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WO1999021927A1 - Composition de revetement de fluoropolymere et article ainsi revetu - Google Patents

Composition de revetement de fluoropolymere et article ainsi revetu Download PDF

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Publication number
WO1999021927A1
WO1999021927A1 PCT/JP1998/004604 JP9804604W WO9921927A1 WO 1999021927 A1 WO1999021927 A1 WO 1999021927A1 JP 9804604 W JP9804604 W JP 9804604W WO 9921927 A1 WO9921927 A1 WO 9921927A1
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Prior art keywords
fluoropolymer
integer
group
general formula
coating composition
Prior art date
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Ceased
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PCT/JP1998/004604
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English (en)
Japanese (ja)
Inventor
Yoshihiro Soda
Koichiro Ogita
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Daikin Industries Ltd
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Daikin Industries Ltd
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Priority to JP2000518024A priority Critical patent/JP3649124B2/ja
Priority to KR10-2000-7003943A priority patent/KR100530720B1/ko
Publication of WO1999021927A1 publication Critical patent/WO1999021927A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • 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
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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
    • C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D171/02—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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
    • 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
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C08J2427/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2427/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2427/12—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the present invention relates to fluoropolymer coating compositions and painted articles. Background technology
  • a fluoropolymer coating composition has been added with an anion-ion surface active agent as a film-forming aid, but is liable to foam. Pinholes are easily formed on the coating film, and the film-forming properties are not sufficient.Thick coating is also difficult, so that corrosion resistance due to abrasion of the coating film and In addition to the decrease in non-adhesiveness, the molded article, which should be white in nature, had drawbacks such as coloring due to firing.
  • the purpose of the present invention is to provide a specific polyester resin which can be applied thickly and which forms a coating film having excellent wear resistance, corrosion resistance and non-adhesiveness.
  • the present invention provides fine particles of fluoropolymer and 0.1% by weight based on the weight of the fine particles.
  • a fluoropolymer coating composition comprising about 300% by weight of a polyester resin, an oxidation catalyst, and a liquid carrier. -When the resin is of the general formula (I):
  • R 1 is the same or different, and each is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • Y 1 is an oxygen atom, an ether group, An ester group, a urethane group or a thioenyl group
  • A is an alkylenoxy residue having 3 or more carbon atoms (but it may be polymerized)
  • the molecular weight of the alkylenoxy moiety is 1 X
  • B is U letterhead down group,'s a Chi O twenty-one Norre based or was Ri do acid group (the other, mosquito Tsu co- ⁇ in alternating copolymer Polymerization And the temperature at which the resin decomposes and evaporates is determined by the decomposition temperature of the fluoropolymer.
  • the present invention relates to fluoropolymer coating compositions that fall within the scope described above.
  • the present invention also provides that the fluoropolymer coating composition is overcoated such that it forms a fused coating having a thickness of at least 30 m.
  • the fluoropolymer coating composition is overcoated such that it forms a fused coating having a thickness of at least 30 m.
  • the invention uses a specific polyester resin in the form of an emulsion and incorporates an oxidation catalyst. This is a fluoropolymer coating that has the greatest characteristics, especially in that thick coating is possible and there is no coloring after baking.
  • a composition is a specific polyester resin in the form of an emulsion and incorporates an oxidation catalyst.
  • the specific polyether-based resin is a resin represented by the general formula (I): R i -Y 1 (A-B) -R 1 (I), and is an ethyl resin. Since it does not have a lenoxide residue, it is hydrophobic, water-dispersible, has no surface-active ability, and is a fluorophore used in the present invention.
  • R 1 is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, which is the same or different from the viewpoint of hydrophobicity.
  • Y 1 is preferably an oxygen atom, an ether group or an ester group from the viewpoint of thermal decomposition, and is a pentane group or a thio group from the viewpoint of ease of production. It is preferably a knoll group.
  • A is an anolexylene oxy residue having 3 or more carbon atoms, preferably 3 to 4 carbon atoms from the viewpoint of hydrophobicity and water dispersibility, and may be polymerized. It is preferable that the molecular weight of the alkylenoxyside moiety is 1 ⁇ 10 ⁇ to 1 ⁇ 10 4 .
  • the above ⁇ is a urethane group, a thional group or a phosphoric acid group from the viewpoint of ease of production.
  • brackets in the general formula (I) are preferably residues obtained by alternate copolymerization.
  • Such a polyether-based resin represented by the general formula (I) is hydrophobic, is water-dispersible, and has a high stability in terms of stability and workability. It is preferably used in the form of a region. In addition, since it is an emulsion, it is easily dispersed evenly with fluoropolymer particles.
  • resin represented by the general formula (I) include, for example, a case where the ⁇ is a ⁇ -retan group.
  • m is an integer from 1 to 100
  • n is an integer from 10 to 200
  • C 0 NH—J 1 NHC 0 is, for example, a trilge isocyanate.
  • TDI urethane residues
  • HMDI hexamethylene range isocyanate
  • IPDI isophorone range
  • XDI silicone isocyanate
  • MDI diphenylmethanthate isocyanate
  • the structure of (1) is preferable from the viewpoint of thermal decomposition.
  • the structure of (3) is preferred from the viewpoint of thermal decomposability.
  • the structure is to be improved, the structure of (5) is preferred from the viewpoint of thermal decomposability.
  • the fluoropolymer in the present invention refers to a fluorine atom, a chlorine atom, or a monoethylenic unsaturated monomer which is completely substituted by these two types.
  • PTFE polytetrafluoroethylene
  • copolymer examples include tetrafluoroethylene and 0- fluoro (vinyl alcohol) copolymers.
  • PFA tetrafluoroethylene
  • 0- fluoro (vinyl alcohol) copolymers examples include tetrafluoroethylene and 0- fluoro (vinyl alcohol) copolymers.
  • FEP non-copolymer
  • PFA is preferred because it is non-adhesive and has excellent heat resistance.
  • Examples of the mixture of the single polymer and the copolymer include PTFE and PFA, PTFE and FEP, PTFE and PFA and FEP, and PFA and FEP.
  • a mixture of PTFE and PFA is preferred because of its excellent non-adhesiveness and heat resistance.
  • the number average molecular weight of PTFE can be found in the Journal of Applied
  • the number average molecular weight of FEP is determined by measuring the melt flow velocity (MFR) by the method described in ASTMD-212 and determining the melt viscosity (MV) by equation (1).
  • MFR melt flow velocity
  • MV melt viscosity
  • Mn number average molecular weight
  • the fine particles of the fluoropolymer are fine particles obtained by a method such as, for example, the milk-polymerization of fluorofluorin.
  • the average particle size is from 0.01 to 100 / zm, preferably from 0.1 to 5 / zm. If the particle size is less than 0.01 m, the film-forming property tends to be weakened, and if it exceeds 100 ⁇ , a gun nozzle used for coating is used. There is a tendency for clogging and clogging.
  • the aqueous dispersion of the fine particles of the fluoropolymer obtained in the above-mentioned emulsification polymerization, or an aqueous dispersion thereof is obtained.
  • fine particles in powder form can be used, they are preferably used in the form of an aqueous dispersion from the viewpoint of the stability due to the electrical repulsion of the particles.
  • the concentration of the solid component is from 20 to 80% by weight and preferably from 40 to 70% by weight from the viewpoint of coating film formation.
  • the hydrophobic water can be used with a polyether-based resin that has no dispersibility and surface activity.
  • the poly As an ether-based polymer surfactant, for example,
  • R is a hydrogen atom or an alkylene group having 1 to 20 carbon atoms
  • Y is an oxygen atom, an ether group, an ester group, a urethane group, or a thione group.
  • C is an ethylenoxy residue
  • D is a propylenoxy residue
  • a is 30 to 200
  • B is an integer from 20 to 500
  • c is! ⁇
  • Z is a polyvalent aliphatic saturated hydrocarbon group having 1 to 5 carbon atoms
  • R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
  • Y is an oxygen atom
  • ether a hydroxyl group, an ester group, a urethane group, a thioninole group or a phosphate group
  • C is an ethylenoxy residue
  • D is a propyl residue.
  • a lenoside residue a is an integer of 30 to 200, b is an integer of 20 to 500, c is 1 to; an integer of L0, ⁇
  • e is an integer from 1 to 4 (however,
  • the above-mentioned powers are irritating, and these are hydrophilic because they have an ethylenoxide residue.
  • R when R is an alkyl group, the number of carbon atoms is preferably 1 to 18 from the viewpoint of thermal decomposability. Yes.
  • Y an oxygen atom, an ether group or an ester group is preferable from the viewpoint of thermal decomposition.
  • An integer of 40 to 600 is preferable from the viewpoint of film forming property and thermal decomposability, and b is an integer of 30 to 120. Preferable in terms of thickening. For c: A value of 5 is preferable in terms of leveling properties.
  • R is 1 to 18 in terms of the number of carbon atoms in the case of R in the phenol group.
  • Y an oxygen atom, Ether groups or ester groups are preferred.
  • a is an integer of 20 to 300 from the viewpoint of film forming property and thermal decomposition property, and b is 30 to: An integer is preferred from the viewpoint of thickening, and d is preferably an integer of 20 to 300 from the viewpoints of film forming properties and thermal decomposition.
  • R when R is an alkylene group, the number of carbon atoms is preferably 1 to 18 from the viewpoint of thermal decomposability. It is better.
  • Y an oxygen atom, an ether group or an ester group is preferred from the viewpoint of thermal decomposability.
  • a is preferably an integer of 15 to 60 from the viewpoint of thickening property and thermal decomposability, and b is an integer of 40 to 600. It is preferable from the point of view of film forming property, and it is preferable that d is an integer of 15 to 60 from the viewpoint of thickening and thermal decomposition. .
  • the carbon number of Z the point force of thickening and thermal decomposability, the force of 2 or 3 and the force of 'preferably, R
  • the carbon number of the alkyl group is preferably from 1 to 18 from the viewpoint of thickening property and thermal decomposition property.
  • Y an oxygen atom, an ether group or an ester group is preferable from the viewpoint of thermal decomposability.
  • a is an integer of 40 to 600 in terms of film forming property and thermal decomposability
  • b is 30 to 120
  • Integers are preferred from the viewpoint of thickening
  • c is preferably from 1 to 5 from the viewpoint of leveling property. For this reason, it is preferable that the value of 1 is good in decomposability at the time of baking.
  • the number of carbon atoms of Z is preferably 2 or 3 from the viewpoint of thickening and thermal decomposition.
  • R is an alkyl group
  • the number of carbon atoms is preferably from 1 to 18 from the viewpoint of thermal decomposition.
  • Y From the viewpoint of thermal decomposability, an oxygen atom, an ether group or an ester group is preferred.
  • it is preferable that it is an integer of 20 to 300, from the viewpoint of film forming property and thermal decomposability, and as b,
  • An integer of 30 to 120 is preferred from the viewpoint of thickening property.
  • a value of 20 to 300 means film forming property and thermal decomposition. It is preferable from the viewpoint of the property, and as e, it is preferable that the value of 1 is good in the decomposability at the time of burning.
  • the number of carbon atoms of Z is preferably 2 or 3 from the viewpoint of viscosity increase and thermal decomposition.
  • R is an alkyl group
  • the number of carbon atoms is preferably from 1 to 18 from the viewpoint of thermal decomposition.
  • Y an oxygen atom, an ether group or an ester group is preferable from the viewpoint of thermal decomposition.
  • it is preferable that it is an integer of 15 to 60 from the viewpoint of viscosity increase and thermal decomposition.
  • An integer of 40 to 600 is preferably a film forming point force, and as d, a value of 15 to 60 means thickening property and heat content. It is preferable from the viewpoint of resolvability. As e, 1 is more preferable because of the decomposability at the time of burning.
  • the above-mentioned polyether-based high molecular surfactant has a function of increasing viscosity and forming a film, and for example, a propylene oxide residue portion is changed to a lipophilic residue.
  • a hydrophilic high molecular surface active agent having a structure in which an ethylene oxide residue portion is a lyophilic group. It decomposes and evaporates within the range of the melting temperature of the fluoropolymer, and is an alternating copolymer (for example, the general formula (II) or (V)).
  • A b
  • the total molecular weight of the ethylenoxide residues of these polyether-based high molecular surfactants is 1 ⁇ 10 3 to 2 ⁇ 10 5 .
  • polyether-based high molecular surface active agent represented by the general formula (II) include, for example,
  • the structure of (7) is preferred from the viewpoint of thermal decomposition.
  • polyether-based polymer surfactant represented by the general formula (III) include, for example,
  • the structure of (9) is preferable from the viewpoint of thermal decomposability.
  • polyether-based polymer surface active agent represented by the general formula (IV) include, for example,
  • the structure of (11) is preferred from the viewpoint of thermal decomposability.
  • polyether-based high molecular surface active agent represented by the general formula (V) include, for example,
  • the structure of (13) is preferred from the viewpoint of thermal decomposability.
  • polyether-based high molecular surfactant represented by the general formula (VI) include, for example,
  • polyether-based polymer surfactant represented by the general formula (VII) include, for example, (17) CH 2 _0 CH (CH 3 ) CH20) a (CH 2 CH 20 ) b (CH (CH 3 ) CH 20 ) d H
  • a block polymer such as that shown by b) can be obtained, but from the viewpoint of thermal decomposability, The structure of 17) is preferable.
  • the thickening is achieved by using the polyether-based high molecular surfactants represented by the general formulas (II) to (IV) alone.
  • general formula (III) is preferred, and if two or more types are used, combinations in general formulas (II) to (IV) For example, all combinations are possible, but from the point of thickening and imparting repelling properties.
  • Preference is given to the combination of II) and (III).
  • a preferred combination of the specific examples is, for example, a combination of (7) and (9) or (10) in the above specific examples.
  • a combination of (8) and (9) or (10) is preferable because of its thermal decomposability.
  • the polyether-based high molecular surfactants represented by the general formulas (V) to (VII) alone.
  • the group represented by the general formulas (V) to (VII) is preferred from the viewpoint of stickiness, and the general formula (VI) is preferred, and if only two or more types are used, For example, all combinations Although the warp is possible, the combination of (V) and (VI) is preferable in terms of thickening and imparting repelling properties.
  • a preferred combination of the specific examples is, for example, a combination of (13), (15) or (16) in the above specific examples.
  • Combinations of (14) and (15) or (16) are preferred in terms of thermal decomposition.
  • the polyether represented by the general formula (II) when combined with the resin of the polyether type represented by the general formula (I), the polyether represented by the general formula (II) can be used. Tell based high molecular surface active agents are preferred.
  • the liquid carrier in the present invention is, for example, water and water and methanol, alcohol, alcohol, propyl alcohol, and the like.
  • -Alcohols ethyl alcohol, ethylene glycol, triethylene, etc., such as alcohol, isopropanol, alcohol, etc.
  • Polyvalent alcohols such as glycolone, glycerin, ketones such as acetone, gethynoamine, triethyla Amins such as MIN, ETANO-REAMIN, JETANOREAMIN, TRIENONOREAMIN, etc., and tetrahydrofuran Mixtures with any of the ethers, etc., will be produced.
  • Prevention of aggregation so we set only if the film-forming property points or al water your goodness of beauty water and ⁇ Mi emissions such is not the good or.
  • One of the features of the present invention is that an oxidation catalyst is blended. Fluoropolymer coatings are ultimately fired at a temperature above the melting point of the fluoropolymer, but the use of polyether resin Because the part to be transformed and the above-mentioned surfactant are partially denatured and remain, the coating film which should be originally a beautiful white color is colored. It will be born. This problem is particularly apparent in the case of thick coating, for which the present invention is aimed. .
  • an oxidation catalyst is blended in order to rapidly and completely decompose and remove such a residue that may be a coloring source.
  • Oxidation catalysts are classified into a reactive type and a catalytic type, and any of them can be used in the present invention.
  • Reactive oxidation catalysts include, for example, ammonium nitrate, potassium nitrate, sodium nitrate, aluminum nitrate, sodium nitrite, and the like. Nitrates or nitrites of metals such as aluminum; acetates such as sodium acetate are produced. Of these, potassium nitrate, sodium nitrite, and sodium acetate have high heat resistance of the catalyst itself and high-temperature sintering of fluorine resin paint. It is preferable because the catalytic activity at the time is high.
  • the catalytic oxidation catalyst examples include nickel salts such as nickel nitrate, nickel sulfate, salted nickel, etc .; It is capable of producing cerium salts such as cerium salt, cerium acetate, and cerium octylate.
  • nickel salts such as nickel nitrate, nickel sulfate, salted nickel, etc .
  • cerium salts such as cerium salt, cerium acetate, and cerium octylate.
  • cerium chloride, cerium nitrate, cerium octylate, and nigel nitrate are catalysts for high-temperature firing of fluororesin paints. It is preferred because of its high activity.
  • the amount of the acid catalyst is 0.01 to 10% by weight of the fluoropolymer, preferably 0.01 to 3% by weight, more preferably 0.1 to 3% by weight. 0 to 5% by weight. Too little will leave a colored source. If too much, the additives and surfactants are rapidly decomposed, and the coating becomes porous, adversely affecting the durability, corrosion resistance, and stain resistance of the coating. It affects.
  • the oxidation catalyst can be added in powder form or in a form dispersed or dissolved in a liquid such as water or an organic solvent.
  • a liquid such as water or an organic solvent.
  • the content of the composition is not more than 15% by weight (hereinafter, referred to as “%”) within a range that does not impair the physical properties of the composition. example, if preparative Le et emissions, key sheet les down, that Ki C 9 ⁇ C i] nonpolar solvents aromatic hydrocarbons, etc. the out and this Ru physicians use as a liquid carrier.
  • mica particles, mica particles coated with pigments, metal flakes, or two or more of these fillers must be added. Can be obtained. These fillers have the function of improving thick coating and anti-scratching properties, and even in these, mica is applied to the coating film. O Good for giving a view
  • the particle size of the mica particles is from 10 to 100 m, preferably from 15 to 50 zm, and it is preferable that the particle size is less than 10 ⁇ m. There is a tendency that the brilliant feeling of the film and the anti-scratch property become poor, and if it exceeds 100 ⁇ m, there is a tendency that the non-adhesive performance is reduced.
  • Metal flakes include, for example, titanium, ginoleconium, aluminum, zinc, antimony, tin, iron, nickel, etc. Titanium and zirconium are preferred from the point of view of the mosquitoes and pomegranates, and the size is 10 to 100 / m. If the size is less than 1 O jum, there is a tendency for the coating film to have brilliant and scratch-resistant properties. Adhesion performance tends to decrease.
  • various additives can be used, for example, desiccants such as Sinidai Cobalt, silicone oils, etc. Do etc. of defoamers, main switch zone les cell Honoré Russia over scan, PVA, mosquitoes Le Bo key sheet of bi two Le port Li M a, etc. thickeners, C 9 ⁇ C i E aromatic coal Repelling agents such as hydrogen hydride and glycol-based solvents, pigments such as oxidized titanium, vengar, carbon black, etc. are usually used. You just need to add it by the method described in the above, and it will help you! The amount is 50% or less, preferably 35% or less, based on the weight of the fluoropolymer described above, and the added amount exceeds 50%. Tends to lose non-stickiness.
  • desiccants such as Sinidai Cobalt, silicone oils, etc. Do etc. of defoamers, main switch zone les cell Honoré Russia over scan, PVA, mosquitoes Le Bo key sheet of bi two Le port Li
  • ammonia water or other liquids such as mono, di, triethanolamine, etc. as necessary. ! ] can do .
  • the amount of the fluorocarbon It is 0.1 to 300% by weight based on the weight of the coalesced fine particles, and preferably 0.5 to 100%. Up to 30% is even more preferred, the effect is ineffective when the amount used is less than 0.1%, and when burning exceeds 300%. In addition, shrinkage becomes severe, and it becomes difficult to form a coating film.
  • the amount of the filler used is 0.2 to 20%, based on the total weight of the filler and the fluoropolymer, and 1 to 5% L. More preferably, the content is 2 to 10%, more preferably, and if the amount is less than 0.2%, the abrasion resistance of the coating film is deteriorated. There is a tendency that the non-adhesiveness decreases when the content exceeds 20%.
  • the concentration of the solid component of the fluoropolymer coating composition of the present invention is 20 to 80%, and 40 to 70%. It is preferable that when the concentration is less than 20%, a coating film tends to be unable to form, and when the concentration exceeds 80%, spraying is possible. There is no tendency.
  • parts an aqueous dispersion of fine particles of a fluoropolymer (solid content: 60%) and stir the mixture under stirring.
  • 0.05 to 198 parts of the activator, 2 to 22 parts of the liquid carrier and, if necessary, 0.05 to 10 parts of the additive are sequentially introduced.
  • stirring the mixture at 5 to 30 ° C. for 10 to 40 minutes until the mixture becomes uniform, the fluoropolymer coating composition of the present invention can be obtained.
  • the composition of the present invention may be applied to various substrates by a conventional method, for example, metal, hollow, glass, ceramic, or the like. After roughening the surface by mixing and sand-blasting the surface of the mix, a primer mixture (Polyflon Enzyme, manufactured by Daikin Industries, Ltd.) Prime mel (EK-199 BKN) and soak in the composition, or spray, roll, coat, or doctor the composition. The coating is performed at a temperature sufficient to dissolve the fluoropolymer in the coated composition (340 to 415 ° C). Bake for 10 to 30 minutes in C).
  • a primer mixture Polyflon Enzyme, manufactured by Daikin Industries, Ltd.
  • Prime mel EK-199 BKN
  • the coating is performed at a temperature sufficient to dissolve the fluoropolymer in the coated composition (340 to 415 ° C). Bake for 10 to 30 minutes in C).
  • the thickness of the molten coating is 30 / m or more, and the upper limit is not particularly limited.
  • a specific polyether-based resin and a sludge of the polyether-based high molecular surfactant are left in the coating film, and the non-adhesiveness is rapidly reduced. Therefore, 30 to 70 / zm is preferable.
  • the composition of the present invention may be used, for example, in metal cooking utensils, Although most useful for painting rypans, this composition may also be used to coat other products that require corrosion resistance. .
  • Other products are made of materials that can withstand the glass or the baking temperature used, e.g., bearings, e.g., bearings , Knobs, Wires, Metallic Foil, Boilers, Pipes, Ship Bottoms, Oven Linings, Iron Bottom Plates, Baking Pans, Rice Cookers, Gril Pots, electric pots, ice trays, snow shovels, plows, shots, conveyors, horns, molds, dies, saws, etc. You can use tools like knives, kitchen knives, hoppers, and other industrial containers (especially for the semiconductor industry) and molds.
  • the fluoropolymer coating composition of the present invention is preferably made of, for example, a sponge.
  • the composition can be applied thickly and can form a coating film having excellent abrasion resistance, corrosion resistance, non-adhesion and whiteness, and the composition can be overcoated. Goods can maintain quality for a long time.
  • composition can form a coating that is thicker, more abrasion-resistant, corrosion-resistant, non-adhesive, and excellent in whiteness, and the composition can be overcoated. Refurbished goods can maintain their quality for a longer period of time.
  • This composition can further form a coating film having excellent gloss, corrosion resistance, and excellent whiteness, and the product overcoated with the composition is In addition, quality can be maintained for a long time.
  • the composition can be applied thickly and can form a coating having excellent abrasion resistance, corrosion resistance, non-adhesion and whiteness, and the composition can be overcoated. Goods can maintain quality for a long time.
  • This composition can form a coating film that is thicker and more excellent in whiteness, and a product overcoated with the composition can be used for a longer time. The quality can be maintained.
  • This composition can further form a coating film which is excellent in thick coating, glossiness, corrosion resistance, and whiteness, and is overcoated with the composition.
  • the product can maintain its quality for a long time.
  • Example 1 The components shown below were mixed in the order described.
  • PTFE aqueous dispersion Polyfluorodispersion D-l manufactured by Daikin Industries, Ltd.
  • an aqueous dispersion having a solid content of 60% based on PTFE
  • It contains 6% of polyoxyethylene alkyl phenol ether (EO 10) as a dispersion stabilizer.
  • EO polyoxyethylene alkyl phenol ether
  • Polyester resin emulsion manufactured by Sanyo Chemical Industry Co., Ltd., 0 -Marine UA—200, a molecular weight of about 200,000
  • Oxidation catalyst sodium nitrite 10% by weight aqueous solution
  • Viscosity Measured by rotating the rotor at 60 rpm for 2 minutes using a B-type rotational viscometer (No. 2 rotor) (temperature 25 ° C).
  • the primer mixture (Polyflon Enamel EK-1909B KN (Polymer) manufactured by Daikin Industries, Ltd.) )
  • a primer made of an ano-re-dum priming so that the thickness after drying becomes 15 m after drying.
  • Black limit film thickness Spray-painted on aluminum plate of non-blast, baked under the above-mentioned drying (air-drying, quick-drying) and baking conditions, electromagnetic It was measured with a formula film thickness gauge.
  • Paints having the compositions shown in Table 1 were prepared in the same manner as in Example 1, and evaluated in the same manner as in Example 1.
  • Oxyethylene propylene copolymer random copolymer (Newport 75H — 90000, 20% aqueous solution manufactured by Sanyo Chemical Industries, Ltd.).
  • R is H
  • Y is an oxygen atom
  • a 300
  • b 75
  • c 1.
  • Oxyethylene propylene copolymer block copolymer (Newport PE128, 20% aqueous solution manufactured by Sanyo Chemical Industry Co., Ltd.).
  • R is H
  • Y is an oxygen atom
  • a is 1822
  • b is 69
  • d is 182.
  • Oxyethylene propylene copolymer block copolymer (Newport V — 10 — C, 20% aqueous solution manufactured by Sanyo Chemical Industries, Ltd.) .
  • R is H
  • Y is an oxygen atom
  • a is 182
  • b is 69
  • d is 182
  • Z is a trivalent aliphatic saturated hydrocarbon
  • e is 3.
  • the fluoropolymer polymer coating composition of the present invention can be applied in a thick coat, has abrasion resistance, corrosion resistance, It is possible to form a coating film that is excellent in non-adhesiveness and has no coloring, and uses the specific polyether-based resin emulsion described above. It is excellent in workability, safety and environment, and it is evenly dispersed in the paint, so the film-forming effect is large and the composition is overcoated. Goods can maintain whiteness and quality for a long time.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de revêtement de copolymère qui peut s'appliquer en couche épaisse et qui est capable de former un film de revêtement présentant de bonnes qualités de résistance à l'usure et à la corrosion, d'absence de tendance au collant, et de blancheur. L'invention concerne également un article ayant reçu une couche de finition de la composition. Cette composition comprend de fines particules d'un fluoropolymère, d'une résine de polyéther pour une proportion en masse de 0,1% à 300% par rapport à la masse des fines particules, d'un convertisseur catalytique d'oxydation, et d'un support liquide. En l'occurrence, la résine de polyéther est représentée par la formule générale (I): R1-Y1-(A-B)-R1. Dans cette formule, R1 est hydrogène ou alkyle. Y1 est atome d'oxygène, ou groupe éther, ester, uréthane ou thionyle. A est un reste d'un oxyde d'alkylène portant au moins 3 atomes de carbone nécessitant que la masse moléculaire du groupe fonctionnel alkylène oxyde soit de 1x10?3 à 1x104¿. Enfin, B qui est un groupe uréthane, thionyle ou phosphate nécessitant que le segment entre parenthèses représente un reste obtenu par copolymérisation alternée, présente une température de décomposition ou de vaporisation qui n'excède par la température de décomposition du fluoropolymère.
PCT/JP1998/004604 1997-10-24 1998-10-13 Composition de revetement de fluoropolymere et article ainsi revetu Ceased WO1999021927A1 (fr)

Priority Applications (2)

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JP2000518024A JP3649124B2 (ja) 1997-10-24 1998-10-13 フルオロ重合体コーティング組成物および塗装物品
KR10-2000-7003943A KR100530720B1 (ko) 1997-10-24 1998-10-13 불소 중합체 코팅 조성물 및 도장물품

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JP9/291883 1997-10-24

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Cited By (4)

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JP2008500448A (ja) * 2004-05-19 2008-01-10 フレクスコン カンパニー インク 基材をコートおよび印刷するための液体調合物
WO2014021420A1 (fr) 2012-08-01 2014-02-06 ダイキン工業株式会社 Ustensile de cuisson
US8796370B2 (en) 2007-08-10 2014-08-05 Daikin Industries, Ltd. Coating composition
JP2017529418A (ja) * 2014-08-04 2017-10-05 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． 粉末組成物

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8664323B2 (en) * 2010-06-25 2014-03-04 3M Innovative Properties Company Fluorinated composition, method of coating the composition, and article thereby
CN105440170B (zh) * 2016-01-29 2018-07-20 中远关西涂料（上海）有限公司 一种改性氟碳树脂及由其制备的无异氰酸酯氟碳树脂

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JPH02222439A (ja) * 1989-02-23 1990-09-05 Daikin Ind Ltd フッ化ビニリデン系重合体の水性組成物
JPH03154628A (ja) * 1989-11-09 1991-07-02 Nippon Niyuukazai Kk 合成樹脂エマルジョン用濡れ剤
WO1996013555A1 (fr) * 1994-11-01 1996-05-09 Daikin Industries, Ltd. Composition de revetement fluoropolymere, et article ainsi revetu
JPH08269286A (ja) * 1995-03-24 1996-10-15 Ausimont Spa 有機溶媒におけるポリテトラフルオロエチレン分散物およびそれに使用される分散剤
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JPS5250323A (en) * 1975-10-22 1977-04-22 Onoda Cement Co Ltd Water-dispersed vinyl fluoride resin paint composition
JPH02222439A (ja) * 1989-02-23 1990-09-05 Daikin Ind Ltd フッ化ビニリデン系重合体の水性組成物
JPH03154628A (ja) * 1989-11-09 1991-07-02 Nippon Niyuukazai Kk 合成樹脂エマルジョン用濡れ剤
WO1996013555A1 (fr) * 1994-11-01 1996-05-09 Daikin Industries, Ltd. Composition de revetement fluoropolymere, et article ainsi revetu
JPH08269286A (ja) * 1995-03-24 1996-10-15 Ausimont Spa 有機溶媒におけるポリテトラフルオロエチレン分散物およびそれに使用される分散剤
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008500448A (ja) * 2004-05-19 2008-01-10 フレクスコン カンパニー インク 基材をコートおよび印刷するための液体調合物
US9777167B2 (en) 2004-05-19 2017-10-03 Flexcon Company, Inc. Liquid formulations for coating and printing substrates
US9777168B2 (en) 2004-05-19 2017-10-03 Flexcon Company, Inc. Liquid formulations for coating and printing substrates
US8796370B2 (en) 2007-08-10 2014-08-05 Daikin Industries, Ltd. Coating composition
WO2014021420A1 (fr) 2012-08-01 2014-02-06 ダイキン工業株式会社 Ustensile de cuisson
JP2014042824A (ja) * 2012-08-01 2014-03-13 Daikin Ind Ltd 調理器具
JP2017529418A (ja) * 2014-08-04 2017-10-05 ソルベイ スペシャルティ ポリマーズ イタリー エス．ピー．エー． 粉末組成物
US11001721B2 (en) 2014-08-04 2021-05-11 Solvay Specialty Polymers Italy S.P.A. Powder composition

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CN1276818A (zh) 2000-12-13
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JP3649124B2 (ja) 2005-05-18
CN1239646C (zh) 2006-02-01
TW517076B (en) 2003-01-11

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