Classifications

• • 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
  • 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
  • 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

Definitions

• the present invention provides a resin composition for a low dielectric material containing a triazine compound, a film for a laminated substrate, a laminated substrate, a method for producing a resin composition for a low dielectric material, and a lamination, for use as a low dielectric material for electronic devices and the like.
• the present invention relates to a method for manufacturing a substrate film and a method for manufacturing 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 polymer containing an alicyclic structure and a triazine structure, and a transparent material containing the polymer. This technique aims to provide a polymer having a triazine structure that can be used for transparent materials with high heat resistance.
• a triazine compound having a specific structure not only has excellent mechanical and thermal properties, but also has excellent properties as a low dielectric constant material and a low dielectric loss tangent material, leading to the completion of the present invention. rice field.
• 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.
• n is an integer of 2 or more
• R is a linear, branched or cyclic aliphatic group, a linear, branched or cyclic aliphatic oxy group, a linear Aromatic, branched or cyclic aliphatic secondary amino groups, aromatic groups or substituted aromatic groups, aromatic oxy groups or substituted aromatic oxy groups, aromatic secondary amino groups or substituted groups the aromatic secondary amino group having the fluorinated aliphatic group, the fluorinated aliphatic oxy group, the fluorinated aliphatic secondary amino group, the fluorinated aromatic group, fluorine represents a fluorinated aromatic oxy group or a fluorinated aromatic secondary amino group.
• Ar represents a linear, branched or cyclic aliphatic group or a divalent aromatic group having a fluorinated linear, branched or cyclic aliphatic group.
• R in the general formula (1) is represented by any one of the following general formulas (2) to (4), and Ar in the formula (1) is the following general formula (5)
• the resin composition for a low dielectric material represented by any one of (15).
• the resin composition for a low dielectric material wherein the triazine compound has a dielectric constant (D k ) of 2.7 or less and/or a dielectric loss tangent (D f ) of 0.004 or less.
• the resin composition for a low dielectric material wherein the triazine compound has a glass transition temperature of 160° C. or higher.
• the resin composition for a low dielectric material containing the triazine 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 a 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 compound represented by the following general formula (18) for a low dielectric material.
• a method for producing a resin composition A method for producing a resin composition.
• n is an integer of 2 or more
• R is a linear, branched or cyclic aliphatic group, a linear, branched or cyclic An aliphatic oxy group, a linear, branched or cyclic aliphatic secondary amino group, an aromatic group or an aromatic group having a substituent, an aromatic oxy group or an aromatic oxy group having a substituent, an aromatic a secondary amino group or an aromatic secondary amino group having a substituent, the fluorinated aliphatic group, the fluorinated aliphatic oxy group, the fluorinated aliphatic secondary amino group, fluorinated represents the above aromatic group, the above fluorinated aromatic oxy group, or the above fluorinated aromatic secondary amino group.
• Ar represents a linear, branched or cyclic aliphatic group or a divalent aromatic group having a fluorinated linear, branched or cyclic aliphatic group.
• 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 films for the laminated substrate.
• n is an integer of 2 or more
• R is a linear, branched or cyclic aliphatic group, a linear, branched or cyclic aliphatic oxy group, a linear Aromatic, branched or cyclic aliphatic secondary amino groups, aromatic groups or substituted aromatic groups, aromatic oxy groups or substituted aromatic oxy groups, aromatic secondary amino groups or substituted groups the aromatic secondary amino group having the fluorinated aliphatic group, the fluorinated aliphatic oxy group, the fluorinated aliphatic secondary amino group, the fluorinated aromatic group, fluorine represents a fluorinated aromatic oxy group or a fluorinated aromatic secondary amino group.
• Ar represents a linear, branched or cyclic aliphatic group or a divalent aromatic group having a fluorinated linear, branched or cyclic aliphatic group.
• the triazine compound is a compound represented by the following general formula (2A), or Ar in the formula (1A) is represented by the following general formula (11A), and R is the following general formula ( 3A)
• the resin composition for a low dielectric material represented by any one of (5A).
• R 1 represents a structure represented by any one of the following general formulas (3A) to (5A).
• R 2 represents a structure represented by any one of general formulas (6A) to (10A) and (12A) below.
• [3A] The resin composition for a low dielectric material, containing a triazine compound in which the repeating unit represented by n in the general formula (1A) has an average degree of polymerization of 2 to 100.
• [4A] The resin composition for a low dielectric material, wherein the triazine compound has a dielectric constant Dk of 2.7 or less and a dielectric loss tangent Df of 0.004 or less.
• [5A] The resin composition for a low dielectric material, wherein the triazine compound has a glass transition temperature of 160° C. or higher.
• [6A] The resin composition for a low dielectric material, comprising the triazine compound and an epoxy resin.
• the resin composition for a low dielectric material further comprising an inorganic filler, modifier or flame retardant.
• the resin composition for a low dielectric material 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.
• [12A] A method for producing the resin composition for a low dielectric material, wherein a compound represented by the following general formula (13A) and a compound represented by the following general formula (14A) are mixed and polymerized.
• R is a linear, branched or cyclic aliphatic group, a linear, branched or cyclic aliphatic oxy group, a linear , a branched or cyclic aliphatic secondary amino group, an aromatic group or an aromatic group having a substituent, an aromatic oxy group or an aromatic oxy group having a substituent, an aromatic secondary amino group or a substituent
• Aromatic secondary amino group having, the fluorinated aliphatic group, the fluorinated aliphatic oxy group, the fluorinated aliphatic secondary amino group, the fluorinated aromatic group, fluorinated represents the above aromatic oxy group or a fluorinated aromatic secondary amino group.
• Ar represents a linear, branched or cyclic aliphatic group or a divalent aromatic group having a fluorinated linear, branched or cyclic aliphatic group.
• [15A] 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.
• [16A] A method for producing a laminated substrate, comprising laminating two or more of the films for a 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.
• the resin composition for low dielectric materials of this embodiment contains a specific triazine 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 of dielectric constant and dielectric loss tangent measurement conditions will be described later.
• a low dielectric material is a material that 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 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
• R is a linear, branched or cyclic aliphatic group, a linear, branched or cyclic aliphatic oxy group, a linear A chain, branched or cyclic aliphatic secondary amino group, an aromatic group or an aromatic group having a substituent, an aromatic oxy group or an aromatic oxy group having a substituent, an aromatic secondary amino group or a substituent an aromatic secondary amino group having a group, the fluorinated aliphatic group, the fluorinated aliphatic oxy group, the fluorinated aliphatic secondary amino group, the fluorinated aromatic group, It represents a fluorinated aromatic oxy group or a fluorinated aromatic secondary amino group.
• 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 compounds 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 compound contained in the resin composition for a low dielectric material of the present embodiment is the average degree of polymerization, and the value of the average degree of polymerization is 2 to 600. is preferred.
• the aliphatic group those having 1 to 14 carbon atoms are preferable.
• the aliphatic groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, and tert.
• aliphatic oxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, and octyloxy. group, nonyloxy group, decyloxy group, cyclobutoxy group, cyclopentyloxy group, or cyclohexyloxy group.
• aliphatic secondary amino groups include dimethylamino group, diethylamino group, methylethylamino group, dipropylamino group, methylpropylamino group, dibutylamino group, methylbutylamino group, N-methylcyclohexylamino group and dicyclohexylamino group. , a pyrrolidino group, a piperidino group, or a morpholino group. As the aromatic group, those having 6 to 18 carbon atoms are preferred.
• the aromatic group includes a phenyl group, a methylphenyl group, a dimethylphenyl group, a cumenyl group, a mesityl group, a tert-butylphenyl group, a naphthyl group, and the like.
• the aromatic oxy group includes phenoxy group, methylphenoxy group, dimethylphenoxy group, naphthoxy group and the like.
• the aromatic secondary amino group includes an N-methylanilino group and a diphenylamino group.
• the fluorinated aromatic group includes a trifluoromethylphenyl group, a bistrifluoromethylphenyl group, a trifluoromethylphenoxy group, a bistrifluoromethylphenoxy group, an N-methyltrifluoromethylanilino group, or a trifluoromethyldiphenylamino group.
• base, etc. Ar represents a linear, branched or cyclic aliphatic group or a divalent aromatic group having a fluorinated linear, branched or cyclic aliphatic group.
• aliphatic groups include methyl group, trifluoromethyl group, methylene group, ethylene group, trimethylene group, tetramethylene group, propylene group, butylene group, pentylene group, hexylene group, cyclopentalene group, cyclohexylene group and isopropylidene group.
• the resin containing the triazine compound of the present embodiment is an aliphatic group-containing triazine resin when R is an aliphatic group, and a fluorinated aliphatic resin when R is a fluorinated aliphatic group. group-containing triazine resins.
• the degree to which R is fluorinated can be chosen 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. For example, 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 may be different.
• the above-described chemical structure of the triazine 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.
• FT-IR infrared spectrum
• NMR nuclear magnetic resonance spectrum
• 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 thereof include various aromatic residues obtained by abstracting two phenolic hydroxyl groups from various dihydric phenols. Examples of arylene groups can be appropriately selected from various phenylene groups, naphthylene groups, biphenylene groups, and the like. Other alkyl groups, aryl groups, or the like may be bonded to Ar.
• the triazine compound of the present embodiment has a structure in which R in general formula (1) below is represented by any one of general formulas (2) to (4) below.
• Ar may be a compound represented by a structure represented by any one of the following general formulas (5) to (15).
• the formula (2) may be represented as DCPT, the formula (3) as DCPpT, and the formula (4) as DCHAT.
• formula (5) is BisA
• formula (6) is BisZ
• formula (7) is BisP3MZ
• formula (8) is BisPHTG
• formula (9) is BisPCDE
• formula (10) is HPTM5I
• formula (11) is BisC
• formula (12) is BisTMP
• formula (13) is BisCHP
• formula ( 14) is sometimes expressed as BisAF
• equation (15) as BPFL equation (15) as BPFL.
• the dielectric constant is particularly low, the dielectric loss tangent is low, the transparency is high, the solubility is high, and the heat resistance is high.
• the triazine compound of the present embodiment preferably has an average degree of polymerization of 2 to 600 for the repeating unit represented by n in the general formula (1).
• the repeating unit represented by n has an average degree of polymerization of 2 to 600, a compound having an appropriate molecular weight can be obtained when used as a resin composition for a low dielectric material.
• the average degree of polymerization is preferably 2-300.
• the average degree of polymerization may be 2-100.
• the molecular weight of the triazine compound of the present embodiment is such that the number average molecular weight M n is 3 ⁇ 10 3 to 40 ⁇ 10 4 and the weight average molecular weight is It is preferred that M w is between 6 ⁇ 10 3 and 80 ⁇ 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 compound of the present embodiment may have a dielectric constant (D k ) of 2.7 or less and/or a dielectric loss tangent (D f ) of 0.006 or less. It is also preferable that the dielectric loss tangent (D f ) is 0.004 or less.
• the dielectric constant (D k ) and dielectric loss tangent (D f ) are values measured by an existing dielectric property measuring device. As an existing dielectric property measuring device, for example, a cavity resonator type device or the like can be used.
• the triazine compound of the present embodiment preferably has a dielectric constant (D k ) of 2.6 or less, and more preferably has a dielectric loss tangent (D f ) of 0.003 or less.
• the triazine compound of the resin composition for low dielectric materials of the present embodiment preferably has a glass transition temperature of 160° C. or higher, more preferably 200° C. or higher. It is also preferable that the 5% thermal decomposition temperature is 340 to 500°C.
• the glass transition temperature of the triazine compound of the resin composition for low dielectric materials of the present embodiment is measured using differential scanning calorimetry (DSC), thermomechanical analysis (TMA), dynamic viscoelasticity measurement (DMA), or the like. be able to.
• the 5% thermal decomposition temperature of the resin composition for low dielectric materials of this 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 the low dielectric material of the present embodiment preferably contains the triazine compound and epoxy resin, bismaleimide resin or cyanate resin.
• epoxy resin a bismaleimide resin, or a cyanate resin
• a resin composition for a low dielectric material excellent in heat resistance 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 Phosphates, phosphate esters such as 2-ethylhexyldiphenyl phosphate, tris(2,6 dimethylphenyl) phosphate, resorcin diphenyl phosphate, ammonium polyphosphate, polyphosphoric acid amide, red phosphorus, guanidine phosphate, condensed phosphorus such as dialkylhydroxymethyl phosphonates Phosphorus atom-containing compounds including acid ester compounds; nitrogen atom-containing compounds such as melamine; inorganic flame retardant compounds such as aluminum hydroxide, magnesium
• 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 with 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 generally 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, and it is more preferable to use them for devices that transmit and receive these.
• the resin composition for a low dielectric material according to the present embodiment can be suitably used for devices using electromagnetic waves of frequencies such as 60 GHz used for wireless LANs and 75 to 79 GHz used for vehicle radars.
• the resin composition for a low dielectric material of this 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 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 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 contains, 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 is formed by impregnating a fiber base material such as glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc. with a resin composition for low dielectric materials to form an insulating layer.
• 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. As described above, the resin composition for the low dielectric material of the present embodiment has a high affinity with epoxy resin, bismaleimide resin, or cyanate resin. 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 triazine-containing compound with a low dielectric constant, a low dielectric loss tangent, a high transparency, a high solubility, and a high heat resistance. It can be used preferably.
• the triazine-containing compound 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 200 ° C.
• the triazine-containing compound of the present embodiment has a particularly low dielectric constant, low dielectric loss tangent, high transparency, high solubility, and high heat resistance at high frequencies. It can be suitably used as a constituent material for 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 compound represented by formula (18) is obtained.
• n is an integer of 2 or more
• R is a linear, branched or cyclic aliphatic group, linear, branched or a cyclic aliphatic oxy group, a linear, branched or cyclic aliphatic secondary amino group, an aromatic group or an aromatic group having a substituent, an aromatic oxy group or an aromatic oxy group having a substituent, an aromatic secondary amino group or an aromatic secondary amino group having a substituent, the fluorinated aliphatic group, the fluorinated aliphatic oxy group, the fluorinated aliphatic secondary amino group, fluorine represents a fluorinated aromatic group, a fluorinated aromatic oxy group, or a fluorinated aromatic secondary amino group.
• Ar represents a linear, branched or cyclic aliphatic group or a divalent aromatic group having a fluorinated linear, branched or cyclic aliphatic group.
• 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.
• the compound of formula (16) is a dichloride in which both ends of the triazine ring are substituted with chlorine among the monomers constituting the compound of formula (18).
• the compound of formula (17) is a bisphenol in which both ends of the Ar group of formula (18) are substituted with OH groups.
• the compounds of the formula (16) and the formula (17) are mixed and heated in the presence of an alkali metal compound and an organic solvent to polymerize and react with the compound of the formula (18). A triazine compound is obtained.
• alkali metal compound any compound can be used as long as it can neutralize the hydrogen chloride produced by the polymerization of the formulas (16) and (17).
• an alkali metal compound for example, alkali metal carbonates, hydrogencarbonates, hydroxides, etc., and particularly hydroxides are preferably used.
• the alkali metal include lithium, sodium, potassium, rubidium and cesium, with sodium and potassium being preferred.
• sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydroxide or potassium hydroxide can be used, and sodium hydroxide or potassium hydroxide is particularly preferred. can be used for These various alkali metal compounds may be used alone or in combination of two or more.
• the organic solvent one that can smoothly proceed with the polymerization reaction can be appropriately used.
• the organic solvent include aliphatic compounds, aromatic compounds and derivatives thereof, and examples of substituents include nitro group, cyano group and halogen element.
• substituents include nitrobenzene, benzonitrile, methylene chloride, chloroform, 1,4-dioxane, and tetrahydrofuran (THF).
• THF tetrahydrofuran
• a phase transfer catalyst may be added to the compound of formula (17) during the reaction.
• PTC phase transfer catalyst
• quaternary ammonium salts quaternary phosphonium salts, or crown ethers with alkyl chains can be used.
• quaternary ammonium salts include tetrabutylammonium bromide (TBAB) and cetyltrimethylammonium bromide (CTMAB).
• the polymerization temperature can be appropriately adjusted depending on the compounds, additives, and solvent used, but it can usually be carried out at 10 to 100°C.
• polymerization can be carried out at 20 to 35°C.
• 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.
• the polymerization is preferably carried out at 80°C to 100°C.
• an aqueous solution of an alkali metal compound and PTC are added to the compound of formula (16). Furthermore, the compound of formula (17) and an organic solvent are added here. These are vigorously stirred at the polymerization temperature to allow the reaction to take place for a sufficient period of time. After the polymerization reaction is fully completed, the triazine compound of formula (18) is 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 contains a triazine compound, It is preferably produced by mixing 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, tertiary phosphines, or acid anhydrides 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 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 include phenoxy resins, polyamide resins, polyimide resins, polyetherimide resins, polyethersulfone resins, polyphenylene ether resins, polyphenylene sulfide resins, polyester resins, polystyrene resins, polyethylene terephthalate resins, cycloolefin resins, fluorine A resin or the like can be used.
• flame retardants that can be used include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, inorganic flame retardant compounds, and the like.
• 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 the 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 board.
• 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 There is a method of pre-mixing other coupling agents and/or additives such as release agents, inorganic fillers, etc., and then thoroughly mixing them using an extruder, kneader, roll, etc. until they are uniform. 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 materials of the present embodiment as a resist ink
• an epoxy resin, a bismaleimide resin or a cyanate resin, an organic solvent, a pigment, and talc are used.
• a filler or the like to form a resist ink composition apply the composition onto a printed circuit board by screen printing, and then form a cured 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, for example, in addition to the resin composition for low dielectric materials and epoxy resin, curing acceleration and a silane coupling agent 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.
• the triazine compound of this embodiment may be a compound represented by the general formula (2A) described above.
• R 1 represents a structure represented by any one of general formulas (3A) to (5A).
• R 2 represents a structure represented by any one of general formulas (6A) to (10A) and (12A).
• Ar in Formula (1A) may be a compound represented by Formula (11A).
• the method for producing a resin composition for a low dielectric material includes mixing the compound represented by the general formula (13A) and the compound represented by the general formula (14A). , to obtain a triazine compound represented by the general formula (15A).
• the compound of formula (13A) is a dichloride in which both ends of the triazine ring are substituted with chlorine among the monomers constituting the compound of formula (1A).
• the compound of formula (14A) is a diol in which both ends of the Ar group of formula (1A) are substituted with OH groups.
• a compound of formula (2A) is produced by configuring R in formula (13A) as R 1 in formula (2A) and formula (14A) as a diol in which a benzene ring and an OH group are bonded to both ends of R 2 You may
• permittivity/dielectric loss tangent measuring device cavity resonator type
• TE mode TM mode (10 GHz, 20 GHz)
• TM mode 10 GHz, 20 GHz
• Various reagents were commercially available and were purified by conventional methods as necessary.
• Various reaction solvents were dried and purified by conventional methods as necessary.
• R is the formula (2) and Ar is a triazine compound of formula (5) (DCPT-BisA, Example 1), a triazine compound of formula (6) (DCPT-BisZ, Example 2), a triazine compound of formula (7) (DCPT-BisP3MZ, Example 3), a triazine compound of formula (8) (DCPT-BisPHTG, Example 4), a triazine compound of formula (9) (DCPT-BisPCDE, Example 5), a triazine compound of formula (10) (DCPT-HPTM5I, Example 6), a triazine compound of formula (11) (DCPT-BisC, Example 7), a triazine compound of formula (12) (DCPT-BisTMP, Example 8), a triazine compound of formula (13) (DCPT-BisCHP, Example 9), Triazine compound of formula (14) (DCPT-BisAF, Example 10) Triazine compound of formula (5) (DCPT-BisA, Example 1),
• R is the formula (3) and Ar is a triazine compound of formula (5) (DCPpT-BisA, Example 12), a triazine compound of formula (8) (DCPpT-BisPHTG, Example 13), a triazine compound of formula (12) (DCPpT-BisTMP, Example 14), Triazine compound of formula (14) (DCPpT-BisAF, Example 15) was prepared.
• Ar is a triazine compound of formula (5) (DCPpT-BisA, Example 12), a triazine compound of formula (8) (DCPpT-BisPHTG, Example 13), a triazine compound of formula (12) (DCPpT-BisTMP, Example 14), Triazine compound of formula (14) (DCPpT-BisAF, Example 15) was prepared.
• R is the formula (4) and Ar is a triazine compound of formula (5) (DCHAT-BisA, Example 16), a triazine compound of formula (8) (DCHAT-BisPHTG, Example 17), a triazine compound of formula (9) (DCHAT-BisPCDE, Example 18), was prepared.
• DCPT Triazine dichloride Triazine dichloride
• Cyanuric chloride (18.44 g, 0.100 mol) and dehydrated tetrahydrofuran (THF, 200 mL) are placed in a three-necked flask (500 mL), equipped with a stirrer, dropping funnel, nitrogen inlet tube, and thermometer, and cooled to -10°C. did. While stirring this THF solution, a phenylmagnesium bromide THF solution (1 mol/L, 100 mL, 0.100 mol) was slowly added dropwise from a dropping funnel so as not to raise the temperature of the reaction solution.
• the synthesized compound had a yield of 13.1 g, a yield of 58%, and a melting point of 120°C.
• the analysis results using the equipment described above are as follows: FT-IR (KBr, cm ⁇ 1 ): 3047 (Ar—H), 1527 (C ⁇ N), 1258 (CN), 770 (C—Cl) 1 H-NMR (CDCl 3 , ppm): 8.50 (d, 2H, o-Ar-H), 7.66 (t, 1H, p-Ar-H), 7.53 (t, 2H, m -Ar-H) 13 C-NMR (CDCl 3 , ppm): 175.0, 172.2, 134.9, 132.8, 130.1, 129.2 Elemental analysis ( C9H5N3Cl2 ): calculated C , 47.82 %; H, 2.23%; N: 18.59%, found C, 48.11%; H, 2.43 %; N: 18.68%.
• DCPpT Triazine dichloride Triazine dichloride (DCPpT) used in each example was synthesized as follows. Cyanuric chloride (18.44 g, 0.100 mol) and dehydrated dichloromethane (150 mL) were added to a three-necked flask (300 mL), equipped with a dropping funnel, a nitrogen inlet tube and a thermometer, and cooled to 0°C. While stirring this dichloromethane solution, a solution of piperidine (8.52 g, 0.100 mol) dissolved in dehydrated dichloromethane (50 mL) was added dropwise at 0° C. and stirred for 2 hours.
• the synthesized compound had a yield of 10.72 g, a yield of 46%, and a melting point of 90-91°C.
• the analysis results using the equipment described above are as follows: FT-IR (KBr, cm ⁇ 1 ): 2940-2860 (CH), 1552 (C ⁇ N), 1170 (CN), 842 (C—Cl) 1 H-NMR (CDCl 3 , ppm): 3.82 (t, 4H, CH 2 ), 1.74-1.70 (m, 2H, CH 2 ), 1.67-1.63 (m, 4H , CH2 ) 13 C-NMR (CDCl 3 , ppm): 170.2, 163.6, 45.4, 25.7, 24.3 Elemental analysis ( C8H10N4Cl2 ): calculated C, 41.22%; H, 4.32% ; N: 24.04 %, found C, 41.01%; H, 4.68 %; N: 24.30%.
• DCHAT Triazine dichloride Triazine dichloride
• Cyanuric chloride (18.44 g, 0.100 mol) and dehydrated THF (50 mL) were added to a three-necked flask (300 mL), equipped with a dropping funnel, a nitrogen inlet tube and a thermometer, and cooled to 0°C.
• a solution of dicyclohexylamine (18.13 g, 0.100 mol) in THF (30 mL) was added dropwise at 0° C. and stirred for 2 hours.
• the reaction solution was liquid-separated with saturated saline, and anhydrous sodium sulfate was added to the organic layer and stirred to dehydrate.
• THF was distilled off from the filtrate obtained by suction filtration to obtain a crude product. Recrystallization was performed twice from a hexane/chloroform mixed solvent, and the obtained white columnar crystals were dried under reduced pressure at 50°C.
• the synthesized compound had a yield of 11.3 g, a yield of 34%, and a melting point of 167-168°C.
• the analysis results using the equipment described above are as follows: FT-IR (KBr, cm ⁇ 1 ): 2923 (CH), 1562 (C ⁇ N), 1227 (CN), 793 (C—Cl) 13 C-NMR (CDCl 3 , ppm): 169.0, 164.0, 56.8, 29.7, 26.1, 25.4. Elemental analysis ( C15H22N4Cl2 ): calculated C , 54.72 %; H, 6.73%; N, 17.02%, found C, 54.68%; H, 6.56. %; N, 17.17%.
• Example 1 The polymer of Example 1, DCPT-BisA, was synthesized as follows. Bisphenol A (BisA) (0.571 g, 2.50 mmol) and 1 M sodium hydroxide aqueous solution (5.1 mL) were placed in an eggplant flask (100 mL) together with a stirrer and dissolved. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred. A solution of DCPT (0.565 g, 2.50 mmol) dissolved in dehydrated dichloromethane (5.0 mL) was added to an eggplant flask and vigorously stirred at room temperature for 18 hours.
• Bisphenol A (BisA) 0.571 g, 2.50 mmol
• 1 M sodium hydroxide aqueous solution 5.1 mL
• CTMAB Cetyltrimethylammonium bromide
• a solution of DCPT 0.565
• the synthesized compound has a yield of 0.68 g, a yield of 71%, a logarithmic viscosity of 0.94 dL/g (30° C., 0.5 g/dL of N-methyl-2-pyrrolidone solution), and a number average molecular weight (Mn ): 82,000, weight average molecular weight (Mw): 279,000, molecular weight distribution (Mw/Mn): 3.4, average degree of polymerization (n): 214.
• This polymer was dissolved in N,N-dimethylacetamide (DMAc) and cast onto a glass plate. It was dried under reduced pressure at 150° C. for 12 hours to obtain a colorless and transparent cast film (thickness: 40 ⁇ m).
• DMAc N,N-dimethylacetamide
• Example 2 The polymer of Example 2, DCPT-BisZ, was synthesized as follows. 4,4′-Cyclohexylidenebisphenol (BisZ) (0.671 g, 2.50 mmol) and 1M aqueous sodium hydroxide solution (5.1 mL) were placed in an eggplant flask (100 mL) with a stirrer and dissolved. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred.
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound was yield: 0.95 g, yield: 90%, logarithmic viscosity: 1.02 dL/g (30°C, 0.5 g/dL tetrahydrofuran solution).
• Example 3 The polymer of Example 3, DCPT-BisP3MZ, was synthesized as follows. 4-[1-(4-Hydroxyphenol)-3-methylcyclohexyl]phenol (BisP3MZ) (0.706 g, 2.50 mmol) and 1 M sodium hydroxide aqueous solution (5.1 mL) were stirred in an eggplant flask (100 mL). It was put together with the child and allowed to dissolve. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred.
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound has a yield of 0.76 g, a yield of 70%, a logarithmic viscosity of 0.92 dL/g (30° C., 0.5 g/dL of N-methyl-2-pyrrolidone solution), and a number average molecular weight (Mn ): 72,000, weight average molecular weight (Mw): 144,000, molecular weight distribution (Mw/Mn): 2.0, average degree of polymerization (n): 165.
• Example 4 The polymer of Example 4, DCPT-BisPHTG, was synthesized as follows. 4-[1-(4-Hydroxyphenol)-3,5,5-trimethylcyclohexyl]phenol (BisPHTG) (0.776 g, 2.50 mmol) and 1 M aqueous sodium hydroxide solution (5.1 mL) were placed in an eggplant flask (100 mL). ) was added with a stirrer and dissolved. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred.
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound has a yield of 0.95 g, a yield of 82%, a logarithmic viscosity of 1.84 dL/g (30° C., 0.5 g/dL of N-methyl-2-pyrrolidone solution), and a number average molecular weight (Mn ): 264,000, weight average molecular weight (Mw): 422,000, molecular weight distribution (Mw/Mn): 1.6.
• Example 5 The polymer of Example 5, DCPT-BisPCDE, was synthesized as follows. 4,4′-Cyclododecylidenebisphenol (BisPCDE) (0.881 g, 2.50 mmol) and 1 M sodium hydroxide aqueous solution (5.1 mL) were placed in an eggplant flask (100 mL) with a stirrer and dissolved. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred.
• BisPCDE 4,4′-Cyclododecylidenebisphenol
• 1 M sodium hydroxide aqueous solution 5.1 mL
• the synthesized compound has a yield of 1.03 g, a yield of 81%, a logarithmic viscosity of 0.91 dL/g (30° C., 0.5 g/dL of N-methyl-2-pyrrolidone solution), and a number average molecular weight (Mn ): 166,000, weight average molecular weight (Mw): 332,000, and molecular weight distribution (Mw/Mn): 2.0.
• Example 6 The polymer of Example 6, DCPT-HPTM5I, was synthesized as follows. 3-(4-Hydroxyphenyl)-1,1,3-trimethyl-5-indanol (HPTM5I) (0.671 g, 2.50 mmol) and 1 M sodium hydroxide aqueous solution (5.1 mL) were placed in an eggplant flask (100 mL). Put in with a stirrer and dissolve. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred.
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound has a yield of 0.93 g, a yield of 88%, a logarithmic viscosity of 0.62 dL/g (30° C., 0.5 g/dL of N-methyl-2-pyrrolidone solution), and a number average molecular weight (Mn ): 135,000, weight average molecular weight (Mw): 283,500, and molecular weight distribution (Mw/Mn): 2.1.
• Example 7 The polymer of Example 7, DCPT-BisC, was synthesized as follows. A triazine compound was similarly synthesized using BisC in place of HPTM5I in Example 6.
• the synthesized compound has a yield of 78%, logarithmic viscosity of 1.00 dL/g (30°C, 0.5 g/dL of chloroform solution), number average molecular weight (Mn) by GPC (THF) of 138,000, weight Average molecular weight (Mw): 262,000, molecular weight distribution (Mw/Mn): 1.9.
• Example 8 The polymer of Example 8, DCPT-BisTMP, was synthesized as follows. A triazine compound was similarly synthesized using BisTMP in place of HPTM5I in Example 6.
• the synthesized compound has a yield of 76%, logarithmic viscosity of 1.12 dL/g (30°C, 0.5 g/dL of chloroform solution), number average molecular weight (Mn) by GPC (THF) of 184,000, weight Average molecular weight (Mw): 313,000, molecular weight distribution (Mw/Mn): 1.7.
• Example 9 The polymer of Example 9, DCPT-BisCHP, was synthesized as follows. A triazine compound was similarly synthesized using BisCHP in place of HPTM5I in Example 6.
• the synthesized compound has a yield of 76%, logarithmic viscosity of 0.49 dL/g (30°C, 0.5 g/dL of chloroform solution), number average molecular weight (Mn) by GPC (THF): 59,000, weight Average molecular weight (Mw): 124,000, molecular weight distribution (Mw/Mn): 2.1, average degree of polymerization (n): 108.
• Example 10 The polymer of Example 10, DCPT-BisAF, was synthesized as follows. 2,2-bis(4-hydroxyphenyl)hexafluoropropane (BisAF) (0.841 g, 2.50 mmol) and 1 M sodium hydroxide aqueous solution (5.1 mL) were placed in an eggplant flask (100 mL) with a stirrer and dissolved. let me Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred.
• BisAF 2,2-bis(4-hydroxyphenyl)hexafluoropropane
• 1 M sodium hydroxide aqueous solution 5.1 mL
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound has a yield of 1.02 g, a yield of 83%, a logarithmic viscosity of 1.21 dL/g (30° C., 0.5 g/dL of N-methyl-2-pyrrolidone solution), and a number average molecular weight (Mn ): 257,000, weight average molecular weight (Mw): 771,000, molecular weight distribution (Mw/Mn): 3.0.
• Example 11 The polymer of Example 11, DCPT-BPFL, was synthesized as follows. A 1 M sodium hydroxide aqueous solution (5.1 mL) and cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) were placed in an eggplant flask (100 mL) with a stirrer and stirred. A solution of 9,9-bis(4-hydroxyphenyl)fluorene (BPFL) (0.876 g, 2.50 mmol) and DCPT (0.565 g, 2.50 mmol) dissolved in dehydrated nitrobenzene (5.0 mL) was added to an eggplant flask.
• BPFL 9,9-bis(4-hydroxyphenyl)fluorene
• DCPT 0.565 g, 2.50 mmol
• the synthesized compound was yield: 0.52 g, yield: 42%, logarithmic viscosity: 1.25 dL/g (30°C, 0.5 g/dL N-methyl-2-pyrrolidone solution).
• Example 12 The polymer of Example 12, DCPpT-BisA, was synthesized as follows. Bisphenol A (0.571 g, 2.50 mmol) and 1 M sodium hydroxide aqueous solution (5.1 mL) were placed in an eggplant flask (100 mL) with a stirrer and dissolved. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred. A solution of DCPpT (0.583 g, 2.50 mmol) dissolved in dehydrated benzonitrile (5.0 mL) was added to an eggplant flask and vigorously stirred at 80° C.
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound had a yield of 0.49 g, a yield of 51%, and a logarithmic viscosity of 0.53 dL/g (30°C, 0.5 g/dL chloroform solution).
• Example 13 The polymer of Example 13, DCPpT-BisPHTG, was synthesized as follows. BisPHTG (0.776 g, 2.50 mmol) and 1 M sodium hydroxide aqueous solution (5.1 mL) were placed in an eggplant flask (100 mL) with a stirrer and dissolved. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added and stirred. A solution of DCPpT (0.583 g, 2.50 mmol) dissolved in dehydrated nitrobenzene (5.0 mL) was added to an eggplant flask and vigorously stirred at 80° C. for 18 hours.
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound has a yield of 1.08 g, a yield of 92%, a logarithmic viscosity of 0.86 dL/g (30° C., 0.5 g/dL of chloroform solution), a number average molecular weight (Mn) of 103,000, Weight average molecular weight (Mw): 206,000, molecular weight distribution (Mw/Mn): 2.0.
• Example 14 The polymer of Example 14, DCPpT-BisTMP, was synthesized as follows. A triazine compound was similarly synthesized using BisTMP in place of BisPHTG in Example 13.
• the synthesized compound has a yield of 78%, a logarithmic viscosity of 0.48 dL/g (30°C, 0.5 g/dL of chloroform solution), a number average molecular weight (Mn) of 37,000, and a weight average molecular weight (Mw) of : 59,000, molecular weight distribution (Mw/Mn): 1.6, average degree of polymerization (n): 78.
• Example 15 The polymer of Example 15, DCPpT-BisAF, was synthesized as follows. BisAF (0.841 g, 2.50 mmol) and 1 M sodium hydroxide aqueous solution (5.1 mL) were placed in an eggplant flask (100 mL) with a stirrer and dissolved. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added and stirred. A solution of DCPpT (0.583 g, 2.50 mmol) dissolved in dehydrated nitrobenzene (5.0 mL) was added to an eggplant flask and vigorously stirred at 80° C. for 18 hours.
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound has a yield of 1.15 g, a yield of 93%, a logarithmic viscosity of 0.47 dL/g (30° C., 0.5 g/dL of chloroform solution), a number average molecular weight (Mn) of 80,000, Weight average molecular weight (Mw): 160,000, molecular weight distribution (Mw/Mn): 2.0, average degree of polymerization (n): 161.
• Example 16 The polymer of Example 16, DCHAT-BisA, was synthesized as follows. Bisphenol A (0.571 g, 2.50 mmol) and 5.1 mL of 1 M sodium hydroxide aqueous solution were placed in an eggplant flask (100 mL) together with a stirrer and dissolved. Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred. A solution of DCHAT (0.823 g, 2.50 mmol) dissolved in dehydrated nitrobenzene (5.0 mL) was added to an eggplant flask and vigorously stirred at 100° C. for 18 hours.
• CTMAB Cetyltrimethylammonium bromide
• the synthesized compound had a yield of 1.12 g, a yield of 92%, and a logarithmic viscosity of 0.57 dL/g (30°C, 0.5 g/dL chloroform solution).
• Example 17 The polymer of Example 17, DCHAT-BisPHTG, was synthesized as follows. A triazine compound was similarly synthesized using BisPHTG in place of BisA in Example 16.
• the synthesized compound had a yield of 83% and a logarithmic viscosity of 0.71 dL/g (30°C, 0.5 g/dL chloroform solution).
• Example 18 The polymer of Example 18, DCHAT-BisPCDE, was synthesized as follows. A triazine compound was similarly synthesized using BisPCDE in place of BisA in Example 16.
• the synthesized compound had a yield of 72% and a logarithmic viscosity of 0.57 dL/g (30°C, 0.5 g/dL chloroform solution).
• Cetyltrimethylammonium bromide (CTMAB, 0.277 g, 0.760 mmol) (30 mol % relative to the monomer) was added as a phase transfer catalyst and stirred.
• acetic acid was added for neutralization, poured into methanol (250 mL) to precipitate a polymer, collected by suction filtration, and dried under reduced pressure at room temperature for 6 hours.
• the resulting polymer was dissolved in chloroform and poured into methanol for reprecipitation. After recovering the polymer, it was dried under reduced pressure at 150° C. for 12 hours.
• Tables 2 and 3 show the results of examining the solubility of the compounds of Reference Examples 1 to 6 and 10 at room temperature or by heating. Solubility was measured at 10 mg/5.0 mL. ++: Dissolvable at room temperature. +: Dissolved by heating. +-: only partially dissolved. -: Insoluble.
• each reference example is a stable compound, it was shown to be soluble in certain organic solvents and to have excellent workability such as purification by reprecipitation and film formation by solution casting.
• TGA thermogravimetry
• DSC differential scanning calorimetry
• TMA thermomechanical analysis
• DMA dynamic viscoelasticity measurement
• Tables 4 and 5 T5 % is the 5% weight loss temperature
• T10 % is the 10% weight loss temperature, 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.
• the glass transition temperature (Tg) in Table 5 is a value measured by DSC in nitrogen at a heating rate of 20°C/min, a value measured by TMA in nitrogen at a heating rate of 10°C/min, a value measured by DMA in nitrogen, It is a value measured at a heating rate of 2° C./min.
• the coefficient of thermal expansion (CTE) is a value measured at 100 to 150°C by TMA.
• Tables 6, 7 and 8 show the results of examining the optical properties and dielectric properties of the compounds of Reference Examples 1 to 6 and 10 under the above equipment conditions.
• Table 6 shows the values of the refractive index (n) of film samples having a film thickness (d) of 40 to 70 ⁇ m.
• the in-plane refractive index (n TE ) of the film in TE mode and the out-of-plane refractive index (n TM ) of the film in TM mode were measured at F-line (486 nm), d-line (588 nm) and C-line (656 nm).
• ⁇ n d is the birefringence
• V d is the Abbe number
• n TE and n TM are the wavelength d It is measured by a line.
• Table 7 shows values of dielectric constant (D k ) and dielectric loss tangent (D f ) measured by the cavity resonator. Measurements were made at 10 GHz and 20 GHz in TE mode and at 10 GHz in TM mode.
• Table 8 shows the cutoff wavelength ( ⁇ cutoff ), 80% transmitted wavelength ( ⁇ 80% ), and transmittance at 400 nm (T 400 ) according to the UV-visible absorption spectrum.
• Table 6 shows that all of Reference Examples 1 to 6 and 10 have a dielectric constant of 2.7 or less as determined from the average refractive index.
• all of Reference Examples 1 to 6 and 10 have D k (dielectric constant) of 2.7 or less and D f (dielectric loss tangent) of 0.03 or less, which are sufficiently low. rice field.
• the resin composition was well obtained with a yield of 40% or more for each reference example.
• Reference Examples 13 and 15 showed yields of 90% or more by selecting nitrobenzene as the organic solvent. In all of the reference examples, it was shown that high molecular weight products were obtained.
• Test Example 6 Solubility of compounds of Reference Examples 12, 13 and 15
• Table 10 shows the results of examining the solubility of the compounds of each reference example at room temperature or with heating. Solubility was measured at 10 mg/5.0 mL. The description of the table is the same as that of Test Example 2.
• each reference example is a stable compound, it was shown to be soluble in certain organic solvents and to be excellent for reprecipitation purification and molding.
• Test Example 7 Thermal Properties of Compounds of Reference Examples 12, 13 and 15
• Tables 11 and 12 show the results. The description of the table is the same as that of Test Example 3.
• Test Example 8 Optical properties and dielectric properties of compounds of Reference Examples 12, 13 and 15
• Tables 13 and 14 show the results of examining the optical properties and dielectric properties of the compounds of each reference example under the above equipment conditions.
• the transmittance of Reference Examples 13 and 15 is shown in Table 15. The description of the table is the same as that of Test Example 4.
• the resin composition was well obtained with a yield of 60% or more for each reference example.
• a yield of 90% or more was observed by selecting nitrobenzene as an organic solvent, and a high molecular weight product was obtained.
• Test Example 10 Solubility of compounds of Reference Examples 16 and 20
• Table 17 shows the results of examining the solubility of the compounds of each Reference Example at room temperature or with heating. Solubility was measured at 10 mg/5.0 mL. The description of the table is the same as that of Test Example 2.
• Test Example 11 Thermal properties of the compound of Reference Example 16
• the compound of Reference Example 16 was subjected to the above-described thermogravimetric measurement, differential scanning calorimetry, thermomechanical analysis, and dynamic viscoelasticity measurement, and the results of examining the thermal properties are shown in Tables 18 and 19. The description of the table is the same as that of Test Example 3.
• Test Example 12 Optical properties and dielectric properties of the compound of Reference Example 16
• Tables 20, 21 and 22 show the results of examining the optical properties and dielectric properties of the compound of Reference Example 16 under the above equipment conditions. The description of the table is the same as that of Test Example 4.
• Tables 20 and 21 show that D k ( ⁇ , permittivity) of Reference Example 16 is 2.7 or less, which is sufficiently low.
• 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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