WO2019235439A1 - Dispersion liquide, procédé de production de feuille métallique comprenant une résine et procédé de production de carte de circuit imprimé - Google Patents

Dispersion liquide, procédé de production de feuille métallique comprenant une résine et procédé de production de carte de circuit imprimé Download PDF

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Publication number
WO2019235439A1
WO2019235439A1 PCT/JP2019/022029 JP2019022029W WO2019235439A1 WO 2019235439 A1 WO2019235439 A1 WO 2019235439A1 JP 2019022029 W JP2019022029 W JP 2019022029W WO 2019235439 A1 WO2019235439 A1 WO 2019235439A1
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Prior art keywords
group
polymer
dispersion
formula
resin
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PCT/JP2019/022029
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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 JP2020523101A priority Critical patent/JPWO2019235439A1/ja
Priority to CN201980037698.5A priority patent/CN112236473B/zh
Priority to KR1020207028062A priority patent/KR20210018190A/ko
Publication of WO2019235439A1 publication Critical patent/WO2019235439A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/22—Esters containing halogen
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0011—Working of insulating substrates or insulating layers
    • H05K3/0017—Etching of the substrate by chemical or physical means

Definitions

  • the present invention relates to a powder dispersion containing a powder of tetrafluoroethylene polymer and a specific dispersant, a metal foil with resin, and a method for producing a printed circuit board.
  • Tetrafluoroethylene polymers such as polytetrafluoroethylene (PTFE) have excellent physical properties such as chemical resistance, water and oil repellency, heat resistance, and electrical properties, and are used in various forms such as powders, dispersions, and films. And various uses utilizing the physical properties are known (see Patent Documents 1 and 2).
  • tetrafluoroethylene-based polymers have attracted attention as printed circuit board materials that are excellent in electrical characteristics such as low dielectric constant and low dielectric loss tangent and heat resistance that can withstand solder reflow, and are compatible with high-frequency frequencies.
  • a metal foil with a resin having an insulating resin layer on the surface of the metal foil is used as a printed board by etching the metal foil.
  • a tetrafluoroethylene-based polymer having a low relative dielectric constant and dielectric loss tangent has been studied as the insulating resin layer.
  • Various materials for forming a resin-attached metal foil having a resin layer containing a tetrafluoroethylene-based polymer have been proposed.
  • Patent Document 1 proposes a powder dispersion in which a powder of a tetrafluoroethylene polymer is dispersed in a solvent.
  • This powder dispersion has the advantage that various physical properties of the metal foil with resin can be arbitrarily adjusted by the compounding components and the advantage that the metal foil with resin can be formed simply by coating and drying on the surface of the metal foil.
  • Patent Document 3 discloses PTFE powder, (meth) acrylate (CH 2 ⁇ CHC (O) OCH (CH 3 ) O (CF 2 ) 6 F, etc.) having a fluorine-containing block site, and alkylene glycol mono (meta).
  • Patent Document 4 describes a resin-coated metal foil having a PTFE layer formed from a dispersion in which PTFE powder is dispersed in a solvent, and a method of forming a transmission line on the metal foil to obtain a printed circuit board.
  • Patent Document 5 describes a dispersion containing PTFE powder.
  • the powder dispersion has low dispersibility.
  • the viscosity of the dispersion becomes high, and the amount of diluting components (solvent, etc.) must be increased to form a layer (coating film). May be limited, the production efficiency may be reduced, or the blending of other additives may be limited.
  • the physical properties (wetability, adhesiveness, smoothness, etc.) of the layer (coating film) containing the tetrafluoroethylene-based polymer formed from the dispersion may be lowered.
  • the dispersion medium of the dispersion is an organic solvent
  • the decrease in dispersibility and layer (coating film) formability tends to be remarkable.
  • a resin-coated metal foil in which another substrate (prepreg, etc.) is laminated on the surface of a resin layer containing a tetrafluoroethylene-based polymer, or a surface on which the resin layer is coated There is a mode of stacking and packaging the substrates (coverlay film or the like). In these embodiments, it is necessary to firmly laminate the resin layer and another substrate without deteriorating the physical properties of the metal foil and the resin layer from the viewpoint of electrical characteristics and productivity of the printed board.
  • the adhesiveness of the resin-coated copper foil of Patent Document 3 is said to be manifested by the decomposition of the copolymer accompanying the elimination of the fluorine-containing block site in the copolymer, but in order to decompose the copolymer, the copper foil is used in a high temperature environment. It is necessary to leave it alone (see the description of [0007], [0210], etc. in Patent Document 3). If the resin-coated metal foil is left in a high temperature environment for this purpose, the metal foil with the resin may deteriorate due to the phenomenon that the metal foil deteriorates due to rusting or the formation of the resin layer is hindered by the decomposition of the copolymer and the homogeneity of the resin layer decreases. The physical properties may be impaired.
  • the present inventors suppress these phenomena, and can form a resin-coated metal foil having a fluororesin layer with excellent adhesion without impairing the physical properties of the resin-coated metal foil.
  • a dispersion was found. That is, the present inventors have found a dispersion of a powder containing a tetrafluoroethylene polymer having a relatively low viscosity and having dispersibility and layer (coating film) formability.
  • the present invention includes the following dispersion, a method for producing a resin-coated metal foil, and a method for producing a printed circuit board.
  • Q FI represents an alkylene group or an oxyalkylene group.
  • Z FI represents a polyfluoroalkyl group or a polyfluoroalkenyl group.
  • X 1I , X 2I, and X 3I are: X 1I , X 2I, and X 3I are each independently an alkyl group or an aryl group, X 1I and X 2I are a hydrogen atom, and X 3I is an aryl group, Whether X 1I and X 2I are each independently a hydrogen atom or an alkyl group and X 3I is an alkoxy group, or X 1I is a hydrogen atom or an alkyl group, and X 2I and X 3I jointly form an alkylene group , Either.
  • Z FII represents a perfluoroalkylene group.
  • nII represents an integer of 2 to 30.
  • R FII represents a perfluoroalkyl group.
  • X HII represents a hydrogen atom or a methyl group.
  • Z HII represents an alkylene group.
  • mII represents an integer of 3 to 200.
  • R HII represents a hydrogen atom, an alkyl group or an aryl group.
  • the dispersant is based on a monomer represented by the following formula (FIII), a unit based on an alkyl (meth) acrylate, a unit based on the monomer represented by the following formula (HIII), and acrylonitrile or acrylamide.
  • Formula (FIII) CH 2 CX FIII C (O) O-Q FIII -R FIII
  • Formula (HIII) CH 2 CX HIII C (O)-(OZ HIII ) mIII -OR HIII
  • X FIII represents a hydrogen atom, a chlorine atom or a methyl group.
  • Q FIII represents an alkylene group or an oxyalkylene group.
  • R FIII represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an etheric oxygen atom, or a polyfluoroalkenyl group.
  • X HIII represents a hydrogen atom or a methyl group.
  • Z HIII represents an alkylene group.
  • mIII represents an integer of 3 to 200.
  • R HIII represents a hydrogen atom, an alkyl group or an aryl group.
  • the dispersant includes a unit based on a monomer represented by the following formula (FIV) and a unit based on the monomer represented by the following formula (HIV), having a fluorine content of 15 to 50% by mass and an oxy
  • the dispersion according to [1] which is a polymer having an alkylene group content of 10 to 70% by mass.
  • Formula (FIV) CH 2 CX FIV C (O) O-Q FIV -R FIV
  • X FIV represents a hydrogen atom, a chlorine atom or a methyl group.
  • Q FIV represents an alkylene group or an oxyalkylene group.
  • R FIV represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an etheric oxygen atom, or a polyfluoroalkenyl group.
  • X HIV represents a hydrogen atom or a methyl group.
  • ZHIV represents an alkylene group.
  • mIV represents an integer of 3 to 200.
  • R HIV represents an alkyl group or an aryl group.
  • the dispersant includes a unit based on the monomer represented by the following formula (FV) and a unit based on the monomer represented by the following formula (HV), and has a fluorine content of 20 to 40% by mass and a hydroxyl value.
  • Formula (FV) CH 2 CX FV C (O) OQ FV -R FV
  • Formula (HV) CH 2 CX HV C (O) -Q HV —OH
  • X FV represents a hydrogen atom, a chlorine atom or a methyl group.
  • Q FV represents an alkylene group or an oxyalkylene group.
  • R FV represents a polyfluoroalkyl group, a polyfluoroalkyl group containing an etheric oxygen atom, or a polyfluoroalkenyl group.
  • XHV represents a hydrogen atom or a methyl group.
  • Q HV represents an alkylene group or a cycloalkylene group.
  • the tetrafluoroethylene-based polymer has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group.
  • the dispersion liquid in any one of.
  • the manufacturing method of metal foil with resin which obtains foil.
  • the present invention is a powder dispersion excellent in mixing properties, coating properties, and dispersibility with different types of resin materials (including varnishes thereof), without impairing the physical properties of the substrate such as metal foil.
  • a powder dispersion capable of easily forming a resin-coated metal foil having a fluororesin layer having excellent adhesiveness.
  • the dispersion of the present invention is a dispersion containing a tetrafluoroethylene polymer powder excellent in dispersibility and formability of a layer (coating film) such as wettability, adhesiveness, thixotropy and smoothness. .
  • a layer (coating film) formed from the dispersion of the present invention (hereinafter also referred to as “layer (coating film)”) is particularly excellent in wettability and adhesiveness, and is a resin useful as a material for printed circuit boards. It can be suitably used for the production of attached metal foil and the like.
  • the dispersion of the present invention has a relatively low viscosity and is excellent in redispersibility, and the resin layer is also excellent in light transmittance and transparency.
  • D50 of powder is a volume-based cumulative 50% diameter of powder determined by a laser diffraction / scattering method. That is, the particle size distribution of the powder is measured by the laser diffraction / scattering method, the cumulative curve is obtained by setting the total volume of the powder particle population to 100%, and the particle diameter at the point where the cumulative volume is 50% on the cumulative curve. is there.
  • D90 of powder is a volume-based cumulative 90% diameter of powder determined in the same manner.
  • Polymer melt viscosity is based on ASTM D 1238, using a flow tester and a 2 ⁇ -8L die, and a polymer sample (2 g) that has been pre-heated at the measurement temperature for 5 minutes is loaded with 0.7 MPa. It is the value measured by holding at the measurement temperature.
  • the “polymer melting temperature” is a temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
  • Viscosity is a value measured using a B-type viscometer at room temperature (25 ° C.) under a rotation speed of 30 rpm. The measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
  • the “thixo ratio” is a value ( ⁇ 1 / ⁇ 2 ) calculated by dividing the viscosity ⁇ 1 measured at a rotational speed of 30 rpm by the viscosity ⁇ 2 measured at a rotational speed of 60 rpm.
  • “10-point average roughness (Rz JIS )” is a value defined in Annex JA of JIS B 0601: 2013.
  • the “unit” in the polymer may be an atomic group directly formed from a monomer by a polymerization reaction, and an atomic group in which a part of the structure is converted by treating the polymer obtained by the polymerization reaction by a predetermined method. It may be.
  • a unit based on a specific monomer may be represented by adding a monomer name after “unit”.
  • a unit based on the monomer FI is also referred to as “unit FI”.
  • “(Meth) acrylate” is a generic term for acrylate and methacrylate
  • (meth) acrylamide derivative is a generic term for acrylamide derivatives and methacrylamide derivatives.
  • “(Meth) acryloyloxy group” is a generic name for acryloyloxy group and methacryloyloxy group
  • “(meth) acryloyl group” is a generic name for acryloyl group and methacryloyl group.
  • “Thermal decomposition starting temperature” is determined by using a thermogravimetric measuring device (TG) and a thermogravimetric differential thermal analyzer (TG-DTA), dispersing agent (10 mg), mixed gas (90% by volume of helium and 10% by volume of oxygen). ) When the temperature is raised at a rate of 10 ° C / min in an atmosphere, the mass reduction rate is 1% by mass / min or more.
  • the dispersion of the present invention comprises a powder of tetrafluoroethylene-based polymer (hereinafter also referred to as “TFE-based polymer”) (hereinafter also referred to as “F powder”), a solvent, and a dispersant. It is a dispersion liquid dispersed in a shape.
  • the dispersant is composed of a monovalent fluorine-containing hydrocarbon group which may contain an etheric oxygen atom, a tert-alkoxycarbonyl group, a sec-alkoxycarbonyl group, an aralkyloxycarbonyl group, a polyoxyalkylene group and an alcoholic hydroxyl group.
  • polymer dispersant having at least one group selected from the group consisting of Note that the alkyl group in the one kind of group may contain an unsaturated bond (double bond or triple bond) in part of the carbon atom-carbon atom bond, and forms a ring structure. Also good.
  • the polymer dispersant is a polymer different from the TFE-based polymer.
  • the polymer dispersant preferably has the monovalent fluorine-containing hydrocarbon group and the one kind of group in the side chain of the polymer.
  • the fluorine content of the polymer dispersant is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, and particularly preferably 25 to 45% by mass.
  • the content of the polyoxyalkylene group in the polymer dispersant is preferably 10 to 60% by mass, and more preferably 20 to 50% by mass.
  • the polyoxyalkylene group content in the polymer dispersant is also referred to as “AO content”.
  • the hydroxyl value of the polymer dispersant is preferably 10 to 330 mgKOH / g.
  • the monovalent fluorine-containing hydrocarbon group is preferably a group having a polyfluoroalkyl group, a polyfluoroalkenyl group or a perfluoro (oxyalkylene) group.
  • the monovalent fluorine hydrocarbon group preferably does not have a methylenedioxy group or a derivative group thereof (—OCH 2 O—, —OCH (CH 3 ) O—, etc.).
  • the tert-alkoxycarbonyl group is preferably a group represented by the formula —C (O) OC (—X T ) 3 .
  • 3 X T in the formula may be the same, or different, represent a monovalent hydrocarbon group. Also, two X T may form a divalent hydrocarbon group jointly.
  • the sec-alkoxycarbonyl group is preferably a group represented by the formula —C (O) OCH (—X S ) 2 .
  • Two X S in the formula may be the same or different and each represents a monovalent hydrocarbon group. Also, two X S may form a divalent hydrocarbon group jointly.
  • the aralkyloxycarbonyl group is preferably a group represented by the formula —C (O) OCH 2 —Ar.
  • Ar in the formula represents an aryl group.
  • the oxyalkylene group constituting the polyoxyalkylene group preferably has 2 to 4 carbon atoms, particularly preferably 2.
  • the polyoxyalkylene group may be composed of two or more oxyalkylene groups.
  • the number of oxyalkylene groups constituting the polyoxyalkylene group is preferably 2 to 200.
  • the polyoxyalkylene group is a divalent group, but may be a monovalent group in which a hydroxyl group is bonded to a carbon atom at one end or a monovalent group is bonded.
  • the monovalent group having a polyoxyalkylene group includes a polyoxyalkylene group having a monovalent group (alkoxy group, aryloxy group, etc.) having an oxygen atom at the terminal end of the polyoxyalkylene group or a hydroxyl group. An alkylene group is preferred.
  • the polymer dispersant contains a monovalent fluorine-containing hydrocarbon group, a tert-alkoxycarbonyl group, a sec-alkoxycarbonyl group, and
  • the dispersion is a polymer (polymer dispersant I) having at least one group selected from the group consisting of aralkyloxycarbonyl groups in the side chain.
  • the dispersion I is considered to have excellent dispersion stability because the F powder is highly stabilized by the interaction with the fluoro moiety of the polymer dispersant I. Furthermore, it is considered that the polymer dispersant I forms a hydrophilic component by detaching a specific part of the side chain (the one kind of group) in a low temperature atmosphere. Therefore, when forming a layer (coating film) from the dispersion I, specifically, when the solvent is distilled off from the dispersion I by heating, such a hydrophilic component is generated, and only the dense packing of the F powder is promoted. It is also considered that it flows to the surface of the coating and promotes the formation of a hydrophilic layer (coating).
  • a layer (coating film) having high surface hydrophilicity and homogeneity and excellent adhesion can be easily obtained from the dispersion I without impairing the physical properties of the TFE polymer and the base material (metal foil, etc.). It is thought that it was formed.
  • the polymer dispersant I is preferably a polymer having a polyfluoroalkyl group or a polyfluoroalkenyl group and a group represented by the formula —OC (—X 1I ) (— X 2I ) (— X 3I ) in the side chain.
  • X 1I, X 2I and X 3I is, X 1I, or X 2I and X 3I are each independently an alkyl group or an aryl group, X 1I and X 2I is a hydrogen atom X 3I is an aryl group Or X 1I and X 2I are each independently a hydrogen atom or an alkyl group and X 3I is an alkoxy group, or X 1I is a hydrogen atom or an alkyl group, and X 2I and X 3I jointly form an alkylene group. Either to form.
  • the alkylene group formed by jointly X 2I and X 3I may be linear or branched, and may form a ring structure in the group. Further, the alkylene group may contain an unsaturated bond or a hetero atom.
  • a perfluoroalkyl group having 1 to 6 carbon atoms is preferable, and — (CF 2 ) 4 F and — (CF 2 ) 6 F are particularly preferable.
  • a perfluoroalkenyl group having 1 to 12 carbon atoms is preferable, and —OCF (CF 3 ) C ( ⁇ C (CF 3 ) 2 ) (CF (CF 3 ) 2 ) is particularly preferable.
  • X 1I , X 2I and X 3I each independently preferably have 1 to 16 carbon atoms.
  • X 1I, X 2I and X 3I is, X 1I, or X 2I and X 3I are each independently an alkyl group, or X 1I and X 2I is a hydrogen atom X 3I is an aryl group, X 1I It is preferably a hydrogen atom and X 2I and X 3I jointly form an alkylene group, and X 1I , X 2I and X 3I are each independently a methyl group, or X 1I and Either X 2I is a hydrogen atom and X 3I is a phenyl group, or X 1I is a hydrogen atom and X 2I and X 3I jointly form a hexylene group or an alkylene group having a bridged ring structure. It is particularly preferable.
  • Specific examples of the group represented by the formula —OC (—X 1I ) (— X 2I ) (— X 3I ) include the following groups. In the formula, *
  • the polymer dispersant I includes a unit (unit FI) based on a monomer (monomer FI) represented by the formula CH 2 ⁇ CR FI C (O) O—Q FI —Z FI and a formula CH 2 ⁇ CR HI C (O A polymer containing a unit (unit HI) based on a monomer (monomer HI) represented by) OC (—X 1I ) (— X 2I ) (— X 3I ) is preferred.
  • R FI represents a hydrogen atom, a chlorine atom or a methyl group.
  • R HI represents a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group.
  • QFI represents an alkylene group or an oxyalkylene group.
  • ZFI represents a polyfluoroalkyl group or a polyfluoroalkenyl group.
  • X 1I , X 2I and X 3I each have the same meaning as described above, and the preferred range is also the same.
  • R FI and R HI are preferably each independently a hydrogen atom or a methyl group.
  • the number of carbon atoms in the carbon-containing group in QFI and ZFI is preferably 1 to 16 independently.
  • Q FI is preferably —CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 —, —CH 2 CH 2 O— or —CH 2 CH 2 CH 2 CH 2 O—.
  • CH 2 CHC (O) OCH 2 CH 2 (CF 2) 4 F
  • CH 2 CClC (O) OCH 2 CH 2 (CF 2) 4 F
  • CH 2 C (CH 3) C (O) OCH 2 CH 2 (CF 2) 4 F
  • CH 2 CHC (O) OCH 2 CH 2 (CF 2) 6 F
  • CH 2 CClC (O) OCH 2 CH 2 (CF 2) 6 F
  • CH 2 C ( CH 3) C (O) OCH 2 CH 2 (CF 2) 6 F
  • CH 2 CHC (O) OCH 2 CH 2
  • monomer HI examples include the following monomers.
  • Monomer HI may be used individually by 1 type, and may use 2 or more types.
  • the content of the unit FI with respect to all the units contained in the polymer dispersant I is preferably 20 to 60 mol%, particularly preferably 20 to 40 mol%.
  • the content of the unit HI with respect to all the units contained in the polymer dispersant I is preferably 40 to 80 mol%, particularly preferably 60 to 80 mol%.
  • the polymer dispersant I may consist only of units based on the unit FI and the unit HI, and may further contain other units.
  • the fluorine content of the polymer dispersant I is preferably 10 to 45% by mass, particularly preferably 15 to 40% by mass.
  • the polymer dispersant I is preferably nonionic.
  • the mass average molecular weight of the polymer dispersant I is preferably 2000 to 80000, and particularly preferably 6000 to 20000.
  • the second preferred dispersion of the present invention is a polymer (polymer dispersant II) in which the polymer dispersant contains units based on (meth) acrylates having perfluoropolyether chains. It is a dispersion liquid. Dispersion II is excellent in dispersibility, and is excellent in formability of a layer (coating film) such as wettability, adhesiveness, thixotropy, and smoothness. The reason is not necessarily clear, but can be considered as follows. Since the perfluoropolyether chain in the polymer dispersant II contains a fluorine atom, it has an excellent affinity with the TFE polymer.
  • the perfluoropolyether chain contains an etheric oxygen atom
  • the molecular mobility is increased as compared with the perfluoroalkylene chain
  • the polymer dispersant II is considered to be easily entangled with the F powder particles.
  • the poly (meth) acryloyloxy moiety constituting the main polymer chain of the polymer dispersant II has high molecular mobility and excellent solvophilicity. Therefore, the dispersion containing the polymer dispersant II is excellent in dispersibility, and the coating film (coating film) formed from the polymer dispersant II is excellent in physical properties (wetting properties, adhesiveness, smoothness, etc.).
  • the polymer dispersant II comprises units based on monomers having perfluoropolyether chains and (meth) acryloyl groups.
  • a monomer is a general term for a monomer having a (meth) acryloyloxy group and a perfluoropolyether chain and a monomer having a group represented by the formula CH 2 ⁇ CHC (O) NH— and a perfluoropolyether chain.
  • monomers include not only monofunctional (meth) acrylates but also bifunctional (meth) acrylates having (meth) acryloyloxy groups at both ends of the perfluoropolyether chain.
  • a monomer represented by the following formula (FII) (monomer FII) is preferable.
  • FII monomer represented by the following formula (FII)
  • FII monomer represented by the following formula (FII)
  • FII monomer represented by the following formula (FII)
  • FII monomer represented by the following formula (FII)
  • Q FII is a divalent linking group, and includes —OCH 2 CF 2 —, —NHC (O) —, —ONHC (O) —, —ONHC (O) NHCF 2 —, —OCH 2 CH 2 NHC (O). OCH 2 CF 2 — or —OCH 2 CH 2 NHC (O) NHCF 2 — is preferable.
  • Z FII is a perfluoroalkylene group, more preferably a perfluoroalkylene group having 1 to 4 carbon atoms, and is a difluoromethylene group (—CF 2 —) or a perfluoroethylene group (—CF 2 CF 2 —). Is particularly preferred.
  • Z FII may consist of one group or two or more groups. In the latter case, the arrangement of different types of perfluoroalkylene groups may be random or block.
  • nII is from 2 to 30, and preferably from 3 to 20.
  • R FII is a perfluoroalkyl group, preferably a C 1-6 perfluoroalkyl group, particularly preferably —CF 3 or —CF 2 CF 3 .
  • the monomer FII is more preferably a monomer represented by the following formula (FII1).
  • Formula (FII1) CH 2 ⁇ CX FII C (O) —Q FII1 — (OCF 2 ) nII1 ⁇ (OCF 2 CF 2 ) nII2 —OR FII1
  • the symbols in the formula have the following meanings.
  • X FII has the same meaning as described above.
  • Q FII1 represents —OCH 2 CF 2 —, —NHC (O) —, —ONHC (O) —, —OCH 2 CH 2 NHC (O) NHCF 2 —, —OCH 2 CH 2 NHC (O) OCH 2 CF 2 — or —OCH 2 CH 2 NHC (O) NHCF 2 — is shown.
  • nII1 is 0 to 20
  • nII2 is 2 to 30, and the sum of both is 2 to 30.
  • R FII1 represents —CF 3 or —CF 2 CF 3 .
  • a monomer having a difluorooxymethylene group (—OCF 2 —) is excellent in decomposability in a high-temperature atmosphere, so that it is easy to improve the wettability of the surface of the layer (coating film).
  • the polymer dispersant II may contain only the unit FII, or may further contain units other than the unit FII.
  • the polymer dispersant II preferably contains a unit based on (meth) acrylate having a polyoxyalkylene group in addition to the unit FII. In this case, as described above, the molecular mobility of the polymer dispersant II is further improved, the viscosity of the dispersion is lowered, and the compatibility with various solvents and other additives is easily improved.
  • a monomer (monomer HII) represented by the following formula (HII) is preferable.
  • a monomer having a chain length in such a predetermined range is selected, not only the dispersibility of the dispersion liquid is excellent, but also physical properties such as wettability, adhesion, and smoothness of the layer (coating film) are easily improved.
  • Formula (HII) CH 2 CX HII C (O)-(OZ HII ) mII -OR HII
  • X HII is a hydrogen atom or a methyl group.
  • Z HII is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, such as an ethylene group (—CH 2 CH 2 —), a propylene group (—CH 2 CH (CH 3 ) —) or n— A butylene group (—CH 2 CH 2 CH 2 CH 2 —) is particularly preferred.
  • mII number of Z HII may consist one group may consist of two or more groups. In the latter case, the arrangement of different types of alkylene groups may be random or block.
  • mII is an integer of 3 to 200.
  • R HII is a hydrogen atom, an alkyl group or an aryl group, and is preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, such as a hydrogen atom, a methyl group, a nonyl group, A lauryl group, a stearyl group, a phenyl group, a stearylphenyl group, a laurylphenyl group or a nonylphenyl group is preferred, and a hydrogen atom, a methyl group or a nonylphenyl group is particularly preferred.
  • the monomer HII include CH 2 ⁇ C (CH 3 ) C (O) (OCH 2 CH 2 ) 4 OH, CH 2 ⁇ C (CH 3 ) C (O) (OCH 2 CH 2 ) 9 OH.
  • the monomer HII is preferably a monomer represented by the following formula (HII1) or a monomer represented by the following formula (HII2).
  • Formula (HII1) CH 2 ⁇ CX HII C (O) — (OZ HII ) mII1 —OH
  • Formula (HII2) CH 2 ⁇ CX HII C (O) — (OZ HII ) mII2 —OR HII1
  • X HII and Z HII each have the same meaning as described above.
  • mII1 is 3 to 30.
  • mII2 is 20 to 150.
  • R HII1 represents a methyl group or a phenyl group.
  • the fluorine content of the polymer dispersant II is preferably 20 to 50% by mass. Since the lower limit of the fluorine content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the fluorine content is in the above range, the affinity of the dispersant for each component of the dispersant is balanced, and in addition to the dispersibility of the dispersion, the formability of the layer (coating film) is easily improved. For example, the layer (coating film) is characterized by high wettability and excellent adhesion.
  • the fluorine content of the polymer dispersant II can be calculated from the type of monomer used in the synthesis and the amount charged.
  • the content (AO content) of the polyoxyalkylene group in the polymer dispersant II is preferably 10 to 60% by mass. Since the lower limit of the AO content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the AO content is in the above range, the affinity of the polymer dispersant II with respect to each of the TFE polymer and the solvent is balanced, and in addition to the dispersibility of the dispersion, the formability of the layer (coating film) Is easy to improve. Specifically, the layer (coating film) easily exhibits the physical properties of the TFE polymer itself.
  • the AO content can be calculated from the type of monomer used in the synthesis and the amount charged. Moreover, if the polymer dispersing agent II whose fluorine content and AO content are in the above ranges is used, the viscosity of the dispersion liquid is likely to decrease.
  • the amount of the unit FII with respect to the total units contained in the polymer dispersant II is preferably 10 to 100 mol%, more preferably 20 to 70 mol%.
  • the amount of the unit based on the unit HII with respect to the total unit contained in the polymer dispersant II is preferably 0 to 90 mol%, more preferably 30 to 80 mol%.
  • the total amount of unit FII and unit HII with respect to all units contained in polymer dispersant II is preferably 90 to 100 mol%.
  • the polymer dispersant II is preferably nonionic.
  • the weight average molecular weight of the polymer dispersant II is preferably 2000 to 80000, and particularly preferably 6000 to 20000.
  • a third preferred dispersion of the present invention (hereinafter also referred to as “dispersion III”) comprises a unit in which the polymer dispersant is based on an acrylate monomer having a monovalent fluorine-containing hydrocarbon group, and a monovalent hydrocarbon.
  • Dispersion which is a polymer (polymer dispersant III) comprising a unit based on (meth) acrylate having a group, a unit based on (meth) acrylate having a polyoxyalkylene group, and a unit based on a monomer having a nitrogen-containing group It is.
  • Dispersion III is excellent in dispersibility and excellent in the formability of a layer (coating film) such as wettability, adhesiveness, thixotropy and smoothness. The reason is not necessarily clear, but is considered as follows. Since the polymer dispersant III includes a unit based on an acrylate monomer having a monovalent fluorine-containing hydrocarbon group, the polymer dispersant III has a high affinity with the TFE polymer, and thus can highly adhere to the powder particles.
  • the polymer dispersant III since the polymer dispersant III includes a highly hydrophilic (highly polar) unit based on a (meth) acrylate having a polyoxyalkylene group and a unit based on a monomer having a nitrogen-containing group, it has an affinity for a solvent. High nature. For this reason, the dispersion liquid III is excellent in the dispersibility of F powder.
  • Polymer Dispersant III also contains units based on (meth) acrylates with high hydrophobicity (low polarity) and monovalent hydrocarbon groups, so that electrical interactions occur between highly polar groups. It is considered that the original function of the polar group (high affinity with the solvent) is effectively expressed.
  • the polymer dispersant III is likely to be entangled with the powder particles due to an increase in molecular mobility accompanying a decrease in glass transition temperature due to the presence of a unit based on a monomer having a nitrogen-containing group. From this point of view, the dispersion liquid III has very high dispersibility.
  • the polymer dispersant III during heating, the monovalent hydrocarbon group and the nitrogen-containing group are easily detached from the polymer chain, and are easily decomposed by generation of radicals. For this reason, it is considered that the polymer dispersant III hardly remains in the layer (coating film). Therefore, the layer (coating film) is excellent in wettability, adhesiveness, thixotropy, smoothness and the like.
  • the thermal decomposition start temperature of the polymer dispersant III can be adjusted by the content of each unit, and is preferably 250 ° C. or lower, more preferably 200 ° C. or lower.
  • An acrylate monomer having a monovalent fluorine-containing hydrocarbon group is a polymerizable group such as a (meth) acryloyloxy group or ⁇ -chloroacryloyloxy group, a polyfluoroalkyl group, or a polyfluoroalkyl group having an etheric oxygen atom.
  • a general term for monomers having a monovalent fluorine-containing hydrocarbon group such as a polyfluoroalkenyl group.
  • a monomer represented by the following formula (FIII) (monomer FIII) is preferable.
  • Formula (FIII) CH 2 CX FIII C (O) O-Q FIII -R FIII
  • X FIII is a hydrogen atom, a chlorine atom or a methyl group
  • Q FIII is an alkylene group or an oxyalkylene group, and is preferably an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms.
  • R FIII is a polyfluoroalkyl group having 1 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms containing an etheric oxygen atom
  • Q FIII is a methylene group (—CH 2 —) or An ethylene group (—CH 2 CH 2 —) is preferred.
  • R FIII is a polyfluoroalkenyl group having 4 to 12 carbon atoms
  • Q FIII is an oxyethylene group (—CH 2 CH 2 O—) or an oxybutylene group (—CH 2 CH 2 CH 2 CH 2 O-) is preferred.
  • R FIII is a polyfluoroalkyl group, a polyfluoroalkyl group containing an etheric oxygen atom or a polyfluoroalkenyl group, a polyfluoroalkyl group having 1 to 6 carbon atoms, and a C3 to 6 carbon atoms containing etheric oxygen atoms.
  • a polyfluoroalkyl group or a polyfluoroalkenyl group having 4 to 12 carbon atoms is preferable, and — (CF 2 ) 4 F, — (CF 2 ) 6 F, —CF 2 OCF 2 CF 2 OCF 2 CF 3 , — CF (CF 3 ) OCF 2 CF 2 CF 3 , —CF (CF 3 ) C ( ⁇ C (CF 3 ) 2 ) (CF (CF 3 ) 2 ) or —C (CF 3 ) C ( ⁇ C (CF ( CF 3 ) 2 ) 2 ) is more preferred, — (CF 2 ) 4 F, — (CF 2 ) 6 F, —CF 2 OCF 2 CF 2 OCF 2 CF 3 or —CF (CF 3 ) OCF 2 CF 2 It is particularly preferred is CF 3.
  • R FIII is further preferably — (CF 2 ) 4 F or — (CF 2 ) 6 F.
  • -(CF 2 ) 6 F is most preferred.
  • a monomer having a linear polyfluoroalkyl group is preferable because it is available at a relatively low cost.
  • a (meth) acrylate having a monovalent hydrocarbon group (hereinafter also referred to as “monomer HCIII”) is a (meth) acryloyloxy group and a monovalent hydrocarbon such as an alkyl group, an alkenyl group, an aryl group or an aralkyl group. And a general term for monomers having a group.
  • the alkyl group may be linear, branched, or cyclic.
  • the monovalent hydrocarbon group in the monomer HCIII includes a cycloalkyl group having 6 to 10 carbon atoms, a bridged cyclic alkyl group having 9 to 12 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an alkyl group having 6 to 30 carbon atoms. Groups are preferred. From the viewpoint of obtaining a dispersion excellent in the dispersibility of the dispersion, the monovalent hydrocarbon group is more preferably an alkyl group having 6 to 30 carbon atoms, and further preferably an alkyl group having 10 to 20 carbon atoms. preferable. In this case, the physical properties such as thixotropy of the layer (coating film) are also easily improved.
  • the monovalent hydrocarbon group is a bridged cyclic alkyl group having 9 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms. More preferred is an isobornyl group or a benzyl group.
  • —Ph represents a phenyl group
  • —CH ⁇ Nb represents a pheny
  • the (meth) acrylate having a polyoxyalkylene group is a monomer having a (meth) acryloyloxy group and a polyoxyalkylene group.
  • a monomer represented by the following formula (HIII) (monomer HIII) is preferable.
  • HIII monomer having a chain length in such a predetermined range
  • Formula (HIII) CH 2 CX HIII C (O)-(OZ HIII ) mIII -OR HIII
  • the symbols in the formula have the following meanings.
  • X HIII is a hydrogen atom or a methyl group.
  • Z HIII is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, such as an ethylene group (—CH 2 CH 2 —), a propylene group (—CH 2 CH (CH 3 ) —) or n— A butylene group (—CH 2 CH 2 CH 2 CH 2 —) is particularly preferred.
  • Z HIII may consist of one kind of group or may consist of two or more kinds of groups. In the latter case, the arrangement of different types of alkylene groups may be random or block.
  • mIII is 3 to 200, preferably 6 to 100, more preferably 9 to 70, and further preferably 12 to 40 from the viewpoint of particularly excellent wettability and smoothness of the layer (coating film).
  • R HIII is a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, such as a methyl group, a nonyl group, a lauryl group, A stearyl group, a phenyl group, a stearylphenyl group, a laurylphenyl group or a nonylphenyl group is preferable, and a methyl group is particularly preferable.
  • a monomer represented by the following formula (HIII1) and a monomer represented by the following formula (HIII2) are more preferable for each terminal of the polyoxyalkylene group.
  • Formula (HIII1) CH 2 ⁇ CX HIII C (O) — (OZ HIII ) mIII1 —OH
  • X HIII and Z HIII each have the same meaning as described above.
  • mIII1 is 3 to 40, preferably 6 to 20.
  • mIII2 is 10 to 100, and 20 to 75 is particularly preferable.
  • R HIII2 represents a methyl group or a phenyl group.
  • a monomer having a nitrogen-containing group (hereinafter also referred to as “monomer NIII”) is a polymerizable group such as a vinyl group, a vinyloxy group, a (meth) acryloyl group, or a (meth) acryloyloxy group, a cyano group, and an amino group.
  • a general term for monomers having nitrogen-containing groups such as amide groups and imidazolyl groups.
  • acrylonitrile or acrylamide is preferable, and acrylonitrile is more preferable.
  • the dispersibility of the dispersion is excellent, but also physical properties such as wettability and adhesion of the layer (coating film) are more likely to be improved.
  • the polymer dispersant III has the above nitrogen-containing group, the molecular mobility of the polymer dispersant III is increased, and the fluidity in the dispersion is also increased, so that the polymer dispersant III is easily entangled with the powder particles.
  • the thixotropy of the dispersion is improved. Therefore, in this case, the dispersibility of the dispersion and the formability of the layer (coating film) are further improved.
  • the fluorine content of the polymer dispersant III is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, and further preferably 25 to 45% by mass. Since the lower limit of the fluorine content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the fluorine content is in the above range, the affinity of the polymer dispersant III to each component of the polymer dispersant III is balanced, and in addition to the dispersibility of the dispersion, the formability of the layer (coating film) Easy to improve. For example, the layer (coating film) is characterized by high wettability and excellent smoothness and adhesiveness.
  • the fluorine content of the polymer dispersant III can be calculated from the type of monomer used in the synthesis and the amount charged.
  • the polyoxyalkylene group content (AO content) of the polymer dispersant III is preferably 10 to 60% by mass, more preferably 20 to 50% by mass. Since the lower limit of the AO content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the AO content is in the above range, the affinity of the polymer dispersant for each of the TFE polymer and the solvent is balanced, and in addition to the dispersibility of the dispersion, the layer (coating film) formability is improved. Easy to do. Specifically, the layer (coating film) easily exhibits the physical properties of the TFE polymer itself.
  • the AO content of the polymer dispersant III can be calculated from the type of monomer used in the synthesis and the amount charged.
  • the amount of the unit based on the unit FIII with respect to the total unit contained in the polymer dispersant III is preferably 30 to 60 mol%, more preferably 40 to 50 mol%.
  • the amount of the unit HCIII with respect to all units contained in the polymer dispersant III is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.
  • the amount of the unit AOIII based on the total units contained in the polymer dispersant III is preferably 5 to 30 mol%, more preferably 10 to 20 mol%.
  • the amount of unit NIII with respect to the total units contained in polymer dispersant III is preferably 10 to 40 mol%, more preferably 15 to 30 mol%. If the amount of each unit with respect to all units contained in the polymer dispersant III is in the above range, the dispersibility of the dispersion is further improved, and various physical properties of the layer (coating film) are expressed in a balanced manner. In addition, the thermal decomposition starting temperature of the polymer dispersant III is further lowered.
  • the polymer dispersant III may be composed of only the above-described four types of units, and may further include additional units other than the above-described four types of units within a range not impairing the effects of the present invention.
  • the monomer which forms an additional unit is not specifically limited.
  • the total amount of the above-mentioned four types of units relative to all units contained in the polymer dispersant III is preferably 90 to 100 mol%, particularly preferably 99 to 100 mol%. That is, the polymer dispersant III is preferably a polymer that substantially consists of only the above-mentioned four types of units.
  • the polymer dispersant III is preferably nonionic.
  • the weight average molecular weight of the polymer dispersant III is preferably 2000 to 80000, more preferably 6000 to 20000.
  • Preferred specific examples of the polymer dispersant III include a unit based on the monomer represented by the following formula (FIII1), a unit based on the monomer represented by the following formula (HCIII1), the unit HIII1 or the unit HIII2, and acrylonitrile.
  • Formula (HCIII1) CX HCIII1 C (O) O—R HCIII1
  • X FIII1 is a hydrogen atom or a methyl group.
  • R FIII1 is — (CF 2 ) 4 F or — (CF 2 ) 6 F.
  • X HCIII1 is a hydrogen atom or a methyl group.
  • R HCIII1 is an alkyl group having 6 to 30 carbon atoms, and is preferably a linear alkyl group having 6 to 30 carbon atoms.
  • the amount of units based on unit FIII1, unit HCIII1, unit HIII1 or unit HIII2, and acrylonitrile relative to all units contained in the quaternary polymer is 30 to 60 mol%, 5 to 30 mol%, 5 to 30 in this order. Mol%, 10 to 40 mol%.
  • the polymer dispersant has a unit based on a fluoroacrylate monomer and a one-end-capped polyoxyalkylene group (meth). It is a dispersion which is a polymer (polymer dispersant IV) containing units based on acrylate.
  • the fluorine content of the polymer dispersant IV is 10 to 50% by mass
  • the polyoxyalkylene group content (AO content) of the polymer dispersant IV is 10 to 60% by mass.
  • Dispersion IV is excellent in dispersibility and excellent in layer (coating film) formability such as wettability, adhesiveness, thixotropy and smoothness.
  • the polymer dispersant IV has a fluorine-containing site and a polyoxyalkylene group capped with a terminal hydroxyl group, and the AO content and the fluorine content are adjusted to the above predetermined ranges, respectively. There are some points.
  • the AO content and the fluorine content in the polymer dispersant IV are in a trade-off relationship, and it is not easy to adjust the AO content and the fluorine content to balance the affinity for the TFE polymer and the organic solvent. Absent.
  • the fluorine content of the polymer dispersant IV is the structure of the fluoroacrylate monomer and the content thereof
  • the AO content of the polymer dispersant IV is the structure of the (meth) acrylate having a one-end-capped polyoxyalkylene group and the content thereof. It depends on the content. For example, if the former monomer having a high fluorine content is selected and the content is increased, a polymer dispersant having a high fluorine content can be prepared. However, such a polymer dispersant is improved in affinity with the TFE-based polymer, but its AO content is relatively decreased, and thus the affinity with the organic solvent is considered to be decreased.
  • the dispersibility itself of the dispersion containing such a dispersant is lowered.
  • the inventors have selected the structure and content of both monomers, and adjusted the fluorine content and the AO content of the polymer dispersant IV to the above predetermined range.
  • the dispersibility was improved.
  • the layer (coating film) The present invention was completed by knowing that the physical properties of
  • the fluoroacrylate monomer is a (meth) acryloyloxy group or ⁇ -chloroacryloyloxy group and a fluorine-containing organic group such as a polyfluoroalkyl group, a polyfluoroalkyl group having an etheric oxygen atom, or a polyfluoroalkenyl group. It is a general term for the monomer possessed.
  • a monomer (monomer FIV) represented by the following formula (FIV) is preferable. When such a monomer is selected, not only the dispersibility of the dispersion is excellent, but also physical properties such as wettability, adhesion, and smoothness of the layer (coating film) are more likely to be improved.
  • Formula (FIV) CH 2 CX FIV C (O) O-Q FIV -R FIV
  • X FIV is a hydrogen atom, a chlorine atom or a methyl group.
  • Q FIV is an alkylene group or an oxyalkylene group, and is preferably an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms.
  • R FIV is a polyfluoroalkyl group having 1 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms containing an etheric oxygen atom
  • Q FIV is a methylene group (—CH 2 —).
  • an ethylene group (—CH 2 CH 2 —) is preferable.
  • R FIV is a polyfluoroalkenyl group having 4 to 12 carbon atoms
  • Q FIV is an oxyethylene group (—CH 2 CH 2 O—) or an oxybutylene group (—CH 2 CH 2 CH 2 CH 2 O-) is preferred.
  • R FIV is a polyfluoroalkyl group, a polyfluoroalkyl group containing an etheric oxygen atom or a polyfluoroalkenyl group, a polyfluoroalkyl group having 1 to 6 carbon atoms, and a C3 to 6 carbon atoms containing etheric oxygen atoms.
  • a polyfluoroalkyl group or a polyfluoroalkenyl group having 4 to 12 carbon atoms is preferable, and — (CF 2 ) 4 F, — (CF 2 ) 6 F, —CF 2 OCF 2 CF 2 OCF 2 CF 3 , — CF (CF 3 ) OCF 2 CF 2 CF 3 , —CF (CF 3 ) C ( ⁇ C (CF 3 ) 2 ) (CF (CF 3 ) 2 ) or —C (CF 3 ) C ( ⁇ C (CF ( CF 3 ) 2 ) 2 ) is more preferred, — (CF 2 ) 4 F, — (CF 2 ) 6 F, —CF 2 OCF 2 CF 2 OCF 2 CF 3 or —CF (CF 3 ) OCF 2 CF 2 It is particularly preferred is CF 3.
  • R FIV may be — (CF 2 ) 4 F or — (CF 2 ) 6 F. -(CF 2 ) 6 F is most preferable.
  • fluoroacrylate monomers include CH 2 ⁇ C (CH 3 ) C (O) OCH 2 CH 2 (CF 2 ) 6 F, CH 2 ⁇ CHC (O) OCH 2 CH 2 (CF 2 ) 6 F.
  • CH 2 ⁇ C (CH 3 ) C (O) OCH 2 CH 2 (CF 2 ) 4 F, CH 2 ⁇ CClC (O) OCH 2 CH 2 (CF 2 ) 4 F, CH 2 ⁇ C (CH 3 ) C (O) OCH 2 CH 2 CH 2 CH 2 OCF (CF 3) (C ( C (CF 3) 2) (CF (CF 3) 2))
  • the (meth) acrylate having a single-end-capped polyoxyalkylene group includes a (meth) acryloyloxy group, a hydrocarbon group bonded to the terminal carbon atom of the polyoxyalkylene group and the polyoxyalkylene group via an oxygen atom, Is a general term for monomers having As the (meth) acrylate having a single-end-capped polyoxyalkylene group, a monomer (monomer HIV) represented by the following formula (HIV) is preferable.
  • Z HIV is an alkylene group, preferably an alkylene group having 1 to 4 carbon atoms, and is an ethylene group (—CH 2 CH 2 —), a propylene group (—CH 2 CH (CH 3 ) —) or n— A butylene group (—CH 2 CH 2 CH 2 CH 2 —) is particularly preferred.
  • MIV number of Z HIV may consist one group may consist of two or more groups. In the latter case, the arrangement of different types of alkylene groups may be random or block.
  • mIV is 3 to 200, preferably 6 to 100, more preferably 9 to 70, and particularly preferably 12 to 40 from the viewpoint of particularly excellent wettability and smoothness of the layer (coating film).
  • R HIV is an alkyl group or an aryl group, preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and includes a methyl group, a nonyl group, a lauryl group, a stearyl group, a phenyl group, A stearylphenyl group, a laurylphenyl group or a nonylphenyl group is more preferred, and a methyl group is particularly preferred.
  • CH 2 C (CH 3 ) C (O) (OCH 2 CH 2) 4 OCH 3
  • CH 2 C (CH 3) C (O) (OCH 2 CH 2) 9 OCH 3
  • CH 2 C (CH 3) C (O) (OCH 2 CH 2) 23 OCH 3
  • CH 2 C (CH 3) C (O) (OCH 2 CH 2) 66 OCH 3
  • CH 2 C (CH 3) C (O) (OCH 2 CH 2) 90 OCH
  • CH 2 C (CH 3) C (O) (OCH 2 CH 2) 120 OCH 3
  • CH 2 C (CH 3) C ( O) (OCH 2 CH 2) 30 O (CH 2) 12 H
  • CH 2 C (CH 3) C (O) (OCH 2 CH 2) 30 O (CH 2) 18 H
  • CH 2 CHC (O ) (OCH 2 CH 2 ) 4 O (CH 2 ) 12 H
  • CH 2 CHC (O) (OCH 2 CH 2 ) 9 OCH 3
  • CH 2 CHC (O) (OCH 2 CH 2 )
  • the fluorine content of the polymer dispersant IV is 10 to 50% by mass, preferably 20 to 40% by mass. Since the lower limit of the fluorine content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the fluorine content is within the above range, the affinity for each component of the polymer dispersant IV is balanced, and in addition to the dispersibility of the dispersion, the layer (coating film) formability is easily improved. For example, the layer (coating film) is characterized by high wettability and excellent smoothness and adhesiveness.
  • the fluorine content of the polymer dispersant IV can be calculated from the type of monomer used in the synthesis and the amount charged.
  • the AO content of the polymer dispersant IV is 20 to 70% by mass, preferably 20 to 50% by mass, and particularly preferably 25 to 45% by mass. Since the lower limit of the AO content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the AO content is in the above range, the affinity of the polymer dispersant IV with respect to each of the TFE polymer and the organic solvent is balanced, and in addition to the dispersibility of the dispersion, its layer (coating film) formability Is easy to improve. Specifically, the coating film obtained from the dispersion IV easily exhibits the physical properties of the TFE polymer itself.
  • the AO content of the polymer dispersant IV can be calculated from the type of monomer used in the synthesis and the amount charged.
  • the amount of the unit FIV based on the total units contained in the polymer dispersant IV is preferably 60 to 90 mol%, particularly preferably 70 to 90 mol%.
  • the amount of unit HIV with respect to the total units contained in the polymer dispersant IV is preferably 10 to 40 mol%, particularly preferably 10 to 30 mol%.
  • the polymer dispersant IV may be composed of only the above-described two types of units, and may further include additional units other than the above-described two types of units within the range not impairing the effects of the present invention.
  • the monomer which forms an additional unit is not specifically limited.
  • the total amount of the above-mentioned two types of units relative to all the units contained in the polymer dispersant IV is preferably 90 to 100 mol%, particularly preferably 99 to 100 mol%. That is, the polymer dispersant IV is preferably a polymer consisting essentially of the above-mentioned two types. The polymer dispersant IV is preferably nonionic. The mass average molecular weight of the polymer dispersant IV is preferably from 2000 to 80000, particularly preferably from 6000 to 20000.
  • Preferred specific examples of the polymer dispersant IV include a unit based on the monomer (monomer FIV1) represented by the following formula (FIV1) and a unit based on the monomer (monomer HIV1) represented by the following formula (HIV1). And a polymer having a fluorine content of 20 to 40% by mass and an AO content of 20 to 50% by mass.
  • Formula (FIV1) CH 2 CX FIV1 C (O) O—CH 2 CH 2 —R FIV1
  • X FIV1 is a hydrogen atom or a methyl group.
  • R FIV1 is — (CF 2 ) 4 F or — (CF 2 ) 6 F.
  • XHIV1 is a hydrogen atom or a methyl group.
  • mIV1 is 9 to 70, preferably 12 to 40.
  • the amount of unit FIV1 is 60 to 90 mol%, preferably 70 to 90 mol%, based on all units contained in the polymer.
  • the amount of unit HIV1 based on the total units contained in the polymer is 10 to 40 mol%, preferably 10 to 30 mol%.
  • the total amount of unit FIV1 and unit HIV1 with respect to all units contained in the polymer is 90 to 100 mol%, preferably 100 mol%.
  • the polymer dispersant is composed of a unit based on a fluoromonomer having a fluoroalkyl group or a fluoroalkenyl group and a hydroxyalkyl group or a hydroxycyclohexane. It is a dispersion liquid which is a polymer dispersant (polymer dispersant V) containing a unit based on (meth) acrylate having an alkyl group.
  • the fluorine content of the polymer dispersant V is 15 to 45% by mass, and the hydroxyl value of the polymer dispersant V is 100 to 330 mgKOH / g.
  • Dispersion V is excellent in dispersibility and excellent in the formability of layers (coating films) such as wettability, adhesiveness, thixotropy and smoothness.
  • the reason is that the polymer dispersant V has a fluorine-containing site and a hydroxyl group, and each of the hydroxyl value and the fluorine content is adjusted to the predetermined range.
  • the hydroxyl value and fluorine content of the polymer dispersant V are in a trade-off relationship, and it is not easy to balance the affinity for the TFE polymer and the solvent by adjusting the hydroxyl value and the fluorine content.
  • the fluorine content of the polymer dispersant V is attributed to the structure and content of the fluoromonomer
  • the hydroxyl value of the polymer dispersant V is attributed to the structure and content of the (meth) acrylate.
  • a fluoromonomer having a high fluorine content is selected and its content is increased
  • a polymer dispersant having a high fluorine content can be prepared.
  • such a polymer dispersant is improved in affinity with the TFE-based polymer, but its hydroxyl value is relatively decreased, so that the affinity with the solvent is considered to be decreased. As a result, it is considered that the dispersibility of the dispersion containing such a polymer dispersant is lowered.
  • the present inventors tried to examine the structure of the fluoromonomer and the structure of the (meth) acrylate. As a result, when a predetermined fluoromonomer and a predetermined (meth) acrylate having a molecular weight smaller than the hydroxyl group content are selected and the fluorine content and the hydroxyl value are adjusted to the above predetermined range, a dispersion liquid is obtained.
  • the present invention has been completed by finding out that the dispersibility of the material is improved and the physical properties of the layer (coating film) formed from the dispersion are excellent.
  • the fluoromonomer is preferably a monomer having a polymerizable group such as a (meth) acryloyloxy group or an ⁇ -chloro-acryloyloxy group, and a fluoroalkyl group or a fluoroalkenyl group.
  • a monomer (monomer FV) represented by the following formula (FV) is more preferable.
  • Formula (FV) CH 2 CX FV C (O) OQ FV -R FV
  • X FV is a hydrogen atom, a chlorine atom or a methyl group.
  • Q FV is an alkylene group or an oxyalkylene group, and is preferably an alkylene group having 1 to 4 carbon atoms or an oxyalkylene group having 2 to 4 carbon atoms.
  • R FV is a polyfluoroalkyl group having 1 to 6 carbon atoms or a polyfluoroalkyl group having 3 to 6 carbon atoms containing an etheric oxygen atom
  • Q FV is a methylene group (—CH 2 —).
  • an ethylene group (—CH 2 CH 2 —) is preferable.
  • R FV is a polyfluoroalkenyl group having 4 to 12 carbon atoms
  • Q FV is an oxyethylene group (—CH 2 CH 2 O—) or an oxybutylene group (—CH 2 CH 2 CH 2 CH 2 O-) is preferred.
  • R FV is a polyfluoroalkyl group, a polyfluoroalkyl group containing an etheric oxygen atom or a polyfluoroalkenyl group, a polyfluoroalkyl group having 1 to 6 carbon atoms, and a C3 to 6 carbon atoms containing etheric oxygen atoms.
  • a polyfluoroalkyl group or a polyfluoroalkenyl group having 4 to 12 carbon atoms is preferred, and — (CF 2 ) 4 F, — (CF 2 ) 6 F, —CF 2 OCF 2 CF 2 OCF 2 CF 3 , — CF (CF 3 ) OCF 2 CF 2 CF 3 , —CF (CF 3 ) C ( ⁇ C (CF 3 ) 2 ) (CF (CF 3 ) 2 ) or —C (CF 3 ) C ( ⁇ C (CF ( CF 3 ) 2 ) 2 ) is more preferred, — (CF 2 ) 4 F, — (CF 2 ) 6 F, —CF 2 OCF 2 CF 2 OCF 2 CF 3 or —CF (CF 3 ) OCF 2 CF 2 It is particularly preferred is CF 3.
  • R FV is further preferably — (CF 2 ) 4 F or — (CF 2 ) 6 F.
  • -(CF 2 ) 6 F is most preferable.
  • a monomer having a linear polyfluoroalkyl group is preferable because it is available at a relatively low cost.
  • the (meth) acrylate having a hydroxyalkyl group or a hydroxycycloalkyl group is a general term for compounds having a (meth) acryloyloxy group and a hydroxyalkyl group or a hydroxycycloalkyl group.
  • the hydroxyalkyl group may be linear or branched.
  • the cyclic structure of the hydroxycycloalkyl group may be a monocyclic structure or a bridged cyclic structure.
  • the monomer (monomer HV) represented by the following Formula (HV) is preferable.
  • a monomer has a smaller molecular weight than the hydroxyl group content. If the fluorine content and the hydroxyl value of the polymer dispersant V are adjusted within a predetermined range, the dispersibility of the dispersion and the wettability of the layer (coating film) are obtained. In particular, it is easy to improve physical properties such as adhesiveness.
  • Formula (HV) CH 2 ⁇ CX HV C (O) O—Q HV —OH The symbols in the formula have the following meanings.
  • XHV is a hydrogen atom or a methyl group.
  • Q HV is an alkylene group or a cycloalkylene group, preferably an alkylene group having 2 to 12 carbon atoms or a cycloalkylene group having 4 to 12 carbon atoms, and particularly preferably an alkylene group having 2 to 6 carbon atoms. preferable.
  • -Cy- represents a 1,4-cyclohexylene group.
  • the fluorine content of the polymer dispersant V is 15 to 45% by mass, preferably 20 to 40% by mass. Since the lower limit of the fluorine content is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the fluorine content is in the above range, the affinity of the dispersant for each component of the dispersant is balanced, and in addition to the dispersibility of the dispersion, the formability of the layer (coating film) is easily improved. For example, the layer (coating film) is characterized by high wettability and excellent adhesion.
  • the fluorine content of the polymer dispersion V can be calculated from the type of monomer used in the synthesis and the amount charged.
  • the hydroxyl value of the polymer dispersant V is 100 to 330 mgKOH / g, preferably 150 to 300 mgKOH / g. Since the lower limit of the hydroxyl value is in the above range, the dispersibility of the dispersion is excellent. Since the upper limit of the hydroxyl value is in the above range, the affinity of the polymer dispersant V for each of the TFE polymer and the solvent is balanced, and in addition to the dispersibility of the dispersion, the layer (coating film) formability is improved. Easy to do. Specifically, the F layer easily exhibits the physical properties of the TFE polymer itself. The hydroxyl value of the polymer dispersant V can be calculated from the type of monomer used in the synthesis and the amount charged.
  • the amount of the unit FV with respect to the total units contained in the polymer dispersant V is preferably 5 to 40 mol%, particularly preferably 10 to 25 mol%.
  • the amount of unit HV with respect to all units contained in the polymer dispersant V is preferably 60 to 95 mol%, particularly preferably 75 to 90 mol%.
  • the polymer dispersant V may consist of only the unit FV and the unit HV, and may further contain an additional unit other than the unit FV and the unit HV within a range not impairing the effects of the present invention.
  • the monomer which forms an additional unit is not specifically limited.
  • the total amount of the unit FV and the unit HV with respect to all the units contained in the polymer dispersant V is preferably 90 to 100 mol%, particularly preferably 99 to 100 mol%. That is, the polymer dispersant V is preferably a polymer that substantially consists of only the unit FV and the unit HV. The polymer dispersant V is preferably nonionic. The weight average molecular weight of the polymer dispersant V is preferably 2000 to 80000, and particularly preferably 6000 to 20000.
  • polymer dispersant V examples include a unit based on the monomer (monomer FV1) represented by the following formula (FV1) and a unit based on the monomer (monomer FV1) represented by the following formula (HV1), and fluorine Examples thereof include a polymer having a content of 20 to 40% by mass and a hydroxyl value of 150 to 300 mgKOH / g.
  • Formula (FV1) CH 2 CX FV1 C (O) O—CH 2 CH 2 —R FV1
  • HV1) CH 2 CX HV1 C (O) -Q HV1 —OH
  • X FV1 is a hydrogen atom or a methyl group.
  • R FV1 is — (CF 2 ) 4 F or — (CF 2 ) 6 F.
  • XHV1 is a hydrogen atom or a methyl group.
  • Q HV1 is an alkylene group having 2 to 6 carbon atoms.
  • the amount of the unit FV1 with respect to all units contained in the polymer dispersant V of the above specific example is 5 to 40 mol%, preferably 10 to 25 mol%.
  • the amount of the unit HV1 with respect to the total units contained in the polymer dispersant V of the specific example is 60 to 95 mol%, preferably 75 to 90 mol%.
  • the total amount of the unit FV1 and the unit HV1 with respect to all units contained in the polymer dispersant V of the above specific example is 90 to 100 mol%, and preferably 100 mol%.
  • the TFE polymer in the present invention is a polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE).
  • TFE-based polymer may be a TFE homopolymer or a copolymer of TFE and another monomer copolymerizable with TFE (hereinafter also referred to as a comonomer).
  • the TFE-based polymer preferably contains 90 to 100 mol% of TFE units with respect to all units contained in the polymer.
  • TFE polymers include polytetrafluoroethylene (PTFE), TFE and ethylene copolymer (ETFE), TFE and propylene copolymer, TFE and perfluoro (alkyl vinyl ether) (PAVE) copolymer (PFA), TFE and hexafluoropropylene. (HFP) copolymer (FEP), TFE and chlorotrifluoroethylene copolymer.
  • Melting temperature of the TFE-based polymer 1 ⁇ 10 2 ⁇ 1 ⁇ 10 6 Pa ⁇ s is preferably at 380 ° C., preferably 1 ⁇ 10 2 ⁇ 1 ⁇ 10 6 Pa ⁇ s at 340 °C, 1 ⁇ 10 at 300 ° C. 2 to 1 ⁇ 10 6 Pa ⁇ s is preferable.
  • a preferred embodiment of the TFE polymer includes low molecular weight PTFE.
  • the low molecular weight PTFE may be PTFE in which only the shell portion satisfies the melt viscosity in a core-shell structure including a core portion and a shell portion.
  • PTFE obtained by irradiating high molecular weight PTFE (melt viscosity is about 1 ⁇ 10 9 to 1 ⁇ 10 10 Pa ⁇ s) (International Publication No. 2018/026012, International Publication) No.
  • the low molecular weight PTFE may be a polymer obtained by polymerizing TFE alone or may be a copolymer obtained by copolymerizing TFE and a comonomer (International Publication No. 2009/20187). (See No. etc.) 99.5 mol% or more is preferable with respect to all the units contained in the polymer, more preferably 99.8 mol% or more, and even more preferably 99.9 mol% or more. When the TFE unit is in the above range, the physical properties of PTFE can be maintained.
  • the comonomer include a fluoromonomer described later, and HFP, PAVE, or FAE is preferable.
  • PTFE having a core-shell structure examples include PTFE described in JP-T-2005-527652 and International Publication No. 2016/170918.
  • a method of lowering the molecular weight of the shell part using a chain transfer agent see JP-A-2015-232082, etc.
  • TFE during the production of the shell part
  • a method of copolymerizing the comonomer see JP-A-09-087334.
  • the amount of comonomer used is preferably 0.001 to 0.05 mol% with respect to TFE.
  • the amount of comonomer used is preferably 0.001 to 0.05 mol% with respect to TFE.
  • the standard specific gravity of low molecular weight PTFE is preferably 2.14 to 2.22, more preferably 2.16 to 2.20.
  • the standard specific gravity can be measured according to ASTM D4895-04.
  • a preferred embodiment of the TFE-based polymer is a copolymer of TFE and a comonomer, and a fluoropolymer (hereinafter referred to as “polymer F”) containing more than 0.5 mol% of a comonomer-based unit with respect to all units contained in the copolymer. Also mentioned.).
  • the melting point of the polymer F is preferably 240 ° C. or higher and lower than 330 ° C., more preferably 260 to 320 ° C., and particularly preferably 295 to 310 ° C. In this case, the heat resistance and melt moldability of the polymer are balanced.
  • the polymer F include ETFE, FEP, PFA and the like. As the polymer F, PFA and FEP are more preferable, and PFA is particularly preferable from the viewpoints of electric characteristics (dielectric constant, dielectric loss tangent) and heat resistance.
  • the TFE-based polymer has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group (hereinafter referred to as “functional group”) because of its excellent adhesiveness.
  • the functional group may be imparted by plasma treatment or the like.
  • the functional group may be contained in a unit in the TFE polymer, or may be contained in a 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.
  • the polymer F a polymer containing a unit having a functional group and a TFE unit is preferable. Moreover, it is preferable that the polymer F in this case contains other units (PAVE unit, HFP unit etc. which are mentioned later).
  • a carbonyl group-containing group is preferable from the viewpoint of adhesion between the layer (coating film) and the metal foil.
  • the carbonyl group-containing group include a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, an acid anhydride residue (—C (O) O (O) C—), a fatty acid residue, and the like.
  • An acid anhydride residue is preferred.
  • the unit having a functional group is preferably a unit based on a monomer having a functional group, a unit based on a monomer having a carbonyl group-containing group, a unit based on a monomer having a hydroxy group, a unit based on a monomer having an epoxy group, and an isocyanate group
  • a unit based on a monomer having a carbonyl group is more preferred, and a unit based on a monomer having a carbonyl group-containing group is particularly preferred.
  • 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 (meth) acrylate are preferable, and a cyclic monomer having an acid anhydride residue is particularly preferable.
  • a cyclic monomer itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (also referred to as “hymic anhydride”, hereinafter also referred to as “NAH”) and maleic anhydride are preferable.
  • an HFP unit As a unit other than the unit having a functional group and the TFE unit, an HFP unit, a PAVE unit and an FAE unit are preferable.
  • the polymer F a polymer including a unit having a functional group, a TFE unit, and a PAVE unit or an HFP unit is preferable.
  • Specific examples of the polymer F include the polymer (X) described in International Publication No. 2018/16644.
  • the proportion of TFE units in the polymer F is preferably 90 to 99 mol% of the total units constituting the polymer F.
  • the proportion of PAVE units or HFP units in the polymer F is preferably 0.5 to 9.97 mol% of all units constituting the polymer F.
  • the proportion of units having a functional group in the polymer F is preferably 0.01 to 3 mol% of all units constituting the polymer F.
  • F powder in the present invention contains a TFE polymer.
  • the F powder may contain components other than the TFE-based polymer as long as the effects of the present invention are not impaired.
  • the F powder preferably contains the TFE-based polymer as a main component. 80 mass% or more is preferable and, as for content of TFE type polymer in F powder, 100 mass% is especially preferable.
  • other resins that can be contained in the F powder include aromatic polyesters, polyamideimides, thermoplastic polyimides, polyphenylene ethers, and polyphenylene oxides.
  • the D50 of the F powder is preferably 0.05 to 6 ⁇ m, more preferably 0.1 to 3 ⁇ m, and particularly preferably 0.2 to 3.0 ⁇ m. In this range, the fluidity and dispersibility of the F powder are improved, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the TFE polymer are most easily developed.
  • D90 of the F powder is preferably 8 ⁇ m or less, more preferably 6 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
  • D90 of F powder is preferably 0.3 ⁇ m or more, particularly preferably 0.8 ⁇ m or more.
  • the bulk density of the F powder is preferably 0.05 g / mL or more, particularly preferably 0.08 to 0.5 g / mL.
  • the close-packed bulk density of the F powder is preferably 0.05 g / mL or more, particularly preferably 0.1 to 0.8 g / mL.
  • the method for producing F powder is not particularly limited, and the methods described in [0065] to [0069] of International Publication No. 2016/017801 can be employed. In addition, as long as desired powder is marketed, you may use F powder.
  • the solvent in the present invention is a dispersion medium, is a solvent (compound) that is liquid inactive and does not react with F powder at 25 ° C., has a lower boiling point than components other than the solvent contained in the powder dispersion, and is heated.
  • a solvent that can be volatilized and removed by, for example, is preferable.
  • the solvent may be a polar solvent or a nonpolar solvent.
  • the polar solvent may be protic or aprotic.
  • the polar solvent may be an aqueous solvent or a non-aqueous solvent.
  • As the solvent a non-aqueous polar solvent is preferable.
  • a solvent may be used individually by 1 type and 2 or more types may be used together.
  • the solvent is a solvent that does not volatilize instantaneously, is preferably a solvent having a boiling point of 80 to 275 ° C., and is particularly preferably a solvent having a boiling point of 125 to 250 ° C. In this range, when the dispersion applied to the surface of the metal foil is maintained at a predetermined temperature, the volatilization of the solvent and the partial decomposition and flow of the dispersant proceed effectively, and the dispersant segregates on the surface.
  • the solvent examples include water, methanol, ethanol, 1-propanol (boiling point: 97 ° C), 2-propanol (boiling point: 82 ° C), 1-butanol (boiling point: 117 ° C), 1-methoxy-2-propanol.
  • the solvent is preferably an organic solvent from the viewpoint of more easily adjusting the liquid physical properties (viscosity, thixo ratio, etc.) of the dispersion, and from the viewpoint of further improving the dispersion stability of the dispersion, amide, alcohol, sulfoxide, Esters, ketones, aromatic hydrocarbons or glycol ethers are preferred, esters, ketones and amides are more preferred, methyl ethyl ketone, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, cyclohexanone and cyclopentanone are particularly preferred, methyl ethyl ketone, cyclohexanone and N-methyl-2-pyrrolidone is more preferred.
  • the solvent of the dispersion IV of the present invention is preferably an organic solvent, more preferably an amide, alcohol, sulfoxide, ester, ketone and glycol ether, particularly preferably a ketone and amide, methyl ethyl ketone, cyclohexanone and N-methyl-2. -Pyrrolidone is more preferred.
  • the proportion of the TFE polymer in the dispersion of the present invention is preferably 5 to 60% by mass, more preferably 30 to 50% by mass, and particularly preferably 35 to 45% by mass. Within this range, it is easy to form a layer (coating film) excellent in electrical characteristics and mechanical strength.
  • the proportion of the dispersant in the dispersion of the present invention is preferably 0.1 to 30% by mass, more preferably 1 to 30% by mass, particularly preferably 3 to 15% by mass, and further preferably 5 to 10 parts by mass. Within this range, the physical properties (uniformity, hydrophilicity, wettability, adhesion, etc.) of the layer (coating film) are more likely to be improved.
  • the proportion of the solvent in the dispersion of the present invention is preferably 15 to 65% by mass, more preferably 25 to 60% by mass, and particularly preferably 25 to 50 parts by mass. In this range, the coating property of the dispersion is excellent, and the appearance defect of the layer (coating film) hardly occurs.
  • the dispersion of the present invention may contain other materials other than the F powder, the dispersant and the solvent as long as the effects of the present invention are not impaired. Other materials may or may not dissolve in the dispersion.
  • the other material may be a non-curable resin or a curable resin.
  • the non-curable resin include a heat-meltable resin and a non-meltable resin.
  • the heat-meltable resin include thermoplastic polyimide.
  • Examples of the non-meltable resin include a cured product of a curable resin.
  • the curable resin include a polymer or oligomer having a reactive group. Examples of the reactive group include a carbonyl group-containing group, a hydroxy group, an amino group, and an epoxy group.
  • the curable resin examples include epoxy resin, thermosetting polyimide, polyamic acid which is a polyimide precursor, thermosetting acrylic resin, phenol resin, thermosetting polyester resin, thermosetting polyolefin resin, modified polyphenylene ether resin, polyfunctional ether
  • examples thereof include cyanate ester resins, polyfunctional maleimide-cyanate ester resins, polyfunctional maleimide resins, vinyl ester resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamine-urea cocondensation resins.
  • the epoxy resin examples include naphthalene type epoxy resin, cresol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, Examples thereof include a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, an alkylphenol novolak type epoxy resin, an aralkyl type epoxy resin, and a biphenol type epoxy resin.
  • the bismaleimide resin examples include a resin composition (BT resin) described in JP-A-7-70315 and a resin described in International Publication No. 2013/008667.
  • Examples of the diamine and polyvalent carboxylic dianhydride forming the polyamic acid include [0020] of Japanese Patent No. 5766125, [0019] of Japanese Patent No. 5766125, [0055] of [2012] of JP-A-2012-145676, [ [0057] and the like.
  • thermoplastic resins such as thermoplastic polyimide and heat-meltable cured products of curable resins.
  • thermoplastic resins polyester resin, polyolefin resin, styrene resin, polycarbonate, thermoplastic polyimide, polyarylate, polysulfone, polyarylsulfone, aromatic polyamide, aromatic polyether amide, polyphenylene sulfide, polyaryl ether ketone, Polyamideimide, liquid crystalline polyester, polyphenylene ether and the like can be mentioned, and thermoplastic polyimide, liquid crystalline polyester and polyphenylene ether are preferable.
  • thixotropic agents include thixotropic agents, antifoaming agents, inorganic fillers, reactive alkoxysilanes, dehydrating agents, plasticizers, weathering agents, antioxidants, thermal stabilizers, lubricants, antistatic agents, whitening agents.
  • the colorant include a colorant, a conductive agent, a release agent, a surface treatment agent, a viscosity modifier, and a flame retardant.
  • the viscosity of the dispersion of the present invention is preferably 50 to 10,000 mPa ⁇ s, more preferably 70 to 5000 mPa ⁇ s, still more preferably 100 to 3000 mPa ⁇ s, and particularly preferably 150 to 1000 mPa ⁇ s.
  • the dispersion stability and coating properties of the dispersion are excellent, and a layer (coating film) can be easily formed.
  • the viscosity of the dispersion of the present invention may be preferably 100 to 10,000 mPa ⁇ s.
  • the viscosity of the dispersion of the present invention may be preferably 50 to 3000 mPa ⁇ s. In that case, 70 to 1500 mPa ⁇ s is more preferable, 80 to 1000 mPa ⁇ s is more preferable, and 100 to 500 mPa ⁇ s is particularly preferable. In this case, the coating property of the dispersion liquid is excellent when a varnish with another resin material is formed.
  • the thixo ratio of the dispersion of the present invention is preferably 1.0 to 2.2. In this case, the dispersibility and coating property of the dispersion are excellent, and a layer (coating film) can be easily formed. Further, the thixo ratio of the dispersion of the present invention is preferably 1.4 to 2.2, more preferably 1.45 to 2.10, and further preferably 1.5 to 2.0. In this case, the dispersibility of the dispersion and the coating property are excellent, and a more uniform layer (coating film) can be formed. In addition, the thixo ratio of the present invention may be preferably 1.0 to 1.5. In that case, 1.05 to 1.45 is more preferable, 1.1 to 1.4 is more preferable, and 1.1 to 1.3 is particularly preferable.
  • the viscosity of the dispersion II of the present invention can be less than 100 mPa ⁇ s, preferably 1 to 75 mPa ⁇ s, and more preferably 10 to 50 mPa ⁇ s.
  • a dispersion having such a viscosity is not too high in viscosity, so that it is easy to handle and has excellent compatibility with varnishes of different resin materials.
  • the viscosity of a dispersion liquid can be adjusted in arbitrary ranges if a viscosity modifier etc.
  • the thixo ratio of the dispersion II of the present invention is preferably 1.0 to 2.2, more preferably 1.4 to 2.2, and further preferably 1.5 to 2.0.
  • the dispersion of the present invention can form a resin layer containing a TFE polymer (hereinafter also referred to as “F layer”). It is preferable to form the F layer on the surface of the substrate from the dispersion of the present invention. In forming the F layer, it is preferable to form the wet layer by applying the dispersion of the present invention to the surface of the substrate, and then heating the wet film to distill off the solvent to form the F layer.
  • F layer a resin layer containing a TFE polymer
  • metal foil is preferable.
  • the metal foil material include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, aluminum alloy, titanium, and titanium alloy.
  • the metal foil include rolled copper foil and electrolytic copper foil.
  • a rust preventive layer oxide film such as chromate
  • a heat-resistant layer or the like may be formed on the surface of the metal foil.
  • the ten-point average roughness of the surface of the metal foil is preferably 0.2 to 1.5 ⁇ m. In this case, the adhesiveness with the F layer tends to be good.
  • the thickness of the metal foil is preferably 1 to 40 ⁇ m, particularly preferably 2 to 20 ⁇ m.
  • the surface of the metal foil may be treated with a silane coupling agent, the entire surface of the metal foil may be treated with a silane coupling agent, or a part of the surface of the metal foil is treated with a silane coupling agent. May be.
  • This invention provides the manufacturing method of metal foil with a resin which apply
  • the metal foil with resin in the present invention has an F layer on at least one surface of the metal foil. That is, the metal foil with resin may have an F layer only on one side of the metal foil, or may have an F layer on both sides of the metal foil.
  • the warp rate of the metal foil with resin is preferably 25% or less, and particularly preferably 7% or less. In this case, the handling property when processing the resin-coated metal foil into a printed board and the transmission characteristics of the obtained printed board are excellent.
  • the warpage rate of the resin-attached metal foil was determined by measuring a 180 mm square test piece from the resin-attached metal foil and measuring the test piece as defined in JIS C 6471: 1995 (corresponding international standard IEC 249-1: 1982). Is a value measured according to The dimensional change rate of the metal foil with resin is preferably ⁇ 1% or less, particularly preferably ⁇ 0.2% or less. In this case, it is easy to process the resin-coated metal foil into a printed circuit board and to further multilayer it.
  • the dimensional change rate of the resin-attached metal foil was determined by cutting the resin-attached metal foil into 150 mm squares, drilling holes at the four corners using a 0.3 mm drill, and measuring the positions of the holes with a three-dimensional measuring instrument.
  • the metal foil of the metal foil is removed by etching, dried at 130 ° C. for 30 minutes, and can be calculated from the difference in the positions of the holes before and after etching when the positions of the holes opened at the four corners are measured with a three-dimensional measuring instrument.
  • the water contact angle on the surface of the F layer is preferably 70 to 100 °, particularly preferably 70 to 90 °. In this case, the adhesion between the F layer and the other substrate is more excellent. If the said range is more than a minimum, the electrical property (low dielectric loss and low dielectric constant) at the time of processing a metal foil with resin to a printed circuit board will be more excellent.
  • the thickness of the F layer is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and particularly preferably 5 ⁇ m or more.
  • the thickness of the F layer is preferably 50 ⁇ m or less, preferably 15 ⁇ m or less, and particularly preferably less than 10 ⁇ m. In this range, it is easy to balance the electrical characteristics when the resin-coated metal foil is processed into a printed board and the warpage suppression of the resin-coated metal foil.
  • the composition and thickness of each F layer are preferably the same from the viewpoint of suppressing warpage of the metal foil with resin.
  • the relative dielectric constant of the F layer is preferably 2.0 to 3.5, more preferably 2.0 to 3.0.
  • a resin-coated metal foil can be suitably used for a printed circuit board or the like that requires a low dielectric constant.
  • Ra of the surface of the F layer is less than the thickness of the F layer, and is preferably 2.2 to 8 ⁇ m. In this range, it is easy to balance the adhesiveness and workability of the resin-coated metal foil.
  • the coating method may be any method as long as a stable wet film made of a powder dispersion is formed on the surface of the metal foil after coating, and is a 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, slot die coating method and the like.
  • the temperature in the low temperature region is preferably 80 ° C. or higher and lower than 180 ° C., more preferably 100 to 175 ° C., and particularly preferably 120 ° C. to 170 ° C.
  • the dispersant contained in the dispersion of the present invention can form a hydrophilic component, the resin having the F layer with excellent adhesion without impairing the physical properties of the metal foil and the F layer. Attached metal foil can be formed.
  • region shows the temperature of atmosphere.
  • the holding of the low temperature region may be performed in one step, or may be performed in two or more steps at different temperatures.
  • Examples of the method for holding in the low temperature region include a method using an oven, a method using a ventilation drying furnace, and a method of irradiating heat rays such as infrared rays.
  • the atmosphere in holding the low temperature region may be in any state under normal pressure or reduced pressure.
  • the holding atmosphere may be any of an oxidizing gas (oxygen gas, etc.) atmosphere, a reducing gas (hydrogen gas, etc.) atmosphere, and an inert gas (helium gas, neon gas, argon gas, nitrogen gas, etc.) atmosphere. It may be.
  • the atmosphere in the holding is preferably an atmosphere containing oxygen gas from the viewpoint of promoting the oxidative decomposition of the dispersant and further improving the adhesion of the F layer.
  • the oxygen gas concentration (volume basis) in the atmosphere containing oxygen gas is preferably 1 ⁇ 10 2 to 3 ⁇ 10 5 ppm, particularly preferably 0.5 ⁇ 10 3 to 1 ⁇ 10 4 ppm. In this range, it is easy to balance the oxidative decomposition of the dispersant and the suppression of oxidation of the metal foil.
  • the holding time in the low temperature region is preferably 0.1 to 10 minutes, particularly preferably 0.5 to 5 minutes.
  • the TFE polymer is further baked in a temperature region (hereinafter, also referred to as “calcined region”) above the holding temperature in the low temperature region, and F on the surface of the metal foil. It is preferable to form a layer.
  • the temperature of the firing region indicates the temperature of the atmosphere.
  • the fusion of the TFE polymer proceeds in a state where the F powder is densely packed and the hydrophilic component derived from the dispersant is effectively segregated on the surface.
  • a layer is formed. If the powder dispersion contains a heat-meltable resin, an F layer composed of a mixture of a TFE polymer and a soluble resin is formed. If the powder dispersion contains a thermosetting resin, the TFE polymer and the thermosetting resin are formed. F layer consisting of the cured product is formed.
  • Examples of the firing 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.
  • pressurization may be performed with a heating plate, a heating roll, or the like.
  • a heating method a method of irradiating far infrared rays is preferable because firing can be performed in a short time and the far infrared furnace is relatively compact.
  • infrared heating and hot air heating may be combined.
  • the effective wavelength band of far infrared rays is preferably 2 to 20 ⁇ m, more preferably 3 to 7 ⁇ m from the viewpoint of promoting uniform fusion of the TFE polymer.
  • the atmosphere in firing may be any state under normal pressure or reduced pressure.
  • the atmosphere is any of an oxidizing gas (oxygen gas, etc.) atmosphere, a reducing gas (hydrogen gas, etc.) atmosphere, and an inert gas (helium gas, neon gas, argon gas, nitrogen gas, etc.) atmosphere.
  • a reducing gas atmosphere or an inert gas atmosphere is preferable.
  • the atmosphere in firing is preferably a gas atmosphere composed of an inert gas and having a low oxygen gas concentration, and a gas atmosphere composed of nitrogen gas and having an oxygen gas concentration (volume basis) of less than 500 ppm is preferred.
  • the oxygen gas concentration (volume basis) is particularly preferably 300 ppm or less.
  • the oxygen gas concentration (volume basis) is usually 1 ppm or more. In this range, further oxidative decomposition of the dispersant is suppressed, and the hydrophilicity of the F layer is easily improved.
  • the temperature of the firing region is preferably 250 ° C. to 400 ° C. or less, particularly preferably 300 to 380 ° C.
  • the holding time in the firing region is preferably 30 seconds to 5 minutes, particularly preferably 1 to 2 minutes.
  • the F layer in the metal foil with resin is a conventional insulating material (cured product of thermosetting resin such as polyimide), heating for a long time is required to cure the thermosetting resin.
  • the F layer can be formed by heating in a short time by fusing the TFE polymer.
  • a powder dispersion liquid contains a thermosetting resin, a calcination temperature can be made low.
  • the manufacturing method of this invention is a method with a small heat load to the metal foil at the time of forming F layer in resin-coated metal foil, and is a method with little damage to metal foil.
  • the metal foil with resin in the present invention may be subjected to a surface treatment on the surface of the F layer in order to control the linear expansion of the F layer or to further improve the adhesion of the F layer.
  • Surface treatment methods for forming the surface of the F layer include annealing treatment, corona discharge treatment, atmospheric pressure plasma treatment, vacuum plasma treatment, UV ozone treatment, excimer treatment, chemical etching, silane coupling treatment, and surface roughening treatment. Can be mentioned.
  • the temperature in the annealing treatment is preferably from 80 to 190 ° C, particularly preferably from 120 to 180 ° C.
  • the pressure in the annealing treatment is preferably 0.001 to 0.030 MPa, particularly preferably 0.005 to 0.015 MPa.
  • the annealing treatment time is preferably 10 to 300 minutes, particularly preferably 30 to 120 minutes.
  • the plasma irradiation apparatus in the plasma treatment include a high frequency induction method, a capacitively coupled electrode method, a corona discharge electrode-plasma jet method, a parallel plate type, a remote plasma type, an atmospheric pressure plasma type, an ICP type high density plasma type, and the like.
  • the gas used for the plasma treatment include oxygen gas, nitrogen gas, rare gas (such as argon), hydrogen gas, ammonia gas, and the like, and rare gas or nitrogen gas is preferable.
  • Specific examples of the gas used for the plasma treatment include argon gas, a mixed gas of hydrogen gas and nitrogen gas, and a mixed gas of hydrogen gas, nitrogen gas and argon gas.
  • an atmosphere having a volume fraction of a rare gas or nitrogen gas of 70% by volume or more is preferable, and an atmosphere of 100% by volume is particularly preferable.
  • Ra on the surface of the F layer is adjusted to 2.0 ⁇ m or less, and fine irregularities are easily formed on the surface of the F layer.
  • the surface of the F layer of the resin-coated metal foil obtained in the present invention is highly hydrophilic and excellent in adhesiveness, it can be easily and firmly laminated with other substrates.
  • the other substrate include a heat resistant resin film, a prepreg as a precursor of a fiber reinforced resin plate, a laminate having a heat resistant resin film layer, and a laminate having a prepreg layer.
  • the heat-resistant resin means a polymer compound having a melting temperature of 280 ° C. or higher, or a polymer compound having a maximum continuous use temperature defined by JIS C 4003: 2010 (IEC 60085: 2007) of 121 ° C. or higher. .
  • a prepreg is a sheet-like substrate obtained by impregnating a base material (tow, woven fabric, etc.) of reinforcing fibers (glass fiber, carbon fiber, etc.) with a thermosetting resin or a thermoplastic resin.
  • the heat resistant resin film is a film including one or more kinds of heat resistant resins, and may be a single layer film or a multilayer film. Examples of the heat resistant resin include polyimide, polyarylate, polysulfone, polyarylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyaryletherketone, polyamideimide, and liquid crystalline polyester.
  • Examples of the method of laminating another base material on the surface of the F layer of the metal foil with resin in the present invention include a method of hot pressing the metal foil with resin and another substrate.
  • the pressing temperature is preferably equal to or lower than the melting point of the TFE polymer, more preferably 120 to 300 ° C, and particularly preferably 160 to 220 ° C. In this range, the F layer and the prepreg can be firmly bonded while suppressing the thermal deterioration of the prepreg.
  • the pressing temperature is preferably 310 to 400 ° C. In this range, the F layer and the heat resistant resin film can be firmly bonded while suppressing the heat deterioration of the heat resistant resin film.
  • the hot pressing is preferably performed under a reduced pressure atmosphere, and particularly preferably performed at a vacuum degree of 20 kPa or less. In this range, air bubbles can be prevented from entering the interfaces of the F layer, the substrate, and the metal foil in the laminate, and deterioration due to oxidation can be suppressed. Moreover, it is preferable to raise the temperature after reaching the vacuum degree during hot pressing. If the temperature rises before reaching the degree of vacuum, the F layer is compressed in a softened state, that is, in a state with a certain degree of fluidity and adhesion, which causes bubbles.
  • the pressure in the hot press is preferably 0.2 MPa or more. The upper limit of the pressure is preferably 10 MPa or less. In this range, the F layer and the substrate can be firmly adhered while suppressing breakage of the substrate.
  • the metal foil with resin and the laminate thereof in the present invention can be used as a flexible copper clad laminate or a rigid copper clad laminate for the production of a printed board.
  • an interlayer insulating film may be formed on the pattern circuit, and a conductor circuit may be further formed on the interlayer insulating film.
  • the interlayer insulating film can be formed by, for example, the powder dispersion in the present invention.
  • a solder resist may be laminated on the pattern circuit.
  • a solder resist can be formed with the powder dispersion liquid in this invention, for example.
  • a coverlay film may be laminated on the pattern circuit.
  • dispersion liquid of this invention was demonstrated, this invention is not limited to the structure of embodiment mentioned above.
  • the dispersion of the present invention may be added to the above-described embodiment with any other configuration, or may be replaced with any configuration that exhibits the same function.
  • Powder 1 Powder (D50: 1.7 ⁇ m, D90) of a copolymer (melting point: 300 ° C.) containing 97.9 mol%, 0.1 mol%, and 2.0 mol% of TFE units, NAH units, and PPVE units in this order. : 3.8 ⁇ m, loosely packed bulk density: 0.269 g / mL, closely packed bulk density: 0.315 g / mL).
  • Powder 2 Powder of substantially TFE homopolymer (melt viscosity at 380 ° C .: 1.4 ⁇ 10 4 ) containing 99.5 mol% or more of TFE units (D50: 0.3 ⁇ m, D90: 0.6 ⁇ m) .
  • the physical properties of the polymer and powder were measured according to the following method.
  • ⁇ Polymer melt viscosity> In accordance with ASTM D 1238, using a flow tester and a 2 ⁇ -8L die, a polymer sample (2 g) previously heated at the measurement temperature for 5 minutes is held at the measurement temperature with a load of 0.7 MPa. It was measured.
  • ⁇ Polymer melting temperature> Using a differential scanning calorimeter (Seiko Instruments, DSC-7020), the TFE polymer was heated at a rate of 10 ° C./min and measured.
  • ⁇ D50 and D90 of powder> Using a laser diffraction / scattering particle size distribution measuring device (LA-920 measuring instrument, manufactured by Horiba, Ltd.), the powder was dispersed in water and measured.
  • Dispersant 11 monomeric F 1 and monomer H 1 and monomer H 2 and Monomer R 1 copolymer (nonionic).
  • Dispersant 12 copolymer of monomer O 1 and monomer AO 1 (nonionic).
  • Dispersant 13 Copolymer of monomer F 1 and monomer R 1 (nonionic).
  • Dispersant 14 copolymer of monomer F 1 and monomer AO 1 (nonionic).
  • Dispersant 15 monomeric F 1 and monomer H 1 and monomer R 1 copolymer (nonionic).
  • Dispersant 21 Polymer containing 45 mol% and 55 mol% of monomer F 2 units and monomer AO 2 units in this order.
  • Dispersant 22 Polymer containing 38 mol% and 62 mol% of monomer F 1 unit and monomer AO 2 unit in this order.
  • Dispersant 23 Ring-opening adduct of hexafluoropropylene oxide.
  • Dispersant 31 A quaternary polymer containing 1 unit of monomer F, 3 units of monomer R, 31 units of monomer AO, and acrylonitrile unit in this order, 48 mol%, 16 mol%, 14 mol%, and 22 mol%.
  • Dispersant 32 A quaternary polymer containing 1 unit of monomer F, 3 units of monomer R, 32 units of monomer AO, and acrylonitrile unit in this order, 50 mol%, 15 mol%, 15 mol%, 20 mol%.
  • Dispersant 33 A ternary polymer containing 1 unit of monomer F, 3 units of monomer R, and 32 units of monomer AO in this order, 55 mol%, 23 mol%, and 22 mol%.
  • Dispersant 41 a polymer containing 81 mol% and 19 mol% of monomer F 1 unit and monomer AO 41 unit in this order (fluorine content: 35 mass%, AO content: 34 mass%).
  • Dispersant 42 a polymer containing 68 mol% and 32 mol% of monomer F 1 unit and monomer AO 42 unit in this order (fluorine content: 13 mass%, AO content: 74 mass%).
  • Dispersant 43 Polymer containing 1 unit of monomer F and 41 units of monomer AO in this order in an amount of 56 mol% and 44 mol% (fluorine content: 19 mass%, AO content: 60 mass%).
  • Dispersant 44 Polymer containing 42 mol% and 58 mol% of monomer F 1 unit and monomer AO 41 unit in this order (fluorine content: 12 mass%, AO content: 70 mass%).
  • Dispersant 45 Polymer containing 76 mol% and 24 mol% of monomer F 1 unit and monomer AO 43 unit in this order (fluorine content: 12 mass%, AO content: 78 mass%).
  • Dispersant 51 A polymer containing 1 mol of monomer F and 5 units of monomer AO in this order, 16 mol% and 84 mol% (fluorine content: 22 mass%, hydroxyl value: 263 mg KOH / g).
  • Dispersant 52 A polymer containing 1 mol of monomer F and 5 units of monomer AO in this order, 8 mol% and 92 mol% (fluorine content: 13 mass%, hydroxyl value: 333 mg KOH / g).
  • Dispersant 53 Polymer containing 55 mol% and 45 mol% of monomer F 1 unit and monomer AO 5 unit in this order (fluorine content: 46 mass%, hydroxyl value: 85 mgKOH / g).
  • Copper foil 1 low-roughened copper foil (thickness 12 ⁇ m, surface ten-point average roughness 0.6 ⁇ m).
  • [solvent] CHN: cyclohexanone
  • MEK methyl ethyl ketone
  • NMP N-methyl-2-pyrrolidone
  • Example 1 Example of production and evaluation of dispersion I Preparation of Dispersion Liquid 11 was prepared by mixing 30 parts by mass of Powder 1, 6 parts by mass of a solution containing 25% by mass of Dispersant 11, and 64 parts by mass of CHN. In the dispersion 11 which was allowed to stand for 1 month, the powder settled in the form of a hard cake could be easily loosened, and the dispersion 11 was excellent in redispersibility. Moreover, the viscosity (25 degreeC) of the dispersion liquid 11 measured by the rotation speed of 6 rpm, 30 rpm, and 60 rpm was 773 mPa * s, 197 mPa * s, and 109 mPa * s in this order.
  • the viscosity (25 degreeC) measured at the rotation speed of 6 rpm, 30 rpm, and 60 rpm of the dispersion liquid prepared using MEK instead of CHN is 1427 mPa ⁇ s, 328 mPa ⁇ s, and 176 mPa ⁇ s in this order. Met.
  • Dispersions 12 to 16 were obtained in the same manner as in the preparation of dispersion 11, except that the types of F powder and dispersant were changed. The results are summarized in Table 1.
  • Resin-coated copper foils 11 to 16 were produced in the same manner as the resin-coated copper foil 11 except that the type of the dispersion and the conditions of the ventilation drying oven (atmosphere temperature, oxygen gas concentration of the atmosphere gas) were changed.
  • the water contact angle of the F layer, the smoothness of the F layer, and the color tone of the metal foil of each copper foil with resin were evaluated according to the following criteria.
  • ⁇ Smoothness of F layer> The F-irradiated layer was visually observed from above and evaluated according to the following criteria. ⁇ : The pattern is not confirmed. (Triangle
  • a dispersion 17 was prepared by mixing.
  • a resin-coated copper foil is produced in the same manner as in the above-described production example of the resin-coated copper foil 11 except that the dispersion liquid 17 is used instead of the dispersion liquid 11, and the copper foil is further removed by etching to form the F layer.
  • a film was obtained.
  • the film had a total light transmittance of 96%, a diffuse transmittance of 1.6%, and a haze value of 1.7%. Moreover, yellowing was not confirmed by the film and the film was excellent in transparency.
  • Example of Preparation / Evaluation of Dispersion 4 parts by mass of a solution containing 25% by mass of dispersant 15, 8 parts by mass of a solution containing 25% by mass of dispersant 14, and 58 parts by mass of NMP are mixed.
  • Dispersion 18 was prepared by mixing parts by mass. In the dispersion 18 which was allowed to stand for 1 month, the powder settled in the form of a hard cake could be easily loosened, and the dispersion 18 was excellent in redispersibility.
  • Example 2 Example of production and evaluation of dispersion II Preparation of Dispersion A dispersion 21 was prepared by mixing 40 parts by weight of Powder 1 with a solution containing 55 parts by weight of NMP and 5 parts by weight of the dispersant 21. Dispersions 22 to 23 were obtained in the same manner as the preparation of the dispersion 21 except that the type of the dispersant was changed. The results are summarized in Table 4.
  • a dispersion is applied to the surface of the copper foil 1 using a die coater, passed through a ventilation drying oven (atmosphere temperature: 120 ° C.) for 1 minute, and further in a far-infrared oven (temperature: 340 ° C.). It was passed through for 3 minutes to obtain a resin-coated copper foil having an F layer (thickness 5 ⁇ m) of polymer 1 on the surface of the copper foil. In this manner, resin-coated copper foils 21 to 23 were obtained for the respective dispersions 21 to 23.
  • the surface of the F layer of the copper foil with resin was visually observed and evaluated according to the following criteria. [Evaluation criteria] A: No yuzu pattern was observed on the surface of the F layer. X: Yuzu pattern was observed on the surface of the F layer.
  • Example 3 Example of production and evaluation of dispersion III Preparation of Dispersion A dispersion 31 was prepared by mixing 5 parts by weight of the dispersant 31 and 45 parts by weight of the powder 1 with 50 parts by weight of NMP. Dispersions 32 to 33 were obtained in the same manner as the preparation of the dispersion 31 except that the type of the dispersant was changed. The results are summarized in Table 6.
  • Example 4 Example of production and evaluation of dispersion IV Preparation of Dispersion A dispersion 41 was prepared by mixing 64 parts by weight of NMP and 3 parts by weight of the dispersant 41 and further mixing 33 parts by weight of the powder 1. Dispersions 42 to 45 were obtained in the same manner as the preparation of dispersion 41 described above, except that the type of dispersant was changed. The dispersibility of the dispersion was evaluated according to the following criteria.
  • ⁇ Dispersibility of the dispersion> The dispersion state of the dispersion was visually confirmed and evaluated according to the following criteria. ⁇ : Sedimented, but re-dispersed when gently stirred. (Triangle
  • Example of Manufacture / Evaluation of Copper Foil with Resin A dispersion 41 is applied to the surface of the copper foil 1 using a die coater. A resin-coated copper foil 41 having an F layer (thickness: 5 ⁇ m) was obtained. Further, resin-coated copper foils 42 and 43 were produced in the same manner except that the dispersions 42 and 43 were used instead of the dispersion 41. The smoothness of the F layer in the copper foil with resin was evaluated under the same conditions as in Example 2. The results are summarized in Table 9.
  • Example of Manufacture / Evaluation of Laminate The surface of the F layer of the resin-coated copper foil 41 was vacuum plasma treated under the same conditions as in Example 1. FR-4 was laminated as a prepreg on the surface of the F layer of the resin-coated copper foil 41 after the treatment, and vacuum hot pressing was performed under the same conditions as in Example 1 to obtain a laminate. As a result of measuring the peel strength of the laminate in the same manner as in Example 1, it was 8 N / cm.
  • Example 5 Example of production and evaluation of dispersion V Preparation of Dispersion Liquid 35 was prepared by mixing 35 parts by weight of MEK and 5 parts by weight of dispersant 51, and further mixing 60 parts by weight of powder 1. Dispersions 52 to 53 were obtained in the same manner as the preparation of dispersion 51 except that the type of dispersant was changed. The dispersibility of the dispersion was evaluated according to the following criteria. ⁇ Dispersibility of the dispersion> The dispersion state of the dispersion was visually confirmed and evaluated according to the following criteria. ⁇ : Sedimented, but re-dispersed when gently stirred. X: Re-dispersion was not caused even when shearing was applied. The results are summarized in Table 10.
  • Example of Manufacturing Copper Foil with Resin and Laminate Dispersion 51 was applied to the surface of copper foil 1 using a die coater, and polymer was applied to the surface of copper foil 1 in the same manner as in the manufacturing example of copper foil with resin in Example 2.
  • a resin-coated copper foil 51 having one F layer (thickness: 5 ⁇ m) was obtained.
  • the surface of the F layer of the copper foil 51 with resin was vacuum plasma treated under the same conditions as in Example 1.
  • FR-4 was laminated as a prepreg on the surface of the F layer of the resin-coated copper foil 51 after the treatment, and the laminate 51 was obtained by vacuum hot pressing under the same conditions as in Example 1.
  • the peel strength of the laminate 51 was measured in the same manner as in Example 1. As a result, it was 6 N / cm.
  • the dispersion liquid of the present invention can easily form a fluororesin layer containing a fluoropolymer and excellent in adhesiveness.
  • Films, fiber reinforced films, prepregs, metal laminates, printed circuit boards, etc. are used for antenna parts, printed circuit boards, aircraft It can be used as materials for automobile parts, automobile parts, sports equipment, food industry supplies, saws, sliding bearings, etc.
  • Japanese Patent Application No. 2018-108740 filed on June 06, 2018, Japanese Patent Application No. 2018-173420 filed on September 18, 2018, Japanese Patent Application filed on October 30, 2018 Application No. 2018-203957, Japanese Patent Application No. 2018-203959 filed on Oct. 30, 2018, Japanese Patent Application No. 2018-209241 filed on Nov. 06, 2018, and No. 21/2018
  • the entire contents of the specification, claims and abstract of Japanese Patent Application No. 2018-218321, which are incorporated herein by reference, are incorporated herein by reference.

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Abstract

L'invention concerne une dispersion liquide qui présente une excellente dispersibilité et une excellente aptitude à former une couche présentant d'excellentes propriétés de mouillabilité, d'adhésivité, de thixotropie, de lissé, etc., et qui contient une poudre de polymère de tétrafluoroéthylène. La dispersion liquide contient une poudre de polymère de tétrafluoroéthylène, un solvant et un agent de dispersion, la poudre y étant dispersée sous la forme de particules. L'agent de dispersion est un polymère comportant : un groupe hydrocarboné fluoré monovalent comprenant éventuellement un atome d'oxygène éthéré ; et au moins un groupe choisi dans le groupe constitué de groupes tert-alcoxycarbonyle, de groupes sec-alcoxycarbonyle, de groupes aralkyloxycarbonyle, de groupes polyoxyalkylène et de groupes hydroxy alcooliques.
PCT/JP2019/022029 2018-06-06 2019-06-03 Dispersion liquide, procédé de production de feuille métallique comprenant une résine et procédé de production de carte de circuit imprimé WO2019235439A1 (fr)

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JP2020523101A JPWO2019235439A1 (ja) 2018-06-06 2019-06-03 分散液、樹脂付金属箔の製造方法、及びプリント基板の製造方法
CN201980037698.5A CN112236473B (zh) 2018-06-06 2019-06-03 分散液、带树脂的金属箔的制造方法、及印刷基板的制造方法
KR1020207028062A KR20210018190A (ko) 2018-06-06 2019-06-03 분산액, 수지가 부착된 금속박의 제조 방법, 및 프린트 기판의 제조 방법

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JP2018-203959 2018-10-30
JP2018203957 2018-10-30
JP2018-203957 2018-10-30
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WO2021132055A1 (fr) * 2019-12-25 2021-07-01 Ａｇｃ株式会社 Liquide de dispersion
JP7098075B1 (ja) 2022-01-19 2022-07-08 第一工業製薬株式会社 分散剤、分散液及び物品
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CN112236473B (zh) 2022-12-27
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