WO2020184437A1 - Composition liquide, poudre, et procédé de production de ladite poudre - Google Patents

Composition liquide, poudre, et procédé de production de ladite poudre Download PDF

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Publication number
WO2020184437A1
WO2020184437A1 PCT/JP2020/009684 JP2020009684W WO2020184437A1 WO 2020184437 A1 WO2020184437 A1 WO 2020184437A1 JP 2020009684 W JP2020009684 W JP 2020009684W WO 2020184437 A1 WO2020184437 A1 WO 2020184437A1
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Prior art keywords
powder
liquid composition
polymer
resin
aromatic
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PCT/JP2020/009684
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English (en)
Japanese (ja)
Inventor
敦美 山邊
細田　朋也
渉 笠井
達也 寺田
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Ａｇｃ株式会社
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Priority to CN202080019920.1A priority Critical patent/CN113574118A/zh
Priority to JP2021505026A priority patent/JP7371681B2/ja
Priority to KR1020217020343A priority patent/KR20210137426A/ko
Publication of WO2020184437A1 publication Critical patent/WO2020184437A1/fr

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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
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/082—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising vinyl resins; comprising acrylic resins
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/09—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyesters
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/26—Tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/16—Powdering or granulating by coagulating dispersions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
    • C08L65/02—Polyphenylenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C09D127/18—Homopolymers or copolymers of tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the present invention relates to a liquid composition, a powder, and a method for producing a powder.
  • a metal foil with a resin layer having a metal foil and an insulating resin layer is used as a printed wiring substrate by forming a metal conductor wiring (transmission circuit) by processing the metal foil.
  • a printed wiring board used for transmitting a high-frequency signal is required to have excellent transmission characteristics, and an insulating resin layer having a low relative permittivity and a low dielectric loss tangent is required.
  • a liquid composition for forming such an insulating resin layer a liquid composition containing an aromatic epoxy resin and a powder of a tetrafluoroethylene-based polymer (see Patent Document 1) is a polyphenylene ether resin and a tetrafluoroethylene-based polymer. Liquid compositions containing the powder (see Patent Document 2) have been proposed.
  • addition polymerization type or polycondensation type aromatic resins having oxygen atoms such as polyimide, polyamide, polyether, epoxy resin, polyester and polycarbonate, and tetrafluoroethylene resins such as polytetrafluoroethylene are various. It has excellent physical properties and is also called super engineering plastic. Therefore, the usage mode is expanding, and the molecular structure (monomer structure such as monomer type and combination thereof, polymer structure such as stereoregularity and molecular weight distribution) is improved, and its precursor is used.
  • a liquid composition containing a resin or a precursor thereof is increasingly prepared and used as a coating agent (see Patent Documents 3 to 6).
  • tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE), a copolymer of tetrafluoroethylene and perfluoro (alkyl vinyl ether) (PFA), and a copolymer of tetrafluoroethylene and hexafluoropropylene (FEP) are demolded. It has excellent physical properties such as properties, electrical properties, water and oil repellency, chemical resistance, weather resistance, and heat resistance, and is used in various industrial applications.
  • PTFE polytetrafluoroethylene
  • PFA perfluoro (alkyl vinyl ether)
  • FEP hexafluoropropylene
  • Patent Document 9 describes a powder prepared from a liquid composition containing a tetrafluoroethylene polymer powder, a predetermined solvent, and a polymer insoluble in this solvent, in which a solvent-insoluble polymer is attached to the surface of powder particles. Proposed.
  • the liquid composition of Patent Document 1 or 2 contains an aromatic resin known as an electrically insulating resin or a precursor thereof, and a tetrafluoroethylene-based polymer having a low relative permittivity and dielectric loss tangent, a molded product thereof (
  • the present inventors have found that while the electrical characteristics of the prepreg, the metal plate with the resin layer, the printed wiring substrate, etc.) can be expected to be improved, there are the following problems. That is, when the content ratio of the aromatic resin among the components of the liquid composition is increased, the liquid composition becomes thickened and difficult to handle, and the physical properties of the obtained molded product tend to deteriorate.
  • Aromatic resins or precursors thereof often contain oxygen atoms such as ester bonds, ether bonds, and imide bonds as bonders in the main skeleton of the resin. If the oxygen atom content and the aromatic ring content of the resin material are increased in order to express these resin physical properties to a high degree, the flame retardancy of the obtained liquid composition and its molded product will decrease. .. Even if a known flame retardant is added to the liquid composition in order to eliminate such inconvenience, the liquid composition is not homogeneously dispersed, the flame retardancy is not improved, and the original physical properties of the liquid composition or the molded product are easily impaired.
  • the molded product formed from the liquid composition also has a problem that the surface smoothness, processability and adhesiveness are poor. .. Further, in the preparation of such a liquid composition, when the powder of the tetrafluoroethylene polymer is directly added to the varnish (liquid composition) of the aromatic resin, the liquid composition is easily denatured due to thickening or the like. The present inventors are also aware of this problem. Further, the present inventors have also found that it is difficult to sufficiently improve the physical properties (processability, flame retardancy, electrical characteristics, etc.) of the molded product formed from the liquid composition in this case.
  • the tetrafluoroethylene polymer is a non-fibrillar heat-meltable polymer (PFA, FEP, etc.)
  • the polymer insoluble in the liquid medium does not easily adhere to the surface of the powder particles. The effect is not yet sufficient (see paragraph number 0104, etc. of the same document).
  • An object of the present invention is to provide a liquid composition having a viscosity excellent in handleability, which comprises a tetrafluoroethylene polymer powder having a good dispersion state and a high-concentration aromatic resin.
  • INDUSTRIAL APPLICABILITY According to the present invention, even when added to a liquid composition containing a tetrafluoroethylene resin or an aromatic resin, deterioration such as thickening is suppressed and a liquid composition having high homogeneity can be formed.
  • the purpose is to provide powder. It is also an object of the present invention to provide a method for producing such a powder.
  • the liquid composition according to [1] wherein the ratio of the content ratio of the tetrafluoroethylene-based polymer to the content ratio of the aromatic resin is 0.1 to 0.5.
  • the aromatic resin is an aromatic polyimide resin, an aromatic polycarbonate resin, an aromatic polyamide resin, an aromatic polyester resin, an aromatic polyether sulfone resin, an aromatic maleimide resin, a polyphenylene ether resin, a polyphenylene sulfide resin, and an aromatic resin.
  • tetrafluoroethylene polymer powder is the following powder (1), the following powder (2), or the following powder (3).
  • Powder (1) A powder of a heat-meltable tetrafluoroethylene-based polymer composed of a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether), the volume-based cumulative 50% diameter of which is 10 to 60 ⁇ m. powder.
  • Powder (2) Thermo-meltable tetrafluoro containing 90 to 99 mol% of units based on tetrafluoroethylene, 1 to 3 mol% of units based on perfluoro (alkyl vinyl ether), and units based on a monomer having an oxygen-containing polar group.
  • the powder (1) is a heat-meltable tetrafluoroethylene polymer powder containing 92 to 98 mol% of units based on tetrafluoroethylene and 2 to 8 mol% of units based on perfluoro (alkyl vinyl ether).
  • the liquid composition according to [5] which is a powder having a volume-based cumulative 50% diameter of 10 to 60 ⁇ m.
  • the liquid composition according to [5] or [6], wherein the volume-based cumulative 50% diameter of the powder (1) is 16 to 40 ⁇ m.
  • the powder (1) contains a first powder having a volume-based cumulative 50% diameter of 8 ⁇ m or less and a second powder having a volume-based cumulative 50% diameter of 16 to 40 ⁇ m, relative to the content ratio of the second powder.
  • the liquid composition according to any one of [1] to [9] is applied to the surface of a metal plate and heated to form a resin layer containing a dried product of the liquid composition.
  • a method for manufacturing a metal plate with a resin layer which obtains a metal plate with a resin layer having the metal plate and the resin layer.
  • Powder (1) A powder of a heat-meltable tetrafluoroethylene-based polymer composed of a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether), the volume-based cumulative 50% diameter of which is 10 to 60 ⁇ m. powder.
  • Powder (2) Thermo-meltable tetrafluoro containing 90 to 99 mol% of units based on tetrafluoroethylene, 1 to 3 mol% of units based on perfluoro (alkyl vinyl ether), and units based on a monomer having an oxygen-containing polar group.
  • the surface treatment agent is a surfactant or a silane coupling agent.
  • the liquid composition of the present invention contains a powder of a heat-meltable tetrafluoroethylene polymer having a good dispersed state and an aromatic resin at a high concentration, and is excellent in handleability.
  • a prepreg in which a fiber base material is impregnated with a resin component at a high concentration and held, or a base material having an insulating resin having an arbitrary thickness.
  • a liquid composition containing at least one resin material selected from the group consisting of a non-meltable tetrafluoroethylene polymer and an aromatic resin and a liquid medium is provided. It is possible to provide an additive containing a powder of a heat-meltable tetrafluoroethylene-based polymer, which can improve the physical properties (surface smoothness, flame retardancy, processability, etc.) of the molded product formed from the above. Further, according to the method for producing a powder of the present invention, a powder containing a hot-meltable tetrafluoroethylene-based polymer can be obtained.
  • the "viscosity of the liquid composition” is the viscosity of the liquid composition measured at 25 ° C. and a rotation speed of 30 rpm using a B-type viscometer. The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
  • the "thixotropy of the liquid composition” is a value calculated by dividing the viscosity ⁇ 1 measured under the condition of rotation speed of 30 rpm at 25 ° C. by the viscosity ⁇ 2 measured under the condition of rotation speed of 60 rpm ( ⁇ 1 / ⁇ 2 ).
  • Thermal meltable polymer means a polymer exhibiting melt fluidity, and the melt flow rate is 0.1 to 1000 g / 10 minutes at a temperature 20 ° C. or higher higher than the melt temperature of the polymer under the condition of a load of 49 N. It means a polymer in which a temperature is present.
  • the "melt flow rate” means the melt mass flow rate (MFR) of the polymer defined in JIS K 7210: 1999 (ISO 1133: 1997).
  • the "polymer melting temperature (melting point)” is the temperature corresponding to the maximum value of the polymer melting peak measured by the differential scanning calorimetry (DSC) method.
  • the “melt viscosity of the polymer” is based on ASTM D 1238, and a polymer sample (2 g) that has been preheated at the measurement temperature for 5 minutes using a flow tester and a 2 ⁇ -8L die is loaded with 0.7 MPa. It is a value measured by holding it at the measured temperature.
  • the “polymer storage modulus” is a value measured based on ISO 6721-4: 1994 (JIS K7244-4: 1999).
  • the “ten-point average roughness (Rzjis) of the substrate or metal plate” is a value specified in Annex JA of JIS B 0601: 2013.
  • "Powder volume-based cumulative 50% diameter (D50)” is a powder particle size using a laser diffraction / scattering type particle size distribution measuring device (LA-920 measuring device manufactured by HORIBA, Ltd.) by dispersing the powder in water. The distribution is measured, the cumulative curve is obtained with the total volume of the powder particle population as 100%, and the particle size is the point at which the cumulative volume is 50% on the cumulative curve.
  • the “powder volume-based cumulative 90% diameter (D90)” is the particle size at the point where the cumulative volume is 90% on the similarly obtained cumulative curve.
  • the “powder volume-based cumulative 100% diameter (D100)” is the particle size at the point where the cumulative volume is 100% on the similarly obtained cumulative curve.
  • the “unit” in the polymer may be an atomic group formed directly from one molecule of the monomer by the polymerization reaction, and the polymer obtained by the polymerization reaction is treated by a predetermined method to convert a part of the structure. It may be the atomic group.
  • the unit based on the monomer A contained in the polymer is also simply referred to as "unit A".
  • "(Meta) acrylate” is a general term for acrylate and methacrylate.
  • liquid composition (1) is a powder (hereinafter, “F powder”) of a heat-meltable tetrafluoroethylene polymer (hereinafter, also referred to as “F polymer”). It is a liquid composition containing an aromatic resin and a liquid medium and having a viscosity at 25 ° C. of 10000 mPa ⁇ s or less.
  • the liquid composition (1) is a powder dispersion in which F powder is dispersed in the liquid composition.
  • the content ratio of the aromatic resin is 10% by mass or more, and the ratio (mass ratio) of the content ratio of the F polymer to the content ratio of the aromatic resin is 1.2 or less.
  • the liquid composition (1) even if the content ratio of the aromatic resin is high, the F powder is in a good dispersed state, the viscosity of the liquid composition converges within a predetermined range, and the handleability (coatability, impregnation property, etc.) Is excellent. It is considered that this is because the ratio is in a predetermined range and the aromatic resin contained in a high concentration promotes the dispersion of the F powder both in solute and solvent. As a result, it is considered that the dispersion rate of the F powder in the liquid composition (1) is higher than the sedimentation rate, and the physical properties of the liquid composition (1) are less likely to be impaired.
  • a molded product prepreg, a metal plate with a resin layer, a printed wiring board, etc.
  • a molded product having excellent electrical characteristics can be formed even if the content ratio of the F polymer is relatively low. it is conceivable that.
  • the content ratio of the aromatic resin in the liquid composition (1) is 10% by mass or more, preferably 20% by mass or more, and more preferably 40% by mass or more.
  • the upper limit is preferably 80% by mass.
  • the ratio of the content ratio of the F polymer to the content ratio of the aromatic resin in the liquid composition (1) is 1.2 or less, preferably less than 1, more preferably 0.1 to 0.5, and 0.1 to 0.1 to 0.5. 0.4 is particularly preferable.
  • the liquid composition (1) can impart the physical properties of the F polymer, such as electrical properties, to the molded product even if the content ratio of the F polymer is relatively low.
  • the viscosity of the liquid composition (1) is 10,000 mPa ⁇ s or less, preferably 100 to 5000 mPa ⁇ s, and more preferably 500 to 4000 mPa ⁇ s.
  • the F polymer in the liquid composition (1) is a hot-meltable polymer having a unit based on tetrafluoroethylene (hereinafter, also referred to as “TFE”).
  • TFE tetrafluoroethylene
  • the F polymer may be a copolymer of TFE and a comonomer copolymerizable with TFE, or may be a polymer that can be said to be substantially a homopolymer of TFE as long as it is thermally meltable.
  • the F polymer preferably has 90 to 100 mol% of TFE units with respect to all the units constituting the polymer.
  • the fluorine content of the F polymer is preferably 70 to 76% by mass, more preferably 72 to 76% by mass.
  • F polymer examples include heat-meltable polytetrafluoroethylene, a copolymer of TFE and ethylene (ETFE), a copolymer of TFE and propylene, and TFE and perfluoro (alkyl vinyl ether) (hereinafter, also referred to as "PAVE").
  • PFA copolymer
  • HFP Copolymer of TFE and hexafluoropropylene
  • FEE fluoroalkylethylene
  • chlorotri examples include copolymers with fluoroethylene.
  • the copolymer may have a unit based on another comonomer.
  • the F polymer is a hot meltable polymer, and an F polymer having a melting temperature of 260 to 320 ° C. is preferable.
  • the F polymer is excellent in resistance to physical stress such as shearing force and processability, and is not easily deteriorated when the liquid composition (1) is prepared or used. As a result, it tends to be more excellent in dispersibility and homogeneity.
  • the storage elastic modulus of the F polymer at 200 to 260 ° C. is preferably 0.1 to 5.0 MPa, more preferably 0.5 to 3.0 MPa. In this case, it is easy to suppress the warp of the laminated body formed from the liquid composition (1).
  • the melt viscosity of the F polymer 1 ⁇ 10 2 ⁇ 1 ⁇ 10 6 Pa ⁇ s is preferably at 380 ° C., and more preferably 1 ⁇ 10 2 ⁇ 1 ⁇ 10 6 Pa ⁇ s at 300 ° C..
  • the F powder is densely packed to easily form a highly smooth resin layer.
  • the resin layer is likely to reduce damage (peeling, swelling, etc.) of other layers as a heat insulating layer in the solder reflow process.
  • the F polymer include low molecular weight PTFE, modified PTFE, FEP and PFA.
  • the low molecular weight PTFE and modified PTFE also include copolymers of TFE and trace amounts of comonomer (HFP, PAVE, FAE, etc.).
  • the F polymer is preferably an F polymer having a TFE unit and a functional group.
  • the functional group a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group are preferable. Further, the oxygen-containing polar group described later is also preferable.
  • the functional group may be contained in a unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer.
  • Examples of the latter polymer include polymers having a functional group as a terminal group derived from a polymerization initiator, a chain transfer agent, or the like. Further, an F polymer having a functional group obtained by subjecting the F polymer to plasma treatment or ionization wire treatment can also be mentioned.
  • the F polymer having a functional group is preferably a TFE unit and an F polymer having a unit having a functional group from the viewpoint of dispersibility of the F powder in the liquid composition (1) and interaction with an aromatic resin.
  • a unit based on a monomer having a functional group is preferable, and a unit based on a monomer having a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group or an isocyanate group is more preferable.
  • a cyclic monomer having an acid anhydride residue As the monomer having a carbonyl group-containing group, a cyclic monomer having an acid anhydride residue, a monomer having a carboxy group, a vinyl ester and a (meth) acrylate are preferable, and a cyclic monomer having an acid anhydride residue is more preferable.
  • Cyclic monomers having an acid anhydride residue include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride, hereinafter also referred to as "NAH”) and anhydride.
  • Maleic acid is particularly preferred.
  • F polymer having a functional group examples include a TFE unit, an HFP unit, a PAVE unit or a FAE unit, and a unit based on a monomer having a functional group (hereinafter, also referred to as “functional unit”).
  • F polymer can be mentioned.
  • CF 2 CFOCF 3
  • CF 2 CFOCF 2 CF 3
  • CF 2 CFOCF 2 CF 2 CF 3
  • PPVE also referred to as “PPVE”
  • CF 2 CFOCF 2 CF 2 CF 2 CF 3
  • CF 2 CFO (CF 2 ) 8 F.
  • Such an F polymer has 90 to 99 mol% of TFE units, 0.5 to 9.97 mol% of HFP units, PAVE units or FAE units, and 0.01 to 0.01 to functional units with respect to all the units constituting the polymer. It is preferable to have 3 mol% each.
  • Specific examples of such F-polymers include the polymers described in International Publication No. 2018/16644.
  • the F powder in the liquid composition (1) may contain a component (aromatic resin or the like) other than the F polymer, but it is preferable that the F polymer is the main component.
  • the content of the F polymer in the F powder is preferably 80% by mass or more, more preferably 100% by mass. Further, the surface of the F powder may be coated with silica.
  • the D50 of the F powder is preferably 10 to 60 ⁇ m, more preferably 12 to 50 ⁇ m, and particularly preferably 16 to 40 ⁇ m. In this range, the F powder is less likely to settle and easily disperse without impairing the state (viscosity, etc.) of the liquid composition (1).
  • a preferred embodiment of the F powder is a blended powder containing a first powder having a D50 of 8 ⁇ m or less and a second powder having a D50 of 16 to 50 ⁇ m.
  • the D50 of the first powder is preferably 0.1 ⁇ m or more.
  • the ratio (mass ratio) of the content ratio of the first powder to the content ratio of the second powder in the F powder is preferably 0.5 or less, more preferably 0.2 or less.
  • the ratio is preferably 0.01 or more. If the first and second powders are included in such a mass ratio, these powders are highly packed and easily form a resin layer having high smoothness and few voids. Even when the F powder is composed of a plurality of types of powders having different D50s, the D50 as a whole may be 10 to 60 ⁇ m.
  • the F powder is preferably the following powder (1), the following powder (2), or the following powder (3).
  • Powder (1) A powder of an F polymer composed of TFE units and PAVE units, the D50 of which is 10 to 60 ⁇ m.
  • Powder (2) An F polymer powder containing 90 to 99 mol% of TFE units, 1 to 3 mol% of PAVE units and a unit based on a monomer having an oxygen-containing polar group, the D100 of which is 8 ⁇ m or less. ,powder.
  • Powder (3) A powder containing an F polymer and a surface treatment agent, the D50 of which is less than 25 ⁇ m. Details of the powders (1) to (3) will be described later.
  • the aromatic resin in the liquid composition (1) is a resin different from the F polymer.
  • the aromatic resin in the present invention also means a precursor of an aromatic resin that becomes an aromatic resin by heating or the like, and is an aromatic resin or a precursor thereof and a molecule of an aromatic resin such as a cross-linking agent or a curing agent. It also means a combination with components that form the skeleton.
  • the precursor of the aromatic resin include a monomer forming the aromatic resin and a partial reaction product (also referred to as a prepolymer, a semi-reactant product, or a semi-cured product) of the monomer.
  • the aromatic resin may be in a liquid state or in a solid state.
  • the aromatic resin may be a non-curable resin or a curable resin. Examples of the non-curable resin include a thermosetting resin and a cured product of a thermosetting resin.
  • the aromatic resin is selected from the group consisting of aromatic polyimide resin, aromatic polycarbonate resin, aromatic polyamide resin, aromatic polyester resin, aromatic polyether sulfone resin, polyphenylene ether resin, polyphenylene sulfide resin and aromatic epoxy resin.
  • the aromatic resin and its precursor are preferable.
  • the aromatic resin is further chemically modified with a reactive group (vinyl group, (meth) acryloyloxy group, hydroxy group, amino group, epoxy group, etc.) and a halogen atom (bromine atom, fluorine atom, etc.). May be good.
  • the aromatic resin include an aromatic epoxy resin, an aromatic polyimide resin, a polyamic acid which is a precursor of the aromatic polyimide resin, an aromatic polyester resin, a polyphenylene ether resin, and a precursor thereof. ..
  • the F polymer also functions as a flame retardant, and the flame retardancy of the molded product formed from the liquid composition of the present invention is likely to be improved.
  • Aromatic epoxy resins include naphthalene type, cresol novolac type, bisphenol A type, bisphenol F type, bisphenol S type, cresol novolac type, phenol novolac type, alkylphenol novolac type, biphenol type, trishydroxyphenylmethane type and the like.
  • Epoxy resin can be mentioned. Examples thereof include an epoxidized product of a condensate of phenol and an aromatic aldehyde having a phenolic hydroxy group, a diglycidyl ether of bisphenol, a diglycidyl ether of naphthalene diol, and a glycidyl ether of phenol.
  • aromatic tetracarboxylic dianhydride that forms the aromatic polyimide resin or its precursor (polyamic acid)
  • aromatic tetracarboxylic dianhydride that forms the aromatic polyimide resin or its precursor (polyamic acid)
  • aromatic tetracarboxylic dianhydride that forms the aromatic polyimide resin or its precursor (polyamic acid)
  • pyromellitic dianhydride 3,3'4,4'-biphenyltetracarboxylic dianhydride.
  • aromatic diamines that form the aromatic polyimide resin or its precursor (polyamic acid) include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3'-diaminodiphenyl ether, and 4,4'.
  • aromatic polyester resin examples include solvent-soluble liquid crystal aromatic polyesters.
  • aromatic polyesters include the polymers described in paragraphs [0019] to [0042] of JP-A-2010-031256, and more specifically, 2-hydroxy-6-naphthoic acid, isophthalic acid and the like.
  • examples thereof include a reaction product of diphenyl ether-4,4'-dicarboxylic acid, 4-hydroxyacetonilide, and acetic anhydride.
  • polyphenylene ether resin or a precursor thereof include 2,6-dimethylphenol, a polyphenol derivative, and a reaction product of both.
  • the liquid composition (1) contains an F polymer having poor interaction with other substances, the powder (F powder) is well dispersed without deterioration such as thickening. According to the present invention, it is also possible to provide a liquid composition containing a high concentration aromatic resin in which F powder is dispersed, which does not substantially contain a component that promotes dispersion of F powder.
  • the component include a fluorine-based surfactant, a silicone-based surfactant, and a hydrocarbon-based surfactant. That is, the liquid composition (1) does not contain the fluorine-containing compound other than the component, particularly the F polymer, or when the liquid composition (1) contains the fluorine-containing compound, the content of the fluorine-containing compound with respect to the content ratio of the F polymer.
  • the ratio of the ratio is preferably 0.05 or less.
  • the ratio is more preferably 0.01 or less.
  • the liquid composition (1) is easier to manufacture and adjust its physical properties.
  • the aromatic resin having a fluorine atom is not included in the fluorine-containing compound.
  • the liquid composition (1) contains a liquid medium.
  • the content ratio of the liquid medium in the liquid composition (1) is preferably 40% by mass or less, more preferably 5 to 30% by mass.
  • the content ratio of the aromatic resin and the content ratio of the F polymer to the content ratio are within a predetermined range, even if a liquid medium is contained, the deterioration of the F polymer due to the content ratio is suppressed and increased. Hard to stick.
  • the aromatic resin is contained in a high concentration, the F powder does not easily settle even if a liquid medium is contained, and the dispersion stability is excellent.
  • the liquid medium is a compound that is liquid at 25 ° C. and is appropriately selected depending on the type of aromatic resin.
  • the liquid medium is preferably a compound having a lower boiling point than the other components contained in the liquid composition (1) and can be removed by volatilization. Two or more kinds of liquid media may be used in combination.
  • liquid medium examples include water, alcohol (ethanol, 2-propanol, 1-butanol, etc.), nitrogen-containing compounds (N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.).
  • the liquid composition (1) preferably contains an inorganic filler from the viewpoint of further suppressing the warpage of the formed molded product.
  • the inorganic filler include silica, alumina, and boehmite. Spherical silica is preferable from the viewpoint of improving workability in addition to suppressing warpage.
  • the content ratio of the inorganic filler in the liquid composition (1) is preferably 25% by mass or less.
  • the liquid composition (1) may further contain an agent other than the above-mentioned components.
  • Such agents include thixotropic agents, defoamers, silane coupling agents, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, and conductive agents.
  • thixotropic agents include thixotropic agents, defoamers, silane coupling agents, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, and conductive agents.
  • examples include agents, mold release agents, surface treatment agents, viscosity modifiers, and flame retardants.
  • the liquid composition (1) requires F powder and an aromatic resin under the condition that the content ratio of the aromatic resin is 10% by mass or more and the ratio of the content ratio of the F polymer to the liquid composition is 1.2 or less. Depending on the situation, it can be produced by mixing with other components, and it is preferable to add F powder to a liquid raw material composition containing an aromatic resin. As described above, since the F powder has high dispersibility in the aromatic resin, a liquid composition having a high content ratio of the aromatic resin can be easily produced.
  • the liquid composition (1) contains F powder having a good dispersed state and an aromatic resin at a high concentration, and is excellent in handleability.
  • a prepreg containing the dried product of the liquid composition (1) and the fiber base material can be obtained.
  • the dried product is a solid product formed from the liquid composition (1).
  • the liquid composition (1) is curable, it is a cured product formed from the liquid composition (1).
  • 1) contains a liquid medium, it is a solidified product formed by removing the liquid medium from the liquid medium.
  • these cured products also include aspects of semi-cured products.
  • the prepreg is a prepreg containing a dried product of the liquid composition (1) and a fiber base material, and can be said to be a prepreg containing an F polymer and an aromatic resin as a matrix resin, and has high homogeneity of the F polymer. Moreover, it is a prepreg in which an aromatic resin is impregnated and maintained at a high concentration.
  • the fiber base material includes a reinforcing fiber bundle composed of a plurality of reinforcing fibers, a cloth woven from the reinforcing fiber bundle, a unidirectional reinforcing fiber bundle in which a plurality of reinforcing fibers are aligned in one direction, and the unidirectional reinforcing fiber.
  • a unidirectional cloth composed of bundles, a fiber bundle in which these are combined, and a fiber bundle in which a plurality of reinforcing fiber bundles are stacked.
  • the reinforcing fiber continuous long fibers having a length of 10 mm or more are preferable.
  • the reinforcing fibers need not be continuous over the entire length in the length direction or the entire width in the width direction of the reinforcing fiber sheet, and may be divided in the middle.
  • Examples of the reinforcing fiber include inorganic fiber, metal fiber, and organic fiber.
  • Examples of the inorganic fiber include carbon fiber, graphite fiber, glass fiber, silicon carbide fiber, silicon nitride fiber, alumina fiber, silicon carbide fiber, and boron fiber.
  • Examples of the metal fiber include aluminum fiber, brass fiber, and stainless steel fiber.
  • Examples of the organic fiber include aromatic polyamide fiber, polyaramid fiber, polyparaphenylene benzoxazole (PBO) fiber, polyphenylene sulfide fiber, polyester fiber, acrylic fiber, nylon fiber and polyethylene fiber.
  • As the reinforcing fiber used for the prepreg for the printed circuit board glass fiber is preferable, and open fiber glass cloth is more preferable.
  • the reinforcing fibers may be surface-treated. Two or more types of reinforcing fibers may be used in combination.
  • the impregnated material may be heated.
  • the heating conditions may be such that when the liquid composition (1) is curable, it may be heated at the curing temperature or higher, and when the liquid composition (1) contains a liquid medium, it may be above the boiling point of the liquid medium. And heat it. Drying may be carried out in one step at a constant temperature, or in two or more steps at different temperatures. Examples of the drying method include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays. Drying may be carried out under either normal pressure or reduced pressure.
  • the dry atmosphere may be any of an oxidizing gas atmosphere (oxygen gas, etc.), a reducing gas atmosphere (hydrogen gas, etc.), and an inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas, etc.). ..
  • a metal plate and a resin layer are provided in this order, and the resin layer is a metal plate with a resin layer containing a dried product of the liquid composition (1) (hereinafter, also referred to as a metal plate with a resin layer (1)). (Note) can be provided.
  • the above-mentioned prepreg can also be used as the dried product.
  • the metal plate (1) with a resin layer contains an aromatic resin having electrical insulating properties and an F polymer having a low relative permittivity and dielectric loss tangent, and the F polymer has high homogeneity, excellent electrical characteristics, and is resistant to warping.
  • the relative permittivity (20 GHz) of the metal plate (1) with a resin layer is preferably 3.6 or less, and more preferably 3.2 or less.
  • the dielectric loss tangent (20 GHz) is preferably 0.009 or less, more preferably 0.003 or less.
  • the coefficient of linear expansion of the metal plate (1) with a resin layer is preferably ⁇ 10 to +10 ppm / ° C.
  • Examples of the material of the metal plate include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, titanium alloy and the like.
  • the thickness of the metal plate is preferably 1 to 30 ⁇ m.
  • Examples of the metal plate include copper foils such as rolled copper foils and electrolytic copper foils.
  • a rust preventive layer (oxide film such as chromate), a heat resistant layer, a roughening treatment layer, and a silane coupling agent treatment layer may be provided on the surface of the metal plate.
  • the ten-point average roughness of the surface of the metal plate is preferably 0.2 to 2.5 ⁇ m. In this case, the adhesiveness between the metal plate and the resin layer tends to be good.
  • the metal plate with a resin layer (1) may have a metal plate in contact with at least one surface of the resin layer.
  • the layer structure include a metal plate / resin layer, a metal plate / resin layer / metal plate, a resin layer / metal plate / resin layer, and a metal plate / resin layer / other substrate / resin layer / metal plate.
  • metal plate / resin layer means that the metal plate and the resin layer are laminated in this order, and the same applies to other layer configurations.
  • the metal plate (1) with a resin layer is manufactured by superimposing the liquid composition (1) or a dried product of the liquid composition (1) (such as the prepreg described above) on the surface of the metal plate and further heating the metal plate (1).
  • the heating conditions when the above-mentioned prepreg is used, it is preferable to heat at 160 to 220 ° C. Further, the heating at this time is preferably adopted by a hot pressing method. That is, it is preferable that the above-mentioned prepreg is superposed on the surface of the metal plate and thermocompression bonded at a pressure of 0.2 to 10 MPa.
  • the hot press is preferably performed in a vacuum atmosphere of 20 kPa or less from the viewpoint of suppressing deterioration due to air bubble mixing and oxidation.
  • the surface of the resin layer may be surface-treated in order to control the coefficient of linear expansion of the resin layer and further improve the adhesiveness of the resin layer.
  • the surface treatment include annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling treatment, and fine roughening treatment.
  • the temperature is preferably 80 to 190 ° C.
  • the pressure is preferably 0.001 to 0.030 MPa
  • the time is preferably 10 to 300 minutes.
  • the metal plate (1) with a resin layer contains a high concentration of aromatic resin and uniformly contains an F polymer, so that it has excellent physical properties such as electrical characteristics and chemical resistance (etching resistance), and is a flexible printed wiring board.
  • a printed wiring substrate can be manufactured from the metal plate (1) with a resin layer by a method of processing into a metal conductor wiring by a modified semi-additive method or the like.
  • This printed wiring board has a metal conductor wiring and a resin layer in this order.
  • the resin layer is a dried product of the liquid composition (1), and examples thereof include metal conductor wiring / resin layer and metal conductor wiring / resin layer / metal conductor wiring.
  • an interlayer insulating film may be formed on the metal conductor wiring, and then the metal conductor wiring may be further formed on the interlayer insulating film.
  • the interlayer insulating film may also be formed by the liquid composition (1).
  • a solder resist or a coverlay film may be laminated on the metal conductor wiring.
  • the solder resist and the coverlay film may be formed by the liquid composition (1).
  • a multilayer printed wiring board in which the above-mentioned layer structure is multilayered can be mentioned.
  • a preferred embodiment of the multilayer printed wiring board is that the outermost layer of the multilayer printed wiring board is a resin layer containing a dried product of the liquid composition (1), and has one or more layer configurations of metal conductor wiring / the resin layer.
  • a part of the resin layer may be replaced with an F polymer layer containing F polymer as a main component, and specifically, metal conductor wiring / resin layer / metal conductor wiring / F polymer. It may have a layer structure such as a layer / a metal conductor wiring / the resin layer.
  • the multilayer printed wiring board of this aspect has excellent heat resistance of the outermost layer, and the interface peeling between the metal conductor wiring and the resin layer is unlikely to occur even by heating during processing, for example, heating at 300 ° C. in the solder reflow process. ..
  • the powder of the present invention is also referred to as a liquid composition (hereinafter, also referred to as "liquid composition (p)") containing at least one resin material selected from the group consisting of a non-meltable tetrafluoroethylene polymer and an aromatic resin. ) Is a powder used in addition to.
  • the powder of the present invention will also be referred to as "additive (1)”.
  • the additive (1) is the following powder (1), the following powder (2), or the following powder (3).
  • Powder (1) A powder of an F polymer composed of TFE units and PAVE units, the D50 of which is 10 to 60 ⁇ m.
  • Powder (2) An F polymer powder containing 90 to 99 mol% of TFE units, 1 to 3 mol% of PAVE units and a unit based on a monomer having an oxygen-containing polar group, the D100 of which is 8 ⁇ m or less.
  • Powder (3) A powder containing an F polymer and a surface treatment agent, the D50 of which is less than 25 ⁇ m.
  • the F polymer in the powder (1) a polymer containing 92 to 98 mol% of TFE units and 2 to 8 mol% of PAVE units is preferable.
  • the F polymer in the powder (2) is referred to as a unit based on a monomer having an oxygen-containing polar group (hereinafter, also referred to as “polar monomer”) (hereinafter, “polar unit”) as compared with the F polymer in the powder (1). It is characterized by having (described).
  • the F polymer in the powder (3) may be the same F polymer as the F polymer in the powder (1) or the powder (2), or may be another F polymer. Examples of the F polymer in the powder (3) include the F polymer constituting the F powder in the liquid composition (1).
  • the F polymer in the powder (1) is referred to as “added polymer (1)”
  • the F polymer in the powder (2) is referred to as “added polymer (2)”
  • the F polymer in the powder (3) is referred to as “added polymer (3)”. Also written.
  • each polymer is generically referred to, it is also referred to as “added polymer”
  • each powder is generically referred to, it is also referred to as “added powder”.
  • the ratio (mol%) of each unit in the added polymer is the ratio of each unit to all the units constituting the added polymer.
  • the additive (1) has excellent dispersibility in the liquid composition (p) containing a resin material, and the molded product (including a molded part such as a resin layer; the same applies hereinafter) obtained from the additive is flame-retardant and processed. Physical properties such as sex can be imparted. In addition, the obtained molded product maintains or further improves its original physical properties. The reason is not always clear, but it is considered that the added powder contains the added polymer having a predetermined polymer composition and has a predetermined particle size.
  • the powder (1) contains the added polymer (1) containing PAVE units, and its D50 is relatively large.
  • the added polymer (1) preferably contains 2 to 8 mol% of PAVE units.
  • the fluidity is high both chemically and physically.
  • D50 is relatively large, the surface area per mass is reduced, and the contact with the components of the liquid composition (p) is relatively reduced, so that the low affinity between the components is alleviated and the dispersibility thereof is improved. It is also considered to improve.
  • each particle constituting the powder (1) is regarded as an aggregate of the primary particles of the added polymer 1, it is considered that the bulk density of the powder (1) is lowered.
  • the powder (1) added to the liquid composition (p) has a higher dispersion rate than the sedimentation rate, and is good without impairing the physical properties of the liquid composition (p). It is thought that it was dispersed in.
  • the molded product formed from the liquid composition (p) to which the powder (1) is added has the original characteristics (weather resistance, heat resistance, chemical resistance, impact resistance, electrical characteristics, etc.) due to the resin material. It is presumed that the high physical properties due to the added polymer could be exhibited while maintaining the same.).
  • the powder (2) contains the additive polymer (2) containing a polar unit, and is considered to have a strong interaction with the resin material of the liquid composition (p), but its D100 is relatively small, in other words. If so, it does not contain powder with a large particle size or its content is low. Therefore, thickening of the liquid composition (p) and sedimentation of the components due to the interaction between the resin material and the powder (2) are likely to be suppressed. As a result, the molded product formed from the liquid composition (p) to which the powder (2) is added can exhibit high physical properties due to the added polymer (2) while maintaining the original properties due to the resin material. It is presumed that it was.
  • the powder (3) contains a surface treatment agent, even if its D50 is a small particle size of less than 25 ⁇ m, it is highly dispersed in the liquid composition (p) without thickening. Therefore, a relatively large amount of resin material can be stably dissolved or dispersed in the liquid composition (p). Further, the liquid composition (p) to which the powder (3) is added is not easily deteriorated.
  • the amount of the powder (1) and the powder (2) added to the liquid composition (p) is preferably such that the ratio of the mass of the added polymer to the mass of the resin material is 0.1 to 1, preferably 0.2 to 1. An amount of 0.8 is more preferable, and an amount of 0.3 to 0.7 is even more preferable. In this case, it is easy to adjust the viscosity of the liquid composition (p) within a predetermined range. Specifically, the viscosity of the liquid composition (p) to which the powder is added at 25 ° C. is preferably less than 10000 mPa ⁇ s, more preferably 100 to 5000 mPa ⁇ s, still more preferably 500 to 4000 mPa ⁇ s.
  • the amount of the powder (3) added to the liquid composition (p) is preferably such that the ratio of the mass of the added polymer to the mass of the resin material is 0.1 to 0.5, preferably 0.1 to 0.4. The amount is more preferred. In this case, since the amount of the resin material contained in the liquid composition (p) is sufficiently large, excellent physical properties (flame retardancy, processability, etc.) are imparted to the resin layer formed from the liquid composition (3). it can.
  • the viscosity of the liquid composition (p) to which the powder (3) is added at 25 ° C. is preferably less than 10000 mPa ⁇ s, more preferably 50 to 5000 mPa ⁇ s, still more preferably 100 to 1000 mPa ⁇ s.
  • the additive powder in the additive (1) preferably contains the added polymer as a main component.
  • the content of the added polymer in the added powder is preferably 80% by mass or more, more preferably 100% by mass.
  • the added powder may contain the above resin material itself.
  • the components such as the surface treatment agent, which is a component other than the added polymer in the powder (3), the composition of the powder (3), and the like will be described later in the description of the method for producing the powder (3).
  • the D50 of the powder (1) is preferably 10 to 50 ⁇ m, more preferably 12 to 40 ⁇ m, and even more preferably 14 to 30 ⁇ m. In this range, the powder (1) is particularly excellent in dispersibility in the liquid composition (p).
  • the D100 of the powder (1) is preferably 100 ⁇ m or less.
  • the D100 of the powder (2) is preferably 5 ⁇ m or less.
  • the D100 of the powder (2) is preferably 0.3 ⁇ m or more, and more preferably 1 ⁇ m or more. In this range, the powder (2) is particularly excellent in dispersibility in the liquid composition (p).
  • the D50 of the powder (2) is preferably 0.1 to 3 ⁇ m.
  • the D50 of the powder (3) is less than 25 ⁇ m, preferably 10 ⁇ m or less, more preferably 0.05 to 8 ⁇ m, still more preferably 0.1 to 6 ⁇ m.
  • the D90 of the powder (3) is preferably 40 ⁇ m or less, more preferably 15 ⁇ m or less. In D50 and D90 in this range, the fluidity and dispersibility of the powder become good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the resin layer formed from the powder (3) are likely to be exhibited.
  • the added powder may be corona treated, plasma treated, electron beam treated or radiation treated.
  • Oxygen-containing polar groups > C (O), -C (O) F, etc.
  • the dispersibility of the added powder and the surface of the molded product (resin layer) can be introduced. Adhesiveness is more likely to improve.
  • oligomer functions as a dispersant or a plasticizer, it is easy to improve the dispersibility of the added powder and the processability of the molded product. Furthermore, when a molded product is formed from a liquid composition, the surface of the molded product to be formed is roughened by the gas generated by the decomposition and volatilization of the oligomer, and the molded product is physically (anchored) or chemically adhered. It can also be expected to improve sex. Further, it is considered that the added powder is physically brittle and easily disintegrated by electron beam treatment or radiation treatment. Therefore, in the molded product, the added polymer and the resin material are more likely to interact with each other, and physical properties such as flame retardancy due to the added polymer are likely to be remarkably exhibited.
  • the powder (1) is preferably produced by subjecting a dispersion liquid containing primary particles of a copolymer of TFE and PAVE obtained by aqueous polymerization to a coagulation treatment or a freeze-drying treatment.
  • each particle constituting the powder is an aggregate of primary particles of the added polymer (1), and the bulk density is lowered and the dispersibility is easily improved.
  • the powder (2) for example, the powder described in International Publication No. 2016/017801 or International Publication No. 2019/098202 is preferable.
  • the added polymer (1) preferably contains 92 to 98 mol% of TFE units and 2 to 8 mol% of PAVE units with respect to all the units constituting the polymer.
  • the added polymer (1) may consist of only TFE units and PAVE units, and may further contain other units.
  • the ratio of TFE units in the added polymer (1) is more preferably 94 mol% or more, further preferably 96 mol% or more.
  • the ratio of TFE units is more preferably 97.8 mol% or less, still more preferably 97.7 mol% or less.
  • the ratio of PAVE units in the added polymer (1) is more preferably 2.1 mol% or more, further preferably 2.3 mol% or more.
  • the ratio of PAVE units is preferably 6 mol% or less, more preferably 4 mol% or less.
  • the ratio of the other units is preferably 5.9 mol% or less, more preferably 3.7 mol% or less, still more preferably 1.7 mol%.
  • the ratio of TFE units in the added polymer (2) is preferably 94 mol% or more, preferably 96 mol% or more.
  • the ratio of TFE units is preferably 99 mol% or less, more preferably 98 mol% or less.
  • the ratio of PAVE units in the added polymer (2) is preferably 1.2 mol% or more, more preferably 1.5 mol% or more.
  • the ratio of PAVE units is preferably 2.7 mol% or less, and more preferably 2.4 mol% or less.
  • the ratio of polar units in the added polymer (2) is preferably 0.01 mol% or more, more preferably 0.05 mol% or more.
  • the ratio of PAVE units is preferably 3 mol% or less, more preferably 1 mol% or less.
  • the added polymer (2) may consist of only TFE units, PAVE units and polar units, and may further contain other units.
  • HFP units and FAE units are preferable.
  • a hydroxyl group-containing group, a carbonyl group-containing group, an acetal group and a phosphono group (-OP (O) OH 2 ) are preferable, and a carbonyl group-containing group is more preferable.
  • a hydroxyl group-containing group a group containing an alcoholic hydroxyl group is preferable, and -CF 2 CH 2 OH, -C (CF 3 ) 2 OH and 1,2-glycol group (-CH (OH) CH 2 OH) are more preferable. preferable.
  • the carbonyl group-containing group is a group containing a carbonyl group (> C (O)), and the carbonyl group-containing group includes a carboxyl group, an alkoxycarbonyl group, an amide group, an isocyanate group, and a carbamate group (-OC (O) NH 2 ).
  • Acid anhydride residues (-C (O) OC (O)-), imide residues (-C (O) NHC (O)-etc.) and carbonate groups (-OC (O) O-) are preferred.
  • the polar monomer include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (NAH) and maleic anhydride.
  • the melt viscosity of the added polymer at 380 ° C. is preferably 1 ⁇ 10 2 to 1 ⁇ 10 8 Pa ⁇ s, more preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s.
  • the melting temperature of the added polymer is preferably 200 to 320 ° C, more preferably 260 to 320 ° C. In this case, when the substrate with the resin layer is produced, the adhesiveness of the resin layer to the substrate can be further improved.
  • the added polymer may be treated with fluorine gas.
  • Fluorine gas treatment introduces a fluorine-containing group such as -CF 3 at the end of the polymer chain of the added polymer. This makes it easier to adjust the dispersibility of the added powder.
  • a part of the added polymer is decomposed by the fluorine gas treatment to form an oligomer.
  • the added powder will contain an oligomer derived from the added polymer. Since such an oligomer functions as a dispersant or a plasticizer, it is easy to further improve the dispersibility of the added powder and the processability of the molded product.
  • the surface of the molded product to be formed is roughened by the gas generated by the decomposition and volatilization of the oligomer, and the physical (anchor effect) of the molded product or Improvement of chemical adhesiveness can also be expected.
  • the additive (1) may be used as a powder by adding it to the liquid composition (p) as it is, or by adding it to the liquid composition (p) as an additive liquid dispersed in the liquid. You may.
  • the additive (1) preferably further contains a liquid medium as a polar solvent, and is one selected from the group consisting of water, esters, amides and ketones from the viewpoint of satisfactorily dispersing the added powder. It is preferable to contain the above polar solvent.
  • the content of the added polymer in the additive liquid is preferably 20 to 50% by mass with respect to the polar solvent.
  • the polar solvent can be appropriately selected depending on the type of the liquid composition (p).
  • ester examples include ethyl lactate, ethyl acetate and butyl acetate.
  • examples of the amide include N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone.
  • examples of the ketone include methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, and cyclohexanone.
  • the additive liquid preferably further contains a surfactant from the viewpoint of further improving the dispersibility of the added powder.
  • the content of the surfactant in the additive liquid is preferably 1 to 10% by mass with respect to the added polymer.
  • the surfactant is not particularly limited as long as it is a compound having a hydrophilic group and a hydrophobic group, and a fluorine-based surfactant, a silicone-based surfactant or an acetylene-based surfactant is preferable, and a fluorine-based surfactant is preferable. Is preferable.
  • the surfactant is preferably nonionic.
  • fluorine-based surfactant fluoromonool, fluoropolyol, fluorosilicone and fluoropolyether are preferable.
  • fluoropolyol a copolymer of fluoro (meth) acrylate and (meth) acrylate having a hydroxyl group is preferable, and (meth) acrylate having a polyfluoroalkyl group or a polyfluoroalkenyl group and (meth) having a polyoxyalkylene monool group. Acrylate is more preferred.
  • the fluorosilicone is preferably a polyorganosiloxane having a CF bond in a part of the side chain.
  • the fluoropolyether is preferably a compound in which a part of hydrogen atoms of the polyoxyalkylene alkyl ether is replaced with a fluorine atom.
  • Suitable resin materials in the additive (1) include polyimide-based aromatic resins, polyamide-based aromatic resins, polyether-based aromatic resins, epoxy-based aromatic resins, polyimide-based aromatic resins, and polyester-based aromatic resins.
  • aromatic resins selected from the group consisting of resins and polycarbonate-based aromatic resins. These resin materials are preferable because they are excellent in various physical properties and have a high affinity with the added polymer.
  • a preferred embodiment of the aromatic resin is the same as that in the liquid composition (1).
  • a liquid composition (hereinafter, also referred to as “liquid composition (2)”) containing the aromatic resin and the additive powder can be provided.
  • the liquid composition (2) is a powder dispersion in which the added powder is dispersed in the liquid composition (2).
  • the ratio of the mass of the added polymer to the mass of the aromatic resin in the liquid composition (2) is preferably 0.1 to 1, more preferably 0.2 to 0.8, and 0.3. An amount of about 0.7 is more preferable.
  • the liquid composition (2) preferably contains 20% by mass or more of the aromatic resin, more preferably 40% by mass or more, and further preferably 50% by mass or more, based on the total mass thereof.
  • the upper limit is preferably 80% by mass.
  • the viscosity of the liquid composition (2) is preferably less than 10000 mPa ⁇ s, more preferably 100 to 5000 mPa ⁇ s, and even more preferably 500 to 4000 mPa ⁇ s.
  • the liquid composition (2) preferably further contains a polar solvent.
  • the content of the polar solvent in the liquid composition (2) is preferably 20% by mass or more, more preferably 40% by mass or more.
  • the content is preferably 60% by mass or less.
  • the viscosity of the obtained liquid composition (2) can be easily adjusted to the above range.
  • the added polymer is a heat-meltable polymer with high fluidity and has excellent resistance to alteration with physical stress such as shearing force. Therefore, even if a polar solvent as a dispersion medium is contained, the liquid composition is altered (increased). It is easy to suppress stickiness etc.).
  • the liquid composition (2) preferably further contains an inorganic filler. If an inorganic filler is contained, the warp of the substrate with a resin layer described later can be reduced.
  • the coefficient of linear expansion (absolute value) of the resin layered substrate is preferably 40 ° C./ppm or less, more preferably 25 ° C./ppm or less, and even more preferably 10 ° C./ppm or less.
  • Such a substrate with a resin layer having a low coefficient of linear expansion is suitable as a printed wiring board material.
  • inorganic filler examples include silica, mica, talc, clay, bentonite, montmorillonite, kaolinite, wallastonite, calcium carbonate, titanium oxide, alumina, barium sulfate, potassium titanate, and glass.
  • the inorganic filler may be in the form of particles or fibers.
  • the specific surface area of the silica particles is preferably at least 6.5m 2 / g, more preferably 6.5 ⁇ 1000m 2 / g, more preferably 10 ⁇ 800m 2 / g, particularly preferably 20 ⁇ 700m 2 / g.
  • the pore volume of the silica particles is preferably 0.05 to 3.0 mL / g, more preferably 0.1 to 2.0 mL / g.
  • the D50 of the silica particles is preferably 0.005 to 100 ⁇ m, more preferably 0.02 to 20 ⁇ m.
  • the base polymer or the added polymer does not easily penetrate into the silica particles, and the effect of forming an air phase in the resin layer makes it easy to improve the electrical characteristics of the molded product.
  • silica particles include hollow silica particles having a mesoporous structure in the shell portion, hollow silica particles having a non-porous structure in the shell portion, and porous silica particles.
  • the content of the inorganic filler in the liquid composition (2) is preferably 0.1 to 5% by mass, more preferably 0.3 to 1% by mass. In this case, it is easy to obtain a molded product having excellent electrical characteristics while reducing the coefficient of linear expansion.
  • the liquid composition (2) of the present invention may further contain an agent other than the above-mentioned components. Examples of such an agent include an agent similar to that in the liquid composition (1).
  • the substrate with a resin layer (2) When the liquid composition (2) is applied to the surface of the substrate and heated to form a resin layer, the substrate and the resin layer are laminated in this order (hereinafter, the substrate with a resin layer (2)). Also described.) Is obtained.
  • the thickness of the substrate is preferably 1 to 30 ⁇ m.
  • a copper foil such as a rolled copper foil or an electrolytic copper foil is preferable.
  • a rust preventive layer (oxide film such as chromate), a heat resistant layer, a roughening treatment layer, and a silane coupling agent treatment layer may be provided on the surface of the substrate.
  • the ten-point average roughness of the surface of the substrate is preferably 0.2 to 2.5 ⁇ m.
  • the liquid composition can be applied by spray method, roll coating method, spin coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, kiss coating method, bar coating method, die coating method, fountain Mayer bar method, It can be carried out by a method such as the slot die coating method.
  • the heating is the same as the heating mode in the metal plate (1) with a resin layer.
  • the dispersibility of the added polymer (added powder) is high, and the homogeneity of the added polymer and the aromatic resin in the formed resin layer is high.
  • the homogeneity of such components can be defined by the ratio of the amounts of fluorine atoms present on both surfaces of the resin layer of the substrate with the resin layer.
  • the amount of fluorine atoms present on the surface of the polymer layer can be quantified by energy dispersive X-ray analysis.
  • the substrate and the resin layer are laminated in this order, and the resin layer contains the aromatic resin and the added polymer, and is added to the mass of the aromatic resin contained in the resin layer.
  • the ratio of the mass of the polymer is 0.1 to 1, and the ratio of the amount of fluorine atoms present on the other surface to the amount of fluorine atoms present on one surface of the resin layer is 0.8 to 1.2.
  • a substrate with a resin layer can be provided.
  • the amount ratio of fluorine atoms present on both surfaces of the resin layer is preferably 0.9 to 1.1.
  • the substrate with a resin layer (2) may have a substrate in contact with at least one surface of the resin layer.
  • the layer structure is the same as that of the metal plate (1) with a resin layer.
  • the thickness of the resin layer in the substrate with the resin layer (2) is preferably 1 to 100 ⁇ m.
  • the substrate with a resin layer (2) also has high peel strength between the resin layer and the substrate. The peel strength is preferably 7 N / cm or more, more preferably 10 N / cm or more, and even more preferably 13 N / cm or more.
  • the substrate with a resin layer (2) is a substrate having a resin layer containing an aromatic resin, which is a super engineering plastic, and an additive polymer, and is excellent in physical properties such as flame retardancy, electrical properties, and chemical resistance (etching resistance). It is useful as a material for printed wiring boards such as flexible printed wiring boards and rigid printed wiring boards.
  • a metal substrate such as a metal foil as a substrate
  • a printed wiring board can be manufactured by a method of processing a metal conductor wiring by an electrolytic plating method (semi-additive method, modified semi-additive method, etc.). Therefore, such a printed wiring board has a metal conductor wiring and a resin layer in this order.
  • the aspect of the printed wiring board is the same as the specific aspect of the printed wiring board in the metal plate (1) with a resin layer.
  • a suitable mode of the resin material in the liquid composition (2) includes non-meltable PTFE.
  • the non-meltable PTFE may be a fibril-forming ability, a PTFE (ultra high molecular weight PTFE), a low molecular weight PTFE, or a modified PTFE.
  • the low molecular weight PTFE or modified PTFE also includes a copolymer of TFE and a trace amount of comonomer (HFP, PAVE, FAE, etc.).
  • a treated powder is obtained by adding the additive (1) to a liquid composition containing a non-meltable PTFE powder and water to obtain a dispersion liquid, and further removing water from the dispersion liquid.
  • the added polymer contained in the additive (1) is a heat-meltable polymer having high fluidity and has excellent alteration resistance to physical stress such as shearing force. Therefore, it is dispersed even if it contains water as a polar solvent. Easy to prepare liquid. Further, in the dispersion liquid, the respective powders interact with each other to a high degree, so that a highly homogeneous dispersion liquid is formed.
  • a treated powder in which the added polymer is highly bound to the non-meltable PTFE can be obtained.
  • a method for removing water from the prepared dispersion a method of freezing the dispersion and sublimating the water to remove the water, or a method of coagulating the dispersion to recover the powder can be adopted.
  • the additive (1) is added to a liquid composition containing a non-meltable PTFE powder and a polar solvent to obtain a dispersion liquid, and the dispersion liquid is applied to the surface of a substrate and heated to form a resin layer. Then, a substrate with a resin layer in which the substrate and the resin layer are laminated in this order can be obtained. Since the resin layer of the substrate with the resin layer uniformly contains the melt-processable added polymer, it is excellent in processability.
  • the substrate the same substrate as the above-mentioned substrate can be used, and a metal foil is preferable.
  • the same method as the above-mentioned coating method can be adopted.
  • the heating is preferably performed at a temperature equal to or higher than the melting temperature of the added polymer, and more preferably at a temperature at which the non-meltable PTFE is sintered.
  • the specific temperature is 350 to 380 ° C.
  • the same conditions as those described above can be adopted.
  • This substrate with a resin layer is a substrate having a resin layer in which non-meltable PTFE and a melt-processable additive polymer are highly compatible with each other, and has physical properties such as processability, electrical characteristics, and chemical resistance (etching resistance). It is excellent and can be processed into printed wiring boards such as flexible printed wiring boards and rigid printed wiring boards. Further, the substrate may be removed from the substrate with the resin layer, and the resin layer may be recovered as a film (single film). Since the recovered film exhibits good stretched physical properties, various functional membrane materials (microfiltration membrane (MF membrane), ultrafiltration membrane (UF membrane), reverse osmosis membrane (RO membrane)) can be obtained by stretching. It is useful as a membrane material such as an ion exchange membrane (IE membrane), a diafiltration membrane (MD membrane), or a gas separation membrane).
  • IE membrane ion exchange membrane
  • MD membrane diafiltration membrane
  • gas separation membrane ion exchange membrane
  • the powder (3) is a powder having a D50 of less than 25 ⁇ m, which contains an F polymer and a surface treatment agent.
  • the mass ratio of the surface treatment agent to the F polymer contained in the powder is preferably more than 0.01 and 0.25 or less.
  • the present invention also comprises a powder having a D50 of less than 25 ⁇ m, which comprises an F polymer and a surface treatment agent, and the mass ratio of the surface treatment agent to the F polymer contained in the powder is more than 0.01 and 0.25 or less.
  • the method for producing a powder of the present invention is a powder containing an F polymer and a surface treatment agent, which concentrates a powder dispersion containing an F polymer raw material powder, a surface treatment agent and a liquid medium, and further separates the liquid medium.
  • the method for producing a powder wherein the mass ratio of the surface treatment agent to the F polymer contained in the produced powder is more than 0.01 and 0.25 or less.
  • this method (1) the method for producing this powder will also be referred to as "this method (1)”.
  • the powder obtained by the present method (1) is a powder having a mass ratio of the surface treatment agent to the F polymer of more than 0.01 and 0.25 or less among the powders (3) as described above.
  • the F polymer in the present method (1) a polymer having a polar functional group is preferable, and a polymer having a carbonyl group-containing group is more preferable, from the viewpoint of enhancing the interaction with the surface treatment agent. Therefore, the F polymer in the powder (3) is also preferably a polymer having a polar functional group.
  • the powder obtained by the present method (1) is a powder containing a highly interacting F polymer and a surface treatment agent, and is a powder included in the category of the powder (3).
  • the reason why the powder obtained by this method (1) is excellent in dispersibility in the liquid composition is not always clear, but it is considered as follows.
  • the interaction between the F polymer and the surface treatment agent is strengthened. It is considered that separation of the liquid medium from the concentrated powder dispersion promotes the formation of a powder containing the F polymer and the surface treatment agent while maintaining such an interaction.
  • the particle size of the raw material powder is relatively small, for example, if the average particle size of the powder is less than 25 ⁇ m, the specific surface area of the raw material powder becomes large, and the interaction between the F polymer and the surface treatment agent is synergistic. It is easy to obtain a powder containing a highly surface treatment agent.
  • the interaction between the surface treatment agent and the raw material powder may be a physical interaction caused by the surface treatment agent adhering to or binding to the surface of the raw material powder, and the F polymer of the raw material powder and the surface treatment agent may be used. It may be a chemical interaction caused by a chemical bond with.
  • the D50 of the raw material powder in the present method (1) is preferably less than 25 ⁇ m, more preferably 0.05 to 8 ⁇ m. By using such a small raw material powder of D50, it is easy to obtain a powder having a D50 of less than 25 ⁇ m.
  • the raw material powder may contain a resin other than the F polymer, but is preferably made of the F polymer.
  • the amount of the F polymer contained in the powder is preferably 80% by mass or more, more preferably 100% by mass.
  • the resin include aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.
  • the surface treatment agent examples include a surfactant, a silane coupling agent, a hydrophilic agent and the like, and a surfactant and a silane coupling agent are preferable, and a surfactant is more preferable.
  • a surfactant is a compound having a hydrophilic part and a hydrophobic part
  • a silane coupling agent is a compound having a hydrolyzable group bonded to a silanol group or a silicon atom
  • a hydrophilic agent is a compound having a hydrophilic part. .
  • Examples of the hydrophilic portion of the surfactant and the hydrophilizing agent include a polyoxyethylene group, an alcohol hydroxyl group, an acetal group, a hemiacetal group and the like.
  • hydrophobic portion of the surfactant examples include a fluorinated hydrocarbon group, a long-chain hydrocarbon group, an acetylene group, a polysiloxane group and the like.
  • hydrophilizing agent examples include compounds containing a polyoxyethylene group, polyhydroxy compounds, polymers containing an acetal group or a hemiacetal group, and the like.
  • a silicon compound represented by the general formula: R 4 p- Si- (OR 5 ) 4-p (in the formula, R 4 is an alkyl group having 1 to 12 carbon atoms, R 5 is an alkyl group having 1 to 4 carbon atoms, and p is an integer of 1 to 3).
  • Specific examples of the compound containing a polyoxyethylene group include a compound represented by the general formula: H (OCH 2 CH 2 ) m (OR 2 ) n OH (in the formula, R 2 has 3 or 4 carbon atoms. M and n are independently integers of 1 to 5), and the compound represented by the general formula: R 3 O (CH 2 CH 2 O) O H (in the formula, R).
  • Reference numeral 3 is an alkyl group having a hydrogen atom or an alkyl group having 10 to 15 carbon atoms, and O represents an average number of added moles, which is an integer of 1 to 15).
  • the polyhydroxy compound include polyvinyl alcohol, polyethylene glycol, polyethylene oxide, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, starch, agarose, and lactose.
  • Specific examples of the polymer containing an acetal group or a hemiacetal group include a ternary polymer containing a unit based on vinyl butyral, a unit based on vinyl acetate, and a unit based on vinyl alcohol. The ratio of each unit may be set in consideration of the ease of interaction with the F polymer.
  • the surfactant examples include a fluorine-based surfactant, a silicone-based surfactant, and an acetylene-based surfactant.
  • a fluorine-based surfactant is preferable.
  • Specific examples of the fluorine-based surfactant include compounds represented by the general formula: R f1- OY (in the formula, R f1 is a polyfluoroalkyl group having 1 to 12 carbon atoms, and Y is a polyfluoroalkyl group. -(CH 2 ) a OH or-(CH 2 CH 2 O) b (CH 2 CH (CH 3 ) O) c H, where a is an integer of 1 to 12 and b is 1 to 20. It is an integer, and c is an integer of 0 to 12).
  • a perfluoroalkyl group, a perfluoroalkyl group having an etheric oxygen atom, or a perfluoroalkenyl group is preferable.
  • the fluorine-based surfactant include polymers having a perfluoroalkyl group or a perfluoroalkenyl group and a polyoxyethylene group or an alcoholic hydroxyl group in their side chains, respectively.
  • the polymer is preferably nonionic.
  • the weight average molecular weight of the polymer is preferably 2000 to 80,000, more preferably 6000 to 20000.
  • the fluorine content of the polymer is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
  • the content of the oxyethylene group of the polymer is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
  • the hydroxyl value of the polymer is preferably 10 to 300 mgKOH / g.
  • the number of carbon atoms of the perfluoroalkyl group or the perfluoroalkenyl group is preferably 4 to 16. Further, an ether oxygen atom may be inserted between the carbon atoms of the perfluoroalkyl group or the perfluoroalkenyl group.
  • the polyoxyethylene group may have an oxyalkylene group having 3 or more carbon atoms. In this case, the oxyethylene group and the oxyalkylene group having 3 or more carbon atoms may be randomly arranged or may be arranged in a block shape. As the oxyalkylene group having 3 or more carbon atoms, a polyoxypropylene group is preferable.
  • the polymer include a copolymer of a (meth) acrylate having a perfluoroalkyl group or a perfluoroalkenyl group and a (meth) acrylate having a polyoxyethylene group or an alcoholic hydroxyl group.
  • fluorine-based surfactants include the "Futergent” series (manufactured by Neos), the “Surflon” series (manufactured by AGC Seimi Chemical), the “Megafuck” series (manufactured by DIC), and the “Unidyne” series (manufactured by DIC). (Made by Daikin Industries, Ltd.).
  • the liquid medium in this method (1) may be liquid at 25 ° C.
  • the liquid medium preferably dissolves the surface treatment agent. That is, the surface treatment agent is preferably soluble in a liquid medium.
  • the solubility of the surface treatment agent in the liquid medium at 25 ° C. is preferably 5 or more. The solubility is preferably 30 or less. If the surface treatment agent is soluble in the liquid medium, the interaction between the surface treatment agent and the F polymer in concentration is likely to be further improved.
  • the liquid medium is preferably an aprotic polar solvent. In this case, the interaction between the surface treatment agent and the F polymer in concentration is likely to be further improved.
  • As the liquid medium amides, alcohols, sulfoxides, esters or ketones are preferable, and ketones or amides are more preferable.
  • liquid medium examples include water, methanol, ethanol, isopropanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, diethyl ether, dioxane, ethyl lactate, and acetate.
  • examples thereof include ethyl, butyl acetate, methyl ethyl ketone, methyl isopropyl ketone, cyclopentanone, cyclohexanone, ethylene glycol monoisopropyl ether, and cellosolve (methyl cellosolve, ethyl cellosolve, etc.).
  • Suitable specific liquid media include methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone. Two or more kinds of liquid media may be used in combination.
  • the amount (ratio) of the F polymer contained in the powder dispersion in the method (1) is preferably 10% by mass or more, more preferably 20 to 50% by mass.
  • the amount (ratio) of the liquid medium contained in the powder dispersion liquid in the present method (1) is preferably 15 to 55% by mass, more preferably 25 to 50% by mass.
  • the amount (ratio) of the surface treatment agent contained in the powder dispersion in the method (1) is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
  • the ratio of the amount (ratio) of the surface treatment agent to the amount (ratio) of the F polymer in the powder dispersion is preferably more than 0.01 and 0.25 or less.
  • the powder may be forcibly precipitated by performing a precipitation treatment on the powder dispersion liquid.
  • the precipitation treatment may be carried out by repeating heating and cooling of the powder dispersion, for example, the operation of heating the powder dispersion to a temperature of 100 ° C. and then cooling to a temperature of 0 ° C. may be repeated.
  • the fluidity of the powder dispersion is increased by heating to facilitate the incorporation of the surface treatment agent into the raw material powder, and the raw material powder incorporating the surface treatment agent by cooling is likely to be precipitated in the powder dispersion as a powder.
  • the precipitation treatment can also be performed by replacing the liquid medium of the powder dispersion liquid. Specifically, the concentration of the powder dispersion and the addition of the (high boiling point) poor solvent to the powder dispersion are repeated.
  • the surface treatment agent is easily incorporated into the raw material powder by substituting the liquid medium with a poor solvent, and the raw material powder incorporating the surface treatment agent is precipitated as a powder in the powder dispersion.
  • the precipitation treatment can also be performed by a salting out operation on the powder dispersion.
  • a solute having a higher solubility in a liquid medium than the surface treatment agent is added to the powder dispersion to facilitate the incorporation of the surface treatment agent into the raw material powder, and the raw material powder incorporating the surface treatment agent is used as a powder. It can be deposited in the dispersion.
  • F polymer powder may be added to the powder dispersion as seed crystals. In the above precipitation treatment, any two or more may be combined.
  • the powder dispersion liquid may be subjected to a powder coagulation treatment to forcibly deposit the powder.
  • the powder dispersion liquid to which the coagulant is added is stirred while being concentrated, and the raw material powder incorporating the surface treatment agent is precipitated in the powder dispersion liquid as a powder.
  • the coagulant include nitric acid, hydrochloric acid, sulfuric acid, magnesium chloride, calcium chloride, sodium chloride, aluminum sulfate, magnesium sulfate, and barium sulfate.
  • the liquid medium is separated from the powder dispersion in which the powder is precipitated. Examples of the method for separating the liquid medium include decantation, filtration, and centrifugation. By such an operation, the excess surface treatment agent that has not been incorporated into the powder is separated.
  • the separated powder may be dried, or may be added to a resin-containing liquid described later to produce a liquid composition without drying.
  • the D50 of the powder (3) which is the powder obtained by the present method (1), is as described above.
  • the sparsely packed bulk density of the powder obtained by this method (1) is more preferably 0.08 to 0.5 g / mL.
  • the densely packed bulk density of the powder obtained by this method (1) is more preferably 0.1 to 0.8 g / mL.
  • the mass ratio of the amount of the surface treatment agent to the amount of the F polymer contained in the powder obtained by this method (1) is more than 0.01 and 0.25 or less. Yes, preferably 0.05 to 0.2. In this case, it is easy to produce a liquid composition while preventing deterioration regardless of the particle size.
  • Polymer 4 Copolymer containing 98.3 mol% and 1.7 mol% of TFE units and PPVE units in this order (melting temperature 305 ° C).
  • Polymer 5 A copolymer containing 98.0 mol%, 0.1 mol% and 1.9 mol% of TFE units, NAH units and PPVE units in this order and having a polar functional group (melting temperature 300 ° C.).
  • Polymer 6 A copolymer containing 98.7 mol% and 1.3 mol% of TFE units and PPVE units in this order and having no polar functional group (melting temperature 305 ° C.).
  • Powder 1 Powder consisting of polymer 1 with D50 of 26.4 ⁇ m
  • Powder 2 Powder consisting of polymer 2 with D50 of 18.8 ⁇ m
  • Powder 3 Powder consisting of polymer 2 with D50 of 2.3 ⁇ m
  • Powder 4 Polymer 2 Powder with D50 of 66.2 ⁇ m
  • Powder 5 Powder consisting of Polymer 1 with D50 of 1.7 ⁇ m and D100 of 4.9 ⁇ m.
  • Powder 6 Powder of polymer 3 with D50 of 18.8 ⁇ m
  • Powder 7 Powder of polymer 4 with D50 of 17.5 ⁇ m
  • Powder 8 Powder of polymer 3 with D50 of 6.4 ⁇ m and D100 of 7.9 ⁇ m
  • Powder powder 9 powder made of polymer 1 with D50 of 1.5 ⁇ m and D100 of 4.6 ⁇ m
  • Powder powder 10 powder made of polymer 5 with D50 of 2.0 ⁇ m and D90 of 5.2 ⁇ m
  • Powder powder 11 polymer 6 A powder having a D50 of 2.1 ⁇ m and a D90 of 5.5 ⁇ m. Manufactured in the same manner as the described powder.
  • the D100 of powders 6, 7 and 8 is 100 ⁇ m or less, respectively.
  • Raw Material Composition 1 A thermocurable resin containing a precursor of a polyphenylene ether-based resin and a curing agent, and further containing methyl ethyl ketone, in which the content ratio of the aromatic resin (hereinafter, also referred to as “WAR”) is 10% by mass or more.
  • Liquid Composition Raw Material Composition 2 A thermocurable liquid composition containing a precursor of a polyphenylene ether resin and a curing agent, and further containing methyl ethyl ketone, having a WA of less than 10% by mass.
  • Raw material composition 3 3, 3' NMP solution of precursor 1 of a polyimide aromatic resin containing 4,4'-biphenyltetracarboxylic acid dianhydride (BPDA), p-phenylenediamine (PPD) and a curing agent (total mass of precursor 1: 25).
  • BPDA 4,4'-biphenyltetracarboxylic acid dianhydride
  • PPD p-phenylenediamine
  • curing agent total mass of precursor 1: 25.
  • Surface treatment agent 1 A methacrylate-based polymer (fluorine content 35% by mass, hydroxyl value: 19 mgKOH) having a perfluoroalkyl group, a polyoxyalkylene group, and an alcoholic hydroxyl group in their side chains.
  • the surface treatment agent 1 is a nonionic fluorine-based surfactant that is soluble in MEK.
  • Metal plate Copper foil 1: Ultra-low roughness electrolytic copper foil (manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., CF-T4X-SV, thickness: 18 ⁇ m, Rzjis: 1.2 ⁇ m)
  • Example 1 Manufacturing / evaluation example (1)
  • Example 1-1 Production example of liquid composition (liquid composition 1)
  • the raw material composition 1 was filled in a horizontal ball mill container, then the powder 1 was added and mixed using a stirring blade to obtain a liquid composition 1 in which the powder 1 was dispersed (containing an aromatic resin).
  • Ratio hereinafter, also referred to as “WAR”: 10% by mass or more
  • content ratio of F polymer to content of aromatic resin hereinafter, also referred to as “WF / WAr”: 0.3
  • the liquid composition 1 had a viscosity of 800 mPa ⁇ s, and the powder did not settle even after being allowed to stand at 25 ° C. for 3 days.
  • Liquid composition 2 The raw material composition 1 was filled in a horizontal ball mill container, then the blended powder of powder 1 and powder 5 was added and mixed using a stirring blade to obtain a liquid composition 2 (WAR: 10 mass). % Or more, WF / WAr: 0.3). The blended powder contains 1 part by mass of powder 5 with respect to 5 parts by mass of powder 1.
  • the liquid composition 2 had a viscosity of 1300 mPa ⁇ s, and the powder did not settle even after being allowed to stand at 25 ° C. for 3 days.
  • Liquid compositions 3-7) Liquid compositions 3 to 7 were obtained in the same manner as in Liquid Composition 1 except that the types and mixing ratios of the powder and the raw material composition were changed as shown in Table 1. When the liquid compositions 6 and 7 were heated and the liquid medium was distilled off to increase the WAr value of the liquid composition, the viscosity was remarkably increased and a stable liquid composition could not be obtained. Table 1 summarizes the formulations and properties of the liquid compositions 1 to 7.
  • prepreg 1 A fiber-spread glass cloth (average thickness 14 ⁇ m) treated with 3-aminopropylmethyldimethoxysilane was immersed in the liquid composition 1. The immersion material was heated at 150 ° C. for 10 minutes to obtain prepreg 1. (Prepreg 2 to prepreg 7) Prepregs 2 to 7, respectively, were obtained in the same manner except that the liquid compositions 2 to 7 were used instead of the liquid composition 1.
  • Example 1-3 Production example and evaluation example of metal foil with resin (metal plate with resin layer) (metal foil with resin 1) The laminate of the copper foil 1 and the prepreg 1 is superposed and vacuum heat pressed under the heat pressing conditions of a temperature of 185 ° C., a pressure of 3.0 MPa, and a time of 60 minutes, and a solidified layer (liquid) of the copper foil 1 and the prepreg 1 is formed. A resin-attached metal foil 1 having a resin layer made of a dried product of the composition 1) was obtained in this order.
  • the resin-attached metal foil 1 has a peel strength of 10 N / cm between the copper foil 1 and the resin layer, and can be subjected to a solder reflow test (a test in which a resin-attached metal foil is floated on solder at 288 ° C. for 5 seconds 5 times). , The phenomenon that the copper foil 1 floats from the resin layer (peeling phenomenon) did not occur.
  • the relative permittivity (measurement frequency 20 GHz) of the resin layer was 3.05 or less, and the dielectric loss tangent was 0.016 or less.
  • Metal foil with resin 2 to metal foil with resin 7 Metal foils 2 to 7 with resin were produced and evaluated in the same manner except that prepregs 2 to 7 were used instead of prepreg 1. The above results are summarized in Table 1.
  • the metal foil with resin having excellent physical properties is obtained due to the significant decrease in thickening and dispersion stability. I could't get it.
  • the homogeneity of the F polymer in the resin layer is impaired, and a metal foil with a resin having excellent electrical properties cannot be obtained. It was.
  • the amount of the resin component held in the prepreg was insufficient, and a metal foil with a resin having excellent electrical properties could not be obtained.
  • Example 2 Manufacturing / evaluation example (Part 2)
  • Example 2-1 Preparation of liquid composition (liquid composition 8)
  • a horizontal ball mill container is filled with 100 parts by mass of the raw material composition 3, then 5 parts by mass of powder 6 is added and mixed using zirconia balls having a diameter of 15 mm, and the liquid composition in which the powder 6 is dispersed. I got thing 8.
  • the WAr (content of the precursor 1) in the liquid composition 8 is 24% by mass, and the WF / WAr is 0.2.
  • liquid composition 9 The liquid composition 9 was prepared in the same manner as the liquid composition 8 except that the amount of the powder 6 added was 30 parts by mass.
  • liquid composition 10 The liquid composition 10 was prepared in the same manner as the liquid composition 8 except that the powder 6 was changed to the powder 7.
  • liquid composition 11 The liquid composition 11 was prepared in the same manner as the liquid composition 8 except that the powder 6 was changed to the powder 8.
  • liquid composition 12 The liquid composition 12 was prepared in the same manner as the liquid composition 8 except that the powder 6 was changed to the powder 9.
  • the surfaces of the resin layer of the copper foil with the resin layer obtained in the liquid composition 8 and Example 12 were excellent in surface smoothness with no visible bumps or stripes.
  • the same result as above can be obtained by using a solvent-soluble liquid crystal polyester resin or a polyphenylene ether resin instead of the polyimide aromatic resin or its precursor.
  • Example 3 Manufacturing / evaluation example (Part 3)
  • Example 3-1 Preparation of modified powder
  • the mass ratio of the amount of surface treatment agent to the amount of F polymer contained in the modified powder obtained below is the mass and surface of the F polymer added to the powder dispersion used.
  • the mass of the treatment agent, the mass of the F polymer contained in the filtrate obtained by filtering the powder dispersion, and the mass of the surface treatment agent were measured and determined.
  • Example 3-2 Preparation of liquid composition (liquid composition)
  • the modified powder 1 was directly added to the raw material composition 4 to prepare a liquid composition 13.
  • the mass of the powder 1 of the polymer 6 / the mass of the polyimide resin was 25 parts by mass / 75 parts by mass (WF / WAr: 0.33, WAr: more than 10% by mass).
  • Example 2-2 The liquid composition 14 was obtained in the same manner except that the modified powder 1 was changed to the powder 10.
  • ⁇ Thickening rate of liquid composition The thickening rate of each liquid composition with respect to the polyimide resin varnish was measured and evaluated according to the following criteria. [Evaluation criteria] ⁇ (excellent): The thickening rate was 100% or less. ⁇ (impossible): The thickening rate was more than 100%. As a result, the liquid composition 13 was " ⁇ " and the liquid composition 14 was "x".
  • a resin-containing liquid containing a precursor of a polyphenylene ether resin, a cross-linking agent, and MEK was prepared.
  • the total amount of the precursor of the polyphenylene ether resin and the cross-linking agent contained in this resin-containing liquid was 10% by mass or more.
  • the above powder 1 was added and mixed using a stirring blade.
  • a liquid composition 15 viscosity: 1000 mPa ⁇ s or less
  • the liquid composition 15 was applied on the surface of a copper foil having a thickness of 18 ⁇ m by a roll-to-roll method by a gravure reverse method to form a liquid film.
  • the copper foil on which the liquid film was formed was passed through a drying oven at 120 ° C. for 5 minutes and dried by heating. Then, the dry film was heated at 380 ° C. for 3 minutes in a far-infrared oven under a nitrogen atmosphere.
  • the thickness of the resin layer was 8 ⁇ m.
  • the liquid composition of the present invention is suitable for forming a prepreg in which a high-concentration resin component is impregnated and held in a fiber substrate or a thick insulating resin layer having high component homogeneity, and has excellent electrical characteristics and heat resistance. It is useful as a material for parts, printed wiring boards (flexible printed wiring boards, rigid printed wiring boards), coverlay films, solder resists, insulation layers for power semiconductors, aircraft parts, and automobile parts.
  • the powder of the present invention is used as a component of a liquid composition for using antenna parts, printed wiring boards, aircraft parts, automobile parts, sports equipment, food industry supplies, saws, sliding bearings and other coated articles. it can.
  • printed wiring boards are useful as substrates for electronic devices such as radars, network routers, backplanes, and wireless infrastructures that require high-frequency characteristics, substrates for various sensors for automobiles, and substrates for engine management sensors. It is suitable for applications aimed at reducing transmission loss in the millimeter wave band and improving flame retardancy.
  • Japanese patent application No. 2019-044624 filed on March 12, 2019, Japanese patent application No. 2019-044627 filed on March 12, 2019, Japanese patent filed on May 23, 2019. Disclosure of the specification of the present invention is incorporated herein by reference to the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2019-125278 filed on Application 2019-096837 and July 04, 2019. As a matter of fact.

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  • Chemical & Material Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne une composition liquide comprenant une poudre d'un polymère à base de tétrafluoroéthylène thermofusible dans un bon état dispersé et une concentration élevée d'une résine aromatique et ayant une viscosité excellente en termes de maniabilité.　La composition liquide selon la présente invention est une composition liquide comprenant une poudre de polymère à base de tétrafluoroéthylène thermofusible, une résine aromatique et un milieu liquide, le pourcentage de teneur en résine aromatique étant d'au moins 10 % en masse, le rapport du pourcentage de teneur en polymère à base de tétrafluoroéthylène sur le pourcentage de la teneur en résine aromatique étant d'au plus 1,2, et la viscosité étant d'au plus 10 000 mPa·s à 25 °C. L'invention concerne également une poudre de polymère à base de tétrafluoroéthylène thermofusible qui est ajoutée à une composition liquide contenant : un matériau de résine tel qu'une résine aromatique ; et un milieu liquide, et qui est utilisé pour obtenir une telle composition liquide.
PCT/JP2020/009684 2019-03-12 2020-03-06 Composition liquide, poudre, et procédé de production de ladite poudre WO2020184437A1 (fr)

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CN202080019920.1A CN113574118A (zh) 2019-03-12 2020-03-06 液态组合物、粉末以及粉末的制造方法
JP2021505026A JP7371681B2 (ja) 2019-03-12 2020-03-06 液状組成物、パウダー、及び、パウダーの製造方法
KR1020217020343A KR20210137426A (ko) 2019-03-12 2020-03-06 액상 조성물, 파우더, 및, 파우더의 제조 방법

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CN116635161A (zh) * 2020-12-28 2023-08-22 Ａｇｃ株式会社 水性分散液及其制造方法
WO2022215831A1 (fr) * 2021-04-09 2022-10-13 주식회사 엘지화학 Composition de résine thermodurcissable, produit durci et préimprégné de celle-ci, et feuille stratifiée, feuille stratifiée de feuille métallique, et carte de circuit imprimé ayant ledit produit durci ou pré-imprégné durci
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CN113372863A (zh) * 2021-06-22 2021-09-10 深圳市汇海鑫科技有限公司 一种高导热高导电有机胶粘剂及其制备方法

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