WO2018008421A1 - Composition de revêtement en poudre, film de revêtement, et article revêtu - Google Patents

Composition de revêtement en poudre, film de revêtement, et article revêtu Download PDF

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Publication number
WO2018008421A1
WO2018008421A1 PCT/JP2017/023031 JP2017023031W WO2018008421A1 WO 2018008421 A1 WO2018008421 A1 WO 2018008421A1 JP 2017023031 W JP2017023031 W JP 2017023031W WO 2018008421 A1 WO2018008421 A1 WO 2018008421A1
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polymer
mol
group
powder
vinylidene fluoride
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PCT/JP2017/023031
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English (en)
Japanese (ja)
Inventor
普巳子 茂内
中谷　安利
敏雄 宮谷
博丈 今田
智洋 城丸
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ダイキン工業株式会社
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Publication of WO2018008421A1 publication Critical patent/WO2018008421A1/fr

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    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/16—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer formed of particles, e.g. chips, powder or granules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/18—Monomers containing fluorine
    • C08F14/22—Vinylidene fluoride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • 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
    • C09D127/16—Homopolymers or copolymers of vinylidene fluoride
    • 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
    • C09D5/03—Powdery paints

Definitions

  • the present invention relates to a powder coating material, a coating film, and a coated article.
  • the fluororesin is excellent in heat resistance, chemical resistance, and weather resistance, and has excellent properties such that the surface of the molded product or coating film is non-adhesive and has a small coefficient of friction.
  • it is difficult to adhere to other materials attempts have been made to improve adhesiveness by introducing a functional group into the fluororesin.
  • Patent Document 1 discloses a cyclic hydrocarbon monomer having a repeating unit (a) based on tetrafluoroethylene and / or chlorotrifluoroethylene, a dicarboxylic anhydride group, and a polymerizable unsaturated group in the ring.
  • a repeating unit (b) Containing a repeating unit (b) based on the repeating unit (b) and other monomer (excluding tetrafluoroethylene, chlorotrifluoroethylene and the cyclic hydrocarbon monomer), the repeating unit (a) and the repeating unit
  • the repeating unit (a) is 50 to 99.89 mol% and the repeating unit (b) is 0.01 to 5 mol% based on the total molar amount of (b) and the repeating unit (c).
  • a unit (c) is from 0.1 to 49.99 mol%, the fluorine-containing, wherein the volume flow rate is 0.1 ⁇ 1000 mm 3 / sec Polymers have been described.
  • Patent Document 2 discloses a fluorine-containing ethylene having a carbonate group or a carboxylic acid halide group at a polymer chain terminal or a side chain, and the number of these groups is 150 or more with respect to 1 ⁇ 10 6 carbon atoms in the main chain.
  • a fluorine-containing adhesive material made of a conductive polymer is described.
  • Patent Document 3 discloses a binder containing a fluorine-containing polymer, wherein the fluorine-containing polymer is a polymer unit based on vinylidene fluoride and an amide group (—CO—NRR ′ (R and R ′ are the same). Or differently, each represents a hydrogen atom or an optionally substituted alkyl group.)) Or an amide bond (—CO—NR ′′ — (R ′′ represents a hydrogen atom, an optionally substituted alkyl).
  • Patent Document 4 contains a repeating unit (A) based on tetrafluoroethylene, a repeating unit (B) based on ethylene, and a repeating unit (C2) based on a monomer having an acid anhydride group and a polymerizable unsaturated bond.
  • Fluorine-containing dispersion medium having a powder (Y) content of 1 to 30 parts by mass and a boiling point of 50 to 200 ° C. (100 parts by mass of the polymer powder (X))
  • a primer composition is described in which the content of Z) is 20 to 500 mass.
  • JP 2006-152234 A International Publication No. 99/45044 JP 2013-2119016 A JP2015-134865A
  • An object of this invention is to provide the powder coating material which does not produce foam at the time of coating-film formation, and can form the coating film excellent in adhesiveness with a base material.
  • the present invention provides a coated film having a good appearance and excellent adhesion of the substrate, and a coated article having a good appearance of the coated film and having the substrate and the coated film firmly adhered to each other. The purpose is to do.
  • the present invention relates to a powder coating material comprising a polymer containing vinylidene fluoride units and having at least one terminal group selected from the group consisting of —CONH 2 groups and —COOH groups at the ends of the main chain. It is.
  • the polymer preferably has 50 or more end groups per 10 6 main chain carbon atoms of the polymer.
  • the polymer contains a vinylidene fluoride unit and a tetrafluoroethylene unit, the vinylidene fluoride unit is 10.0 to 98.0 mol% of the total monomer units constituting the polymer, and the tetrafluoroethylene unit is the above It is preferably 2.0 to 90.0 mol% of all monomer units constituting the polymer.
  • This invention is also a coating film characterized by being formed from the above-mentioned powder coating material.
  • the present invention is also a coated article comprising a substrate and a coating film of the above-described powder coating material provided on the substrate.
  • the powder coating material of the present invention comprises a polymer containing vinylidene fluoride units and having at least one terminal group selected from the group consisting of —CONH 2 group and —COOH group at the main chain terminal. To do.
  • the relationship between the presence of these end groups and the adhesion of the polymer containing the vinylidene fluoride unit is a finding found by the present inventors. In the case of a polymer that does not contain vinylidene fluoride units, even if these end groups are included, no significant improvement in adhesion as in the case of polymers containing vinylidene fluoride units is observed.
  • the polymer preferably has 50 or more end groups per 10 6 main chain carbon atoms of the polymer.
  • the number of end groups is more preferably 80 or more.
  • the upper limit is not particularly limited, and all of the ends of the main chain may be the above-mentioned end groups, but may be 10,000, preferably 1000.
  • the number of —CONH 2 groups appears at 2900 to 3100 cm ⁇ 1 due to CH 2 groups of the main chain in the infrared absorption spectrum obtained by performing infrared spectrum analysis on a film having a thickness of 200 ⁇ m.
  • the absorbance of the peak is normalized to 1.0, and the absorbance A of the peak due to the NH bond of the terminal NH 2 group appearing in the vicinity of 3400 to 3470 cm ⁇ 1 of the spectrum is obtained and calculated by the following formula.
  • Number of —CONH 2 groups per 10 6 main chain carbon atoms 4258 ⁇ A
  • the number of —COOH groups is 2900 to 3100 cm ⁇ 1 due to the CH 2 group of the main chain in the obtained infrared absorption spectrum by performing infrared spectrum analysis on a film having a thickness of 200 ⁇ m.
  • the absorbance of the peak that appears is normalized to 1.0, and the absorbance A of the peak due to the C ⁇ O bond of the terminal COOH group that appears in the vicinity of 1700 to 1780 cm ⁇ 1 of the spectrum is obtained and calculated by the following equation.
  • Number of —COOH groups per 10 6 main chain carbon atoms 4057 ⁇ A
  • the polymer preferably has 0 to 40 —OCOOR groups at the end of the main chain per 10 6 main chain carbon atoms, more preferably 0 to 20 units. 0 is more preferable.
  • R in the —OCOOR group is preferably a linear or branched alkyl group, and the alkyl group may have 1 to 15 carbon atoms.
  • the polymer contains vinylidene fluoride units.
  • the vinylidene fluoride unit is preferably 10.0 to 100 mol%, more preferably 10.0 to 98.0 mol% of the total monomer units constituting the fluororesin, More preferably, it is 0.0 to 95.0 mol%.
  • a tetrafluoroethylene unit is included further.
  • vinylidene fluoride units are 10.0 to 98.0 mol% of all monomer units constituting the polymer, and tetrafluoroethylene units are 2.0 to 90% of all monomer units constituting the polymer. It is preferably 0.0 mol%. More preferably, the vinylidene fluoride unit is 15.0 to 95.0 mol% of all monomer units constituting the polymer, and the tetrafluoroethylene unit is 5.0 to 5.0% of all monomer units constituting the polymer. 85.0 mol%.
  • CX 11 X 12 CX 13 (CX 14 X 15 ) n11 X 16 (Wherein X 11 to X 16 are the same or different and each represents H, F or Cl, and n11 represents an integer of 0 to 8, except for tetrafluoroethylene and vinylidene fluoride)
  • the vinylidene fluoride unit is 10.0 to 97.9 mol% of the total monomer units constituting the polymer, and the tetrafluoroethylene
  • the unit is 2.0 to 89.9 mol% of the total monomer unit constituting the polymer, and the ethylenically unsaturated monomer unit is 0.1 to 5.0 mol% of the total monomer unit constituting the polymer. It may be.
  • vinylidene fluoride units are 10.0 to 49.9 mol% of all monomer units constituting the polymer, and tetrafluoroethylene units are 50.0 to 85% of all monomer units constituting the polymer. 0.0 mol%, and the ethylenically unsaturated monomer unit is 0.1 to 5.0 mol% of the total monomer units constituting the polymer. More preferably, the vinylidene fluoride unit is 15.0 to 49.9 mol% of the total monomer units constituting the polymer, and the tetrafluoroethylene unit is 50.0% to the total monomer units of the polymer. 70.0 mol%, and the ethylenically unsaturated monomer unit is 0.1 to 5.0 mol% of the total monomer units constituting the polymer.
  • the polymer is 55.0-90.0 mol% tetrafluoroethylene, 5.0 to 49.9 mol% vinylidene fluoride, and 0.1 to 10.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), It is preferable that the polymer contains a copolymer unit.
  • the polymer is 55.0-90.0 mol% tetrafluoroethylene, 9.2-44.2 mol% vinylidene fluoride, and A polymer containing 0.1 to 0.8 mol% of an ethylenically unsaturated monomer represented by the formula (2) and a copolymer unit is also preferred.
  • the polymer is 55.0-90.0 mol% tetrafluoroethylene, 5.0-44.8 mol% vinylidene fluoride, 0.1 to 10.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and 0.1 to 0.8 mol% of an ethylenically unsaturated monomer represented by the formula (2), It is also preferable that the polymer contains a copolymer unit.
  • the polymer is 58.0-85.0 mol% tetrafluoroethylene, 9.5-39.8 mol% vinylidene fluoride, 0.1 to 5.0 mol% of an ethylenically unsaturated monomer represented by the formula (1), and 0.1 to 0.5 mol% of an ethylenically unsaturated monomer represented by the formula (2), It may be a polymer containing the copolymerized unit.
  • the polymer When the content of each monomer is within the above range, the polymer is excellent in mechanical strength, chemical resistance and low permeability at high temperatures.
  • the low permeability at a high temperature is, for example, low permeability to methane, hydrogen sulfide, CO 2 , methanol, hydrochloric acid and the like.
  • the content of each monomer in the polymer can be calculated by appropriately combining NMR and elemental analysis depending on the type of monomer.
  • the polymer preferably has a melt flow rate (MFR) of 0.1 to 100 g / 10 min, and more preferably 1 to 50 g / 10 min since higher adhesion can be obtained. More preferably, it is / 10 min.
  • MFR melt flow rate
  • the above MFR is based on ASTM D3307-01, using a melt indexer (manufactured by Toyo Seiki Co., Ltd.), and the mass (g / 10 min) of the polymer flowing out per 10 minutes from a nozzle having an inner diameter of 2 mm and a length of 8 mm. is there.
  • the temperature and load at the time of measurement can be selected according to the melting point of the polymer.
  • the MFR is a value measured at 265 ° C. under a 5 kg load when the melting point of the polymer is 200 ° C. or higher.
  • the MFR is a value measured under a load of 230 ° C. and 2.16 kg when the melting point of the polymer is 140 ° C. or higher and lower than 200 ° C.
  • the polymer is preferably a fluororesin.
  • the polymer preferably has a melting point of 140 ° C. or higher, and the upper limit may be 290 ° C. A more preferred lower limit is 150 ° C., and an upper limit is 270 ° C.
  • the melting point is measured by using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) according to ASTM D-4591 at a heating rate of 10 ° C./min, and the temperature corresponding to the peak of the endothermic curve obtained is measured. The melting point.
  • the polymer preferably has a thermal decomposition starting temperature (1% mass loss temperature) of 360 ° C. or higher.
  • a more preferred lower limit is 370 ° C., and a more preferred lower limit is 380 ° C. If the said thermal decomposition start temperature is in the said range, an upper limit can be 410 degreeC, for example.
  • the thermal decomposition starting temperature is a temperature at which 1% by mass of the polymer subjected to the heating test is decomposed, and the mass of the polymer subjected to the heating test using a differential thermal / thermogravimetric measuring apparatus [TG-DTA] is This is a value obtained by measuring the temperature when the mass decreases by 1% by mass.
  • the polymer can be produced by a production method including a step of obtaining a polymer by polymerizing vinylidene fluoride in the presence of a polymerization initiator and a step of amidating the polymer.
  • This production method is suitable for producing a polymer having a —CONH 2 group at the end of the main chain.
  • the amidation treatment can be performed by bringing the polymer obtained by polymerization into contact with ammonia water, ammonia gas, or a nitrogen compound capable of generating ammonia.
  • ammonia water By adding ammonia water to the polymer obtained by polymerization, the polymer before treatment can be brought into contact with ammonia water.
  • ammonia water one having an ammonia concentration of 0.01 to 28% by mass can be used, and the contact time can be 1 minute to 24 hours.
  • the number of —CONH 2 groups can be adjusted by adjusting the concentration of ammonia water and the contact time.
  • Examples of the method for bringing the polymer before treatment into contact with ammonia gas include a method in which the polymer before treatment is placed in a reaction vessel and ammonia gas is supplied into the reaction vessel.
  • the supply of ammonia gas into the reaction vessel may be performed after mixing with a gas inert to amidation to form a mixed gas.
  • the gas inert to the amidation is not particularly limited, and examples thereof include nitrogen gas, argon gas, and helium gas.
  • the ammonia gas is preferably 1% by mass or more of the mixed gas, more preferably 10% by mass or more, and may be 80% by mass or less as long as it is within the above range.
  • the amidation treatment is preferably performed at 0 ° C. or more and 100 ° C. or less, more preferably 5 ° C. or more, further preferably 10 ° C. or more, more preferably 90 ° C. or less, and further preferably 80 ° C. or less. It is. If the temperature is too high, the polymer may be decomposed or fused, and if it is too low, the treatment may take a long time, which is not preferable in terms of productivity.
  • the duration of the amidation treatment is usually about 1 minute to 24 hours, although it depends on the amount of polymer.
  • the amidation treatment is preferably carried out so that the ratio of the —CONH 2 group of the polymer after the amidation treatment to the —OCOOR group of the polymer before the amidation treatment is 25% or more. .
  • the ratio is more preferably 50% or more, further preferably 60% or more, particularly preferably 80% or more, and may be 100%.
  • the polymer can also be produced by a production method comprising a step of obtaining a polymer by polymerizing vinylidene fluoride in the presence of a polymerization initiator and a step of bringing the polymer into contact with sodium hydroxide.
  • This production method is suitable for producing a polymer having a —COOH group at the end of the main chain.
  • the polymer before treatment can be brought into contact with sodium hydroxide.
  • sodium hydroxide aqueous solution one having a sodium hydroxide concentration of 1 mol% can be used, and the contact time may be 1 minute to 12 hours.
  • the number of —COOH groups can be adjusted by adjusting the concentration of sodium hydroxide aqueous solution and the contact time.
  • the contact with the sodium hydroxide is preferably performed at 0 ° C. or more and 200 ° C. or less, more preferably 5 ° C. or more, still more preferably 10 ° C. or more, more preferably 90 ° C. or less, still more preferably It is 80 degrees C or less. If the temperature is too high, the polymer may be decomposed or fused, and if it is too low, the treatment may take a long time, which is not preferable in terms of productivity.
  • the treatment with sodium hydroxide is preferably carried out so that the ratio of the —COOH group of the polymer after the treatment to the —OCOOR group of the polymer before the treatment is 25% or more.
  • the ratio is more preferably 50% or more, further preferably 60% or more, particularly preferably 80% or more, and may be 100%.
  • the polymerization of the vinylidene fluoride may be solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc., but emulsion polymerization or suspension polymerization is preferable from the viewpoint of easy industrial implementation, and suspension polymerization. Is more preferable.
  • an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used, but an oil-soluble radical polymerization initiator is preferable.
  • the oil-soluble radical polymerization initiator may be a known oil-soluble peroxide such as dialkyl peroxydicarbonate, di-n-propylperoxydicarbonate, disec-butylperoxydicarbonate, etc.
  • Peroxycarbonates, peroxyesters such as t-butylperoxyisobutyrate and t-butylperoxypivalate, dialkyl peroxides such as di-t-butylperoxide, and the like are also used as di ( ⁇ -hydro -Dodecafluoroheptanoyl) peroxide, di ( ⁇ -hydro-tetradecafluoroheptanoyl) peroxide, di ( ⁇ -hydro-hexadecafluorononanoyl) peroxide, di (perfluorobutyryl) peroxide, di (Perful Valeryl) Par Xide, di (perfluorohexanoyl) peroxide, di (perfluoroh
  • the water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, potassium salts, sodium salts. , T-butyl permalate, t-butyl hydroperoxide and the like.
  • a reducing agent such as sulfites and sulfites may be used in combination with the peroxide, and the amount used may be 0.1 to 20 times that of the peroxide.
  • the oil-soluble radical polymerization initiator is preferably a dialkyl peroxycarbonate, and is selected from the group consisting of diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, and disec-butyl peroxydicarbonate. At least one is preferred.
  • a surfactant a chain transfer agent, and a solvent
  • conventionally known ones can be used.
  • a known surfactant can be used.
  • a nonionic surfactant, an anionic surfactant, a cationic surfactant, or the like can be used.
  • fluorine-containing anionic surfactants are preferred, and may contain ether-bonded oxygen (that is, oxygen atoms may be inserted between carbon atoms), or are linear or branched having 4 to 20 carbon atoms.
  • a fluorine-containing anionic surfactant is more preferable.
  • the addition amount (with respect to polymerization water) is preferably 50 to 5000 ppm.
  • Examples of the chain transfer agent include hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; acetates such as ethyl acetate and butyl acetate; Examples include alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride.
  • the addition amount may vary depending on the size of the chain transfer constant of the compound used, but is usually used in the range of 0.01 to 20% by mass with respect to the polymerization solvent.
  • Examples of the solvent include water, a mixed solvent of water and alcohol, and the like.
  • a fluorine-based solvent may be used in addition to water.
  • the fluorine-based solvent include hydrochlorofluoroalkanes such as CH 3 CClF 2 , CH 3 CCl 2 F, CF 3 CF 2 CCl 2 H, CF 2 ClCF 2 CFHCl; CF 2 ClCFClCF 2 CF 3 , CF 3 CFClCFClCF 3, etc.
  • Perfluoroalkanes such as perfluorocyclobutane, CF 3 CF 2 CF 2 CF 3 , CF 3 CF 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CF 2 CF 2 CF 3 , etc. Among them, perfluoroalkanes are preferable.
  • the amount of the fluorine-based solvent used is preferably 10 to 100% by mass with respect to the aqueous medium from the viewpoint of suspendability and economy.
  • the polymerization temperature is not particularly limited, and may be 0 to 100 ° C.
  • the polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent to be used, and the polymerization temperature, but it may usually be 0 to 9.8 MPaG.
  • the powder coating is densified under the condition that the specific gravity of 90% or more of the true specific gravity (specific gravity of the melt-formed product) is obtained by using a roll or the like with the raw powder of the polymer obtained by the polymerization method.
  • fine particles and fibrous particles in the range of 3 to 40% by mass of the entire particle size distribution of the pulverized product are removed by airflow classification, and coarse particles of 1 to 20% by mass of the entire particle size distribution of the pulverized product are further classified. It is desirable to manufacture by the method of removing. Further, it is more desirable to heat-treat at a temperature higher than the melting start temperature of the polymer after classification of the coarse particles.
  • the raw powder of the polymer is compressed into a sheet using a roll or the like under a condition that 90% or more, preferably 95 to 99% of the true specific gravity is obtained.
  • the specific gravity after compression is less than 90% of the true specific gravity, the apparent density of the particles obtained after pulverization is low and the fluidity is poor.
  • the specific gravity after compression exceeds 99% of the true specific gravity, the particles obtained after pulverization have a non-uniform shape, and the apparent density is low and the fluidity is poor.
  • the sheet thickness is set to 0.05 to 5 mm, preferably 0.1 to 3 mm.
  • the roll to be used is preferably one in which two or more rolls are arranged in a vertical type, an inverted L type, a Z type, and the like, and specifically includes a calendar roll, a mixing roll, a roller compactor, and the like.
  • a strong shearing force is applied to the polymer bulk powder during sheeting, and pores and bubbles present in the bulk powder can be removed to obtain a uniform sheet.
  • the sheet is pulverized by a pulverizer after pulverizing so that the average particle diameter becomes 0.1 to 10 mm by a pulverizer.
  • Crushing is performed by fixing a screen or a mesh having a hole having a size of a pulverized particle size and crushing it, or by crushing by passing several rolls having grooves or undulations, and averaging.
  • the particle size is preferably 0.1 to 10 mm.
  • the pulverization is generally performed by a mechanical pulverizer.
  • the mechanical pulverizer includes an impact type such as a cutter mill, a hammer mill, a pin mill, and a jet mill, and a grinding type in which the rotary blade and the outer peripheral stator are pulverized by a shearing force caused by unevenness.
  • a high shearing method is preferable from the viewpoint of pulverization efficiency.
  • the grinding temperature is -200 to 100 ° C. In the freeze pulverization, the temperature is usually -200 to -100 ° C, but may be pulverized at room temperature (10 to 30 ° C).
  • Liquid nitrogen is generally used for freeze pulverization, but the equipment is enormous and the pulverization cost is high. It is appropriate to grind at room temperature (10 ° C.) to 100 ° C., preferably at a temperature close to room temperature (10 ° C. to 30 ° C.) in that the process becomes simple and the grinding cost can be reduced.
  • the obtained powder particles are not in a non-uniform form such as fine particle aggregates or pellets, but have a uniform particle size distribution, and the average particle size is 5 to 100 ⁇ m.
  • Fine particles and fibrous particles may be removed by classification, and coarse particles may be further removed by classification.
  • Airflow classification may be used for classification.
  • the pulverized particles are sent to a cylindrical classification chamber by reduced-pressure air, dispersed by a swirling airflow in the room, and fine particles are classified by centrifugal force.
  • the fine particles are collected from the center to a cyclone and a bag filter and formed into a sheet again.
  • a rotating body such as a conical cone or a rotor is installed so that the pulverized particles and the air can perform a swirl motion uniformly.
  • a classification cone may be used for classification.
  • the classification point is adjusted by adjusting the air volume of the secondary air and the gap between the classification cones.
  • the air volume in the classification chamber according to the number of rotations of the rotor.
  • the wind pressure of the blower is 0.1 to 1 MPa, preferably 0.3 to 0.6 MPa.
  • the classification range is 3 to 40% by mass, preferably 5 to 30% by mass, and 3 to 40% by mass of fine particles and fibrous particles are removed.
  • the fine particles to be removed are less than 3% by mass, the fluidity of the powder cannot be improved, and the leveling property of the formed film is inferior because the particle size distribution is extremely wide.
  • the fine particles to be removed exceed 40% by mass, it is not suitable in terms of cost.
  • Examples of the method for removing coarse particles include airflow classification, vibration sieve, ultrasonic sieve, and the like.
  • the classification range depending on the particle size is 1 to 20% by mass, preferably 2 to 10% by mass of the entire particle size distribution of the pulverized product, and coarse particles in this range are removed.
  • Fine particles and fibrous particles recovered in the airflow classification can be formed into a sheet again in the same manner as the raw powder.
  • the coarse particles classified in the airflow classification or the vibration sieve can be returned to the pulverizer and pulverized again.
  • the classified powder When the classified powder is momentarily brought into contact with an air flow that is equal to or higher than the melting start temperature of the above polymer using a continuous air flow heating dryer, the powder particle surface becomes rounded, the apparent density and the powder flow The properties can be further improved, and a preferable powder coating can be obtained.
  • the contact temperature of continuous air flow type heat drying is 1000 ° C. or less, preferably 200 to 800 ° C., and the contact time is 0.1 to 10 seconds.
  • gas heating is preferable in terms of energy saving.
  • the heat-treated powder can be further removed by classifying coarse particles with an air flow sieve or a vibrating sieve to obtain a powder coating material having a narrow particle size distribution.
  • the powder coating material preferably has an average particle size of powder particles of 10 to 1000 ⁇ m.
  • the average particle size of the powder particles is determined by the purpose, and is generally 20 to 40 ⁇ m in the case of a thin coating powder coating having a dry film thickness of 100 ⁇ m or less. In the case of a thick coating powder coating 40 to 80 ⁇ m is preferable, and in the case of a powder coating for lotioning, 200 to 500 ⁇ m is preferable.
  • the average particle diameter is a value obtained by measurement with a laser diffraction particle size distribution measuring apparatus. As the average particle diameter, a volume-based median diameter measurement value can be cited using a Microtrac MT3300EXII particle size analyzer manufactured by Nikkiso Co., Ltd.
  • the powder coating material of this invention may contain other resins other than the said polymer as needed.
  • the other resins are not particularly limited as long as they can be used for powder coatings, and may be either thermoplastic resins or thermosetting resins.
  • the other resin is preferably a heat-resistant resin, and more preferably one that does not decompose at the heating temperature when the powder coating material is applied.
  • the heat resistant resin include silicone resin, fluorosilicone resin, polyamide resin, polyamideimide resin, polyimide resin, polyester resin, epoxy resin, polyphenylene sulfide resin, phenol resin, acrylic resin, and polyethersulfone resin. .
  • One or more of the other resins may be used.
  • the powder coating material of this invention may contain an additive etc. with the said polymer as needed.
  • the additive is not particularly limited as long as it is added to a general powder coating material.
  • coloring pigments such as titanium oxide and cobalt oxide
  • Other pigments such as pigments and calcined pigments
  • Filler For the purpose of imparting conductivity, a conductivity imparting material such as conductive carbon may be used.
  • the additive may also be a leveling agent, antistatic agent, ultraviolet absorber, radical scavenger and the like.
  • This invention is also a coating film characterized by being formed from the above-mentioned powder coating material. Since the said coating film is formed from the above-mentioned powder coating material, it shows very excellent adhesion.
  • the present invention is also a coated article comprising a substrate and a coating film of the above-described powder coating material provided on the substrate.
  • a primer layer may be provided between the base material and the coating film.
  • the coating film is excellent in adhesion, the base material and the coating film can be directly adhered with sufficient adhesion. Is possible.
  • the substrate is preferably made of metal, ceramic, resin or glass.
  • the metal is not particularly limited, and examples thereof include iron; stainless steel such as SUS304, SUS316L, and SUS403; aluminum; plated steel plate that has been subjected to zinc plating, aluminum plating, and the like.
  • the ceramic is not particularly limited as long as it has heat resistance, and examples thereof include ceramics, porcelain, alumina material, zirconia material, and silicon oxide material.
  • the resin include silicone resin, fluorosilicone resin, polyamide resin, polyamideimide resin, polyimide resin, polyester resin, epoxy resin, polyphenylene sulfide resin, phenol resin, acrylic resin, and polyethersulfone resin.
  • the base material is not particularly limited as long as it is generally desired to form a lining with a polymer.
  • a base material that is desired to impart corrosion resistance is suitable.
  • substrates include, for example, tanks, vessels, towers, valves, pumps, fittings, other piping materials and other anticorrosive linings; chemical / medical instruments, wafer baskets, coil bobbin tower packing, chemicals And other anticorrosive materials such as valves and pump impellers.
  • the base material may be subjected to cleaning, roughening, or the like as pretreatment as necessary.
  • the pretreatment includes, for example, removal of oil from the base material by solvent, cleaning agent, baking off, etc .; chemical etching using hydrochloric acid, sulfuric acid, alkali, etc .; blasting treatment using silica sand, alumina powder, etc.
  • the pretreatment includes, for example, removal of oxides on the surface of the substrate by means of the above, the provision of irregularities for increasing the surface area, and the like.
  • blasting it is also possible to coat a material such as ceramic by spraying and to coat it.
  • the coated article can be produced by applying the powder coating described above on the substrate, drying as necessary, and then firing to form the coating film.
  • the method for applying the above-mentioned powder coating is not particularly limited, and examples thereof include spraying, electrostatic spraying, electrostatic spray coating, fluidized immersion coating, electrostatic fluidized immersion coating, and a rotational training method.
  • the calcination is not particularly limited as long as the temperature is higher than the melting point, softening point or glass transition point of the polymer and does not cause decomposition of the polymer. Run for 60 minutes. When the above-mentioned powder coating is applied by rotrining, the coating film is formed and baked at the same time.
  • the coating film preferably has a film thickness after firing of 100 to 10,000 ⁇ m.
  • the thickness is less than 100 ⁇ m, the excellent properties of the polymer may not be sufficiently exhibited.
  • the thickness exceeds 10,000 ⁇ m, cracks or the like may occur.
  • a more preferred upper limit is 5000 ⁇ m.
  • the powder coating material of the present invention can be used in rice cookers, pots, hot plates, irons, frying pans, home bakery, etc. for home appliances / kitchen relations, and for industrial use, rolls for OA equipment, belts for OA equipment, It is widely applied to mold release applications such as paper rolls, calender rolls for film production, injection molds, etc .; and corrosion resistance applications such as stirring blades, tank inner surfaces, vessels, towers, and centrifuges.
  • coated article of the present invention is not particularly limited, for example, coating materials for various electric wires such as heat-resistant enamel wires; information equipment parts (paper separation claw, printer guide, gear, bearing), connector, vernier socket, IC sockets, oil field electrical components, relays, electromagnetic shielding, relay cases, switches, covers, terminal board buses and other electrical / electronic industry related applications; valve seats, hydraulic seals, backup rings, piston rings, wear bands, vanes, Ball bearing retainer, roller, cam, gear, bearing, labyrinth seal, pump part, mechanical linkage, bushing, fastener, spline liner, bracket, hydraulic piston, chemical pump casing, valve, valve, tower packing, coil bobbin, packing, Connector, gas Machine industry related applications such as valve seals, thrust washers, seal rings, gears, bearings, tappets, engine parts (pistons, piston rings, valve steers), transmission parts (spool valves, ball check valves, sealing), Applications related to the vehicle industry such as rocker arms; jet engine parts (bushings), oil field
  • Examples of the use of the coated article of the present invention include stirring blades, tank inner surfaces, vessels, towers, centrifuges, pumps, valves, piping, ventilation holes, ducts, heat exchangers, plating jigs, tank lorry inner surfaces, screw conveyors, etc.
  • Corrosion-resistant applications such as semiconductor factory ducts; industrial mold release applications such as OA rolls, OA belts, papermaking rolls, film production calendar rolls, injection molds; rice cookers, pots, hot plates, irons, frying pans , Home bakery, pan tray, gas table top plate, pan top plate, pan, pot, and other household appliances and kitchen-related applications; precision mechanism sliding members including various gears, papermaking rolls, calendar rolls, mold release parts, casings, valves , Valves, packing, coil bobbins, oil seals, joints, antenna caps, connectors, gaskets , Valve seals, buried bolts, industrial parts related applications such as built-in nut and the like.
  • Examples 1, 2, 4 and 5 Polymer powders having the compositions shown in Table 1 were reacted by contacting with ammonia water (amidation treatment). By changing the concentration of ammonia water, the reaction temperature, and the reaction time, the reaction was carried out so that the number of —CONH 2 groups became the number shown in Table 1. The following evaluation was performed about the powder coating material containing the obtained polymer. The results are shown in Table 1.
  • Example 3 Polymer powder having the composition shown in Table 1 was allowed to react with an aqueous sodium hydroxide solution. The following evaluation was performed about the powder coating material containing the obtained polymer. The results are shown in Table 1.
  • Polymer composition The polymer before contact with aqueous ammonia or aqueous sodium hydroxide was subjected to 19 F-NMR using a nuclear magnetic resonance apparatus AC300 (manufactured by Bruker-Biospin) at a measurement temperature of (polymer melting point + 20) ° C. Measurement was performed, and an integral value of each peak and an elemental analysis were appropriately combined depending on the type of monomer.
  • a nuclear magnetic resonance apparatus AC300 manufactured by Bruker-Biospin
  • Melt flow rate [MFR] MFR conforms to ASTM D3307-01, and uses a melt indexer (manufactured by Toyo Seiki Co., Ltd.) under the following conditions, the mass of the polymer flowing out from a nozzle having an inner diameter of 2 mm and a length of 8 mm per 10 minutes (g / 10 Min) was defined as MFR.
  • a piece of each powder (or pellet) of -CONH 2- group polymer was compression-molded at room temperature to prepare a film having a thickness of 200 ⁇ m ( ⁇ 5 ⁇ m). Infrared spectral analysis of these films was performed. The obtained IR spectrum was analyzed by scanning 128 times using Perkin-Elmer Spectrum Ver3.0, and the absorbance of the peak was measured. The film thickness was measured with a micrometer. In the obtained infrared absorption spectrum, the absorbance of the peak appearing at 2900 to 3100 cm ⁇ 1 due to the CH 2 group of the main chain was normalized to 1.0. The absorbance of the peak due to the NH bond of the —CONH 2 group appearing in the vicinity of 3400 to 3470 cm ⁇ 1 of the spectrum is determined.
  • the baseline is automatically determined, and the peak height A is obtained as the peak absorbance.
  • a piece of each powder (or pellet) of the —COOH group number polymer was compression molded at room temperature to prepare a film having a thickness of 200 ⁇ m ( ⁇ 5 ⁇ m). Infrared spectral analysis of these films was performed. The obtained IR spectrum was analyzed by scanning 128 times using Perkin-Elmer Spectrum Ver3.0, and the absorbance of the peak was measured. The film thickness was measured with a micrometer. In the obtained infrared absorption spectrum, the absorbance of the peak appearing at 2900 to 3100 cm ⁇ 1 due to the CH 2 group of the main chain was normalized to 1.0. The absorbance of the peak due to the C ⁇ O bond of the —COOH group appearing in the vicinity of 1700 to 1780 cm ⁇ 1 of the spectrum is determined.
  • the baseline is automatically determined, and the peak height A is obtained as the peak absorbance.
  • a piece of each powder (or pellet) of a number polymer of —OCOOR groups was compression-molded at room temperature to prepare a film having a thickness of 200 ⁇ m ( ⁇ 5 ⁇ m). Infrared spectral analysis of these films was performed. The obtained IR spectrum was analyzed by scanning 128 times using Perkin-Elmer Spectrum Ver3.0, and the absorbance of the peak was measured. The film thickness was measured with a micrometer. In the obtained infrared absorption spectrum, the absorbance of the peak appearing at 2900 to 3100 cm ⁇ 1 due to the CH 2 group of the main chain was normalized to 1.0.
  • the absorbance of the peak due to the C ⁇ O bond of the —OCOOR group appearing in the vicinity of 1780 to 1830 cm ⁇ 1 of the spectrum is determined.
  • the baseline is automatically determined, and the peak height A is obtained as the peak absorbance.
  • TFE Tetrafluoroethylene
  • VDF Vinylidene fluoride
  • HFP Hexafluoropropylene
  • Unsaturated monomer CH 2 ⁇ CH—C 6 F 13 * 1: Almost all of the ends of the main chain are —CONH 2 groups. * 2: Almost all of the ends of the main chain are —CF 2 H groups—: Not measured

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Abstract

La présente invention concerne une composition de revêtement en poudre qui ne génère pas de bulles durant la formation du film de revêtement et qui est capable de former des films de revêtement présentant une excellente adhésion aux substrats. La composition de revêtement en poudre est caractérisée en ce qu'elle contient un polymère qui comprend un motif fluorure de vinylidène et présente, à une terminaison de chaîne principale, au moins un groupe terminal sélectionné dans le groupe constitué des groupes -CONH2 et -COOH.
PCT/JP2017/023031 2016-07-08 2017-06-22 Composition de revêtement en poudre, film de revêtement, et article revêtu WO2018008421A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111919521A (zh) * 2018-03-30 2020-11-10 大金工业株式会社 电波吸收材料以及电波吸收片

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Publication number Priority date Publication date Assignee Title
JPS60240713A (ja) * 1984-05-10 1985-11-29 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー 溶融加工しうるテトラフルオロエチレン共重合体とその製法
JPS6198709A (ja) * 1984-10-18 1986-05-17 イー・アイ・デユポン・デ・ニモアス・アンド・カンパニー 熱安定性テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）コポリマー
JPH11106699A (ja) * 1997-10-02 1999-04-20 Du Pont Mitsui Fluorochem Co Ltd テトラフルオロエチレン共重合体組成物で被覆された鋼製物品
JP2000017197A (ja) * 1998-04-30 2000-01-18 Daikin Ind Ltd 熱硬化性粉体塗料組成物
WO2002088227A1 (fr) * 2001-04-26 2002-11-07 Daikin Industries, Ltd. Poudre de polymere contenant du fluor, procede de production associe et article revetu
JP2003096377A (ja) * 2001-09-25 2003-04-03 Asahi Glass Co Ltd 熱硬化性フッ素樹脂粉体塗料組成物
JP2009263609A (ja) * 2008-03-31 2009-11-12 Daikin Ind Ltd 粉体塗料及びプライマー
WO2015159890A1 (fr) * 2014-04-18 2015-10-22 旭硝子株式会社 Peinture en poudre et article peint
WO2016088846A1 (fr) * 2014-12-05 2016-06-09 旭硝子株式会社 Procédé de réparation de pellicule d'enrobage et produit enrobé

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Publication number Priority date Publication date Assignee Title
JPS60240713A (ja) * 1984-05-10 1985-11-29 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー 溶融加工しうるテトラフルオロエチレン共重合体とその製法
JPS6198709A (ja) * 1984-10-18 1986-05-17 イー・アイ・デユポン・デ・ニモアス・アンド・カンパニー 熱安定性テトラフルオロエチレン／パーフルオロ（アルキルビニルエーテル）コポリマー
JPH11106699A (ja) * 1997-10-02 1999-04-20 Du Pont Mitsui Fluorochem Co Ltd テトラフルオロエチレン共重合体組成物で被覆された鋼製物品
JP2000017197A (ja) * 1998-04-30 2000-01-18 Daikin Ind Ltd 熱硬化性粉体塗料組成物
WO2002088227A1 (fr) * 2001-04-26 2002-11-07 Daikin Industries, Ltd. Poudre de polymere contenant du fluor, procede de production associe et article revetu
JP2003096377A (ja) * 2001-09-25 2003-04-03 Asahi Glass Co Ltd 熱硬化性フッ素樹脂粉体塗料組成物
JP2009263609A (ja) * 2008-03-31 2009-11-12 Daikin Ind Ltd 粉体塗料及びプライマー
WO2015159890A1 (fr) * 2014-04-18 2015-10-22 旭硝子株式会社 Peinture en poudre et article peint
WO2016088846A1 (fr) * 2014-12-05 2016-06-09 旭硝子株式会社 Procédé de réparation de pellicule d'enrobage et produit enrobé

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111919521A (zh) * 2018-03-30 2020-11-10 大金工业株式会社 电波吸收材料以及电波吸收片

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