WO2022202886A1 - 低誘電材料用の樹脂組成物、積層基板用フィルム、積層基板、低誘電材料用の樹脂組成物の製造方法、積層基板用フィルムの製造方法及び積層基板の製造方法 - Google Patents

低誘電材料用の樹脂組成物、積層基板用フィルム、積層基板、低誘電材料用の樹脂組成物の製造方法、積層基板用フィルムの製造方法及び積層基板の製造方法 Download PDF

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WO2022202886A1
WO2022202886A1 PCT/JP2022/013425 JP2022013425W WO2022202886A1 WO 2022202886 A1 WO2022202886 A1 WO 2022202886A1 JP 2022013425 W JP2022013425 W JP 2022013425W WO 2022202886 A1 WO2022202886 A1 WO 2022202886A1
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Prior art keywords
resin composition
low dielectric
dielectric material
film
resin
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PCT/JP2022/013425
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English (en)
French (fr)
Japanese (ja)
Inventor
好行 大石
祐二 芝▲崎▼
匡 塚本
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Iwate University NUC
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Iwate University NUC
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Priority to CN202280022862.7A priority Critical patent/CN117062876A/zh
Priority to JP2023509240A priority patent/JP7849888B2/ja
Priority to US18/551,810 priority patent/US20240209148A1/en
Publication of WO2022202886A1 publication Critical patent/WO2022202886A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • 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
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • 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
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

  • the present invention provides a resin composition for a low dielectric material containing a triazine-containing polyether compound, a film for a laminated substrate, a laminated substrate, and a resin composition for a low dielectric material, for use as a low dielectric material for electronic devices and the like.
  • the present invention relates to a method, a method for producing a film for a laminated substrate, and a method for producing a laminated substrate.
  • aromatic polyethers have excellent heat resistance and relatively excellent mechanical strength, so they are widely used in the automotive and mechanical fields as so-called engineering resins.
  • engineering resins As a more preferable engineering resin, development of a new structure that is an even more excellent engineering resin that achieves both heat resistance and thermal stability is underway.
  • Patent Document 1 discloses a phenyltriazine compound bound to an aryl group. This technique aims to provide an aromatic polyether resin which is excellent in heat resistance and thermal stability, is excellent in mechanical strength, etc., and can be advantageously used as an engineering resin.
  • the present invention has been made in view of the above circumstances, and is suitable as a low dielectric material because of its low dielectric constant, low dielectric loss tangent, high transparency, high solubility, and high heat resistance. It is an object of the present invention to provide a resin composition that can be used for a film, a film for a laminated substrate using the same, a laminated substrate, and a method for producing them.
  • a resin composition for a low dielectric material containing a triazine-containing polyether compound having a repeating unit represented by the following general formula (1).
  • n is an integer of 2 or more
  • Ar represents a divalent aromatic group with or without a substituent.
  • R is hydrogen, a linear, branched or cyclic aliphatic group, an aromatic group with or without a substituent, a fluorinated aliphatic group, or a fluorinated aromatic group; show.
  • the resin composition for a low dielectric material containing a triazine-containing polyether compound in which the repeating unit represented by n in the general formula (1) has an average degree of polymerization of 2 to 200.
  • the resin composition for a low dielectric material, wherein the triazine-containing polyether compound has a dielectric constant Dk of 2.8 or less and/or a dielectric loss tangent Df of 0.003 or less.
  • the resin composition for a low dielectric material, wherein the triazine-containing polyether compound has a glass transition temperature of 200° C. or higher.
  • the resin composition for a low dielectric material comprising the triazine-containing polyether compound and an epoxy resin, bismaleimide resin or cyanate resin.
  • the resin composition for a low dielectric material further comprising an inorganic filler, a modifier or a flame retardant.
  • the above-mentioned resin composition for low dielectric materials which is used in equipment for transmitting and receiving high-frequency electromagnetic waves having a frequency of 0.1 to 500 GHz.
  • the resin composition for a low dielectric material which is used for printed wiring boards, flexible printed wiring boards, sealing materials for electronic parts, resist inks, conductive pastes, insulating materials, or insulating boards.
  • a film for a laminated substrate comprising an insulating material containing the resin composition for a low dielectric material on at least one surface thereof.
  • a laminated substrate comprising two or more of the films for a laminated substrate.
  • a method for producing the resin composition for the low dielectric material A compound represented by the following general formula (16) and a compound represented by the following general formula (17) are mixed and polymerized to obtain a triazine-containing polyether compound represented by the following general formula (18).
  • a method for producing a resin composition for dielectric materials [In formulas (16), (17) and (18), n is an integer of 2 or more, and Ar represents a divalent aromatic group with or without a substituent.
  • R is hydrogen, a linear, branched or cyclic aliphatic group, an aromatic group with or without a substituent, a fluorinated aliphatic group, or a fluorinated aromatic group; show.
  • a method for producing a resin composition for a low dielectric material used as an insulating material between layers of a laminated substrate comprising: A method for producing a resin composition for a low dielectric material, wherein the triazine-containing polyether compound, epoxy resin, bismaleimide resin or cyanate resin, curing accelerator and organic solvent are mixed.
  • a method for producing a film for a laminated substrate comprising applying an insulating material containing the resin composition for a low dielectric material to at least one surface of a resin film.
  • a method for producing a laminated substrate comprising laminating two or more of the films for the laminated substrate.
  • a resin composition that can be suitably used as a low dielectric material because it has a low dielectric constant, a low dielectric loss tangent, a high transparency, a high solubility, and a high heat resistance.
  • a film for a laminated substrate, a laminated substrate, and a method for producing them are obtained.
  • FIG. 2 is a diagram showing FT-IR spectra of Reference Examples 1 to 4 of this example.
  • the resin composition for the low dielectric material of this embodiment contains a specific triazine-containing polyether compound.
  • a low dielectric material is a material with a low dielectric constant and/or a low dielectric loss tangent. That is, it is a low dielectric constant material or a low dielectric loss tangent material, and is hereinafter generically referred to as a "low dielectric material”. Definitions such as conditions for measuring the dielectric constant will be described later.
  • a low dielectric material is used in a portion of an electronic device or electronic component that requires a low dielectric constant and/or a low dielectric loss tangent.
  • a portion requiring a low dielectric constant and/or a low dielectric loss tangent is, for example, a portion that requires insulation, and includes insulating parts such as an insulating plate and insulating parts of a printed wiring board.
  • Printed wiring boards also include flexible printed wiring boards. Since the compound contained in the material of the present embodiment has a low dielectric constant and/or a low dielectric loss tangent, especially at high frequencies, it can be used as electronic components and electronic devices, especially for high-frequency compatible electronic components and electronic devices. is preferred.
  • the triazine-containing polyether compound contained in the resin composition of this embodiment has a repeating unit represented by the following general formula (1).
  • n is an integer of 2 or more
  • Ar is an arylene group, and represents a divalent aromatic group with or without a substituent.
  • the substituent is a group different from the group (atomic group) to be bonded, and can be bonded by replacing some atoms (preferably hydrogen) of the group to be bonded.
  • An aromatic group broadly refers to a group containing the structure of a compound or partially substituted compound having aromatic character.
  • Aliphatic groups broadly refer to groups containing structures of organic or partially substituted compounds that do not have aromatic character.
  • n represents the number of repeating units of the structure represented by formula (1) and is an integer of 2 or more.
  • the average value of the degree of polymerization n of the triazine-containing polyether compound contained in the resin composition for the low dielectric material of the present embodiment is the average degree of polymerization, and the value of the average degree of polymerization ranges from 2 to 200. It is preferably 1, and may be 2-100.
  • R is an organic substituent and may be hydrogen or may be a linear, branched or cyclic aliphatic group. Also, R may be an aromatic group with or without a substituent. In addition, R may be any of the aforementioned aliphatic groups that are fluorinated or any of the aforementioned aromatic groups that are fluorinated.
  • the degree to which R is fluorinated may be selected widely, from one of the carbon attachment sites in R to all carbon attachment sites other than those attached to the group to which it is attached.
  • R when R is a methyl group, 1 to 3 hydrogen atoms of the methyl group may be substituted with fluorine atoms, but 2 to 3 hydrogen atoms are preferred.
  • R in formula (1) may be the same substituent or different.
  • the above-described chemical structure of the triazine-containing polyether compound contained in the resin composition of the present embodiment is determined by infrared spectrum (FT-IR), nuclear magnetic resonance spectrum (NMR, such as 1 H-NMR, 13 C-NMR, 19 F-NMR), elemental analysis, or the like.
  • Examples of the arylene group for Ar include various divalent aromatic compounds obtained by extracting a total of two hydrogen atoms or other substituents bonded to aromatic rings in various aromatic compounds or aromatic ring-containing compounds. can be appropriately selected from group residues. Examples of arylene groups can be appropriately selected from various phenylene groups, naphthylene groups, biphenylene groups, and the like.
  • Ar includes other alkyl groups, alkylene groups, alkylidene groups, cycloalkyl groups, cycloalkylene groups, cycloalkylidene groups, aryl groups, arylene groups, fluorinated alkyl groups, fluorinated alkylene groups, fluorinated aryl groups, or fluorinated An arylene group or the like may be bonded.
  • the triazine-containing polyether compound of the present embodiment may be a triazine-containing polyether compound in which Ar is represented by any one of the following general formulas (2) to (15).
  • formula (2) is BisA
  • formula (3) is BisAF
  • formula (4) is BisPHTG
  • formula (5) is BisPIND
  • formula (6) is BisC
  • formula (7) is TMBisA
  • formula (8) is BisCHP
  • formula (9) is BisZ
  • formula (10) is BisP3MZ
  • formula (11) is BisPCDE
  • formula ( 12) may also be expressed as DTPM
  • equation (13) as BPFL
  • equation (14) as DMBPFL
  • equation (15) as TBISRX.
  • the triazine-containing polyether compound of the present embodiment preferably has an average degree of polymerization of 2 to 200 for repeating units represented by n in the general formula (1).
  • the repeating unit represented by n has an average degree of polymerization of 2 to 200, a compound having an appropriate molecular weight can be obtained when used as a resin composition for a low dielectric material.
  • the molecular weight of the triazine-containing polyether compound of the present embodiment is a number average molecular weight (M n ) of 3 ⁇ 10 3 to 40 ⁇ 10 when Ar in the above formulas (2) to (15) is used. 4 , and more preferably 3 ⁇ 10 3 to 20 ⁇ 10 4 .
  • the weight average molecular weight (M w ) is preferably 6 ⁇ 10 3 to 40 ⁇ 10 4 , more preferably 6 ⁇ 10 3 to 40 ⁇ 10 4 .
  • the molecular weight of the compound of this embodiment can be measured using gel permeation chromatography (GPC) or the like. The average degree of polymerization can be determined from this molecular weight and the structure of the compound described above.
  • the triazine-containing polyether compound of the present embodiment preferably has a dielectric constant Dk of 2.8 or less and/or a dielectric loss tangent Df of 0.003 or less.
  • the dielectric constant Dk and the dielectric loss tangent Df are values measured by an existing dielectric property measuring device.
  • an existing dielectric property measuring device for example, a cavity resonator type device or the like can be used.
  • the triazine-containing polyether compound of the present embodiment preferably has a dielectric constant Dk of 2.7 or less.
  • the dielectric loss tangent D f is preferably 0.003 or less, more preferably 0.002 or less.
  • the triazine-containing polyether compound may have a dielectric constant Dk of 2.7 or less and a dielectric loss tangent Df of 0.002 or less.
  • the triazine-containing polyether compound of the present embodiment preferably has a glass transition temperature of 200° C. or higher, more preferably 260° C. or higher. It is also preferable that the 5% thermal decomposition temperature is 400 to 600°C.
  • the glass transition temperature of the triazine-containing polyether compound of the present embodiment can be measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA), dynamic viscoelasticity measurement (DMA), and the like.
  • the 5% thermal decomposition temperature of the triazine-containing polyether compound of the present embodiment is obtained by measuring the weight loss temperature.
  • the weight loss temperature can be measured using, for example, thermogravimetry (TGA).
  • the resin composition for low dielectric materials of the present embodiment preferably contains the triazine-containing polyether compound and epoxy resin, bismaleimide resin, cyanate resin, or the like.
  • epoxy resin By containing an epoxy resin, a resin composition for low dielectric materials having excellent heat resistance, mechanical properties and dielectric properties can be obtained.
  • the epoxy resin is not particularly limited, but in that a cured product having excellent heat resistance can be obtained, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol sulfide type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, Tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol aralkyl type epoxy resin, naphthol- Phenol-cocondensed novolak-type epoxy resin, naphthol-cresol co-
  • the bismaleimide resin is not particularly limited, but in that a cured product having excellent heat resistance can be obtained, for example, diphenylmethane type bismaleimide resin, metaphenylene type bismaleimide resin, bisphenol A diphenyl ether type bismaleimide resin, diphenyl ether type bismaleimide resin, A maleimide resin, a diphenylsulfone-type bismaleimide resin, a diphenoxybenzene-type bismaleimide resin, an aniline novolac-type bismaleimide resin, or the like may be used. Each of these may be used alone, or two or more of them may be used in combination.
  • the cyanate resin is not particularly limited, but in that a cured product having excellent heat resistance can be obtained, for example, bisphenol A type cyanate resin, tetramethylbisphenol F type cyanate resin, hexafluorobisphenol A type cyanate resin, bisphenol E type A cyanate resin, a bisphenol M-type cyanate resin, a novolak-type cyanate resin, a cyclopentadienylbisphenol-type cyanate resin, or the like may be used. Each of these may be used alone, or two or more of them may be used in combination.
  • the resin composition for the low dielectric material of the present embodiment further contains an inorganic filler, a modifier or a flame retardant.
  • an inorganic filler for example, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, magnesium hydroxide, or the like may be used.
  • the modifier can be appropriately selected from various thermosetting resins, thermoplastic resins, etc. Examples include phenoxy resins, polyamide resins, polyimide resins, polyetherimide resins, polyethersulfone resins, polyphenylene ether resins, and polyphenylene sulfide resins.
  • polyester resin polystyrene resin, polyethylene terephthalate resin, cycloolefin resin, fluorine resin, or the like may be used.
  • the flame retardant can be appropriately selected from, for example, halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds, and the like.
  • Halogen compounds such as resin; trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl Phosphate, phosphate ester such as 2-ethylhexyldiphenyl phosphate, tris(2,6-dimethylphenyl) phosphate, resorcin diphenyl phosphate; condensation of ammonium polyphosphate, polyphosphate amide, red phosphorus, guanidine phosphate, dialkylhydroxymethyl phosphonate, etc.
  • Phosphorus atom-containing compounds such as phosphoric acid or ester compounds
  • nitrogen atom-containing compounds such as melamine
  • inorganic flame retardant compounds
  • the resin composition for a low dielectric material of the present embodiment is preferably used for equipment that transmits and receives high-frequency electromagnetic waves having a frequency of 0.1 to 500 GHz.
  • the resin composition for a low dielectric material of the present embodiment is preferably used for devices that transmit and receive microwave or millimeter wave electromagnetic waves.
  • microwaves refer to electromagnetic waves with a frequency of 0.25 to 100 GHz
  • millimeter waves refer to electromagnetic waves with a frequency of 30 to 300 GHz.
  • the resin composition for a low dielectric material according to the present embodiment can also be suitably used in devices that use electromagnetic waves of frequencies such as 60 GHz for wireless LANs and 75 to 79 GHz for vehicle radars.
  • the resin composition for a low dielectric material of the present embodiment has a sufficiently low dielectric constant and dielectric loss tangent, and is particularly suitable for use with high-frequency electromagnetic waves.
  • the resin composition for low dielectric materials of the present embodiment is preferably used for printed wiring boards, flexible printed wiring boards, sealing materials for electronic parts, resist inks, conductive pastes, insulating materials or insulating plates.
  • the resin composition for low dielectric materials of the present embodiment has sufficiently low dielectric constant and dielectric loss tangent, and is suitable for use in these members. Furthermore, it is particularly suitable for use in these members in equipment that uses high-frequency electromagnetic waves. More specific examples include resin compositions for copper-clad laminates, interlayer insulating materials for build-up printed circuit boards, build-up films, and the like.
  • a resin composition for encapsulating electronic parts a resin composition for resist ink, a binder for friction materials, a conductive paste, a resin casting material, an adhesive, or a coating material such as an insulating paint.
  • the resin composition for a low dielectric material of this embodiment is preferably used as an insulating material between layers of a laminated substrate.
  • the resin composition is preferably prepared by mixing the triazine-containing polyether compound, the epoxy resin, the bismaleimide resin, or the cyanate resin, the curing accelerator and the organic solvent, as in the manufacturing method described below. .
  • the film for laminated substrates of this embodiment has an insulating material containing the resin composition for the low dielectric material on at least one surface.
  • an insulating material containing the resin composition for the low dielectric material By laminating a plurality of films for laminated substrates, these films can be used for laminated substrates, which will be described later.
  • a film for a laminated substrate is composed of a film layer, which will be described later, and an insulating layer containing an insulating material. The insulating layer is provided on at least one surface of the film layer by a manufacturing method to be described later.
  • the film layer can be configured using an appropriately selected film material, such as a resin film or a metal film.
  • a resin film or a metal film such as polyethylene, polypropylene, polyvinyl chloride, polycycloolefin, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, polyimide, release paper, copper foil, aluminum foil, or the like can be used.
  • the thickness of the laminated substrate film of the present embodiment is not particularly limited, but can be selected from the range of 10 to 150 ⁇ m, preferably from 25 to 50 ⁇ m.
  • the film for laminated substrates of the present embodiment may further have a protective film on its surface.
  • the protective film can prevent dust from adhering to the surface of the film layer and the insulating layer before use and from scratching, and can prevent performance such as insulation from deteriorating before use.
  • the constituent material of the protective film may be selected from the same materials as those of the film layer described above.
  • the thickness of the protective film may range from 1 to 40 ⁇ m.
  • the laminated substrate film and protective film may be subjected to matte treatment, corona treatment, release treatment, or the like.
  • the laminated board is in the form of a conductor laminated board or a build-up printed board, and a conductor layer made of a conductor such as a metal and the insulating layer are laminated, a set of the conductor layer and the insulating layer is formed. It may also be a film for laminated substrates.
  • the resin composition for a low dielectric material of this embodiment has excellent physical properties, heat resistance, a low dielectric constant, and a low dielectric loss tangent.
  • it is also extremely useful as an insulating material between layers composed of films for laminated substrates.
  • Such an insulating material is manufactured by including, in particular, a resin composition for low-dielectric materials, an epoxy resin, a bismaleimide resin, or a cyanate resin as essential components, and, if necessary, an organic solvent and a curing accelerator which will be described later. preferably.
  • the laminated substrate of this embodiment comprises two or more films for laminated substrates. It is preferable that the laminated substrate is formed by laminating the film for a laminated substrate.
  • the laminated substrate film may be an intermediate layer or a base layer in the laminated substrate. Moreover, it may be used for a layer on which a circuit is formed or a layer on which a circuit is not formed. Formation of the circuit can be performed by metal plating or the like.
  • the laminated substrate of this embodiment can also be a conductor laminated substrate.
  • a laminated substrate may be provided with an insulating layer made of a prepreg containing the resin composition for the low dielectric material and a conductor layer.
  • a prepreg for insulation forms an insulating layer by impregnating a fiber base material such as glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, or glass roving cloth with a resin composition for low dielectric materials.
  • the conductor layer can be made of metal, such as copper.
  • the laminated substrate of the present embodiment can be a laminated substrate in the form of a build-up printed circuit board.
  • a laminated board in the form of a build-up printed board can be obtained.
  • Compositions and the like of the insulating layer and conductor layer can be arbitrarily selected from those described above.
  • the resin composition for the low dielectric material of the present embodiment can be used by appropriately mixing components conventionally known as raw materials for the low dielectric material.
  • the resin composition for the low dielectric material of this embodiment has a high affinity with epoxy resin, bismaleimide resin, or cyanate resin, so it can be mixed with a thermosetting resin material. An effect of improving dielectric properties and thermal properties can also be expected.
  • the resin composition for a low dielectric material of the present embodiment has a low dielectric constant, low dielectric loss tangent, high transparency, high solubility, and high heat resistance of the triazine-containing polyether.
  • the triazine-containing polyether of the present embodiment has a low dielectric constant, a low dielectric loss tangent, a high transparency, a high solubility, and a high heat resistance, so that it can be suitably used as a printed wiring board.
  • conventionally known polymer materials there are almost no materials that achieve a glass transition temperature of more than 260 ° C.
  • the triazine-containing polyether of the present embodiment has a particularly low dielectric constant at high frequencies, a low dielectric loss tangent, high transparency, high solubility, and high heat resistance. It can be suitably used as a constituent material for electronic equipment.
  • a method for producing a resin composition for a low dielectric material comprises mixing a compound represented by the following general formula (16) and a compound represented by the following general formula (17), polymerizing them, and A triazine-containing polyether compound represented by formula (18) is obtained.
  • n is an integer of 2 or more
  • Ar is an arylene group, and represents a divalent aromatic group with or without a substituent.
  • n represents the number of repeating units of the structure represented by formula (18), and is not particularly limited as long as it is an integer of 2 or more. Examples of substituents include those having 1 to 18 carbon atoms.
  • Preferred substituents include alkyl groups such as methyl, alkylene groups such as methylene, alkylidene groups such as isopropylidene, cycloalkyl groups such as cyclohexyl, cycloalkylene groups such as cyclohexylene, cycloalkylidene groups such as cyclohexylidene, phenyl aryl groups such as aryl groups, arylene groups such as phenylene, fluorinated alkyl groups such as trifluoromethyl, fluorinated alkylene groups such as perfluorohexylene, fluorinated aryl groups such as trifluoromethylphenyl, fluorine such as trifluoromethylphenylene and an arylene group.
  • R is an organic substituent and may be hydrogen or may be a linear, branched or cyclic aliphatic group. Also, R may be an aromatic group with or without a substituent. In addition, R may be any of the aforementioned aliphatic groups that are fluorinated or any of the aforementioned aromatic groups that are fluorinated. Examples of organic substituents include those having 1 to 18 carbon atoms.
  • Preferred organic substituents are methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group and hexyl.
  • the compounds of formula (16) and formula (17) are mixed and polymerized by heating and reacting in a polar solvent in the presence of an alkali metal compound to obtain formula (18). to obtain a compound of
  • any compound can be used as long as the compound of formula (17) can be replaced with an alkali metal salt.
  • an alkali metal compound for example, an alkali metal carbonate, hydrogencarbonate, hydroxide, or the like, particularly a carbonate, is preferably used.
  • the alkali metal include lithium, sodium, potassium, rubidium and cesium, with sodium and potassium being preferred.
  • sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide or potassium hydroxide can be used. It can be used preferably.
  • These various alkali metal compounds may be used alone or in combination of two or more.
  • polar solvent one that can smoothly proceed with the polymerization reaction can be used as appropriate.
  • polar solvents include 1,3-dimethyl-2-imidazolidone (DMI), tetramethylurea (TMU), N,N'-dimethylpropyleneurea (DMPU), N,N-dimethylformamide (DMF ), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), N-cyclohexyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide (DMSO), sulfolane (SUL), and diphenylsulfone etc.
  • DMI 1,3-dimethyl-2-imidazolidone
  • TNU tetramethylurea
  • DMPU N,N'-dimethylpropyleneurea
  • DMF N,N-dimethylformamide
  • DMAc N,N-dimethylacetamide
  • NMP N-methyl-2-pyr
  • an appropriate amount of an inert solvent component such as toluene or xylene may be added at an appropriate point during the reaction using the polar solvent.
  • the polymerization temperature can be appropriately adjusted depending on the compounds, additives and solvents used, but it is usually preferably 140 to 300°C, more preferably 180 to 250°C. If the temperature is less than this range, it is not efficient because a sufficient reaction rate and degree of polymerization cannot be obtained. Moreover, if the temperature exceeds this range, the resulting compound may undergo decomposition or deterioration.
  • the polymerization reaction time can also be appropriately adjusted depending on the components used and the polymerization temperature, but is usually about 0.1 to 20 hours. For example, when NMP or DMI is used as the polar solvent, polymerization proceeds sufficiently in 3 to 4 hours at a polymerization temperature of 190 to 200°C. In order to increase the molecular weight, it is preferable to carry out the polymerization for 15 to 20 hours, or to use the state in which the polymerization is sufficiently performed such as the stirring bar is stopped as a measure of the completion of the polymerization.
  • an inert solvent component is added to the compounds of formulas (16) and (17), an alkali metal compound, and a polar solvent, followed by heating, and the polymerization temperature is gradually increased to room temperature. to 140-150°C. While maintaining the temperature, the inert solvent component and water are azeotropically removed. Then, the temperature is raised to the polymerization temperature, and the inert solvent component is completely removed while maintaining the temperature. After the inert solvent component is removed, the polymerization temperature is maintained and the polymerization is performed for the polymerization reaction time to obtain the compound of formula (18). After the polymerization reaction is fully completed, it is allowed to cool to room temperature and recovered with methanol. After that, further steps such as washing with methanol or the like, drying under reduced pressure, and/or reprecipitation with an organic solvent may be performed.
  • the resin composition for a low dielectric material of the present embodiment is a resin composition for a low dielectric material used as an insulating material between layers of a laminated substrate
  • the resin composition for a low dielectric material is a triazine-containing poly It is preferably produced by mixing an ether compound, an epoxy resin, a bismaleimide resin, or a cyanate resin, a curing accelerator and an organic solvent. Since the curing reaction of the resin composition for the low dielectric material proceeds rapidly by mixing the curing accelerator in the production, the insulating material can be easily produced.
  • the insulating layer is quickly formed, which is suitable for industrial production.
  • the resin composition for low dielectric materials becomes a so-called varnish during production, and can be easily applied to other members as an insulating material.
  • the coatability is improved when the insulating layer is formed by coating the surface of the film.
  • any compound capable of accelerating the curing of the above compounds can be used as appropriate.
  • imidazoles, tertiary amines, acid anhydrides, or tertiary phosphines may be used.
  • the amount to be added can also be appropriately adjusted depending on the composition of the compound, but is preferably in the range of 0.01 to 2% by mass with respect to the total mass of the resin composition for low dielectric materials.
  • a solvent capable of dissolving the above compound to form a varnish can be appropriately selected.
  • organic solvents such as acetamide or N-methylpyrrolidone can be used.
  • propylene glycol monomethyl ether acetate, cyclohexanone or methyl ethyl ketone can be preferably used.
  • the amount to be added can also be appropriately adjusted depending on the composition of the compound, but in order to form a varnish, the non-volatile content should be in the range of 50 to 70% by mass with respect to the total mass of the resin composition for low dielectric materials. is preferred.
  • the resin composition for a low dielectric material of the present embodiment is produced by further mixing an inorganic filler, a modifier or a flame retardant.
  • Inorganic fillers can be, for example, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, or magnesium hydroxide.
  • conductive fillers such as silver powder and copper powder can be used as inorganic fillers.
  • modifiers examples include phenoxy resins, polyamide resins, polyimide resins, polyetherimide resins, polyethersulfone resins, polyphenylene ether resins, polyphenylene sulfide resins, polyester resins, polystyrene resins, polyethylene terephthalate resins, and the like.
  • the flame retardant for example, a halogen compound, a phosphorus atom-containing compound, a nitrogen atom-containing compound, an inorganic flame retardant compound, or the like can be used.
  • an insulating material containing a resin composition for a low dielectric material is applied to at least one surface of a resin film.
  • the varnish-like resin composition for a low dielectric material is applied to at least one surface of a resin film as described above.
  • the organic solvent is volatilized by heating or blowing hot air to form an insulating layer.
  • the resin composition for the low dielectric material preferably has a non-volatile content excluding volatile components such as the organic solvent in a range of 30 to 60% by mass. Within this range, the coatability of the compound on a film and the formability of a laminated substrate film are particularly favorable.
  • the thickness of the insulating layer to be formed is equal to or greater than the thickness of the conductor layer of the circuit board on which the laminated board is installed, which will be described later.
  • 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 is preferably 10 to 100 ⁇ m.
  • Method for manufacturing laminated substrate In the method for manufacturing a laminated substrate of this embodiment, two or more films for the laminated substrate are laminated.
  • a protective film When manufacturing a printed wiring board using the laminated substrate of the present embodiment, if the film for the laminated substrate is protected by a protective film, after peeling these, the layer is directly in contact with the circuit board. It can be carried out by laminating on one side or both sides of the circuit board, for example, by a vacuum lamination method.
  • the method of lamination may be a batch type or a continuous roll type.
  • the film and circuit board may be heated (preheated) before lamination, if necessary.
  • the fiber base material is impregnated with the resin composition for low dielectric materials prepared in the form of a varnish, and heated at a heating temperature according to the type of solvent used, preferably at 50 to 170° C. to obtain a cured product.
  • An insulating layer of prepreg is obtained. Paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, matted glass, glass roving cloth, or the like can be used as the fiber substrate.
  • thermocompression bonding is, specifically, a method of carrying out at a temperature of 170 to 250° C. under a pressure of 1 to 10 MPa. Moreover, it is preferable to perform the thermocompression bonding for 10 minutes to 3 hours.
  • the laminated board and printed board may be formed in the following procedure. That is, a wiring board having a circuit formed thereon is coated with a resin composition for a low dielectric material using a spray coating method, a curtain coating method, or the like, and then cured. Next, after drilling predetermined through holes or the like as necessary, the surface is treated with a roughening agent, washed with hot water to form unevenness, and then plated with a metal such as copper.
  • the plating method is preferably electroless plating or electrolytic plating.
  • the roughening agent an oxidizing agent, an alkali, an organic solvent, or the like can be used.
  • Such an operation is repeated as desired to alternately build up insulating layers and conductor layers having a predetermined circuit pattern, thereby obtaining a build-up substrate.
  • the drilling of the through-hole part is preferably performed after the formation of the outermost insulating layer.
  • the resin composition for low dielectric material of the present embodiment In order to adjust the resin composition for low dielectric material of the present embodiment to a sealing material for electronic parts, the resin composition for low dielectric material, epoxy resin, bismaleimide resin, or cyanate resin, if necessary After pre-mixing other coupling agents and / or additives such as mold release agents and inorganic fillers, etc., it is sufficiently mixed until uniform using an extruder, kneader, roll, etc. are mentioned.
  • the resin composition obtained by the above-described method is heated to prepare a semi-cured sheet, which is used as an encapsulant tape. A method of placing on a chip, heating to 100 to 150° C. to soften and mold, and curing completely at 170 to 250° C. can be mentioned.
  • the resin composition for low dielectric material of the present embodiment as a resist ink
  • the resin composition for low dielectric material epoxy resin, bismaleimide resin, or cyanate resin, an organic solvent, a pigment
  • a resist ink composition is prepared by adding talc, a filler, and the like, and then the composition is applied onto a printed circuit board by screen printing, followed by curing the resist ink.
  • organic solvents used here include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, cyclohexanone, dimethylsulfoxide, dimethylformamide, dioxolane, tetrahydrofuran, propylene glycol monomethyl ether.
  • Acetate, ethyl lactate and the like can be mentioned.
  • the resin composition for low dielectric materials of the present embodiment is used as an insulating material, for example, an insulating material between semiconductor layers
  • a curing accelerator and a silane coupling agent are blended to prepare a composition, which is applied onto a silicon substrate by spin coating or the like.
  • the cured coating film is in direct contact with the semiconductor, it is preferable to make the coefficient of linear expansion of the insulating material close to that of the semiconductor so that cracks do not occur due to the difference in coefficient of linear expansion in a high-temperature environment.
  • the resin composition for a low dielectric material of the present embodiment is used as a conductive paste
  • fine conductive particles are dispersed in the resin composition for a low dielectric material to form a composition for an anisotropic conductive film.
  • method a method of using a paste resin composition for circuit connection which is liquid at room temperature, or an anisotropic conductive adhesive.
  • TGA Thermogravimetry
  • DSC Differential scanning calorimetry
  • TMA Thermomechanical analysis
  • DMA Dynamic viscoelasticity measurement
  • DMA Dynamic viscoelasticity measurement
  • permittivity/dielectric loss tangent measuring device cavity resonator type
  • TE mode (10 GHz) Commercially available reagents were used and purified by conventional methods as necessary.
  • BFPT 2,4-bis(4-fluorophenyl)-2-phenyl-1,3,5-triazine
  • BFPT used in each example was synthesized as follows. 4-fluorobenzamidine hydrochloride (7.460 g, 42.73 mmol), benzylideneaniline (3.625 g, 20.00 mmol), sodium bicarbonate ( 3.781 g, 45.00 mmol) and N,N-dimethylformamide (DMF, 35 mL) were added, the temperature was raised stepwise to 85° C., and the reaction was carried out at 85° C. for 96 hours. After that, it was allowed to cool to room temperature.
  • the reaction solution was poured into distilled water and chloroform was added.
  • the chloroform solution was washed three times with distilled water using a separating funnel.
  • the recovered chloroform solution was dried over anhydrous sodium sulfate overnight, and the anhydrous sodium sulfate was removed by suction filtration.
  • the chloroform solution was concentrated by an evaporator and poured into methanol (500 mL) to precipitate a crude product. This was collected by suction filtration, washed with methanol under reflux, and dried under reduced pressure at room temperature to obtain a crude brown needle crystal product (1.61 g, 23.3%).
  • the crude product was recrystallized with a mixed solvent of chloroform and methanol and dried under reduced pressure at 80° C. for 24 hours.
  • the synthesized compound was in the form of white needle crystals, yield: 1.46 g, yield: 21.1%, melting point: 258-259°C.
  • Example 1 The compound of Example 1, a polyether (BFPT-BisA) of the following formula, was synthesized as follows. BFPT (0.6907 g, 2.00 mmol) and bisphenol A (0.4566 g, 2.00 mmol) are placed in a two-necked flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube, and potassium carbonate ( 0.3334 g, 2.40 mmol), N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component were added.
  • NMP N-methyl-2-pyrrolidone
  • a Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was established.
  • the temperature was raised stepwise to 150° C. with stirring, toluene was refluxed at 150° C. for 2 hours, and water was removed with a Dean-Stark trap. After that, the temperature was raised to 190° C. and the mixture was stirred for 1 hour to remove toluene.
  • polymerization was carried out at 190° C. for 2 hours. It was allowed to cool to room temperature to obtain a viscous polymerization solution.
  • the polymer was precipitated by pouring into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature for 12 hours. The resulting polymer was dissolved in NMP and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature for 12 hours.
  • This polymer was dissolved in NMP to prepare a 12 wt% solution.
  • This solution was cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 1 hour.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 38 ⁇ m).
  • Example 2 The compound of Example 2, a polyether of the following formula (BFPT-BisAF), was synthesized as follows. BFPT (0.6907 g, 2.00 mmol) and bisphenol AF (0.6725 g, 2.00 mmol) are placed in a two-necked flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube, and potassium carbonate ( 0.3334 g, 2.40 mmol), N,N'-dimethylimidazolidone (DMI, 6.5 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component.
  • BFPT a polyether of the following formula
  • BFPT-BisAF a polyether of the following formula
  • a Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was established.
  • the temperature was raised stepwise to 150° C. with stirring, toluene was refluxed at 150° C. for 2 hours, and water was removed with a Dean-Stark trap. After that, the mixture was heated to 190° C. and stirred for 1 hour to remove toluene. After that, polymerization was carried out at 190° C. for 2 hours. It was allowed to cool to room temperature to obtain a viscous polymerization solution.
  • the polymer was precipitated by pouring into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in tetramethylurea (TMU) and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • TNU tetramethylurea
  • the polymer was dissolved in TMU to prepare a 9 wt% solution. This solution was cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 1 hour. A glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 37 ⁇ m).
  • Example 3 The compound of Example 3, a polyether of the following formula (BFPT-BisPHTG), was synthesized as follows. BFPT (0.6907 g, 2.00 mmol) and BisP-HTG (0.6209 g, 2.00 mmol) were placed in a two-necked flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube, and potassium carbonate was added as an alkali metal compound. (0.3334 g, 2.40 mmol), N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component were added.
  • NMP N-methyl-2-pyrrolidone
  • a Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was established.
  • the temperature was raised stepwise to 150° C. with stirring, toluene was refluxed at 150° C. for 2 hours, and water was removed with a Dean-Stark trap. Thereafter, the temperature was raised to 190° C. and stirred for 1 hour to remove toluene. After that, polymerization was carried out at 190° C. for 2 hours. After allowing to cool to room temperature, a brown viscous polymerization solution was obtained.
  • the polymer was precipitated by pouring into methanol, washed with hot methanol after recovery, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in NMP and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • the polymer was dissolved in TMU to prepare a 15 wt% solution. This solution was cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours. A glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 38 ⁇ m).
  • Example 4 The compound of Example 4, a polyether of the following formula (BFPT-BisPIND) was synthesized as follows. BFPT (0.6907 g, 2.00 mmol) and BisPIND (0.5368 g, 2.00 mmol) are placed in a two-necked flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube, and potassium carbonate (0 .3334 g, 2.40 mmol), N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component.
  • NMP N-methyl-2-pyrrolidone
  • a Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was established.
  • the temperature was raised stepwise to 150° C. with stirring, toluene was refluxed at 150° C. for 2 hours, and water was removed with a Dean-Stark trap. Thereafter, the temperature was raised to 190° C. and stirred for 1 hour to remove toluene. After that, polymerization was carried out at 190° C. for 2 hours. After allowing to cool to room temperature, a brown viscous polymerization solution was obtained.
  • the polymer was precipitated by pouring into methanol, washed with hot methanol after recovery, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in NMP and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • the polymer was dissolved in TMU to prepare a 10 wt% solution. This solution was cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours. A glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 43 ⁇ m).
  • Example 5 The compound of Example 5, a polyether of the following formula (BFPT-BisC), was synthesized as follows.
  • BisA in Example 1 was changed to BisC, and polymerization was carried out in NMP (5.0 mL) at 190°C for 3 hours to synthesize a polyether in the same manner.
  • the polymer was dissolved in NMP, cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 47 ⁇ m).
  • Example 6 The compound of Example 6, a polyether of the following formula (BFPT-TMBisA), was synthesized as follows. Polyether was similarly synthesized by replacing BisA in Example 1 with TMBisA and polymerizing in NMP (5 mL) at 200° C. for 3 hours.
  • NMP 5 mL
  • the polymer was dissolved in NMP, cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 63 ⁇ m).
  • Example 7 The compound of Example 7, a polyether of the following formula (BFPT-BisCHP), was synthesized as follows.
  • BisA in Example 1 was changed to BisCHP and polymerization was carried out in NMP (5 mL) at 190° C. for 3 hours to synthesize a polyether in the same manner.
  • the polymer was dissolved in NMP, cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 53 ⁇ m).
  • Example 8 The compound of Example 8, a polyether of the following formula [BFPT-BisZ/BisAF (25 mol %/75 mol %)] was synthesized as follows. BisA in Example 1 was changed to BisZ (25 mol %) and BisAF (75 mol %), and polymerization was carried out in NMP (5 mL) at 190° C. for 3 hours to synthesize a polyether in the same manner.
  • the polymer was dissolved in NMP, cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 84 ⁇ m).
  • NMP N-methyl-2-pyrrolidone
  • TMU tetramethylurea
  • DI N,N'-dimethylimidazolidone
  • DMPU N,N'-dimethylpropyleneurea
  • cyclopentanone cyclohexanone
  • THF tetrahydrofuran
  • Example 9 The compound of Example 9, a polyether of the following formula [BFPT-BisP3MZ/BisAF (50 mol %/50 mol %)] was synthesized as follows. BisA in Example 1 was changed to BisP3MZ (50 mol %) and BisAF (50 mol %), and polymerization was carried out in NMP (5 mL) at 190° C. for 3 hours to similarly synthesize polyether.
  • NMP 5 mL
  • the polymer was dissolved in NMP, cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 58 ⁇ m).
  • Example 10 The compound of Example 10, a polyether of the following formula (BFPT-BisPCDE), was synthesized as follows.
  • BisA in Example 1 was changed to BisPCDE, and polymerization was carried out in NMP (5 mL) at 190° C. for 3 hours to synthesize a polyether in the same manner.
  • the polymer was dissolved in DMPU, cast onto a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 76 ⁇ m).
  • Example 11 The compound of Example 11, a polyether (BFPT-DTPM) of the following formula, was synthesized as follows. By replacing BisA in Example 1 with DTPM, polymerization was carried out in NMP (5.0 mL) at 190° C. for 3 hours to similarly synthesize a polyether.
  • NMP 5.0 mL
  • the polymer was dissolved in NMP, cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 70 ⁇ m).
  • Example 12 The compound of Example 12, the polyether of the following formula (BFPT-BPFL) was synthesized as follows. BFPT (0.6340 g, 1.84 mmol) and BPFL (0.6433 g, 1.84 mmol) are placed in a two-necked flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube. .3060 g, 2.20 mmol), N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was created.
  • NMP N-methyl-2-pyrrolidone
  • the temperature was raised stepwise to 150° C. with stirring, and toluene was refluxed at 150° C. for 2 hours to remove water produced by the Dean-Stark trap. Thereafter, the temperature was raised to 190° C. and stirred for 1 hour to remove toluene. After that, polymerization was carried out at 190° C. for 2 hours. After cooling to room temperature, a viscous polymerization solution was obtained. The polymer was precipitated by pouring into methanol, washed with hot methanol after recovery, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in NMP and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • This compound yield 1.134 g, yield: 94%, logarithmic viscosity: 0.88 dL / g (30 ° C., 0.5 g / dL NMP solution), number average molecular weight ( Mn): 77,000, weight average molecular weight (Mw): 206,000, molecular weight distribution (Mw/Mn): 2.7, average degree of polymerization (n): 117.
  • This polymer was dissolved in TMU to prepare a 12 wt % solution. This solution was cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours. A glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 64 ⁇ m).
  • Solubility Soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran (THF), cyclopentanone, cyclohexanone. rice field.
  • Example 13 The compound of Example 13, a polyether of the following formula (BFPT-DMBPFL) was synthesized as follows. Polymerization was carried out in NMP (5.0 mL) at 190° C. for 3 hours by replacing BisA in Example 1 with DMBPFL to synthesize a polyether in the same manner.
  • NMP 5.0 mL
  • the polymer was dissolved in NMP, cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 79 ⁇ m).
  • Example 14 The compound of Example 14, a polyether of the following formula (BFPT-TBISRX) was synthesized as follows. By replacing BisA in Example 1 with TBISRX, polymerization was carried out in NMP (5.0 mL) at 190° C. for 3 hours to similarly synthesize a polyether.
  • NMP 5.0 mL
  • the polymer was dissolved in NMP, cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours.
  • a glass plate was immersed in distilled water, the film was peeled off, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 85 ⁇ m).
  • R hydrogen (H) (BFPT) and Ar is Bis A compound of formula (2) (BFPT-BisA, Reference Example 1), Bis AF compound of formula (3) (BFPT-BisAF, Reference Example 2) Compound of BisP-HTG of Formula (4) (BFPT-PisP-HTG, Reference Example 3) BisP-IND compound of formula (5) (BFPT-BisP-IND, Reference Example 4) compound was prepared.
  • the reaction solution was poured into distilled water and chloroform was added.
  • the chloroform solution was washed three times with distilled water in a separating funnel.
  • the recovered chloroform solution was dried over anhydrous sodium sulfate overnight, and the anhydrous sodium sulfate was removed by suction filtration.
  • the chloroform solution was concentrated by an evaporator and poured into methanol (500 mL) to precipitate a crude product. This was collected by suction filtration, washed with methanol under reflux, and dried under reduced pressure at room temperature to obtain a crude brown needle crystal product (1.61 g, 23.3%).
  • the crude product was recrystallized with a mixed solvent of chloroform and methanol and dried under reduced pressure at 80° C. for 24 hours.
  • the synthesized compound was in the form of white needle crystals, yield: 1.46 g, yield: 21.1%, melting point: 259-262°C.
  • the analysis results using the above-mentioned equipment are as follows.
  • 1 H-NMR (CDCl 3 , ppm): 8.80-8.73 (m, 6H), 7.62 (t, 1H), 7.57 (t, 2H), 7.27-7.23 ( m, 4H).
  • Reference example 1 The compound of Reference Example 1, polyether (BFPT-BisA), was synthesized as follows. BFPT (0.6907 g, 2.00 mmol) and bisphenol A (0.4566 g, 2.00 mmol) are placed in a two-necked flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube, and potassium carbonate ( 0.3334 g, 2.40 mmol), N,N'-dimethylimidazolidone (DMI, 6.5 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was created.
  • BFPT 0.6907 g, 2.00 mmol
  • bisphenol A 0.4566 g, 2.00 mmol
  • potassium carbonate 0.3334 g, 2.40 mmol
  • DMI N,N'-dimethylimidazolidone
  • the temperature was raised stepwise to 150° C. with stirring, and toluene was refluxed at 150° C. for 2 hours to remove the water produced by the Dean-Stark trap. After that, the temperature was raised to 190° C. and the mixture was stirred for 2 hours to remove toluene. After that, polymerization was carried out at 190° C. for 2 hours. After allowing to cool to room temperature, a brown viscous polymerization solution was obtained. The polymer was precipitated by pouring into methanol, washed with hot methanol after recovery, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in N-methyl-2-pyrrolidone (NMP) and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • NMP N-methyl-2-pyrrolidone
  • This polymer was dissolved in NMP to prepare a 12 wt% solution.
  • This solution was cast on a glass plate, heated stepwise to 200° C. under reduced pressure, and dried under reduced pressure at 200° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 38 ⁇ m).
  • Reference example 2 The compound of Reference Example 2, polyether (BFPT-BisAF), was synthesized as follows. BFPT (0.6907 g, 2.00 mmol) and bisphenol AF (0.6725 g, 2.00 mmol) are placed in a two-necked flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube, and potassium carbonate ( 0.3334 g, 2.40 mmol), N,N'-dimethylimidazolidone (DMI, 6.5 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component. A Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was established.
  • BFPT 0.6907 g, 2.00 mmol
  • bisphenol AF 0.6725 g, 2.00 mmol
  • potassium carbonate 0.3334 g, 2.40 mmol
  • DMI N,N'-dimethylimidazo
  • the temperature was raised stepwise to 150° C. with stirring, and toluene was refluxed at 150° C. for 2 hours to remove the water produced by the Dean-Stark trap. After that, the temperature was raised to 190° C. and the mixture was stirred for 2 hours to remove toluene. After that, polymerization was carried out at 190° C. for 2 hours. After allowing to cool to room temperature, a brown viscous polymerization solution was obtained. The polymer was precipitated by pouring into methanol, washed with hot methanol after recovery, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in tetramethylurea (TMU) and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • TNU tetramethylurea
  • Reference example 3 The compound of Reference Example 3, polyether (BFPT-BisPHTG), was synthesized as follows. BFPT (0.6907 g, 2.00 mmol) and BisPHTG (0.6209 g, 2.00 mmol) are placed in a two-necked flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube, and potassium carbonate (0 .3334 g, 2.40 mmol), N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component were added.
  • NMP N-methyl-2-pyrrolidone
  • a Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was established.
  • the temperature was raised stepwise to 150° C. with stirring, and toluene was refluxed at 150° C. for 2 hours to remove the water produced by the Dean-Stark trap. After that, the temperature was raised to 190° C. and the mixture was stirred for 2 hours to remove toluene. After that, polymerization was carried out at 190° C. for 3 hours. After allowing to cool to room temperature, a brown viscous polymerization solution was obtained. The polymer was precipitated by pouring into methanol, washed with hot methanol after recovery, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in NMP and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • This polymer was dissolved in tetramethylurea (TMU) to prepare a 15 wt% solution.
  • TMU tetramethylurea
  • This solution was cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 38 ⁇ m).
  • TMU tetramethylurea
  • Reference example 4 The compound of Reference Example 4, polyether (BFPT-BisPIND), was synthesized as follows. BFPT (0.6907 g, 2.00 mmol) and BisPIND (0.5368 g, 2.00 mmol) are placed in a two-neck flask (50 mL) equipped with a stirrer and a nitrogen gas inlet tube, and potassium carbonate (0 .3334 g, 2.40 mmol), N-methyl-2-pyrrolidone (NMP, 5.0 mL) as a neutral polar solvent, and toluene (20 mL) as an inert solvent component were added. A Dean-Stark trap and a Liebig condenser were attached, and a nitrogen gas atmosphere was created.
  • NMP N-methyl-2-pyrrolidone
  • the temperature was raised stepwise to 150° C. with stirring, and toluene was refluxed at 150° C. for 2 hours to remove the water produced by the Dean-Stark trap. After that, the temperature was raised to 190° C. and the mixture was stirred for 2 hours to remove toluene. After that, polymerization was carried out at 190° C. for 3 hours. After allowing to cool to room temperature, a brown viscous polymerization solution was obtained. The polymer was precipitated by pouring into methanol, washed with hot methanol after recovery, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in NMP and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • This polymer was dissolved in tetramethylurea (TMU) to prepare a 10 wt % solution.
  • TMU tetramethylurea
  • This solution was cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 43 ⁇ m).
  • TMU tetramethylurea
  • the temperature was raised stepwise to 150° C. with stirring, and toluene was refluxed at 150° C. for 2 hours to remove water produced by the Dean-Stark trap. After that, the temperature was raised to 190° C. and the mixture was stirred for 2 hours to remove toluene. After that, polymerization was carried out at 190° C. for 2 hours. After cooling to room temperature, a brown viscous polymerization solution was obtained. The polymer was precipitated by pouring into methanol, recovered, washed with hot methanol, and dried under reduced pressure at room temperature. The resulting polymer was dissolved in tetramethylurea (TMU) and poured into methanol to precipitate a white flake polymer. After recovering the polymer, it was dried under reduced pressure at room temperature.
  • TNU tetramethylurea
  • This compound yield 1.043 g, yield: 87%, logarithmic viscosity: 0.50 dL / g (30 ° C., 0.5 g / dL NMP solution), number average molecular weight (Mn): 46,000, weight average Molecular weight (Mw): 88,000, molecular weight distribution (Mw/Mn): 1.9.
  • This polymer was dissolved in TMU to prepare a 12 wt % solution.
  • This solution was cast on a glass plate, heated stepwise to 160° C. under reduced pressure, and dried under reduced pressure at 160° C. for 3 hours to prepare a colorless and transparent cast film (thickness: 64 ⁇ m).
  • the analysis results using the above-mentioned equipment are as follows.
  • Solubility Soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran (THF), cyclopentanone, cyclohexanone.
  • NMP N-methyl-2-pyrrolidone
  • TMU tetramethylurea
  • DMI N,N'-dimethylimidazolidone
  • chloroform tetrahydrofuran
  • THF tetrahydrofuran
  • carbonization yield 58% (in nitrogen, 800° C.
  • the amount of polar solvent is 5 mL (that is, the ratio of 25% by volume to 20 mL of toluene), and the polymerization temperature is 190 ° C., a high yield and a high logarithmic viscosity was gotten. Furthermore, when the amount of polar solvent was increased to 6.5 mL, extremely high yields and extremely high logarithmic viscosities were obtained. On the other hand, when the polymerization temperature was 170 to 180° C. and NMP or TMU was used as the polar solvent, the yield and logarithmic viscosity decreased slightly, and discoloration was observed, but production was possible.
  • Reference Test Example 2 Synthesis study of compounds of Reference Examples 1 to 4.
  • the compounds of Reference Examples 1 to 4 were synthesized under the conditions described above. Each reference example was synthesized in the same steps except that DMI was replaced with NMP. The results are shown in Tables 2 and 3.
  • each of Reference Examples 1 to 4 could be synthesized with a high yield above a certain level.
  • the yield, logarithmic viscosity, and number average molecular weight (Mn) were higher and discoloration was less when NMP was used.
  • FIG. 1 shows the FT-IR spectra of Reference Examples 1 to 4 synthesized using DMI as a polar solvent.
  • Table 4 shows the results of elemental analysis for each reference example. Calcd. is a calculated value, Found. is the measured value.
  • Reference Example 1 was soluble in N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU) and N,N'-dimethylimidazolidone (DMI).
  • NMP N-methyl-2-pyrrolidone
  • THF tetrahydrofuran
  • DMAc N,N-dimethylacetamide
  • N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran (THF), cyclopentanone, cyclohexanone was soluble.
  • NMP N-methyl-2-pyrrolidone
  • TMP tetramethylurea
  • DI N,N'-dimethylimidazolidone
  • chloroform tetrahydrofuran
  • cyclopentanone, cyclohexanone was soluble.
  • Reference Example 5 contains N-methyl-2-pyrrolidone (NMP), tetramethylurea (TMU), N,N'-dimethylimidazolidone (DMI), chloroform, tetrahydrofuran ( THF), cyclopentanone and cyclohexanone.
  • NMP N-methyl-2-pyrrolidone
  • TEU tetramethylurea
  • DMI N,N'-dimethylimidazolidone
  • chloroform chloroform
  • tetrahydrofuran THF
  • cyclopentanone cyclohexanone
  • thermogravimetry TGA
  • DSC differential scanning calorimetry
  • TMA thermomechanical analysis
  • DMA dynamic viscoelasticity measurement
  • Tables 7 and 8 show the results obtained.
  • Table 7 shows glass transition temperature (Tg) and coefficient of thermal expansion (CTE).
  • the glass transition temperature is a value measured in nitrogen at a heating rate of 20° C./min by DSC, a value measured in nitrogen at a heating rate of 10° C./min by TMA, and a temperature rising rate of 2° C./min in nitrogen by DMA. It is a value measured at min.
  • CTE is a value measured by TMA at 150-200°C.
  • T 5% and T 10% in Table 8 are the 5% reduction temperature and the 10% reduction temperature, respectively, and are values measured by TGA in nitrogen or air at a heating rate of 10°C/min.
  • Char yield is the carbonization yield in weight percent at 800° C. in nitrogen.
  • each reference example had a glass transition temperature of around 240° C. or higher, indicating high heat resistance. From the results in Table 8, 5% thermal decomposition and 10% thermal decomposition occurred at 400 ° C. or higher in air and 500 ° C. or higher in nitrogen, indicating high thermal stability. .
  • Table 9 shows the results of examining the dielectric properties of the compounds of Reference Examples 1 to 4 under the above-described dielectric constant measurement conditions.
  • n indicates the refractive index measured by a prism coupler, measured at the F-line (486 nm), d-line (588 nm) and C-line (656 nm).
  • the TE mode represents the in-plane refractive index of the film
  • the TM mode represents the out-of-plane refractive index of the film.
  • V d is the Abbe number
  • n TE and n TM were measured with the d-line (588 nm).
  • Dielectric constant (Dk) and dielectric loss tangent (Df) are values measured with a cavity resonator.
  • a resin composition having a low dielectric constant, a low dielectric loss tangent, a high transparency, a high solubility, and a high heat resistance can be suitably used as a low dielectric material, and a method for producing the same. can get.

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