Classifications

• • 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
  • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
  • C08J3/05—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media from solid 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
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
  • C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
• • 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
• • 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
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/63—Additives non-macromolecular organic

Definitions

• the present invention relates to a method for producing a container in which a liquid composition containing a tetrafluoroethylene polymer powder is contained in a container, and a liquid composition containing a tetrafluoroethylene polymer powder.
• 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 liquid composition containing a tetrafluoroethylene polymer powder and a surfactant can be applied to the surface of various substrates to impart physical properties based on the tetrafluoroethylene polymer to the surface, and thus can be used as a coating agent. It is useful (see Patent Document 1). Further, such a liquid composition is required to be maintained in a hygienic state in which germs and the like are difficult to propagate. In order to satisfy this requirement, a method of adding an amine to a liquid composition to adjust its pH to an alkaline region has been proposed (see Patent Document 2).
• the storage stability and handleability of the liquid composition containing the tetrafluoroethylene polymer powder and the surfactant are still insufficient.
• the liquid composition has improved dispersibility due to the action of the surfactant, but is in a state of being easily foamed. Therefore, when the liquid composition is transferred (filled in a container) or when each component is mixed in the container to prepare a liquid composition, bubbles accompanying the liquid phase flow greatly improve the work efficiency. There is a problem of reducing it.
• a method of adding a defoaming agent to the liquid composition can be considered, but when the defoaming agent lowers the physical properties of the liquid composition or the layer (coating film) formed from the defoaming agent. It may reduce physical properties.
• the liquid composition is stored after adjusting the pH to an alkaline range, there is a problem that the tetrafluoroethylene polymer itself or the liquid composition is likely to be deteriorated (colored or the like) or the odor becomes severe.
• the present inventors can effectively suppress foaming of the liquid composition by setting the gas phase temperature in the container to a predetermined temperature in the liquid phase flow in the container, and transfer the liquid composition. It was found that the work efficiency in preparation and preparation is improved.
• the present inventors can first prepare an acidic liquid composition by using a predetermined fluorine-based surfactant, and have an antibacterial effect without causing alteration or generation of an unpleasant odor. It was found that it was expressed. Furthermore, it was also found that the antibacterial effect is remarkably enhanced when a specific preservative is used in combination.
• the present invention has the following aspects.
• the liquid phase flow is a flow associated with filling the liquid composition into the container or a flow associated with the preparation of the liquid composition in the container.
• [3] The production method of [1] or [2], wherein an external force is applied to the liquid phase in the container in the liquid phase flow.
• [4] The production method according to any one of [1] to [3], which keeps the liquid phase temperature in the container below the cloud point of the surfactant in the liquid phase flow.
• [5] The method for producing any of [1] to [4], wherein the surfactant is a nonionic surfactant.
• the surfactant is a surfactant having an alcoholic hydroxyl group or a polyoxyalkylene group.
• the surfactant comprises an alkylene oxide adduct of a polyfluoroalkyl alcohol, or a copolymer of a monomer having a perfluoroalkyl group or a perfluoroalkenyl group and a monomer having an oxyalkylene group [9] to [12]. ] Any liquid composition.
• an accommodating body containing a liquid composition in which foaming is well suppressed and a liquid composition having excellent storage stability and handleability 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 (melting point)” is the temperature corresponding to the maximum value of the polymer melting peak measured by the differential scanning calorimetry (DSC) method.
• the "average particle size of powder (D50)” is a volume-based cumulative 50% diameter of powder obtained by a laser diffraction / scattering method.
• the particle size distribution of the powder is measured by the laser diffraction / scattering method, the cumulative curve is obtained with the total volume of the powder particle population as 100%, and the particle diameter at the point where the cumulative volume is 50% on the cumulative curve. is there.
• “Powder D90” is the volume-based cumulative 90% diameter of the powder measured in the same manner.
• the powders D50 and D90 are obtained by dispersing the powder in water and using a laser diffraction / scattering type particle size distribution measuring device (LA-920 measuring device manufactured by HORIBA, Ltd.).
• “Viscosity” is the viscosity of a liquid measured at room temperature (25 ° C.) and at a rotation speed of 30 rpm using a B-type viscometer.
• the measurement is repeated 3 times, and the average value of the measured values for 3 times is used.
• the "thixotropy” is a value calculated by dividing the liquid viscosity ⁇ 1 measured under the condition of 30 rpm by the viscosity ⁇ 2 of the liquid measured under the condition of 60 rpm ( ⁇ 1 /). ⁇ 2 ).
• the "unit” in the polymer may be an atomic group formed directly from the monomer by the polymerization reaction, and the polymer obtained by the polymerization reaction is treated by a predetermined method to convert a part of the structure. It may be.
• the unit based on monomer A contained in the polymer is also simply referred to as "monomer A unit".
• (Meta) acrylate is a general term for acrylate and methacrylate.
• a thermogravimetric analyzer (TG) and a thermogravimetric differential thermal analyzer (TG-DTA) are used, and the preservative (10 mg) is mixed with a mixed gas (90% by volume of helium and oxygen). 10% by volume)
• the temperature is such that the mass reduction rate becomes 1% by mass / min or more when the temperature is raised at a pace of 10 ° C./min in an atmosphere.
• a liquid composition containing a powder of a tetrafluoroethylene polymer (hereinafter, also referred to as "F polymer”), a surfactant, and a liquid dispersion medium is contained in a container.
• F polymer tetrafluoroethylene polymer
• This is a method for producing an inclusion body, which is a method for setting the gas phase temperature in the container to be equal to or higher than the clouding point of the surfactant in the liquid phase flow in the container.
• the gas phase temperature means the temperature of the space (gas phase portion) in the container.
• the liquid composition is a dispersion liquid (powder dispersion liquid) in which the powder of the F polymer is dispersed in the form of particles.
• the cloud point of the surfactant means that the molecular movement of the surfactant becomes violent as the temperature rises, and the interaction between the surfactants and between the surfactant and the liquid dispersion medium (hydrogen bond).
• Etc. is the temperature at which it drops sharply. That is, the cloud point of the surfactant can be said to be a temperature at which the action of the surfactant disappears or extremely decreases.
• the surfactant cannot be dissolved or micelles are formed in the liquid dispersion medium at a temperature equal to or higher than the cloud point of the surfactant, resulting in turbidity.
• the surfactant used for dispersing the powder of the F polymer has a strong surfactant action, so that the degree of the surfactant is severe, and it takes a long time to defoam the surfactant.
• the gas phase temperature is set to be equal to or higher than the cloud point of the surfactant, so that the action of the surfactant in the foam disappears or decreases, and the foam is quickly extinguished. It is considered that the liquid composition contained therein was efficiently obtained. The above effects are more prominently exhibited in the preferred embodiments of the present invention described later.
• Examples of the liquid phase flow in this method include a flow when the liquid composition is filled or dispensed into the container, and a flow when the liquid composition is prepared in the container. This method is particularly likely to increase the efficiency (yield) of operations (filling, preparation) in these flows.
• the flow when preparing the liquid composition in the container includes the flow when redispersing the powder precipitated in the liquid composition contained in the container, and further the flow when the liquid composition contained in the container is used. Examples include the flow when dissolving or dispersing other components, and the flow when producing a liquid composition in a container. The latter flow is preferably carried out by flowing the liquid dispersion medium and the surfactant in the container, and further adding powder in sequence.
• liquid phase flow in this method it is preferable to apply an external force to the liquid phase in the container from the viewpoint of suppressing the adhesion of the powder to the inner wall surface of the container.
• the liquid phase is more likely to foam, but the effect of this method of promoting defoaming by setting the gas phase temperature in the container to the cloud point of the surfactant or higher is likely to work remarkably.
• Examples of the liquid phase in the container include the liquid composition itself, a liquid mixed with the liquid composition (for example, resin varnish), and a liquid dispersion medium.
• Examples of the operation of applying an external force to the liquid phase in the container include stirring the liquid phase, irradiating the liquid phase with high frequency waves, and vibrating or rocking the container. Therefore, specific operations in the liquid phase flow include an operation of simply filling or dispensing the liquid composition into the container, an operation of adding the liquid composition to the resin varnish contained in the container, and an operation of stirring thereafter. , The operation of mixing and stirring the components of the liquid composition in the container to prepare the liquid composition, and the operation of redispersing the powder precipitated in the liquid composition contained in the container by stirring, high frequency irradiation, and vibration. Can be mentioned.
• the gas phase temperature in this method is appropriately set according to the cloud point of the surfactant, and is preferably 60 to 100 ° C., more preferably 70 to 90 ° C. If the vapor phase temperature is set, bubbles can be suppressed more reliably, and the liquid dispersion medium is less likely to volatilize.
• the gas phase temperature inside the container is preferably adjusted by supplying hot air into the container or heating the top surface of the container (the lid that closes the upper opening of the container body). In this way, the gas phase temperature can be preferentially increased while suppressing the increase in the liquid phase temperature in the container. When supplying hot air into the container, it is more preferable to supply the hot air toward the gas-liquid interface in the container.
• the gas phase temperature in this method may be consistently (continuously) maintained above the cloud point of the surfactant when the liquid phase is flowed in the container, and when the liquid phase is flowed in the container, it may be maintained. It may be intermittently held above the cloud point of the surfactant.
• the gas phase temperature may be adjusted by intermittently supplying hot air while checking the state of bubbles in the container.
• the liquid phase temperature in the container is set below the cloud point of the surfactant from the viewpoint of fully exerting the action of the surfactant in the liquid phase (liquid composition, etc.).
• the liquid phase temperature means the temperature of the liquid (liquid phase portion) in the container, and the liquid phase includes the liquid composition itself and the liquid (for example, resin) mixed with the liquid composition as described above. Alligator), liquid dispersion medium is included.
• the liquidus temperature is appropriately set according to the cloud point of the surfactant and the boiling point of the liquid dispersion medium, and is preferably 0 to 50 ° C., more preferably 5 to 40 ° C.
• the liquid phase temperature in this method may be consistently (continuously) kept below the cloud point of the surfactant when the liquid phase is flowed in the container, and when the liquid phase is flowed in the container, it may be kept below the cloud point. It may be intermittently kept below the cloud point of the surfactant.
• the D50 of the powder in this method is preferably 0.01 to 10 ⁇ m, more preferably 0.05 to 8 ⁇ m, further preferably 0.1 to 6 ⁇ m, and particularly preferably 0.2 to 3 ⁇ m.
• the D90 of the powder is preferably 10 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 6 ⁇ m or less.
• a powder having such a small particle size has a large surface area as a whole, and a liquid composition containing such a powder is particularly liable to foam. For this reason, it is preferable to use this method when producing an container containing a liquid composition.
• the sparse filling bulk density of the powder is preferably 0.08 to 0.5 g / mL.
• the densely packed bulk density of the powder is preferably 0.1 to 0.8 g / mL.
• the F polymer in this method is a polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE).
• the F polymer may be a homopolymer of TFE or a copolymer of TFE and another comonomer. Further, one type of F polymer may be used alone, or two or more types may be used.
• the F polymer preferably contains 90 to 100 mol% of TFE units with respect to all the units constituting the polymer.
• the fluorine content of the F polymer is preferably 70 to 76% by mass, more preferably 72 to 76% by mass.
• F polymers include polytetrafluoroethylene (PTFE), TFE and ethylene copolymer (ETFE), TFE and propylene copolymer, TFE and perfluoro (alkyl vinyl ether) (PAVE) copolymer (PFA), and TFE and hexa.
• examples include copolymers with fluoropropylene (HFP) (FEP), copolymers with TFE and fluoroalkylethylene (FAE), and copolymers with TFE and chlorotrifluoroethylene (CTFE).
• 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. The low molecular weight PTFE or modified PTFE also includes copolymers of TFE and trace amounts of comonomer (HFP, PAVE, FAE, etc.).
• the F polymer is preferably an F polymer having a TFE unit and a functional group.
• the functional group is preferably a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group or an isocyanate group.
• 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.
• the F polymer having a functional group is preferably a TFE unit and an F polymer having a unit having a functional group from the viewpoint of dispersibility of the powder in the liquid composition.
• the unit having a functional group is preferably a unit based on a monomer having a functional group, and more preferably a unit based on the above-mentioned monomer having a functional group.
• the monomer having a functional group is preferably a monomer having an acid anhydride residue, and itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter, "NAH"). Also referred to as) or maleic anhydride is more preferred.
• Preferable specific examples of 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 CH (CF 2 ) 2 F
• CH 2 CH (CF 2 ) 3 F
• CH 2 CH (CF 2 ) 4 F
• CH 2 CF (CF 2 ) 3 H
• such an F polymer has a TFE unit of 90 to 99 mol%, an HFP unit, a PAVE unit or a FAE unit of 0.5 to 9.97 mol%, and a functional group with respect to all the units constituting the polymer.
• F polymers containing 0.01 to 3 mol% of units respectively.
• Specific examples of such F polymers include the polymers described in International Publication No. 2018/16644.
• the melt viscosity of the F polymer in this method 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.
• the melting temperature of the F polymer in this method is preferably 200 to 320 ° C, more preferably 260 to 320 ° C. If such an F polymer is used, a layer (coating film) that is dense and has excellent adhesion is likely to be formed.
• the surfactant in this method is preferably a nonionic surfactant having a cloud point.
• the surfactant is preferably a compound having an alcoholic hydroxyl group or a polyoxyalkylene group, and more preferably a compound having an alcoholic hydroxyl group or a polyoxyalkylene group.
• a fluorine-based surfactant is preferable from the viewpoint of highly interacting with the F polymer and the liquid dispersion medium to further improve the physical properties of the liquid composition.
• the fluorine-based surfactant is a component (compound) different from that of the F polymer.
• the fluorine-based surfactant in this method is preferably an alkylene oxide adduct of a polyfluoroalkyl alcohol, or a copolymer of a monomer having a perfluoroalkyl group or a perfluoroalkenyl group and a monomer having an oxyalkylene group. These compounds are preferable because they have a high interaction with the F polymer and easily improve the dispersibility of the liquid composition.
• Examples of the alkylene oxide adduct include compounds represented by the formula R f1 (OCH 2 CH 2 ) a (OCH 2 CH (CH 3 )) b OH (in the formula, R f1 is a poly having 1 to 12 carbon atoms. It is a fluoroalkyl group, where a is 1 to 12 and b is 0 to 12). a is preferably 4 to 8. b is preferably 1 to 2.
• the copolymer a copolymer of a (meth) acrylate having a perfluoroalkyl group or a perfluoroalkenyl group and a (meth) acrylate having an oxyalkylene group is preferable.
• the affinity (interaction) of the fluorine-based surfactant with respect to the F polymer and the liquid dispersion medium is balanced, and the liquid composition in the present invention is formed in addition to the dispersion stability of the powder.
• Membrane properties are likely to improve.
• the weight average molecular weight of the copolymer is preferably 2000 to 80,000, more preferably 6000 to 20000.
• the fluorine content of the copolymer is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
• the content of the oxyalkylene group in the copolymer is preferably 10 to 60% by mass, more preferably 20 to 50% by mass.
• the hydroxyl value of the copolymer is preferably 10 to 300 mgKOH / g.
• the number of carbon atoms of the perfluoroalkyl group or the perfluoroalkenyl group is preferably 4 to 16.
• An ether oxygen atom may be inserted between the carbon atoms of the perfluoroalkyl group or the perfluoroalkenyl group.
• the oxyalkylene group may be composed of one kind of oxyalkylene group or two or more kinds of oxyalkylene group. In the latter case, different types of oxyalkylene groups may be arranged in a random manner or in a block shape.
• the oxyalkylene group is preferably an oxyethylene group or an oxypropylene group, more preferably an oxyethylene group.
• the copolymer include a copolymer of a (meth) acrylate having a perfluoroalkyl group or a perfluoroalkenyl group and a (meth) acrylate having a polyoxyalkylene group and an alcoholic hydroxyl group.
• copolymers include "Futergent” series (manufactured by Neos), “Surflon” series (manufactured by AGC Seimi Chemical), “Megafuck” series (manufactured by DIC), and “Unidyne” series (Daikin). (Made by Kogyo Co., Ltd.).
• the liquid dispersion medium in this method is a liquid dispersion medium that is liquid at 25 ° C. and does not react with F powder, and has a lower boiling point and is more volatile than the components other than the liquid dispersion medium contained in the liquid composition. Is preferable.
• the liquid dispersion medium one type may be used alone, or two or more types may be used in combination.
• the liquid dispersion medium may be polar or non-polar, and is preferably polar.
• the liquid dispersion medium may be water, an aqueous dispersion medium (a dispersion medium containing water and a water-soluble compound), or a non-aqueous dispersion medium.
• the boiling point of the liquid dispersion medium is preferably 80 to 275 ° C, more preferably 100 to 250 ° C. In this range, when the liquid dispersion medium is volatilized from the liquid composition to form a layer (coating film), the powder effectively flows and dense packing tends to proceed.
• liquid dispersion medium examples include water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-methoxy-2-propanol, N, N-dimethylformamide, N, N-dimethylacetamide, and methyl ethyl ketone.
• the liquid dispersion medium is preferably an aqueous dispersion medium.
• the aqueous dispersion medium forms a strong hydrogen bond with the surfactant. For this reason, the liquid composition containing the aqueous dispersion medium tends to foam, but the effect of this method for promoting defoaming by setting the gas phase temperature in the container to the cloud point of the surfactant or higher tends to work remarkably.
• the aqueous dispersion medium may consist only of water, or may be an aqueous dispersion medium. In this case, the proportion of water is preferably 90% by mass or more, and particularly preferably 95% by mass or more.
• the proportion of the F polymer in the liquid composition in this method is preferably 25 to 75% by mass, more preferably 30 to 60% by mass, and even more preferably 30 to 45% by mass. In this range, the storage stability and handleability of the contained liquid composition are likely to be improved.
• the ratio of the surfactant to the liquid composition is preferably 1 to 20% by mass, more preferably 3 to 15% by mass. In this range, the storage stability and handleability of the contained liquid composition are likely to be improved.
• the ratio of the liquid dispersion medium to the liquid composition is preferably 15 to 55% by mass, more preferably 25 to 50% by mass. In this range, the storage stability and handleability of the contained liquid composition are likely to be improved.
• the liquid composition in this method may contain other resin materials.
• other resin materials include epoxy resin, polyimide resin, polyamic acid which is a polyimide precursor, acrylic resin, phenol resin, liquid crystal polyester resin, polyolefin resin, modified polyphenylene ether resin, polyfunctional cyanate ester resin, and polyfunctional.
• Maleimide-Cyanic acid ester resin polyfunctional maleimide resin, vinyl ester resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, melamine-urea cocondensate resin, styrene resin, polycarbonate resin, polyimide resin, polysulfone, poly Examples thereof include allyl sulfone, aromatic polyamide resin, aromatic polyether amide, polyphenylene sulfide, polyallyl ether ketone, polyamideimide, and polyphenylene ether. These other resin materials may or may not be dissolved in the liquid composition. Further, the other resin material may be thermosetting or thermoplastic. Further, other resin materials may be modified.
• the liquid composition in this method is a thixotropic agent, a defoaming agent, a silane coupling agent, a dehydrating agent, a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, and a whitening agent.
• Coloring agent, conductive agent, mold release agent, surface treatment agent, viscosity modifier, flame retardant and other components may be contained.
• the viscosity of the liquid composition in this method at 25 ° C. is preferably 10 to 10000 mPa ⁇ s, more preferably 50 to 5000 mPa ⁇ s, and even more preferably 100 to 1000 mPa ⁇ s.
• the liquid composition has excellent liquid properties (dispersibility and coatability) and compatibility with different materials.
• the thixotropy ratio of the liquid composition in this method is preferably 1 to 2.5, more preferably 1.2 to 2. In this case, not only the liquid physical properties of the liquid composition are excellent, but also the homogeneity of the layer (coating film) is likely to be improved.
• the contained liquid composition obtained by this method is useful as a coating agent for forming a layer (coating film) containing an F polymer on the surface of a base material.
• the material of the base material is not particularly limited, and glass or metal is preferable.
• the shape of the base material is not particularly limited, and may be any shape such as a plate shape, a spherical shape, and a fibrous shape.
• the thickness of the layer (coating film) to be formed is not particularly limited, and is preferably 0.1 to 1000 ⁇ m. When the above liquid composition is used, the layer and coating are excellent in adhesion regardless of the material and shape of the base material, the thickness of the layer (coating film), etc., and the original physical properties of the F polymer are sufficiently expressed. Films and molded products can be obtained.
• the above liquid composition can be used for manufacturing molded products such as films, impregnated materials (prepregs, etc.), laminated plates (metal laminated plates such as metal foils with polymer layers), mold releasability, electrical characteristics, water and oil repellency, and resistance. It can be used in the manufacture of molded products for applications that require chemical resistance, weather resistance, heat resistance, slipperiness, abrasion resistance, and the like.
• the obtained molded products are useful as antenna parts, printed substrates, aircraft parts, automobile parts, sports equipment, food industry supplies, paints, cosmetics, etc.
• wire coating materials aircraft bearings
• Electrical insulation tape Insulation tape for oil drilling
• Material for printed substrate Material for printed substrate
• Separation membrane precision filtration membrane, ultrafiltration membrane, reverse osmosis membrane, ion exchange membrane, dialysis membrane, gas separation membrane, etc.
• electrode binder For lithium secondary batteries, fuel cells, etc.
• copy rolls furniture, automobile dashboards, covers for home appliances, sliding members (load bearings, sliding shafts, valves, bearings, gears, cams, belt conveyors, food transport It is useful as a bearing for containers), tools (shovels, shavings, cuttings, saws, etc.), boilers, hoppers, pipes, ovens, baking molds, chutes, dies, toilet bowls, and container covering materials.
• the laminated board is obtained by applying the above liquid composition to the surface of a base material and heating it to form a polymer layer containing an F polymer.
• a laminate has a base material and a polymer layer in this order.
• the liquid composition can be applied by a spray method, a roll coating method, a spin coating method, a gravure coating method, a micro gravure coating method, a gravure offset method, a knife coating method, a kiss coating method, a bar coating method, a die coating method, or a fountain Mayer bar method. , Slot die coat method and other methods.
• the heating is preferably performed in a temperature range in which the F polymer is fired.
• the heating may be carried out in one step at a constant temperature, or may be carried out in two or more steps at different temperatures.
• 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 base material is not particularly limited, and may be any of a metal base material such as copper, aluminum, and iron, a glass base material, a resin base material, a silicon base material, and a ceramic base material.
• the shape of the base material is not particularly limited, and may be flat, curved, uneven, foil-shaped, plate-shaped, film-shaped, or fibrous.
• Specific examples of the laminate formed from the liquid composition include a metal foil with a resin in which the base material is a metal foil and the metal foil and the polymer layer are provided in this order.
• An adhesive layer may be provided separately between the metal foil and the polymer layer, but since the polymer layer has excellent adhesiveness, the adhesive layer may not be provided.
• the metal constituting the metal foil examples include copper, copper alloy, stainless steel, nickel, nickel alloy (including 42 alloy), aluminum, and aluminum alloy.
• a copper foil is preferable, a rolled copper foil having no distinction between the front and back sides or an electrolytic copper foil having a distinction between the front and back sides is more preferable, and a rolled copper foil is further preferable. Since the rolled copper foil has a small surface roughness, transmission loss can be reduced even when a metal foil with resin is processed into a printed wiring board.
• a rust preventive layer oxide film such as chromate
• a heat resistant layer a roughening treatment layer, and a silane coupling agent treatment layer may be provided on the surface of the metal foil.
• the thickness of the metal foil may be a thickness that can exhibit sufficient functions in the application of the metal foil with resin.
• the thickness of the metal foil is preferably 2 to 40 ⁇ m, more preferably 2 to 15 ⁇ m.
• the resin-attached metal foil may have a polymer layer in contact with at least one surface of the metal foil.
• the layer structure include a metal foil / polymer layer, a metal foil / polymer layer / metal foil, a polymer layer / metal foil / polymer layer, and a metal foil / polymer layer / other substrate / polymer layer / metal foil.
• the "metal foil / polymer layer” indicates that the metal foil and the polymer layer are laminated in this order, and the same applies to other layer configurations.
• the thickness of the polymer layer is preferably 1 to 100 ⁇ m, more preferably 5 to 75 ⁇ m, still more preferably 10 to 50 ⁇ m.
• the metal foil with resin has high peel strength between the polymer layer and the metal foil. The peel strength is preferably 10 N / cm or more.
• the metal foil with resin includes a polymer layer containing F polymer, it is excellent in physical properties such as heat resistance and electrical characteristics, and is useful as an electronic substrate material such as a flexible printed wiring board and a rigid printed wiring board.
• a printed wiring board can be manufactured from a metal foil with resin by etching a metal foil and processing it into a metal conductor wiring (transmission circuit) having a predetermined pattern.
• 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.
• a plurality of printed wiring boards having the above configuration may be multi-layered.
• the liquid composition may be used to form an interlayer insulating film, a solder resist, or a coverlay film on a printed wiring board.
• the metal foil may be removed from the resin-attached metal foil to prepare a film containing an F polymer composed of a single polymer layer.
• wet etching and dry etching can be used for removing the metal foil, and it is preferable to use wet etching.
• Wet etching is preferably performed using an acid solution.
• the functional groups are activated by the acid solution, so that the adhesiveness of the surface (contact surface) of the film after the metal foil is removed is likely to be enhanced.
• activation of the functional group conversion of an acid anhydride group into a 1,2-dicarboxylic acid group can be mentioned.
• An inorganic acid aqueous solution such as hydrochloric acid, dilute nitric acid or hydrofluoric acid can be used as the acid solution.
• an inorganic acid aqueous solution such as hydrochloric acid, dilute nitric acid or hydrofluoric acid can be used as the acid solution.
• the impregnated material (coated base material) is obtained by immersing the base material in the above liquid composition, pulling up the base material from the liquid composition, heating the base material, and coating the base material with a coating layer containing an F polymer. ..
• the definition and shape of the base material in the impregnated material and the heating conditions are the same as the definition and shape of the base material in the above-mentioned laminate and the heating conditions, including their preferable modes and ranges.
• the base material is preferably a fiber base material. If a fiber base material is used, the impregnation rate of the liquid composition is sufficiently increased.
• a heat-resistant woven fabric that can withstand heating is preferable, a glass fiber woven fabric, a carbon fiber woven fabric, an aramid fiber woven fabric or a metal fiber woven fabric is more preferable, and a glass fiber woven fabric or a carbon fiber woven fabric is further preferable.
• a plain weave glass fiber woven fabric composed of E glass yarn for electrical insulation defined in JIS R 3410: 2006 is used as the fiber base material.
• the liquid composition of the present invention (hereinafter, also referred to as “the present composition”) includes an F polymer powder, a water-soluble surfactant exhibiting acidity (hereinafter, also referred to as “acidic surfactant”), and the like. Including with water.
• This composition is a dispersion liquid (powder dispersion liquid) in which F polymer powder is dispersed in the form of particles. Then, the present composition exhibits acidity (pH 5 or less) as a whole.
• the acidic surfactant is a compound different from the F polymer.
• the present composition is characterized in that the acidic surfactant itself, which highly disperses the powder, is water-soluble and acidic.
• the acidic surfactant releases protons as an acid source and continues to promote stable dispersion of the powder. Therefore, in this composition, not only the antibacterial effect is exhibited well, but also the powder (F polymer) itself and the present composition are not easily deteriorated.
• the present composition is difficult for germs and the like to propagate, can be stored for a long period of time, and includes an embodiment of a molded product (a polymer layer formed on the surface of a base material) formed from the present composition.
• a molded product a polymer layer formed on the surface of a base material formed from the present composition.
• the physical properties (electrical properties, heat resistance, etc.) of the F polymer itself are well maintained.
• the present composition is less likely to generate an unpleasant odor generated when amines are used for pH adjustment. The above effects are more prominently exhibited in a preferred embodiment of the present composition described later.
• the D50 of the powder in the present composition is preferably 40 ⁇ m or less, more preferably 20 ⁇ m or less, still more 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 even more 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 molded product are most likely to be exhibited.
• the sparse filling bulk density of the powder is preferably 0.08 to 0.5 g / mL.
• the densely packed bulk density of the powder is 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 composition may contain a resin other than the F polymer, but is preferably made of the F polymer.
• 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 composition is a polymer containing a unit (TFE unit) based on tetrafluoroethylene (TFE), may be a homopolymer of TFE, or may be a copolymer of TFE and another comonomer. ..
• the F polymer preferably contains 90 to 100 mol% of TFE units with respect to all the units constituting the polymer.
• the fluorine content of the F polymer is preferably 70 to 76% by mass, more preferably 72 to 76% by mass.
• F polymers include polytetrafluoroethylene (PTFE), TFE and ethylene copolymer (ETFE), TFE and propylene copolymer, TFE and perfluoro (alkyl vinyl ether) (PAVE) copolymer (PFA), and TFE and hexa.
• PTFE polytetrafluoroethylene
• ETFE ethylene copolymer
• PAVE perfluoro (alkyl vinyl ether) copolymer
• PFA perfluoro (alkyl vinyl ether) copolymer
• TFE and hexa examples include copolymers with fluoropropylene (HFP) (FEP), copolymers with TFE and fluoroalkylethylene (FAE), and copolymers with TFE and chlorotrifluoroethylene (CTFE).
• the copolymer may further contain units based on other comonomeres.
• PTFE In addition to homopolymers of TFE, PTFE also includes copolymers of trace amounts of comonomer (PAVE, HFP, FAE, etc.) and TFE (so-called modified PTFE).
• the modified PTFE preferably contains 99.5 mol% or more of TFE units, more preferably 99.9 mol% or more, based on all the units contained in this polymer.
• the melt viscosity of the modified PTFE at 380 ° C. is preferably 1 ⁇ 10 2 to 1 ⁇ 10 8 Pa ⁇ s, more preferably 1 ⁇ 10 3 to 1 ⁇ 10 6 Pa ⁇ s.
• modified PTFE include low molecular weight PTFE.
• Low-molecular-weight PTFE is obtained by irradiating high-molecular-weight PTFE (melt viscosity is about 1 ⁇ 10 9 to 1 ⁇ 10 10 Pa ⁇ s) with radiation (International Publication No. 2018/026012, International Publication No. 2018). (Polymer described in / 026017 etc.) may be used, and PTFE (Japanese Patent Laid-Open No. 2009-1745, International Publication No. 2010/114033) obtained by using a chain transfer agent when polymerizing TFE to produce PTFE. No., Polymer described in Japanese Patent Application Laid-Open No.
• a polymer having a core-shell structure composed of a core portion and a shell portion, and only the shell portion has the above-mentioned melt viscosity (Polymer described in Japanese Patent Application Laid-Open No. 2005-527652, International Publication No. 2016/170918, Japanese Patent Application Laid-Open No. 09-087334, etc.) may be used.
• the standard specific gravity of low molecular weight PTFE (specific gravity measured according to ASTM D4895-04) is preferably 2.14 to 2.22, and more preferably 2.16 to 2.20.
• modified PTFE, PFA or FEP is preferable from the viewpoint of easily imparting excellent physical properties (electrical properties, etc.) to the molded product.
• the F polymer is preferably an F polymer having an acidic functional group from the viewpoint of enhancing the interaction with the acidic surfactant.
• An acidic functional group is an acidic group or a group derived from an acidic group. Since the present composition exhibits acidity by the action of an acidic surfactant, alteration of the F polymer having an acidic functional group and the like can be preferably prevented, and physical properties based on the F polymer can be appropriately imparted to the molded product. In other words, the composition is suitable for use with F polymer powders having acidic functional groups.
• the adhesiveness (peeling strength) between the polymer layer and the base material can be enhanced when the polymer layer is molded on the surface of the base material.
• a carbonyl group-containing group is preferable.
• the carbonyl group-containing group is a group containing a carbonyl group (> C (O)), a monocarboxyl group, an alkoxycarbonyl group, an acid anhydride residue (-C (O) OC (O)-), and a dicarboxylic acid residue. Examples include groups (-CH (C (O) OH) CH 2 C (O) OH, etc.).
• the F polymer having an acidic functional group a copolymer containing a unit based on a monomer having an acidic functional group (hereinafter, also referred to as “acid monomer”) and a TFE unit, and an acidic functional group introduced by plasma treatment or corona treatment.
• acid monomer a monomer having an acidic functional group
• examples thereof include polymers in which the acidic functional groups have been introduced by the action of a polymerization initiator or a chain transfer agent.
• the F polymer having an acidic functional group is preferably a polymer having a TFE unit and a unit based on an acid monomer (hereinafter, also referred to as "acid unit”), and is based on a TFE unit, a unit based on PAVE (PAVE unit), and an HFP.
• a polymer having a unit (HFP unit) or a unit based on FAE (FAE unit) (hereinafter, also collectively referred to as "PAE unit”) and an acid unit is more preferable.
• the ratio of TFE units is preferably 50 to 99 mol%, more preferably 90 to 99 mol%, of all the units constituting the F polymer.
• the PAVE unit is preferably a PAVE unit or an HFP unit, and more preferably a PAVE unit.
• the PAE unit may be two or more types.
• the ratio of PAE units is preferably 0 to 10 mol%, more preferably 0.5 to 9.97 mol%, of all the units constituting the F polymer. Examples of PAVE and FAE include the compounds exemplified in this method.
• the acid monomer examples include itaconic anhydride, citraconic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride (also known as hymic anhydride; hereinafter also referred to as “NAH”) or maleic anhydride.
• the ratio of the acid unit is preferably 0.01 to 3 mol% of all the units constituting the F polymer.
• the F polymer in this case may further contain units other than the TFE unit, the PAE unit and the acid unit.
• the monomer forming the above unit include ethylene, propylene, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, and chlorotrifluoroethylene.
• the proportion of the other units in the F polymer is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, of all the units constituting the F polymer.
• the F polymer is preferably an F polymer having a CH bond in the main chain.
• the CH bond include a CH bond contained at the end of the F polymer and a CH bond contained in a unit based on a hydrocarbon-based monomer (acid monomer or the like).
• the CH bond is activated by the action of the adjacent CF bond, and is in a state where it easily reacts with a base. Since the present composition exhibits acidity by the action of an acidic surfactant, even such an F polymer has high stability, and thus physical properties based on the F polymer can be appropriately imparted to the molded product.
• the composition is suitable for use with F-polymer powders having a CH bond in the main chain.
• the melting temperature of the F polymer is preferably 200 to 320 ° C, more preferably 260 to 320 ° C. In this case, it is easy to further improve the adhesiveness of the powder. Further, if such an F polymer is used, a molded product having excellent surface flatness can be easily formed.
• 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.
• the solubility [g / 100 g-H 2 O] of the acidic surfactant in water at 25 ° C. in this composition is preferably 10 or more, and more preferably 10 to 30.
• the pH of the aqueous solution obtained by dissolving the acidic surfactant in water in an amount of 10% by mass is preferably 5 or less, more preferably 4 or less, still more preferably 3 to 4.
• the pH of this composition is 5 or less, preferably 2.5 to 4.5.
• the composition having such a high acidity is more excellent in antibacterial effect.
• the acidic surfactant in the present composition is preferably a water-soluble fluorine-based surfactant that exhibits acidity.
• the acidic surfactant preferably contains a nonionic compound as a compound that exhibits a surface-active action. In this case, since there is no release of metal ions or the like that form salts in the present composition that exhibits strong acidity, the original physical properties of the F polymer are not easily impaired.
• the acidic surfactant in the present composition preferably contains an alkylene oxide adduct of a polyfluoroalkyl alcohol, or a copolymer of a monomer having a perfluoroalkyl group or a perfluoroalkenyl group and a monomer having an oxyalkylene group. These compounds are preferable because they have a high interaction with the F polymer and not only easily improve the dispersibility of the present composition, but also easily adjust the acidity thereof at the time of preparation thereof.
• the alkylene oxide adduct is a reaction product obtained by adding an alkylene oxide to a polyfluoroalkyl alcohol, and if the reaction conditions are selected and the number of alkylene oxides added and the terminal structure are adjusted, the acidity thereof can be adjusted. Easy to adjust.
• the carboxylic acid compound can be adjusted by oxidizing at least a part of the terminal structure, and the acidity of the surfactant can be adjusted by the presence of the carboxylic acid compound.
• the above-mentioned copolymer is a reaction product obtained by copolymerizing both monomers, and its acidity can be easily adjusted by selecting the reaction conditions and post-treatment conditions in the copolymerization.
• the carboxylic acid compound can be adjusted by oxidizing at least a part of the terminal structure of the monomer having an oxyalkylene group, and the acidity of the surfactant can be adjusted by the presence of the carboxylic acid compound.
• the preferred embodiment of the alkylene oxide adduct and the copolymer is the same as that of the alkylene oxide adduct and the copolymer in the present method described above.
• the dispersion medium in this composition contains water.
• the dispersion medium may contain a dispersion medium other than water.
• the dispersion medium may be a liquid at 25 ° C.
• the dispersion medium is preferably a water-soluble polar dispersion medium from the viewpoint of being easily mixed uniformly with water. When such a dispersion medium is used, the dispersibility of the powder in the liquid composition is further enhanced. In this case, the proportion of water is preferably 90% by mass or more, more preferably 95% by mass or more.
• the water-soluble polar dispersion medium may be protic or aprotic. As the polar dispersion medium, one type may be used alone, or two or more types may be used in combination.
• the polar dispersion medium is preferably an amide, alcohol, sulfoxide, ester, ketone or glycol ether, and more preferably a ketone or amide.
• the water-soluble polar dispersion medium examples include methanol, ethanol, isopropanol, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, methyl ethyl ketone, methyl isopropyl ketone, and cyclo.
• examples thereof include pentanone, cyclohexanone, ethylene glycol monoisopropyl ether, and cellosolve (methyl cellosolve, ethyl cellosolve, etc.).
• the water-soluble polar dispersion medium is particularly preferably methyl ethyl ketone, cyclohexanone or N-methyl-2-pyrrolidone.
• the composition further preferably contains a preservative.
• a preservative When used in combination with a preservative, the antibacterial effect of this composition is significantly enhanced.
• the preservative is preferably pyrolytic.
• the thermal decomposition start temperature of the preservative is preferably 210 ° C. or lower, more preferably 100 to 210 ° C., and even more preferably 125 to 200 ° C. Since the preservative at such a thermal decomposition start temperature is difficult to decompose at room temperature, the antibacterial effect can be suitably enhanced in the present composition.
• the preservative is preferably a nonionic organic compound.
• such a preservative Due to the high interaction with the F polymer and the surfactant, such a preservative easily adheres to the surface of the powder particles, and can effectively exert an effect of enhancing the antibacterial effect.
• preservatives are easily decomposed by heating when forming a molded product, they are unlikely to remain in the obtained molded product, thereby preventing deterioration of the electrical characteristics (low dielectric constant, etc.) and heat resistance of the molded product. Or it can be suppressed.
• preservatives include isothiazoline compounds, imidazole compounds, guanidine compounds, triazole compounds, benzothiazole compounds, nitroalcohol compounds, nitropropane compounds, dithiol compounds, thiophene compounds, and dithiocarbamate compounds.
• preservatives containing isothiazolin-based compounds are preferably used. Examples of commercially available products of such preservatives include "Biohope" and "KB-838" manufactured by KI Kasei Co., Ltd.
• the amount of the F polymer contained in the present composition is preferably 10% by mass or more, more preferably 20 to 50% by mass. In this case, it is easy to form a molded product having excellent physical properties (particularly, electrical characteristics).
• the amount of the surfactant contained in the present composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. In this case, the dispersibility of the powder in the present composition is further enhanced, and the physical properties (thermal conductivity, scratch resistance, etc.) of the molded product are more likely to be improved.
• the amount of the dispersion medium (including the case of water alone) contained in the present composition is preferably 15 to 55% by mass, more preferably 25 to 50% by mass.
• the coatability of the present composition is excellent, and the film-forming property is likely to be improved.
• the amount of the preservative contained in the present composition is preferably 1% by mass or less, more preferably 0.5% by mass or less.
• the present composition may contain other resin materials and other components as long as the effects of the present invention are not impaired.
• the preferred embodiments of the other resin material and other components in the composition are the same as the preferred embodiments of the other resin material and other components in the present method.
• the viscosity of the composition at 25 ° C. is preferably 10,000 mPa ⁇ s or less, more preferably 50 to 5000 mPa ⁇ s, and even more preferably 100 to 1000 mPa ⁇ s.
• the thixotropy of the present composition is preferably 1 to 2.5, more preferably 1.2 to 2. In this case, not only the dispersibility of the present composition is excellent, but also the homogeneity of the molded product is likely to be improved.
• this composition it is preferable to mix this composition with a polymer-containing liquid exhibiting alkalinity and adjust the pH to more than 5, and it is more preferable to adjust the pH to alkaline before use.
• a polymer-containing liquid exhibiting alkalinity and adjust the pH to more than 5, and it is more preferable to adjust the pH to alkaline before use.
• the acidic composition is applied to a base material (particularly a metal base material) to form a molded product
• deterioration or deterioration of the base material can be easily prevented.
• deterioration and deterioration of the polymer mixed with the present composition can be prevented, and the obtained molded product can be suitably imparted with properties based on the polymer to be mixed.
• the polymer-containing liquid include a liquid composition in which PTFE powder is dispersed in water. This liquid composition is usually adjusted to a pH in the alkaline region by adding ammonia or the like. If a molded product is formed by mixing the liquid composition and the present composition
• the present composition When the present composition is applied to the surface of a base material and heated to form a polymer layer containing an F polymer, a laminate having the base material and the polymer layer in this order can be obtained.
• the definition of the laminate formed from the composition is similar to that of the laminate in the present method, including preferred embodiments and ranges.
• the method for producing the container and the liquid composition of the present invention have been described above, the present invention is not limited to the configuration of the above-described embodiment.
• the method for producing an inclusion body and the liquid composition of the present invention may additionally have any other configuration or are replaced with any configuration that produces the same effect in the configuration of the above embodiment. You can.
• Powder 1 Powder composed of PTFE having no acidic functional group (D50: 0.3 ⁇ m)
• Powder 2 A powder (melting temperature: 300 ° C.) containing 98.0 mol%, 0.1 mol%, and 1.9 mol% of TFE units, NAH units, and PPVE units in this order and having a functional group.
• D50 1.8 ⁇ m
• D90 5.2 ⁇ m
• Surfactant 1 Formula F (CF 2 ) 6 CH 2 CH 2 O (CH 2 CH 2 O) 7 CH 2 CH (CH 3 ) Represented by OH, ethylene oxide and propylene oxide are added to the fluoroalkyl alcohol in this order.
• Alkylene oxide adduct of fluoroalkyl alcohol obtained by addition reaction (nonionic, cloud point: 60 ° C., solubility: 30 or more [g / 100 g-H 2 O], pH: 3.5)
• Surfactant 2 Copolymer of methacrylate having a perfluoroalkenyl group and methacrylate having a polyoxyalkylene group and an alcoholic hydroxyl group (nonionic, cloud point: 62 ° C., solubility: 30 or more [g / 100 g-H 2 O] , PH: 3.5)
• aqueous dispersion liquid composition
• Example 1 (Comparative Example)
• Example 2 Diisopropylamine was added to the aqueous dispersion 1 to obtain an aqueous dispersion 2 having a pH adjusted to 9.0.
• Example 3 (Comparative example)
• Hydrochloric acid was added to the aqueous dispersion 1 to obtain an aqueous dispersion 3 having a pH adjusted to 3.0.
• Example 4 After putting 40 parts by mass of powder 1, 10 parts by mass of surfactant 1 and 50 parts by mass of distilled water into a pot, zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to prepare an aqueous dispersion 4 (pH: 4.5).
• Example 5 An aqueous dispersion 5 (pH: 4.5) was prepared in the same manner as in Example 4 except that the surfactant 2 was used instead of the surfactant 1.
• Example 6 40 parts by mass of powder 2, 10 parts by mass of surfactant 1, and 0.5 parts by mass of an isothiazolin-based compound-containing preservative (KAI Kasei Co., Ltd., "Biohope"), 49. After putting 5 parts by mass of distilled water into the pot, zirconia balls were put into the pot. Then, the pot was rolled at 150 rpm for 1 hour to prepare an aqueous dispersion 6 (pH: 4.5). (Example 7) An aqueous dispersion 7 (pH: 4.5) was prepared in the same manner as in Example 6 except that the surfactant 2 was used instead of the surfactant 1.
• Example 8 An aqueous dispersion of PTFE (pH: 9, manufactured by AGC Co., Ltd., "AD-911E") and an aqueous dispersion 6 are mixed to obtain PTFE with respect to the total content of PTFE and a polymer having an acidic functional group.
• Example 9 (Comparative example)
• a liquid composition from a storage tank containing a liquid composition liquid temperature: 25 ° C., viscosity: 200 mPa ⁇ s) containing 40 parts by mass of powder 2, 10 parts by mass of surfactant 2, and 50 parts by mass of water.
• a liquid composition liquid temperature: 25 ° C., viscosity: 200 mPa ⁇ s
• another container internal volume 3 L
• the liquid composition violently foamed and foam was formed, so that filling took a long time.
• Example 10 When the liquid composition is filled into the container as in Example 9, as a result of passing hot air at 70 ° C. through the gas phase portion in the container, the formation of bubbles is suppressed and the liquid composition is filled in a short time (within 1 minute). Is finished.
• Example 11 (Comparative example) After pouring 10 parts by mass of surfactant 1 and 50 parts by mass of water into a tank equipped with a stirrer and a temperature control mechanism, the temperature inside the tank was maintained at 25 ° C., and the inside of the tank was stirred while stirring. Further, as a result of sequentially adding 40 parts by mass of the powder 2, the foaming was intense, and it took a long time to produce the liquid composition. (Example 12) When the powder 2 is put into the tank as in Example 11, the liquid phase temperature in the tank is maintained at 25 ° C., and hot air is circulated in the tank to keep the gas phase temperature in the tank at 70 ° C.
• Example 13 When the powder 2 is put into the tank as in Example 11, the liquid phase temperature in the tank is maintained at 25 ° C., and the lid of the container is heated with hot air to maintain the gas phase temperature in the tank at 80 ° C. Since the formed foam comes into contact with the lid and quickly defoams, the sequential addition of powder 2 is completed quickly, and the liquid phase in the tank can be vigorously stirred, so that the liquid composition can be produced in a short time. Completed.
• the liquid composition in the present invention can be used for producing films, impregnated materials (prepregs, etc.), laminates, etc., and can be used for applications requiring electrical properties, heat resistance, and the like. Further, the laminate can be processed and used for antenna parts, printed wiring boards, insulating layers of power semiconductors, aircraft parts, automobile parts and the like.

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• 2020
  • 2020-06-10 JP JP2021526107A patent/JPWO2020250919A1/ja active Pending
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