくはハロゲン原子又は低級炭素置換基で２つが式（３）の基である場合、Ｘ１環及びＸ２環のいずれかが２つの式（３）の基で置換されていてもよく、Ｘ１環及びＸ２環が１つずつ式（３）の基で置換されていてもよく、Ｘ１環及びＸ２環が１つずつ式（３）の基で置換されていることが好ましい。この場合、式（２）で表される環は０、１、又は２つのハロゲン原子又は低級炭素置換基で置換されるところ、ハロゲン原子又は低級炭素置換基の（Ｘ１環の置換数：Ｘ２環の置換数）は（１：０）、（０：１）、（２：０）、（１：１）、又は（０：２）であり得る。ＲＸａ～ＲＸｄの１つが水素原子若しくはハロゲン原子又は低級炭素置換基で３つが式（３）の基である場合、Ｘ１環及びＸ２環のいずれかが３つの式（３）の基で置換されていてもよく、Ｘ１環が２つＸ２環が１つの式（３）の基で置換されていてもよく、Ｘ１環が１つＸ２環が２つの式（３）の基で置換されていてもよく、Ｘ１環が２つＸ２環が１つの式（３）の基で置換されている又はＸ１環が１つＸ２環が２つの式（３）の基で置換されていることが好ましい。この場合、式（２）で表される環は０又は１つのハロゲン原子又は低級炭素置換基で置換されるところ、ハロゲン原子又は低級炭素置換基の（Ｘ１環の置換数：Ｘ２環の置換数）は（１：０）、又は（０：１）であり得る。ＲＸａ～ＲＸｄの全てが式（３）の基である場合、Ｘ１環及びＸ２環のいずれかが４つの式（３）の基で置換されていてもよく、Ｘ１環が３つＸ２環が１つの式（３）の基で置換されていてもよく、Ｘ１環が１つＸ２環が３つの式（３）の基で置換されていてもよく、Ｘ１環が２つＸ２環が２つの式（３）の基で置換されていてもよく、Ｘ１環が２つＸ２環が２つの式（３）の基で置換されていることが好ましい。 In formula (1), when the ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are linked is a ring represented by formula (2), R Xa , R Xb , and R Xc , and R Xd . When the X ring in formula (1) is of formula (2), three of R Xa to R Xd are hydrogen atoms, halogen atoms or lower carbon substituents, and one is a group of formula (3), then X 1 Any of the ring and the X 2 ring may be substituted with a group of formula (3). In this case, when the ring represented by formula (2) is substituted with 0, 1, 2, or 3 halogen atoms or lower carbon substituents, the number of halogen atoms or lower carbon substituents (X 1 ring substitution : X 2 -ring substitutions) are (1:0), (0:1), (2:0), (1:1), (0:2), (3:0), (2:1) , (1:2), or (0:3). When two of R Xa to R Xd are hydrogen atoms or halogen atoms or lower carbon substituents and two are groups of formula (3), any one of X 1 ring and X 2 ring is two groups of formula (3) and one X 1 ring and one X 2 ring may be substituted with a group of formula (3), and one X 1 ring and X 2 ring each may be substituted with a group of formula (3) is preferably substituted with In this case, when the ring represented by formula (2) is substituted with 0, 1, or 2 halogen atoms or lower carbon substituents, the number of halogen atoms or lower carbon substituents (X number of substitutions in one ring: X 2 ring substitutions) can be (1:0), (0:1), (2:0), (1:1), or (0:2). When one of R Xa to R Xd is a hydrogen atom or a halogen atom or a lower carbon substituent and three are groups of formula (3), any one of X 1 ring and X 2 ring is three groups of formula (3) optionally substituted with a group of formula (3) having two X 1 rings and one X 2 ring, and having one X 1 ring and two X 2 rings of formula (3) X 1 ring is substituted with a group of formula (3 ), or X 1 ring is 1 and X 2 rings are 2 Formula (3) is preferably substituted with a group of In this case, when the ring represented by formula (2) is substituted with 0 or 1 halogen atoms or lower carbon substituents, the number of halogen atoms or lower carbon substituents (X 1 ring substitution number: X 2 ring number of substitutions) can be (1:0) or (0:1). When all of R Xa to R Xd are groups of formula (3), any one of ring X 1 and ring X 2 may be substituted with four groups of formula (3), and ring X 1 may be substituted with three groups of formula (3). one X 2 ring may be substituted with one group of formula (3), one X 1 ring may be substituted with three groups of formula (3), X 1 ring may be substituted with two groups of formula (3), and preferably two rings of X 1 and X 2 are substituted with two groups of formula (3).
　式（１）の一部である基である、式（１’）： Formula (1'), which is a group that is part of formula (1):
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
（式（１’）中、Ｘ環は前記に同じ。）
で示される４価の基として、特に好ましくは以下の式で表される基が挙げられる。すなわち、 (In formula (1′), the X ring is the same as described above.)
Particularly preferred examples of the tetravalent group represented by are groups represented by the following formulae. i.e.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
又は or
Figure JPOXMLDOC01-appb-C000048
Figure JPOXMLDOC01-appb-C000048
又は or
Figure JPOXMLDOC01-appb-C000049
Figure JPOXMLDOC01-appb-C000049
（式（２ｇ）中、Ｙは前記に同じ。）
で表される基である。 (In formula (2 g ), Y is the same as above.)
is a group represented by
　Ｒ１は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子（好ましくは酸素原子）で置換されていてもよい。当該一部の炭素原子は、ケイ素原子に直接結合していない炭素原子であることが好ましい。また、当該置換されていてもよい一部の炭素原子は、１又は複数（例えば２、３、４、５、又は６）個の炭素原子であり、好ましくは１個の炭素原子である。なお、合成の簡便さの観点等から同一ケイ素原子に結合したＲ１は同一であることが好ましい。また、式（１）において存在する全てのＲ１が同一であることがより好ましい。 R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are It may be substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms (preferably oxygen atoms). The partial carbon atoms are preferably carbon atoms that are not directly bonded to silicon atoms. Also, the partially optionally substituted carbon atoms are one or more (for example, 2, 3, 4, 5, or 6) carbon atoms, preferably one carbon atom. From the viewpoint of ease of synthesis, etc., it is preferable that the R 1s bonded to the same silicon atom are the same. It is also more preferred that all R 1s present in formula (1) are the same.
　Ｒ１で示される炭素数１～１８のアルキル基としては、直鎖又は分岐鎖状のアルキル基であり、例えば、メチル基、エチル基、ｎ－プロピル基、イソプロピル基、ｎ－ブチル基、イソブチル基、ｔｅｒｔ－ブチル基、ｎ－ペンチル基、ネオペンチル基、ｔｅｒｔ－ペンチル基、ｎ－ヘキシル基、ｎ－ヘプチル基、２，２，４－トリメチルペンチル基、ｎ－オクチル基、イソオクチル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ドデシル基等が挙げられる。好ましくは炭素数１～１０のアルキル基であり、より好ましくは炭素数１～６のアルキル基であり、さらに好ましくは炭素数１～３のアルキル基であり、特に好ましくはメチル基である。 The alkyl group having 1 to 18 carbon atoms represented by R 1 is a linear or branched alkyl group, such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, neopentyl group, tert-pentyl group, n-hexyl group, n-heptyl group, 2,2,4-trimethylpentyl group, n-octyl group, isooctyl group, n- nonyl group, n-decyl group, n-dodecyl group and the like. An alkyl group having 1 to 10 carbon atoms is preferable, an alkyl group having 1 to 6 carbon atoms is more preferable, an alkyl group having 1 to 3 carbon atoms is more preferable, and a methyl group is particularly preferable.
　Ｒ１で示される炭素数２～９のアルケニル基としては、直鎖又は分岐鎖状のアルケニル基であり、例えば、ビニル基、アリル基、２－プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基等が挙げられる。好ましくは炭素数２～４のアルケニル基である。 The alkenyl group having 2 to 9 carbon atoms represented by R 1 is a linear or branched alkenyl group, such as vinyl group, allyl group, 2-propenyl group, butenyl group, pentenyl group, hexenyl group, A heptenyl group, an octenyl group, a nonenyl group and the like can be mentioned. Alkenyl groups having 2 to 4 carbon atoms are preferred.
　Ｒ１で示されるシクロアルキル基としては、３～８員環のシクロアルキル基が挙げられ、例えば、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、メチルシクロヘキシル基等が挙げられる。 The cycloalkyl group represented by R 1 includes 3- to 8-membered cycloalkyl groups such as cyclopentyl, cyclohexyl, cycloheptyl and methylcyclohexyl groups.
　Ｒ１で示されるアリール基としては、単環又は二環のアリール基が挙げられ、例えば、フェニル基、トリル基、キシリル基、エチルフェニル基、ナフチル基等が挙げられる。中でも、フェニル基が好ましい。 The aryl group represented by R 1 includes monocyclic or bicyclic aryl groups such as phenyl group, tolyl group, xylyl group, ethylphenyl group and naphthyl group. Among them, a phenyl group is preferred.
　Ｒ１で示されるアラルキル基としては、アリール基（特にフェニル基）で置換された炭素数１～４のアルキル基が挙げられ、例えば、ベンジル基、α－フェネチル基、β－フェネチル基、β－メチルフェネチル基等が挙げられる。 The aralkyl group represented by R 1 includes alkyl groups having 1 to 4 carbon atoms substituted with an aryl group (especially a phenyl group), such as benzyl group, α-phenethyl group, β-phenethyl group, β- A methylphenethyl group and the like can be mentioned.
　Ｒ１は、好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基である。 R 1 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group.
　Ｒ２は、炭素数１～１８（１、２、３、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５、１６、１７、又は１８）のアルキレン基を示す。当該アルキレン基は、直鎖又は分岐鎖状のアルキレン基であり、好ましくは直鎖状のアルキレン基である。例えば、メチレン基、メチルメチレン基、エチルメチレン基、ジメチルメチレン基、ジエチルメチレン基、ジメチレン基（－ＣＨ２ＣＨ２－）、トリメチレン基（－ＣＨ２ＣＨ２ＣＨ２－）、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基、トリデカメチレン基等が挙げられる。例えば、炭素数２～１８のアルキレン基、好ましくは炭素数２～１０のアルキレン基であり、より好ましくは炭素数２～８のアルキレン基であり、さらに好ましくは炭素数２～６のアルキレン基であり、特に好ましくは炭素数２～５のアルキレン基である。 R 2 is an alkylene group having 1 to 18 carbon atoms (1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18) indicates The alkylene group is a linear or branched alkylene group, preferably a linear alkylene group. For example, methylene group, methylmethylene group, ethylmethylene group, dimethylmethylene group, diethylmethylene group, dimethylene group (--CH 2 CH 2 --), trimethylene group (--CH 2 CH 2 CH 2 --), tetramethylene group, penta methylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, tridecamethylene group and the like. For example, an alkylene group having 2 to 18 carbon atoms, preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 8 carbon atoms, and still more preferably an alkylene group having 2 to 6 carbon atoms. and particularly preferably an alkylene group having 2 to 5 carbon atoms.
　前記炭素数１～１８のアルキレン基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子（好ましくは酸素原子）で置換されていてもよい。当該一部の炭素原子は、ケイ素原子及び３～８員環又はエポキシ環のいずれにも直接結合していない炭素原子であることが好ましい。また、当該置換されていてもよい一部の炭素原子は、１又は複数（例えば２、３、４、５、又は６）個の炭素原子であり、好ましくは１個の炭素原子である。 Part of the carbon atoms of the alkylene group having 1 to 18 carbon atoms may be substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms (preferably oxygen atoms). The partial carbon atoms are preferably carbon atoms that are not directly bonded to any of silicon atoms and 3- to 8-membered rings or epoxy rings. Also, the partially optionally substituted carbon atoms are one or more (for example, 2, 3, 4, 5, or 6) carbon atoms, preferably one carbon atom.
　当該基としては、Ｒ２のケイ素原子に結合する側を（＊）とした場合に、例えば、（＊）－炭素数２～９のアルキレン－Ｏ－炭素数１～８のアルキレン－、好ましくは（＊）－炭素数２～４のアルキレン－Ｏ－炭素数１～３のアルキレン－、より好ましくは（＊）－炭素数２～４のアルキレン－Ｏ－炭素数１～２のアルキレン－、特に好ましくは（＊）－炭素数３のアルキレン－Ｏ－メチレン－が挙げられる。 Examples of such groups include (*)-C 2-9 alkylene-O-C 1-8 alkylene-, preferably (*)-C2-4 alkylene-O-C1-3 alkylene-, more preferably (*)-C2-4 alkylene-O-C1-2 alkylene-, especially (*)-C3 alkylene-O-methylene- is preferred.
　具体的には、例えば、（＊）－（ＣＨ２）２－Ｏ－ＣＨ２－、（＊）－（ＣＨ２）３－Ｏ－ＣＨ２－、（＊）－（ＣＨ２）３－Ｏ－（ＣＨ２）２－、（＊）－（ＣＨ２）５－Ｏ－（ＣＨ２）４－などが挙げられ、これらの中でも（＊）－（ＣＨ２）３－Ｏ－ＣＨ２－が好ましい。 Specifically, for example, (*)-(CH 2 ) 2 -O-CH 2 -, (*)-(CH 2 ) 3 -O-CH 2 -, (*)-(CH 2 ) 3 -O -(CH 2 ) 2 -, (*)-(CH 2 ) 5 -O-(CH 2 ) 4 - and the like, among which (*)-(CH 2 ) 3 -O-CH 2 - preferable.
　ｍは１～６の整数（すなわち１、２、３、４、５、又は６）を示す。また、ｎは０～３の整数（すなわち、０、１、２、又は３）を示す。ここで、式（３）のＲ２が結合している基（ケイ素原子に結合していない側）を式（４）で示す（以下、「式（４）の基」ということがある）と、以下のようになる。 m represents an integer from 1 to 6 (ie 1, 2, 3, 4, 5, or 6). Also, n represents an integer from 0 to 3 (ie, 0, 1, 2, or 3). Here, the group to which R 2 of formula (3) is bonded (the side not bonded to the silicon atom) is represented by formula (4) (hereinafter sometimes referred to as "the group of formula (4)"). , becomes:
Figure JPOXMLDOC01-appb-C000050
Figure JPOXMLDOC01-appb-C000050
　式（４）の基について、ｍが１～６の整数である場合を具体的に構造式で記載すると、ｍ＝１の場合は Regarding the group of formula (4), when m is an integer of 1 to 6, if m = 1, then
Figure JPOXMLDOC01-appb-C000051
Figure JPOXMLDOC01-appb-C000051
ｍ＝２の場合は When m=2
Figure JPOXMLDOC01-appb-C000052
Figure JPOXMLDOC01-appb-C000052
ｍ＝３の場合は When m=3
Figure JPOXMLDOC01-appb-C000053
Figure JPOXMLDOC01-appb-C000053
ｍ＝４の場合は When m=4
Figure JPOXMLDOC01-appb-C000054
Figure JPOXMLDOC01-appb-C000054
ｍ＝５の場合は When m=5
Figure JPOXMLDOC01-appb-C000055
Figure JPOXMLDOC01-appb-C000055
ｍ＝６の場合は When m=6
Figure JPOXMLDOC01-appb-C000056
Figure JPOXMLDOC01-appb-C000056
と示される。 is shown.
　なお、式（４）の基は、ｍが０の場合には、エポキシ環のみが残り、ｎが０～３の整数であるため、以下のいずれかの基を示す。 When m is 0, the group of formula (4) represents any one of the following groups because only the epoxy ring remains and n is an integer of 0 to 3.
Figure JPOXMLDOC01-appb-C000057
Figure JPOXMLDOC01-appb-C000057
　なお、ｍが０の場合は、式（１）で表されるエポキシ樹脂は、グリシジル基を有することとなり、よってグリシジル基を有さない脂環式エポキシ樹脂には該当しない。このため、前記脂環式エポキシ樹脂の好ましい例としては、上記の通り、ｍは１～６の整数を示す。また、ｍが０を示す場合、式（１）で表されるエポキシ樹脂はグリシジル基を有するエポキシ樹脂の一例ということができる。 When m is 0, the epoxy resin represented by formula (1) has a glycidyl group, and therefore does not correspond to an alicyclic epoxy resin having no glycidyl group. Therefore, as described above, m is an integer of 1 to 6 as a preferred example of the alicyclic epoxy resin. Further, when m indicates 0, the epoxy resin represented by formula (1) can be said to be an example of an epoxy resin having a glycidyl group.
　式（３）において、Ｒ２及びＲ３は、３～８員環又はエポキシ環に結合する。なお、ｎは３～８員環又はエポキシ環に結合するＲ３の数を示している。 In formula (3), R 2 and R 3 are attached to a 3- to 8-membered ring or epoxy ring. Incidentally, n indicates the number of R3 's bonded to the 3- to 8-membered ring or epoxy ring.
　Ｒ３は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよい。当該一部の炭素原子は、３～８員環又はエポキシ環に直接結合していない炭素原子であることが好ましい。また、当該置換されていてもよい一部の炭素原子は、１又は複数（例えば２、３、４、５、又は６）個の炭素原子であり、好ましくは１個の炭素原子である。 R 3 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are It may be substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms. The partial carbon atoms are preferably carbon atoms that are not directly bonded to a 3- to 8-membered ring or epoxy ring. Also, the partially optionally substituted carbon atoms are one or more (for example, 2, 3, 4, 5, or 6) carbon atoms, preferably one carbon atom.
　Ｒ３で示される炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基及びアラルキル基はそれぞれ、上記Ｒ１で示される対応する置換基と同様のものが挙げられる。 The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 9 carbon atoms, the cycloalkyl group, the aryl group and the aralkyl group represented by R 3 are the same as the corresponding substituents represented by R 1 above . mentioned.
　Ｒ３として、好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基又はエチル基である。 R 3 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group.
　中でも好ましい式（３）の基の例として、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じであって、且つ、Ｒ１が全て同一であり、Ｒ３が（複数存在する場合には）全て同一である基が挙げられる。当該基は、式（１）で表されるエポキシ樹脂には１、２、３又は４存在し、それぞれの基が同一又は異なってよく、同一であることが好ましい。 Examples of particularly preferred groups of formula (3) include R 1 , R 2 , R 3 , m, and n being the same as above, R 1 being all the same, and R 3 being (a plurality of where all are the same). There are 1, 2, 3 or 4 such groups in the epoxy resin represented by formula (1), and each group may be the same or different, preferably the same.
　また式（４）の基として、特に好ましい具体例としては、Ｒ３は前記に同じであり、ｍが１、２、３又は４を示し、ｎが０、１又は２を示す基が挙げられ、なかでもより好ましくは、例えば以下の基（いずれもＲ３は前記に同じ）が挙げられる。 Particularly preferred specific examples of the group of formula (4) include groups in which R 3 is the same as above, m is 1, 2, 3 or 4, and n is 0, 1 or 2. Among them, more preferably, for example, the following groups (where R 3 is the same as above).
Figure JPOXMLDOC01-appb-C000058
Figure JPOXMLDOC01-appb-C000058
　式（４）の基は、式（１）で表されるエポキシ樹脂には１，２、３又は４存在するが、それぞれの基が同一又は異なってよく、同一であることが好ましい。 1, 2, 3, or 4 groups of formula (4) are present in the epoxy resin represented by formula (1), and each group may be the same or different, and is preferably the same.
　また、Ｘ環を構成する炭化水素環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子は、低級炭素置換基又はハロゲン原子（好ましくは低級炭素置換基）で置換されていてもよい。つまり、Ｘ環が飽和炭化水素環又は不飽和炭化水素環、あるいは飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環である場合は、これらの環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子は、低級炭素置換基又はハロゲン原子（好ましくは低級炭素置換基）で置換されていてもよく、またＸ環が飽和炭化水素環及び／又は不飽和炭化水素環が２個連結した構造を有する環である場合は、これら連結された飽和炭化水素環及び／又は不飽和炭化水素環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子は、低級炭素置換基又はハロゲン原子（好ましくは低級炭素置換基）で置換されていてもよい。なお、Ｘ環が式（２）で表される環である場合をより具体的に説明すると、Ｘ１環及びＸ２環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子に結合した水素原子は、低級炭素置換基又はハロゲン原子（好ましくは低級炭素置換基）で置換されていてもよい、といえる。 In addition, a hydrogen atom bonded to a carbon atom constituting a hydrocarbon ring constituting ring X and not bonded to R Xa , R Xb , R Xc and R Xd is a lower carbon substituent or It may be substituted with a halogen atom (preferably a lower carbon substituent). That is, when the X ring is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, these rings are constituted a hydrogen atom bonded to a carbon atom that is a carbon atom and to which R Xa , R Xb , R Xc and R Xd are not bonded is substituted with a lower carbon substituent or a halogen atom (preferably a lower carbon substituent) and when the X ring is a ring having a structure in which two saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are linked, these linked saturated hydrocarbon rings and/or unsaturated hydrocarbon rings A hydrogen atom bonded to a carbon atom constituting a hydrogen ring and not bonded to R Xa , R Xb , R Xc and R Xd is a lower carbon substituent or a halogen atom (preferably a lower carbon-substituted group). When the X ring is a ring represented by formula (2), the carbon atoms constituting the X 1 ring and the X 2 ring and R Xa , R Xb , R Xc , It can be said that the hydrogen atoms bonded to the carbon atoms to which R and R Xd are not bonded may be substituted with lower carbon substituents or halogen atoms (preferably lower carbon substituents).
　本明細書においては、Ｘ環を構成する炭化水素環を構成する炭素原子であって且つＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが結合していない炭素原子を「ＲＸａ－ｄ非結合炭素原子」ということがある。 In the present specification, a carbon atom constituting a hydrocarbon ring constituting ring X and to which R Xa , R Xb , R Xc and R Xd are not bonded is referred to as "R Xa-d non-bonded It is sometimes called a carbon atom.
　ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されていてもよい低級炭素置換基又はハロゲン原子は、１つのＲＸａ－ｄ非結合炭素原子に１つだけ結合することが好ましい。つまり、ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換される場合においては、ＲＸａ－ｄ非結合炭素原子に結合した水素原子のうち１つの水素原子だけが低級炭素置換基又はハロゲン原子で置換されることが好ましい。また、当該置換の数（すなわち低級炭素置換基及びハロゲン原子の合計）は、ＲＸａ－ｄ非結合炭素原子の数より少ないことが好ましい。当該置換の数は、より具体的には１～６（１、２、３、４、５、又は６）が好ましく、１～４がより好ましく、１～２がさらに好ましい。また、特にＸ環が式（２）で表される環である場合には、置換される水素原子はＹが結合していない炭素原子に結合した水素原子であることが好ましい。 It is preferred that only one lower carbon substituent or halogen atom, which optionally replaces the hydrogen atom bonded to the R 1 Xa -d non-bonding carbon atom, is bonded to one R 1 Xa-d non-bonding carbon atom. That is, when the hydrogen atoms bonded to the R Xa-d non-bonding carbon atoms are substituted, only one of the hydrogen atoms bonded to the R Xa-d non-bonding carbon atoms is a lower carbon substituent or a halogen Atoms are preferred. Also, the number of such substitutions (ie, the sum of lower carbon substituents and halogen atoms) is preferably less than the number of R Xa-d non-bonding carbon atoms. More specifically, the number of such substitutions is preferably 1 to 6 (1, 2, 3, 4, 5, or 6), more preferably 1 to 4, even more preferably 1 to 2. Moreover, particularly when the X ring is a ring represented by formula (2), the substituted hydrogen atom is preferably a hydrogen atom bonded to a carbon atom to which Y is not bonded.
　ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち少なくとも１つが低級炭素置換基であって、且つＲＸａ－ｄ非結合炭素原子に低級炭素置換基が少なくとも１つ結合する場合、全ての低級炭素置換基が同一であることが好ましい。つまり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄ中に低級炭素置換基が存在し、且つＲＸａ－ｄ非結合炭素原子に結合する低級炭素置換基が存在する場合、全ての低級炭素置換基が同一であることが好ましい。また、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち少なくとも１つがハロゲン原子であって、且つＲＸａ－ｄ非結合炭素原子にハロゲン原子が少なくとも１つ結合する場合、全てのハロゲン原子が同一であることが好ましい。つまり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄ中にハロゲン原子が存在し、且つＲＸａ－ｄ非結合炭素原子に結合するハロゲン原子が存在する場合、全てのハロゲン原子が同一であることが好ましい。 When at least one of R Xa , R Xb , R Xc , and R Xd is a lower carbon substituent, and at least one lower carbon substituent is attached to an R Xa-d non-bonding carbon atom, all lower It is preferred that the carbon substituents are identical. That is, when lower carbon substituents are present in R Xa , R Xb , R Xc , and R Xd and there are lower carbon substituents attached to R Xa-d non-bonding carbon atoms, all lower carbon substitutions It is preferred that the groups are identical. Further, when at least one of R Xa , R Xb , R Xc , and R Xd is a halogen atom, and at least one halogen atom is bonded to a non-bonding carbon atom of R Xa-d , all halogen atoms are preferably identical. That is, when halogen atoms are present in R Xa , R Xb , R Xc , and R Xd and there are halogen atoms bonded to R Xa-d non-bonding carbon atoms, all halogen atoms are the same. is preferred.
　さらに具体的に説明すると、例えば、上記式（１’）で表される４価の基が To explain more specifically, for example, the tetravalent group represented by the above formula (1') is
Figure JPOXMLDOC01-appb-C000059
Figure JPOXMLDOC01-appb-C000059
である場合、式（１）で表されるエポキシ樹脂として、式（１－Ｘ１） , the epoxy resin represented by formula (1) is represented by formula (1-X1)
Figure JPOXMLDOC01-appb-C000060
Figure JPOXMLDOC01-appb-C000060
（式（１－Ｘ１）中、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸｇ１及びＲＸｇ２は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂を好ましく例示できる。式（１－Ｘ１）において、ＲＸａ、ＲＸｂ、ＲＸｃ、ＲＸｄ、ＲＸｇ１及びＲＸｇ２が、それぞれ、ベンゼン環上の異なる炭素原子に結合していることがより好ましい。式（１－Ｘ１）で表されるエポキシ樹脂の中でも、ＲＸｇ１及びＲＸｇ２が水素原子であるものが好ましい。 (In formula (1-X1), R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same or different and are a hydrogen atom, a lower alkyl group, a lower alkoxy or a lower alkenyl group) can be preferably exemplified. In formula (1-X1), R Xa , R Xb , R Xc , R Xd , R Xg1 and R Xg2 are more preferably bonded to different carbon atoms on the benzene ring. Among the epoxy resins represented by formula (1-X1), those in which R 1 Xg1 and R 1 Xg2 are hydrogen atoms are preferred.
　式（１－Ｘ１）で表されるエポキシ樹脂の中でも、さらに好ましいものとして式（１－Ｘ１ａ）： Among the epoxy resins represented by formula (1-X1), formula (1-X1a) is more preferable:
Figure JPOXMLDOC01-appb-C000061
Figure JPOXMLDOC01-appb-C000061
（式（１－Ｘ１ａ）中、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸｇ１及びＲＸｇ２は、前記に同じ。）で表されるエポキシ樹脂や、式（１－Ｘ１ｂ）： (In formula (1-X1a), R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same as above.), or an epoxy resin represented by the formula (1-X1b):
Figure JPOXMLDOC01-appb-C000062
Figure JPOXMLDOC01-appb-C000062
（式（１－Ｘ１ｂ）中、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸｇ１及びＲＸｇ２は、前記に同じ。）で表されるエポキシ樹脂が、例示できる。 (In formula (1-X1b), R Xa , R Xb , R Xc , and R Xd are the same as above, and R Xg1 and R Xg2 are the same as above.) can.
　式（１－Ｘ１ａ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａ及びＲＸｂが水素原子でＲＸｃ及びＲＸｄが式（３）の基であり、ＲＸｇ１及びＲＸｇ２が水素原子である場合や、ＲＸａ及びＲＸｃが水素原子でＲＸｂ及びＲＸｄが式（３）の基であり、ＲＸｇ１及びＲＸｇ２が水素原子である場合がより好ましい。 Among the epoxy resins represented by formula (1-X1a), for example, R 1 Xa and R 1 Xb are hydrogen atoms, R 1 Xc and R 1 Xd are groups of formula (3), and R 1 Xg1 and R 1 Xg2 are hydrogen atoms. In some cases, R 1 Xa and R 1 Xc are hydrogen atoms, R 1 Xb and R 1 Xd are groups of formula (3), and R 1 Xg1 and R 1 Xg2 are hydrogen atoms.
　また、式（１－Ｘ１ｂ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａが水素原子でＲＸｂ、ＲＸｃ及びＲＸｄが式（３）の基であり、ＲＸｇ１及びＲＸｇ２が水素原子である場合がより好ましい。 Further, among the epoxy resins represented by formula (1-X1b), for example, R 1 Xa is a hydrogen atom, R 1 Xb , R 1 Xc and R 1 Xd are groups of formula (3), and R 1 Xg1 and R 1 Xg2 are hydrogen atoms. Atoms are more preferred.
　また、上記式（１’）で表される４価の基が In addition, the tetravalent group represented by the above formula (1') is
Figure JPOXMLDOC01-appb-C000063
Figure JPOXMLDOC01-appb-C000063
（式（２ｇ）中、Ｙは前記に同じ。）
で表される基である場合、式（１）で表されるエポキシ樹脂として、式（１－Ｘ２） (In formula (2 g ), Y is the same as above.)
When it is a group represented by the formula (1-X2) as the epoxy resin represented by the formula (1)
Figure JPOXMLDOC01-appb-C000064
Figure JPOXMLDOC01-appb-C000064
　［式（１－Ｘ２）中、Ｙは前記に同じであり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸ１１、ＲＸ１２、及びＲＸ１３並びにＲＸ２１、ＲＸ２２、及びＲＸ２３は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。］で表されるエポキシ樹脂も好ましく例示できる。式（１－Ｘ２）において、ＲＸａ、ＲＸｃ、ＲＸ１１、ＲＸ１２、及びＲＸ１３が、それぞれ異なる炭素原子に結合していることがより好ましく、また、ＲＸｂ、ＲＸｄ、ＲＸ２１、ＲＸ２２、及びＲＸ２３が、それぞれ異なる炭素原子に結合していることがより好ましい。また、ＲＸａ、ＲＸｂ、ＲＸｃ、ＲＸｄ、ＲＸ１１、ＲＸ１２、ＲＸ１３、ＲＸ２１、ＲＸ２２、及びＲＸ２３は、いずれもＹが結合した炭素原子には結合しない。 [In formula (1-X2), Y is the same as above, R Xa , R Xb , R Xc and R Xd are the same as above, R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group. ] can also be preferably exemplified. In formula (1-X2), R Xa , R Xc , R X11 , R X12 and R X13 are more preferably bonded to different carbon atoms, and R Xb , R Xd , R X21 , More preferably, R X22 and R X23 are bonded to different carbon atoms. Further, none of R Xa , R Xb , R Xc , R Xd , R X11 , R X12 , R X13 , R X21 , R X22 and R X23 is bonded to the carbon atom to which Y is bonded.
　式（１－Ｘ２）で表されるエポキシ樹脂の中でも、さらに好ましいものとして式（１－Ｘ２ａ）： Among the epoxy resins represented by formula (1-X2), formula (1-X2a) is more preferable:
Figure JPOXMLDOC01-appb-C000065
Figure JPOXMLDOC01-appb-C000065
（式（１－Ｘ２ａ）中、Ｙは前記に同じであり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸ１１、ＲＸ１２、及びＲＸ１３並びにＲＸ２１、ＲＸ２２、及びＲＸ２３は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂や、式（１－Ｘ２ｂ）： (In formula (1-X2a), Y is the same as above, R Xa , R Xb , R Xc and R Xd are the same as above, R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.), or an epoxy resin represented by formula (1-X2b):
Figure JPOXMLDOC01-appb-C000066
Figure JPOXMLDOC01-appb-C000066
（式（１－Ｘ２ｂ）中、Ｙは前記に同じであり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸ１１、ＲＸ１２、及びＲＸ１３並びにＲＸ２１、ＲＸ２２、及びＲＸ２３は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂や、式（１－Ｘ２ｃ）： (In formula (1-X2b), Y is the same as above, R Xa , R Xb , R Xc and R Xd are the same as above, R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.), or an epoxy resin represented by formula (1-X2c):
Figure JPOXMLDOC01-appb-C000067
Figure JPOXMLDOC01-appb-C000067
（式（１－Ｘ２ｃ）中、Ｙは前記に同じであり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄは、前記に同じであり、ＲＸ１１、ＲＸ１２、及びＲＸ１３並びにＲＸ２１、ＲＸ２２、及びＲＸ２３は、同一又は異なって、水素原子、低級アルキル基、低級アルコキシ基、又は低級アルケニル基を示す。）で表されるエポキシ樹脂が、例示出来る。 (In formula (1-X2c), Y is the same as above, R Xa , R Xb , R Xc and R Xd are the same as above, R X11 , R X12 and R X13 and R X21 , R X22 and R X23 are the same or different and represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, or a lower alkenyl group.) can be exemplified.
　式（１－Ｘ２ａ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基であり、ＲＸ１１及びＲＸ２１が低級炭素置換基であり、ＲＸ１２、ＲＸ１３、ＲＸ２２、及びＲＸ２３が水素原子である場合が好ましい。中でも、Ｙが炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基（特に－Ｃ（ＣＨ３）２－）であり、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基であり、ＲＸ１１及びＲＸ２１が低級アルコキシ基であり、ＲＸ１２、ＲＸ１３、ＲＸ２２、及びＲＸ２３が水素原子である場合が特に好ましい。これらの場合において、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄの式（３）の基が全て同一であり、ＲＸ１１及びＲＸ２１の低級炭素置換基が同一である場合が、より好ましい。 Among the epoxy resins represented by formula (1-X2a), for example, R Xa , R Xb , R Xc and R Xd are groups of formula (3), and R X11 and R X21 are lower carbon substituents. and R X12 , R X13 , R X22 and R X23 are preferably hydrogen atoms. Among them, Y is an alkylene group having 1 to 6 carbon atoms (especially —C(CH 3 ) 2 —) optionally substituted with an alkyl group having 1 to 4 carbon atoms, and R Xa , R Xb , R Xc , and R 1 Xd are groups of formula (3), R 111 and R 1 X21 are lower alkoxy groups, and R 12 , R 13 , R 122 and R 1 X23 are hydrogen atoms. In these cases, it is more preferred that the groups of formula (3) of R Xa , R Xb , R Xc and R Xd are all the same and the lower carbon substituents of R X11 and R X21 are the same.
　また、式（１－Ｘ２ｂ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａ及びＲＸｂが水素原子でＲＸｃ及びＲＸｄが式（３）の基であり、ＲＸ１１、ＲＸ１２、ＲＸ１３、ＲＸ２１、ＲＸ２２、及びＲＸ２３は水素原子の場合が好ましい。この場合において、ＲＸｃ及びＲＸｄの式（３）の基が同一である場合が、より好ましい。 Further, among the epoxy resins represented by formula (1-X2b), for example, R Xa and R Xb are hydrogen atoms, R Xc and R Xd are groups of formula (3), R X11 , R X12 , R X13 , R X21 , R X22 and R X23 are preferably hydrogen atoms. In this case, it is more preferred if the groups of formula (3) of R 1 Xc and R 1 Xd are the same.
　また、式（１－Ｘ２ｃ）で表されるエポキシ樹脂の中でも、例えば、ＲＸａが水素原子でＲＸｂ、ＲＸｃ及びＲＸｄが式（３）の基であり、ＲＸ１１、ＲＸ１２、ＲＸ１３、ＲＸ２１、ＲＸ２２、及びＲＸ２３は水素原子の場合が好ましい。この場合において、ＲＸｂ、ＲＸｃ及びＲＸｄの式（３）の基が同一である場合が、より好ましい。 Further, among the epoxy resins represented by formula (1-X2c), for example, R Xa is a hydrogen atom, R Xb , R Xc and R Xd are groups of formula (3), R X11 , R X12 , R X13 , R X21 , R X22 and R X23 are preferably hydrogen atoms. In this case, it is more preferred if the groups of formula (3) of R Xb , R Xc and R Xd are identical.
　本明細書において、式（１）におけるＸ環、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄ、並びに式（３）の基におけるＲ１、Ｒ２、Ｒ３、ｍ、及びｎに関する説明は、式（４）の基についての説明も含め、いずれも任意に組み合わせることができ、その組み合わせにより示されるいずれのエポキシ樹脂も本発明に用いることができる。 In this specification, the explanations for the X ring, R Xa , R Xb , R Xc , and R Xd in formula (1) and R 1 , R 2 , R 3 , m, and n in the group of formula (3) are , including the explanation of the group of formula (4), can be combined arbitrarily, and any epoxy resin represented by the combination can be used in the present invention.
　式（１）において、（ｉｉａ）ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されておらず、且つ、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、ＲＸａ及びＲＸｂが水素原子でＲＸｃ及びＲＸｄが式（３）の基であるか、（ｉｉｉａ）ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されておらず、且つ、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄのうち、ＲＸａが水素原子でＲＸｂ、ＲＸｃ、及びＲＸｄが式（３）の基であるか、あるいは（ｉｖａ）ＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されておらず、且つ、ＲＸａ、ＲＸｂ、ＲＸｃ、及びＲＸｄの全てが式（３）の基であり得る。 In formula (1), (iia) the hydrogen atom bonded to the R Xa-d non-bonding carbon atom is not substituted, and among R Xa , R Xb , R Xc and R Xd , R Xa and R Xb is a hydrogen atom and R Xc and R Xd are groups of formula ( 3), or (iii) the hydrogen atoms bonded to R Xa-d non-bonding carbon atoms are not substituted, and Among Xb , R Xc and R Xd , R Xa is a hydrogen atom and R Xb , R Xc and R Xd are groups of formula (3), or (iva) R Xa-d is a non-bonded carbon atom The attached hydrogen atoms are unsubstituted, and all of R Xa , R Xb , R Xc , and R Xd can be groups of formula (3).
　（ｉｉａ）の場合、式（１）で示されるエポキシ樹脂は、次の式（１－ｉｉａ）： In the case of (iia), the epoxy resin represented by formula (1) has the following formula (1-iia):
Figure JPOXMLDOC01-appb-C000068
Figure JPOXMLDOC01-appb-C000068
〔式中、Ｘｉｉは、炭化水素環から２個の水素原子を除いて得られる２価の基、又は式（２ｇ－ｉｉａ）： [Wherein, X ii is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring, or the formula (2 g -iia):
Figure JPOXMLDOC01-appb-C000069
Figure JPOXMLDOC01-appb-C000069
（式中、Ｙは、前記に同じ。）で表される２価の基を示し、
Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。〕
で表されるエポキシ樹脂を好ましく包含する。なお、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。 (Wherein Y is the same as above.) represents a divalent group represented by
R 1 , R 2 , R 3 , m and n are the same as above. ]
The epoxy resin represented by is preferably included. R 1 , R 2 , R 3 , m, and n may be the same or different, and are preferably the same.
　Ｘｉｉで示される２価の基として、好ましくはシクロヘキサン－１，４－ジイル基、１，４－フェニレン基が挙げられ、より好ましくは１，４－フェニレン基である。 The divalent group represented by X ii preferably includes a cyclohexane-1,4-diyl group and a 1,4-phenylene group, more preferably a 1,4-phenylene group.
　式（２ｇ－ｉｉａ）で表される２価の基のうち好ましくは、式（２ｇ－ｉｉａ’）： Among the divalent groups represented by the formula (2 g -ia), preferably the formula (2 g -iia'):
Figure JPOXMLDOC01-appb-C000070
Figure JPOXMLDOC01-appb-C000070
（式中、Ｙは前記に同じ。）
で表される基である。 (In the formula, Y is the same as above.)
is a group represented by
　式（２ｇ－ｉｉａ’）において、Ｙが結合手、ジメチルメチレン基、酸素原子、又は－ＳＯ２－である基が特に好ましい。 A group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or —SO 2 — in the formula (2 g -ia′) is particularly preferred.
　Ｘｉｉとして、中でも好ましくはシクロヘキサン－１，４－ジイル基、１，４－フェニレン基、式（２ｇ－ｉｉａ’）が挙げられ、より好ましくは１，４－フェニレン基である。 Among them, X ii preferably includes a cyclohexane-1,4-diyl group, a 1,4-phenylene group and formula (2 g -iia'), and more preferably a 1,4-phenylene group.
　例えば、式（１－ｉｉａ）において、ｍは同一で１、２、３、又は４（特に好ましくは、ｍは同一で４）、ｎは同一で０（すなわち、Ｒ３により環は置換されていない）を、Ｘｉｉは炭化水素環（特に好ましくはベンゼン環）から２個の水素原子を除いて得られる２価の基を、Ｒ１は同一で炭素数１～３のアルキル基を、Ｒ２は同一でケイ素原子及び３～６員環又はエポキシ環のいずれにも直接結合していない１個の炭素原子が酸素原子で置換されていてもよい炭素数２～６のアルキレン基を、それぞれ示すことで表されるエポキシ樹脂を、より好ましく本発明に用いることができる。 For example, in formula (1-ia), m is the same and 1, 2, 3, or 4 (particularly preferably, m is the same and 4), n is the same and 0 (i.e., the ring is substituted by R 3 ), X ii is a divalent group obtained by removing two hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), R 1 is the same alkyl group having 1 to 3 carbon atoms, R 2 are the same and each is an alkylene group having 2 to 6 carbon atoms and one carbon atom not directly bonded to a silicon atom or a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom; Epoxy resins represented by the following can be more preferably used in the present invention.
　（ｉｉｉａ）の場合、式（１）で示されるエポキシ樹脂は、次の式（１－ｉｉｉａ）： In the case of (iiia), the epoxy resin represented by formula (1) has the following formula (1-iiia):
Figure JPOXMLDOC01-appb-C000071
Figure JPOXMLDOC01-appb-C000071
〔式中、Ｘｉｉｉは、炭化水素環から３個の水素原子を除いて得られる３価の基、又は式（２ｇ－ｉｉｉａ）： [Wherein, X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring, or formula (2 g -iiia):
Figure JPOXMLDOC01-appb-C000072
Figure JPOXMLDOC01-appb-C000072
（式中、Ｙは、前記に同じ。）で表される３価の基を示し、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。〕
で表されるエポキシ樹脂を好ましく包含する。なお、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。 (wherein Y is the same as above), and R 1 , R 2 , R 3 , m and n are the same as above. ]
The epoxy resin represented by is preferably included. R 1 , R 2 , R 3 , m, and n may be the same or different, and are preferably the same.
　Ｘｉｉｉで示される３価の基として、好ましくは以下の基： As the trivalent group represented by Xiii , preferably the following groups:
Figure JPOXMLDOC01-appb-C000073
Figure JPOXMLDOC01-appb-C000073
が挙げられる。 is mentioned.
　式（２ｇ－ｉｉｉａ）で表される３価の基のうち好ましくは、式（２ｇ－ｉｉｉａ’）： Of the trivalent groups represented by formula (2 g -iiia), preferred is formula (2 g -iiia'):
Figure JPOXMLDOC01-appb-C000074
Figure JPOXMLDOC01-appb-C000074
（式中、Ｙは前記に同じ。）
で表される基である。 (In the formula, Y is the same as above.)
is a group represented by
　式（２ｇ－ｉｉｉａ’）において、Ｙが結合手、ジメチルメチレン基、酸素原子、又は－ＳＯ２－である基が特に好ましい。 In formula (2 g -iiia'), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or -SO 2 - is particularly preferred.
　例えば、式（１－ｉｉｉａ）において、ｍは同一で１、２、３、又は４（特に好ましくは、ｍは同一で４）、ｎは同一で０（すなわち、Ｒ３により環は置換されていない）を、Ｘｉｉｉは炭化水素環（特に好ましくはベンゼン環）から３個の水素原子を除いて得られる３価の基を、Ｒ１は同一で炭素数１～３のアルキル基を、Ｒ２は同一でケイ素原子及び３～６員環又はエポキシ環のいずれにも直接結合していない１個の炭素原子が酸素原子で置換されていてもよい炭素数２～６のアルキレン基を、それぞれ示すことで表されるエポキシ樹脂を、より好ましく本発明に用いることができる。 For example, in formula (1-iiia), m is the same and 1, 2, 3, or 4 (particularly preferably, m is the same and 4), n is the same and 0 (i.e., the ring is substituted by R 3 X iii is a trivalent group obtained by removing three hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), R 1 is the same alkyl group having 1 to 3 carbon atoms, R 2 are the same and each is an alkylene group having 2 to 6 carbon atoms and one carbon atom not directly bonded to a silicon atom or a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom; Epoxy resins represented by the following can be more preferably used in the present invention.
　（ｉｖａ）の場合、式（１）で示されるエポキシ樹脂は、次の式（１－ｉｖａ）： In the case of (iva), the epoxy resin represented by formula (1) has the following formula (1-iva):
Figure JPOXMLDOC01-appb-C000075
Figure JPOXMLDOC01-appb-C000075
〔式中、Ｘｉｖは、前記（１’）で示される４価の基であって、且つＸ環においてＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されていない基を示し、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。〕
で表されるエポキシ樹脂を包含する。なお、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。 [Wherein, X iv is a tetravalent group represented by the above (1′), and represents a group in which the hydrogen atom bonded to the R Xa-d non-bonding carbon atom in the X ring is not substituted, R 1 , R 2 , R 3 , m and n are the same as above. ]
Including the epoxy resin represented by. R 1 , R 2 , R 3 , m, and n may be the same or different, and are preferably the same.
　Ｘｉｖで示される４価の基として、好ましくは以下の基： As the tetravalent group represented by X iv , preferably the following groups:
Figure JPOXMLDOC01-appb-C000076
Figure JPOXMLDOC01-appb-C000076
が挙げられる。 is mentioned.
　Ｘｉｖで示される４価の基として、式（２ｇ）で表される４価の基であってＲＸａ－ｄ非結合炭素原子に結合した水素原子が置換されていない基のうち、好ましくは、式（２ｇ－ｉｖａ’）： The tetravalent group represented by X iv is preferably a tetravalent group represented by the formula (2 g ) in which the hydrogen atom bonded to the R Xa-d non-bonding carbon atom is not substituted. is the formula (2 g −iva′):
Figure JPOXMLDOC01-appb-C000077
Figure JPOXMLDOC01-appb-C000077
（式中、Ｙは前記に同じ。）
で表される基が挙げられる。 (In the formula, Y is the same as above.)
The group represented by is mentioned.
　式（２ｇ－ｉｖａ’）において、Ｙが結合手、ジメチルメチレン基、酸素原子、又は－ＳＯ２－である基が特に好ましい。 In formula (2 g -iva'), a group in which Y is a bond, a dimethylmethylene group, an oxygen atom, or -SO 2 - is particularly preferred.
　例えば、式（１－ｉｖａ）において、ｍは同一で１、２、３、又は４（特に好ましくは、ｍは同一で４）、ｎは同一で０（すなわち、Ｒ３により環は置換されていない）を、Ｘｉｖは炭化水素環（特に好ましくはベンゼン環）から４個の水素原子を除いて得られる４価の基を、Ｒ１は同一で炭素数１～３のアルキル基を、Ｒ２は同一でケイ素原子及び３～６員環又はエポキシ環のいずれにも直接結合していない１個の炭素原子が酸素原子で置換されていてもよい炭素数２～６のアルキレン基を、それぞれ示すことで表されるエポキシ樹脂を、より好ましく本発明に用いることができる。 For example, in formula (1-iva), m is the same and 1, 2, 3, or 4 (particularly preferably, m is the same and 4), n is the same and 0 (i.e., the ring is substituted by R 3 ), X iv is a tetravalent group obtained by removing 4 hydrogen atoms from a hydrocarbon ring (particularly preferably a benzene ring), R 1 is the same alkyl group having 1 to 3 carbon atoms, R 2 are the same and each is an alkylene group having 2 to 6 carbon atoms and one carbon atom not directly bonded to a silicon atom or a 3- to 6-membered ring or an epoxy ring may be substituted with an oxygen atom; Epoxy resins represented by the following can be more preferably used in the present invention.
　また、式（１）で表されるエポキシ樹脂のうち、より好ましいものとして、例えば、式（１－ＩＩｂ）： Further, among the epoxy resins represented by formula (1), more preferable ones are, for example, formula (1-IIb):
Figure JPOXMLDOC01-appb-C000078
Figure JPOXMLDOC01-appb-C000078
（式中、Ｒ１、Ｒ２、Ｒ３、Ｘｉｉ、及びｎは前記に同じ。）
で表されるエポキシ樹脂を挙げることもできる。なお、Ｒ１、Ｒ２、Ｒ３、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。
式（１－ＩＩｂ）において、Ｘｉｉが１，４－フェニレン基又は式（２ｇ－ｉｉａ’）で表される基（好ましくは１，４－フェニレン基）であり、Ｒ１が同一又は異なって（好ましくは同一で）炭素数１～３のアルキル基（特にメチル基）であり、ｎが共に０（すなわち環はＲ３で置換されていない）であり、Ｒ２が同一又は異なって（好ましくは同一で）炭素数２～６のアルキレン基（好ましくはジメチレン基：－（ＣＨ２）２－）であるものがより好ましい。 (Wherein, R 1 , R 2 , R 3 , X ii and n are the same as above.)
The epoxy resin represented by can also be mentioned. R 1 , R 2 , R 3 and n may be the same or different, and are preferably the same.
In formula (1-IIb), X ii is a 1,4-phenylene group or a group represented by formula (2 g -iia') (preferably 1,4-phenylene group), and R 1 is the same or different are (preferably the same) an alkyl group having 1 to 3 carbon atoms (especially a methyl group), both n are 0 (that is, the ring is not substituted with R 3 ), and R 2 are the same or different ( An alkylene group having 2 to 6 carbon atoms (preferably a dimethylene group: -(CH 2 ) 2 -) is more preferable.
　また、式（１）で表されるエポキシ樹脂のうち、より好ましいものとして、さらに例えば、式（１－ＩＩＩａ）： Further, among the epoxy resins represented by formula (1), more preferable ones include formula (1-IIIa):
Figure JPOXMLDOC01-appb-C000079
Figure JPOXMLDOC01-appb-C000079
（式中、Ｒ１、Ｒ２、Ｒ３、Ｘｉｉｉ、及びｎは前記に同じ。）
で表されるエポキシ樹脂を挙げることもできる。なお、Ｒ１、Ｒ２、Ｒ３、及びｎは、いずれも、それぞれ同一又は異なっていてよく、同一であることが好ましい。
式（１－ＩＩＩａ）において、Ｘｉｉｉが (Wherein, R 1 , R 2 , R 3 , X iii , and n are the same as above.)
The epoxy resin represented by can also be mentioned. R 1 , R 2 , R 3 and n may be the same or different, and are preferably the same.
In formula (1-IIIa), X iii is
Figure JPOXMLDOC01-appb-C000080
Figure JPOXMLDOC01-appb-C000080
若しくは or
Figure JPOXMLDOC01-appb-C000081
Figure JPOXMLDOC01-appb-C000081
又は式（２ｇ－ｉｉｉａ’）で表される基であり、Ｒ１が同一又は異なって（好ましくは同一で）炭素数１～３のアルキル基（特にメチル基）であり、ｎが共に０（すなわち環はＲ３で置換されていない）であり、Ｒ２が同一又は異なって（好ましくは同一で）炭素数２～６のアルキレン基（好ましくはジメチレン基：－（ＣＨ２）２－）であるものがより好ましい。 or a group represented by the formula (2 g -iiia'), wherein R 1 is the same or different (preferably the same) alkyl group having 1 to 3 carbon atoms (especially methyl group), and n is 0 (that is, the ring is not substituted with R 3 ), and R 2 is the same or different (preferably the same) alkylene group having 2 to 6 carbon atoms (preferably dimethylene group: —(CH 2 ) 2 —) is more preferable.
　本発明のエポキシ樹脂組成物において、式（１）で表されるエポキシ樹脂は、単独で又は２種以上を組み合わせて用いることができる。 In the epoxy resin composition of the present invention, the epoxy resin represented by formula (1) can be used alone or in combination of two or more.
　式（１）で表されるエポキシ樹脂は、公知の方法に基づいて又は準じて、例えば特許文献（英国特許第１１２３９６０号公報）等の記載に基づいて又は準じて、製造することができる。また例えば、次の反応式で表される反応により式（１－ｉｉａ）で示されるエポキシ樹脂を製造することができる。 The epoxy resin represented by formula (1) can be produced based on or according to a known method, for example, based on or according to the description in the patent document (British Patent No. 1123960). Further, for example, the epoxy resin represented by the formula (1-ia) can be produced by the reaction represented by the following reaction formula.
Figure JPOXMLDOC01-appb-C000082
Figure JPOXMLDOC01-appb-C000082
（式中、Ｒ２Ａは、炭素数２～１８のアルケニル基であり、この基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよい。Ｒ１、Ｒ２、Ｒ３、及びＸｉｉは前記に同じ。）
　Ｒ２Ａで示される炭素数２～１８のアルケニル基としては、直鎖又は分岐鎖状のアルケニル基であり、直鎖状が好ましい。具体的には、例えば、ビニル基、アリル基、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノルボルネニル基、シクロヘキセニル基等が挙げられる。好ましくは炭素数２～１０のアルケニル基であり、より好ましくは炭素数２～８のアルケニル基であり、さらに好ましくは炭素数２～６のアルケニル基であり、特に好ましくはビニル基、アリル基又はブテニル基である。なお、当該アルケニル基は、α－アルケニル基であることが好ましい。 (Wherein, R 2A is an alkenyl group having 2 to 18 carbon atoms, in which some of the carbon atoms are substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms. R 1 , R 2 , R 3 and X ii are the same as above.)
The alkenyl group having 2 to 18 carbon atoms represented by R 2A is a linear or branched alkenyl group, preferably linear. Specific examples include vinyl group, allyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, norbornenyl group, cyclohexenyl group and the like. It is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, still more preferably an alkenyl group having 2 to 6 carbon atoms, and particularly preferably a vinyl group, an allyl group, or It is a butenyl group. The alkenyl group is preferably an α-alkenyl group.
　これらの炭素数２～１８のアルケニル基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子（好ましくは酸素原子）で置換されていてもよい。当該一部の炭素原子は、エポキシ環に直接結合していない炭素原子であることが好ましい。また、当該置換されてもよい一部の炭素原子は、１又は複数（例えば２、３、４、５、又は６）個の炭素原子であり、好ましくは１個の炭素原子である。当該基としては、例えば、炭素数２～９アルケニル－Ｏ－炭素数１～８アルキレン－、好ましくは炭素数２～４アルケニル－Ｏ－炭素数１～３アルキレン－、より好ましくは炭素数２～４アルケニル－Ｏ－炭素数１～２アルキレン－、特に好ましくは炭素数３アルケニル－Ｏ－ＣＨ２－が挙げられる。具体的には、例えば、ＣＨ２＝ＣＨ－Ｏ－ＣＨ２－、ＣＨ２＝ＣＨ－ＣＨ２－Ｏ－ＣＨ２－、ＣＨ２＝ＣＨ－ＣＨ２－Ｏ－（ＣＨ２）２－、ＣＨ２＝ＣＨ－（ＣＨ２）３－Ｏ－（ＣＨ２）４－などが挙げられ、これらの中でもＣＨ２＝ＣＨ－ＣＨ２－Ｏ－ＣＨ２－（アリルオキシメチル基）が好ましい。 Some of the carbon atoms in these alkenyl groups having 2 to 18 carbon atoms may be substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms (preferably oxygen atoms). The partial carbon atoms are preferably carbon atoms that are not directly bonded to the epoxy ring. Also, the part of the carbon atoms that may be substituted is one or more (for example, 2, 3, 4, 5, or 6) carbon atoms, preferably one carbon atom. Such groups include, for example, alkenyl-O with 2 to 9 carbon atoms-alkylene with 1 to 8 carbon atoms-, preferably alkenyl-O with 2 to 4 carbon atoms-alkylene with 1 to 3 carbon atoms-, more preferably 2 to 3 carbon atoms. 4-alkenyl-O-C1-2 alkylene-, particularly preferably 3-carbon alkenyl-O-CH 2 -. Specifically, for example, CH 2 ═CH—O—CH 2 —, CH 2 ═CH —CH 2 —O —CH 2 —, CH 2 ═CH —CH 2 —O—(CH 2 ) 2 —, CH 2 =CH—(CH 2 ) 3 —O—(CH 2 ) 4 — and the like, among which CH 2 ═CH—CH 2 —O—CH 2 — (allyloxymethyl group) is preferred.
　式（１－ｉｉａ）で表されるエポキシ樹脂は、式（５－ｉｉａ）で表される化合物と式（６）で表される化合物をヒドロシリル化反応させて製造することができる。ヒドロシリル化反応は、通常、触媒の存在下、溶媒の存在下又は非存在下で実施することができる。また、式（５－ｉｉａ）で表される化合物にかえて、式（５－ｉｉｉａ）： The epoxy resin represented by formula (1-ia) can be produced by hydrosilylating the compound represented by formula (5-ia) and the compound represented by formula (6). The hydrosilylation reaction can generally be carried out in the presence or absence of a solvent in the presence of a catalyst. Further, instead of the compound represented by the formula (5-iia), the formula (5-iiia):
Figure JPOXMLDOC01-appb-C000083
Figure JPOXMLDOC01-appb-C000083
（式中、Ｒ１及びＸｉｉｉは前記に同じ。）
　又は式（５－ｉｖａ）： (In the formula, R 1 and X iii are the same as above.)
or formula (5-iva):
Figure JPOXMLDOC01-appb-C000084
Figure JPOXMLDOC01-appb-C000084
（式中、Ｒ１及びＸｉｖは前記に同じ。）
又は式（５－ｉａ）： (Wherein, R 1 and X iv are the same as above.)
or formula (5-ia):
Figure JPOXMLDOC01-appb-C000085
Figure JPOXMLDOC01-appb-C000085
（式中、Ｘｉは炭化水素環から１個の水素原子を除いて得られる１価の基を示し、Ｒ１は前記に同じ。）
で表される化合物を用いることにより、上記式（１－ｉｉｉａ）又は（１－ｉｖａ）で表されるエポキシ樹脂や１個の式（３）の基が炭化水素環に結合した構造を有するエポキシ樹脂を製造することもできる。また、これらの化合物の構造において、Ｘｉ～Ｘｉｖが、それぞれ、Ｘ環から１個の水素原子を除いて得られる１価の基、Ｘ環から２個の水素原子を除いて得られる２価の基、Ｘ環から３個の水素原子を除いて得られる３価の基、又はＸ環から４個の水素原子を除いて得られる４価の基、に置換された構造の化合物を用いることで、式（１）で示される種々の化合物を製造することができる。 (In the formula, Xi represents a monovalent group obtained by removing one hydrogen atom from a hydrocarbon ring, and R 1 is the same as above.)
By using the compound represented by, the epoxy resin represented by the above formula (1-iiia) or (1-iva) or the epoxy having a structure in which one group of formula (3) is bonded to a hydrocarbon ring Resin can also be produced. In the structures of these compounds, X i to X iv are each a monovalent group obtained by removing one hydrogen atom from the X ring, and 2 obtained by removing two hydrogen atoms from the X ring. Use a compound with a structure substituted with a valent group, a trivalent group obtained by removing 3 hydrogen atoms from the X ring, or a tetravalent group obtained by removing 4 hydrogen atoms from the X ring Thus, various compounds represented by formula (1) can be produced.
　ヒドロシリル化反応に用いられる触媒は、公知の触媒でよく、例えば、白金カーボン、塩化白金酸、白金のオレフィン錯体、白金のアルケニルシロキサン錯体、白金のカルボニル錯体等の白金系触媒；トリス（トリフェニルフォスフィン）ロジウム等のロジウム系触媒；ビス(シクロオクタジエニル)ジクロロイリジウム等のイリジウム系触媒が挙げられる。上記の触媒は溶媒和物（例えば、水和物、アルコール和物等）の形態であってもよく、また使用にあたり触媒をアルコール（例えば、エタノール等）に溶解して溶液の形態で用いることもできる。なお触媒は、単独で又は２種以上を組み合わせて用いることができる。 The catalyst used in the hydrosilylation reaction may be a known catalyst, for example, platinum-based catalysts such as platinum carbon, chloroplatinic acid, platinum olefin complexes, platinum alkenylsiloxane complexes, platinum carbonyl complexes; fin) Rhodium-based catalysts such as rhodium; and iridium-based catalysts such as bis(cyclooctadienyl)dichloroiridium. The above catalysts may be in the form of solvates (e.g. hydrates, alcoholates, etc.), or may be used in the form of solutions by dissolving the catalysts in alcohols (e.g., ethanol, etc.). can. In addition, a catalyst can be used individually or in combination of 2 or more types.
　触媒の使用量は、触媒としての有効量でよく、例えば、上記式（５－ｉａ）、（５－ｉｉａ）、（５－ｉｉｉａ）、又は（５－ｉｖａ）で表される化合物と式（６）で表される化合物との合計量１００質量部に対して ０．００００１～２０質量部、好ましくは０．０００５～５質量部である。 The amount of the catalyst used may be an effective amount as a catalyst. 0.00001 to 20 parts by mass, preferably 0.0005 to 5 parts by mass, per 100 parts by mass of the total amount of the compound represented by 6).
　前記ヒドロシリル化反応は溶媒を用いなくても進行するが、溶媒を用いることにより穏和な条件で反応を行うことができる。溶媒としては、例えば、トルエン、キシレンなどの芳香族炭化水素溶媒；ヘキサン、オクタンなどの脂肪族炭化水素溶媒；テトラヒドロフラン、ジオキサンなどのエーテル系溶媒；エタノール、イソプロパノールなどのアルコール系溶媒などが挙げられ、これらは単独で又は２種以上組み合わせてもよい。 Although the hydrosilylation reaction proceeds without using a solvent, the use of a solvent allows the reaction to be carried out under mild conditions. Examples of the solvent include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane and octane; ether solvents such as tetrahydrofuran and dioxane; alcohol solvents such as ethanol and isopropanol; These may be used alone or in combination of two or more.
　式（６）で表される化合物の使用量は、例えば、式（５－ｉａ）、（５－ｉｉａ）、（５－ｉｉｉａ）、又は（５－ｉｖａ）で表される化合物中のＳｉ－Ｈ基１モルに対して、通常、０．５～２モル、好ましくは０．６～１．５モル、より好ましくは０．８～１．２モルである。 The amount of the compound represented by formula (6) to be used is, for example, the Si- It is generally 0.5 to 2 mol, preferably 0.6 to 1.5 mol, more preferably 0.8 to 1.2 mol, per 1 mol of H group.
　反応温度は、通常０℃～１５０℃、好ましくは１０℃～１２０℃であり、反応時間は、通常１時間～２４時間程度である。 The reaction temperature is usually 0°C to 150°C, preferably 10°C to 120°C, and the reaction time is usually about 1 hour to 24 hours.
　反応終了後、反応液から溶媒を留去するなど、公知の単離手法を用いることにより、式（１）で表されるエポキシ樹脂を得ることができる。 After the reaction is completed, the epoxy resin represented by formula (1) can be obtained by using a known isolation method such as distilling off the solvent from the reaction solution.
　また、前記脂環式エポキシ樹脂としては、式（Ｉ）：
ＲＩａ－ＺＩ－ＲＩｂ　（Ｉ）
（式中、ＲＩａ及びＲＩｂは、同一又は異なって、式（４）の基（但しｍは０では無い）を示し、－ＺＩ－は、結合手又は連結基を示し、連結基が－（ＣＨ２）Ｉａ－Ｏ－（ＣＨ２）Ｉｂ－、又は－（ＣＨ２）Ｉｃ－ＣＯＯ－（ＣＨ２）Ｉｄ－を示す。ここで、Ｉａ及びＩｂは同一又は異なって０、１、２、３、又は４を示し、Ｉｃ及びＩｄは同一又は異なって０、１、２、３、又は４を示す。）で表されるエポキシ樹脂も好ましく例示される。なお、ここでの、－ＺＩ－が示す基である、－（ＣＨ２）Ｉａ－Ｏ－（ＣＨ２）Ｉｂ－、又は－（ＣＨ２）Ｉｃ－ＣＯＯ－（ＣＨ２）Ｉｄ－は、いずれも、左側がＲＩａ－と結合している側である。 Further, as the alicyclic epoxy resin, the formula (I):
RIa -ZI - RIb (I)
(Wherein, R Ia and R Ib are the same or different and represent a group of formula (4) (where m is not 0), -Z I - represents a bond or a linking group, and the linking group is —(CH2) Ia —O—(CH2) Ib —, or —(CH2) Ic —COO—(CH2) Id —, wherein Ia and Ib are the same or different and are 0, 1, 2, 3, or 4, and Ic and Id are the same or different and represent 0, 1, 2, 3, or 4.) is also preferably exemplified. Here, the group represented by -Z I -, -(CH2) Ia -O-(CH2) Ib - or -(CH2) Ic -COO-(CH2) Id - is the side that binds to R Ia -.
　式（Ｉ）において、式（４）の基は、ｍが４を示すことが好ましい。また、ｎは０を示すことが好ましい。 In formula (I), it is preferred that m represents 4 in the group of formula (4). Moreover, it is preferable that n represents 0.
　式（Ｉ）において、ＲＩａ及びＲＩｂは、同一であることが好ましい。－ＺＩ－は、結合手を示すことが好ましい。またあるいは、－ＺＩ－は、－（ＣＨ２）Ｉｃ－ＣＯＯ－（ＣＨ２）Ｉｄ－を示すことが好ましく、特にＩｃは０、Ｉｄは１を示すことが好ましい。 In formula (I), R Ia and R Ib are preferably the same. -Z I - preferably represents a bond. Alternatively, -Z I - preferably represents -(CH2) Ic -COO-(CH2) Id -, particularly preferably Ic is 0 and Id is 1.
　なかでも、ＲＩａ及びＲＩｂは同一で、－ＺＩ－は結合手を示すことが好ましい。 Among them, R Ia and R Ib are preferably the same, and -Z I - represents a bond.
　また、前記脂環式エポキシ樹脂としては、式（ＩＩ）：
ＲＩＩａ－ＺＩＩ－ＲＩＩｂ　（ＩＩ）
（式中、ＲＩＩａ及びＲＩＩｂは、同一又は異なって式（３）の基（但しｍは０では無い）を示し、－ＺＩＩ－は結合手、－（ＣＨ２）ｊ－（ｊは１、２、３、又は４を示す）、－ＣＨ（ＣＨ３）－ＣＨ２－、－ＣＨ２－ＣＨ（ＣＨ３）－、又は－Ｃ（ＣＨ３）２－、－Ｏ－（Ｓｉ（Ｒ１）２Ｏ）ＩＩａ－を示す。ここで、ＩＩａは０～８の整数（０、１、２、３、４、５、６、７、８）を示し、Ｒ１は前記に同じである。）で表されるエポキシ樹脂も好ましく例示される。 Further, as the alicyclic epoxy resin, the formula (II):
R IIa -Z II -R IIb (II)
(Wherein, R IIa and R IIb are the same or different and represent a group of formula (3) (where m is not 0), —Z II — is a bond, —(CH 2 ) j — (j is 1, 2, 3, or 4), —CH(CH 3 )—CH 2 —, —CH 2 —CH(CH 3 )—, —C(CH 3 ) 2 —, —O—(Si( R 1 ) 2 O) IIa —, where IIa is an integer of 0 to 8 (0, 1, 2, 3, 4, 5, 6, 7, 8) and R 1 is the same as above; ) is also preferably exemplified.
　式（ＩＩ）において、式（３）の基は、ｍが４を示すことが好ましい。また、ｎは０を示すことが好ましい。また、Ｒ２は炭素数１、２、又は３のアルキレン基であることが好ましい。また、Ｒ１は同一又は異なって（好ましくは同一であって）メチル基又はエチル基であることが好ましい。式（ＩＩ）において、ＲＩＩａ及びＲＩＩｂは、同一で、且つ、両方が式（３）の基（ｍは４を示す）を示すことが好ましい。－ＺＩＩ－は、ＩＩａが０～１を示すことが好ましい。 In formula (II), m preferably denotes 4 in the group of formula (3). Moreover, it is preferable that n represents 0. Also, R 2 is preferably an alkylene group having 1, 2, or 3 carbon atoms. Also, R 1 is preferably the same or different (preferably the same) and is a methyl group or an ethyl group. In formula (II), R IIa and R IIb are preferably identical and both denote a group of formula (3) (m denotes 4). In -Z II -, IIa preferably represents 0-1.
　また、前記脂環式エポキシ樹脂としては、式（ＩＩＩ）： Further, as the alicyclic epoxy resin, the formula (III):
Figure JPOXMLDOC01-appb-C000086
Figure JPOXMLDOC01-appb-C000086
（式中、ＲＩＩＩａは、同一又は異なって、Ｒ１又は下記式（３’）： (Wherein, R IIIa are the same or different, R 1 or the following formula (3′):
Figure JPOXMLDOC01-appb-C000087
Figure JPOXMLDOC01-appb-C000087
（式中、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じである。）の基を示し、但し少なくとも２個以上のＲＩＩＩａが式（３’）の基を示し、
Ｒ１は前記に同じであり、ＩＩＩｃは２～６の整数である。）で表されるエポキシ樹脂も好ましく例示される。なお、式（３’）の基は、式（３）の基において、基－Ｓｉ（Ｒ１）２－が除かれた基であり、よって上記式（３）の基についての説明は、基－Ｓｉ（Ｒ１）２－についての説明を除き、式（３’）についても適用される。 (wherein R 2 , R 3 , m, and n are the same as above), provided that at least two R IIIa represent a group of formula (3′);
R 1 is the same as above and IIIc is an integer of 2-6. ) is also preferably exemplified. The group of formula (3′) is the group of formula (3) from which the group —Si(R 1 ) 2 — has been removed. Except for the description of —Si(R 1 ) 2 —, it also applies to formula (3′).
　式（ＩＩＩ）におけるＲ１としては、好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基又はエチル基である。式（ＩＩＩ）としては、ＩＩＩｃが４、５、又は６を示すことが好ましい。また、ＲＩＩＩａは全てが式（３’）であることが好ましい。 R 1 in formula (III) is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. For formula (III), IIIc preferably represents 4, 5, or 6. Further, all of R IIIa are preferably represented by formula (3′).
　また、式（ＩＩＩ）で表されるエポキシ樹脂のなかでも、より好ましい一例として、ＩＩＩｃが４の場合のエポキシ樹脂について詳説する。 Also, among the epoxy resins represented by formula (III), as a more preferable example, an epoxy resin in which IIIc is 4 will be described in detail.
Figure JPOXMLDOC01-appb-C000088
Figure JPOXMLDOC01-appb-C000088
（式中、Ｒ１は、同一又は異なって、前記に同じであり、ＲＩＩＩａは、同一又は異なって、前記に同じ。）で表されるエポキシ樹脂が挙げられる。当該エポキシ樹脂のＲＩＩＩａは全てが式（３’）の基であることが好ましく、さらに有する式（３’）の基が全て同一であることが好ましい。また、有する式（３’）の基において、Ｒ２は炭素数１～４のメチレン基であることが好ましく、メチレン基、ジメチレン基（－ＣＨ２ＣＨ２－）又はトリメチレン基（－ＣＨ２ＣＨ２ＣＨ２－）であることがより好ましい。また、ｍは４であることが好ましい。また、ｎは０であることが好ましい。また、式（ＩＩＩ－１）において存在する４つのＲ１は全て同一であることが好ましく、メチル基又はエチル基であることがより好ましい。 (wherein R 1 is the same or different and is the same as above, and R IIIa is the same or different and is the same as above). All of R IIIa of the epoxy resin are preferably groups of formula (3′), and it is preferred that all of the groups of formula (3′) are the same. In addition, in the group of formula (3′) having, R 2 is preferably a methylene group having 1 to 4 carbon atoms, such as a methylene group, a dimethylene group (—CH 2 CH 2 —) or a trimethylene group (—CH 2 CH 2 CH 2 —) is more preferred. Moreover, it is preferable that m is four. Moreover, it is preferable that n is 0. Further, all four R 1s present in formula (III-1) are preferably the same, and more preferably a methyl group or an ethyl group.
　また、前記脂環式エポキシ樹脂としては、より具体的には、次式：  Further, more specifically, the alicyclic epoxy resin has the following formula:
Figure JPOXMLDOC01-appb-C000089
Figure JPOXMLDOC01-appb-C000089
（式中、Ｒ１は、前記に同じであり、ｎＩＶａは同一又は異なって０～５の整数（０、１、２、３、４、又は５）であり、ｎＩＶｂは同一又は異なって０又は１の整数であり、ｎＩＶｃは１～３の整数（１、２、又は３）である。）で表されるエポキシ樹脂も、好ましく例示される。 (wherein R 1 is the same as above, n IVa is the same or different and is an integer of 0 to 5 (0, 1, 2, 3, 4, or 5), and n IVb is the same or different is an integer of 0 or 1, and n IVc is an integer of 1 to 3 (1, 2, or 3)) is also preferably exemplified.
　当該エポキシ樹脂において、ｎＩＶｃが２又は３である場合において、ｎＩＶｂは同一又は異なってもよい。式（ＩＶ）のＲ１としては、好ましくは炭素数１～３のアルキル基であり、より好ましくはメチル基又はエチル基である。ｎＩＶａは０又は１が好ましく、より好ましくは０である。ｎＩＶｂは０がより好ましい。ｎＩＶｃは１又は２が好ましく、より好ましくは１である。 In the epoxy resin, when nIVc is 2 or 3, nIVb may be the same or different. R 1 in formula (IV) is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. nIVa is preferably 0 or 1, more preferably 0. nIVb is more preferably 0. nIVc is preferably 1 or 2, more preferably 1.
　なお、本明細書において、 In addition, in this specification,
Figure JPOXMLDOC01-appb-C000090
Figure JPOXMLDOC01-appb-C000090
は teeth
Figure JPOXMLDOC01-appb-C000091
Figure JPOXMLDOC01-appb-C000091
を意味する。 means
　また、前記脂環式エポキシ樹脂としては、より具体的には、次の式で表されるエポキシ樹脂も好ましく例示される。（なお、これらのエポキシ樹脂は、上記式（Ｉ）において、－ＺＩ－が結合手を示し、ＲＩａ、ＲＩｂが式（４）（ｍ＝４）を示す場合に包含される。） As the alicyclic epoxy resin, more specifically, an epoxy resin represented by the following formula is also preferably exemplified. (These epoxy resins are included when -Z I - represents a bond in formula (I) above and R Ia and R Ib represent formula (4) (m=4).)
Figure JPOXMLDOC01-appb-C000092
Figure JPOXMLDOC01-appb-C000092
より具体的には次の式で表される。 More specifically, it is represented by the following formula.
Figure JPOXMLDOC01-appb-C000093
Figure JPOXMLDOC01-appb-C000093
　なお、上記の説明において、ｍが０を示すとき、エポキシ樹脂はグリシジル基を有するエポキシ樹脂を包含する場合がある。前記脂環式エポキシ樹脂としては、グリシジル基をも有する脂環式エポキシ樹脂を包含するが、グリシジル基を１つも有さない脂環式エポキシ樹脂が好ましい。 In the above description, when m indicates 0, the epoxy resin may include an epoxy resin having a glycidyl group. The alicyclic epoxy resins include alicyclic epoxy resins also having glycidyl groups, but alicyclic epoxy resins having no glycidyl groups are preferred.
（グリシジル基を有するエポキシ樹脂）
　本開示のエポキシ樹脂組成物は、さらにグリシジル基を有するエポキシ樹脂を含んでもよい。グリシジル基を有するエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、含窒素環エポキシ樹脂（例えばトリグリシジルイソシアヌレート、ヒダントイン型エポキシ樹脂）、グリシジルアミン型エポキシ樹脂、脂肪族系エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルエステル型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂等が挙げられる。また、これらの樹脂には、ハロゲン化されているもの、あるいは水素添加されているものであってもよい。 (Epoxy resin having a glycidyl group)
The epoxy resin composition of the present disclosure may further contain an epoxy resin having a glycidyl group. Examples of epoxy resins having a glycidyl group include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, phenol novolac type epoxy resins, cresol novolak type epoxy resins, nitrogen-containing ring epoxy resins (e.g., triglycidyl isocyanurate , hydantoin type epoxy resin), glycidylamine type epoxy resin, aliphatic type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin An epoxy resin etc. are mentioned. Further, these resins may be halogenated or hydrogenated.
　これらのなかでも、硬化物の誘電特性を向上させる観点から、ビスフェノールＡ型エポキシ樹脂、ビフェニル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフタレン型エポキシ樹脂、アントラセン型エポキシ樹脂が好ましい。グリシジル基を有するエポキシ樹脂は、１種のみが用いられてもよく、２種以上が併用されてもよい。 Among these, bisphenol A type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, and anthracene type epoxy resin are preferable from the viewpoint of improving the dielectric properties of the cured product. Only one type of epoxy resin having a glycidyl group may be used, or two or more types may be used in combination.
　なお、上記の説明において、ｍが０を示すとき、エポキシ樹脂はグリシジル基を有するエポキシ樹脂となる。すなわち本開示の（Ｂ）エポキシ樹脂としては、グリシジル基を有さない脂環式エポキシ樹脂を含み、更に、ｍが０を示すグリシジル基を有するエポキシ樹脂を含んでもよい。 In the above description, when m indicates 0, the epoxy resin has a glycidyl group. That is, the (B) epoxy resin of the present disclosure includes an alicyclic epoxy resin having no glycidyl group, and may further include an epoxy resin having a glycidyl group in which m is 0.
　本開示のエポキシ樹脂組成物が脂環式エポキシ樹脂とグリシジル基を有するエポキシ樹脂とを含む場合、本発明の効果をより一層効果的に発揮する観点から、エポキシ樹脂組成物に含まれる（Ｂ）エポキシ樹脂中（脂環式エポキシ樹脂とグリシジル基を有するエポキシ樹脂の合計）、脂環式エポキシ樹脂の含有量は２５質量％以上が好ましく、より好ましくは３０質量％以上、更に好ましくは３５質量％以上である。また、４０、４５、５０、５５、６０、６５、７０、７５、８０、８５、９０、又は９５質量％以上であってもよい。 When the epoxy resin composition of the present disclosure contains an alicyclic epoxy resin and an epoxy resin having a glycidyl group, (B) is included in the epoxy resin composition from the viewpoint of more effectively exhibiting the effects of the present invention. The content of the alicyclic epoxy resin in the epoxy resin (total of the alicyclic epoxy resin and the epoxy resin having a glycidyl group) is preferably 25% by mass or more, more preferably 30% by mass or more, and still more preferably 35% by mass. That's it. Moreover, it may be 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95% by mass or more.
　また、（Ｂ）エポキシ樹脂が全て脂環式エポキシ樹脂であってもよい。 Also, (B) epoxy resins may all be alicyclic epoxy resins.
〔（Ｃ）硬化剤〕
　前記エポキシ樹脂組成物は、硬化剤として、活性エステル硬化剤を含む。活性エステル硬化剤は、エステル基（好ましくは反応活性の高いエステル基）を有する化合物である。活性エステル硬化剤としては、具体的には、エステル基を１分子中に２個以上有する化合物が好適である。エステル基を１分子中に２個以上有する化合物としては、例えば、フェノールエステル類、ナフトールエステル類、チオフェノールエステル類、Ｎ－ヒドロキシアミンエステル類、複素環ヒドロキシ化合物のエステル類等が好ましく挙げられる。 [(C) Curing agent]
The epoxy resin composition contains an active ester curing agent as a curing agent. An active ester curing agent is a compound having an ester group (preferably an ester group with high reactivity). As the active ester curing agent, specifically, a compound having two or more ester groups in one molecule is suitable. Preferred examples of compounds having two or more ester groups in one molecule include phenol esters, naphthol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, and the like.
　前記活性エステル硬化剤は、カルボン酸化合物及び／又はチオカルボン酸化合物とヒドロキシ化合物及び／又はチオール化合物との縮合反応によって得られるもの（すなわち、カルボン酸化合物及びチオカルボン酸化合物からなる群より選択される少なくとも１種と、ヒドロキシ化合物及びチオール化合物からなる群より選択される少なくとも１種との、縮合物）が好ましい。特に耐熱性向上の観点から、カルボン酸化合物とヒドロキシ化合物とから得られる縮合物が好ましく、カルボン酸化合物とフェノール化合物及び／又はナフトール化合物とから得られる縮合物がより好ましい。このような縮合物（活性エステル硬化剤）は、エポキシ樹脂硬化剤として好ましく用いることができる。 The active ester curing agent is obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound (that is, at least one selected from the group consisting of carboxylic acid compounds and thiocarboxylic acid compounds. Condensates of one and at least one selected from the group consisting of hydroxy compounds and thiol compounds) are preferred. In particular, from the viewpoint of improving heat resistance, a condensate obtained from a carboxylic acid compound and a hydroxy compound is preferred, and a condensate obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Such a condensate (active ester curing agent) can be preferably used as an epoxy resin curing agent.
　また、活性エステル硬化剤として、例えば特開２００９－２３５１６５号公報、特開２００４－２７７４６０号公報、又はＷＯ２０１３／０６１６８８に開示されている活性エステル化合物を用いることもできる。特開２００９－２３５１６５号公報に記載の活性エステル化合物を用いることがより好ましい。特開２００９－２３５１６５号公報、特開２００４－２７７４６０号公報、及びＷＯ２０１３／０６１６８８の明細書および／または図面に記載される活性エステル化合物に関する内容は参照により本明細書に組み込まれる。 Also, as the active ester curing agent, for example, an active ester compound disclosed in JP-A-2009-235165, JP-A-2004-277460, or WO2013/061688 can be used. It is more preferable to use the active ester compound described in JP-A-2009-235165. The contents of the active ester compounds described in the specifications and/or drawings of JP-A-2009-235165, JP-A-2004-277460, and WO2013/061688 are incorporated herein by reference.
　活性エステル硬化剤としては、なかでも、ジシクロペンタジエニルジフェノール構造を含むエステル化合物が好ましい。 Among them, an ester compound containing a dicyclopentadienyldiphenol structure is preferable as the active ester curing agent.
　活性エステル化合物として、下記式：  　As an active ester compound, the following formula:
Figure JPOXMLDOC01-appb-C000094
Figure JPOXMLDOC01-appb-C000094
　（式中、Ｒ７は置換基を有してもよいフェニル基又はナフチル基であり、ｙは０又は１の整数を表し、ｚは繰り返し単位の平均で０．０５～２．５である。）で表される化合物が特に好ましく挙げられる。Ｒ７は好ましくは置換基を有してもよいナフチル基である。ｙは好ましくは０である。ｚは好ましくは０．２５～１．５である。電気特性・耐熱性の観点からＲ７が置換基を有してもよいナフチル基であり、ｙが０であり、ｚが０．２５～１．５であることがより好ましい。前記式で表される活性エステル硬化剤としては、ＨＰＣ－８０００－６５Ｔ（ＤＩＣ社製、エステル当量 約２２３ｇ／ｅｑ）等が挙げられる　活性エステル化合物は単独で又は２種以上を組み合わせて用いることが出来る。 (In the formula, R 7 is an optionally substituted phenyl group or naphthyl group, y represents an integer of 0 or 1, and z is an average of repeating units of 0.05 to 2.5. ) are particularly preferred. R7 is preferably a naphthyl group which may have a substituent. y is preferably zero. z is preferably between 0.25 and 1.5. From the viewpoint of electrical properties and heat resistance, it is more preferable that R7 is an optionally substituted naphthyl group, y is 0, and z is 0.25 to 1.5. Examples of the active ester curing agent represented by the above formula include HPC-8000-65T (manufactured by DIC, ester equivalent weight: about 223 g/eq), etc. The active ester compound may be used alone or in combination of two or more. I can.
　また市販のエステル化合物を本発明の活性エステル硬化剤として用いることもできる。このような市販エステル化合物としては、ジシクロペンタジエニルジフェノール構造を含むエステル化合物、フェノールノボラックのアセチル化物、フェノールノボラックのベンゾイル化物等が好ましく、なかでもジシクロペンタジエニルジフェノール構造を含むエステル化合物がより好ましい。 A commercially available ester compound can also be used as the active ester curing agent of the present invention. As such a commercially available ester compound, an ester compound containing a dicyclopentadienyldiphenol structure, an acetylated product of phenol novolak, a benzoylated product of phenol novolak, etc. are preferable, and among them, an ester containing a dicyclopentadienyldiphenol structure is preferable. Compounds are more preferred.
　より詳細には、例えば、ジシクロペンタジエニルジフェノール構造を含むエステル化合物として、ＥＸＢ９４５１、ＥＸＢ９４６０、ＥＸＢ９４６０Ｓ－６５Ｔ、ＨＰＣ－８０００－６５Ｔ（ＤＩＣ社製、エステル当量約２２３）、フェノールノボラックのアセチル化物としてＤＣ８０８（三菱ケミカル社製、エステル当量約１４９）、フェノールノボラックのベンゾイル化物としてＹＬＨ１０２６（三菱ケミカル社製、エステル当量約２００）、ＹＬＨ１０３０（三菱ケミカル社製、エステル当量約２０１）、ＹＬＨ１０４８（三菱ケミカル社製、エステル当量約２４５）、等が挙げられる。 More specifically, for example, ester compounds containing a dicyclopentadienyl diphenol structure include EXB9451, EXB9460, EXB9460S-65T, HPC-8000-65T (manufactured by DIC, ester equivalent weight: about 223), acetylated phenol novolak DC808 (manufactured by Mitsubishi Chemical Corporation, ester equivalent of about 149), YLH1026 (manufactured by Mitsubishi Chemical Corporation, ester equivalent of about 200) as a benzoylated phenol novolak, YLH1030 (manufactured by Mitsubishi Chemical Corporation, ester equivalent of about 201), YLH1048 (Mitsubishi Chemical (Ester equivalent: about 245), etc.
　前記エポキシ樹脂組成物は、（Ｃ）硬化剤として、活性エステル硬化剤以外の硬化剤を含んでいてもよい。活性エステル硬化剤以外の硬化剤としては、エポキシ樹脂を硬化する機能を有するものであれば、特に限定されず、例えば、アミン系硬化剤、アミド系硬化剤、酸無水物系硬化剤、フェノール系硬化剤、ベンゾオキサジン系硬化剤、ナフトール系硬化剤、メルカプタン系硬化剤、イソシアネート系硬化剤、シアネートエステル系硬化剤、カルボジイミド系硬化剤、マレイミド樹脂などが挙げられる。硬化剤は、求める特性に応じて使い分けることが可能であり、単独で用いてもよく、また、２種以上を併用してもよい。 The epoxy resin composition may contain a curing agent other than the active ester curing agent as (C) the curing agent. The curing agent other than the active ester curing agent is not particularly limited as long as it has a function of curing the epoxy resin. Curing agents, benzoxazine-based curing agents, naphthol-based curing agents, mercaptan-based curing agents, isocyanate-based curing agents, cyanate ester-based curing agents, carbodiimide-based curing agents, maleimide resins, and the like. Curing agents can be selectively used according to desired properties, and may be used alone or in combination of two or more.
　このような活性エステル硬化剤以外の硬化剤としては、より具体的には、例えば、フェノール、クレゾール、ハイドロキノン、レゾルシン、ｐ－プロピルフェノール、ノニルフェノール等の置換フェノール類、１－ナフトール、２－ナフトール、１，２－ナフタレンジオール、１－メチル－２－ナフトール、６－ｔｅｒｔ－ブチル－２－ナフトール等の置換ナフトール類、ノボラック型フェノール樹脂、レゾール型フェノール樹脂、アラルキル型フェノール樹脂、ジシクロペンタジエン型フェノール樹脂等のフェノール樹脂等が好ましく挙げられる。
中でも、
フェノール、ナフトール（１－ナフトール、２－ナフトール）、又は式（Ｋ）： Examples of curing agents other than active ester curing agents include, more specifically, phenol, cresol, hydroquinone, resorcinol, p-propylphenol, substituted phenols such as nonylphenol, 1-naphthol, 2-naphthol, Substituted naphthols such as 1,2-naphthalenediol, 1-methyl-2-naphthol and 6-tert-butyl-2-naphthol, novolac-type phenolic resins, resol-type phenolic resins, aralkyl-type phenolic resins, dicyclopentadiene-type phenols Phenolic resins such as resins are preferred.
Among them,
Phenol, naphthol (1-naphthol, 2-naphthol), or formula (K):
Figure JPOXMLDOC01-appb-C000095
Figure JPOXMLDOC01-appb-C000095
（式中、ｋは１～１０（１、２、３、４、５、６、７、８、９、又は１０）の整数を示し、ｋ’は０又は１を示し、ＲＫ１は水素原子またはメチル基を示し、ＲＫ２は (Wherein, k is an integer of 1 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10), k' is 0 or 1, and R K1 is a hydrogen atom or represents a methyl group, and R K2 is
Figure JPOXMLDOC01-appb-C000096
Figure JPOXMLDOC01-appb-C000096
又は or
Figure JPOXMLDOC01-appb-C000097
Figure JPOXMLDOC01-appb-C000097
で表される基を示し、ＲＫ３は、芳香族環又は炭化水素環を示す。）で表される化合物が好ましく挙げられる。ＲＫ３が芳香族環である場合、より具体的には、例えばフェニレン基、ナフチレン基、ビフェニレン基等が挙げられる。また、ＲＫ３が炭化水素環である場合、より具体的には、例えば上記Ｘ環についての説明で挙げた、飽和炭化水素環又は不飽和炭化水素環、あるいは飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環が挙げられ、より具値的には例えばフェニレン基、ナフチレン基、ビフェニレン基等が挙げられる。なお、式（Ｋ）から分かるとおり、ＲＫ３は２価の基を示しており、よって、ＲＫ３が芳香族環又は炭化水素環を示すとは、より詳細には、芳香族環又は炭化水素環における環を構成する炭素に結合した水素原子が２個外れてなる２価の基を示す、ということができる。 and R K3 represents an aromatic ring or a hydrocarbon ring. ) are preferably mentioned. When RK3 is an aromatic ring, more specific examples include a phenylene group, a naphthylene group, a biphenylene group and the like. Further, when R K3 is a hydrocarbon ring, more specifically, for example, the saturated hydrocarbon ring or unsaturated hydrocarbon ring, or the saturated hydrocarbon ring and/or unsaturated ring mentioned in the description of the X ring above. A ring having a structure in which 2 to 6 hydrocarbon rings are condensed can be mentioned, and more specific examples include a phenylene group, a naphthylene group, a biphenylene group and the like. As can be seen from the formula (K), R K3 represents a divalent group, therefore, R K3 represents an aromatic ring or a hydrocarbon ring more specifically It can be said that the ring represents a divalent group in which two hydrogen atoms bonded to carbon atoms constituting the ring are removed.
　エポキシ樹脂組成物が活性エステル硬化剤と活性エステル硬化剤以外の硬化剤を含む場合、本発明の効果をより一層効果的に発揮する観点から、エポキシ樹脂組成物に含まれる（Ｃ）硬化剤中（活性エステル硬化剤及びそれ以外の硬化剤の合計）の、活性エステル硬化剤の含有量は３０質量％以上が好ましく、より好ましくは４０質量％以上、更に好ましくは５０質量％以上である。また、６０、６５、７０、７５、８０、８５、９０、又は９５質量％以上であってもよい。 When the epoxy resin composition contains an active ester curing agent and a curing agent other than the active ester curing agent, from the viewpoint of more effectively exhibiting the effects of the present invention, the (C) curing agent contained in the epoxy resin composition The content of the active ester curing agent in (total of the active ester curing agent and other curing agents) is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more. Moreover, it may be 60, 65, 70, 75, 80, 85, 90, or 95% by mass or more.
　また、（Ｃ）硬化剤が全て活性エステル硬化剤であってもよい。 Also, all of the (C) curing agents may be active ester curing agents.
　エポキシ樹脂組成物における（Ｃ）硬化剤の配合割合は、本発明の効果を発揮できる範囲であればよく、エポキシ樹脂のエポキシ基に対する硬化剤の官能基の当量比（エステル基／エポキシ基）が０．３～１．５となる割合であることが好ましく、０．５～１．３であることがより好ましく、０．６～１．２程度であることがさらに好ましい。 The blending ratio of (C) the curing agent in the epoxy resin composition may be within a range where the effects of the present invention can be exhibited, and the equivalent ratio of the functional group of the curing agent to the epoxy group of the epoxy resin (ester group/epoxy group) is The ratio is preferably 0.3 to 1.5, more preferably 0.5 to 1.3, even more preferably about 0.6 to 1.2.
　また、（Ｃ）硬化剤が全て活性エステル硬化剤である場合、本発明に係るエポキシ樹脂組成物における活性エステル硬化剤の配合割合は、本発明の効果を発揮できる範囲であればよく、エポキシ樹脂のエポキシ基に対する活性エステル硬化剤のエステル基の当量比（エステル基／エポキシ基）が０．５～１．５となる割合であることが好ましく、０．５～１．３であることがより好ましく、０．６～１．２であることがさらに好ましい。 Further, when all the curing agents (C) are active ester curing agents, the mixing ratio of the active ester curing agent in the epoxy resin composition according to the present invention may be within a range where the effects of the present invention can be exhibited. The equivalent ratio of the ester group of the active ester curing agent to the epoxy group of the active ester curing agent (ester group/epoxy group) is preferably 0.5 to 1.5, more preferably 0.5 to 1.3. It is preferably from 0.6 to 1.2, and more preferably from 0.6 to 1.2.
　また、（Ｃ）硬化剤が活性エステル以外の硬化剤を含む場合、本発明の効果を発揮できる範囲であればよく、エポキシ樹脂のエポキシ基に対する硬化剤の官能基の当量比（官能基／エポキシ基）が０．５～１．５となる割合であることが好ましく、０．５～１．３であることがより好ましく、０．６～１．２あることがさらに好ましい。 In addition, when the (C) curing agent contains a curing agent other than an active ester, the equivalent ratio of the functional group of the curing agent to the epoxy group of the epoxy resin (functional group / epoxy group) is preferably from 0.5 to 1.5, more preferably from 0.5 to 1.3, even more preferably from 0.6 to 1.2.
〔（Ｄ）硬化促進剤〕
　硬化促進剤としては、例えば、１－メチルイミダゾール、２－メチルイミダゾール、２－エチルイミダゾール、２－フェニルイミダゾール、２－エチル－４－メチルイミダゾール、１，２－ジメチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾール、２－ウンデシルイミダゾール等のイミダゾール類；２－メチル－イミダゾリン、２－フェニルイミダゾリン等のイミダゾリン誘導体類；２－（ジメチルアミノメチル）フェノール、トリエチレンジアミン、トリエタノールアミン、ピリジン、４－ジメチルアミノピリジン、１，４－ジアザビシクロ［２．２．２］オクタン、１，８－ジアザビシクロ（５，４，０）ウンデセン－７、１，５－ジアザビシクロ（４，３，０）－ノネン－５）、１，８－ビス（ジメチルアミノ）ナフタレン、１，１，３，３－テトラメチルグアニジン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン等の第３級アミン類；トリフェニルホスフィン、ジフェニルホスフィン、トリブチルホスフィン等の有機ホスフィン類；オクチル酸スズなどの金属化合物；エチルトリフェニルホスホニウムブロミド、テトラフェニルホスホニウムテトラフェニルボレート等のホスホニウム塩類などが挙げられる。これらのなかでも、樹脂組成物の硬化性を向上させる観点から、アニオン性硬化促進剤であるイミダゾール類、第３級アミン類が好ましく、より好ましくは、１－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェニルイミダゾール、１，２－ジメチルイミダゾール、１－ベンジル－２－メチルイミダゾール、トリエチレンジアミン、４－ジメチルアミノピリジン、１，４－ジアザビシクロ［２．２．２］オクタン、１，８－ジアザビシクロ（５，４，０）ウンデセン－７、１，５－ジアザビシクロ（４，３，０）－ノネン－５）、１，１，３，３－テトラメチルグアニジン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エンであり、さらに好ましくは１－メチルイミダゾール、２－エチル－４－メチルイミダゾール、１，２－ジメチルイミダゾール、４－ジメチルアミノピリジン、１，８－ジアザビシクロ（５，４，０）ウンデセン－７、１，５－ジアザビシクロ（４，３，０）－ノネン－５）、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エンである。 [(D) Curing accelerator]
Curing accelerators include, for example, 1-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl-2- imidazoles such as methylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, 2-undecylimidazole; 2-methyl-imidazoline, imidazoline derivatives such as 2-phenylimidazoline; 2-(dimethyl aminomethyl)phenol, triethylenediamine, triethanolamine, pyridine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo(5,4,0)undecene-7, 1,5-diazabicyclo(4,3,0)-nonene-5), 1,8-bis(dimethylamino)naphthalene, 1,1,3,3-tetramethylguanidine, 7-methyl-1,5,7 - tertiary amines such as triazabicyclo[4.4.0]dec-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene; triphenylphosphine, organic phosphines such as diphenylphosphine and tributylphosphine; metal compounds such as tin octylate; and phosphonium salts such as ethyltriphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate. Among these, from the viewpoint of improving the curability of the resin composition, imidazoles and tertiary amines, which are anionic curing accelerators, are preferable, and more preferably 1-methylimidazole, 2-ethyl-4- methylimidazole, 2-phenylimidazole, 1,2-dimethylimidazole, 1-benzyl-2-methylimidazole, triethylenediamine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, 1,8 -diazabicyclo(5,4,0)undecene-7,1,5-diazabicyclo(4,3,0)-nonene-5), 1,1,3,3-tetramethylguanidine, 7-methyl-1,5 ,7-triazabicyclo[4.4.0]dec-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, more preferably 1-methylimidazole , 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)undecene-7, 1,5-diazabicyclo(4,3,0 )-nonene-5), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,5,7-triazabicyclo[4.4.0]deca -5-ene.
　（Ｄ）硬化促進剤の使用量は特に限定されないが、樹脂層中の（Ｂ）エポキシ樹脂１００質量部に対して、例えば好ましくは０．０１～１０質量部であり、より好ましくは０．１～５質量部である。 The amount of the curing accelerator (D) used is not particularly limited, but is preferably 0.01 to 10 parts by mass, more preferably 0.1 part by mass, based on 100 parts by mass of the epoxy resin (B) in the resin layer. ~5 parts by mass.
　なお、硬化促進剤は、１種を単独で、又は２種以上を組み合わせて用いることができる。 The curing accelerator can be used singly or in combination of two or more.
〔（Ａ）ヒドロキシ基含有化合物〕
　本開示のエポキシ樹脂組成物は、ヒドロキシ基含有化合物を含み、前記ヒドロキシ基含有化合物の分子量は２００以上であり、２００～５０００であることが好ましい。前記ヒドロキシ基含有化合物の分子量の下限は、好ましくは２５０、より好ましくは３００であり、分子量の上限は、好ましくは４０００、より好ましくは３０００、さらに好ましくは２０００である。前記ヒドロキシ基含有化合物の分子量が上記の範囲内であると、Ｂステージフィルムの取扱い性を高めることができ、かつ、硬化物の耐熱性を向上させることができる。 [(A) Hydroxy Group-Containing Compound]
The epoxy resin composition of the present disclosure contains a hydroxy group-containing compound, and the molecular weight of the hydroxy group-containing compound is 200 or more, preferably 200 to 5,000. The lower limit of the molecular weight of the hydroxy group-containing compound is preferably 250, more preferably 300, and the upper limit of the molecular weight is preferably 4,000, more preferably 3,000, and even more preferably 2,000. When the molecular weight of the hydroxy group-containing compound is within the above range, the handleability of the B-stage film can be improved, and the heat resistance of the cured product can be improved.
　前記ヒドロキシ基含有化合物としては、分子中にヒドロキシ基を少なくとも１つ含むものであればよく、例えば、セチルアルコール、ミリスチルアルコール、ステアリルアルコール、オレイルアルコール、エイコシルアルコール、イソプロピリデンビシクロヘキサノール、ビフェニルジメタノール、ポリエチレングリコール、ポリプロピレングリコール等の、１分子中の炭素数が１０以上のアルコールが挙げられる。これらのアルコールは、第１級、第２級、又は第３級アルコールのいずれでもよい。直鎖若しくは分岐鎖状のアルキルアルコールであってもよい。また、１分子中に１個以上のエポキシ基を有する化合物と、１分子中に１個以上のヒドロキシ基、カルボキシ基、第１級若しくは第２級アミノ基、又はメルカプト基を有する化合物と、の反応により得られる２級ヒドロキシ基を、１分子中に１つ以上有する化合物も、ヒドロキシ基含有化合物として用いることができる。 The hydroxy group-containing compound may contain at least one hydroxy group in the molecule, and examples thereof include cetyl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, eicosyl alcohol, isopropylidenebicyclohexanol, and biphenyldimethanol. , polyethylene glycol, polypropylene glycol, and other alcohols having 10 or more carbon atoms in one molecule. These alcohols may be primary, secondary or tertiary alcohols. It may be a linear or branched alkyl alcohol. Also, a compound having one or more epoxy groups in one molecule and a compound having one or more hydroxy groups, carboxy groups, primary or secondary amino groups, or mercapto groups in one molecule. A compound having one or more secondary hydroxy groups in one molecule obtained by the reaction can also be used as the hydroxy group-containing compound.
　また、ヒドロキシ基含有化合物としては、その骨格に、次の３つの式： In addition, the hydroxy group-containing compound has the following three formulas in its skeleton:
Figure JPOXMLDOC01-appb-C000098
Figure JPOXMLDOC01-appb-C000098
（式中、Ｒ３及びｎは前記に同じ。）のいずれかで表される構造を有する化合物が好ましく挙げられる。なお、これらの式においては、ｎは１又は０であることが好ましく、また、Ｒ３はメチル基又はエチル基であることが好ましい。また、中央及び右側の式において、Ｒ３で表される置換基は、ナフチル基のいずれの炭素原子に結合していてもよいことを表す。以下も同様である。 (In the formula, R 3 and n are the same as described above). In these formulas, n is preferably 1 or 0, and R3 is preferably a methyl group or an ethyl group. Also, in the formulas on the middle and right sides, the substituent represented by R3 may be bonded to any carbon atom of the naphthyl group. The same applies to the following.
　また、当該３つの式をまとめて、式： Also, by combining the three formulas, the formula:
Figure JPOXMLDOC01-appb-C000099
Figure JPOXMLDOC01-appb-C000099
で表すことがある。すなわち、当該式においてＲｅｎがＯに結合している側を＊で表すと can be expressed as That is, if the side where R en is bonded to O in the formula is represented by *
Figure JPOXMLDOC01-appb-C000100
Figure JPOXMLDOC01-appb-C000100
は、 teeth,
Figure JPOXMLDOC01-appb-C000101
Figure JPOXMLDOC01-appb-C000101
の３つの基のいずれかを示す。また、このことから分かるように、＊－Ｒｅｎは、 any of the three groups of Also, as can be seen from this, *-R en is
Figure JPOXMLDOC01-appb-C000102
Figure JPOXMLDOC01-appb-C000102
のいずれかを示す。以下も同様である。 indicates either The same applies to the following.
　なお、このような化合物の中でも、その骨格に、式： It should be noted that among such compounds, the skeleton has the formula:
Figure JPOXMLDOC01-appb-C000103
Figure JPOXMLDOC01-appb-C000103
で表される骨格を有する化合物がより好ましい。 A compound having a skeleton represented by is more preferable.
　このようなヒドロキシ基含有化合物としては、より具体的には、式（Ａｅｎ１）： More specifically, such hydroxy group-containing compounds include compounds of the formula (A en 1):
Figure JPOXMLDOC01-appb-C000104
Figure JPOXMLDOC01-appb-C000104
（ただし、式中のシクロヘキサン環においてＯＨ基が結合する炭素原子と－Ｏ－Ｒｅｎ基が結合する炭素原子とは結合している）で表される基、
若しくは式（Ａｅｎ２）： (provided that the carbon atom to which the OH group is bonded and the carbon atom to which the —O—R en group is bonded in the cyclohexane ring in the formula are bonded),
or formula (A en 2):
Figure JPOXMLDOC01-appb-C000105
Figure JPOXMLDOC01-appb-C000105
（ただし、式中のシクロヘキサン環においてＯＨ基が結合する炭素原子と－Ｏ－Ｒｅｎ基が結合する炭素原子とは結合している）で表される基、
若しくは式（Ａｅｎ３）： (provided that the carbon atom to which the OH group is bonded and the carbon atom to which the —O—R en group is bonded in the cyclohexane ring in the formula are bonded),
or formula (A en 3):
Figure JPOXMLDOC01-appb-C000106
Figure JPOXMLDOC01-appb-C000106
で表される基、
若しくは式（Ａｅｎ４）： A group represented by
or formula (A en 4):
Figure JPOXMLDOC01-appb-C000107
Figure JPOXMLDOC01-appb-C000107
で表される基、
を有する化合物がさらに好ましく挙げられる。 A group represented by
Further preferably, a compound having
　なお、式（Ａｅｎ１）が表す基は以下の４つの基であるが、中でも左端の基及び右端の基が好ましい。 The groups represented by the formula (A en 1) are the following four groups, among which the leftmost group and the rightmost group are preferred.
Figure JPOXMLDOC01-appb-C000108
Figure JPOXMLDOC01-appb-C000108
　また、式（Ａｅｎ２）が表す基は以下の３つの基であるが、中でも左端の基が好ましい。 The groups represented by the formula (A en 2) are the following three groups, among which the leftmost group is preferred.
Figure JPOXMLDOC01-appb-C000109
Figure JPOXMLDOC01-appb-C000109
　上記式（Ａｅｎ１）～（Ａｅｎ４）で表される基を有する、ヒドロキシ基含有化合物について、さらに詳細に記載する。 The hydroxy group-containing compounds having the groups represented by the above formulas (A en 1) to (A en 4) will be described in more detail.
　式（Ａｅｎ１）の基を有する化合物としては、例えば式（Ａｅｎ１－１）： Compounds having a group of formula (A en 1) include, for example, formula (A en 1-1):
Figure JPOXMLDOC01-appb-C000110
Figure JPOXMLDOC01-appb-C000110
で表される化合物が挙げられる。　式（Ａｅｎ１－１）において、ＲＡｅｎ１ａ及びＲＡｅｎ１ｂは、同一又は異なって（同一であることが好ましい）、式（Ａｅｎ１）で表される基、又は式（Ａｅｎ１－３）： The compound represented by is mentioned. In formula (A en 1-1), R Aen1a and R Aen1b are the same or different (preferably the same), a group represented by formula (A en 1), or a group represented by formula (A en 1-3 ):
Figure JPOXMLDOC01-appb-C000111
Figure JPOXMLDOC01-appb-C000111
（式中、Ｒｅｎ、Ｒ１及びＲ２は前記に同じであり、ｈは０又は１を示す。）で表される基を示す。式（Ａｅｎ１－３）において、Ｒ１は同一又は異なっていてよく、同一であることが好ましい。また、式（Ａｅｎ１－３）においては、Ｒ１はメチル基又はエチル基であることが好ましく、また、Ｒ２は、メチレン基、ジメチレン基（－ＣＨ２ＣＨ２－）又はトリメチレン基（－ＣＨ２ＣＨ２ＣＨ２－）であることが好ましい。 (wherein R en , R 1 and R 2 are the same as above, and h represents 0 or 1). In formula (A en 1-3), R 1 may be the same or different, preferably the same. In formula (A en 1-3), R 1 is preferably a methyl group or an ethyl group, and R 2 is a methylene group, a dimethylene group (-CH 2 CH 2 -) or a trimethylene group ( -CH 2 CH 2 CH 2 -) is preferred.
　例えば、式（Ａｅｎ１－３）で表される基の中でも、好ましい一例として式（Ａｅｎ１－３’）： For example, among the groups represented by the formula (A en 1-3), a preferred example is the formula (A en 1-3′):
Figure JPOXMLDOC01-appb-C000112
Figure JPOXMLDOC01-appb-C000112
（式中、Ｒｅｎ、Ｒ１、Ｒ２、及びｈは前記に同じ。）で表される基が挙げられる。 (wherein, R en , R 1 , R 2 and h are the same as above).
　また、式（Ａｅｎ１－１）において、ＺＡｅｎ１は、結合手、－Ｏ－、－ＣＯＯ－、－ＣＯＯ－ＣＨ２－、又は－ＺＡｅｎ１ｉ（ＲＡｅｎ１ｃ）（ＲＡｅｎ１ｄ）－で表される２価の基を示す。ここで、ＺＡｅｎ１が－ＺＡｅｎ１ｉ（ＲＡｅｎ１ｃ）（ＲＡｅｎ１ｄ）－である場合は、式（Ａｅｎ１－１）で表される化合物は、式（Ａｅｎ１ｉ－１）： In formula (A en 1-1), Z Aen1 is a bond, -O-, -COO-, -COO-CH 2 -, or -Z Aen1i (R Aen1c )(R Aen1d )-. indicates a divalent group. Here, when Z Aen1 is -Z Aen1i (R Aen1c )(R Aen1d )-, the compound represented by formula (A en 1-1) is represented by formula (A en 1i-1):
Figure JPOXMLDOC01-appb-C000113
Figure JPOXMLDOC01-appb-C000113
で表される化合物である。式（Ａｅｎ１ｉ－１）において、ＲＡｅｎ１ａ及びＲＡｅｎ１ｂは前記に同じであり、ＲＡｅｎ１ｃ及びＲＡｅｎ１ｄは、同一又は異なって、水素原子、又は式（Ａｅｎ１）で表される基、若しくは式（Ａｅｎ１－３）で表される基を示す。式（Ａｅｎ１ｉ－１）において、好ましくは、ＲＡｅｎ１ａ、ＲＡｅｎ１ｂ、ＲＡｅｎ１ｃ、及びＲＡｅｎ１ｄはいずれも同じ基を示すか、ＲＡｅｎ１ａ、ＲＡｅｎ１ｂ、及びＲＡｅｎ１ｃはいずれも同じ基を示しＲＡｅｎ１ｄは水素原子を示すか、あるいは、ＲＡｅｎ１ａ及びＲＡｅｎ１ｂはいずれも同じ基を示しＲＡｅｎ１ｃ及びＲＡｅｎ１ｄはいずれも水素原子を示す。 It is a compound represented by In formula (A en 1i-1), R Aen1a and R Aen1b are the same as above, and R Aen1c and R Aen1d are the same or different and are a hydrogen atom or a group represented by formula (A en 1); or a group represented by formula (A en 1-3). In formula (A en 1i-1), R Aen1a , R Aen1b , R Aen1c and R Aen1d preferably all represent the same group, or R Aen1a , R Aen1b and R Aen1c all represent the same group. Either R Aen1d represents a hydrogen atom, or both R Aen1a and R Aen1b represent the same group and both R Aen1c and R Aen1d represent a hydrogen atom.
　また、式（Ａｅｎ１ｉ－１）において、ＺＡｅｎ１ｉは、上記式（１’）で表される４価の基、又は上記式（１’－１）で表される４価の基を示す。中でも、ＺＡｅｎ１ｉは、 In the formula (A en 1i-1), Z Aen1i represents a tetravalent group represented by the above formula (1′) or a tetravalent group represented by the above formula (1′-1). . Among them, Z Aen1i
Figure JPOXMLDOC01-appb-C000114
Figure JPOXMLDOC01-appb-C000114
又は or
Figure JPOXMLDOC01-appb-C000115
Figure JPOXMLDOC01-appb-C000115
で表される基、あるいは上記式（１’－１）で表される４価の基であることが好ましい。 or a tetravalent group represented by the above formula (1'-1).
　特に、ＺＡｅｎ１ｉが上記式（１’）で表される４価の基であるときは、ＲＡｅｎ１ａ、ＲＡｅｎ１ｂ、及びＲＡｅｎ１ｃはいずれも同じ基を示しＲＡｅｎ１ｄは水素原子を示す場合は、ＺＡｅｎ１ｉは、以下のいずれかの基： In particular, when Z Aen1i is a tetravalent group represented by formula (1′) above, and R Aen1a , R Aen1b and R Aen1c all represent the same group and R Aen1d represents a hydrogen atom, Z Aenli is any of the following groups:
Figure JPOXMLDOC01-appb-C000116
Figure JPOXMLDOC01-appb-C000116
であることが好ましく、ＲＡｅｎ１ａ及びＲＡｅｎ１ｂはいずれも同じ基を示しＲＡｅｎ１ｃ及びＲＡｅｎ１ｄはいずれも水素原子を示す場合は、ＺＡｅｎ１ｉは、以下のいずれかの基： and when both R Aen1a and R Aen1b represent the same group and both R Aen1c and R Aen1d represent a hydrogen atom, Z Aen1i is any of the following groups:
Figure JPOXMLDOC01-appb-C000117
Figure JPOXMLDOC01-appb-C000117
であることが好ましい。また、ＺＡｅｎ１ｉが上記式（１’）で表される４価の基であるときは、式（Ａｅｎ１－３）で表される基においてｈは１であることが好ましい。 is preferred. When Z Aen1i is a tetravalent group represented by formula (1′) above, h is preferably 1 in the group represented by formula (A en 1-3).
　また、ＺＡｅｎ１ｉが上記式（１’－１）で表される４価の基であるときは、ＲＡｅｎ１ａ、ＲＡｅｎ１ｂ、ＲＡｅｎ１ｃ及びＲＡｅｎ１ｄは、いずれも同じ基であることが好ましく、いずれも式（Ａｅｎ１－３）で表される基であってｈが０である基であることがより好ましい。 Further, when Z Aen1i is a tetravalent group represented by the above formula (1′-1), R Aen1a , R Aen1b , R Aen1c and R Aen1d are preferably the same group, any is more preferably a group represented by formula (A en 1-3) and h is 0.
　式（Ａｅｎ２）の基を有する化合物としては、例えば式（Ａｅｎ２－１）： Examples of compounds having a group of formula (A en 2) include formula (A en 2-1):
Figure JPOXMLDOC01-appb-C000118
Figure JPOXMLDOC01-appb-C000118
（式中、Ｒ１は、前記に同じであり、ｑは同一又は異なって０～５の整数（０、１、２、３、４、又は５）であり、ｒは同一又は異なって０又は１の整数であり、ｓは１～３の整数（１、２、又は３）であり、Ｒｅｎは上記に同じ。但し、ＯＨ基及びＯＲｅｎ基が結合するシクロヘキサン環においては、ｒは０を示す。）で表される化合物が挙げられる。中でも、式（Ａｅｎ２ｉ－１）： (wherein R 1 is the same as above, q is the same or different and is an integer of 0 to 5 (0, 1, 2, 3, 4, or 5), r is the same or different and is 0 or is an integer of 1, s is an integer of 1 to 3 (1, 2, or 3), and R en is the same as above, provided that in the cyclohexane ring to which the OH group and the OR en group are bonded, r is 0 is shown.). Among others, the formula (A en 2i-1):
Figure JPOXMLDOC01-appb-C000119
Figure JPOXMLDOC01-appb-C000119
（式中、Ｒｅｎ、ｒ及びｓは前記に同じ。但し、ＯＨ基及びＯＲｅｎ基が結合するシクロヘキサン環においては、ｒは０を示す。）で表される化合物が好ましい。なお、式（Ａｅｎ２－１）又は式（Ａｅｎ２ｉ－１）で表される化合物において、Ｒｅｎは同一又は異なってよく、同一であることが好ましい。 (In the formula, R en , r and s are the same as above. However, in the cyclohexane ring to which the OH group and the OR en group are bonded, r is 0.) is preferred. In the compound represented by formula (A en 2-1) or formula (A en 2i-1), R en may be the same or different, and are preferably the same.
　なお、式（Ａｅｎ２－１）又は式（Ａｅｎ２ｉ－１）で表される化合物であって、ＯＨ基及びＯＲｅｎ基が結合するシクロヘキサン環においてｒは１を示す化合物は、式（Ａｅｎ２）の基を有する化合物ではないが、ヒドロキシ基含有化合物としては好ましく用いることができる。 The compound represented by the formula (A en 2-1) or the formula (A en 2i-1), wherein r is 1 in the cyclohexane ring to which the OH group and the OR en group are bonded, has the formula ( Although it is not a compound having a group of A en 2), it can be preferably used as a hydroxy group-containing compound.
　また、式（Ａｅｎ２）の基を有する化合物としては、例えば、式（Ａｅｎ２－２）： Further, compounds having a group of formula (A en 2) include, for example, formula (A en 2-2):
Figure JPOXMLDOC01-appb-C000120
Figure JPOXMLDOC01-appb-C000120
（式中、Ｒｅｎは上記に同じ）で表される化合物も好ましい。なお、式（Ａｅｎ２－２）で表される化合物において、Ｒｅｎは同一又は異なってよく、同一であることが好ましい。 (wherein R en is the same as above) is also preferred. In the compound represented by formula (A en 2-2), R en may be the same or different, and are preferably the same.
　式（Ａｅｎ３）の基を有する化合物としては、例えば式（Ａｅｎ３－１）： Compounds having a group of formula (A en 3) include, for example, formula (A en 3-1):
Figure JPOXMLDOC01-appb-C000121
Figure JPOXMLDOC01-appb-C000121
（式中、Ｘ１環及びＸ２環、Ｙ、並びにＲｅｎ及びＲ２は、前記に同じ。）で表される化合物が好ましい。ｉは０、１、２、３、又は４を示し、ｊは０～１０の整数（１、２、３、４、５、６、７、８、９、又は１０）を示す。また、当該式において、Ｒ２は同一又は異なってよい。また、当該式において、Ｒｅｎは、上述したように、Ｏに結合している側を＊で表すと (wherein, ring X1 and ring X2 , Y, and R en and R 2 are the same as above) are preferred. i represents 0, 1, 2, 3, or 4, and j represents an integer from 0 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10). Also, in the formula, R 2 may be the same or different. Further, in the formula, as described above, when the side of R en that is bonded to O is represented by *
Figure JPOXMLDOC01-appb-C000122
Figure JPOXMLDOC01-appb-C000122
と表される。言い換えれば、当該式で波線で表される側にＲ２が結合している。なお、式（Ａｅｎ３－１）で表される化合物において、Ｒｅｎは同一又は異なってよく、同一であることが好ましい。 is represented. In other words, R 2 is bound to the side represented by the dashed line in the formula. In the compound represented by formula (A en 3-1), R en may be the same or different, and are preferably the same.
　式（Ａｅｎ４）の基を有する化合物としては、例えば式（Ａｅｎ４－１）： Compounds having a group of formula (A en 4) include, for example, formula (A en 4-1):
Figure JPOXMLDOC01-appb-C000123
Figure JPOXMLDOC01-appb-C000123
（式中、Ｘ１環及びＸ２環、Ｙ、Ｒｅｎ、Ｒ２、並びにｉ及びｊは、前記に同じ。）で表される化合物が好ましい。また、当該式において、Ｒ２は同一又は異なってよい。また、Ｒｅｎは同一又は異なってよく、同一であることが好ましい。 (Wherein, X 1 ring and X 2 ring, Y, R en , R 2 , and i and j are the same as defined above) are preferred. Also, in the formula, R 2 may be the same or different. Moreover, R en may be the same or different, and are preferably the same.
　当該化合物において、Ｙは結合手であることが好ましい。また、Ｘ１環及びＸ２環はいずれもベンゼン環であることが好ましい。また、Ｒ２は、メチレン基、ジメチレン基（－ＣＨ２ＣＨ２－）、又はトリメチレン基（－ＣＨ２ＣＨ２ＣＨ２－）、であることが好ましい。また、Ｒ２は、同一であることが好ましい。 In the compound, Y is preferably a bond. Moreover, both the X 1 ring and the X 2 ring are preferably benzene rings. Also, R 2 is preferably a methylene group, a dimethylene group (--CH 2 CH 2 --), or a trimethylene group (--CH 2 CH 2 CH 2 --). Also, R 2 is preferably the same.
　中でも、式（Ａｅｎ４ｉ－１）： Among others, the formula (A en 4i-1):
Figure JPOXMLDOC01-appb-C000124
Figure JPOXMLDOC01-appb-C000124
（ｉ及びｊは前記に同じ。）で表される化合物が好ましい。また、ｉが０のとき、ｊは０～６であることがより好ましく、０～４であることがさらに好ましい。また、ｉが1以上（例えば１～４）のとき、ｊは１～８であることがより好ましく、１～６であることがさらに好ましい。 (i and j are the same as above) are preferred. Further, when i is 0, j is more preferably 0-6, more preferably 0-4. Further, when i is 1 or more (eg, 1 to 4), j is more preferably 1 to 8, more preferably 1 to 6.
　当該好ましい化合物の代表例を、より具体的に記載すると、式（Ａ１）： A more specific representative example of the preferred compound is the formula (A1):
Figure JPOXMLDOC01-appb-C000125
Figure JPOXMLDOC01-appb-C000125
（ただし、式中のシクロヘキサン環において、ＯＨ基が結合する炭素原子と、置換基Ｒ３を有していてもよいフェノキシ基が結合する炭素原子とは、結合している）で表される基、
若しくは式（Ａ２）： (However, in the cyclohexane ring in the formula, the carbon atom to which the OH group is bonded and the carbon atom to which the phenoxy group optionally having a substituent R3 is bonded are bonded) group represented by ,
Or formula (A2):
Figure JPOXMLDOC01-appb-C000126
Figure JPOXMLDOC01-appb-C000126
（ただし、式中のシクロヘキサン環においてＯＨ基が結合する炭素原子と、置換基Ｒ３を有していてもよいフェノキシ基が結合する炭素原子とは、結合している）で表される基、若しくは式（Ａ３）： (wherein the carbon atom to which the OH group is bonded in the cyclohexane ring in the formula and the carbon atom to which the phenoxy group optionally having a substituent R3 is bonded are bonded) group represented by Or formula (A3):
Figure JPOXMLDOC01-appb-C000127
Figure JPOXMLDOC01-appb-C000127
で表される基、
若しくは式（Ａ４）： A group represented by
Or formula (A4):
Figure JPOXMLDOC01-appb-C000128
Figure JPOXMLDOC01-appb-C000128
で表される基、
を有する化合物がより好ましく挙げられる。 A group represented by
More preferably, a compound having
　式（Ａ１）の基を有する化合物としては、例えば式（Ａ１－１）： Examples of compounds having a group of formula (A1) include formula (A1-1):
Figure JPOXMLDOC01-appb-C000129
Figure JPOXMLDOC01-appb-C000129
で表される化合物が挙げられる。　式（Ａ１－１）において、ＲＡ１ａ及びＲＡ１ｂは、同一又は異なって（同一であることが好ましい）、式（Ａ１）で表される基、又は式（Ａ１－３）： The compound represented by is mentioned. In formula (A1-1), R A1a and R A1b are the same or different (preferably the same), a group represented by formula (A1), or formula (A1-3):
Figure JPOXMLDOC01-appb-C000130
Figure JPOXMLDOC01-appb-C000130
（式中、Ｒ１及びＲ２は前記に同じであり、ｈは０又は１を示す。Ｒ３及びｎも前記に同じである。）で表される基を示す。式（Ａ１－３）において、Ｒ１は同一又は異なっていてよく、同一であることが好ましい。また、式（Ａ１－３）においては、Ｒ１はメチル基又はエチル基であることが好ましく、また、Ｒ２は、メチレン基、ジメチレン基（－ＣＨ２ＣＨ２－）又はトリメチレン基（－ＣＨ２ＣＨ２ＣＨ２－）であることが好ましい。 (wherein R 1 and R 2 are the same as above, h represents 0 or 1, and R 3 and n are also the same as above). In formula (A1-3), R 1 may be the same or different, preferably the same. In formula (A1-3), R 1 is preferably a methyl group or an ethyl group, and R 2 is a methylene group, a dimethylene group (--CH 2 CH 2 --) or a trimethylene group (--CH 2 CH 2 CH 2 —).
　例えば、式（Ａ１－３）で表される基の中でも、好ましい一例として式（Ａ１－３’）： For example, among the groups represented by formula (A1-3), a preferred example is formula (A1-3'):
Figure JPOXMLDOC01-appb-C000131
Figure JPOXMLDOC01-appb-C000131
（式中、Ｒ１、Ｒ２、及びｈは前記に同じ。）で表される基が挙げられる。 (wherein R 1 , R 2 and h are the same as above).
　また、式（Ａ１－１）において、ＺＡ１は、結合手、－Ｏ－、－ＣＯＯ－、－ＣＯＯ－ＣＨ２－、又は－ＺＡ１ｉ（ＲＡ１ｃ）（ＲＡ１ｄ）－で表される２価の基を示す。ここで、ＺＡ１が－ＺＡ１ｉ（ＲＡ１ｃ）（ＲＡ１ｄ）－である場合は、式（Ａ１－１）で表される化合物は、式（Ａ１ｉ－１）： In formula (A1-1), Z A1 is a bond, —O—, —COO—, —COO—CH 2 —, or —Z A1i (R A1c )(R A1d )—2 indicates a valence group. Here, when Z A1 is -Z A1i (R A1c )(R A1d )-, the compound represented by formula (A1-1) is represented by formula (A1i-1):
Figure JPOXMLDOC01-appb-C000132
Figure JPOXMLDOC01-appb-C000132
で表される化合物である。式（Ａ１ｉ－１）において、ＲＡ１ａ及びＲＡ１ｂは前記に同じであり、ＲＡ１ｃ及びＲＡ１ｄは、同一又は異なって、水素原子、又は式（Ａ１）で表される基、若しくは式（Ａ１－３）で表される基を示す。式（Ａ１ｉ－１）において、好ましくは、ＲＡ１ａ、ＲＡ１ｂ、ＲＡ１ｃ、及びＲＡ１ｄはいずれも同じ基を示すか、ＲＡ１ａ、ＲＡ１ｂ、及びＲＡ１ｃはいずれも同じ基を示しＲＡ１ｄは水素原子を示すか、あるいは、ＲＡ１ａ及びＲＡ１ｂはいずれも同じ基を示しＲＡ１ｃ及びＲＡ１ｄはいずれも水素原子を示す。 It is a compound represented by In formula (A1i-1), R A1a and R A1b are the same as above, R A1c and R A1d are the same or different and are a hydrogen atom, a group represented by formula (A1), or a group represented by formula (A1) -3) represents a group. In formula (A1i-1), R A1a , R A1b , R A1c and R A1d preferably all represent the same group, or R A1a , R A1b and R A1c all represent the same group and R A1d represents a hydrogen atom, or both R A1a and R A1b represent the same group and both R A1c and R A1d represent a hydrogen atom.
　また、式（Ａ１ｉ－１）において、ＺＡ１ｉは、上記式（１’）で表される４価の基、又は上記式（１’－１）で表される４価の基を示す。中でも、ＺＡ１ｉは、 In formula (A1i-1), Z A1i represents a tetravalent group represented by formula (1′) above or a tetravalent group represented by formula (1′-1) above. Among them, Z A1i
Figure JPOXMLDOC01-appb-C000133
Figure JPOXMLDOC01-appb-C000133
又は or
Figure JPOXMLDOC01-appb-C000134
Figure JPOXMLDOC01-appb-C000134
で表される基、あるいは上記式（１’－１）で表される４価の基であることが好ましい。 or a tetravalent group represented by the above formula (1'-1).
　特に、ＺＡ１ｉが上記式（１’）で表される４価の基であるときは、ＲＡ１ａ、ＲＡ１ｂ、及びＲＡ１ｃはいずれも同じ基を示しＲＡ１ｄは水素原子を示す場合は、ＺＡ１ｉは、以下のいずれかの基： In particular, when Z A1i is a tetravalent group represented by formula (1′) above, and R A1a , R A1b and R A1c all represent the same group and R A1d represents a hydrogen atom, Z A1i is any of the following groups:
Figure JPOXMLDOC01-appb-C000135
Figure JPOXMLDOC01-appb-C000135
であることが好ましく、ＲＡ１ａ及びＲＡ１ｂはいずれも同じ基を示しＲＡ１ｃ及びＲＡ１ｄはいずれも水素原子を示す場合は、ＺＡ１ｉは、以下のいずれかの基： and when both R A1a and R A1b represent the same group and both R A1c and R A1d represent a hydrogen atom, Z A1i is any of the following groups:
Figure JPOXMLDOC01-appb-C000136
Figure JPOXMLDOC01-appb-C000136
であることが好ましい。また、ＺＡ１ｉが上記式（１’）で表される４価の基であるときは、式（Ａ１－３）で表される基においてｈは１であることが好ましい。 is preferably Further, when Z A1i is a tetravalent group represented by formula (1′) above, h is preferably 1 in the group represented by formula (A1-3).
　また、ＺＡ１ｉが上記式（１’－１）で表される４価の基であるときは、ＲＡ１ａ、ＲＡ１ｂ、ＲＡ１ｃ及びＲＡ１ｄは、いずれも同じ基であることが好ましく、いずれも式（Ａ１－３）で表される基であってｈが０である基であることがより好ましい。 Further, when Z A1i is a tetravalent group represented by the above formula (1′-1), R A1a , R A1b , R A1c and R A1d are preferably the same group, and any is more preferably a group represented by formula (A1-3) in which h is 0.
　式（Ａ２）の基を有する化合物としては、例えば式（Ａ２－１）： Examples of compounds having a group of formula (A2) include formula (A2-1):
Figure JPOXMLDOC01-appb-C000137
Figure JPOXMLDOC01-appb-C000137
（式中、Ｒ１は、前記に同じであり、ｑは同一又は異なって０～５の整数であり、ｒは同一又は異なって０又は１の整数であり、ｓは１～３の整数である。但し、ＯＨ基及びフェノキシ基が結合するシクロヘキサン環においては、ｒは０を示す。）で表される化合物が挙げられる。中でも、式（Ａ２ｉ－１）： (wherein R 1 is the same as above, q is the same or different and is an integer of 0 to 5, r is the same or different and is an integer of 0 or 1, s is an integer of 1 to 3, However, in the cyclohexane ring to which the OH group and the phenoxy group are bonded, r represents 0.). Among them, formula (A2i-1):
Figure JPOXMLDOC01-appb-C000138
Figure JPOXMLDOC01-appb-C000138
（式中、ｒ及びｓは前記に同じ。但し、ＯＨ基及びフェノキシ基が結合するシクロヘキサン環においては、ｒは０を示す。）で表される化合物が好ましい。 (In the formula, r and s are the same as above. However, in the cyclohexane ring to which the OH group and the phenoxy group are bonded, r is 0.) is preferred.
　なお、式（Ａ２－１）又は式（Ａ２ｉ－１）で表される化合物であって、ＯＨ基及びフェノキシ基が結合するシクロヘキサン環においてｒは１を示す化合物は、式（Ａ２）の基を有する化合物ではないが、ヒドロキシ基含有化合物としては好ましく用いることができる。 The compound represented by formula (A2-1) or formula (A2i-1), wherein r is 1 in the cyclohexane ring to which the OH group and the phenoxy group are bonded, has the group of formula (A2) Although it is not a compound having a hydroxy group, it can be preferably used as a hydroxy group-containing compound.
式（Ａ２）の基を有する化合物としては、例えば式（Ａ２－２）： Examples of compounds having a group of formula (A2) include formula (A2-2):
Figure JPOXMLDOC01-appb-C000139
Figure JPOXMLDOC01-appb-C000139
で表される化合物も好ましい。 Compounds represented by are also preferred.
　式（Ａ３）の基を有する化合物としては、例えば式（Ａ３－１）： Examples of compounds having a group of formula (A3) include formula (A3-1):
Figure JPOXMLDOC01-appb-C000140
Figure JPOXMLDOC01-appb-C000140
（式中、Ｘ１環及びＸ２環、Ｙ、並びにＲ２は、前記に同じ。）で表される化合物が好ましい。ｉは０、１、２、３、又は４を示し、ｊは０～１０の整数（１、２、３、４、５、６、７、８、９、又は１０）を示す。また、当該式において、Ｒ２は同一又は異なってよい。 (In the formula, X 1 ring and X 2 ring, Y and R 2 are the same as above.) is preferred. i represents 0, 1, 2, 3, or 4, and j represents an integer from 0 to 10 (1, 2, 3, 4, 5, 6, 7, 8, 9, or 10). Also, in the formula, R 2 may be the same or different.
　当該化合物において、Ｙは結合手であることが好ましい。また、Ｘ１環及びＸ２環はいずれもベンゼン環であることが好ましい。また、Ｒ２は、メチレン基、ジメチレン基（－ＣＨ２ＣＨ２－）、又はトリメチレン基（－ＣＨ２ＣＨ２ＣＨ２－）、であることが好ましい。また、Ｒ２は、同一であることが好ましい。 In the compound, Y is preferably a bond. Moreover, both the X 1 ring and the X 2 ring are preferably benzene rings. Also, R 2 is preferably a methylene group, a dimethylene group (--CH 2 CH 2 --), or a trimethylene group (--CH 2 CH 2 CH 2 --). Also, R 2 is preferably the same.
　中でも、式（Ａ３ｉ－１）： Among them, formula (A3i-1):
Figure JPOXMLDOC01-appb-C000141
Figure JPOXMLDOC01-appb-C000141
（ｉ及びｊは前記に同じ。）で表される化合物が好ましい。なお、ｉが０又は１であることが特に好ましい。また、ｉが０のとき、ｊは０～６であることがより好ましく、０～４であることがさらに好ましい。また、ｉが1以上（例えば１～４）のとき、ｊは１～８であることがより好ましく、１～６であることがさらに好ましい。 (i and j are the same as above) are preferred. In addition, it is particularly preferable that i is 0 or 1. Further, when i is 0, j is more preferably 0-6, more preferably 0-4. Further, when i is 1 or more (eg, 1 to 4), j is more preferably 1 to 8, more preferably 1 to 6.
　式（Ａ４）の基を有する化合物としては、例えば式（Ａ４－１）： Examples of compounds having a group of formula (A4) include formula (A4-1):
Figure JPOXMLDOC01-appb-C000142
Figure JPOXMLDOC01-appb-C000142
（式中、Ｘ１環及びＸ２環、Ｙ、Ｒ２、並びにｉ及びｊは、前記に同じ。）で表される化合物が好ましい。また、当該式において、Ｒ２は同一又は異なってよい。 (In the formula, X 1 ring and X 2 ring, Y, R 2 , and i and j are the same as above) are preferred. Also, in the formula, R 2 may be the same or different.
　当該化合物において、Ｙは結合手であることが好ましい。また、Ｘ１環及びＸ２環はいずれもベンゼン環であることが好ましい。また、Ｒ２は、メチレン基、ジメチレン基（－ＣＨ２ＣＨ２－）、又はトリメチレン基（－ＣＨ２ＣＨ２ＣＨ２－）、であることが好ましい。また、Ｒ２は、同一であることが好ましい。 In the compound, Y is preferably a bond. Moreover, both the X 1 ring and the X 2 ring are preferably benzene rings. Also, R 2 is preferably a methylene group, a dimethylene group (--CH 2 CH 2 --), or a trimethylene group (--CH 2 CH 2 CH 2 --). Also, R 2 is preferably the same.
　中でも、式（Ａ４ｉ－１）： Among them, formula (A4i-1):
Figure JPOXMLDOC01-appb-C000143
Figure JPOXMLDOC01-appb-C000143
（ｉ及びｊは前記に同じ。）で表される化合物が好ましい。また、ｉが０のとき、ｊは０～６であることがより好ましく、０～４であることがさらに好ましい。また、ｉが1以上（例えば１～４）のとき、ｊは１～８であることがより好ましく、１～６であることがさらに好ましい。 (i and j are the same as above) are preferred. Further, when i is 0, j is more preferably 0-6, more preferably 0-4. Further, when i is 1 or more (eg, 1 to 4), j is more preferably 1 to 8, more preferably 1 to 6.
　また、次の化合物も好ましいヒドロキシ基含有化合物の例として挙げられる。 In addition, the following compounds are also examples of preferred hydroxy group-containing compounds.
Figure JPOXMLDOC01-appb-C000144
Figure JPOXMLDOC01-appb-C000144
（式中、ｒは同一又は異なって０又は１の整数であり、ｓ’は０～２の整数である。）で表される化合物が挙げられる。 (wherein r is the same or different and is an integer of 0 or 1, and s' is an integer of 0 to 2).
　また、ヒドロキシ基含有化合物としては、エポキシ樹脂と硬化剤を反応させた化合物を用いることができる。当該反応化合物を得るための前記エポキシ樹脂としては、上記した（Ｂ）エポキシ樹脂として挙げたエポキシ樹脂を用いることができる。また、当該反応化合物を得るための硬化剤としては、上記した（Ｃ）硬化剤として挙げた硬化剤を用いることがでる。ヒドロキシ基含有化合物として、上記（Ｂ）と上記（Ｃ）とを反応させた化合物を用いることもできる。また、当該反応化合物としては、（β）脂環式エポキシ樹脂及びグリシジル基を有するエポキシ樹脂からなる群より選択される少なくとも１種のエポキシ樹脂と、（γ）フェノール、クレゾール、ハイドロキノン、レゾルシン、ｐ－プロピルフェノール、ノニルフェノール等の置換フェノール類、１－ナフトール、２－ナフトール、１，２－ナフタレンジオール、１－メチル－２－ナフトール、６－ｔｅｒｔ－ブチル－２－ナフトール等の置換ナフトール類、ノボラック型フェノール樹脂、レゾール型フェノール樹脂、アラルキル型フェノール樹脂等のフェノール樹脂等からなる群より選択される少なくとも１種の硬化剤と、を反応させた化合物が好ましい。なお、（γ）の硬化剤としては、中でも、フェノール、ナフトール（１－ナフトール、２－ナフトール）、及び上記式（Ｋ）で表される化合物からなる群より選択される少なくとも１種の硬化剤が好ましい。 Also, as the hydroxy group-containing compound, a compound obtained by reacting an epoxy resin and a curing agent can be used. As the epoxy resin for obtaining the reaction compound, the epoxy resins exemplified as the (B) epoxy resin can be used. Moreover, as a curing agent for obtaining the reaction compound, the curing agent mentioned above as the curing agent (C) can be used. A compound obtained by reacting the above (B) with the above (C) can also be used as the hydroxy group-containing compound. In addition, as the reaction compound, (β) at least one epoxy resin selected from the group consisting of alicyclic epoxy resins and epoxy resins having a glycidyl group, and (γ) phenol, cresol, hydroquinone, resorcin, p -substituted phenols such as propylphenol and nonylphenol, substituted naphthols such as 1-naphthol, 2-naphthol, 1,2-naphthalenediol, 1-methyl-2-naphthol and 6-tert-butyl-2-naphthol, novolac A compound obtained by reacting with at least one curing agent selected from the group consisting of phenolic resins such as phenolic resins, resol phenolic resins, and aralkyl phenolic resins is preferred. The curing agent (γ) is, among others, at least one curing agent selected from the group consisting of phenol, naphthol (1-naphthol, 2-naphthol), and compounds represented by the above formula (K). is preferred.
　（β）のエポキシ樹脂が有するエポキシ基（脂環式エポキシ基を含む）を上記式（４）で表すこととし、便宜上ｎ＝０の場合を選択して以下の説明に用いる。（ｎが１、２、又は３の場合も以下の説明は妥当する。）式（４）でｎ＝０の場合を式（４’）：  The epoxy group (including the alicyclic epoxy group) of the epoxy resin (β) is represented by the above formula (4), and for the sake of convenience, the case of n = 0 is selected and used in the following description. (The following explanation is also valid when n is 1, 2, or 3.) Equation (4') when n = 0 in equation (4):
Figure JPOXMLDOC01-appb-C000145
Figure JPOXMLDOC01-appb-C000145
で表す。（γ）の硬化剤は、いずれもＯＨ基を含有する。ここで説明の便宜上（γ）の硬化剤をＲ－ＯＨと表す。上で挙げた具体的な（γ）の硬化剤の化合物から理解出来るように、Ｒ－ＯＨのＯＨ基はベンゼン環又はナフタレン環の水素原子に置換した基である。 Represented by All of the (γ) curing agents contain OH groups. Here, for convenience of explanation, the curing agent (γ) is expressed as R—OH. As can be understood from the above specific curing agent compounds (γ), the OH group of R—OH is a group substituted with a hydrogen atom of a benzene ring or a naphthalene ring.
　そうすると、（β）のエポキシ樹脂と（γ）の硬化剤とが反応すると、（β）のエポキシ基が開環して（γ）のＯＨ基部分と繋がった、次式で表される構造が生じると推測される。 Then, when the epoxy resin (β) reacts with the curing agent (γ), the epoxy group of (β) is ring-opened and connected to the OH group portion of (γ), resulting in a structure represented by the following formula. presumed to occur.
Figure JPOXMLDOC01-appb-C000146
Figure JPOXMLDOC01-appb-C000146
　当該構造から理解できるように、エポキシ基が開環して新たなＯＨ基を生じる。さらには、（γ）Ｒ－ＯＨのＯＨ基はベンゼン環又はナフタレン環の水素原子に置換した基であったことから、当該構造は、上記式： As can be understood from the structure, the epoxy group is ring-opened to generate a new OH group. Furthermore, since the OH group of (γ) R—OH was a group substituted with a hydrogen atom of a benzene ring or a naphthalene ring, the structure is represented by the above formula:
Figure JPOXMLDOC01-appb-C000147
Figure JPOXMLDOC01-appb-C000147
で表す構造に包含される。 is included in the structure represented by
　以上のことから、（β）のエポキシ樹脂と（γ）の硬化剤との反応化合物は、好ましく（Ａ）ヒドロキシ基含有化合物として用い得ることが理解できる。 From the above, it can be understood that the reaction compound of (β) the epoxy resin and (γ) the curing agent can be preferably used as (A) the hydroxy group-containing compound.
　（β）のエポキシ樹脂と（γ）の硬化剤との反応は、例えば触媒の存在下、溶媒の存在下又は非存在下で実施することができる。当該反応に用いられる触媒は、公知の触媒でよく、例えば、２－メチルイミダゾール、２－エチルイミダゾール、２－フェニルイミダゾール、２－エチル－４－メチルイミダゾール、１，２－ジメチルイミダゾール、１－ベンジル－２－メチルイミダゾール、１－（２－シアノエチル）－２－エチル－４－メチルイミダゾール、２－ウンデシルイミダゾール等のイミダゾール類；２－メチル－イミダゾリン、２－フェニルイミダゾリン等のイミダゾリン誘導体類；２－（ジメチルアミノメチル）フェノール、トリエチレンジアミン、トリエタノールアミン、ピリジン、４－ジメチルアミノピリジン、１，４－ジアザビシクロ［２．２．２］オクタン、１，８－ジアザビシクロ（５，４，０）ウンデセン－７、１，５－ジアザビシクロ（４，３，０）－ノネン－５）、１，８－ビス（ジメチルアミノ）ナフタレン、１，１，３，３－テトラメチルグアニジン、７－メチル－１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン、１，５，７－トリアザビシクロ［４．４．０］デカ－５－エン等の第３級アミン類；トリフェニルホスフィン、ジフェニルホスフィン、トリブチルホスフィン等の有機ホスフィン類；オクチル酸スズなどの金属化合物；エチルトリフェニルホスホニウムブロミド、テトラフェニルホスホニウムテトラフェニルボレート等のホスホニウム塩類などが挙げられる。なお触媒は、単独で又は２種以上を組み合わせて用いることができる。触媒の使用量は、触媒としての有効量でよく、例えば、（β）と（γ）との合計量１００質量部に対して ０．０１～２０質量部、好ましくは０．１～５質量部である。また、反応温度は、通常６０℃～２００℃、好ましくは１００℃～１８０℃であり、反応時間は、通常１０分～２時間程度である。 The reaction between the epoxy resin (β) and the curing agent (γ) can be carried out in the presence or absence of a solvent, for example, in the presence of a catalyst. The catalyst used for the reaction may be a known catalyst such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 1-benzyl -imidazoles such as 2-methylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole and 2-undecylimidazole; imidazoline derivatives such as 2-methyl-imidazoline and 2-phenylimidazoline;2 -(dimethylaminomethyl)phenol, triethylenediamine, triethanolamine, pyridine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo(5,4,0)undecene -7,1,5-diazabicyclo(4,3,0)-nonene-5), 1,8-bis(dimethylamino)naphthalene, 1,1,3,3-tetramethylguanidine, 7-methyl-1, Tertiary amines such as 5,7-triazabicyclo[4.4.0]dec-5-ene and 1,5,7-triazabicyclo[4.4.0]dec-5-ene; organic phosphines such as phenylphosphine, diphenylphosphine and tributylphosphine; metal compounds such as tin octylate; and phosphonium salts such as ethyltriphenylphosphonium bromide and tetraphenylphosphonium tetraphenylborate. In addition, a catalyst can be used individually or in combination of 2 or more types. The amount of the catalyst used may be an effective amount as a catalyst, for example, 0.01 to 20 parts by mass, preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total amount of (β) and (γ). is. The reaction temperature is generally 60° C. to 200° C., preferably 100° C. to 180° C., and the reaction time is generally about 10 minutes to 2 hours.
　ヒドロキシ基含有化合物は、Ｂステージ化（硬化性樹脂の半硬化状態化）及び硬化時に揮発しにくいという観点から、大気圧条件下において沸点が１８０℃以上であることが好ましく、より好ましくは１９０℃以上であり、さらに好ましくは２００℃以上である。 The hydroxy group-containing compound preferably has a boiling point of 180° C. or higher, more preferably 190° C. under atmospheric pressure conditions, from the viewpoint of B-stage (semi-cured state of the curable resin) and resistance to volatilization during curing. or more, and more preferably 200° C. or more.
　ヒドロキシ基含有化合物は１種単独で又は２種以上を組み合わせて用いることができる。 The hydroxy group-containing compounds can be used singly or in combination of two or more.
　得られる硬化物の誘電特性及び耐熱性を向上させる観点から、ヒドロキシ基含有化合物の水酸基当量は８０～１０００が好ましい。当該範囲の上限又は下限は例えば１００、１２０、１４０、１６０、１８０、２００、２５０、３００、３５０、４００、４５０、５００、５５０、６００、６５０、７００、７５０、８００、８５０、９００，又は９５０であってもよい。当該範囲は、より好ましくは１００～８００であり、更に好ましくは１２０～６００である。 From the viewpoint of improving the dielectric properties and heat resistance of the resulting cured product, the hydroxyl group-containing compound preferably has a hydroxyl group equivalent weight of 80 to 1,000. The upper or lower limit of the range is e.g. may be The range is more preferably 100-800, more preferably 120-600.
　（Ａ）ヒドロキシ基含有化合物の配合量は、エポキシ樹脂組成物に含有される（Ｂ）エポキシ樹脂１００質量部に対して、好ましくは０．１～３０質量部であり、より好ましくは０．５～２５質量部であり、更に好ましくは１．０～２０質量部である。 The amount of (A) the hydroxy group-containing compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 parts by mass, based on 100 parts by mass of the epoxy resin (B) contained in the epoxy resin composition. to 25 parts by mass, more preferably 1.0 to 20 parts by mass.
　本開示のエポキシ樹脂組成物は、効果を損なわない範囲で、必要に応じてフィラー、熱可塑性樹脂、添加剤等を含有してもよい。 The epoxy resin composition of the present disclosure may contain fillers, thermoplastic resins, additives, etc., as necessary, as long as the effects are not impaired.
　前記フィラーとしては、エポキシ樹脂組成物及びその硬化物において必要とされる流動性、耐熱性、低熱膨張性、機械特性、硬度、耐擦傷性、又は接着性などを考慮し、単独で、又は複数種を混合して用いることができる。例えば、シリカ（より具体的には結晶性シリカ、溶融シリカ、球状溶融シリカ等）、酸化チタン、酸化ジルコニウム、酸化亜鉛、酸化スズ、窒化珪素、炭化珪素、窒化ホウ素、炭酸カルシウム、珪酸カルシウム、チタン酸カリウム、窒化アルミニウム、酸化インジウム、アルミナ、酸化アンチモン、酸化セリウム、酸化マグネシウム、酸化鉄、スズドープ酸化インジウム（ＩＴＯ）などの無機化合物が挙げられる。また、金、銀、銅、アルミニウム、ニッケル、鉄、亜鉛、ステンレスなどの金属が挙げられる。また、モンモリロナイト、タルク、マイカ、ベーマイト、カオリン、スメクタイト、ゾノライト、バーキュライト、セリサイトなどの鉱物が挙げられる。その他のフィラーとしては、カーボンブラック、アセチレンブラック、ケッチェンブラック、カーボンナノチューブなどの炭素化合物；水酸化アルミニウム、水酸化マグネシウムなどの金属水酸化物；ガラスビーズ、ガラスフレーク、ガラスバルーンなどの各種ガラスなどを挙げることができる。また、フィラーは粉体をそのまま使用してもよく、樹脂中に分散させたものを用いてもよい。 As the filler, considering the fluidity, heat resistance, low thermal expansion, mechanical properties, hardness, scratch resistance, adhesiveness, etc. required in the epoxy resin composition and its cured product, one or more Mixtures of seeds can be used. For example, silica (more specifically, crystalline silica, fused silica, spherical fused silica, etc.), titanium oxide, zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium carbonate, calcium silicate, titanium inorganic compounds such as potassium oxide, aluminum nitride, indium oxide, alumina, antimony oxide, cerium oxide, magnesium oxide, iron oxide, tin-doped indium oxide (ITO); Metals such as gold, silver, copper, aluminum, nickel, iron, zinc and stainless steel are also included. Also included are minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, xonolite, verculite and sericite. Other fillers include carbon compounds such as carbon black, acetylene black, ketjen black and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; various glasses such as glass beads, glass flakes and glass balloons. can be mentioned. Further, the filler may be used as a powder as it is, or may be used after being dispersed in a resin.
　前記熱可塑性樹脂としては、例えば、ポリオレフィン樹脂、アクリル樹脂、フェノキシ樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリウレタン樹脂、ポリアリレート樹脂、ポリフェニレンエーテル樹脂、ポリアセタール樹脂、フッ素樹脂およびこれらが酸変性されたもの等が挙げられる。本発明にかかるエポキシ樹脂組成物との相溶性、エポキシ樹脂組成物の塗膜性、硬化物の誘電特性が向上する観点から、ポリオレフィン樹脂、アクリル樹脂、フェノキシ樹脂、ポリアリレート樹脂、ポリフェニレンエーテル樹脂、フッ素樹脂およびこれらが酸変性されたものが好ましく、これらの中でもポリオレフィン樹脂、酸変性ポリオレフィン樹脂、フェノキシ樹脂、ポリフェニレンエーテル樹脂、フッ素樹脂がさらに好ましい。 Examples of the thermoplastic resin include polyolefin resins, acrylic resins, phenoxy resins, polyamide resins, polyester resins, polycarbonate resins, polyurethane resins, polyarylate resins, polyphenylene ether resins, polyacetal resins, fluorine resins, and acid-modified resins thereof. things, etc. From the viewpoint of improving the compatibility with the epoxy resin composition according to the present invention, the coating properties of the epoxy resin composition, and the dielectric properties of the cured product, polyolefin resins, acrylic resins, phenoxy resins, polyarylate resins, polyphenylene ether resins, Fluororesins and acid-modified fluororesins are preferred, and among these, polyolefin resins, acid-modified polyolefin resins, phenoxy resins, polyphenylene ether resins, and fluororesins are more preferred.
　前記添加剤としては、例えば、酸化防止剤、無機蛍光体、滑剤、紫外線吸収剤、熱光安定剤、帯電防止剤、重合禁止剤、消泡剤、溶剤、老化防止剤、接着性改良剤、難燃剤、界面活性剤、保存安定性改良剤、オゾン老化防止剤、増粘剤、可塑剤、放射線遮断剤、核剤、カップリング剤、導電性付与剤、リン系過酸化物分解剤、顔料、金属不活性化剤、物性調整剤等が挙げられる。 Examples of the additives include antioxidants, inorganic phosphors, lubricants, ultraviolet absorbers, heat and light stabilizers, antistatic agents, polymerization inhibitors, antifoaming agents, solvents, anti-aging agents, adhesion improvers, Flame retardant, surfactant, storage stability improver, antiozonant, thickener, plasticizer, radiation shielding agent, nucleating agent, coupling agent, conductivity imparting agent, phosphorus peroxide decomposer, pigment , metal deactivators, physical property modifiers, and the like.
　本開示のエポキシ樹脂組成物は、上記（Ａ）～（Ｄ）、並びに、必要に応じて他の成分を、混合することにより製造することができる。混合方法は、均一に混合できる方法であれば特に限定はない。本発明のエポキシ樹脂組成物には、必要に応じ、本発明の効果に悪影響を与えない範囲で溶剤（例えば、トルエン、キシレン、メチルエチルケトン、アセトン、シクロヘキサノン、メチルシクロヘキサン、シクロヘキサン等）を添加してもよい。 The epoxy resin composition of the present disclosure can be produced by mixing the above (A) to (D) and, if necessary, other components. The mixing method is not particularly limited as long as it is a method that enables uniform mixing. A solvent (e.g., toluene, xylene, methyl ethyl ketone, acetone, cyclohexanone, methylcyclohexane, cyclohexane, etc.) may be optionally added to the epoxy resin composition of the present invention within a range that does not adversely affect the effects of the present invention. good.
　本開示のエポキシ樹脂組成物は、フィルム状に成形したＢステージフィルムの工程を経て硬化物にしてもよいし、Ｂステージフィルムの工程を経ることなく硬化物としてもよい。 The epoxy resin composition of the present disclosure may be made into a cured product through the process of forming a B-stage film into a film, or may be made into a cured product without going through the process of forming a B-stage film.
　エポキシ樹脂組成物のＢステージフィルムを得る方法としては、例えば前記溶剤にエポキシ樹脂組成物を溶解した樹脂ワニスを調製し、この樹脂ワニスを離型フィルム上に塗布することにより作製できる。より具体的には、少なくとも片面に離型処理が施されたＰＥＴ（ポリエチレンテレフタレート）フィルム、ＰＰ（ポリプロピレン）フィルム、ＰＥ（ポリエチレン）フィルム、ＰＥＥＫ（ポリエーテルエーテルケトン）フィルムなどの離型処理面上に、本開示の樹脂組成物を塗布した後、適当な条件（例えば、温度：８０～１８０℃、時間：２～１０分）により半硬化状態（Ｂステージ）になるまで乾燥させて接着フィルムを得ることができる。塗布方法は、特に限定されず、例えば、コンマコーター、ダイコーター、グラビアコーター等の方法が挙げられる。 As a method for obtaining the B-stage film of the epoxy resin composition, for example, a resin varnish is prepared by dissolving the epoxy resin composition in the solvent, and this resin varnish can be applied on the release film. More specifically, on the release-treated surface of PET (polyethylene terephthalate) film, PP (polypropylene) film, PE (polyethylene) film, PEEK (polyetheretherketone) film, etc., which has been subjected to release treatment on at least one side After applying the resin composition of the present disclosure, the adhesive film is dried under appropriate conditions (for example, temperature: 80 to 180 ° C., time: 2 to 10 minutes) until it reaches a semi-cured state (B stage). Obtainable. The coating method is not particularly limited, and examples thereof include methods using a comma coater, die coater, gravure coater, and the like.
　前記Ｂステージフィルムの厚さは、導体層の厚さ以上とすることが好ましい。回路基板が有する導体の厚さは通常５～７０μｍの範囲であるため、Ｂステージフィルムは１０～３００μｍの厚さとすることが好ましい。Ｂステージフィルムは、ＰＥＴ等の基材から剥がしてＢステージフィルムとして用いてもよく、金属箔又は基材フィルムと、該金属箔又は該基材フィルムの表面に積層されたＢステージフィルムとを備える積層フィルムの形態で用いることができる。 The thickness of the B-stage film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductors on the circuit board is usually in the range of 5-70 μm, the B-stage film preferably has a thickness of 10-300 μm. The B-stage film may be peeled off from a substrate such as PET and used as a B-stage film, and includes a metal foil or a substrate film and a B-stage film laminated on the surface of the metal foil or the substrate film. It can be used in the form of a laminated film.
　前記Ｂステージフィルムは、更に加熱（例えば１５０～３００℃）することで硬化することができる。硬化時間は、その組成によって異なり、例えば２時間又はそれ以下である。 The B-stage film can be cured by further heating (for example, 150 to 300°C). Curing times are dependent on the composition and may be, for example, 2 hours or less.
　本開示のエポキシ樹脂組成物を、Ｂステージフィルムの工程を経ることなく硬化物とする方法は、例えば、該組成物を加熱することで硬化させることができる。硬化温度は、例えば１５０～３００℃である。硬化時間は、組成液によって異なり、例えば２時間又はそれ以下で設定することができる。 A method of making the epoxy resin composition of the present disclosure into a cured product without going through the B-stage film process can be, for example, by heating the composition. The curing temperature is, for example, 150-300.degree. The curing time varies depending on the composition liquid, and can be set to, for example, 2 hours or less.
（プリント基板材料）
　前記樹脂フィルムを基材フィルム上に形成することにより積層フィルムを得ることができる。また、前記樹脂ワニスをガラスクロスやガラス不織布に塗布・含侵させ、加熱乾燥してＢステージ化し、プリプレグを得ることができる。このプリプレグの一方又は両面の面に金属箔（例えば、銅箔）を配し、積層し、加熱形成することにより、金属箔張積層板を得ることができる。 (Printed circuit board material)
A laminated film can be obtained by forming the resin film on a substrate film. Also, a prepreg can be obtained by coating and impregnating a glass cloth or glass nonwoven fabric with the resin varnish, followed by heating and drying to form a B-stage. A metal foil-clad laminate can be obtained by disposing a metal foil (eg, copper foil) on one or both surfaces of this prepreg, laminating the prepreg, and heating and forming.
　本開示のエポキシ樹脂組成物を用いたプリント配線板は、絶縁層と、導体層（例えば、銅箔）とを含むプリント配線板であって、前記絶縁層が、前記樹脂フィルムを含む。前記金属箔張積層板は、所定の配線パターンを形成することにより、プリント配線板として好適に用いることができる。 A printed wiring board using the epoxy resin composition of the present disclosure includes an insulating layer and a conductor layer (eg, copper foil), wherein the insulating layer includes the resin film. The metal foil-clad laminate can be suitably used as a printed wiring board by forming a predetermined wiring pattern.
〔硬化性評価〕
　本開示のエポキシ樹脂組成物は、活性エステル硬化剤と脂環式エポキシ樹脂との反応速度が著しく向上しているため、短時間で硬化することができる。 [Curability evaluation]
The epoxy resin composition of the present disclosure can be cured in a short time because the reaction rate between the active ester curing agent and the alicyclic epoxy resin is significantly improved.
　エポキシ樹脂組成物の硬化性評価は、ＦＴ－ＩＲ（赤外線分光器）によりスペクトル測定によって評価することができる。具体的には、樹脂組成物が硬化した際も変化がなく量が一定である構造が示すピークと、エポキシ基が示すピークとの比から、硬化の進度を観察することができる。樹脂組成物が硬化した際も変化がなく量が一定である構造としては、例えばベンゼン環が挙げられる。本開示のエポキシ樹脂組成物がベンゼン環を有する化合物を含有する場合は、本開示のエポキシ樹脂組成物をＦＴ－ＩＲにてスペクトル測定し、得られたスペクトルのベンゼン環とエポキシ基の中赤外領域のピーク比から硬化の進度を観察することができる。すなわち、ベンゼン環構造は樹脂組成物が硬化した際も構造に変化がなく量が一定であるのに対し、エポキシ基は重合に用いられて硬化に伴って量が減少することから、赤外線スペクトルにて、ベンゼン環のピークと、硬化によって量が減少するエポキシ基のピークとを比較することにより、硬化の進度を観察することができる。 　The curability evaluation of the epoxy resin composition can be evaluated by spectral measurement using an FT-IR (infrared spectroscope). Specifically, the progress of curing can be observed from the ratio between the peak of the structure, which does not change even when the resin composition is cured and the amount is constant, and the peak of the epoxy group. A benzene ring is an example of a structure that does not change and remains constant even when the resin composition is cured. When the epoxy resin composition of the present disclosure contains a compound having a benzene ring, the spectrum of the epoxy resin composition of the present disclosure is measured by FT-IR, and the benzene ring and the epoxy group in the obtained spectrum are measured in the mid-infrared range. The progress of cure can be observed from the area peak ratio. In other words, the benzene ring structure does not change in structure even when the resin composition is cured, and the amount is constant, whereas the epoxy group is used for polymerization and decreases in amount as it cures. Cure progress can be observed by comparing the peaks of benzene rings with those of epoxy groups whose amount decreases with cure.
  なお、赤外線吸収のスペクトルによってピークを比較する際に、中赤外領域のピークを用いる。中赤外領域とは、中波長の赤外線領域のことであり、具体的には、波数（振動数）５００～４０００ｃｍ－１（波長２００００～２５００ｎｍ）の領域のことである。中赤外領域において、エポキシ基については、脂環式エポキシ樹脂の場合は７８０～８９０ｃｍ－１、グリシジルエーテル型エポキシ樹脂の場合は９００～９２０ｃｍ－１付近で検出されるピークを用い、ベンゼン環については、ベンゼン環構造にて出現するいくつかのピークの中からいずれかを用いることができる。中赤外領域では、エポキシ基やベンゼン環といった、各構造／官能基一個一個の基本振動・収縮を捕らえることができ、精度よくスペクトル測定することが可能になる。 When comparing the peaks of the infrared absorption spectra, the peaks in the mid-infrared region are used. The mid-infrared region is an infrared region with medium wavelengths, and specifically, a region with a wave number (frequency) of 500 to 4000 cm −1 (wavelength of 20000 to 2500 nm). In the mid-infrared region, for epoxy groups, peaks detected near 780 to 890 cm −1 for alicyclic epoxy resins and near 900 to 920 cm −1 for glycidyl ether type epoxy resins are used, and the peaks detected for benzene rings are can use any one of several peaks appearing in the benzene ring structure. In the mid-infrared region, it is possible to capture the fundamental vibration and contraction of each structure/functional group such as epoxy groups and benzene rings, enabling accurate spectral measurement.
　エポキシ樹脂組成物の硬化初期の半硬化状態（溶剤を留去し、エポキシ基の反応が進んでない状態）をＦＴ－ＩＲで測定し、エポキシ基と樹脂組成物が硬化した際も変化がなく量が一定である構造（例えばベンゼン環）との比を硬化の進度として反応率０％とし、エポキシ樹脂組成物を加熱後、再度ＦＴ－ＩＲを測定し、前記比が変動しない点を反応率１００％と仮定することにより各加熱時間における硬化度を算出する。 The semi-cured state of the epoxy resin composition at the initial stage of curing (the state in which the reaction between the epoxy groups has not progressed after distilling off the solvent) was measured by FT-IR. The ratio to a structure (e.g., benzene ring) that is constant is defined as the degree of curing at a reaction rate of 0%, and after heating the epoxy resin composition, FT-IR is measured again. % to calculate the degree of cure at each heating time.
　さらに、ＦＴ－ＩＲ測定と並行してラビング試験を実施することにより複合的に硬化度を表すことができる。ラビング試験は加熱したエポキシ樹脂組成物に有機溶剤を綿棒やキムワイプにしみ込ませて１０～３０回ラビングする。エポキシ樹脂組成物が硬化不足である場合、架橋構造を構築できていない未反応のモノマーやオリゴマー成分が付着する。一方、硬化が十分に進行している場合、付着がない。このため、着色の有無により硬化状態を判断することができる。 Furthermore, by performing a rubbing test in parallel with the FT-IR measurement, it is possible to express the degree of cure in a composite manner. In the rubbing test, a cotton swab or Kimwipe is impregnated with an organic solvent into the heated epoxy resin composition and rubbed 10 to 30 times. When the epoxy resin composition is insufficiently cured, unreacted monomers and oligomer components that have not been able to build a crosslinked structure adhere. On the other hand, if curing has progressed sufficiently, there is no adhesion. Therefore, the cured state can be determined based on the presence or absence of coloring.
　一般的にエポキシ樹脂組成物に含まれるエポキシ樹脂が１００％反応することは困難である。このため本開示においては、ＦＴ－ＩＲ測定とラビング試験から複合的に硬化度を判断する。具体的には、ＦＴ－ＩＲ測定でエポキシ基の反応率が９０％以上、且つ、ラビング試験で着色無し、となった場合に、エポキシ樹脂組成物が硬化したと判断する。 Generally, it is difficult for the epoxy resin contained in the epoxy resin composition to react 100%. Therefore, in the present disclosure, the degree of cure is determined in a composite manner from FT-IR measurement and rubbing test. Specifically, when the FT-IR measurement shows that the reaction rate of the epoxy group is 90% or more and the rubbing test shows no coloration, the epoxy resin composition is judged to be cured.
　また、本開示のエポキシ樹脂組成物は、硬化物の誘電正接が０．０１５以下であることが好ましく、０．０１２以下若しくは０．０１以下であることがより好ましく、０．００８以下、０．００７以下、０．００６以下、若しくは０．００５以下であることがさらに好ましい。なお、誘電正接は、エポキシ樹脂組成物を基材上に塗布し、乾燥して得られたＢステージフィルムを加熱して硬化物とし、幅３ｍｍ×長さ８０ｍｍ×厚さ１００μｍの試験片に切り出し、この試験片をネットワークアナライザーを用いて測定する（周波数１０ＧＨｚ、２５℃）。 In the epoxy resin composition of the present disclosure, the dielectric loss tangent of the cured product is preferably 0.015 or less, more preferably 0.012 or less or 0.01 or less, 0.008 or less, 0.01 or less. 007 or less, 0.006 or less, or 0.005 or less. In addition, the dielectric loss tangent is obtained by applying an epoxy resin composition on a substrate and heating the B-stage film obtained by drying to obtain a cured product. , the test piece is measured using a network analyzer (frequency 10 GHz, 25° C.).
　また、本開示のエポキシ樹脂組成物は、ガラス転移温度（Ｔｇ）が１１０℃以上であることが好ましく、１２０℃、１２５℃、若しくは１３０℃以上であることがより好ましい。なお、ガラス転移温度は、エポキシ樹脂組成物をＰＥＥＫ上に塗布し、乾燥及び加熱して得られた硬化物を、幅３ｍｍ×長さ４０ｍｍ×厚さ１００μｍの試験片に切り出し、熱分析装置（例えば、ＴＭＡ７１００、日立ハイテクサイエンス社製）を用いて、引張モード、５℃／ｍｉｎで測定する。 In addition, the epoxy resin composition of the present disclosure preferably has a glass transition temperature (Tg) of 110°C or higher, more preferably 120°C, 125°C, or 130°C or higher. The glass transition temperature was determined by applying the epoxy resin composition to PEEK, drying and heating the resulting cured product, cutting it into a test piece of width 3 mm × length 40 mm × thickness 100 μm, and measuring it with a thermal analyzer ( For example, TMA7100 (manufactured by Hitachi High-Tech Science Co., Ltd.) is used, and the measurement is performed in a tensile mode at 5°C/min.
　以下、エポキシ樹脂、活性エステル硬化剤および硬化促進剤を含有するエポキシ樹脂組成物の硬化反応を説明する。当該硬化反応は、一般的に以下の反応スキームによって進行するとされる。なお、以下の反応スキームでは、硬化促進剤として、４－ジメチルアミノピリジンを用いている。なお、以下の（１－１）～（１－４）をまとめて反応スキーム（１）と呼ぶことがある。また、反応スキーム（１）に記載されるＲ１及びＲ２は、これらが異なる原子若しくは置換基を表すことを示すだけであり、上述のＲ１及びＲ２とは異なる意味合いで用いられる。 The curing reaction of an epoxy resin composition containing an epoxy resin, an active ester curing agent and a curing accelerator is described below. The curing reaction generally proceeds according to the following reaction scheme. In the reaction scheme below, 4-dimethylaminopyridine is used as a curing accelerator. The following (1-1) to (1-4) may be collectively referred to as reaction scheme (1). In addition, R 1 and R 2 described in Reaction Scheme (1) only indicate that they represent different atoms or substituents, and are used with different meanings from R 1 and R 2 described above.
Figure JPOXMLDOC01-appb-C000148
Figure JPOXMLDOC01-appb-C000148
　初期状態（１－１）では、左から硬化促進剤（４－ジメチルアミノピリジン）、エポキシ樹脂、活性エステル硬化剤がそれぞれ独立して存在している。（なお、当該スキームにおいて、Ｒ１は任意の有機化合物を示し、Ｒ２は芳香族を有する任意の樹脂成分を示す。）次に、硬化反応の第１段階（１－２）では、エポキシ樹脂と硬化促進剤が反応してアルコキシ基を生じる。その際、エポキシ基（Ｃ－Ｏ－Ｃ三員環）は開環して、エポキシ基はなくなる。さらに、硬化反応の第２段階（１－３）では、アルコキシ基が活性エステル硬化剤のカルボニル基と反応すると共にアリールオキシ基を生じる。次に、硬化反応の第３段階（１－４）では、硬化促進剤が脱離し、アリールオキシ基と反応する。このサイクルを繰り返すことにより３次元架橋が構築される。 In the initial state (1-1), from the left, the curing accelerator (4-dimethylaminopyridine), epoxy resin, and active ester curing agent exist independently. (In the scheme, R1 represents an arbitrary organic compound and R2 represents an arbitrary resin component having an aromatic group.) Next, in the first stage (1-2) of the curing reaction, the epoxy resin and curing The accelerator reacts to give an alkoxy group. At that time, the epoxy group (C—O—C three-membered ring) is ring-opened and the epoxy group disappears. Furthermore, in the second step (1-3) of the curing reaction, the alkoxy group reacts with the carbonyl group of the active ester curing agent and produces an aryloxy group. Then, in the third stage (1-4) of the curing reaction, the curing accelerator is eliminated and reacts with the aryloxy groups. A three-dimensional crosslink is constructed by repeating this cycle.
　一方で、グリシジル基を有さない脂環式エポキシ樹脂は、エポキシ基を構成する２個の炭素原子が脂肪族環を構成する炭素原子でもある構造を有する。そうすると、一般的なスキームの（１－２）で表されるエポキシ基とアニオン性硬化促進剤とのＳＮ２機構で進む反応において、脂環式エポキシ樹脂の場合はエポキシ基を構成する２個の炭素部分において立体障害が存在するため、反応し難くなると考えられる。また、このために、グリシジル基を有さない脂環式エポキシ樹脂を用いる場合、硬化スピードが比較的遅くなってしまうと考えられる。 On the other hand, an alicyclic epoxy resin that does not have a glycidyl group has a structure in which two carbon atoms that constitute an epoxy group are also carbon atoms that constitute an alicyclic ring. Then, in the reaction of the epoxy group represented by (1-2) in the general scheme and the anionic curing accelerator proceeding by the SN2 mechanism, in the case of an alicyclic epoxy resin, two carbon atoms constituting the epoxy group Since steric hindrance exists in the part, it is considered that the reaction becomes difficult. Moreover, it is thought that for this reason, the curing speed becomes relatively slow when using an alicyclic epoxy resin having no glycidyl group.
　しかしながら、本開示のエポキシ樹脂組成物は、ヒドロキシ基含有化合物を含むために、脂環式エポキシ樹脂と活性エステル硬化剤の反応を良好に進行させることができると推測される。ヒドロキシ基含有化合物が活性エステル硬化剤のエステル基とのエステル交換反応によってアリールオキシ基が生成し、当該アリールオキシ基が脂環式エポキシ基と反応するという、反応スキーム（１）と異なる反応経路が生じ、これと反応スキーム（１）とが並行して進行するためであると考えられるからである。このために、硬化時間を短縮することが可能であると考えられる。 However, since the epoxy resin composition of the present disclosure contains a hydroxy group-containing compound, it is presumed that the reaction between the alicyclic epoxy resin and the active ester curing agent can proceed satisfactorily. A reaction route different from reaction scheme (1) is that an aryloxy group is generated by transesterification of a hydroxy group-containing compound with an ester group of an active ester curing agent, and the aryloxy group reacts with an alicyclic epoxy group. This is thought to be due to the fact that this and reaction scheme (1) proceed in parallel. For this reason, it is considered possible to shorten the curing time.
　なお、本明細書において「含む」とは、「本質的にからなる」と、「からなる」をも包含する（The term "comprising" includes "consisting essentially of” and "consisting of."）。また、本開示は、本明細書に説明した構成要件の任意の組み合わせを全て包含する。 In this specification, the term "comprising" includes "consisting essentially of" and "consisting of." Also, the present disclosure encompasses any and all combinations of the constituent elements described herein.
　また、上述した本開示の各実施形態について説明した各種特性（性質、構造、機能等）は、本開示に包含される主題を特定するにあたり、どのように組み合わせられてもよい。すなわち、本開示には、本明細書に記載される組み合わせ可能な各特性のあらゆる組み合わせからなる主題が全て包含される。 In addition, the various characteristics (property, structure, function, etc.) described for each embodiment of the present disclosure described above may be combined in any way to specify the subject matter included in the present disclosure. That is, the present disclosure encompasses all subject matter consisting of any and all possible combinations of the features described herein.
　以下、例を示して本開示の実施形態をより具体的に説明するが、本開示の実施形態は下記の例に限定されるものではない。 Hereinafter, the embodiments of the present disclosure will be described more specifically with examples, but the embodiments of the present disclosure are not limited to the following examples.
製造例１（ヒドロキシ基含有化合物Ａの製造）
　攪拌機、温度計及び冷却器を備え付けた２００ｍＬ容の四つ口フラスコに、窒素雰囲気下で、１，２－エポキシ－４－ビニルシクロヘキサン６．４ｇ、ヘキサクロロ白金酸六水和物の２質量％エタノール溶液０．０５ｇ、トルエン１００ｇを仕込み、液温を７０℃まで昇温させた。その後、１，４－ビス（ジメチルシリル）ベンゼン５．０ｇを１５分間で滴下し、引続き、９０℃で４時間攪拌した。トルエンを濃縮により除去後、無色透明液体の１，４－ビス［２－（３，４－エポキシシクロヘキシル）エチル]ジメチルシリルベンゼン１０．８ｇ（エポキシ当量２２１ｇ／ｅｑ）を取得した。 Production Example 1 (Production of hydroxy group-containing compound A)
6.4 g of 1,2-epoxy-4-vinylcyclohexane and 2 mass% ethanol of hexachloroplatinic acid hexahydrate were placed in a 200 mL four-necked flask equipped with a stirrer, thermometer and condenser under a nitrogen atmosphere. 0.05 g of the solution and 100 g of toluene were charged, and the liquid temperature was raised to 70°C. Thereafter, 5.0 g of 1,4-bis(dimethylsilyl)benzene was added dropwise over 15 minutes, followed by stirring at 90° C. for 4 hours. After toluene was removed by concentration, 10.8 g (epoxy equivalent: 221 g/eq) of 1,4-bis[2-(3,4-epoxycyclohexyl)ethyl]dimethylsilylbenzene as a colorless transparent liquid was obtained.
　窒素下において、３０ｍＬスクリューバイアル管に、撹拌子、前記で得られた１，４－ビス［２－（３，４－エポキシシクロヘキシル）エチルジメチルシリル］ベンゼン１０．０ｇ（０．０２３ｍｏＬ）、フェノール４．３ｇ（０．０４６ｍｏＬ）、４－ジメチルアミノピリジン０．１ｇを加え、１５０℃で１時間撹拌した。次いで、室温まで冷却した。減圧処理を行い、未反応成分を除去することで褐色液体１４．４ｇを取得した。得られた褐色液体の１Ｈ－ＮＭＲスペクトルデータは以下のとおりである。
また、分子量は６３１である。 Under nitrogen, a 30 mL screw vial tube was charged with a stirrer, 10.0 g (0.023 mol) of 1,4-bis[2-(3,4-epoxycyclohexyl)ethyldimethylsilyl]benzene obtained above, phenol 4 .3 g (0.046 mol) and 0.1 g of 4-dimethylaminopyridine were added, and the mixture was stirred at 150° C. for 1 hour. It was then cooled to room temperature. 14.4 g of brown liquid was obtained by carrying out pressure reduction treatment and removing unreacted components. 1H-NMR spectral data of the obtained brown liquid are as follows.
Moreover, the molecular weight is 631.
１Ｈ－ＮＭＲ（ＣＤＣｌ３，４００ＭＨｚ）δ：７．４９（ｄ，４Ｈ），７．２６（ｔ，４Ｈ），６．９４（ｍ，６Ｈ），４．１３－４．２６（ｑ，２Ｈ），３．８３－３．９４（ｑ，２Ｈ），２．０９（ｍ，２Ｈ），１．８０－１．９０（ｍ，４Ｈ），１．５７（ｍ，１２Ｈ），１．３３（ｍ，４Ｈ），０．２６（ｓ，１２Ｈ） 1H-NMR (CDCl3, 400 MHz) δ: 7.49 (d, 4H), 7.26 (t, 4H), 6.94 (m, 6H), 4.13-4.26 (q, 2H), 3.83-3.94 (q, 2H), 2.09 (m, 2H), 1.80-1.90 (m, 4H), 1.57 (m, 12H), 1.33 (m, 4H), 0.26 (s, 12H)
　得られた褐色液体をＨＰＬＣ分析したところ、検出ピークが３点確認され、検出ピークの面積を比べると約１：２：１であった。 When the obtained brown liquid was analyzed by HPLC, 3 detection peaks were confirmed, and when the areas of the detection peaks were compared, it was about 1:2:1.
　以上の結果から、得られた褐色液体は、以下の式ＡＯＨ－１～ＡＯＨ－３で表される３種類の化合物の混合物（構造異性体混合物）であると同定した。さらに、上記合成反応における反応の特段の偏りはないとすると（ＡＯＨ－２）の化合物が他の化合物の２倍量合成されると考えられることから、得られた化合物質量比は（ＡＯＨ－１）：（ＡＯＨ－２）：（ＡＯＨ－３）＝約１：２：１と推測された。 From the above results, the obtained brown liquid was identified as a mixture (structural isomer mixture) of three types of compounds represented by the following formulas A OH -1 to A OH -3. Furthermore, if there is no particular bias in the reaction in the above synthesis reaction, it is considered that the compound (A OH -2) is synthesized in twice the amount of the other compounds, so the mass ratio of the obtained compound is (A OH -1): (A OH -2): (A OH -3) = about 1:2:1.
Figure JPOXMLDOC01-appb-C000149
Figure JPOXMLDOC01-appb-C000149
製造例２（ヒドロキシ基含有化合物Ｂの製造）
　窒素下において、３０ｍＬスクリューバイアル管に、撹拌子、に３‘，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート１０．０ｇ（０．０３８ｍｏＬ）、フェノール７．２ｇ（０．０７６ｍｏＬ）、４－ジメチルアミノピリジン０．１ｇを加え、１５０℃で１時間撹拌した。次いで、室温まで冷却した。減圧処理を行い、未反応成分を除去することで褐色液体１７．３ｇを取得した。得られた褐色液体の１Ｈ－ＮＭＲスペクトルデータは以下のとおりである。
また、分子量は４４１である。 Production Example 2 (Production of hydroxy group-containing compound B)
Under nitrogen, in a 30 mL screw vial tube, stir bar, 10.0 g (0.038 mol) of 3′,4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 7.2 g (0.076 mol) of phenol. , 0.1 g of 4-dimethylaminopyridine was added, and the mixture was stirred at 150° C. for 1 hour. It was then cooled to room temperature. 17.3 g of brown liquid was obtained by carrying out pressure reduction treatment and removing unreacted components. 1H-NMR spectral data of the obtained brown liquid are as follows.
Moreover, the molecular weight is 441.
１Ｈ－ＮＭＲ（ＣＤＣｌ３，４００ＭＨｚ）δ：７．２３（ｔ，４Ｈ），６．９４（ｍ，６Ｈ），４．２３－４．３６（ｍ，２Ｈ），３．５６－４．０３（ｍ，４Ｈ），１．４９－２．８４（ｍ，１４Ｈ） 1H-NMR (CDCl3, 400MHz) δ: 7.23 (t, 4H), 6.94 (m, 6H), 4.23-4.36 (m, 2H), 3.56-4.03 (m , 4H), 1.49-2.84 (m, 14H)
　このスペクトルデータから、得られた褐色液体は下記式（ＢＯＨ－１）～（ＢＯＨ－４）で表される化合物であると同定した。 From this spectral data, the resulting brown liquid was identified as compounds represented by the following formulas (B OH -1) to (B OH -4).
Figure JPOXMLDOC01-appb-C000150
Figure JPOXMLDOC01-appb-C000150
製造例３（ヒドロキシ基含有化合物Ｃの製造）
　窒素下において、３０ｍＬスクリューバイアル管に、撹拌子、１，３－ビス［２－（３，４－エポキシシクロヘキシル）エチル］テトラメチルジシロキサン１０．０ｇ（０．０２６ｍｏＬ）、フェノール４．９ｇ（０．０５２ｍｏＬ）、４－ジメチルアミノピリジン０．１ｇを加え、１５０℃で１時間撹拌した。次いで、室温まで冷却した。減圧処理を行い、未反応成分を除去することで褐色液体１４．４ｇを取得した。得られた褐色液体の１Ｈ－ＮＭＲスペクトルデータは以下のとおりである。
また、分子量は５７１である。 Production Example 3 (Production of hydroxy group-containing compound C)
Under nitrogen, in a 30 mL screw vial tube, stir bar, 10.0 g (0.026 mol) of 1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyldisiloxane, 4.9 g (0.026 mol) of phenol, 4.9 g (0 .052 mol) and 0.1 g of 4-dimethylaminopyridine were added, and the mixture was stirred at 150° C. for 1 hour. It was then cooled to room temperature. 14.4 g of brown liquid was obtained by carrying out pressure reduction treatment and removing unreacted components. 1H-NMR spectral data of the obtained brown liquid are as follows.
Moreover, the molecular weight is 571.
１Ｈ－ＮＭＲ（ＣＤＣｌ３，４００ＭＨｚ）δ：７．２７（ｔ，４Ｈ），６．９４（ｍ，６Ｈ），３．８６－４．３０（ｑ，４Ｈ），２．１５（ｍ，２Ｈ），１．８１（ｍ，４Ｈ），１．６４（ｍ，８Ｈ），１．３３（ｑ，４Ｈ），０．５１（ｔ，４Ｈ），０．０６（ｓ，１２Ｈ） 1H-NMR (CDCl3, 400 MHz) δ: 7.27 (t, 4H), 6.94 (m, 6H), 3.86-4.30 (q, 4H), 2.15 (m, 2H), 1.81 (m, 4H), 1.64 (m, 8H), 1.33 (q, 4H), 0.51 (t, 4H), 0.06 (s, 12H)
　このスペクトルデータから、得られた褐色液体は下記式（ＣＯＨ－１）～（ＣＯＨ－３）で表される化合物であると同定した。 From this spectral data, the resulting brown liquid was identified as compounds represented by the following formulas (C OH -1) to (C OH -3).
Figure JPOXMLDOC01-appb-C000151
Figure JPOXMLDOC01-appb-C000151
製造例４（ヒドロキシ基含有化合物Ｄの製造）
　窒素下において、３０ｍＬスクリューバイアル管に、撹拌子、１，２：５，６－ジエポキシヘキサヒドロインダン１０．０ｇ（０．０６６ｍｏＬ）、フェノール６．２ｇ（０．０６６ｍｏＬ）、４－ジメチルアミノピリジン０．１ｇを加え、１５０℃で１時間撹拌した。次いで、室温まで冷却した。減圧処理を行い、未反応成分を除去することで褐色液体１６．３ｇを取得した。得られた褐色液体の１Ｈ－ＮＭＲスペクトルデータは以下のとおりである。 Production Example 4 (Production of hydroxy group-containing compound D)
Under nitrogen, in a 30 mL screw vial tube, add a stir bar, 10.0 g (0.066 mol) of 1,2:5,6-diepoxyhexahydroindane, 6.2 g (0.066 mol) of phenol, 4-dimethylaminopyridine. 0.1 g was added and stirred at 150° C. for 1 hour. It was then cooled to room temperature. 16.3 g of brown liquid was obtained by carrying out pressure reduction treatment and removing unreacted components. 1H-NMR spectral data of the obtained brown liquid are as follows.
１Ｈ－ＮＭＲ（ＣＤＣｌ３，４００ＭＨｚ）δ：７．２３（ｍ，４Ｈ），６．８３（ｍ，６Ｈ），３．１６－４．６７（ｍ，４Ｈ），１．９４－２．３２（ｍ，６Ｈ），１．５２－１．６７（ｍ，２Ｈ）
また、分子量は３４０である。 1H-NMR (CDCl3, 400MHz) δ: 7.23 (m, 4H), 6.83 (m, 6H), 3.16-4.67 (m, 4H), 1.94-2.32 (m , 6H), 1.52-1.67 (m, 2H)
Moreover, the molecular weight is 340.
　このスペクトルデータから、得られた褐色液体は下記式（ＤＯＨ－１）～（ＤＯＨ－４）で表される化合物であると同定した。 From this spectral data, the resulting brown liquid was identified as compounds represented by the following formulas (D OH -1) to (D OH -4).
Figure JPOXMLDOC01-appb-C000152
Figure JPOXMLDOC01-appb-C000152
実施例、比較例
　表１に記載した配合量の各成分をカップに秤量し、加温・攪拌し均一混合させ、エポキシ樹脂組成物（樹脂ワニス）を調製した。 EXAMPLES and COMPARATIVE EXAMPLES The amounts of each component shown in Table 1 were weighed into a cup, heated and stirred to uniformly mix, and an epoxy resin composition (resin varnish) was prepared.
　表１中の各成分は以下の通りである。なお、表１の各成分の数値は、質量部を示し、溶媒を除いた固形分の量である。 Each component in Table 1 is as follows. In addition, the numerical value of each component in Table 1 indicates parts by mass, and is the amount of solid content excluding the solvent.
・エポキシ樹脂Ａ：脂環式エポキシ樹脂（１，４－ビス［２－（３，４－エポキシシクロヘキシル）エチルジメチルシリル］ベンゼン）（エポキシ当量２２１ｇ／ｅｑ）
・エポキシ樹脂Ｂ：脂環式エポキシ樹脂（セロキサイド２０２１Ｐ；一般名は３’，４’－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート）（ダイセル社製、エポキシ当量１３７ｇ／ｅｑ）
・エポキシ樹脂Ｃ：脂環式エポキシ樹脂（１，３－ビス［２－（３，４－エポキシシクロヘキシル）エチル］テトラメチルジシロキサン）（東京化成工業製、エポキシ当量１９１ｇ／ｅｑ）
・エポキシ樹脂Ｄ：脂環式エポキシ樹脂（ＴＨＩ－ＤＥ）（ＥＮＥＯＳ社製、エポキシ当量８１ｇ／ｅｑ）
・エポキシ樹脂Ｅ：グリシジル型エポキシ樹脂（ＮＣ－３０００Ｈ）（日本化薬社製、エポキシ当量２８６ｇ／ｅｑ）
　なお、エポキシ樹脂Ａ～Ｅの構造式を下記表に示す。 Epoxy resin A: alicyclic epoxy resin (1,4-bis[2-(3,4-epoxycyclohexyl)ethyldimethylsilyl]benzene) (epoxy equivalent weight 221 g/eq)
Epoxy resin B: alicyclic epoxy resin (Celoxide 2021P; general name is 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate) (manufactured by Daicel, epoxy equivalent 137 g/eq)
Epoxy resin C: alicyclic epoxy resin (1,3-bis[2-(3,4-epoxycyclohexyl)ethyl]tetramethyldisiloxane) (manufactured by Tokyo Chemical Industry, epoxy equivalent 191 g / eq)
・ Epoxy resin D: alicyclic epoxy resin (THI-DE) (manufactured by ENEOS, epoxy equivalent 81 g / eq)
・ Epoxy resin E: glycidyl type epoxy resin (NC-3000H) (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 286 g / eq)
The structural formulas of epoxy resins A to E are shown in the table below.
Figure JPOXMLDOC01-appb-T000153
Figure JPOXMLDOC01-appb-T000153
・硬化剤Ａ：活性エステル樹脂ＥＰＩＣＬＯＮ　ＨＰＣ－８０００－６５Ｔ（トルエン溶液、固形分濃度６５％、エステル当量 約２２３ｇ／ｅｑ、ＤＩＣ社製）；以下の式で表される。 • Curing agent A: active ester resin EPICLON HPC-8000-65T (toluene solution, solid content concentration 65%, ester equivalent approximately 223 g/eq, manufactured by DIC); represented by the following formula.
Figure JPOXMLDOC01-appb-C000154
Figure JPOXMLDOC01-appb-C000154
・熱可塑性樹脂Ａ：フェノキシ樹脂（ＹＸ７５５３ＢＨ３０）（固形分濃度３０％、三菱ケミカル社製）
・硬化促進剤Ａ：４－ジメチルアミノピリジン（ＤＭＡＰ、東京化成工業製） - Thermoplastic resin A: phenoxy resin (YX7553BH30) (solid content concentration 30%, manufactured by Mitsubishi Chemical Corporation)
・ Curing accelerator A: 4-dimethylaminopyridine (DMAP, manufactured by Tokyo Chemical Industry Co., Ltd.)
　得られた各実施例及び比較例の樹脂組成物について、以下の項目について評価した。なお、各評価の結果を表１に併せて示す。 The following items were evaluated for the obtained resin compositions of Examples and Comparative Examples. Table 1 also shows the results of each evaluation.
［硬化性評価］
　実施例および比較例で得られた樹脂組成物を、ＰＥＥＫ板上に、乾燥後塗工厚を１００μｍの厚さに狙って塗した。塗工した樹脂ワニスをオーブンで乾燥させ、半硬化（Ｂステージ）状態の試験片とした。ＩＲスペクトル（赤外線吸収スペクトル）測定により、エポキシ樹脂組成物中のエポキシ基とベンゼン環の吸収ピークの比を求め反応率０％とした。次に、試験片を１８０℃加熱し、エポキシ基とベンゼン環の比が変動しなくなった点をエポキシ基が１００％反応したと設定した。消失挙動によって硬化具合を評価し、エポキシ基のピークが消失した加熱時間を確認した。試験片を加熱した際の経時変化において反応率が９０％以上になった加熱時間を確認した。 [Curability evaluation]
The resin compositions obtained in Examples and Comparative Examples were coated on a PEEK plate aiming at a coating thickness of 100 μm after drying. The applied resin varnish was dried in an oven to obtain a semi-cured (B stage) test piece. By IR spectrum (infrared absorption spectrum) measurement, the ratio of the absorption peaks of the epoxy group and the benzene ring in the epoxy resin composition was obtained, and the reaction rate was taken as 0%. Next, the test piece was heated to 180° C., and the point at which the ratio of epoxy groups to benzene rings stopped changing was defined as 100% reaction of epoxy groups. The degree of curing was evaluated by disappearance behavior, and the heating time at which the peak of the epoxy group disappeared was confirmed. The heating time at which the reaction rate became 90% or more was confirmed in the change over time when the test piece was heated.
　加えて、加熱後の試験片にトルエンをしみ込ませた綿棒を押し当てた状態で１０回往復させてラビング試験を行った。綿棒への着色の有無により硬化具合を評価し、着色が無くなった加熱時間を確認した。 In addition, a rubbing test was performed by reciprocating a cotton swab impregnated with toluene against the heated test piece 10 times. The degree of curing was evaluated by the presence or absence of coloring on the cotton swab, and the heating time at which the coloring disappeared was confirmed.
　また、エポキシ基の反応率が９０％以上かつラビング試験により着色が無くなった試験片の硬化時間を求めた。エポキシ基の反応率９０％以上かつラビング試験により着色がなくなった試験片を硬化物サンプルとした。 In addition, the curing time of the test piece in which the reaction rate of the epoxy group was 90% or more and the coloring was removed by the rubbing test was determined. A test piece having a reaction rate of epoxy groups of 90% or more and having no coloration in the rubbing test was used as a cured product sample.
［誘電正接］
　実施例および比較例で得られた樹脂組成物を、ＰＥＥＫ板上に、乾燥後塗工厚を１００μｍの厚さに狙って塗し、当該塗工した樹脂組成物をオーブンで乾燥させた後、１８０℃で硬化が完了するまで加熱して、硬化サンプルを得た。得られた硬化物サンプルを幅３ｍｍ×長さ８０ｍｍ×厚さ１００μｍのサイズに切り出し、試験片とした。得られた試験片はネットワークアナライザーを用い、周波数１０ＧＨｚ、２５℃における誘電正接を測定した（空洞共振器摂動法）。 [Dielectric loss tangent]
The resin compositions obtained in Examples and Comparative Examples were coated on a PEEK plate with a thickness of 100 μm after drying, and the coated resin composition was dried in an oven. Cured samples were obtained by heating at 180° C. until curing was complete. The obtained cured product sample was cut into a size of 3 mm in width×80 mm in length×100 μm in thickness to obtain a test piece. Using a network analyzer, the dielectric loss tangent of the obtained test piece was measured at a frequency of 10 GHz and 25° C. (cavity resonator perturbation method).
［ガラス転移温度］
　実施例および比較例で得られた樹脂組成物を、ＰＥＥＫ板上に、乾燥後塗工厚を１００μｍの厚さに狙って塗した。塗工した樹脂組成物をオーブンで乾燥させた後、１８０℃で６０分間加熱した。得られた試験片は、熱分析装置（ＴＭＡ７１００、日立ハイテクサイエンス社製）を用いて、引張モード、５℃／ｍｉｎでガラス転移温度を測定した。 [Glass-transition temperature]
The resin compositions obtained in Examples and Comparative Examples were coated on a PEEK plate aiming at a coating thickness of 100 μm after drying. After drying the coated resin composition in an oven, it was heated at 180° C. for 60 minutes. The glass transition temperature of the obtained test piece was measured at 5° C./min in tensile mode using a thermal analyzer (TMA7100, manufactured by Hitachi High-Tech Science Co., Ltd.).
　以上の結果を表２にまとめて示す。 The above results are summarized in Table 2.
Figure JPOXMLDOC01-appb-T000155
Figure JPOXMLDOC01-appb-T000155

Claims (6)

  1. （Ａ）ヒドロキシ基含有化合物、（Ｂ）エポキシ樹脂、（Ｃ）硬化剤、及び（Ｄ）硬化促進剤を含み、
    前記（Ａ）ヒドロキシ基含有化合物が分子量２００以上であり、
    前記（Ｂ）エポキシ樹脂がグリシジル基を有さない脂環式エポキシ樹脂を含み、
    前記（Ｃ）硬化剤が活性エステル硬化剤を含む、
    エポキシ樹脂組成物。     (A) a hydroxy group-containing compound, (B) an epoxy resin, (C) a curing agent, and (D) a curing accelerator,
    (A) the hydroxy group-containing compound has a molecular weight of 200 or more,
    The (B) epoxy resin comprises an alicyclic epoxy resin having no glycidyl group,
    The (C) curing agent comprises an active ester curing agent,
    Epoxy resin composition.
  2. グリシジル基を有さない脂環式エポキシ樹脂が、
    式（１－ｉｉａ）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｘｉｉは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から２個の水素原子を除いて得られる２価の基、あるいは式（２ｇ－ｉｉａ）：
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｙは、結合手、炭素数１～４のアルキル基で置換されていてもよい炭素数１～６のアルキレン基、酸素原子（－Ｏ－）、硫黄原子（－Ｓ－）、－ＳＯ－、又は－ＳＯ２－を示す。）で表される２価の基を示し、
    Ｒ１は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    　Ｒ２は同一又は異なって、炭素数１～１８のアルキレン基を示し、この基は、ケイ素原子に直接結合した炭素原子を除く一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    　Ｒ３は同一又は異なって、炭素数１～１８のアルキル基、炭素数２～９のアルケニル基、シクロアルキル基、アリール基又はアラルキル基を示し、これらの基は、一部の炭素原子が、酸素原子及び窒素原子からなる群より選ばれる少なくとも１種の原子で置換されていてもよく、
    ｍは１～６の整数を示し、ｎは０～３の整数を示す。）
    で表されるエポキシ樹脂、
    式（１－ｉｉｉａ）：
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｘｉｉｉは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から３個の水素原子を除いて得られる３価の基、又は式（２ｇ－ｉｉｉａ）：
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｙは、前記に同じ。）で表される３価の基を示し、
    Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。）
    で表されるエポキシ樹脂、
    式（１－ｉｖａ）：
    Figure JPOXMLDOC01-appb-C000005
     （式中、Ｘｉｖは、飽和炭化水素環若しくは不飽和炭化水素環、又は飽和炭化水素環及び／又は不飽和炭化水素環が２～６個縮合した構造を有する環、から４個の水素原子を除いて得られる４価の基、又は式（２ｇ）：
    Figure JPOXMLDOC01-appb-C000006
     （式中、Ｙは、前記に同じ。）で表される３価の基を示し、
    Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。）
    で表されるエポキシ樹脂、
    式（Ｉ）：
    ＲＩａ－ＺＩ－ＲＩｂ　（Ｉ）
    （式中、ＲＩａ及びＲＩｂは、同一又は異なって式（４）：
    Figure JPOXMLDOC01-appb-C000007
     （式中、Ｒ３、ｍ、及びｎは前記に同じ。）の基を示し、
    －ＺＩ－は、結合手、－（ＣＨ２）Ｉａ－Ｏ－（ＣＨ２）Ｉｂ－、又は－（ＣＨ２）Ｉｃ－ＣＯＯ－（ＣＨ２）Ｉｄ－を示し、ここでＩａ及びＩｂは同一又は異なって０、１、２、３、又は４を示し、Ｉｃ及びＩｄは同一又は異なって０、１、２、３、又は４を示す。）
    で表されるエポキシ樹脂、
    式（ＩＩ）：
    ＲＩＩａ－ＺＩＩ－ＲＩＩｂ　（ＩＩ）
    （式中、ＲＩＩａ及びＲＩＩｂは、同一又は異なって式（３）の基：
    Figure JPOXMLDOC01-appb-C000008
     （式中、Ｒ１、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じ。）の基を示し、
    －ＺＩＩ－は、結合手、－（ＣＨ２）－、－（ＣＨ２）２－、－（ＣＨ２）３－、－（ＣＨ２）４－、－ＣＨ（ＣＨ３）－ＣＨ２－、－ＣＨ２－ＣＨ（ＣＨ３）－、又は－Ｃ（ＣＨ３）２－、又は－Ｏ－（Ｓｉ（Ｒ１）２Ｏ）ＩＩａ－を示す。ここで、ＩＩａは０～８の整数を示し、Ｒ１は前記に同じである。）
    で表されるエポキシ樹脂、
    式（ＩＩＩ）：
    Figure JPOXMLDOC01-appb-C000009
     （式中、ＲＩＩＩａは、同一又は異なって、Ｒ１又は下記式（３’）：
    Figure JPOXMLDOC01-appb-C000010
     （式中、Ｒ２、Ｒ３、ｍ、及びｎは前記に同じである。）の基を示し、但し少なくとも２個以上のＲＩＩＩａが式（３’）の基を示し、
    Ｒ１は前記に同じであり、ＩＩＩｃは２～６の整数を示す。）
    で表されるエポキシ樹脂、
    式： 
    Figure JPOXMLDOC01-appb-C000011
     （式中、Ｒ１は、前記に同じであり、ｎＩＶａは同一又は異なって０～５の整数であり、ｎＩＶｂは同一又は異なって０又は１の整数であり、ｎＩＶｃは１～３の整数である。）で表されるエポキシ樹脂、
    並びに
    式：
    Figure JPOXMLDOC01-appb-C000012
     で表されるエポキシ樹脂
    からなる群より選択される少なくとも１種のエポキシ樹脂である、
    請求項１に記載のエポキシ樹脂組成物。     An alicyclic epoxy resin having no glycidyl group is
    Formula (1-ia):
    Figure JPOXMLDOC01-appb-C000001
     (Wherein, X ii is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 2 hydrogen atoms from A divalent group obtained by excluding or formula (2 g -iia):
    Figure JPOXMLDOC01-appb-C000002
     (Wherein, Y is a bond, an alkylene group having 1 to 6 carbon atoms optionally substituted with an alkyl group having 1 to 4 carbon atoms, an oxygen atom (—O—), a sulfur atom (—S—), —SO— or —SO 2 —.) represents a divalent group represented by
    R 1 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are optionally substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms,
    R 2 is the same or different and represents an alkylene group having 1 to 18 carbon atoms, in which some carbon atoms excluding carbon atoms directly bonded to silicon atoms are selected from the group consisting of oxygen atoms and nitrogen atoms; optionally substituted with at least one atom represented by
    R 3 is the same or different and represents an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 9 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group, and in these groups, some of the carbon atoms are optionally substituted with at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms,
    m represents an integer of 1-6, and n represents an integer of 0-3. )
    Epoxy resin represented by
    Formula (1-iiia):
    Figure JPOXMLDOC01-appb-C000003
     (Wherein, X iii is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 3 hydrogen atoms from A trivalent group obtained by excluding or formula (2 g -iiia):
    Figure JPOXMLDOC01-appb-C000004
     (Wherein, Y is the same as above.) Represents a trivalent group represented by
    R 1 , R 2 , R 3 , m and n are the same as above. )
    Epoxy resin represented by
    Formula (1-iva):
    Figure JPOXMLDOC01-appb-C000005
     (Wherein, X iv is a saturated hydrocarbon ring or unsaturated hydrocarbon ring, or a ring having a structure in which 2 to 6 saturated hydrocarbon rings and/or unsaturated hydrocarbon rings are condensed, and 4 hydrogen atoms from A tetravalent group obtained by excluding or formula (2 g ):
    Figure JPOXMLDOC01-appb-C000006
     (Wherein, Y is the same as above.) Represents a trivalent group represented by
    R 1 , R 2 , R 3 , m and n are the same as above. )
    Epoxy resin represented by
    Formula (I):
    RIa -ZI - RIb (I)
    (Wherein, R Ia and R Ib are the same or different from the formula (4):
    Figure JPOXMLDOC01-appb-C000007
     (Wherein, R 3 , m, and n are the same as above) represents a group,
    —Z I — represents a bond, —(CH 2 ) Ia —O—(CH 2 ) Ib —, or —(CH 2 ) Ic —COO—(CH 2 ) Id —, where Ia and Ib are Ic and Id are the same or different and represent 0, 1, 2, 3 or 4; )
    Epoxy resin represented by
    Formula (II):
    R IIa -Z II -R IIb (II)
    (Wherein, R IIa and R IIb are the same or different groups of formula (3):
    Figure JPOXMLDOC01-appb-C000008
     (Wherein, R 1 , R 2 , R 3 , m, and n are the same as above) represents a group,
    -Z II - is a bond, -(CH 2 )-, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -(CH 2 ) 4 -, -CH(CH 3 )-CH 2 - , —CH 2 —CH(CH 3 )—, —C(CH 3 ) 2 —, or —O—(Si(R 1 ) 2 O) IIa —. Here, IIa represents an integer of 0 to 8, and R 1 is the same as above. )
    Epoxy resin represented by
    Formula (III):
    Figure JPOXMLDOC01-appb-C000009
     (Wherein, R IIIa are the same or different, R 1 or the following formula (3′):
    Figure JPOXMLDOC01-appb-C000010
     (wherein R 2 , R 3 , m, and n are the same as above), provided that at least two R IIIa represent a group of formula (3′);
    R 1 is the same as above and IIIc represents an integer of 2-6. )
    Epoxy resin represented by
    formula:
    Figure JPOXMLDOC01-appb-C000011
     (wherein R 1 is the same as above, n IVa is the same or different and is an integer of 0 to 5, n IVb is the same or different and is an integer of 0 or 1, n IVc is 1 to 3 is an integer of.) Epoxy resin represented by
    and the expression:
    Figure JPOXMLDOC01-appb-C000012
     is at least one epoxy resin selected from the group consisting of epoxy resins represented by
    The epoxy resin composition according to claim 1.
  3. ヒドロキシ基含有化合物が、式：
    Figure JPOXMLDOC01-appb-C000013
     （式中、Ｒｅｎは、Ｏに結合している側を＊として、下記式：
    Figure JPOXMLDOC01-appb-C000014
     （式中、Ｒ３及びｎは前記に同じ。）
    で表される３つの基のいずれかを示す）で表される構造を有する化合物である、
    請求項１に記載のエポキシ樹脂組成物。     The hydroxy group-containing compound has the formula:
    Figure JPOXMLDOC01-appb-C000013
     (Wherein, R en is represented by the following formula, with * being the side bonded to O:
    Figure JPOXMLDOC01-appb-C000014
     (In the formula, R 3 and n are the same as above.)
    Representing any of the three groups represented by) is a compound having a structure represented by
    The epoxy resin composition according to claim 1.
  4. ヒドロキシ基含有化合物が、
    式（Ａｅｎ１）：
    Figure JPOXMLDOC01-appb-C000015
     （ただし、式中のシクロヘキサン環においてＯＨ基が結合する炭素原子と－Ｏ－Ｒｅｎ基が結合する炭素原子とは結合しており、Ｒｅｎは式：
    Figure JPOXMLDOC01-appb-C000016
     （式中、Ｒ３及びｎは前記に同じ。）
    で表される３つの基のいずれかを示す。）で表される基を有する化合物、
    式（Ａｅｎ２）：
    Figure JPOXMLDOC01-appb-C000017
     （ただし、式中のシクロヘキサン環においてＯＨ基が結合する炭素原子と－Ｏ－Ｒｅｎ基が結合する炭素原子とは結合しており、Ｒｅｎは前記に同じ。）で表される基を有する化合物、
    式（Ａｅｎ３）：
    Figure JPOXMLDOC01-appb-C000018
     （式中、ＲｅｎのＯに結合している側を＊として、
    Figure JPOXMLDOC01-appb-C000019
     が、下記式：
    Figure JPOXMLDOC01-appb-C000020
     （式中、Ｒ３及びｎは前記に同じ。）
    で表される３つの基のいずれかを示す。）
    で表される基を有する化合物、並びに
    式（Ａｅｎ４）：
    Figure JPOXMLDOC01-appb-C000021
     （式中、Ｒｅｎは前記に同じ。）
    で表される基を有する化合物
    からなる群より選択される少なくとも１種の化合物である、
    請求項３に記載のエポキシ樹脂組成物。     A hydroxy group-containing compound is
    Formula (A en 1):
    Figure JPOXMLDOC01-appb-C000015
     (However, in the cyclohexane ring in the formula, the carbon atom to which the OH group is bonded and the carbon atom to which the —O—R en group is bonded are bonded, and R en is the formula:
    Figure JPOXMLDOC01-appb-C000016
     (In the formula, R 3 and n are the same as above.)
    represents any one of the three groups represented by ) a compound having a group represented by
    Formula (A en 2):
    Figure JPOXMLDOC01-appb-C000017
     (However, in the cyclohexane ring in the formula, the carbon atom to which the OH group is bonded and the carbon atom to which the —OR en group is bonded are bonded, and R en is the same as described above.) Compound,
    Formula (A en 3):
    Figure JPOXMLDOC01-appb-C000018
     (In the formula, the side bonded to O of R en is *,
    Figure JPOXMLDOC01-appb-C000019
     is the following formula:
    Figure JPOXMLDOC01-appb-C000020
     (In the formula, R 3 and n are the same as above.)
    represents any one of the three groups represented by )
    and a compound having a group represented by the formula (A en 4):
    Figure JPOXMLDOC01-appb-C000021
     (In the formula, R en is the same as above.)
    is at least one compound selected from the group consisting of compounds having a group represented by
    The epoxy resin composition according to claim 3.
  5. 請求項１～４のいずれかに記載のエポキシ樹脂組成物を硬化してなる硬化物。 A cured product obtained by curing the epoxy resin composition according to any one of claims 1 to 4.
  6. 請求項５の硬化物を含む絶縁層を有するプリント基板材料。  A printed circuit board material having an insulating layer containing the cured product of claim 5. 
PCT/JP2022/047514 2021-12-27 2022-12-23 Epoxy resin composition WO2023127709A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2021-213398 2021-12-27
JP2021213398 2021-12-27

Publications (1)

Publication Number Publication Date
WO2023127709A1 true WO2023127709A1 (en) 2023-07-06

Family

ID=86999181

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2022/047514 WO2023127709A1 (en) 2021-12-27 2022-12-23 Epoxy resin composition

Country Status (2)

Country Link
TW (1) TW202330697A (en)
WO (1) WO2023127709A1 (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005206672A (en) * 2004-01-21 2005-08-04 Daicel Chem Ind Ltd Nonester type epoxy resin and resin composition
JP2015010153A (en) * 2013-06-28 2015-01-19 日本ゼオン株式会社 Curable epoxy composition, film, laminate film, prepreg, laminate, cured product, and composite
JP2016027097A (en) * 2014-06-30 2016-02-18 味の素株式会社 Resin composition
WO2018131569A1 (en) * 2017-01-10 2018-07-19 住友精化株式会社 Epoxy resin composition
WO2018131567A1 (en) * 2017-01-10 2018-07-19 住友精化株式会社 Epoxy resin composition
JP2020158703A (en) * 2019-03-27 2020-10-01 日立化成株式会社 Resin composition, cured product, semiconductor element and electronic device
JP2021042295A (en) * 2019-09-10 2021-03-18 積水化学工業株式会社 Resin material and multilayer printed board

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005206672A (en) * 2004-01-21 2005-08-04 Daicel Chem Ind Ltd Nonester type epoxy resin and resin composition
JP2015010153A (en) * 2013-06-28 2015-01-19 日本ゼオン株式会社 Curable epoxy composition, film, laminate film, prepreg, laminate, cured product, and composite
JP2016027097A (en) * 2014-06-30 2016-02-18 味の素株式会社 Resin composition
WO2018131569A1 (en) * 2017-01-10 2018-07-19 住友精化株式会社 Epoxy resin composition
WO2018131567A1 (en) * 2017-01-10 2018-07-19 住友精化株式会社 Epoxy resin composition
JP2020158703A (en) * 2019-03-27 2020-10-01 日立化成株式会社 Resin composition, cured product, semiconductor element and electronic device
JP2021042295A (en) * 2019-09-10 2021-03-18 積水化学工業株式会社 Resin material and multilayer printed board

Also Published As

Publication number Publication date
TW202330697A (en) 2023-08-01

Similar Documents

Publication Publication Date Title
US11091627B2 (en) Epoxy resin composition
CN110177820B (en) Epoxy resin composition
US11292872B2 (en) Epoxy resin composition
EP3569628B1 (en) Epoxy resin composition
KR101588488B1 (en) Film-type wafer mold material, molded wafer and semiconductor device
CN114008104B (en) Epoxy resin composition
JP6722485B2 (en) Phenoxy resin containing bisphenol F skeleton, method for producing the same, and resin composition using the same
JP2022099397A (en) Cyclic imide resin composition, prepreg, copper-clad laminate, and printed wiring board
EP4092065A1 (en) Resin composition
WO2023127709A1 (en) Epoxy resin composition
WO2023127708A1 (en) Epoxy resin composition
JP7320805B1 (en) Epoxy resin composition, its cured product and laminate
JP2024062263A (en) Epoxy resin composition
JP7228104B2 (en) Epoxy (meth)acrylate resin composition, curable resin composition, cured product and article
TW202328266A (en) resin composition
JP4540080B2 (en) High softening point o-cresol-novolak type epoxy resin, epoxy resin solution containing the same, epoxy resin composition and method for producing epoxy resin
CN116769274A (en) Resin composition
JP2007077408A (en) Method for producing epoxy resin

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22915932

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2023570951

Country of ref document: JP