Classifications

• • 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
  • C08F16/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
  • C08F16/02—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
• • 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
  • C08F214/00—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
  • C08F214/18—Monomers containing fluorine
• • 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
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
• • 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
  • 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
  • C09D133/00—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 only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols

Definitions

• the present invention relates to an aqueous dispersion containing a fluoropolymer, an aqueous paint, and a coated article.
• Patent Document 1 discloses an aqueous paint containing an aqueous dispersion containing a fluoropolymer containing units based on fluoroethylene and units based on a monomer having a polyoxyalkylene group.
• An aqueous dispersion is required to have excellent storage stability.
• the physical properties required of a coating film formed using an aqueous coating material containing an aqueous dispersion have been further improved, and water repellency (particularly, dynamics that serve as a standard for water attached to the coating film to slide down).
• a coating film excellent in water repellency is demanded.
• the present inventors have found that the aqueous dispersion described in Patent Document 1 has good storage stability, but the water repellency of a coating film formed using an aqueous paint containing the aqueous dispersion is insufficient. I found out.
• the present invention has an object to provide an aqueous dispersion, an aqueous coating material, and a coated article that can form a coating film excellent in water repellency and is excellent in storage stability.
• the inventors of the present invention include a specific amount of a unit based on a monomer represented by the formula X 1 -Y 1 -Z 1 described below, and CF 3 —CH ⁇ CHF and CF 3 —. It has been found that a desired effect can be obtained by using a fluoropolymer containing a unit based on at least one selected from the group consisting of CF ⁇ CH 2 , and the present invention has been achieved. That is, the present inventors have found that the above problem can be solved by the following configuration.
• the symbols in the formula have the following meanings.
• X 1 and X 2 are each independently CH 2 ⁇ CHC (O) O—, CH 2 ⁇ C (CH 3 ) C (O) O—, CH 2 ⁇ CHOC (O) —, CH 2 ⁇ CHCH 2 OC (O) —, CH 2 ⁇ CHO— or CH 2 ⁇ CHCH 2 O—.
• Y 1 is a divalent linking group.
• Z 1 is a group represented by the formula —O (M 1 O) m L 1 or a group represented by the formula —C (O) OR 1 .
• M 1 is an alkylene group having 2 to 4 carbon atoms
• m is an integer of 6 ⁇ 24
• L 1 is hydrogen atom, alkyl group of 4 or less, or the formula -SO 3 carbon - represented by A + (Wherein A + is NH 4 + , Na + or K + ), and R 1 is an alkyl group having 1 to 20 carbon atoms.
• Z 2 is a monovalent hydrocarbon group having 1 to 24 carbon atoms.
• the group represented by the formula —O (M 1 O) m L 1 is a group represented by the formula —O (CH 2 CH 2 O) m H; The aqueous dispersion according to any one of the above.
• the content of the unit based on the monomer represented by the formula X 2 -Z 2 is 10 to 50 mol% with respect to the total units contained in the fluoropolymer, The aqueous dispersion according to any one of the above.
• the fluoropolymer further includes a (meth) acrylate polymer, The aqueous dispersion according to any one of [1] to [9], wherein the fluoropolymer and the (meth) acrylate polymer are core-shell polymers having the fluoropolymer as a core portion and the (meth) acrylate polymer as a shell portion. liquid.
• a coating film excellent in water repellency (particularly, dynamic water repellency that is a measure for water adhering to the coating to slide down, the same shall apply hereinafter) can be formed, and storage stability can be formed. It is possible to provide an aqueous dispersion, an aqueous coating material, and a coated article excellent in the above.
• (Meth) acrylate is a general term for “acrylate” and “methacrylate”.
• the “unit” is a general term for an atomic group derived directly from monomer polymerization and derived from one molecule of the monomer, and an atomic group obtained by chemically converting a part of the atomic group. The content (mol%) of each unit with respect to all units contained in the polymer is obtained by analyzing the polymer by a nuclear magnetic resonance spectrum method, and can be estimated from the charged amount of monomer.
• “Average particle diameter” is a value of D50 determined by a dynamic light scattering method using ELS-8000 (manufactured by Otsuka Electronics Co., Ltd.).
• D50 is a particle diameter value of 50 volume% of the cumulative volume calculated from the small particle side in the particle size distribution of the particle measured by the dynamic light scattering method.
• “Number average molecular weight” is a value measured by gel permeation chromatography using polystyrene as a standard substance. “Number average molecular weight” is also referred to as “Mn”.
• “Hydroxyl value” is a value measured according to the method of JIS K1557-1 (2007).
• the “acid value” is a value measured according to the method of JIS K 0070-3 (1992).
• “Film thickness” is a value measured using an eddy current film thickness meter (trade name “EDY-5000”, manufactured by Sanko Electronics Co., Ltd.).
• a unit (hereinafter also referred to as “unit F”) based on at least one kind (hereinafter also referred to as “monomer F”), a monomer represented by the formula X 1 -Y 1 -Z 1 (hereinafter referred to as “monomer 1”).
• a unit based on a monomer represented by the formula X 2 -Z 2 hereinafter also referred to as “monomer 2” (hereinafter referred to as “unit 1”).
• unit 2 Also referred to as “unit 2”).
• the content of the unit 1 is 1 to 5 mol% with respect to all units contained in the fluoropolymer.
• the fluoropolymer is dispersed in water means a state in which the fluoropolymer is dispersed in water as particles.
• aqueous coating material containing a fluoropolymer containing units based on fluoroethylene for example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene
• fluoroethylene for example, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethylene
• a method of introducing a unit (for example, unit F) based on a monomer having a —CF 3 group such as fluoropropylene into the fluoropolymer can be considered. If the fluoropolymer has —CF 3 groups, it is presumed that —CF 3 groups are arranged on the surface of the coating film to improve the water repellency of the coating film.
• the fluoropolymer contains the unit F
• the water dispersibility of the fluoropolymer is lowered, and the storage stability of the aqueous dispersion containing the fluoropolymer is lowered.
• the water repellency of the coating film and the storage stability of the aqueous dispersion were in a trade-off relationship.
• the present inventors have obtained an aqueous dispersion excellent in storage stability of an aqueous dispersion by including a specific amount of unit 1 in a fluoropolymer containing units F among units based on fluoropropylene.
• the water repellency of the coating film formed using an aqueous paint containing this aqueous dispersion was excellent. This is because when monomer F is used among fluoropropylenes, monomer F is well copolymerized with monomer 1, and the hydrophilicity imparted by unit 1 and the water repellency imparted by unit F are balanced. Conceivable. This effect is particularly prominent within the preferred range of the present invention.
• the coating film formed from the aqueous coating material containing the aqueous dispersion of this invention is also called “this coating film.”
• the proportion of units based on CF 3 —CF ⁇ CH 2 with respect to the total of both units is preferably 10 to 90 mol%, more preferably 60 to 85 mol%.
• the content of unit F is preferably 20 to 80 mol%, more preferably 30 to 70 mol%, based on all units contained in the fluoropolymer. If the content of the unit F is 20 mol% or more, the water repellency of the coating film is further improved. When the content of the unit F is 80 mol% or less, the storage stability of the aqueous dispersion is more excellent.
• the unit 1 contained in the fluoropolymer in the present invention is a unit based on a monomer represented by the formula X 1 -Y 1 -Z 1 .
• Unit 1 contributes to the improvement of the water dispersibility of the fluoropolymer and improves the storage stability of the aqueous dispersion.
• the symbols in the formula have the following meanings.
• Y 1 is a divalent linking group.
• the divalent linking group is preferably a divalent saturated hydrocarbon group having 2 to 12 carbon atoms.
• the divalent saturated hydrocarbon group may be linear or branched. Moreover, the divalent saturated hydrocarbon group may consist of a ring structure or may contain a ring structure.
• Z 1 is a group represented by the formula —C (O) OR 1
• the divalent saturated hydrocarbon group may have a group represented by the formula —SO 3 ⁇ A +. May have an etheric oxygen atom.
• a + is NH 4 + , Na + or K + .
• the divalent saturated hydrocarbon group is preferably an alkylene group containing an alkylene group having 2 to 12 carbon atoms or a cycloalkylene group having 6 to 8 carbon atoms.
• Examples of the divalent saturated hydrocarbon group include a group represented by the formula —CH 2 —cycloC 6 H 10 —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 CH 2 — and a formula —CH.
• a group represented by 2 CH (Y 11 ) — is preferred.
• -CycloC 6 H 10 representss a cyclohexylene group, and the bonding site of (-cycloC 6 H 10- ) is not particularly limited, and is usually 1,4-.
• Y 11 represents an alkyl group having 1 to 10 carbon atoms.
• Z 1 is a group represented by the formula —O (M 1 O) m L 1 or a group represented by the formula —C (O) OR 1 , and the formula —O (M 1 O) m L 1 It is preferable that it is group represented by these.
• M 1 is an alkylene group having 2 to 4 carbon atoms, preferably —CH 2 CH 2 —. When M 1 has 3 or 4 carbon atoms, M 1 may be a linear alkylene group or a branched alkylene group.
• m is an integer of 6 to 24, and an integer of 10 to 20 is more preferable.
• L 1 is a hydrogen atom, an alkyl group having 4 or less carbon atoms, or a group represented by the formula —SO 3 ⁇ A + .
• a + is NH 4 + , Na + or K + .
• R 1 is an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 8 to 15 carbon atoms. The alkyl group may be linear or branched. It is preferable that at least a part of m 1 M 1 is an alkylene group having 2 carbon atoms (CH 2 CH 2 ). When a part of M 1 is an alkylene group having 3 or 4 carbon atoms, m The number of alkylene groups having 2 carbon atoms with respect to M 1 is preferably 50% or more, and more preferably 80% or more. When two or more types of (M 1 O) are present, their bonding order may be random or block.
• L 1 is preferably a hydrogen atom or an alkyl group having 4 or less carbon atoms, and the alkyl group having 4 or less carbon atoms is preferably a methyl group. L 1 is particularly preferably a hydrogen atom.
• Monomer 1 may use 2 or more types together.
• the content of unit 1 is 1 to 5 mol%, preferably 1.0 to 5.0 mol%, based on the total units of the fluoropolymer, from the viewpoint of storage stability of the aqueous dispersion. More than 0 mol% and less than 3.5 mol% is more preferable, and 1.2 mol% to 3.0 mol% is particularly preferable.
• the unit 2 contained in the fluoropolymer in the present invention is a unit based on a monomer represented by the formula X 2 -Z 2 .
• X 2 includes CH 2 ⁇ CHOC (O) —, CH 2 ⁇ CHCH 2 OC (O) —, CH 2 ⁇ CHO— and CH 2 ⁇ CHCH 2 O—.
• CH 2 ⁇ CHOC (O) — and CH 2 ⁇ CHCH 2 OC (O) — are particularly preferred.
• X 2 is CH 2 ⁇ CHOC (O) — or CH 2 ⁇ CHCH 2 OC (O) —, it is considered that the charging of the fluoropolymer is suppressed by the ester bond that is an included polar group. Therefore, this coating film with high surface smoothness is obtained. As a result, this coating film having particularly excellent water repellency can be obtained.
• Z 2 is a monovalent hydrocarbon group having 1 to 24 carbon atoms.
• the monovalent hydrocarbon group may be linear or branched. Moreover, the monovalent hydrocarbon group may consist of a ring structure or may contain a ring structure.
• the monovalent hydrocarbon group may be a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group.
• the monovalent hydrocarbon group is preferably an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, an alkyl group having 2 to 12 carbon atoms, a cycloalkyl group having 6 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.
• An aralkyl group having 7 to 12 carbon atoms is particularly preferred.
• alkyl group examples include a methyl group, an ethyl group, a tert-butyl group, a hexyl group, a nonyl group, a decyl group, and a dodecyl group.
• cycloalkyl group examples include a cyclohexyl group.
• aralkyl group examples include a benzyl group.
• aryl group examples include a phenyl group and a naphthyl group.
• Two or more monomers 2 may be used in combination.
• monomer 2 include ethyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, vinyl acetate, pivalic acid vinyl ester, neononanoic acid vinyl ester (trade name “Veoba 9” manufactured by HEXION), neodecane Acid vinyl ester (trade name “Beoba 10” manufactured by HEXION), benzoic acid vinyl ester tert-butyl (meth) acrylate, and benzyl (meth) acrylate.
• the content of unit 2 is preferably 1 to 50 mol%, more preferably 5 to 40 mol%, based on all units contained in the fluoropolymer.
• the fluoropolymer in the present invention includes all units based on the monomer 2 in which X 2 is CH 2 ⁇ CHOC (O) — or CH 2 ⁇ CHCH 2 OC (O) —.
• the content is preferably 10 to 50 mol%, more preferably 15 to 40 mol%, based on the unit. In this case, the surface smoothness of the coating film is further improved, and the water repellency is particularly excellent.
• the unit contains an ester bond which is a polar group and suppresses charging of a particularly highly hydrophobic fluoropolymer.
• the coating film is formed from the aqueous dispersion of the present invention. It is considered that the particulate fluoropolymer is easily packed densely when formed.
• the fluoropolymer may contain a unit having a hydroxy group or a carboxy group (hereinafter also referred to as “unit 3”) other than the unit based on the monomer represented by the formula X 1 —Y 1 —Z 1 . .
• Unit 3 may be a unit based on a monomer having a hydroxy group or a carboxy group (hereinafter also referred to as “monomer 3”), and the hydroxy group of the fluoropolymer containing the unit having a hydroxy group is converted into a carboxy group. It may be a unit obtained by making it.
• Such units include units in which part or all of the hydroxy groups are converted to carboxy groups by reacting an acid anhydride or the like with a fluoropolymer containing units 3 having a hydroxy group.
• the monomer 1 having a hydroxy group in which L 1 is a hydrogen atom is not included in the category of the monomer 3.
• Monomer 3 does not contain a fluorine atom.
• Examples of the monomer 3 having a carboxy group include unsaturated carboxylic acid and (meth) acrylic acid, and a monomer represented by the formula X 31 -Z 31 (hereinafter also referred to as “monomer 31”) is preferable.
• X 31 is CH 2 ⁇ CH—, CH (CH 3 ) ⁇ CH— or CH 2 ⁇ C (CH 3 ) —, and preferably CH 2 ⁇ CH— or CH (CH 3 ) ⁇ CH—.
• Z 31 is a carboxy group or a carboxyalkyl group having 1 to 12 carbon atoms, and is preferably a carboxy group or a carboxyalkyl group having 1 to 10 carbon atoms.
• Examples of the monomer 3 having a hydroxy group include vinyl ether, vinyl ester, allyl ether, allyl ester, (meth) acrylic acid ester and allyl alcohol having a hydroxy group, and a monomer represented by the formula X 32 -Z 32 ( Hereinafter, also referred to as “monomer 32”) or allyl alcohol is preferable.
• Z 32 is a monovalent saturated hydrocarbon group having 2 to 12 carbon atoms and having a hydroxy group.
• the monovalent saturated hydrocarbon group may be linear or branched. Moreover, the monovalent saturated hydrocarbon group may consist of a ring structure or may contain a ring structure.
• the monovalent saturated hydrocarbon group is preferably an alkyl group containing an alkyl group having 2 to 6 carbon atoms or a cycloalkylene group having 6 to 8 carbon atoms.
• the monomer 3 may use 2 or more types together.
• the hydroxy group or carboxy group of unit 3 becomes a crosslinking point, the crosslinking reaction between the fluoropolymers proceeds through the curing agent, and the strength of the coating film is increased. Since it improves, film physical properties, such as a weather resistance, water resistance, chemical resistance, and heat resistance, improve.
• the content of unit 3 is preferably from 0.1 to 35 mol%, more preferably from 1 to 20 mol%, particularly preferably from 5 to 15 mol%, based on all units contained in the fluoropolymer.
• the fluoropolymer preferably contains 20 to 80 mol%, 1 to 5 mol%, and 1 to 50 mol% of the unit F, the unit 1 and the unit 2 in this order with respect to all units of the fluoropolymer.
• the Mn of the fluoropolymer is preferably 30,000 to 200,000, more preferably 50,000 to 180,000.
• the hydroxyl value of the fluoropolymer is preferably 1 to 150 mgKOH / g.
• the acid value of the fluoropolymer is preferably 1 to 150 mgKOH / g.
• the content of the fluoropolymer in the aqueous dispersion of the present invention is preferably 10 to 70% by mass with respect to the total mass of the aqueous dispersion.
• the aqueous dispersion of the present invention may contain a (meth) acrylate polymer.
• the fluoropolymer and the (meth) acrylate polymer are dispersed in water in the aqueous dispersion.
• “The fluoropolymer and (meth) acrylate polymer are dispersed in water” means a state in which the fluoropolymer and (meth) acrylate polymer are dispersed in water as particles.
• the fluoropolymer and the (meth) acrylate polymer may be a core-shell polymer having a fluoropolymer as a core part and a (meth) acrylate polymer as a shell part.
• the core-shell polymer is dispersed in water as particles (core-shell particles).
• the core-shell particle is a particle having a so-called core-shell structure having a fluoropolymer core and a (meth) acrylate polymer shell located on the surface of the core.
• the shell portion may cover a part of the surface of the core portion, or may cover the entire core portion.
• the fluoropolymer and the (meth) acrylate polymer may be independently dispersed in water. In this case, the fluoropolymer is dispersed in the aqueous dispersion as fluoropolymer particles, and the (meth) acrylate polymer is dispersed as (meth) acrylate polymer particles.
• the (meth) acrylate polymer preferably contains units based on alkyl (meth) acrylate.
• alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and cyclohexyl (meth) acrylate. At least one selected from these groups is preferred.
• Alkyl (meth) acrylate is selected from the group consisting of methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate from the viewpoint of processability of this coating film. More preferred is at least one selected from the group consisting of The content of units based on alkyl (meth) acrylate is preferably 75 to 100 mol% with respect to the total units of the (meth) acrylate polymer.
• the (meth) acrylate polymer preferably further contains units based on hydroxyalkyl (meth) acrylate. Since the hydroxy group in the unit based on hydroxyalkyl (meth) acrylate functions as a crosslinkable group, the curability of the coating film is improved.
• Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate. Is preferred.
• the (meth) acrylate polymer contains a unit based on hydroxyalkyl (meth) acrylate in an amount of more than 0 mol% and not more than 20 mol% with respect to all units of the (meth) acrylate polymer. Is preferred. Two or more hydroxyalkyl (meth) acrylates may be used in combination.
• the (meth) acrylate polymer may contain less than 25 mol% of units other than units based on alkyl (meth) acrylate and units based on hydroxy (meth) acrylate with respect to all units contained in the (meth) acrylate polymer. Good.
• Specific examples of the other monomer include unsaturated carboxylic acid, hydrolyzable silyl group-containing monomer, hydroxyl group-containing alkyl vinyl ether, carboxylic acid vinyl ester, and ⁇ -olefin.
• the content of the fluoropolymer with respect to the total mass of the fluoropolymer and the (meth) acrylate polymer is preferably 30 to 70% by mass, and from the viewpoint of the balance between weather resistance and processability, 40 to 60% by mass is more preferable. preferable.
• the aqueous dispersion of the present invention contains particles of fluoropolymer and particles of (meth) acrylate polymer
• the total content of the particles of fluoropolymer and (meth) acrylate polymer is based on the total mass of the aqueous dispersion. 10 to 70% by mass is preferable.
• the aqueous dispersion of the present invention contains core-shell particles
• the content of the core-shell particles is preferably 10 to 70% by mass with respect to the total mass of the aqueous dispersion.
• the average particle diameter of the fluoropolymer particles, the (meth) acrylate polymer particles, and the core-shell particles is preferably independently from 30 to 300 nm. From the viewpoint of more excellent water repellency of the coating film, 50 to 200 nm is more preferable, and 80 to 150 nm is particularly preferable.
• the aqueous dispersion of the present invention contains only water or a mixture of water and a water-soluble organic solvent as a coating solvent (dispersion medium).
• a water-soluble organic solvent in the mixed solution include methanol, ethanol, propanol, butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, and tripropylene glycol.
• the content of the water-soluble organic solvent in the mixed solution is preferably 1 to 40 parts by mass with respect to 100 parts by mass of water.
• the aqueous dispersion of the present invention preferably contains 10 to 90% by mass of water with respect to the total mass of the aqueous dispersion.
• the aqueous dispersion of the present invention may contain components other than those described above (hereinafter also referred to as “other components”) as long as the effects of the present invention are not impaired.
• other components include surfactants and molecular weight regulators.
• a fluoropolymer containing units F, 1 and 2 is obtained by polymerizing fluoroolefin, monomer 1 and monomer 2 in a system containing water.
• distributed in water is mentioned.
• monomer 1 and monomer 2 monomer 3 may be further used.
• Other monomers may be further used.
• the usage-amount of each component can be suitably determined so that content of each component contained in the aqueous dispersion obtained may become content of each component contained in the aqueous dispersion of this invention mentioned above.
• a surfactant, a radical polymerization initiator, a chain transfer agent, a chelating agent, a pH adjusting agent and the like may be added.
• Specific examples of the polymerization method include an emulsion polymerization method and a suspension polymerization method.
• the polymerization temperature is usually from 0 to 100 ° C.
• the polymerization pressure is usually 0.2 to 5 MPa.
• a dispersion in which a fluoropolymer is dispersed in water is obtained, and then an alkyl (meth) acrylate is polymerized to use the fluoropolymer as a core part.
• an alkyl (meth) acrylate is polymerized to use the fluoropolymer as a core part.
• a first aqueous dispersion containing water and a fluoropolymer dispersed in water, and a (meth) acrylate polymer containing water dispersed in water is mixed with the second aqueous dispersion to obtain an aqueous dispersion in which the fluoropolymer and the (meth) acrylate polymer are dispersed in water.
• hydroxyalkyl (meth) acrylate may be used in combination.
• the aqueous paint of the present invention includes the aqueous dispersion of the present invention, as well as pigments (inorganic colored pigments, organic colored pigments, extender pigments, etc.), curing agents, curing aids, Film-forming aids, thickeners, antifoaming agents, light stabilizers, surface conditioners, dispersants, rust inhibitors, silane coupling agents, antifouling agents, UV absorbers, light stabilizers, color tone adjusters, etc.
• An additive may further be included.
• the water-based paint may further contain a polymer other than the fluoropolymer and (meth) acrylate polymer of the present invention.
• the aqueous paint can be produced by appropriately mixing the aqueous dispersion of the present invention with the above additives.
• the aqueous paint preferably contains 10 to 80% by mass of the aqueous dispersion of the invention based on the total mass of the aqueous paint.
• the content of the aqueous dispersion of the present invention in the aqueous paint is more preferably 10 to 60% by mass relative to the total mass of the aqueous paint. If the said content is 10 mass% or more, the weather resistance of this coating film will improve, and if it is 80 mass% or less, the film formability of this aqueous coating material will improve.
• the water-based paint preferably contains 10 to 90% by mass of a fluoropolymer (the total of these when a (meth) acrylate polymer is included) with respect to the total mass of the water-based paint.
• the coated article of this invention has a base material and the coating film (this coating film) arrange
• the substrate include organic materials such as resin, rubber, and wood, inorganic materials such as concrete, glass, ceramics, and stone, iron, iron alloy, aluminum, and aluminum alloy.
• the film thickness of this coating film is preferably 10 to 100 ⁇ m. If the thickness of the coating film is 10 ⁇ m or more, the water repellency of the coating film is improved, and if it is 100 ⁇ m or less, the weather resistance of the coating film is improved.
• a coated article can be produced by applying the aqueous paint to the surface of a substrate and drying it to form the coating film.
• the aqueous paint may be applied directly to the surface of the substrate, or may be applied after a known surface treatment (such as a base treatment) is applied to the surface of the substrate. Furthermore, after forming the undercoat layer on the substrate, it may be applied onto the undercoat layer. Moreover, when this aqueous coating material contains a hardening
• the application method of the water-based paint include a method using a coating apparatus such as a brush, a roller, dipping, spraying, a roll coater, a die coater, an applicator, and a spin coater.
• the drying temperature and curing temperature after coating are preferably 25 ° C to 300 ° C.
• Examples 1 to 4 and 7 are examples, and examples 5 and 6 are comparative examples. However, the present invention is not limited to these examples.
• surface mentioned later shows a mass reference
• aqueous dispersion 1 containing fluoropolymer particles ( A solid concentration of 48% by mass was obtained.
• the average particle diameter of the fluoropolymer particles in the aqueous dispersion 1 was 115 nm.
• the fluoropolymer contained in the aqueous dispersion 1 includes a unit based on HFO-1234ze, a unit based on HFO-1234yf, a unit based on CM-15EOVE, a unit based on EVE, a unit based on V9, and a unit based on CHMVE.
• the polymer contained 40 mol%, 10 mol%, 2.0 mol%, 10 mol%, 29 mol%, and 9.0 mol% in this order.
• Examples 1 to 7 A pigment (72 g), a dispersant (5 g), an antifoaming agent (0.5 g), and ion-exchanged water (22.5 g) were mixed to obtain a mill base. Next, an aqueous dispersion 1 (70 g), a curing agent (8 g), a film-forming auxiliary (5 g), and a mill base (25 g) were mixed to obtain an aqueous paint 1. Aqueous paints 2 to 7 were obtained in the same manner as the aqueous paint 1 except that the aqueous dispersion 1 was changed to the aqueous dispersions 2 to 7, respectively.
• the storage stability of aqueous dispersion was evaluated from the amount of precipitate produced during storage. 50 mL of the aqueous dispersion was placed in a centrifuge tube and allowed to stand at 25 ° C. for 2 weeks, and the amount of the sediment that had settled at the bottom of the centrifuge tube was read from the scale. A: The amount of the precipitate is 0.1 mL or less. B: The amount of the precipitate is more than 0.1 mL and less than 0.5 mL. C: The amount of the precipitate is 0.5 mL or more.
• the dynamic contact angle of water with respect to the test piece was measured. Using a contact angle meter, drop 10 ⁇ L of pure water onto the surface of a horizontally placed test piece, gradually tilt the test piece, measure the tilt angle at which the droplet starts to slide, and determine the value of the dynamic contact angle. It was.
• S The dynamic contact angle of water with respect to the test piece is 25 degrees or less.
• A The dynamic contact angle of water with respect to the test piece is more than 25 degrees and not more than 30 degrees.
• B The dynamic contact angle of water with respect to the test piece is more than 30 degrees and less than 35 degrees.
• C The dynamic contact angle of water with respect to the test piece is 35 degrees or more.
• Table 2 summarizes the evaluation results of the coatings formed from the respective aqueous dispersions and aqueous paints.

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