WO2021246182A1 - 硬化性樹脂、硬化性樹脂組成物、及び、硬化物 - Google Patents

硬化性樹脂、硬化性樹脂組成物、及び、硬化物 Download PDF

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WO2021246182A1
WO2021246182A1 PCT/JP2021/019096 JP2021019096W WO2021246182A1 WO 2021246182 A1 WO2021246182 A1 WO 2021246182A1 JP 2021019096 W JP2021019096 W JP 2021019096W WO 2021246182 A1 WO2021246182 A1 WO 2021246182A1
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group
curable resin
general formula
resin composition
cured product
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English (en)
French (fr)
Japanese (ja)
Inventor
立宸 楊
龍一 松岡
広義 神成
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to CN202180038963.9A priority Critical patent/CN115916894B/zh
Priority to JP2022505300A priority patent/JP7060181B1/ja
Priority to KR1020227038036A priority patent/KR20230020387A/ko
Priority to US18/007,742 priority patent/US12606655B2/en
Publication of WO2021246182A1 publication Critical patent/WO2021246182A1/ja
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/249—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs characterised by the additives used in the prepolymer mixture
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/22—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/20—Esters of polyhydric alcohols or polyhydric phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
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    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/104—Esters of polyhydric alcohols or polyhydric phenols of tetraalcohols, e.g. pentaerythritol tetra(meth)acrylate
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
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    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
    • 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
    • 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
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • 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
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2347/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers

Definitions

  • the present invention relates to a curable resin having a specific structure, a curable resin composition containing the curable resin, and a cured product, varnish, prepreg, and circuit board obtained by the curable resin composition.
  • vinyl group-containing curable resins having various chemical structures have been conventionally proposed.
  • a curable resin for example, a curable resin such as bisphenol divinylbenzyl ether or novolak polyvinylbenzyl ether has been proposed (see, for example, Patent Documents 1 and 2).
  • these vinyl benzyl ethers cannot give a cured product having sufficiently small dielectric properties, and the obtained cured product has a problem in stable use in a high frequency band, and further, a bisphenol divinyl benzyl ether. Was not sufficiently high in heat resistance.
  • the conventional curable resin containing a vinyl group containing polyvinylbenzyl ether can withstand the low dielectric loss tangent required for electrical insulating material applications, especially for high frequency electrical insulating materials, and lead-free soldering. It did not give a cured product having both heat resistance.
  • flame retardancy is also required for electrical insulating materials such as printed circuit boards, but if a large amount of flame retardant is added to satisfy flame retardancy, flame retardancy and dielectric properties will be improved, such as inferior dielectric properties. At the same time, the current situation was that they were not satisfied.
  • Japanese Unexamined Patent Publication No. 63-68537 Japanese Unexamined Patent Publication No. 64-65110 Special Table 1-503238 Gazette Japanese Unexamined Patent Publication No. 5-43623 Japanese Unexamined Patent Publication No. 9-31006 Japanese Unexamined Patent Publication No. 2005-281618 Japanese Unexamined Patent Publication No. 2005-314556 JP-A-2015-030776 JP-A-2015-189925
  • the problem to be solved by the present invention is a curable resin containing a curable resin having a specific structure that can contribute to heat resistance and low dielectric properties, the curable resin, a radical polymerization initiator, and a flame retardant.
  • a cured product having excellent flame retardancy, heat resistance (high glass transition temperature), and dielectric property (low dielectric property) contributes to these performances, or has these performances.
  • the purpose of the present invention is to provide a varnish, a prepreg, and a circuit board.
  • the present inventors have found a curable resin having a specific structure that can contribute to heat resistance and low dielectric properties, the curable resin, a radical polymerization initiator, and the like.
  • they have found that a varnish, a prepreg, and a circuit board having these performances can be obtained, and have completed the present invention.
  • the present invention is characterized by containing a curable resin represented by the following general formula (1), the curable resin, a radical polymerization initiator (B), and a flame retardant (C).
  • a curable resin represented by the following general formula (1) Z is a hydrocarbon having 2 to 15 carbon atoms
  • Y is a substituent represented by the following general formula (2)
  • n is an integer of 3 to 5.
  • Ra and Rb are independently represented by an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group
  • m is an integer of 0 to 3.
  • X represents a (meth) acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group.
  • the above general formula (1) is preferably represented by the following general formula (1A).
  • the curable resin of the present invention preferably has n of 4.
  • X is a methacryloyloxy group.
  • Z is an aliphatic hydrocarbon.
  • the curable resin composition of the present invention preferably further contains a curable resin (D) other than the curable resin.
  • the component (B) is a dialkyl peroxide-based organic peroxide.
  • the component (C) contains a phosphorus-based flame retardant represented by any of the following general formulas (P-1) to (P-5).
  • P-1 a phosphorus-based flame retardant represented by any of the following general formulas (P-1) to (P-5).
  • R 11 independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms
  • R 12 is an alkylene group or an arylene group.
  • M c + represents a c-valent metal ion
  • R 16 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and forms a cyclic structure together with a phosphorus atom.
  • R 17 represents a vinyl group, a vinylbenzyl group, or a (meth) acryloyloxy group, and f and g independently represent 0 or 1, respectively.
  • R 18 independently represents an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and forms a cyclic structure together with a phosphorus atom.
  • R 19 represents a divalent group having an arylene structure
  • R 20 represents a (meth) acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group
  • h represents 0 or 1. .
  • the curable resin composition of the present invention comprises a group in which the component (D) is composed of an epoxy resin, a phenol resin, an active ester resin, a cyanate ester resin, a maleimide resin, a benzoxazine resin, a polyphenylene ether resin, and a vinyl resin. It is preferably at least one curable resin of choice.
  • the present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.
  • the present invention relates to a varnish obtained by diluting the curable resin composition with an organic solvent.
  • the present invention relates to a prepreg having a reinforcing base material and a semi-cured product of the varnish impregnated in the reinforcing base material.
  • the present invention relates to a circuit board obtained by laminating the prepreg and copper foil and heat-pressing molding.
  • the curable resin of the present invention is excellent in heat resistance and low dielectric property, and the cured product obtained by the curable resin composition containing the curable resin, the radical polymerization initiator, and the flame retardant is flame-retardant. It is useful because it has excellent properties, heat resistance, and low dielectric properties.
  • 6 is a 1 H-NMR spectrum of the curable resin obtained in Example 1.
  • 6 is a 1 H-NMR spectrum of the curable resin obtained in Example 13.
  • the present invention relates to a curable resin represented by the following general formula (1).
  • the curable resin characterized by being represented by the following general formula (1) is referred to as a curable resin (A) (also referred to as “component (A)”).
  • Z is a hydrocarbon having 2 to 15 carbon atoms
  • Y is a substituent represented by the following general formula (2)
  • n represents an integer of 3 to 5.
  • Ra and Rb are independently represented by an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and m is an integer of 0 to 3.
  • X represents a (meth) acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group.
  • the cured product obtained by cross-linking the component (A) has a high cross-linking density and is excellent in heat resistance.
  • the cross-linking group is also a polar group, the presence of a substituent (particularly Ra) adjacent to the cross-linking group suppresses the molecular motility of the cross-linking group to a low level, and the obtained cured product has low dielectric properties (particularly). Low dielectric positive contact) can be satisfied, which is preferable.
  • Z is a hydrocarbon having 2 to 15 carbon atoms, preferably a hydrocarbon having 2 to 10 carbon atoms, and more preferably a hydrocarbon having 2 to 6 carbon atoms.
  • the component (A) becomes a low molecular weight substance, the crosslink density becomes high, and the glass transition temperature of the obtained cured product becomes high as compared with the case of the high molecular weight body. It has excellent heat resistance and is a preferable embodiment.
  • the obtained curable resin becomes a high molecular weight substance, and the crosslink density of the cured product is lower than that in the case where the number of carbon atoms is less than 2, forming a film or the like.
  • the carbon number is 15 or less, the obtained curable resin becomes a low molecular weight substance, and the carbon number is 15.
  • the proportion of the cross-linking group (X) in the component (A) is higher than that in the case of exceeding the above amount, and the cross-linking density is improved accordingly, and the obtained cured product is excellent in heat resistance, which is preferable.
  • the hydrocarbon is not particularly limited as long as it is a hydrocarbon having 2 to 15 carbon atoms, but is preferably an aliphatic hydrocarbon such as an alkane, an alkene, or an alkyne, and is an aromatic hydrocarbon containing an aryl group or the like. , Compounds in which aliphatic hydrocarbons and aromatic hydrocarbons are combined can be mentioned.
  • examples of the alkane include ethane, propane, butane, pentane, hexane, cyclohexane and the like.
  • examples of the alkene include those containing a vinyl group, a 1-methylvinyl group, a propenyl group, a butenyl group, a pentenyl group and the like.
  • examples of the alkyne include those containing an ethynyl group, a propynyl group, a butynyl group, a pentynyl group, a hexynyl group and the like.
  • Examples of the aromatic hydrocarbon include those containing an aryl group such as a phenyl group, a tolyl group, a xylyl group, and a naphthyl group.
  • Examples of the compound in which the aliphatic hydrocarbon and the aromatic hydrocarbon are combined include a benzyl group, a phenylethyl group, a phenylpropyl group, a tolylmethyl group, a tolylethyl group, a tolylpropyl group, a xsilylmethyl group, a xsilylethyl group and a xylyl.
  • Examples thereof include those containing a propyl group, a naphthylmethyl group, a naphthylethyl group, a naphthylpropyl group and the like.
  • aliphatic hydrocarbons and aromatic hydrocarbons consisting only of carbon atoms and hydrogen atoms can be obtained from the viewpoint of obtaining a cured product having low polarity and low dielectric properties (low dielectric constant and low dielectric tangent).
  • Alicyclic hydrocarbons are preferable, and among them, hydrocarbons having a very small polarity and can be industrially adopted as described in the following general formulas (3-1) to (3-6) are preferable, and more preferably.
  • k represents an integer of 0 to 5, preferably 0 to 3, and the following general formulas (3-1), (3-2), and (3).
  • Rc in (3-6) is preferably represented by a hydrogen atom or a methyl group.
  • Ra and Rb independently represent an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a cycloalkyl group, and preferably an alkyl group having 1 to 4 carbon atoms. , Aryl group, or cycloalkyl group.
  • Ra and Rb (particularly Ra adjacent to X, which is a cross-linking group) causes steric hindrance, and the molecular motility of the cross-linking group (X) is further lowered, resulting in lower dielectric properties. It is preferable because a cured product (particularly low dielectric loss tangent) can be obtained. Furthermore, it is more preferable that Ra and Rb do not thermally decompose during heating.
  • m represents an integer of 0 to 3, preferably m is 0 or 1, and more preferably 1.
  • Rb which is a substituent, becomes a steric hindrance, the molecular motion of the crosslinking group (X) is lowered, and the low dielectric property is excellent, which is a preferable embodiment.
  • Rb represents a hydrogen atom.
  • n is the number of substituents, represents an integer of 3 to 5, preferably 3 or 4, and more preferably 4.
  • the component (A) becomes a low molecular weight body, the crosslink density becomes high, and the glass transition temperature of the obtained cured product becomes high as compared with the case of the high molecular weight body. It has excellent heat resistance and is a preferable embodiment.
  • n is 3 or more, the number of cross-linking groups (X) increases, the cross-linking density of the obtained cured product is high, and sufficient heat resistance can be obtained, which is preferable.
  • n is 5 or less, the crosslink density of the cured product does not become excessively high, so that it is easy to form a film or the like, and it is excellent in handleability, flexibility, flexibility, and brittleness. , More preferred.
  • X is a (meth) acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group serving as a cross-linking group, preferably a (meth) acryloyloxy group, and more preferably. , Methacryloyloxy group.
  • the methacryloyloxy group contains a methyl group in the structure of the component (A) as compared with other cross-linking groups (for example, an ether group which is a polar group such as a vinylbenzyl ether group or an allyl ether group). It is presumed that the steric hindrance will be large and the molecular motility will be further lowered, and a cured product having a lower dielectric positive tangent can be obtained, which is preferable. Further, when there are a plurality of cross-linking groups, the cross-linking density is increased and the heat resistance is improved, which is preferable.
  • the crosslinked group X is also a polar group, but when the substituents Ra and Rb (particularly Ra) are adjacent to each other, steric hindrance occurs, the molecular motion of X is suppressed, and the obtained cured product is obtained.
  • the dielectric loss tangent of the above is lowered, which is a preferable embodiment.
  • the general formula (1) is represented by the following general formula (1A) for the component (A).
  • the general formula (1) is represented by the following general formula (1A) for the component (A).
  • the n is preferably 4. Since n in the general formula (1A) is 4, the component (A) has a high cross-linking density and does not have too many cross-linking groups, so that sufficient heat resistance can be obtained and handleability can be obtained. , Excellent flexibility, flexibility, and brittleness resistance, which is a more preferable embodiment.
  • X is a methacryloyloxy group. Since X in the general formula (1A) is a methacryloyloxy group, having the cross-linking group in the component (A) gives a cured product having a low dielectric loss tangent, which is a preferable embodiment. Since the methacryloyloxy group contains a methyl group in the structure of the component (A) as compared with other cross-linking groups (for example, an ether group which is a polar group such as a vinylbenzyl ether group or an allyl ether group).
  • Z is an aliphatic hydrocarbon. Since Z in the general formula (1A) is an aliphatic hydrocarbon, the polarity is lowered and low dielectric properties (low dielectric constant, low dielectric loss tangent) are obtained, which is a more preferable embodiment.
  • Z is preferably an aliphatic hydrocarbon having 2 to 15 carbon atoms, and more preferably an aliphatic hydrocarbon having 2 to 10 carbon atoms.
  • the number of carbon atoms is 2 or more, the crosslink density is low and the brittle resistance is excellent as compared with the case where the number of carbon atoms is less than 2, and when the number of carbon atoms is 15 or less, the number of carbon atoms exceeds 15. In comparison, the crosslink density is high, and the heat resistance is excellent, which is preferable.
  • the aliphatic hydrocarbon is common to the aliphatic hydrocarbon in the example of the hydrocarbon in the general formula (1).
  • Ra, Rb, m, and n are common to Ra, Rb, m, and n in the general formulas (1) and (2).
  • the general formula (1) includes not only the general formula (1A) but also the following general formula (1B), but in the general formula (1A), X, which is a cross-linking group, reacts. Since it is in an easy position, the curing reaction is likely to proceed, and there is no risk of remaining as uncured and lowering the thermal decomposition temperature, which is more preferable.
  • an aldehyde compound or a ketone compound represented by the following general formulas (4) to (9) and a phenol or a derivative thereof represented by the following general formulas (10) to (16) are used.
  • the intermediate phenol compound can be obtained by mixing with and reacting in the presence of an acid catalyst.
  • the k, Ra, and Rb in the following general formulas (4) to (16) are common to the k, Ra, and Rb in the above general formulas (2) and (3-1).
  • the aldehyde compound may be formaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butylaldehyde, pentanal, or the like.
  • aldehyde compounds glyoxal, glutaraldehyde, crotonaldehyde, phthalaldehyde and the like are preferable because they are easily available industrially.
  • ketone compound cyclohexanedione and diacetylbenzene are preferable, and cyclohexanedione is more preferable because it is industrially easily available.
  • the compound (a) is not limited to only one type in its use, and two or more types can be used in combination.
  • the phenol or its derivative (hereinafter, may be referred to as "compound (b)") is not particularly limited, but specifically, cresol such as o-cresol, m-cresol, p-cresol; Phenol; 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol (2,6-dimethylphenol), 3,4-xylenol, 3,5-xylenol, 3,6- Xylenol such as xylenol; ethylphenol such as o-ethylphenol (2-ethylphenol), m-ethylphenol, p-ethylphenol; butylphenol such as isopropylphenol, butylphenol, pt-butylphenol; p-pentylphenol, p.
  • cresol such as o-cresol, m-cresol, p-cresol
  • -Alkylphenols such as octylphenol, p-nonylphenol, p-cumylphenol; o-phenylphenol (2-phenylphenol), p-phenylphenol, 2-cyclohexylphenol, 2-benzylphenol, 2,3,6-trimethylphenol , 2,3,5-trimethylphenol, 2-cyclohexyl-5-methylphenol, 2-t-butyl-5-methylphenol, 2-isopropyl-5-methylphenol, 2-methyl-5-isopropylphenol, 2, 6-t-butylphenol, 2,6-diphenylphenol, 2,6-dicyclohexylphenol, 2,6-diisopropylphenol, 3-benzylbiphenyl-2-ol, 2,4-di-t-butylphenol, 2,4- Examples thereof include diphenylphenol and 2-t-butyl-4-methylphenol.
  • phenols or derivatives thereof may be used alone or in combination of two or more.
  • the steric disorder is too large, there is a concern that the reactivity of the intermediate phenol compound during synthesis may be hindered. Therefore, for example, a compound having a methyl group, an ethyl group, an isopropyl group, a cyclohexyl group, or a benzyl group. It is preferable to use (b).
  • the compound (a) and the compound (b) are mixed in a molar ratio of the compound (b) to the compound (a) (compound (b) / compound (a). )) Is preferably charged at 0.1 to 10, more preferably 0.2 to 8, and reacted in the presence of an acid catalyst to obtain the intermediate phenol compound.
  • Examples of the acid catalyst used in the reaction include inorganic acids such as phosphoric acid, hydrochloric acid and sulfuric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid and other organic acids, and active white clay.
  • Acidic white clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resin, heteropolyrates, etc. can be mentioned, but with a uniform catalyst that can be easily removed by neutralization with a base and washing with water after the reaction. It is preferable to use a certain inorganic acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid.
  • the blending amount of the acid catalyst is such that the acid catalyst is blended in the range of 0.001 to 40 parts by mass with respect to 100 parts by mass of the compound (a) and the compound (b), which are the raw materials to be charged first.
  • 0.001 to 25 parts by mass is preferable from the viewpoint of handleability and economy.
  • the reaction temperature may be usually in the range of 30 to 150 ° C., but in order to suppress the formation of isomer structures, avoid side reactions such as thermal decomposition, and obtain a high-purity intermediate phenol compound, 60 ⁇ 120 ° C. is preferable.
  • the reaction time the reaction does not proceed completely in a short time, and side reactions such as a thermal decomposition reaction of the product occur when the reaction time is long. Therefore, under the reaction temperature conditions, the total reaction time is usually 0. It is in the range of .5 to 24 hours, but preferably in the range of 0.5 to 15 hours in total.
  • Examples of the organic solvent used for synthesizing the intermediate phenol compound include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone and acetophenone, and alcohols such as 2-ethoxyethanol, methanol and isopropyl alcohol.
  • ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone and acetophenone
  • alcohols such as 2-ethoxyethanol, methanol and isopropyl alcohol.
  • the hydroxyl group equivalent (phenol equivalent) of the intermediate phenol compound is preferably 80 to 500 g / eq, and more preferably 100 to 300 g / eq, from the viewpoint of heat resistance.
  • the hydroxyl group equivalent (phenol equivalent) of the intermediate phenol compound is calculated by a titration method, and refers to a neutralization titration method based on JIS K0070.
  • the component (A) is, in the presence of a basic or acidic catalyst, the intermediate phenol compound, anhydrous (meth) acrylic acid, (meth) acrylic acid chloride, chloromethylstyrene, chlorostyrene, allyl chloride, odor. It can be obtained by a known method such as reaction with allyl chloride or the like (hereinafter, may be referred to as “anhydrous (meth) acrylic acid or the like”). By reacting these, a cross-linking group (X) can be introduced into the intermediate phenol compound, and the thermosetting property has a low dielectric constant and a low dielectric loss tangent, which is a preferable embodiment.
  • Examples of the anhydrous (meth) acrylic acid include methacrylic anhydride and methacrylic anhydride.
  • examples of the (meth) acrylic acid chloride include methacrylic acid chloride and acrylic acid chloride.
  • examples of the chloromethylstyrene include p-chloromethylstyrene and m-chloromethylstyrene
  • examples of the chlorostyrene include p-chlorostyrene and m-chlorostyrene as the allyl chloride.
  • 3-chloro-1-propene can be mentioned, and examples of the allyl bromide include 3-bromo-1-propene. These may be used alone or in combination. Above all, it is preferable to use methacrylic anhydride or methacrylic acid chloride, which can obtain a cured product having a lower dielectric loss tangent.
  • the basic catalyst examples include dimethylaminopyridine, tetrabutylammonium bromide (TBAB), alkaline earth metal hydroxide, alkali metal carbonate, and alkali metal hydroxide.
  • the acidic catalyst include sulfuric acid and methanesulfonic acid.
  • dimethylaminopyridine is excellent in terms of catalytic activity.
  • the organic solvent is not particularly limited, and is, for example, ketones such as acetone and methyl ethyl ketone (MEK), alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol.
  • ketones such as acetone and methyl ethyl ketone (MEK)
  • alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol.
  • Methyl cellosolve cellosolves such as ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethoxyethane, aprotonic polar solvents such as acetonitrile, dimethylsulfoxide, dimethylformamide, toluene. And so on.
  • aprotonic polar solvents such as acetonitrile, dimethylsulfoxide, dimethylformamide, toluene.
  • Each of these organic solvents may be used alone, or two or more kinds may be used in combination as appropriate for adjusting the polarity.
  • the reaction product is reprecipitated in a poor solvent, and then the precipitate is prepared in a poor solvent at a temperature of 20 to 100 ° C. to 0.
  • the desired component (A) can be obtained by stirring for 1 to 5 hours, filtering under reduced pressure, and then drying the precipitate at a temperature of 40 to 80 ° C. for 1 to 10 hours.
  • the poor solvent include hexane and the like.
  • the softening point of the component (A) is preferably 150 ° C. or lower, more preferably 20 to 140 ° C. It is preferable that the softening point of the component (A) is within the above range because the processability is excellent.
  • the present invention relates to the curable resin composition, which comprises the curable resin (A), and a radical polymerization initiator (B) and a flame retardant (C) described later.
  • the curable resin composition is useful because it can contribute to flame retardancy, heat resistance, and low dielectric properties.
  • the curable resin composition of the present invention preferably further contains a curable resin (D) (also referred to as "component (D)”) other than the component (A).
  • a curable resin (D) also referred to as "component (D)
  • component (D) also referred to as "component (D)
  • the component (D) includes an epoxy resin, a phenol resin, an active ester resin, a cyanate ester resin, a maleimide resin, a benzoxazine resin, and a polyphenylene ether resin from the viewpoints of high heat resistance, high adhesion, low thermal expansion, and compatibility. , And at least one curable resin selected from the group consisting of vinyl resins.
  • the epoxy resin examples include dicyclopentadiene type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, and bisphenol A novolak type epoxy.
  • phenolic resin examples include phenol novolac, o-cresol novolak, p-cresol novolak, t-butylphenol novolak, dicyclopentadiencresol, polyparavinylphenol, bisphenol A type novolak, phenol aralkyl resin, naphthol aralkyl resin, and biphenyl.
  • Examples of the active ester resin include active ester compounds obtained by reacting a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound.
  • cyanate ester resin examples include bis (4-cyanatophenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, and 2,2-bis (3,5-dimethyl-4-cyanatophenyl).
  • Methan, 2,2-bis (4-cyanatophenyl) -1,1,1,3,3,3-hexafluoropropane, ⁇ , ⁇ '-bis (4-cyanatophenyl) -m-diisopropylbenzene Cyanate esterified product of phenol-added dicyclopentadiene polymer and the like.
  • maleimide resin examples include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebis.
  • Maleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane can be mentioned.
  • benzoxazine resin examples include Fa-type benzoxazine compounds and diaminodiphenylmethane obtained by reacting a bisphenol compound with an amine compound (for example, aniline) such as bisphenol A type benzoxazine compound and bisphenol F type benzoxazine compound.
  • an amine compound for example, aniline
  • examples thereof include Pd-type benzoxazine compounds obtained by the reaction of a phenyldiamine compound and a phenol compound, such as a type benzoxazine compound.
  • polyphenylene ether resin examples include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and polystyrene alloyed polymers, and poly (2). , 6-Dimethyl-1,4-phenylene) ether and styrene-butadiene copolyma alloyed polymers and the like.
  • vinyl resin examples include trialkenyl isocyanurate compounds such as triallyl isocyanurate, polybutadiene resins having 1,2-butadiene, cis-1,4-butadiene, and trans-1,4-butadiene repeating units in the molecule.
  • vinylbenzyl compounds such as styrene and divinylbenzene having a vinylbenzyl group.
  • a maleimide resin, a cyanate ester resin, a polyphenylene ether resin, and a vinyl resin are particularly preferable because they reduce the dielectric loss tangent.
  • the curable resin composition of the present invention preferably contains 0 to 80 parts by mass of the component (D), more preferably 0 to 60 parts by mass, with respect to 100 parts by mass of the component (A). ..
  • the component (D) can be blended within a range that does not impair the characteristics of the present invention, and is appropriately used when it is desired to impart the characteristics derived from the component (D) within a range that does not exceed the component (A). can do.
  • the curable resin composition of the present invention is characterized by containing a radical polymerization initiator (B) (also referred to as "component (B)").
  • B radical polymerization initiator
  • component (B) examples include isobutyl peroxide, ⁇ , ⁇ '-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, and di-n-propylperoxydicarbonate, 1, 1,3,3-Tetramethylbutylperoxyneodecanoate, diisopropylperoxydicarbonate, 1-cyclohexyl-1-methylethylperoxyneodecanoate, di-2-ethoxyethylperoxydicarbonate, Di (2-ethylhexylperoxy) dicarbonate, t-hexylperoxyneodecanate, dimethoxybutylperoxydidecanate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, t-butylperoxyneodeca Noate, t-hexylperoxypivalate, t-butylperoxy
  • a dialkyl peroxide-based organic peroxide is preferable, and among them, ⁇ , ⁇ '-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy)
  • hexin-3 is more preferred.
  • the curable resin composition of the present invention preferably contains 0.05 to 30 parts by mass of the component (B) with respect to 100 parts by mass of the component (A), preferably 0.1 to 20 parts by mass. It is more preferable, and it is further preferable to contain 0.5 to 10 parts by mass. It is preferable that the component (B) is contained in an amount of 0.05 parts by mass or more because the reactivity is improved, the residual low molecular weight component is reduced, and the heat resistance of the obtained cured product is excellent. On the other hand, when the content of the component (B) is 100 parts by mass or less, the obtained cured product can suppress deterioration of the dielectric property, which is a preferable embodiment.
  • the curable resin composition of the present invention is characterized by containing a flame retardant (C) (also referred to as “component (C)").
  • the cured product obtained by using the curable resin composition containing the component (C) is excellent in flame retardancy and is a preferable embodiment.
  • the component (C) can be used without particular limitation, and examples thereof include phosphorus-based flame retardants, nitrogen compounds, silicone-based flame retardants, metal hydroxides, and polysilanes.
  • examples of the phosphorus-based flame retardants are organic. Phosphorus-based flame retardants, reactive organophosphorus flame retardants, organonitrous-containing phosphorus compounds and the like are preferable.
  • organophosphorus flame retardant examples include phenanthren-type phosphorus compounds such as HCA, HCA-HQ and HCA-NQ manufactured by Sanko Co., Ltd., and phosphorus-containing benzoxazines such as HFB-2006M manufactured by Showa Polymer Co., Ltd. Compound, Leofos 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, FP-800 manufactured by Ajinomoto Fine Techno Co., Ltd.
  • phosphate ester compounds such as PX-200 manufactured by Daihachi Chemical Co., Ltd.
  • organic phosphinates such as OP930, OP935, OP945 manufactured by Clariant Co., Ltd. , FX289, FX305 and other phosphorus-containing epoxy resins manufactured by Toto Kasei Co., Ltd., phosphorus-containing phenoxy resins such as ERF001 manufactured by Toto Kasei Co., Ltd., and phosphorus-containing epoxy resins such as YL7613 manufactured by Japan Epoxy Resin Co., Ltd. Can be mentioned.
  • Examples of the reactive organophosphorus flame retardant include MC-2, MC-4, S-2, S-4, V1, V2, V3, V4, V5 and W-1o manufactured by Katayama Chemical Industry Co., Ltd. , W-2h, W-2o, W-3o, W-4o and the like.
  • organic nitrogen-containing phosphorus compound examples include phosphoric acid ester amide compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPEL00 manufactured by Otsuka Chemical Co., Ltd., and FP- manufactured by Fushimi Seisakusho Co., Ltd. Examples thereof include phosphazene compounds such as serials.
  • Examples of the metal hydroxide include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Material Industries Ltd., and B-30, B-325, B-315, and B- of Tomoe Kogyo Co., Ltd.
  • Examples thereof include aluminum hydroxide such as 308, B-303, and UFH-20.
  • Examples of polysilane include SI-10, SI-20, SI-30 manufactured by Osaka Gas Chemical Co., Ltd.
  • a general flame-retardant agent tends to have a high dielectric positive contact due to its use, but as the component (C), PX manufactured by Daihachi Chemical Co., Ltd., particularly from the viewpoint of being able to reduce the dielectric positive contact.
  • C the component
  • PX manufactured by Daihachi Chemical Co., Ltd.
  • Reactive organophosphorus flame retardants such as V1, V2, V3, V4, V5, W-1o, W-2h, W-2o, W-3o and W-4o are preferable.
  • the component (C) contains a phosphorus-based flame retardant represented by any of the following general formulas (P-1) to (P-5).
  • R 11 independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and is preferable from the viewpoint of low dielectric positive tangent. It is a phenyl group having a substituent at the 2,6 position, and particularly preferably a 2,6-dimethylphenyl group.
  • R 12 represents an alkylene group or an arylene group, and is preferably a phenylene group from the viewpoint of heat resistance.
  • a represents an integer of 0 to 3, and is preferably 0 or 1 from the viewpoint of flame retardancy.
  • R 13 independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and is preferable from the viewpoint of low dielectric constant. It is a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a benzyl group, and a phenyl group.
  • M b + represents a b-valent metal ion, and examples of the metal include aluminum, magnesium, sodium, potassium, and calcium, and aluminum is preferable from the viewpoint of flame retardancy.
  • b represents an integer of 1 to 3, and is preferably 3 from the viewpoint of flame retardancy.
  • R 14 independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and is preferable from the viewpoint of low dielectric constant. It is a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group, a benzyl group, and a phenyl group.
  • R 15 represents an alkylene group or an arylene group, and is preferably a phenylene group from the viewpoint of heat resistance.
  • M c + represents a c-valent metal ion, and examples of the metal include aluminum, magnesium, sodium, potassium, and calcium, and aluminum is preferable from the viewpoint of flame retardancy.
  • R 16 independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and is preferably phenyl from the viewpoint of heat resistance. It is a group.
  • a cyclic structure may be formed together with a phosphorus atom, and R 17 represents a vinyl group, a vinylbenzyl group, or a (meth) acryloyloxy group, and is preferably a vinyl group or a vinylbenzyl group from the viewpoint of low dielectric positive tangent.
  • Is. f and g independently indicate 0 or 1, respectively.
  • Examples of the phosphorus-based flame retardant that forms a cyclic structure together with the phosphorus atom include the following general formula (P1). (P1)
  • R 18 independently represents an alkyl group, an aryl group, an aralkyl group, or a cycloalkyl group having 1 to 12 carbon atoms, and is preferably phenyl from the viewpoint of heat resistance. It is a group.
  • a cyclic structure may be formed together with the phosphorus atom, and R 19 represents a divalent group having an arylene structure, and is preferably a phenyl group from the viewpoint of heat resistance.
  • R 20 represents a (meth) acryloyloxy group, a vinylbenzyl ether group, or an allyl ether group, and is preferably a vinylbenzyl ether group from the viewpoint of low dielectric positivity.
  • h indicates 0 or 1.
  • Examples of the phosphorus-based flame retardant that forms a cyclic structure together with the phosphorus atom include the following general formula (P2). (P2)
  • the curable resin composition of the present invention preferably contains 0.05 to 300 parts by mass of the component (C) with respect to 100 parts by mass of the component (A), preferably 0.1 to 200 parts by mass. Is more preferable, and it is more preferably contained in an amount of 1 to 100 parts by mass, and further preferably contained in an amount of 5 to 50 parts by mass.
  • the component (C) is contained in an amount of 0.05 parts by mass or more, the obtained cured product is preferable because sufficient flame retardancy can be obtained.
  • the obtained cured product can suppress deterioration of the dielectric property, which is a preferable embodiment.
  • the curable resin composition of the present invention contains other resins, curing agents, curing accelerators, and the like. It can be used without particular limitation as long as the object of the invention is not impaired.
  • the curable resin composition can be obtained as a cured product by heating or the like without blending a curing agent or a curing accelerator. However, for example, when the component (D) is blended together, it is separately blended. , Curing agent, curing accelerator and the like can be blended.
  • thermoplastic resin In addition to the above-mentioned component (A) and component (D), a thermoplastic resin may be blended if necessary.
  • the thermoplastic resin include styrene butadiene resin, styrene-butadiene-styrene block resin, styrene-isoprene-styrene resin, styrene-maleic anhydride resin, acrylonitrile butadiene resin, polybutadiene resin or their hydrogenated resin, and acrylic. Resin, silicone resin and the like can be used.
  • the characteristics derived from the resin can be imparted to the cured product, which is a preferable embodiment.
  • the performance that can be imparted can contribute to imparting formability, high frequency characteristics, conductor adhesiveness, solder heat resistance, adjustment of glass transition temperature, coefficient of thermal expansion, smear removal property, and the like.
  • curing agent examples include amine compounds, amide compounds, acid anhydride compounds, phenolic compounds, cyanate ester compounds and the like. These curing agents may be used alone or in combination of two or more.
  • ⁇ Hardening accelerator> various substances can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts and the like.
  • phosphorus compounds such as triphenylphosphine or imidazoles are preferable because they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability and the like.
  • These curing accelerators can be used alone or in combination of two or more.
  • organic phosphin compounds TPP, TPP-K, TPP-S, TPTP. -S (Hokuko Kagaku Kogyo Co., Ltd.), amines: dicyandiamide, diaminodiphenylethane, guanylurea, Novacure (Asahi Kasei Kogyo Co., Ltd.), Fujicure (Fuji Kasei Kogyo Co., Ltd.) and other amine adduct compounds, 1,8 -Diazabicyclo [5,4,0] undecene-7, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, etc., imidazoles: 2-phenylimidazole, 1 -Cyanoethyl-2-methylimidazole, 1-cyanoethyl-N
  • acidic catalyst p-toluenesulfonic acid
  • amine compound triethylamine, pyridine, tributylamine, tertiary amine compound
  • quaternary ammonium compound imidazole compound, phosphorus compound
  • organic peroxide dicumyl peroxide.
  • An inorganic filler can be added to the curable resin composition of the present invention, if necessary.
  • the inorganic filler include silica (molten silica, crystalline silica), alumina, barium sulfate, talc, kleni, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, and hoe.
  • examples thereof include aluminum hydroxide, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate.
  • the surface may be treated with a silane coupling agent.
  • the blending amount of the inorganic filler is particularly large, it is preferable to use fused silica.
  • the molten silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the molten silica and suppress the increase in the melt viscosity of the molding material, it is better to mainly use the spherical one. preferable. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica.
  • ⁇ Other compounding agents Various compounding agents such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier can be added to the curable resin composition of the present invention, if necessary.
  • the present invention relates to a cured product obtained by subjecting the curable resin composition to a curing reaction.
  • the curable resin composition in addition to the component (A), the component (B), and the component (C), each component such as the component (D) and the curing agent is uniformly mixed according to the purpose. It can be easily made into a cured product by the same method as a conventionally known method.
  • the cured product include molded products such as laminates, cast products, adhesive layers, coating films, and films.
  • thermosetting and ultraviolet curing reactions examples include thermosetting and ultraviolet curing reactions.
  • the thermosetting reaction is easily carried out even without a catalyst, but the reaction proceeds even faster by using the component (B). Can be made to.
  • a polymerization initiator, a catalyst, or the like can also be used.
  • the present invention relates to a varnish obtained by diluting the curable resin composition with an organic solvent.
  • a method for preparing the varnish a known method can be used, and the curable resin composition can be a resin varnish dissolved (diluted) in an organic solvent.
  • the present invention relates to a prepreg having a reinforcing base material and a semi-cured product of the varnish impregnated in the reinforcing base material.
  • the curable resin composition is semi-cured (or uncured).
  • organic solvent examples include toluene, xylene, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone (MEK), methyl isobutyl ketone, dioxane, tetrahydrofuran and the like. , Alone, or as a mixed solvent of two or more kinds.
  • the reinforcing base material impregnated with the varnish is an inorganic fiber such as glass fiber, polyester fiber, polyamide fiber, a woven fabric or non-woven fabric made of organic fiber, a mat, paper or the like, and these may be used alone or. , Can be used in combination.
  • the mass ratio of the curable resin composition and the reinforcing base material in the prepreg is not particularly limited, but usually, the curable resin composition (resin content in the prepreg) is 20 to 60% by mass. It is preferable to prepare.
  • the conditions for the heat treatment of the prepreg are appropriately selected depending on the type and amount of the organic solvent, catalyst, and various additives used, but are usually at a temperature of 80 to 220 ° C. for 3 minutes to 30 minutes. It is done under such conditions.
  • the cured product of the present invention may be, for example, a laminate having a base material and a layer containing the cured product.
  • the laminate formed from the layer containing the cured product (cured product layer) has a low dielectric constant, a low dielectric loss tangent, and high heat resistance, and is therefore preferable because it can be used for a high-frequency-compatible printed circuit board or the like.
  • the base material used for the laminate may be an inorganic material such as metal or glass, an organic material such as plastic or wood, or the like, and may be used in a timely manner depending on the intended use.
  • glass fiber E glass, D glass, S glass, Q.
  • Glass, spherical glass, NE glass, L glass, T glass, inorganic fiber quartz, total aromatic polyamide: polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont Co., Ltd.), copolyparaphenylene 3,4 'Oxydiphenylene / terephthalamide (Technora (registered trademark), manufactured by Teijin Techno Products Co., Ltd.), Polyester: 2,6-hydroxynaphthoic acid / parahydroxybenzoic acid (Vectran (registered trademark), manufactured by Claret Co., Ltd.), Zexion ( Registered trademark (manufactured by KB Salen), organic fiber: polyparaphenylene benzoxazole (Zylon (registered trademark), manufactured by Toyo Spinning Co., Ltd.), polyimide and the like.
  • the shape of the laminated body may be a flat plate, a sheet, a three-dimensional structure, or a three-dimensional shape. It may have any shape depending on the purpose, such as one having a curvature on the entire surface or a part thereof. Further, there are no restrictions on the hardness, thickness, etc. of the base material. Further, the cured product of the present invention may be used as a base material, and the cured product of the present invention may be further laminated.
  • the laminate When the laminate is used for a circuit board or a semiconductor package substrate, it is preferable to laminate a metal foil, and examples of the metal foil include copper foil, aluminum foil, gold foil, and silver foil, and copper is good in processability. It is preferable to use foil.
  • the layer containing the cured product may be formed by directly coating or molding on the base material, or the already molded product may be laminated.
  • the coating method is not particularly limited, and the spray method, spin coating method, dip method, roll coating method, blade coating method, doctor roll method, doctor blade method, curtain coating method, slit coating method, etc. Examples include a screen printing method and an inkjet method.
  • direct molding in-mold molding, insert molding, vacuum forming, extrusion laminating molding, press molding and the like can be mentioned.
  • the cured product of the present invention may be laminated by applying a precursor that can be the base material and curing the cured product, and the precursor that can be the base material or the curable resin composition of the present invention can be used. It may be cured after being bonded in an uncured or semi-cured state.
  • the precursor that can be the base material is not particularly limited, and various curable resin compositions and the like can also be used.
  • the cured product obtained from the curable resin composition of the present invention is excellent in flame retardancy, heat resistance, and dielectric properties, it can be suitably used for heat-resistant members and electronic members.
  • it can be suitably used for varnishes, prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives, resist materials and the like used in the manufacture of prepregs.
  • it can be suitably used for a matrix resin of a fiber reinforced resin, and is particularly suitable as a flame-retardant and highly heat-resistant prepreg.
  • the heat-resistant members and electronic members thus obtained can be suitably used for various purposes, for example, industrial mechanical parts, general mechanical parts, automobile / railroad / vehicle parts, space / aviation-related parts, electronic / electrical parts, and the like.
  • Examples include, but are not limited to, building materials, containers / packaging materials, daily necessities, sports / leisure products, and housing materials for wind power generation.
  • the present invention relates to a circuit board obtained by laminating the prepreg and copper foil and heat-pressing molding. Specifically, as a method for obtaining a circuit board from the curable resin composition of the present invention, the above prepregs are laminated by a conventional method, copper foils are appropriately laminated, and the temperature is 170 to 300 ° C. under a pressure of 1 to 10 MPa. A method of heat-pressing molding for 10 minutes to 3 hours can be mentioned.
  • the semiconductor encapsulant preferably contains the curable resin composition.
  • the curable resin composition is further mixed with a curing accelerator as an optional component and a compounding agent such as an inorganic filler. If necessary, a method of sufficiently melting and mixing the resin with an extruder, a feeder, a roll, or the like until the mixture becomes uniform can be mentioned.
  • fused silica is usually used as the inorganic filler, but when used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, and silicon nitride, which have higher thermal conductivity than fused silica, are used. It is preferable to use high-filling silicon or the like, or to use fused silica, crystalline silica, alumina, silicon nitride, or the like.
  • the filling ratio is preferably in the range of 30 to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable resin composition, and above all, improvement of flame retardancy, moisture resistance and solder crack resistance, and linear expansion. In order to reduce the coefficient, 70 parts by mass or more is more preferable, and 80 parts by mass or more is further preferable.
  • the semiconductor device preferably contains a cured product obtained by heat-curing the semiconductor encapsulant.
  • the semiconductor encapsulant is cast, or molded using a transfer molding machine, an injection molding machine, or the like, and further. Examples thereof include a method of heat curing at 50 to 250 ° C. for 2 to 10 hours.
  • step 1 first, the curable resin composition appropriately mixed with rubber, filler, etc. is applied to a circuit board on which a circuit is formed by a spray coating method, a curtain coating method, or the like, and then cured.
  • step 2 if necessary, a circuit board coated with the curable resin composition is drilled with a predetermined through-hole portion or the like, treated with a roughening agent, and the surface thereof is washed with hot water. Concavities and convexities are formed on the substrate, and a metal such as copper is plated.
  • step 3 the operations of steps 1 and 2 are sequentially repeated as desired, and the resin insulating layer and the conductor layer having a predetermined circuit pattern are alternately built up to form a build-up substrate.
  • the through-hole portion may be drilled after the outermost resin insulating layer is formed.
  • a roughened surface is formed by heat-pressing a copper foil with a resin obtained by semi-curing the resin composition on the copper foil onto a wiring board on which a circuit is formed at 170 to 300 ° C. It is also possible to manufacture a build-up substrate by omitting the steps of forming and plating.
  • the build-up film preferably contains the curable resin composition.
  • a curable resin composition is applied on a support film and then dried to form a resin composition layer on the support film.
  • the method can be mentioned.
  • the film is softened under the temperature conditions (usually 70 to 140 ° C.) of the laminating in the vacuum laminating method, and is present on the circuit board at the same time as laminating the circuit board. It is important to show fluidity (resin flow) that allows resin filling in the via hole or through hole to be formed, and it is preferable to blend each of the above components so as to exhibit such characteristics.
  • the diameter of the through hole of the circuit board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling in this range.
  • a varnished resin composition is prepared by blending an organic solvent, and then the varnished resin composition is applied to the surface of the support film (Y). Further, a method of forming the resin composition layer (X) by further drying the organic solvent by heating, blowing hot air, or the like can be mentioned.
  • organic solvent used here examples include ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol.
  • ketones such as acetone, methyl ethyl ketone and cyclohexanone
  • acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol.
  • Carbitols, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the non-volatile content is 30 to
  • the thickness of the resin composition layer (X) to be formed usually needs to be equal to or larger than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer (X) is preferably 10 to 100 ⁇ m.
  • the resin composition layer (X) in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.
  • the support film and protective film include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate, polycarbonates and polyimides, and metal foils such as release paper, copper foil and aluminum foil. And so on.
  • the support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.
  • the thickness of the support film is not particularly limited, but is usually 10 to 150 ⁇ m, preferably 25 to 50 ⁇ m.
  • the thickness of the protective film is preferably 1 to 40 ⁇ m.
  • the support film (Y) is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the resin composition layer constituting the build-up film is heat-cured, it is possible to prevent the adhesion of dust and the like in the curing step. When peeling after curing, the support film is usually subjected to a mold release treatment in advance.
  • a multilayer printed circuit board can be manufactured from the build-up film obtained as described above.
  • the resin composition layer (X) is protected by a protective film, after peeling off the resin composition layer (X), the resin composition layer (X) is placed on one or both sides of the circuit board so as to be in direct contact with the circuit board.
  • laminating is performed by a vacuum laminating method.
  • the laminating method may be a batch method or a continuous method using a roll. If necessary, the build-up film and the circuit board may be heated (preheated) as necessary before laminating.
  • the crimping temperature is preferably 70 to 140 ° C.
  • the crimping pressure is 1 to 11 kgf / cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N / m 2 ). It is preferable to laminate under a reduced air pressure of 20 mmHg (26.7 hPa) or less.
  • Examples of the method for obtaining a conductive paste from the curable resin composition of the present invention include a method for dispersing conductive particles in the composition.
  • the conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of the conductive particles used.
  • Example 1 73 g (0.60 mol) of 2,6-xylenol and 20 g (0.15 mol) of terephthalaldehyde were placed in a 100 ml two-necked flask equipped with a cooling tube and dissolved in 300 ml of 2-ethoxyethanol. After adding 10 g of 96% sulfuric acid while cooling in an ice bath, the reaction was carried out in an oil bath at 80 ° C. for 2 hours with stirring. After completion of the reaction, water was added to the obtained reaction mixture (reaction solution) to precipitate crude organisms. The recovered crude product was dissolved in acetone and water was added again to reprecipitate the product.
  • the precipitate was separated by filtration and dried under vacuum to obtain 62 g (0.11 mol) of an intermediate phenol compound.
  • 80 g of toluene and 62 g (0.11 mol) of the intermediate phenol compound were mixed in a 200 mL flask equipped with a thermometer, a cooling tube and a stirrer, and heated to about 85 ° C. 0.55 g (0.0045 mol) of dimethylaminopyridine was added. After all the solids had dissolved, 88.7 g (0.58 mol) of methacrylic anhydride was added slowly. The obtained solution was continuously mixed and maintained at 85 ° C. for 3 hours.
  • Example 2 In a 200 ml three-necked flask equipped with a cooling tube, 73.7 g (0.55 mol) of 2,6-xylenol and 53.7 g of 96% sulfuric acid were charged and dissolved in 30 ml of methanol while flowing nitrogen. The temperature was raised in an oil bath at 70 ° C., 25 g (0.125 mol) of a 50% glutaraldehyde aqueous solution was added over 6 hours with stirring, and then the reaction was carried out with stirring for 12 hours.
  • reaction solution was cooled to room temperature (25 ° C.), 200 ml of toluene was added to the reaction solution, and then the mixture was washed with 200 mL of water. Then, the obtained organic layer was poured into 500 mL of hexane, and the solid precipitated by this was filtered off and dried under vacuum to obtain 22 g (0.039 mol) of an intermediate phenol compound. 20 g of toluene and 22 g (0.039 mol) of the intermediate phenol compound were mixed in a 200 mL flask equipped with a thermometer, a cooling tube and a stirrer, and heated to about 85 ° C.
  • Example 3 The synthesis was carried out in the same manner as in Example 2 except that the 50% glutaraldehyde aqueous solution in Example 2 was changed to 18.1 g (0.125 mol) of a 40% glyoxal solution, and the curability of the following structural formula was carried out. Obtained resin.
  • Example 4 Except that the amount of 2,6-xylenol in Example 2 was changed to 50.9 g (0.38 mol) and the 50% glutaraldehyde aqueous solution was changed to 8.8 g (0.125 mol) of crotonaldehyde.
  • the synthesis was carried out in the same manner as in Example 2 to obtain a curable resin having the following structural formula.
  • Example 5 20 g of toluene and 30.2 g (0.039 mol) of 2,4,6-tris (3', 5'-tert-butyl-4'-hydroxybenzyl) mesitylene in a 200 mL flask equipped with a thermometer, a condenser and a stirrer. was mixed and heated to about 85 ° C. 0.19 g (0.0016 mol) of dimethylaminopyridine was added. After all the solids had dissolved, 38.5 g (0.25 mol) of methacrylic anhydride was added slowly. The obtained solution was continuously mixed and maintained at 85 ° C. for 3 hours.
  • Example 6 The synthesis was carried out in the same manner as in Example 2 except that 2,6-xylenol in Example 2 was changed to 96.9 g (0.55 mol) of 2-cyclohexylphenol, and the curability of the following structural formula was obtained. Obtained resin.
  • Example 7 The synthesis was carried out in the same manner as in Example 2 except that 2,6-xylenol in Example 2 was changed to 93.6 g (0.55 mol) of 2-phenylphenol, and the curability of the following structural formula was obtained. Obtained resin.
  • Example 8 The synthesis was carried out in the same manner as in Example 2 except that 2,6-xylenol in Example 2 was changed to 67.2 g (0.55 mol) of 2-ethylphenol, and the curability of the following structural formula was obtained. Obtained resin.
  • Example 9 The synthesis was carried out in the same manner as in Example 2 except that 2,6-xylenol in Example 2 was changed to 74.9 g (0.55 mol) of 2-isopropylphenol, and the curability of the following structural formula was obtained. Obtained resin.
  • Example 10 The synthesis was carried out in the same manner as in Example 2 except that 2,6-xylenol in Example 2 was changed to 2,5-xylenol to obtain a curable resin having the following structural formula.
  • Example 11 The synthesis was carried out in the same manner as in Example 2 except that 2,6-xylenol in Example 2 was changed to 74.9 g (0.55 mol) of 2,3,6-trimethylphenol, and the following structure was carried out.
  • the curable resin of the formula was obtained.
  • Example 12 The synthesis was carried out in the same manner as in Example 2 except that 2,6-xylenol in Example 2 was changed to 2,4-xylenol to obtain a curable resin having the following structural formula.
  • Example 13 The synthesis was carried out in the same manner as in Example 2 except that 2,6-xylenol in Example 2 was changed to 104.7 g (0.55 mol) of 2-cyclohexyl-5-methylphenol, and the structure was as follows.
  • the curable resin of the formula was obtained. 1 1 H-NMR measurement was performed (see FIG. 3) to determine the structure of the curable resin as a product.
  • Example 14 Synthesis was carried out in the same manner as in Example 13 except that chloromethylstyrene in Example 13 was changed to 26 g (0.34 mol) of allyl chloride to obtain a curable resin having the following structural formula.
  • Example 15 73.7 g (0.55 mol) of 2,6-xylenol and 53.7 g of 96% sulfuric acid were charged in a 200 ml three-necked flask equipped with a cooling tube, and dissolved in 30 ml of methanol while flowing nitrogen. The temperature was raised in an oil bath at 70 ° C., 25 g (0.125 mol) of a 50% glutaraldehyde aqueous solution was added over 6 hours with stirring, and then the reaction was carried out with stirring for 12 hours.
  • reaction solution reaction solution
  • reaction solution was cooled to room temperature (25 ° C.)
  • 200 ml of toluene was added to the reaction solution, and then the mixture was washed with 200 mL of water.
  • the obtained organic layer was poured into 500 mL of hexane, and the solid precipitated by this was filtered off and dried under vacuum to obtain 22 g (0.039 mol) of an intermediate phenol compound.
  • Example 2 The synthesis was carried out in the same manner as in Example 1 above, except that the terephthalaldehyde in Example 1 was changed to 16.2 g (0.1 mol) of benzene-1,3,5-tricarbaldehyde, and the structure was as follows. The curable resin of the formula was obtained.
  • Example 14 (X is an allyl ether group), homopolymerization (crosslinking) of the curable resin alone does not proceed, so only the production confirmation of the curable resin is performed, and the following resin film (cured product) is used. No evaluation based on this is done.
  • the dielectric constant and dielectric loss tangent at a frequency of 10 GHz by the split post dielectric resonator method using a network analyzer N5247A manufactured by Keysight Technology Co., Ltd. was measured.
  • the dielectric loss tangent if it is 10 ⁇ 10 -3 or less, there is no practical problem, preferably 3.0 ⁇ 10 -3 or less, and more preferably 2.5 ⁇ 10 -3 or less. ..
  • the dielectric constant is 3.0 or less, there is no problem in practical use, and it is preferably 2.7 or less, and more preferably 2.5 or less.
  • ⁇ Preparation of curable resin composition> Using the curable resin obtained in the above Examples, blending was performed with the compositions shown in Tables 2 and 3 (raw materials, blending amount) to obtain a curable resin composition. As the curable resin shown in Tables 2 and 3, specifically, the curable resin obtained in Example 2 is cured with the curable resin (A1), and the curable resin obtained with Example 13 is cured. The curable resin (A2) and the curable resin obtained in Example 15 were designated as curable resin (A3). For comparison, a commercially available 4,4'-isopropyridene diphenol dimethacrylate (manufactured by Sigma-Aldrich) having the following structural formula was used as the curable resin (A4). Using these curable resin compositions, samples for evaluation (resin film (cured product)) are prepared based on the conditions (temperature, time, etc.) shown below, and these are used as examples and comparative examples for evaluation. gone.
  • ⁇ Making a resin film (cured product)> The curable resin composition having the contents shown in Tables 2 and 3 below was placed in a 10 cm square square mold, sandwiched between stainless steel plates, and set in a vacuum press. The pressure was increased to 1.5 MPa under normal pressure of 30 ° C. Next, the pressure was reduced to 10 torr, the mixture was heated to 100 ° C. for 30 minutes, and allowed to stand for 1 hour. Then, it was heated to 220 ° C. over 30 minutes and allowed to stand for 2 hours. Then, it was slowly cooled to room temperature (25 ° C.). A uniform resin film (cured product) having an average film thickness of 100 ⁇ m was produced.
  • the obtained resin film (cured product) was measured using a TG-DTA device (TG-8120) manufactured by Rigaku Co., Ltd. at a nitrogen flow of 20 mL / min and a temperature rise rate of 20 ° C./min, and 10%.
  • the weight loss temperature (Td10) was measured.
  • the 10% weight reduction temperature if it is 400 ° C. or higher, there is no practical problem, and it is preferably 410 ° C. or higher, and more preferably 420 ° C. or higher.
  • the dielectric constant and dielectric loss tangent at a frequency of 10 GHz by the split post dielectric resonator method using a network analyzer N5247A manufactured by Keysight Technology Co., Ltd. was measured. If the dielectric loss tangent is 10.0 ⁇ 10 -3 or less, there is no practical problem, and preferably 3.0 ⁇ 10 -3 or less, more preferably 2.5 ⁇ 10 -3. It is as follows. Further, when the dielectric constant is 3.0 or less, there is no problem in practical use, and it is preferably 2.7 or less, and more preferably 2.5 or less.
  • V5 Katayama Chemical Industry Co., Ltd.
  • V5 (9,10-dihydro-9-oxa-10-vinyl-10-phosphaphenanthrene-10-oxide)
  • OP930 OP930 manufactured by Clariant Japan Co., Ltd.
  • PX-200 PX-200 (resorcinol bis (di-2,6-xylenyl phosphate)) agent manufactured by Daihachi Chemical Industry Co., Ltd.
  • DT-4000 DT-4000 (dicyclopentadiene type cyanate resin) manufactured by Lonza Japan Co., Ltd.
  • BMI-5100 BMI-5100 manufactured by Daiwa Kasei Kogyo Co., Ltd. (3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebismaleimide)
  • the cured product obtained by using the curable resin can achieve both heat resistance and low dielectric properties at a level where there is no practical problem. I was able to confirm that there was.
  • Comparative Example 3 since there is no substituent corresponding to Ra in the structure of the curable resin, there are few steric obstacles, and as the molecular motility increases, the dielectric loss tangent becomes very high, which is a comparative example.
  • No. 4 since the central structure of the curable resin has an ester group (oxygen bond), the dielectric loss tangent and the dielectric constant are high, and the central structure of the curable resin (corresponding to Z) has a large carbon number of 17. Therefore, it was confirmed that the crosslink density was low, the Tg was low, and the heat resistance was inferior.
  • Comparative Example 4 since the substituent corresponding to Ra in the structure of the curable resin is a tert-butyl group, it is easily thermally decomposed during heating and the 5% weight loss temperature (Td5) tends to be low. showed that.
  • the cured product obtained has flame retardancy, heat resistance, and low dielectric properties. It was confirmed that there was no problem in practical use.
  • Comparative Example 5 only the component (A) was used, in Comparative Example 6, the components (A) and (B) were used, and in Comparative Example 7, the component (A) and the component (B) were used.
  • Comparative Example 8 a cured product was prepared using a curable resin composition using only the component (A) and the component (C) and a curable resin having no desired structure, so that the cured product was flame-retardant. It was not possible to obtain a product that satisfies all of the heat resistance and the low dielectric property at once.
  • Comparative Example 5 and Comparative Example 7 since the component (B) which is a radical polymerization initiator was not used, the reactivity was lowered, the weight was reduced at the time of high temperature heating, and it was confirmed that the heat resistance was inferior. rice field. Further, in Comparative Example 5 and Comparative Example 6, it was confirmed that the flame retardant was inferior because the component (C) which was a flame retardant was not blended. Further, in Comparative Example 8, since a curable resin having no desired structure was used instead of the component (A), the molecular mobility of the polar group of the cross-linking group became high, the dielectric loss tangent became very high, and the dielectric loss tangent became very high. It was confirmed that the heat resistance was also inferior due to the two cross-linking groups.
  • the curable resin of the present invention and the cured product obtained by using the curable resin composition containing the curable resin are excellent in flame retardancy, heat resistance, and low dielectric property, and thus are excellent in heat-resistant members and electronic members.
  • it can be suitably used for prepregs, circuit boards, build-up films, build-up boards, and the like, as well as adhesives and resist materials.
  • it can be suitably used for a matrix resin of a fiber reinforced resin, and is suitable as a prepreg having high heat resistance.

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JP2024048460A (ja) * 2022-09-28 2024-04-09 四国化成工業株式会社 テトラキスフェノールエタン誘導体、その合成方法およびその利用
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