Classifications

• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
• • 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
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides

Definitions

• the present invention relates to a dispersion containing a liquid dispersion medium, a powder of tetrafluoroethylene-based polymer, and a predetermined fluorine-based dispersant, a method for producing a laminate using the dispersion, and a method for producing a coated woven fabric.
• Tetrafluoroethylene polymers such as polytetrafluoroethylene, copolymers of tetrafluoroethylene and perfluoro (alkyl vinyl ether), and copolymers of tetrafluoroethylene and hexafluoropropylene, have releasability, electrical properties, water and oil repellency, and chemical resistance. It has excellent physical properties such as weather resistance and heat resistance, and is used for various industrial applications.
• a layer (resin layer) of the tetrafluoroethylene-based polymer can be formed on the surface, and the above-mentioned properties can be imparted to the substrate. Therefore, it is useful as a coating agent.
• Patent Document 1 discloses a non-aqueous medium, a powder of a tetrafluoroethylene-based polymer, and a compound represented by the formula R pf- (OQ p1 ) q (OQ p2 ) r -OH (where R pf is a carbon number).
• R pf is a carbon number
• Q p1 and Q p1 represent an alkylene group having 2 to 4 carbon atoms
• q represents an integer of 1 to 12
• r represents an integer of 0 to 12.
• Tetrafluoroethylene-based polymers have inherently low surface tension and low interaction with other materials. For this reason, the dispersion in which the powder is dispersed in the organic dispersion medium has low dispersibility, and the powder tends to precipitate in a cake form. Further, it is not easy to re-disperse the precipitated powder.
• the non-aqueous dispersion described in Patent Document 1 contains the above compound as a dispersant, and is said to be excellent in such dispersibility and redispersibility.
• the dispersion liquid is not limited to the dispersibility and redispersibility of the powder, but is chemically inert, and has other dispersive properties such as viscosity, color tone, and thixotropic ratio, adhesiveness, transparency, and defoaming property. It is also required to be excellent in resin layer forming properties such as hardly falling off powder.
• a dispersion comprising a liquid dispersion medium, a powder of a tetrafluoroethylene-based polymer and a dispersant, wherein the powder is dispersed in the liquid dispersion medium, wherein the dispersant is a fluorine-containing site and a secondary hydroxyl group site or A dispersion, which is a compound having a tertiary hydroxyl group.
• the powder is a powder having a volume-based cumulative 50% diameter of 0.05 to 6 ⁇ m.
• the tetrafluoroethylene-based polymer is a polymer including a unit based on tetrafluoroethylene and a unit based on perfluoro (alkyl vinyl ether), a unit based on hexafluoropropylene, or a unit based on fluoroalkylethylene.
• a woven fabric coated with a resin layer containing a tetrafluoroethylene-based polymer by impregnating a woven fabric with the dispersion according to any one of [1] to [13], and further drying the woven fabric.
• ADVANTAGE OF THE INVENTION in addition to dispersibility and re-dispersibility, it is excellent also in other dispersing properties and resin layer forming properties, and can provide a tetrafluoroethylene-based polymer layer on the surface of various base materials. Is done.
• D50 of powder is a point where the particle size distribution of a powder is measured by a laser diffraction / scattering method, a cumulative curve is obtained with the total volume of a group of powder particles being 100%, and the cumulative volume is 50% on the cumulative curve. (A cumulative 50% diameter based on volume).
• D90 of powder is a point where the particle size distribution of a powder is measured by a laser diffraction / scattering method, a cumulative curve is determined with the total volume of a group of powder particles being 100%, and the cumulative volume on the cumulative curve is 90%. (90% diameter based on volume).
• the “melt viscosity of polymer” was measured according to ASTM D 1238 by using a flow tester and a 2 ⁇ -8L die and applying a 0.7 MPa load to a polymer sample (2 g) that had been heated at a measurement temperature for 5 minutes in advance. Is a value measured at a measurement temperature.
• the melting point (melting temperature) of a polymer is the temperature corresponding to the maximum value of the melting peak measured by differential scanning calorimetry (DSC).
• “Viscosity” is a value measured using a B-type viscometer at room temperature (25 ° C.) and at a rotation speed of 30 rpm. The measurement is repeated three times, and the average value of the three measured values is used.
• the “thixo ratio” is a value calculated by dividing the viscosity ⁇ 1 of the liquid composition measured at a rotation speed of 30 rpm by the viscosity ⁇ 2 of the liquid composition measured at a rotation speed of 60 rpm ( ⁇ 1 / ⁇ 2 ).
• “Ten-point average roughness (Rz JIS )” is a value defined in Annex JA of JIS B 0601: 2013.
• the “unit” in the polymer is a general term for an atomic group derived from one molecule of the monomer formed by polymerization of the monomer, and an atomic group obtained by chemically converting a part of the atomic group.
• the ⁇ unit '' in the polymer may be an atomic group directly formed from a monomer by a polymerization reaction, or an atomic group obtained by treating a polymer obtained by a polymerization reaction by a predetermined method and converting a part of the structure. It may be.
• the dispersion of the present invention includes a liquid dispersion medium, a powder of a tetrafluoroethylene-based polymer (hereinafter, also referred to as “TFE-based polymer”) and a dispersant, and is a dispersion in which the powder is dispersed in the liquid dispersion medium. is there.
• the dispersant is a compound having a fluorine-containing site and a secondary hydroxyl group site or a tertiary hydroxyl group site (hereinafter, also referred to as “predetermined dispersant”).
• Dispersion of the present invention in addition to dispersibility and redispersibility, low chemical activity, excellent viscosity, excellent dispersive properties such as color tone, thixotropic ratio, adhesiveness, transparency, defoaming, powder falling Excellent resin layer forming properties such as difficulty.
• the reason for this is that the secondary or tertiary hydroxyl group of a given dispersant has lower activity (reaction activity, acidity, etc.) and polarity, and lower hydrophilicity than a dispersant having a primary hydroxyl group. Points. That is, it is considered that the predetermined dispersant has a lower interaction with the hydrophilic component than the conventional dispersant, but has a relatively stronger interaction with the TFE-based polymer. As a result, it is considered that a dispersion having low chemical activity and excellent in the properties of the dispersion and the resin layer was obtained. This effect is remarkably exhibited in a preferred embodiment of the present invention described later.
• the D50 of the powder in the present invention is preferably from 0.05 to 6 ⁇ m, particularly preferably from 0.1 to 3 ⁇ m.
• the fluidity and dispersibility of the powder are further enhanced, and the resin layer or layer (hereinafter, also referred to as “F layer”) formed from the dispersion of the present invention has more excellent surface smoothness.
• D90 of the powder is preferably 8 ⁇ m or less, particularly preferably 1.5 to 5 ⁇ m. In this case, the dispersibility of the powder and the homogeneity of the F layer are excellent.
• the loosely packed bulk density and the densely packed bulk density of the powder are preferably from 0.08 to 0.5 g / mL and from 0.1 to 0.8 g / mL in this order.
• the powder in the present invention is a powder containing a TFE-based polymer as a main component.
• the content of the TFE-based polymer in the powder is preferably 80% by mass or more, and particularly preferably 100% by mass.
• Other resins that can be included in the powder include aromatic polyesters, polyamide imides, thermoplastic polyimides, polyphenylene ether, polyphenylene oxide, and the like.
• the secondary or tertiary hydroxyl group of the predetermined dispersant is preferably —CH (CH 3 ) OH, —CH (CH 2 CH 3 ) OH or —C (CH 3 ) 2 OH, and —CH (CH 3 ) OH is particularly preferred.
• the fluorine-containing site of the predetermined dispersant is preferably a polyfluoroalkyl group, a polyfluoroalkyl group containing an etheric oxygen atom, or a polyfluoroalkenyl group, and particularly preferably a polyfluoroalkyl group.
• the number of carbon atoms in the fluorinated moiety is preferably from 4 to 16, particularly preferably from 4 to 12.
• the secondary or tertiary hydroxyl group site and the fluorinated site of the given dispersant may be directly bonded, may be bonded via a linking group, or may be bonded via a linking group. Is preferred. In this case, not only the defoaming property of the dispersion liquid of the present invention is further improved, but also powder falling off when the F layer is formed is more easily suppressed.
• the linking group is preferably a polyoxyalkylene group.
• R F represents a polyfluoroalkyl group or a polyfluoroalkyl group containing an etheric oxygen atom, and includes F (CF 2 ) 4 CH 2 —, F (CF 2 ) 6 CH 2 —, and F (CF 2 ) 4 CH 2 CH 2 —, F (CF 2 ) 6 CH 2 CH 2 — or a group represented by the formula R F1 (CF 2 O) f1.
• Q 1 is a methylene group (—CH 2 —), a dimethylene group (—CH 2 CH 2 —), a trimethylene group (—CH 2 CH 2 CH 2 —) or a tetramethylene group (—CH 2 CH 2 CH 2 CH 2) -), And a dimethylene group is preferred.
• Q 2 represents a propylene group (—CH 2 CH (CH 3 ) —), a propylidene group (—CH (CH 2 CH 3 ) —) or an isopropylidene group (—C (CH 3 ) 2 —); Is preferred.
• the hydroxyl group is bonded to a secondary carbon atom.
• n is an integer of 1 to 3, preferably 1.
• a given dispersant F (CF 2) 6 CH 2 (OCH 2 CH 2) 7 - (OCH 2 CH (CH 3)) OH, F (CF 2) 6 CH 2 (OCH 2 CH 2 ) 12 - (OCH 2 CH ( CH 3)) OH, F (CF 2) 6 CH 2 CH 2 (OCH 2 CH 2) 7 - (OCH 2 CH (CH 3)) OH, F (CF 2) 6 CH 2 CH 2 (OCH 2 CH 2 ) 12 - (OCH 2 CH (CH 3)) OH, F (CF 2) 4 CH 2 CH 2 (OCH 2 CH 2) 7 - (OCH 2 CH (CH 3)) OH , F (CF 2) 4 CH 2 CH 2 (OCH 2 CH 2) 12 - (OCH 2 CH (CH 3)) OH and the like.
• Such a dispersant can be obtained as a commercial product ("Fluowet N083", “Fluowet N050", etc., manufactured by Achroma).
• the liquid dispersion medium in the present invention is a compound that is liquid at 25 ° C. and has a function of dispersing the powder of the present invention, and may be an aqueous medium or a non-aqueous medium.
• the compound of the liquid dispersion medium is preferably a polar compound such as water, a nitrogen-containing compound, a sulfur-containing compound, an ester, a ketone, or a glycol ether, and particularly preferably water.
• the compound is a polar compound
• the secondary hydroxyl group or the tertiary hydroxyl group contained in the predetermined dispersant decreases the interaction with the polar compound, while the interaction with the TFE-based polymer tends to be relatively strong.
• the dispersion properties of the liquid and the properties of the resin layer formation can be further improved.
• the compound of the liquid dispersion medium one type may be used alone, or two or more types may be used in combination.
• the compound of the liquid dispersion medium include water, methanol, ethanol, isopropanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl ether, dioxane, and lactic acid.
• the liquid dispersion medium is preferably an aqueous medium.
• the aqueous medium is a dispersion medium containing water as a main component, and may be composed of only water, or may be a mixed medium of water and a water-soluble organic dispersion medium.
• the TFE-based polymer in the present invention is a polymer containing a unit based on tetrafluoroethylene (TFE) (hereinafter also referred to as “TFE unit”).
• TFE unit tetrafluoroethylene
• the TFE-based polymer is a homopolymer substantially composed of TFE units (hereinafter, also referred to as “PTFE”), and a unit based on TFE units and perfluoro (alkyl vinyl ether) (hereinafter, also referred to as “PAVE”) (hereinafter, referred to as “PAVE”).
• HFP unit a copolymer comprising a TFE unit and a unit based on hexafluoropropylene (hereinafter also referred to as” HFP unit ") or a TFE unit and fluoroalkylethylene (hereinafter” FAE ").
• a copolymer containing a unit (hereinafter, also referred to as a “FAE unit”) based on the above-mentioned formula is preferable.
• PTFE also includes polymers containing a trace amount of units other than TFE units and low molecular weight PTFE.
• the polymer preferably contains more than 99.5 mol%, more preferably more than 99.9 mol%, of TFE units based on all units contained in the polymer.
• the melt viscosity of the polymer at 380 ° C. is preferably 1 ⁇ 10 2 to 1 ⁇ 10 8 Pa ⁇ s, and particularly preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s.
• the low-molecular-weight PTFE may be PTFE obtained by irradiating high-molecular-weight PTFE with radiation (polymers described in WO2018 / 02602, WO2018 / 026017, etc.), and TFE may be used.
• PTFE obtained by using a chain transfer agent when polymerizing to produce PTFE polymers described in JP-A-2009-1745, WO 2010/114033, JP-A-2013-2322082, etc.
• a polymer having a core-shell structure composed of a core portion and a shell portion, wherein only the shell portion has a low molecular weight PTFE Japanese Patent Application Laid-Open No.
• the standard specific gravity of the low molecular weight PTFE (specific gravity measured in accordance with ASTM D4895-04) is preferably from 2.14 to 2.22, more preferably from 2.16 to 2.20.
• the polymer containing TFE units includes polymers containing units other than TFE units.
• the polymer preferably contains more than 0.5 mol% of units based on monomers other than TFE units, based on all units of the polymer.
• the unit other than TFE is preferably a PAVE unit, an HFP unit, a FAE unit or a unit having a functional group described later.
• the polymer containing TFE units preferably has at least one functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an oxetanyl group, an amino group, a nitrile group and an isocyanate group.
• a functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an oxetanyl group, an amino group, a nitrile group and an isocyanate group.
• the functional group may be contained in a unit constituting the TFE-based polymer, may be contained in a terminal group of the polymer main chain, or may be introduced into the TFE-based polymer by plasma treatment or the like.
• the TFE-based polymer having the above functional group in the terminal group of the polymer main chain include a TFE-based polymer having a functional group as a terminal group derived from a polymerization initiator, a chain transfer agent and the like.
• the functional group is preferably a hydroxy group or a carbonyl group-containing group, more preferably a carbonyl-containing group, particularly preferably a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group or an acid anhydride residue, and a carboxy group or an acid anhydride residue. Residues are most preferred.
• the TFE-based polymer is preferably a polymer containing a TFE unit, a PAVE unit, a HFP unit or a FAE unit, and more preferably a polymer containing a TFE unit, a PAVE unit, a HFP unit or a FAE unit, and a unit having a functional group.
• the unit having a functional group is preferably a unit based on a monomer having a functional group.
• a monomer having a hydroxy group or a carbonyl group-containing group is preferable, and a cyclic monomer having an acid anhydride residue is particularly preferable.
• the cyclic monomer include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic anhydride (also called hymic anhydride; hereinafter also referred to as “NAH”), and maleic anhydride. Is preferred.
• PPVE CFOCF 2 CF 2 CF 3
• CF 2 CFOCF 2 CF 2 CF 2 CF 3
• CF 2 CFCFO (CF 2 ) 8 F and PPVE is preferred.
• the TFE unit, the PAVE unit, the HFP unit or the FAE unit and the unit having a functional group are 90 to 99 mol% and 0.5 to 9.97 mol% in this order with respect to all units contained in the polymer. , 0.01 to 3 mol%.
• the melting point of the TFE-based polymer is preferably from 250 to 380 ° C, particularly preferably from 280 to 350 ° C.
• a polymer described in WO2018 / 16644 can be mentioned.
• the content of the TFE-based polymer in the dispersion of the present invention is preferably from 20 to 70% by mass, and particularly preferably from 30 to 60% by mass.
• the content of the predetermined dispersant in the dispersion of the present invention is preferably 0.1 to 10% by mass, and particularly preferably 1 to 5% by mass.
• the content of the liquid dispersion medium in the dispersion of the present invention is preferably from 15 to 75% by mass, and particularly preferably from 25 to 60% by mass.
• the content of water in the liquid dispersion medium is preferably 95% by mass or more, more preferably 99% by mass or more, and particularly preferably 100% by mass.
• the dispersion of the present invention may contain other materials other than the liquid dispersion medium, the powder of the TFE-based polymer, and the predetermined dispersant.
• Other materials include thixotropic agents, fillers, defoamers, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brighteners, coloring agents, and conductive agents , A release agent, a surface treatment agent, a viscosity modifier, and a flame retardant.
• Other materials may or may not dissolve in the dispersion.
• Other materials include a thermosetting resin, a hot-melt resin, a reactive alkoxysilane, and carbon black.
• thermosetting resin epoxy resin, thermosetting polyimide resin, polyamic acid, thermosetting acrylic resin, phenol resin, thermosetting polyester resin, thermosetting polyolefin resin, thermosetting modified polyphenylene ether resin, bismaleimide Resins, polyfunctional cyanate ester resins, polyfunctional maleimide-cyanate ester resins, polyfunctional maleimide resins, vinyl ester resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea co-condensation resins. .
• polyester resin polyolefin resin, styrene resin, polycarbonate, thermoplastic polyimide, polyarylate, polysulfone, polyarylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyaryletherketone, Examples thereof include polyamide imide, liquid crystalline polyester, and polyphenylene ether.
• the glass microspheres preferably comprise silica glass or borosilicate glass.
• the ceramic microspheres comprise barium titanate, particularly preferably barium titanate doped with neodymium or zinc oxide.
• the hollow inorganic microspheres preferably have a dielectric constant of 4 or more at 20 to 50 ° C. and a thermal coefficient of dielectric constant of 150 ppm / ° C. or less.
• the hollow inorganic microspheres may be non-porous or porous.
• the hollow inorganic microspheres may be crystalline or non-crystalline.
• the hollow inorganic microspheres preferably have a density of 0.1 to 0.8 g / cm 3 and an average particle size of 5 to 100 ⁇ m.
• the hollow inorganic microspheres are preferably coated with a silane-based coupling agent, a zirconate-based coupling agent, or a titanate-based coupling agent to be hydrophobic.
• silane coupling agents include phenyltrimethoxysilane, phenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) Triethoxysilane and (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane.
• zirconate-based coupling agent examples include neopentyl (diallyl) oxytri (dioctyl) pyrophosphate zirconate and neopentyl (diallyl) oxytri (N-ethylenediamino) ethyl zirconate.
• titanate coupling agent examples include neopentyl (diallyl) oxytrinedecanoyl titanate, neopentyl (diallyl) oxytri (dodecyl) benzene-sulfonyl titanate, and neopentyl (diallyl) oxytri (dioctyl) phosphate titanate.
• a resin-coated metal foil in which a dispersion liquid of the present invention containing hollow inorganic microspheres is applied to the surface of a copper foil and a liquid dispersion medium is removed to form a resin layer is used as a printed circuit board material having a low dielectric constant heat coefficient. It is suitable.
• the viscosity of the dispersion of the present invention is preferably 1 to 1000 mPa ⁇ s, more preferably 5 to 500 mPa ⁇ s, and particularly preferably 10 to 100 mPa ⁇ s. Within this range, the dispersibility of the dispersion and the coating properties are more easily balanced.
• the thixo ratio ( ⁇ 1 / ⁇ 2 ) of the dispersion of the present invention is preferably from 1 to 2.2. Within this range, the dispersibility of the dispersion and the coating properties are more easily balanced.
• the dispersion of the present invention can be produced by mixing a liquid dispersion medium, a powder of a TFE-based polymer and a predetermined dispersant, and is prepared by mixing a liquid dispersion medium, a predetermined dispersant, and a powder of a TFE-based polymer. Is preferred. At the time of mixing, it is preferable to perform a dispersion treatment using a homodisper or a homogenizer to improve the dispersion state. When using the dispersion of the present invention stored at 0 to 40 ° C., it is preferable to use the dispersion after these dispersion treatments.
• the dispersion of the present invention has excellent dispersion properties and resin layer forming properties, and is useful as a coating agent for forming a layer (resin layer).
• the dispersion liquid of the present invention is easily heated and decomposed by heating when a layer (resin layer) is formed, while suppressing powder falling of the powder.
• Another feature is that a layer (resin layer) with a small amount of residue can be obtained.
• the residual amount of the predetermined dispersant in the F layer is preferably 25% by mass or less, particularly preferably 5% by mass or less, based on the amount of the predetermined dispersant contained in the dispersion used.
• the dispersion of the present invention is applied to the surface of a substrate and heated to form a resin layer (F layer) containing a TFE-based polymer, and the substrate and the resin layer are laminated in this order.
• the resin layer may be formed on at least one surface of the surface of the substrate, the resin layer may be formed on only one surface of the substrate, or the resin layers may be formed on both surfaces of the substrate. You may.
• Examples of the method of applying the dispersion include a spray method, a roll coating method, a spin coating method, a gravure coating method, a microgravure coating method, a gravure offset method, a knife coating method, a kiss coating method, a bar coating method, a die coating method, and a fountain Meyer bar method. And a slot die coating method.
• the resin layer is formed by heating, the substrate on which the dispersion of the present invention is applied is heated to a temperature at which the liquid dispersion medium is volatilized (a temperature range of 100 to 300 ° C.), and the TFE polymer is melted or melted. It is particularly preferable to perform heating by heating to a temperature range for firing (300 to 400 ° C.).
• Examples of the heating method include a method using an oven, a method using a ventilation drying oven, and a method of irradiating heat rays (infrared rays).
• the atmosphere in the heating may be under normal pressure or under reduced pressure.
• the atmosphere may be any of an oxidizing gas (oxygen gas or the like), a reducing gas (hydrogen gas or the like), or an inert gas (helium gas, neon gas, argon gas, nitrogen gas, or the like). Is also good.
• the heating time of the substrate is usually 0.5 to 30 minutes.
• the thickness of the resin layer is preferably 30 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
• the upper limit of the thickness of the resin layer is 0.1 ⁇ m, preferably 2 ⁇ m.
• the peel strength between the substrate and the resin layer is preferably more than 12 N / cm, particularly preferably 15 N / cm or more.
• the upper limit of the peel strength is usually 100 N / cm.
• the substrate may be any one of a metal substrate such as copper, aluminum, and iron, a glass substrate, a resin substrate, a silicon substrate, and a ceramic substrate.
• the shape of the base material may be any of a flat shape, a curved surface shape, and an uneven shape, and may be any of a foil shape, a plate shape, a film shape, and a fiber shape.
• the laminate obtained by the production method of the present invention include a metal foil with a base material being a metal foil and having a metal foil and a resin layer in this order. Between the metal foil and the resin layer, an adhesive layer may be separately provided, but since the resin layer formed from the dispersion of the present invention has excellent adhesiveness, the adhesive layer may not be provided.
• Preferred embodiments of the metal foil include copper foil such as rolled copper foil and electrolytic copper foil.
• the thickness of the metal foil is preferably 3 to 18 ⁇ m, and the thickness of the resin layer is preferably 1 to 50 ⁇ m.
• the metal foil with resin can be used as a printed wiring board having a resin layer as an insulating resin layer if a pattern circuit is formed on the metal foil.
• NC drilling, carbon dioxide laser irradiation, or UV-YAG laser irradiation can also be used.
• the third harmonic (wavelength: 355 nm) or the fourth harmonic (wavelength: 266 nm) can be used.
• an ultraviolet absorber in the resin-attached metal foil, an ultraviolet absorber, a pigment (alumina, zinc oxide, titanium oxide, etc.), a curing agent (triallyl isocyanurate, etc.) and the like are further added to the dispersion of the present invention.
• the heating temperature in forming the resin layer may be adjusted.
• a plating layer may be formed on the inner wall surface of the formed through hole.
• the plating layer can be formed by any of an etching treatment with metallic sodium, a treatment with a permanganate solution, and a plasma treatment, and the plating layer may be formed by a treatment with a permanganate solution or a plasma treatment.
• the laminate obtained by the production method of the present invention include a polyimide film in which the substrate is a polyimide film and at least one of the polyimide film surfaces has a resin layer formed from the dispersion of the present invention. . Between the polyimide film and the resin layer, an adhesive layer may be separately provided, but since the resin layer formed from the dispersion of the present invention has excellent adhesiveness, the adhesive layer may not be provided. .
• Preferred embodiments of the polyimide film include an acid dianhydride containing 2,2 ', 3,3'- or 3,3', 4,4'-biphenyltetracarboxylic dianhydride and paraphenylenediamine
• a polymer film with a diamine is exemplified.
• a specific example of the polyimide film is Apical Type AF (manufactured by Kaneka North America).
• the mass of the laminate is preferably 23.5 g / m 2 or less, and its loop stiffness value is preferably 0.45 g / cm or more.
• the thickness of the resin layer in the laminate is preferably from 1 to 200 ⁇ m, particularly preferably from 5 to 20 ⁇ m.
• the thickness of the polyimide film in the laminate is preferably from 5 to 150 ⁇ m.
• Such a laminate is excellent in electric insulation, abrasion resistance, hydrolysis resistance and the like, and can be used as a packaging material for an electric insulating tape or an electric cable or an electric wire, and is used for aerospace or electric vehicles. It is suitable as a material or a cable material.
• the first base material (the base material in the method for producing a laminate of the present invention; the same applies hereinafter), the resin layer, and the second base material are used.
• a composite laminate in which the materials are laminated in this order is obtained.
• the second base include a metal base such as copper, aluminum, and iron, a glass base, a resin base, a silicon base, and a ceramic base.
• the shape of the second base material may be any of a planar shape, a curved surface shape, and an uneven shape.
• the property of the second base material may be any of a foil shape, a plate shape, a film shape, and a fiber shape.
• the second substrate include a heat-resistant resin substrate and a prepreg that is a precursor of a fiber-reinforced resin plate.
• the prepreg is a sheet-like base material in which a base material (tow, woven fabric, etc.) of a reinforcing fiber (glass fiber, carbon fiber, etc.) is impregnated with a resin (the above-mentioned thermosetting resin, thermoplastic resin, etc.). Material.
• the heat-resistant resin substrate is preferably a film containing a heat-resistant resin.
• the heat-resistant resin substrate may be a single layer or a multilayer.
• heat-resistant resin examples include polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylene sulfide, polyallyletherketone, polyamideimide, liquid crystalline polyester, and PTFE.
• thermocompression bonding method As a method for pressure-bonding the surface of the resin layer of the laminate to the second substrate, a thermocompression bonding method may be used.
• the compression bonding temperature in the thermocompression bonding method is preferably 120 to 300 ° C.
• the thermocompression bonding temperature is preferably 300 to 400 ° C.
• the thermocompression bonding is particularly preferably performed at a degree of vacuum of 20 kPa or less.
• the pressure in thermocompression bonding is preferably from 0.2 to 10 MPa.
• the liquid layer forming material for forming the second resin layer is applied to the surface of the resin layer of the laminate obtained by the production method of the present invention to form the second resin layer, the first base material , A resin layer and a second resin layer are laminated in this order to obtain a composite laminate.
• the liquid layer forming material is not particularly limited, and the dispersion of the present invention may be used.
• the method for forming the second resin layer can also be appropriately determined depending on the properties of the liquid layer forming material used.
• the layer-forming material is the dispersion of the present invention
• the second resin layer can be formed according to the same conditions as in the method of forming a resin layer in the method of manufacturing a laminate of the present invention.
• the resin layer can be multilayered to easily form a thicker resin layer.
• the composite laminate obtained by such a production method include one embodiment of a metal foil with resin or an insulating cover.
• a thin film containing a TFE-based polymer By removing the base material of the laminate obtained by the production method of the present invention, a thin film containing a TFE-based polymer can be obtained.
• the method of removing the base material of the laminate includes a method of removing the base material from the laminate by removing the base material, and a method of dissolving and removing the base material from the laminate.
• the substrate of the laminate is a copper foil
• the thickness of the thin film of the present invention is preferably 30 ⁇ m or less, more preferably 15 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
• the lower limit of the thickness of the thin film is preferably 1 ⁇ m, particularly preferably 4 ⁇ m.
• the present invention provides a method for producing a coated woven fabric, in which a woven fabric is impregnated with the dispersion of the present invention, and the woven fabric is further dried to obtain a woven fabric coated with a TFE-based resin layer.
• the woven fabric is not particularly limited as long as it is a heat-resistant woven fabric that can withstand drying, and is preferably a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric or a metal fiber woven fabric, and is preferably a glass fiber woven fabric or a carbon fiber woven fabric. From the viewpoint of electrical insulation, a plain-woven glass fiber woven fabric composed of E-glass yarn for electrical insulation specified in JISR3410 is particularly preferred.
• the woven fabric may be treated with a silane coupling agent from the viewpoint of increasing the adhesiveness to the resin layer.
• the resin layer formed from the dispersion of the present invention has excellent adhesiveness, the woven fabric may not be treated with the silane coupling agent.
• the total content of the TFE-based polymer in the coated woven fabric is preferably 30 to 80% by mass or more.
• Examples of the method of impregnating the woven fabric with the dispersion of the present invention include a method of immersing the woven fabric in the dispersion and a method of applying the dispersion to the woven fabric.
• the number of times of immersion in the former method and the number of times of application in the latter method may be one, or two or more.
• the method of drying the woven fabric can be appropriately determined depending on the type of the compound of the liquid dispersion medium contained in the dispersion. For example, when the liquid dispersion medium is water, the woven fabric is kept in an atmosphere at 80 to 120 ° C. A method of passing through a ventilation drying oven may be used. In drying the woven fabric, the polymer may be calcined. The method of firing the polymer can be appropriately determined depending on the type of the TFE-based polymer, and includes, for example, a method of passing a woven fabric through a ventilation drying oven in an atmosphere of 300 to 400 ° C. The drying of the woven fabric and the firing of the polymer may be performed in one stage.
• the coated woven fabric obtained by the production method of the present invention is excellent in properties such as high adhesion between the resin layer and the woven fabric, high surface smoothness, and little distortion.
• a resin-coated metal foil obtained by thermocompression-bonding such a coated woven fabric and a metal foil can be suitably used as a printed circuit board material because it has high peel strength and is unlikely to be warped.
• a woven fabric impregnated with the dispersion of the present invention including a woven fabric is applied to the surface of a substrate, and heated and dried to form a TFE-based polymer.
• a coated woven fabric layer including a woven fabric may be formed, and a laminate in which the base material and the coated woven fabric layer are stacked in this order may be manufactured.
• the form is also not particularly limited, and a woven fabric impregnated with the dispersion liquid is applied to a part of the inner wall surface of the molded article such as a tank, a pipe, and a container, and the molded article is heated while rotating.
• a coated woven fabric layer can be formed on the entire inner wall. Therefore, the method for producing a coated woven fabric of the present invention is also useful as a lining method for the inner wall surface of a molded article such as a tank, a pipe, a container, and the like.
• the physical properties of the resin layer of the aqueous dispersion can be improved.
• a resin layer formed from a dispersion obtained by mixing the dispersion of the present invention and the aqueous dispersion is excellent in crack resistance as compared with a resin layer formed from the aqueous dispersion.
• the TFE polymer in the dispersion of the present invention is a TFE polymer having 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. Is preferred.
• the mass ratio of the TFE-based polymer contained in the dispersion of the present invention to the TFE-based polymer contained in the conventional aqueous dispersion of TFE-based polymer is preferably 1.0 or more, more preferably 2.0 or more. Preferably, 4.0 or more is particularly preferable.
• the upper limit of the mass ratio is usually 10.
• ⁇ Laminate peel strength> Fix the position of 50 mm from one end in the longitudinal direction of the laminated body cut out into a rectangular shape (length 100 mm, width 10 mm), and peel off 90 ° from one end in the longitudinal direction to the laminated body at a pulling speed of 50 mm / min.
• the maximum load applied at this time was defined as the peel strength (N / cm).
• a transmission line was formed on the copper foil of the double-sided copper-clad laminate to form a printed circuit board, and the signal transmission loss was measured.
• a 28 GHz signal was processed by a vector network analyzer and measured by a GSG high frequency contact probe (250 ⁇ m pitch).
• a transmission line formed on a printed circuit board a coplanar waveguide with a back conductor was used. The characteristic impedance of the line was set to 50 ⁇ .
• Gold flash plating was applied to the surface of copper, which is the conductor of the printed circuit board.
• the calibration method used was TRL calibration (Thru-Reflect-Line calibration).
• the length of the line was set to 50 mm, and the transmission loss per unit length was measured.
• S-parameter (hereinafter also referred to as S value), which is one of the network parameters used to represent the characteristics of the high-frequency electronic circuit and the high-frequency electronic component, was used.
• S value means that the closer the value is to 0, the smaller the transmission loss is.
• S value is more than -1.6, the evaluation of the transmission loss is " ⁇ ", and when the S value is less than -1.6, the evaluation of the transmission loss is "x".
• Dispersant 1 F (CF 2 ) 6 CH 2 CH 2 O (CH 2 CH 2 O) 7 CH 2 CH (CH 3 ) OH
• Dispersant 2 F (CF 2 ) 6 CH 2 CH 2 O (CH 2 CH 2 O) 12 CH 2 CH (CH 3 ) OH
• Dispersant 3 F (CF 2 ) 6 CH 2 CH 2 O (CH 2 CH 2 O) 7 CH 2 CH 2 OH
• Example 1 Production example of dispersion liquid
• Powder 1 of polymer 1 (D50: 2.6 ⁇ m, D90: 7.1 ⁇ m) was obtained by the method described in paragraph [0123] of WO 2016/017801.
• 150 g of Powder 1, 5 g of Dispersant 1, and 335 g of water were put into a horizontal ball mill pot, and dispersed in a zirconia ball having a diameter of 15 mm to obtain a dispersion 1 in which Powder 1 as a powder of Polymer 1 was dispersed.
• the viscosity of Dispersion 1 was 19 mPa ⁇ s.
• the viscosities measured at a rotation speed of 6 rpm and 60 rpm were 13 mPa ⁇ s and 23 mPa ⁇ s in this order, and the thixo ratio was 1.2.
• Dispersion liquid 2 was obtained in the same manner as in Example 1-1 except that dispersant 1 was changed to dispersant 2.
• the viscosity of the dispersion 2 was 16 mPa ⁇ s.
• the viscosities measured at a rotation speed of 6 rpm and 60 rpm were 13 mPa ⁇ s and 19 mPa ⁇ s in this order, and the thixo ratio was 1.2. Further, Dispersion 2 was easier to foam than Dispersion 1.
• Example 1-3 A dispersion was prepared in the same manner as in Example 1-1 except that Dispersant 1 was changed to Dispersant 3, but the dispersion was remarkably thickened, and a dispersion that could withstand coating was not obtained. .
• Example 2 Production example of laminate (No. 1) [Example 2-1]
• the dispersion liquid 1 is applied to copper foil (electrolytic copper foil manufactured by Fukuda Metal Foil & Powder Co., Ltd., CF-T4X-SV, surface roughness of 10 ⁇ m specified by Rzjis) at 100 ° C. in a nitrogen atmosphere. After drying for 15 minutes, a dried film was formed on the copper foil surface. Powder powder was not visually observed on the dried film on the end face of the copper foil. Further, the laminate was heated at 350 ° C.
• copper foil electrolytic copper foil manufactured by Fukuda Metal Foil & Powder Co., Ltd., CF-T4X-SV, surface roughness of 10 ⁇ m specified by Rzjis
• RF output 300 W
• gap between electrodes 2 inches
• introduced gas argon gas
• introduced gas amount 50 cm 3 / min
• pressure 13 Pa
• processing time using a plasma processing apparatus (AP-1000, manufactured by NORDSON MARCH).
• the plasma treatment was performed on the layer side of the polymer 1 of the laminate under the condition of 1 minute. Ra on the surface of the polymer 1 layer after the plasma treatment was 8 nm.
• a laminate was placed on each side of the FR-4 sheet so that a copper foil was formed as the outermost layer. Pressing was performed to obtain a double-sided copper-clad laminate. The evaluation of the transmission loss was “ ⁇ ”.
• Example 2-2 In the same manner as in Example 2-1, except that Dispersion 1 was changed to Dispersion 2, Dispersion 2 was applied to copper foil, and dried at 100 ° C. for 15 minutes under a nitrogen atmosphere to form a dry film on the copper foil surface. Formed. At this time, powder powder was visually observed on the dried film at the end of the copper foil. Further, similarly, a copper foil with resin, a single-sided copper-clad laminate and a double-sided copper-clad laminate were obtained. The residual amount of the dispersant in the polymer 1 layer of the resin-coated copper foil was 23% by mass, the peel strength of the laminate was 7 N / cm, and the transmission loss of the double-sided copper-clad laminate was evaluated as “ ⁇ ”.
• Dispersion 1 was changed to Dispersion 2
• Dispersion 2 was applied to copper foil, and dried at 100 ° C. for 15 minutes under a nitrogen atmosphere to form a dry film on the copper foil surface. Formed. At this time, powder powder was visually observed on the dried film at
• Example 3 Production example of laminate (No. 2) An aqueous dispersion of PTFE (product number: AD-916E, manufactured by Asahi Glass Co., Ltd.) containing 50% by mass of PTFE powder (D50: 0.3 ⁇ m) is mixed with Dispersion 1, and the PTFE powder and the polymer 1 powder are mixed. Was dispersed in water to obtain a dispersion having a ratio (mass ratio) of Polymer 1 to PTFE of 1.0. In addition, at the time of mixing, the dispersion liquid 1 was treated with a homodisper immediately under the condition of 3000 rpm, and further treated with a homogenizer under the condition of 3000 rpm.
• PTFE product number: AD-916E, manufactured by Asahi Glass Co., Ltd.
• the obtained dispersion is applied to the surface of a stainless steel plate (thickness: 0.5 mm) having a vinyl tape attached to one end, and a rod is slid along the end so that the dispersion is applied to the surface of the stainless steel plate.
• I was distracted.
• the stainless steel plate was dried three times at 100 ° C. for 3 minutes, and further heated at 380 ° C. for 10 minutes.
• the surface of the stainless steel plate contained Polymer 1 and PTFE, and the thickness of the vinyl tape adhered to the edge was reduced. For this reason, a stainless steel plate on which a polymer layer having an inclined thickness was formed was obtained. The stainless steel plate was visually observed, but no crack line was observed even in a region having a film thickness of 50 ⁇ m or more.
• the dispersion of the present invention can easily form a layer of a tetrafluoroethylene-based polymer and can be suitably used for the production of a resin-coated copper foil or a metal laminate used for the production of a printed wiring board. Further, the dispersion of the present invention can be used for the production of molded products such as films and impregnated products (prepregs and the like), and has release properties, electrical properties, water and oil repellency, chemical resistance, weather resistance, heat resistance, It can also be used for the production of molded products for applications requiring slipperiness, wear resistance and the like.
• Molded articles obtained from the dispersion of the present invention are useful as antenna parts, printed circuit boards, aircraft parts, automobile parts, sporting goods, food industry products, paints, cosmetics, and the like.

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• 2019
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