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
  • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
  • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
• • 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
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
• • 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
• • 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
  • 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
  • C09D7/20—Diluents or solvents

Definitions

• the present invention relates to a powder dispersion in which powder is dispersed in at least two liquid compounds and a method for producing the same, and a method for producing a resin-coated substrate using such a powder dispersion.
• Tetrafluoroethylene-based polymers such as polytetrafluoroethylene (PTFE) have excellent physical properties such as chemical resistance, water and oil repellency, heat resistance, and electrical properties, and can be used in various industrial applications by utilizing these physical properties. It's being used.
• a powder dispersion containing a powder of a tetrafluoroethylene polymer is useful as a coating agent because it can impart physical properties of a fluoroolefin polymer to the surface of various substrates by applying it to the surface of various substrates (Patent Document 1). , 2).
• Such a powder dispersion is required to have more excellent defoaming property from the viewpoint of improving efficiency at the time of preparation, and is also required to further improve the film forming property when forming a coating film.
• the present inventors have found that a powder dispersion using a liquid compound (solvent) having a relatively low evaporation rate is excellent in defoaming property and film forming property.
• the present invention has the following aspects. ⁇ 1> Unlike the tetrafluoroethylene polymer powder, the first liquid compound having a boiling point of 80 to 260 ° C., and the first liquid compound, the evaporation rate is 0.01 when the evaporation rate of butyl acetate is 1.
• the second liquid compound is diisobutyl ketone, 4-hydroxy-4-methyl-2-pentanone, isophorone, ethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, -2-ethoxyethyl acetate, 3-Methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate, propylene glycol monopropyl ether, 3-methoxybutyl acetate, propylene glycol monomethyl ether propinate or diethylene glycol monobutyl ether, ⁇ 1> to ⁇ 3.
• the second liquid compound is 4-hydroxy-4-methyl-2-pentanone, isophorone, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate or 3-methoxybutyl acetate.
• ⁇ 6> The powder dispersion liquid according to any one of ⁇ 1> to ⁇ 5>, wherein the average particle size of the powder is 40 ⁇ m or less.
• ⁇ 7> The powder dispersion liquid according to any one of ⁇ 1> to ⁇ 6>, wherein the amount of the powder contained in the powder dispersion liquid is 10% by mass or more.
• ⁇ 8> The powder dispersion liquid according to any one of ⁇ 1> to ⁇ 7>, wherein the tetrafluoroethylene polymer is a heat-meltable polymer having a melting temperature of 140 to 320 ° C.
• ⁇ 9> The powder dispersion liquid according to any one of ⁇ 1> to ⁇ 8>, wherein the tetrafluoroethylene-based polymer is a polymer having a unit and a functional group based on tetrafluoroethylene.
• the polymer is a polymer having a unit based on tetrafluoroethylene and a unit based on a monomer having a functional group.
• a dispersant having a hydrophilic group having a polyoxyalkylene group or a hydroxyl group and a perfluoroalkyl group, a perfluoroalkyl group having an etheric oxygen atom, or a hydrophobic group having a perfluoroalkenyl group is included, ⁇ 1.
• the powder dispersion liquid according to any one of ⁇ 1> to ⁇ 12> is applied to the surface of the substrate and heated to remove the first liquid compound and the second liquid compound, and the tetrafluoroethylene.
• a method for producing a resin-based substrate which comprises firing a system polymer to form a polymer layer containing the tetrafluoroethylene-based polymer to obtain a resin-coated substrate including the substrate and the polymer layer.
• the powder dispersion of the present invention is excellent in defoaming property and film forming property. According to the method for producing a powder dispersion of the present invention, such a powder dispersion can be produced. According to the method for producing a resin-coated substrate of the present invention, a resin-coated substrate having a polymer layer having high surface flatness can be obtained.
• Polymer melt viscosity is based on ASTM D1238, and a polymer sample (2 g) that has been preheated at the measurement temperature for 5 minutes using a flow tester and a 2 ⁇ -8L die is loaded with 0.7 MPa. It is a value measured by holding it at the measurement temperature.
• the “polymer melting temperature” is the temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
• the "average particle size of powder (D50)” is a volume-based cumulative 50% diameter obtained by a laser diffraction / scattering method.
• the particle size distribution is measured by a laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the particle population as 100%, and the particle diameter is the point at which the cumulative volume is 50% on the cumulative curve.
• "Powder D90" is a volume-based cumulative 90% diameter determined by a laser diffraction / scattering method. That is, the particle size distribution is measured by a laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the particle population as 100%, and the particle diameter is the point at which the cumulative volume is 90% on the cumulative curve.
• the particles D50 and D90 are obtained by dispersing the particles in water and analyzing them by a laser diffraction / scattering method using a laser diffraction / scattering type particle size distribution measuring device (LA-920 measuring device manufactured by HORIBA, Ltd.). ..
• the "viscosity of the powder dispersion" is a value measured using a B-type viscometer at room temperature (25 ° C.) under the condition of 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 "thixotropy of the powder dispersion” is a value calculated by dividing the viscosity ⁇ 1 measured under the condition of a rotation speed of 30 rpm by the viscosity ⁇ 2 measured under the condition of a rotation speed of 60 rpm. Each viscosity measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
• (Meta) acrylate is a general term for acrylate and methacrylate.
• the "unit” constituting a polymer is a general term for an atomic group based on one molecule of the monomer directly formed by polymerization of a monomer and an atomic group obtained by chemically converting a part of the atomic group. Units based on a particular monomer may be represented by adding a "unit" to the monomer name.
• the powder dispersion of the present invention is different from a tetrafluoroethylene polymer (hereinafter, also referred to as “F polymer”) powder, a first liquid compound having a boiling point of 80 to 260 ° C., and acetic acid, unlike the first liquid compound. It contains a second liquid compound having an evaporation rate of 0.01 to 0.3 and a boiling point of 140 to 260 ° C. when the evaporation rate of butyl is 1.
• the evaporation rate of the liquid compound when the evaporation rate of butyl acetate is 1 is simply referred to as "evaporation rate”.
• evaporation rate Such a powder dispersion is excellent in defoaming property and film forming property. The reason for this is not always clear, but it can be considered as follows.
• the second liquid compound is a compound having a low evaporation rate and a relatively high boiling point, and generally has a hydrophobic portion and a polar portion and has a large molecular weight.
• a second liquid compound can interact with both the F polymer and the first liquid compound. Therefore, the second liquid compound is considered to function as a powder dispersant by itself.
• the powder dispersion liquid contains a separate dispersant, it is considered to function to enhance the dispersion action of the powder by the dispersant.
• the surface tension of the powder dispersion as a whole is effectively reduced, it is presumed that the dispersion of the powder is promoted and the foaming of the powder dispersion is suppressed (good defoaming property is exhibited).
• the second liquid compound has a low evaporation rate and can be said to be a slow-drying solvent. It is considered that the first liquid compound imparts good fluidity to the powder dispersion liquid and promotes the formation of a coating film having a uniform thickness when the coating film (liquid film) is formed. On the other hand, since the second liquid compound, which is a slow-drying solvent, gradually volatilizes, it is considered that the surface roughness of the coating film due to the sudden generation of bubbles due to volatilization is prevented and the surface flatness of the coating film is improved. It is also considered that the second liquid compound also functions as a leveling agent to enhance the flatness of the coating film when the coating film is dried (prevents the formation of rounded corners).
• the powder dispersion exhibited excellent film forming properties.
• the F polymer powder has a weak interaction between the particles, and a state in which a second liquid compound is interposed between them is likely to be formed. Therefore, if the powder dispersion of the present invention is used, the above effect can be further improved. It is thought that it will be exhibited prominently.
• the powder dispersion liquid is applied to the surface of the substrate and heated to remove the first liquid compound and the second liquid compound, and the F polymer is fired to obtain the F polymer.
• a polymer layer containing the above is formed to obtain a resin-coated substrate including the substrate and the polymer layer. Since the polymer layer of the resin-coated substrate obtained by the present invention is formed by using the powder dispersion liquid of the present invention, it is excellent in surface flatness. The above effects are more prominently exhibited in the preferred embodiments of the present invention described later.
• the D50 of the powder in the present invention is preferably 40 ⁇ m or less, more preferably 20 ⁇ m or less, and particularly preferably 8 ⁇ m or less.
• the D50 of the powder is preferably 0.01 ⁇ m or more, more preferably 0.1 ⁇ m or more, and particularly preferably 1 ⁇ m or more.
• the D90 of the powder is preferably 80 ⁇ m or less, more preferably 50 ⁇ m or less. In D50 and D90 in this range, the fluidity and dispersibility of the powder are good, and the electrical characteristics (low dielectric constant, etc.) and heat resistance of the polymer layer are most likely to be exhibited. In addition, the defoaming property and film forming property of the powder dispersion are further improved.
• the sparse filling bulk density of the powder is more preferably 0.08 to 0.5 g / mL.
• the densely packed bulk density of the powder is more preferably 0.1 to 0.8 g / mL. When the sparsely packed bulk density or the densely packed bulk density is within the above range, the handleability of the powder is excellent.
• the powder in the present invention may contain a resin other than the F polymer, but the powder in the present invention is preferably a powder containing the F polymer as a main component.
• the content of the F polymer in the powder is preferably 80% by mass or more, more preferably 100% by mass.
• the resin include aromatic polyester, polyamide-imide, thermoplastic polyimide, polyphenylene ether, and polyphenylene oxide.
• the F polymer in the present invention is a polymer containing a unit based on tetrafluoroethylene (hereinafter, also referred to as “TFE”).
• TFE tetrafluoroethylene
• the F polymer may be a homopolymer of TFE, or may be a copolymer of TFE and a comonomer copolymerizable with TFE.
• an F polymer containing 90 to 100 mol% of TFE units with respect to all the units constituting the polymer is preferable.
• the fluorine content of the F polymer is preferably 70 to 76% by mass, more preferably 72 to 76% by mass.
• F polymer examples include polytetrafluoroethylene (PTFE), a copolymer of TFE and ethylene (ETFE), a copolymer of TFE and propylene, and a copolymer of TFE and perfluoro (alkyl vinyl ether) (hereinafter, also referred to as "PAVE").
• PFA polytetrafluoroethylene
• ETFE copolymer of TFE and ethylene
• PAVE perfluoro (alkyl vinyl ether)
• FFA a copolymer of TFE and hexafluoropropylene
• FEP a copolymer of TFE and fluoroalkylethylene
• FFE and chlorotrifluoro examples include copolymers with ethylene.
• the copolymer may further contain units based on other comonomeres.
• PTFE include high molecular weight PTFE, low molecular weight PTFE, and modified PTFE having fibril properties.
• low molecular weight PTFE or modified PTFE shall also include copolymers of TFE and trace amounts of comonomer (HFP, PAVE, FAE, etc.).
• an F polymer having a TFE unit and a functional group is preferable.
• the functional group a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group are preferable.
• the functional group may be contained in a unit in the F polymer, or may be contained in the terminal group of the main chain of the polymer. Further, an F polymer having a functional group obtained by plasma-treating or ionizing the F-polymer can also be used.
• a TFE unit and an F polymer having a unit having a functional group are preferable from the viewpoint of dispersibility of the powder in the powder dispersion liquid.
• the unit having a functional group the above-mentioned unit having a functional group is preferable.
• the monomer having a functional group a monomer having an acid anhydride residue is preferable, and itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride. Hereinafter, "NAH” ”) And maleic anhydride are more preferable.
• the F polymer having a functional group include an F polymer having a TFE unit, an HFP unit, a PAVE unit or a FAE unit, and a unit having a functional group.
• CF 2 CFOCF 3
• CF 2 CFOCF 2 CF 3
• CF 2 CFOCF 2 CF 2 CF 3
• PPVE also referred to as “PPVE”
• CF 2 CFOCF 2 CF 2 CF 2 CF 3
• CF 2 CFO (CF 2 ) 8 F.
• Specific examples of such polymer F include 90 to 99 mol% of TFE units, 0.5 to 9.97 mol% of HFP units, PAVE units or FAE units, and functional groups with respect to all the units constituting the polymer. Examples thereof include F polymers containing 0.01 to 3 mol% of the units having each. Specific examples of such a polymer F include the polymers described in International Publication No. 2018/16644.
• the melt viscosity of the F polymer at 380 ° C. is preferably 1 ⁇ 10 2 to 1 ⁇ 10 6 Pa ⁇ s, more preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s.
• a heat-meltable polymer is preferable, and a heat-meltable polymer having a melting temperature higher than both the boiling point of the first liquid compound and the boiling point of the second liquid compound is more preferable.
• the melting temperature of the heat-meltable polymer is preferably 140 to 320 ° C., more preferably 200 to 320 ° C., and even more preferably 260 to 320 ° C. When such an F polymer is used, a polymer layer having better surface flatness is likely to be formed.
• the first liquid compound and the second liquid compound in the present invention are both liquid compounds at 25 ° C., and may be an aqueous solvent or a non-aqueous solvent.
• As the first liquid compound a compound which has a relatively high evaporation rate but does not volatilize instantaneously is preferable.
• the evaporation rate of the first liquid compound is preferably higher than the evaporation rate of the second liquid compound. In other words, the first liquid compound preferably has an evaporation rate greater than 0.3.
• the boiling point of the first liquid compound is 80 to 260 ° C., preferably 100 to 250 ° C., more preferably 120 to 240 ° C.
• the viscosity of the first liquid compound at 20 to 25 ° C. is preferably 5.0 mPa ⁇ s or less, preferably 4.0 mPa ⁇ s or less. More preferred.
• the lower limit of the viscosity is usually 0.1 mPa ⁇ s.
• first liquid compound ketones, esters, amides, alcohols, sulfoxides, glycol ethers and aromatic hydrocarbons are preferable, and ketones, esters, amides and aromatic hydrocarbons are more preferable. If such a first liquid compound is used, the film forming property of the powder dispersion is likely to be improved. Two or more kinds of first liquid compounds may be used in combination.
• the first liquid compound include methyl ethyl ketone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, and the like.
• Cyclohexanone, cyclopentanone, toluene, xylene, 1,2,4-trimethylbenzene and 1,2,3-trimethylbenzene include methyl ethyl ketone, 3-methoxy-N, N-dimethylpropanamide, N-methyl-2. -Pyrrolidone and cyclohexanone are more preferred. It is qualitatively clear that these compounds have a higher evaporation rate than the second liquid compound described later, although the specific numerical value of the evaporation rate is unknown.
• the second liquid compound is a compound different from the first liquid compound, and has a relatively low evaporation rate.
• the evaporation rate of the second liquid compound is 0.01 to 0.3, preferably 0.03 to 0.20, and 0.05 to 0, when the evaporation rate of butyl acetate is 1. .15 is more preferred.
• the boiling point of the second liquid compound is 140 to 260 ° C., preferably 160 to 240 ° C., and more preferably 180 to 220 ° C. If a second liquid compound having an evaporation rate and a boiling point within the above ranges is used, a sufficient amount of the second liquid compound remains in the coating film even after the first liquid compound is heated and distilled off, and then appropriately.
• the second liquid compound can more preferably exert the effect of improving the surface flatness of the polymer layer.
• the difference between the boiling point of the first liquid compound and the boiling point of the second liquid compound is preferably within ⁇ 40 ° C, more preferably within ⁇ 30 ° C.
• Examples of the second liquid compound include diisobutylketone (evaporation rate: 0.2, boiling point: 168 ° C.), 4-hydroxy-4-methyl-2-pentanone (evaporation rate: 0.15, boiling point: 168 ° C.), and isophorone.
• Two or more of these compounds may be used in combination.
• the second liquid compound 4-hydroxy-4-methyl-2-pentanone, isophorone, 3-methoxy-3-methylbutanol, 3-methoxy-3-methylbutyl acetate and 3-methoxybutyl acetate are preferable.
• These compounds can be said to be compounds that can function as surfactants (powder dispersants) and plasticizers, and can easily further improve the flatness of the polymer layer.
• the ratio of the mass of the second liquid compound to the mass of the first liquid compound contained in the powder dispersion is preferably less than 1, preferably 0.1 to 0. .9 is more preferable, and 0.2 to 0.8 is even more preferable.
• the powder dispersion liquid can exhibit good defoaming property and excellent film forming property in a well-balanced manner.
• the powder dispersion of the present invention preferably further contains a dispersant from the viewpoint of further improving the dispersibility of the powder.
• the dispersant is a compound having a hydrophilic group and a hydrophobic group, and as the dispersant, a fluorine-based dispersant, a silicone-based dispersant and an acetylene-based dispersant are preferable, and a fluorine-based dispersant is more preferable. Further, as the dispersant, a nonionic dispersant is preferable.
• the hydrophilic group a polyoxyalkylene group and a hydroxyl group are preferable.
• the polyoxyalkylene group a polyoxyethylene group and a polyoxyalkylene group having an oxyethylene group and a polyoxyalkylene group having 3 or more carbon atoms are preferable.
• the hydrophobic group is appropriately selected depending on the type of dispersant.
• the hydrophobic group is preferably a perfluoroalkyl group, a perfluoroalkyl group having an etheric oxygen atom, and a perfluoroalkenyl group.
• the affinity of the dispersant for each component is balanced, and in addition to the dispersibility of the powder in the powder dispersion, the film-forming property is likely to be further improved.
• fluorine-based dispersant fluoromonool and fluoropolyol are preferable, and the fluorine content is 10 to 50% by mass and the hydroxyl value is 40 to 100 mgKOH / g, or the fluorine content is 10 to 50% by mass. More preferably, it is a fluoropolypoly having a hydroxyl value of 10 to 35 mgKOH / g.
• fluoropolyol examples include polymers containing a unit based on fluoro (meth) acrylate and a unit based on polyoxyalkylene glycol mono (meth) acrylate. This polymer is a polymer other than the F polymer.
• the ratio of the powder to the powder dispersion is preferably 10% by mass or more, more preferably 20 to 50% by mass. In this case, it is easy to form a polymer layer having excellent physical properties (particularly, electrical properties).
• the total ratio (the ratio of the solvent) of the first liquid compound and the second liquid compound to the powder dispersion is preferably 15 to 55% by mass, more preferably 25 to 50% by mass. In this case, the coatability of the powder dispersion is excellent, and the film-forming property is likely to be improved.
• the ratio of the powder dispersion to the powder dispersion is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. In this case, the dispersibility of the powder in the powder dispersion is further enhanced, and the physical properties of the polymer layer are more likely to be improved.
• the powder dispersion may contain other materials as long as the effects of the present invention are not impaired. Other materials may or may not be dissolved in the powder dispersion.
• the other material may be a non-curable resin or a curable resin.
• the non-curable resin include thermosetting resins and non-meltable resins.
• the thermosetting resin include thermoplastic polyimide.
• the non-meltable resin include a cured product of a curable resin.
• the curable resin examples include polymers having a reactive group, oligomers having a reactive group, low molecular weight compounds, and low molecular weight compounds having a reactive group.
• the reactive group examples 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, curable acrylic resin, phenol resin, curable polyester resin, curable polyolefin resin, modified polyphenylene ether resin, and polyfunctional cyanate ester.
• Examples thereof include resins, polyfunctional maleimide-cyanic acid ester resins, polyfunctional maleimide resins, vinyl ester resins, urea resins, diallyl phthalate resins, melanin 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, and aliphatic chain epoxy resin.
• examples thereof include cresol novolac type epoxy resin, phenol novolac type epoxy resin, alkylphenol novolac type epoxy resin, aralkyl type epoxy resin, and biphenol type epoxy resin.
• the bismaleimide resin examples include the resin composition (BT resin) described in JP-A-7-70315 and the resin described in International Publication No. 2013/0083667.
• the polyamic acid usually has a reactive group capable of reacting with the functional group of the F polymer.
• Examples of the diamine and polyvalent carboxylic acid dianhydride forming the polyamic acid include [0020] of Japanese Patent No. 5766125, [0019] of Japanese Patent No. 5766125, and [0055] and [0055] of Japanese Patent Application Laid-Open No. 2012-145676. 0057] and the like.
• thermosetting resin examples include thermoplastic resins such as thermoplastic polyimide and thermosetting cured products of curable resins.
• thermoplastic resin include polyester resin, polyolefin resin, styrene resin, polycarbonate, thermoplastic polyimide, polyarylate, polysulfone, polyallylsulfone, aromatic polyamide, aromatic polyetheramide, polyphenylensulfide, polyallyl etherketone, and polyamide.
• examples thereof include imide, liquid crystal polyester and polyphenylene ether, and thermoplastic polyimide, liquid crystal polyester and polyphenylene ether are preferable.
• such other materials include thixo-imparting agents, defoaming agents, inorganic fillers, reactive alkoxysilanes, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, and more.
• thixo-imparting agents include whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, and flame retardants.
• the viscosity of the powder dispersion at 25 ° C. is preferably 1000 mPa ⁇ s or less, more preferably 50 to 1000 mPa ⁇ s, and even more preferably 100 to 500 mPa ⁇ s.
• the powder dispersion is not only excellent in dispersibility, but also excellent in coatability and compatibility with varnishes of different resin materials.
• the thixotropy ( ⁇ 1 / ⁇ 2 ) of the powder dispersion is preferably 1 to 2.5, more preferably 1.2 to 2. In this case, not only the powder dispersion is excellent in dispersibility, but also the homogeneity of the polymer layer is likely to be improved.
• the powder dispersion of the present invention can be produced by mixing the powder, the first liquid compound, and the second liquid compound.
• the powder, the first liquid compound, and the second liquid compound may be mixed together, or they may be mixed in any combination in order.
• the powder dispersion of the present invention is prepared by mixing a first liquid compound and a second liquid compound in advance to obtain a liquid composition containing them, and then mixing the powder with the liquid composition. preferable. That is, as a method for producing the powder dispersion liquid of the present invention, a method of mixing the powder and the liquid composition containing the first liquid compound and the second liquid compound is preferable. If the powder, the first liquid compound, and the second liquid compound are mixed in this order, foaming is less likely to occur in the powder dispersion.
• a metal foil is preferable, and a copper foil such as a rolled copper foil or an electrolytic copper foil is more preferable.
• a rust preventive layer oxide film such as chromate
• a heat resistant layer may be provided on the surface of the metal foil.
• the ten-point average roughness of the surface of the metal foil is preferably 0.2 to 2.5 ⁇ m. In this case, the peel strength (adhesion) between the metal foil and the polymer layer is likely to be improved.
• the powder dispersion can be applied to the substrate surface by spray method, roll coating method, spin coating method, gravure coating method, micro gravure coating method, gravure offset method, knife coating method, kiss coating method, bar coating method, die coating method, fountain. It can be carried out by a method such as the Mayer bar method or the slot die coat method.
• a film of the powder dispersion liquid is formed on the surface of the substrate.
• the first liquid compound and the second liquid compound are removed from the film of the powder dispersion liquid by heating above the boiling points of the first liquid compound and the second liquid compound, and further heating to the firing temperature of the F polymer is performed.
• a polymer layer containing the calcined F polymer is formed.
• the temperature for volatilizing and removing the liquid compound is preferably lower than the melting temperature of the F polymer, and the firing temperature of the F polymer is preferably equal to or higher than the melting temperature of the F polymer.
• the heating is performed at a temperature of at least two steps.
• the firing temperature of the F polymer depends on the melting temperature of the F polymer, but is preferably 400 ° C. or lower.
• Examples of the heating 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.
• the heating may be carried out under either normal pressure or reduced pressure.
• the heating atmosphere may be any of an oxidizing gas atmosphere (oxygen gas, etc.), a reducing gas atmosphere (hydrogen gas, etc.), and an inert gas atmosphere (helium gas, neon gas, argon gas, nitrogen gas, etc.). Good.
• a resin-coated substrate having a two-layer structure having a substrate and a polymer layer in contact with one surface of the substrate can be obtained. Further, by repeating the production method of the present invention using the obtained two-layer resin-attached substrate, a three-layer resin-attached substrate having polymer layers on both surfaces of the substrate can also be obtained.
• the thickness of the polymer layer is preferably less than 20 ⁇ m, more preferably less than 10 ⁇ m, and particularly preferably 0.1 to 8 ⁇ m. According to the present invention, even such a thin polymer layer can be formed with high surface flatness.
• the resin-coated substrate obtained by the present invention also has high peel strength between the polymer layer and the substrate. The peel strength is preferably 7 N / cm or more, more preferably 10 N / cm or more, and further preferably 13 N / cm or more.
• the resin-coated substrate obtained by the present invention can be laminated with another substrate by using the polymer layer surface as a laminated surface to form a laminated body having a layer structure of three or more layers.
• a laminate include a laminate having a layer structure of a substrate / polymer layer / another substrate, and a laminate having a layer structure of a substrate / polymer layer / another substrate / polymer layer / substrate. ..
• Examples of other substrates include metal foils and resin plates.
• the resin-attached substrate and the laminate obtained by the present invention include a polymer layer formed from F polymer powder, they are excellent in physical properties such as heat resistance, electrical properties, and chemical resistance (etching resistance), and are flexible printed wiring boards. It is useful as a material for printed wiring boards such as substrates and rigid printed wiring boards.
• the substrate of the resin-attached substrate or the other substrate of the laminate is a metal foil, a method of etching the metal foil to process it into a metal conductor wiring (transmission circuit) having a predetermined pattern, or electrolyzing the metal foil.
• a printed wiring board can be manufactured by a method of processing into a metal conductor wiring by a plating method (semi-additive method, modified semi-additive method, etc.).
• Such a printed wiring board has a metal conductor wiring and a polymer layer in this order.
• Examples of the configuration include metal conductor wiring / polymer layer and metal conductor wiring / polymer layer / metal conductor wiring.
• an interlayer insulating film may be formed on the metal conductor wiring, and a metal conductor wiring may be further formed on the interlayer insulating film.
• the interlayer insulating film may also be formed by the powder dispersion liquid.
• a solder resist or a coverlay film may be laminated on the metal conductor wiring. The solder resist and coverlay film may also be formed by the above powder dispersion.
• a multi-layer printed wiring board in which the above-mentioned layer structure is multi-layered can be mentioned.
• a preferred embodiment of the multilayer printed wiring board is an embodiment in which the outermost layer of the multilayer printed wiring board is a polymer layer and has one or more layer configurations of metal conductor wiring / polymer layer.
• the multilayer printed wiring board of this aspect has excellent heat resistance of the outermost layer, and defects are less likely to occur even when heated during processing, for example, heating at 300 ° C. in a solder reflow process.
• the woven fabric is a heat-resistant woven fabric that can withstand heating, and the woven fabric is preferably glass fiber woven fabric, carbon fiber woven fabric, aramid fiber woven fabric, and metal fiber woven fabric, and glass fiber woven fabric and carbon fiber woven fabric. Is more preferable, and from the viewpoint of electrical insulation, a plain woven glass fiber woven fabric composed of E glass yarn for electrical insulation defined in JIS R 3410: 2006 is further preferable.
• the woven fabric may be treated with a silane coupling agent from the viewpoint of enhancing the adhesion to the fired product.
• Examples of the method of impregnating the woven fabric with the powder dispersion of the present invention include a method of immersing the woven fabric in the powder dispersion and a method of applying the powder dispersion to the woven fabric. Since the powder dispersion of the present invention contains an F polymer having excellent adhesiveness to other materials, a coated weave having a high polymer content, in which the woven fabric and the F polymer are firmly adhered at least by the number of times of immersion or application. A cloth is obtained.
• the method of heating the woven fabric can be appropriately determined depending on the type of the liquid component contained in the powder dispersion, and the method of drying in an atmosphere of 80 to 260 ° C. and further firing the powder in an atmosphere of 300 to 400 ° C. Usually adopted.
• the obtained coated woven fabric is excellent in characteristics such as high adhesion between the fired product and the woven fabric, high surface flatness, and little distortion.
• the laminate obtained by thermocompression bonding the woven fabric and the metal foil has high peel strength and is hard to warp, so that it can be suitably used as a printed circuit board material.
• the powder dispersion liquid of the present invention containing a woven fabric to the surface of the base material and heating it, a coated woven fabric layer containing the baked product of the powder and the woven fabric can be formed, and the base material and the coated woven fabric layer can be formed.
• a laminated body laminated in this order can also be manufactured.
• the present invention is not limited to the configuration of the above-described embodiment.
• the powder dispersion of the present invention may additionally have any other configuration in the configuration of the above embodiment, or may be replaced with any configuration that produces the same effect.
• the method for producing the powder dispersion liquid and the method for producing the resin-coated substrate of the present invention may additionally have any other optional steps in the configuration of the above-described embodiment, and any other method that produces the same action may be additionally provided. It may be replaced with the process.
• Example 2 Production of powder dispersion (Example 1) First, a dispersant solution containing a fluorine-based dispersant 1 and 3-methoxy-3-methylbutyl acetate (evaporation rate: 0.10, boiling point: 188 ° C.) was prepared. The amount of the fluorine-based dispersant 1 contained in the dispersant solution was 33% by mass. Next, this dispersant solution and N-methyl-2-pyrrolidone (NMP. Boiling point: 202 ° C., viscosity (20 ° C.): 1.89 mPa ⁇ s) were mixed to prepare a liquid composition. Next, after putting this liquid composition and powder 1 into a pot, zirconia balls were put into the pot.
• NMP N-methyl-2-pyrrolidone
• the pot was rolled at 150 rpm for 1 hour, and the powder 1 was dispersed in the liquid composition to obtain a powder dispersion 1 (viscosity: 120 mPa ⁇ s).
• the amount of powder 1 contained in the powder dispersion 1 is 40% by mass, the amount of fluorine-based dispersant 1 is 5% by mass, the amount of 3-methoxy-3-methylbutyl acetate is 10% by mass, and the amount of NMP. was 45% by mass.
• Example 2 (Comparative example) Powder dispersion 2 (viscosity: 100 mPa ⁇ s) was obtained in the same manner as in Example 1 except that NMP was used instead of 3-methoxy-3-methylbutyl acetate.
• the amount of powder 1 contained in the powder dispersion 2 was 40% by mass, the amount of fluorine-based dispersant 1 was 5% by mass, and the amount of NMP was 55% by mass.
• Example 3 A powder dispersion 3 (viscosity: 180 mPa ⁇ s) was obtained in the same manner as in Example 1 except that powder 2 was used instead of powder 1.
• Example 4 (Comparative example) Powder dispersion 4 (viscosity) in the same manner as in Example 3 except that triethylene glycol monobutyl ether (evaporation rate: less than 0.01, boiling point: 271 ° C.) was used instead of 3-methoxy-3-methylbutyl acetate. : 1500 mPa ⁇ s) was obtained.
• Example 5 (Comparative example) Powder dispersion 5 (viscosity:) in the same manner as in Example 3 except that ethylene glycol monoethyl ether (evaporation rate: 0.38, boiling point: 136 ° C.) was used instead of 3-methoxy-3-methylbutyl acetate. 800 mPa ⁇ s) was obtained.
• Example 6 (Comparative example) A powder dispersion 6 (viscosity: 80 mPa ⁇ s) was obtained in the same manner as in Example 3 except that NMP was used instead of 3-methoxy-3-methylbutyl acetate.
• the amount of powder 2 contained in the powder dispersion 6 was 40% by mass, the amount of fluorine-based dispersant 1 was 5% by mass, and the amount of NMP was 55% by mass.
• a powder dispersion was applied on the surface of a copper foil (substrate) having a thickness of 18 ⁇ m by a gravure reverse method in a roll-to-roll manner to form a liquid film.
• the copper foil on which the liquid film was formed was passed through a drying oven at 120 ° C. for 5 minutes and dried by heating. Then, the dry film was heated at 380 ° C. for 3 minutes in a far-infrared oven under a nitrogen atmosphere.
• the thickness of the polymer layer was 4 ⁇ m.
• ⁇ No unevenness was observed in the thickness of the polymer layer under a fluorescent lamp, and the difference in film thickness between the central portion and the edge portion of the surface of the polymer layer observed by a light interference microscope was more than 10%.
• X Unevenness is observed in the thickness of the polymer layer under a fluorescent lamp, and the difference in film thickness between the central portion and the edge portion of the surface of the polymer layer observed by a light interference microscope is more than 10%.
• the powder dispersion of the present invention can be used in the production of films, impregnated materials (prepregs, etc.), laminates (resin-attached substrates such as resin-attached copper foil), etc. It can be used in applications that require chemical resistance, weather resistance, heat resistance, slipperiness, abrasion resistance, etc. Further, the resin-attached substrate can be processed and used as an antenna component, a printed wiring board, an insulating layer of a power semiconductor, an aircraft component, an automobile component, or the like.

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