Classifications

• • 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
  • C09D133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
  • C08L33/08—Homopolymers or copolymers of acrylic acid esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • 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
  • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
  • C09D133/062—Copolymers with monomers not covered by C09D133/06
  • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
• • 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
  • C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
  • C09D143/04—Homopolymers or copolymers of monomers containing silicon
• • 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
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/16—Antifouling paints; Underwater paints
  • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
  • C09D5/1662—Synthetic film-forming substance
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/10—Transparent films; Clear coatings; Transparent materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• the present invention relates to an aqueous dispersion, a coating film and a coated article.
• Fluorine-containing seed polymer using acrylic monomer as a monomer for seed polymerization is based on the weather resistance, chemical resistance, solvent resistance, heat resistance, and antifouling properties of the included fluoropolymer. Utilizing the processability, transparency, adhesion, and film-forming properties of coalescence, it is used in a wide range of industrial fields such as the automotive industry, semiconductor industry, chemical industry, paints, etc. as raw materials for various products or coating film forming components of paints. ing.
• Patent Document 1 describes a fluorine-containing copolymer aqueous dispersion having a hydroxyl group and a fluorine-containing copolymer aqueous coating composition in which a water-dispersible polyisocyanate compound is dispersed in water.
• the fluorinated copolymer aqueous dispersion is an acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms and / or an alkyl group having a carbon number of 1 to 1.
• Patent Document 2 discloses an acrylic acid alkyl ester having an alkyl group having 1 to 18 carbon atoms and / or methacrylic acid having an alkyl group having 1 to 18 carbon atoms in the presence of 100 parts by weight of vinylidene fluoride polymer particles. It is obtained by emulsion polymerization in an aqueous medium of 5 to 95 parts by weight of a monomer mixture containing an alkyl ester and, if necessary, an ethylenically unsaturated compound copolymerizable with these monomers. A fluoropolymer aqueous dispersion characterized by a particle size of 0.05 to 3 ⁇ m is described.
• Patent Document 3 discloses that at least one monomer selected from the group consisting of acrylic acid esters and methacrylic acid esters, unsaturated carboxylic acids, and hydrolyzable silyl groups, using fluoropolymer particles as seed particles.
• Patent Document 4 has (a) an emulsion of an organic synthetic resin, (b) a coupling agent, and (c) a group other than the organic synthetic resin (a) and capable of reacting with the coupling agent (b).
• a resin composition for a low-contamination water-based paint comprising an organic compound for hydrophilization is described, and reactive ⁇ , ⁇ such as methyl acrylate in the presence of fluoropolymer particles as an organic synthetic resin emulsion.
• An emulsion of a fluorine-containing seed polymer obtained by seed polymerization of a monomer having an unsaturated group is described.
• Patent Document 5 discloses (A) vinylidene fluoride containing, as a structural unit, at least one fluoroolefin unit selected from the group consisting of a tetrafluoroethylene unit, a hexafluoropropylene unit, and a chlorotrifluoroethylene unit, and a vinylidene fluoride unit.
• an aqueous dispersion containing a fluorine-containing seed polymer that can form a coating film that is excellent in solvent resistance, antifouling property, and adhesion to a substrate is not known.
• the present invention aims to provide an aqueous dispersion capable of forming a coating film excellent in solvent resistance, antifouling property (dirt wiping property), and adhesion to a substrate. To do.
• the present invention is an aqueous dispersion comprising composite polymer particles, a polyisocyanate compound and water,
• the composite polymer particles are composed of a fluoropolymer (A) and an acrylic polymer (B), and either one or both of the fluoropolymer (A) and the acrylic polymer (B) contain a hydroxyl group and a hydrolyzable silyl group. It is an aqueous dispersion characterized by the above.
• the fluoropolymer (A) preferably contains at least one fluoroolefin unit selected from the group consisting of vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene.
• the acrylic polymer (B) preferably contains a hydroxyl group-containing (meth) acrylic acid ester unit and a hydrolyzable silyl group-containing unsaturated monomer unit.
• the acrylic polymer (B) preferably contains an acrylic ester unit, a methacrylic ester unit, an unsaturated carboxylic acid unit, a hydroxyl group-containing (meth) acrylic ester unit and a hydrolyzable silyl group-containing unsaturated monomer unit.
• the composite polymer particles preferably have a glass transition temperature of 0 to 70 ° C.
• the aqueous dispersion preferably contains 0.5 to 5.0 equivalents of a polyisocyanate compound with respect to 1 equivalent of a hydroxyl group contained in the fluoropolymer (A) and the acrylic polymer (B).
• the aqueous dispersion preferably further contains a film forming aid.
• the aqueous dispersion is preferably an aqueous paint.
• This invention is also a coating film characterized by being obtained from the above-mentioned aqueous dispersion.
• the present invention also provides a coated article obtained by coating the above-mentioned aqueous dispersion on a substrate.
• the present invention is also a fluorine-containing coating film characterized by having a siloxane bond and a urethane bond.
• the present invention provides a step of preparing a solution by dissolving or dispersing a polyisocyanate compound and a film-forming aid in a solvent, and an aqueous dispersion containing a fluoropolymer (A) and an acrylic polymer (B). It is also the manufacturing method characterized by including the process to add.
• the aqueous dispersion contains composite polymer particles and water, and the composite polymer particles are composed of a fluoropolymer (A) and an acrylic polymer (B), and the fluoropolymer (A) and the acrylic polymer. It is preferable that any one or both of (B) contain a hydroxyl group and a hydrolyzable silyl group.
• the aqueous dispersion of the present invention Since the aqueous dispersion of the present invention has the above-described configuration, it can form a coating film excellent in solvent resistance, antifouling property, and adhesion to a substrate.
• the antifouling property as is apparent from the evaluation method employed in the examples described later, draws a line with oily red, black, and blue magic on the coating film, left for 24 hours at room temperature, and then ethanol. When wiping with gauze soaked in, the characteristic that the said line can be wiped off easily is said.
• the coating film of this invention is equipped with the said structure, it is excellent in solvent resistance, antifouling property, and adhesiveness with a base material.
• the aqueous dispersion of the present invention contains composite polymer particles, a polyisocyanate compound and water.
• the composite polymer particles are composed of a fluoropolymer (A) and an acrylic polymer (B), and either one or both of the fluoropolymer (A) and the acrylic polymer (B) contain a hydroxyl group and a hydrolyzable silyl group. It is characterized by doing. Since the aqueous dispersion of the present invention contains composite polymer particles composed of a polymer containing a hydroxyl group and a hydrolyzable silyl group, it is excellent in solvent resistance, antifouling property, and adhesion to a substrate. A coating film can be formed. If either the hydroxyl group or the hydrolyzable silyl group is missing, an excellent coating film cannot be formed.
• the composite polymer particles preferably contain the fluoropolymer (A) and the acrylic polymer (B) in the same particle.
• the fluoropolymer (A) and the acrylic polymer (B) may be chemically bonded or may not be bonded.
• the hydroxyl group and the hydrolyzable silyl group only need to contain either the fluoropolymer (A) or the acrylic polymer (B).
• One polymer contains a hydroxyl group, and the other polymer is hydrolysable.
• a silyl group may be contained.
• the acrylic polymer (B) preferably contains a hydroxyl group and a hydrolyzable silyl group.
• the hydroxyl group is a group represented by —OH but does not include a hydroxyl group constituting a part of a carboxy group (—COOH).
• the hydrolyzable silyl group has a general formula: A group represented by —SiX 1 n X 2 3-n (X 1 is a C 1-10 alkoxy group, X 2 is H or a C 1-10 alkyl group, and n is an integer of 1 to 3). Preferably there is.
• the hydrolyzable silyl group needs to undergo a cross-linking reaction between silyl groups in the composite particle, so the reactivity is better, the hydrolyzable silyl group is More preferably, it is —Si (OCH 3 ) n X 2 3-n or —Si (OC 2 H 5 ) n X 2 3-n , and —Si (OCH 3 ) 3 or —Si (OC 2 H 5 ) 3 is more preferable.
• the mass ratio (A / B) of the fluoropolymer (A) to the acrylic polymer (B) is preferably 90/10 to 10/90, and preferably 80/20 to 20/80. More preferably, it is 70/30 or less, more preferably 30/70 or more, and particularly preferably 50/50 or more.
• the mass ratio (A / B) is within the above range, it is possible to form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to the substrate. If the amount of the fluoropolymer (A) is too large, the antifouling property of the coating film is improved, but the film forming property of the coating film may be lowered. When there are too many acrylic polymers (B), the film-forming property of a coating film will improve, but there exists a possibility that the antifouling property of a coating film may fall.
• the fluoropolymer (A) preferably contains a fluoroolefin unit.
• fluoroolefin examples include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE),
• Perfluoroolefins such as chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene, trifluoropropylene, hexafluoroisobutene, 2,3,3,3-tetrafluoro
• CTFE chlorotrifluoroethylene
• VF vinyl fluoride
• VdF vinylidene fluoride
• trifluoroethylene trifluoropropylene
• hexafluoroisobutene 2,3,3,3-tetrafluoro
• Non-perfluoroolefins such as propene, 1,3,3,3-tetrafluoropropene, and 1,1,3,3,3-pentafluoropropene are exemplified.
• perfluoro (alkyl vinyl ether) examples include perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), and the like.
• a functional group-containing fluoroolefin can also be used as the fluoroolefin.
• fluoroolefin examples include iodine-containing monomers such as perfluoro (6,6-dihydro-6-iodo-3-oxa-1 described in JP-B-5-63482 and JP-A-62-12734. Periodinated vinyl ethers such as -hexene) and perfluoro (5-iodo-3-oxa-1-pentene) can also be used.
• the fluoroolefin is preferably at least one selected from the group consisting of vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, hexafluoropropylene, and chlorotrifluoroethylene.
• the fluoroolefin is more preferably vinylidene fluoride and at least one selected from the group consisting of tetrafluoroethylene, hexafluoropropylene and chlorotrifluoroethylene.
• the fluoropolymer (A) may contain a non-fluorinated monomer unit copolymerizable with the fluoroolefin in addition to the fluoroolefin unit.
• non-fluorine monomers copolymerizable with the fluoroolefin include olefins such as ethylene, propylene, and isobutylene, vinyl ether monomers, allyl ether monomers, vinyl ester monomers, acrylics, and the like. And monomers based on methacrylic monomers and methacrylic monomers.
• the fluoropolymer (A) preferably includes a vinylidene fluoride unit as the fluoroolefin unit because it can form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to the substrate.
• the vinylidene fluoride unit is preferably 50 mol% or more with respect to all the polymerized units constituting the fluoropolymer (A). 70 mol% or more, more preferably 95 mol% or less.
• the fluoropolymer (A) includes VdF / TFE / CTFE copolymer, VdF / TFE copolymer, VdF / TFE / HFP copolymer, VdF / CTFE copolymer, VdF / HFP copolymer, and PVdF.
• VdF / TFE / CTFE 40 to 99/1 to 50/0 to 30 (mol%)
• VdF / TFE 50 to 99/1 to 50 ( Mol%)
• VdF / TFE / HFP 45 to 99/0 to 35/5 to 50 (mol%)
• VdF / CTFE 40 to 99/1 to 30 (mol%)
• VdF / HFP 50 to More preferably, it is at least one selected from the group consisting of 99/1 to 50 (mol%).
• the acrylic polymer (B) preferably contains at least an acrylic monomer unit.
• the acrylic monomer is preferably a (meth) acrylic acid ester.
• (meth) acrylic acid means acrylic acid or methacrylic acid.
• the acrylic polymer (B) preferably contains an acrylic ester unit or a methacrylic ester unit because it can form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to the substrate. More preferably, it contains an acrylate unit and a methacrylate unit.
• the total amount constituting the acrylic polymer (B) is preferably 64 to 99.8% by mass and more preferably 74 to 95.5% by mass with respect to the body unit.
• the (meth) acrylic acid ester is preferably an alkyl alkyl ester having an alkyl group having 1 to 10 carbon atoms or an alkyl methacrylate having an alkyl group having 1 to 10 carbon atoms.
• Examples of the (meth) acrylic acid ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, methyl methacrylate, n-propyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate,
• Examples include (meth) acrylic acid alkyl esters such as 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate.
• the (meth) acrylic acid ester is preferably at least one selected from the group consisting of methyl methacrylate, n-butyl acrylate, 2-ethylhexyl methacrylate, and cyclohexyl methacrylate.
• the acrylic polymer (B) preferably contains a hydroxyl group-containing monomer unit because it can form a coating film that is more excellent in solvent resistance, antifouling properties, and adhesion to the substrate. More preferably, it comprises at least one hydroxyl group-containing monomer unit selected from the group consisting of (meth) acrylic acid esters and hydroxyl group-containing alkyl vinyl ethers, and the hydroxyl group-containing (meth) acrylic acid is used as the hydroxyl group-containing monomer unit. More preferably, it contains an ester unit.
• the hydroxyl group-containing monomer unit can form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to a substrate, all monomers constituting the acrylic polymer (B)
• the amount is preferably 0.1 to 40% by mass, more preferably 0.8 to 31% by mass, still more preferably 4 to 23% by mass, and more preferably 4 to 18% by mass with respect to the unit. It is particularly preferred.
• hydroxyl group-containing alkyl vinyl ether examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl.
• examples thereof include vinyl ether, 5-hydroxypentyl vinyl ether, 6-hydroxyhexyl vinyl ether, 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether, and glycerol monoallyl ether.
• at least one selected from the group consisting of 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether is preferable.
• hydroxyl group-containing (meth) acrylic acid ester examples include 2-hydroxyethyl methacrylate (2-HEMA), 2-hydroxyethyl acrylate (2-HEA), 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, etc. , At least one selected from the group consisting of HEMA and HEA is preferred.
• the hydroxyl group-containing (meth) acrylic acid ester unit can form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to the substrate, all of the acrylic polymer (B) is formed.
• the amount is preferably from 0.1 to 40% by weight, more preferably from 0.8 to 31% by weight, and even more preferably from 4 to 23% by weight, based on the monomer unit. It is particularly preferable that the content is% by mass. If the hydroxyl group-containing (meth) acrylic acid ester unit is too much, the transparency of the coating film may be impaired, and if it is too small, the coating film becomes soft and the antifouling property and solvent resistance may be impaired.
• the acrylic polymer (B) contains a hydrolyzable silyl group-containing unsaturated monomer unit because it can form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to the substrate. It is preferable.
• the acrylic polymer (B) The content is preferably from 0.1 to 5% by mass, more preferably from 0.5 to 3% by mass, based on the total monomer units. If the amount of the hydrolyzable silyl group-containing unsaturated monomer unit is too large, the transparency of the coating film may be impaired. If the amount is too small, the solvent resistance and substrate adhesion of the coating film may be impaired.
• the acrylic polymer (B) preferably contains an unsaturated carboxylic acid unit because it can form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to the substrate.
• unsaturated carboxylic acid examples include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, itaconic acid, itaconic acid monoester Maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, vinyl pyromellitic acid, undecylenic acid and the like.
• acrylic acid methacrylic acid, vinyl acetic acid, crotonic acid, itaconic acid, maleic acid, maleic acid monoester, At least one selected from the group consisting of fumaric acid, fumaric acid monoester, 3-allyloxypropionic acid, and undecylenic acid is preferred.
• the unsaturated carboxylic acid unit can form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to the substrate, all monomer units constituting the acrylic polymer (B)
• the content is preferably 0.1 to 10% by mass, and more preferably 1 to 5% by mass.
• the acrylic polymer (B) can form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to the substrate, the hydroxyl group-containing (meth) acrylic acid ester unit and hydrolyzable silyl More preferably, it contains a group-containing unsaturated monomer unit.
• the acrylic polymer (B) can form a coating film that is more excellent in solvent resistance, antifouling properties, and adhesion to the base material, it is an acrylic ester unit, a methacrylic ester unit, an unsaturated carboxylic acid. More preferably, it contains a unit, a hydroxyl group-containing (meth) acrylic acid ester unit and a hydrolyzable silyl group-containing unsaturated monomer unit.
• the ratio (mass%) of the acrylic ester unit, methacrylic ester unit, unsaturated carboxylic acid unit, hydroxyl group-containing (meth) acrylic ester unit and hydrolyzable silyl group-containing unsaturated monomer unit was 0 to 40 / It is preferably 42 to 90/1 to 5/1 to 31 / 0.5 to 3.
• the composite polymer particles preferably have an acid value of 1 to 20, more preferably 1 to 10, and still more preferably 7 or more. If the acid value is too high, the adhesion and antifouling properties of the coating film may be inferior. Without the acid value, the stability of the emulsion may be inferior.
• the composite polymer particles preferably have a hydroxyl value of 1 to 40, more preferably 5 to 30. If the hydroxyl value is too high, the transparency of the coating film may be inferior. The hydroxyl value and the acid value can be calculated from the amount of each monomer used to synthesize the composite polymer particles.
• the composite polymer particles preferably have a glass transition temperature (Tg) of 0 to 70 ° C, more preferably 10 to 60 ° C, and even more preferably 20 to 50 ° C. If the glass transition temperature is too low, the antifouling property of the coating film may be impaired, and if it is too high, the film forming property of the coating film may be deteriorated.
• Tg glass transition temperature
• the composite polymer particles preferably have a particle size of 50 to 300 nm, and more preferably 50 to 250 nm.
• the composite polymer particles are obtained by subjecting the fluoroolefin to aqueous dispersion polymerization to obtain an aqueous dispersion containing fluoropolymer (A) particles.
• an acrylic monomer is added in the aqueous dispersion containing the fluoropolymer (A) particles. It can manufacture suitably by the manufacturing method including the process of seed-polymerizing to fluoropolymer (A) particle
• the composite polymer particles are obtained by subjecting the fluoroolefin to aqueous dispersion polymerization to obtain an aqueous dispersion containing fluoropolymer (A) particles, and in the aqueous dispersion containing fluoropolymer (A) particles,
• the acrylic monomer is preferably obtained by a production method including a step of seed polymerization of fluoropolymer (A) particles.
• aqueous dispersion polymerization and the seed polymerization are carried out in the presence of a non-reactive anionic surfactant, a reactive anionic surfactant, a non-reactive nonionic surfactant, a reactive nonionic surfactant, etc., if desired. You can also.
• the aqueous dispersion of the present invention contains a polyisocyanate compound.
• a polyisocyanate compound derived from at least one isocyanate selected from the group consisting of xylylene diisocyanate (XDI) and bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI), hexamethylene diisocyanate Selected from the group consisting of blocked isocyanate compounds based on (HDI), polyisocyanate compounds derived from hexamethylene diisocyanate (HDI), polyisocyanate compounds derived from isophorone diisocyanate (IPDI), and water-dispersible polyisocyanate compounds. At least one compound is preferred.
• the polyisocyanate compound is particularly preferably a water-dispersible polyisocyanate compound.
• polyisocyanate compound from at least one isocyanate selected from the group consisting of xylylene diisocyanate (XDI) and bis (isocyanate methyl) cyclohexane (hydrogenated XDI, H6XDI) (hereinafter also referred to as isocyanate (i)).
• XDI xylylene diisocyanate
• i hydrogenated XDI, H6XDI
• isocyanate (i) an induced polyisocyanate compound
• the adhesion between the coating film obtained from the aqueous dispersion and glass or polyethylene terephthalate becomes more excellent. .
• polyisocyanate compound (I) examples include an adduct obtained by addition polymerization of the isocyanate (i) and a trihydric or higher aliphatic polyhydric alcohol, and an isocyanurate structure (nurate) comprising the isocyanate (i). And a biuret composed of the above-mentioned isocyanate (i).
• adduct examples include the following general formula (1):
• R 1 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms
• R 2 represents a phenylene group or a cyclohexylene group
• k is an integer of 3 to 20.
• R 1 in the general formula (1) is a hydrocarbon group based on the above trivalent or higher aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and 3 to 6 carbon atoms.
• the aliphatic hydrocarbon group is more preferable.
• R 2 is a phenylene group
• a 1,2-phenylene group o-phenylene group
• a 1,3-phenylene group m-phenylene group
• a 1,4-phenylene group p-phenylene group
• R 2 in general formula (1) is the same phenylene group, or two or more may be mixed.
• R 2 is a cyclohexylene group, it may be any of 1,2-cyclohexylene group, 1,3-cyclohexylene group, and 1,4-cyclohexylene group.
• R 2 in general formula (1) is the same cyclohexylene group, or two or more may be mixed.
• the k is a number corresponding to the valence of a trihydric or higher aliphatic polyhydric alcohol. K is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.
• the isocyanurate structure has the following general formula (2) in the molecule:
• isocyanurate structure includes a trimer obtained by the trimerization reaction of the isocyanate, a pentamer obtained by the pentamerization reaction, and a heptamer obtained by the heptamization reaction. Among them, the following general formula (3):
• the isocyanurate structure is preferably a trimer of at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanatomethyl) cyclohexane.
• the biuret is represented by the following general formula (4):
• R 2 has the general formula (1) is the same as R 2 in.
• the polyisocyanate compound (I) includes, among others, at least one isocyanate selected from the group consisting of the above adducts, that is, xylylene diisocyanate and bis (isocyanatomethyl) cyclohexane, and a trihydric or higher aliphatic polyhydric alcohol. Are preferably obtained by addition polymerization.
• the polyisocyanate compound (I) is an adduct of the isocyanate (i) and a trihydric or higher aliphatic polyhydric alcohol
• the trihydric or higher aliphatic polyhydric alcohol is specifically glycerol.
• Trimethylolpropane TMP
• 1,2,6-hexanetriol trimethylolethane
• 2,4-dihydroxy-3-hydroxymethylpentane 1,1,1-tris (bishydroxymethyl) propane
• 2,2 -Trihydric alcohols such as bis (hydroxymethyl) butanol-3
• tetrahydric alcohols such as pentaerythritol and diglycerol
• pentahydric alcohols such as arabit, ribitol, and xylitol (pentit)
• sorbitol, mannitol, galactitol, allozulcit etc.
• hexahydric alcohol (hexit) That.
• trimethylolpropane and pentaerythritol are particularly preferable.
• the xylylene diisocyanate (XDI) used as a component of the adduct is 1,3-xylylene diisocyanate (m-xylylene diisocyanate), 1,2-xylylene diisocyanate (o-xylylene diisocyanate), 1 1,4-xylylene diisocyanate (p-xylylene diisocyanate), among which 1,3-xylylene diisocyanate (m-xylylene diisocyanate) is preferable.
• the bis (isocyanatemethyl) cyclohexane (hydrogenated XDI, H6XDI) used as a component of the adduct includes 1,3-bis (isocyanatemethyl) cyclohexane, 1,2-bis (isocyanatemethyl) cyclohexane, 1, 4-bis (isocyanatomethyl) cyclohexane can be mentioned, among which 1,3-bis (isocyanatomethyl) cyclohexane is preferred.
• An adduct is obtained by addition polymerization of at least one isocyanate selected from the group consisting of xylylene diisocyanate and bis (isocyanatomethyl) cyclohexane and an aliphatic polyhydric alcohol having three or more valences as described above. .
• R 3 represents a phenylene group or a cyclohexylene group
• R 3 represents a phenylene group or a cyclohexylene group
• TMP methylolpropane
• the phenylene group or cyclohexylene group represented by R 3 in the general formula (5) is as described for R 2 in the general formula (1).
• polyisocyanate compound (I) having an isocyanurate structure examples include Takenate D121N (Mitsui Chemicals, H6XDI Nurate, NCO content 14.0%), Takenate D127N (Mitsui Chemicals, Inc.) H6XDI nurate, H6XDI trimer, NCO content 13.5%) and the like.
• the aqueous dispersion has a sufficient pot life (pot life).
• the blocked isocyanate those obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate (hereinafter also referred to as polyisocyanate compound (II)) with a blocking agent are preferable.
• polyisocyanate compound (II) for example, an adduct obtained by addition polymerization of hexamethylene diisocyanate and a trihydric or higher aliphatic polyhydric alcohol, an isocyanurate structure (nurate structure) composed of hexamethylene diisocyanate, And biuret which consists of hexamethylene diisocyanate can be mentioned.
• Examples of the adduct include the following general formula (6):
• R 4 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms.
• K is an integer of 3 to 20).
• R 4 in the general formula (6) is a hydrocarbon group based on the above trivalent or higher aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and 3 to 6 carbon atoms. The aliphatic hydrocarbon group is more preferable.
• the k is a number corresponding to the valence of a trihydric or higher aliphatic polyhydric alcohol. K is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.
• the isocyanurate structure has the following general formula (2) in the molecule:
• isocyanurate structure includes a trimer obtained by the trimerization reaction of the isocyanate, a pentamer obtained by the pentamerization reaction, and a heptamer obtained by the heptamization reaction. Among them, the following general formula (7):
• trimer represented by these is preferable.
• the biuret is represented by the following general formula (8):
• a compound having active hydrogen is preferably used.
• the compound having active hydrogen for example, at least one selected from the group consisting of alcohols, oximes, lactams, active methylene compounds, and pyrazole compounds is preferably used.
• the blocked isocyanate is obtained by reacting a polyisocyanate compound derived from hexamethylene diisocyanate with a blocking agent, and the blocking agent includes alcohols, oximes, lactams, and active methylene compounds. And at least one selected from the group consisting of pyrazole compounds.
• the trihydric or higher aliphatic polyhydric alcohol is specifically Glycerol, trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl) propane , Trihydric alcohols such as 2,2-bis (hydroxymethyl) butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentahydric alcohols such as arabit, ribitol and xylitol (pentit); Lactitol, allozulcit It includes hexavalent alcohols (hexites) or the like is.
• trimethylolpropane and pentaerythritol are particularly preferable.
• the adduct is obtained by addition polymerization of hexamethylene diisocyanate and the above trivalent or higher aliphatic polyhydric alcohol.
• Specific examples of the compound having active hydrogen to be reacted with the polyisocyanate compound (II) include alcohols such as methanol, ethanol, n-propanol, isopropanol, methoxypropanol; acetone oxime, 2-butanone oxime, and cyclohexanone.
• Oximes such as oximes; lactams such as ⁇ -caprolactam; active methylene compounds such as methyl acetoacetate and ethyl malonate; pyrazole compounds such as 3-methylpyrazole, 3,5-dimethylpyrazole, 3,5-diethylpyrazole, etc. And one or more of these can be used.
• active methylene compounds and oximes are preferable, and active methylene compounds are more preferable.
• Duranate 17B-60PX (Asahi Kasei Chemicals Corporation), Coronate 2507 (Nippon Polyurethane Industry Co., Ltd.), Coronate 2513 (Nippon Polyurethane Industry Co., Ltd.), Coronate 2515 (Nippon Polyurethane Industry Co., Ltd.), Sumidur BL- 3175 (manufactured by Sumika Bayer Urethane Co., Ltd.), LuxateHC1170 (manufactured by Olin Chemicals), LuxateHC2170 (manufactured by Olin Chemicals) and the like.
• polyisocyanate compound (III) a polyisocyanate compound derived from hexamethylene diisocyanate (HDI) (hereinafter also referred to as polyisocyanate compound (III)) can be used.
• polyisocyanate compound (III) what was mentioned above as polyisocyanate compound (II) is mentioned.
• polyisocyanate compound (III) examples include Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanurate structure of hexamethylene diisocyanate, NCO content 21.1%), Sumijour N3300 (Sumika Bayer Urethane Co., Ltd.) Made, hexamethylene diisocyanate isocyanurate structure), Takenate D170N (Mitsui Chemicals, hexamethylene diisocyanate isocyanurate structure), Sumidur N3800 (manufactured by Sumika Bayer Urethane Co., Ltd., hexamethylene diisocyanate isocyanurate structure) Prepolymer type) and the like.
• Coronate HX manufactured by Nippon Polyurethane Industry Co., Ltd., isocyanurate structure of hexamethylene diisocyanate, NCO content 21.1%
• Sumijour N3300 Sanika Bayer Urethane Co.
• polyisocyanate compound a polyisocyanate compound derived from isophorone diisocyanate (IPDI) (hereinafter also referred to as polyisocyanate compound (IV)) can be used.
• IPDI isophorone diisocyanate
• IV polyisocyanate compound
• polyisocyanate compound (IV) examples include an adduct obtained by addition polymerization of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol, an isocyanurate structure (nurate structure) composed of isophorone diisocyanate, and Biuret made of isophorone diisocyanate can be mentioned.
• R 5 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms.
• R 6 represents the following general formula (10):
• R 5 in the general formula (9) is a hydrocarbon group based on the above trivalent or higher aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and 3 to 6 carbon atoms. The aliphatic hydrocarbon group is more preferable.
• the k is a number corresponding to the valence of a trihydric or higher aliphatic polyhydric alcohol. K is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.
• the isocyanurate structure has the following general formula (2) in the molecule:
• isocyanurate structure examples include a trimer obtained by a trimerization reaction of isophorone diisocyanate, a pentamer obtained by a pentamerization reaction, a heptamer obtained by a heptamerization reaction, and the like. Among them, the following general formula (11):
• the isocyanurate structure is preferably a trimer of isophorone diisocyanate.
• the biuret is represented by the following general formula (12):
• R 6 has the general formula (9) in the same as R 6 in.
• the polyisocyanate compound (IV) is preferably at least one selected from the group consisting of the adduct and the isocyanurate structure. That is, the polyisocyanate compound (IV) is selected from the group consisting of an adduct obtained by addition polymerization of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol, and an isocyanurate structure composed of isophorone diisocyanate. It is preferable that it is at least one kind.
• polyisocyanate compound (IV) is an adduct of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol
• specific examples of the trihydric or higher aliphatic polyhydric alcohol include glycerol and trimethylol.
• TMP Propane
• 1,2,6-hexanetriol trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl) propane, 2,2-bis ( Trivalent alcohols such as hydroxymethyl) butanol-3; tetravalent alcohols such as pentaerythritol and diglycerol; pentavalent alcohols such as arabit, ribitol, and xylitol (pentit); hexavalents such as sorbitol, mannitol, galactitol, and allozulcit Alcohol (hexit) etc. It is. Of these, trimethylolpropane and pentaerythritol are particularly preferable.
• Adducts suitably used in the present invention can be obtained by addition polymerization of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol as described above.
• R 7 represents the following general formula (10):
• TMP adduct body of isophorone diisocyanate represented by the said General formula (10).
• isocyanurate structures made of isophorone diisocyanate examples include Desmodur Z4470 (manufactured by Sumika Bayer Urethane Co., Ltd., NCO content 11%).
• a water-dispersible polyisocyanate compound can also be used as the polyisocyanate compound.
• the water-dispersible polyisocyanate compound is a polyisocyanate compound that can form an aqueous dispersion when stirred in an aqueous medium.
• Examples of such water-dispersible polyisocyanate compounds include (1) a mixture of a hydrophobic polyisocyanate and a polyisocyanate having a hydrophilic group, and (2) a hydrophilic group having no hydrophobic polyisocyanate and an isocyanate group. And (3) polyisocyanate having a hydrophilic group, and the like.
• the hydrophilic group means an anionic group, a cationic group or a nonionic group.
• the water-dispersible polyisocyanate compound is particularly preferably a polyisocyanate having a hydrophilic group.
• the hydrophobic polyisocyanate has no hydrophilic group.
• 1,4-tetramethylene diisocyanate, ethyl (2,6-diisocyanate) hexanoate, 1,6-hexamethylene diisocyanate Aliphatic diisocyanates such as 1,2, dodecamethylene diisocyanate, 2,2,4- or 2,4,4-trimethylhexamethylene diisocyanate; 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4 -Aliphatic triisocyanates such as isocyanatomethyloctane and 2-isocyanatoethyl (2,6-diisocyanate) hexanoate; 1,3-bis (isocyanatomethylcyclohexane), 1,4-bis (isocyanatomethylcyclohexane) ), 1,3-diisocyanate Cyclohexane, 1,4-diisocyanatocyclo
• polyisocyanate having a hydrophilic group examples include polyethers, polyesters, polyurethanes, vinyl polymers, alkyd resins, fluororesins, and silicon resins having a hydrophilic group and an isocyanate group.
• polyethers polyesters, polyurethanes, vinyl polymers, alkyd resins, fluororesins, and silicon resins having a hydrophilic group and an isocyanate group.
• a polyether or vinyl polymer having a hydrophilic group and an isocyanate group is preferable, and a polyether having a hydrophilic group and an isocyanate group is more preferable.
• These polyisocyanates having a hydrophilic group can be used alone or in combination of two or more.
• Examples of commercially available polyisocyanates having a hydrophilic group include Bihijoule XP 2700 (manufactured by Sumika Bayer Urethane Co., Ltd.).
• the content of the polyisocyanate compound in the aqueous dispersion is such that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the polyisocyanate compound to the hydroxyl group (OH) contained in the composite polymer particles is 0.1 to 5. It is preferably 0 equivalent, more preferably 0.5 to 5.0 equivalent, still more preferably 0.5 to 3.0 equivalent, and 1.0 to 2.0 equivalent. Particularly preferred.
• the polyisocyanate compound is a water-dispersible polyisocyanate compound
• the curability of the aqueous dispersion of the present invention and the coating film appearance and durability of the cured coating film are further improved.
• the equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the water-dispersible polyisocyanate compound to the hydroxyl group (OH) contained in the composite polymer particles is 0.1 to 5.
• a range of 0 equivalents is preferred, a range of 0.3 to 3.0 equivalents is more preferred, a range of 0.3 to 2.0 equivalents is still more preferred, and a range of 0.5 to 1.5 equivalents is particularly preferred.
• the aqueous dispersion of the present invention contains composite polymer particles and the water-dispersible polyisocyanate compound, and those obtained by dissolving or dispersing them in water can be mentioned.
• an aqueous resin composition obtained by water-dispersing composite polymer particles and an aqueous dispersion of a water-dispersible polyisocyanate compound or a water-dispersible polyisocyanate compound diluted with a solvent Etc. water-dispersible polyisocyanate composition
• a stirring method for example, there is a method using various stirrers, and if it is a small amount, it can be easily and uniformly mixed by simple stirring using a stirring bar or the like. It is preferable to use a stirrer because a large amount of water-based paint can be prepared in a short time.
• the mixing ratio of the aqueous resin composition obtained by water-dispersing the composite polymer particles and the water-dispersible polyisocyanate composition can provide a cured coating film excellent in adhesion, hot water-resistant adhesion and solvent resistance. Therefore, a mixture in which the equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the water-dispersible polyisocyanate compound to the hydroxyl group (OH) in the composite polymer particle is 0.1 to 5.0 equivalents. A ratio is preferable, and a mixing ratio of 0.3 to 3.0 equivalents is more preferable. The smaller the amount of the water-dispersible polyisocyanate composition used, the better the antifouling property of the coating film.
• the mixing ratio of the aqueous resin composition obtained by water-dispersing the composite polymer particles and the water-dispersible polyisocyanate composition is preferably as low as possible from the viewpoint of improving antifouling properties. Is preferably 15% by mass or less, more preferably 10% by mass or less, based on the solid content of the aqueous dispersion of the composite polymer particles.
• the mixing ratio is such that the equivalent ratio (NCO / OH) of the isocyanate group (NCO) in the water-dispersible polyisocyanate compound and the hydroxyl group (OH) in the composite polymer particle is 0.1 to 3.0 equivalents.
• the mixing ratio is preferably 0.3 to 2.0 equivalents, more preferably 0.5 to 1.5 equivalents.
• the aqueous dispersion further contains water.
• water In addition to water, you may contain organic solvents, such as alcohol, glycol ether, and ester.
• the aqueous dispersion may contain 10 to 60% by mass of composite polymer particles.
• the aqueous dispersion preferably further contains a film forming aid.
• the film forming aid include a film forming aid having no active hydrogen, such as dipropylene glycol dimethyl ether (DPGDME), diethyl diglycol (DEDG), and diethyl adipate (ADE).
• the active hydrogen is a hydrogen atom contained in a hydroxyl group, an amino group or the like, and reacts with the polyisocyanate compound to lose its activity. Therefore, a film-forming auxiliary having a functional group containing this is not preferable.
• aqueous dispersion is advantageous in that a coating film having excellent transparency is obtained, it is preferable that the aqueous dispersion does not contain a component that impairs transparency, such as a pigment and a filler.
• the aqueous dispersion can be suitably used as an aqueous paint.
• the water-based paint is preferably a water-based clear paint.
• Conventionally known methods and conditions can be adopted as a method for coating the aqueous dispersion. For example, a method of forming a coating film by applying a coating method such as spray coating, roll coating, flow coating, roller, brush, gravure / screen printing, etc. on a substrate, followed by drying at 5 to 200 ° C. It is done. By such a method, it is possible to form a coating film that is more excellent in solvent resistance, antifouling property, and adhesion to a substrate.
• the coating film characterized by being obtained from the above-mentioned aqueous dispersion is excellent in solvent resistance, antifouling property, and adhesion to the substrate.
• the present invention is also a fluorine-containing coating film characterized by having a siloxane bond and a urethane bond.
• the fluorine-containing coating film is preferably a fluorine-containing clear coating film. Since the said fluorine-containing coating film has the said characteristic, it is excellent in solvent resistance, antifouling property, and adhesiveness with a base material. It can be confirmed by a total reflection measurement method (ATR) that the fluorine-containing coating film has a siloxane bond and a urethane bond.
• ATR total reflection measurement method
• the said fluorine-containing coating film can be manufactured from the above-mentioned aqueous dispersion, for example.
• the present invention provides a step of preparing a solution by dissolving or dispersing a polyisocyanate compound and a film-forming aid in a solvent, and an aqueous dispersion containing a fluoropolymer (A) and an acrylic polymer (B). It is also the manufacturing method characterized by including the process to add. After preparing a solution containing the polyisocyanate compound and the film-forming aid in advance, it is added to an aqueous dispersion containing the fluoropolymer (A) and the acrylic polymer (B), so that solvent resistance, antifouling property, and An aqueous dispersion capable of obtaining a coating film that is more excellent in adhesion to the substrate can be prepared.
• the aqueous dispersion contains composite polymer particles and water, and the composite polymer particles are composed of a fluoropolymer (A) and an acrylic polymer (B), and the fluoropolymer (A) and the acrylic polymer. It is preferable that any one or both of (B) contain a hydroxyl group and a hydrolyzable silyl group.
• the polyisocyanate compound, the film-forming aid, and the composite polymer particles are preferably the same as the respective components contained in the aqueous dispersion of the present invention described above.
• the above production method is suitable as a method for producing the above-described aqueous dispersion of the present invention.
• water As a solvent for dissolving or dispersing the polyisocyanate compound and the film-forming aid, water is preferable.
• the present invention also provides a coated article obtained by coating the above-mentioned aqueous dispersion on a substrate.
• a transparent base material is preferable.
• the transparent substrate include plastic substrates such as polyethylene terephthalate, acrylic resin, polycarbonate resin, and fluororesin, glass, and other articles that require transparency.
• plastic substrates such as polyethylene terephthalate, acrylic resin, polycarbonate resin, and fluororesin, glass, and other articles that require transparency.
• the resulting coating film is excellent in solvent resistance and antifouling property, and Excellent adhesion.
• the coated article can be used in a wide range of applications.
• electrical products microwave oven, toaster, refrigerator, washing machine, hair dryer, TV, video, amplifier, radio, electric kettle, rice cooker, radio cassette, cassette deck, compact disc player, video camera, personal computer, etc.
• Interior and exterior air conditioner indoor units, outdoor units, air outlets and ducts, air conditioners such as air purifiers and heaters, lighting fixtures such as fluorescent lamps, chandeliers, reflectors, furniture, machine parts, decorative items , Combs, eyeglass frames, natural fibers, synthetic fibers (threads and woven fabrics obtained from them), office equipment (telephones, facsimiles, copiers (including rolls), photographs, overhead projectors, actual projectors, watches , Slide projector, desk, bookshelf, locker, book Interior / exterior of shelves, chairs, bookends, electronic white boards, etc., automobiles (wheels, door mirrors, moldings, door knobs, license plates, handles, instrument panels, etc.), or kitchen utensils (range
• Average particle size measuring device Microtrack UPA manufactured by HONEYWELL Measurement method: The emulsion to be measured by the dynamic light scattering method was diluted to a measurable concentration with pure water to obtain a sample, which was measured at room temperature. The number average diameter of the obtained data was defined as the particle diameter.
• NMR analysis It measured with the following measuring apparatuses and measurement conditions.
• MFR Melt flow rate
• Tg Glass transition temperature
• Solvent resistance test A clear coating, which will be described later, was applied onto a PET with a bar coater and dried at 20 ° C. for 7 days to prepare a test plate. The coating film surface of this test plate was wiped off with a nonwoven fabric impregnated with methyl ethyl ketone (MEK). The wiping operation was performed until 100 round trips were completed. After the completion of this test, after drying, the film was evaluated as “ ⁇ ” when no dissolution or swelling of the coating film or reduction in gloss was observed, and “X” when dissolution or swelling of the coating film or reduction in gloss was observed.
• MEK methyl ethyl ketone
• Adhesion test A clear coating, which will be described later, was applied onto a PET with a bar coater and dried at 20 ° C. for 7 days to prepare a test plate.
• a cross-cut tape peeling test was performed on the coating film of the test plate according to JIS D0202-1988. Using cellophane tape (“CT24”, manufactured by Nichiban Co., Ltd.), the film was adhered to the film with the belly of the finger and then peeled off. Judgment is represented by the number of squares that do not peel out of 100 squares.
• MMA methyl methacrylate
• n-BA butyl acrylate
• AA acrylic acid
• 2-HEMA 2-hydroxyethyl methacrylate
• SiMA 3-methacryloxypropyltriethoxysilane
• APS ammonium persulfate
• reaction solution is cooled to room temperature to complete the reaction, and 12.5 g of a 50 mass% solution of polyoxyethylene (12) lauryl ether (nonion 1) is added, and the pH is adjusted to 7 to 8 using an aqueous ammonia solution.
• aqueous dispersion of composite polymer particles was obtained (solid content concentration 51.2% by mass).
• the average particle diameter of the obtained composite polymer particles was 190 nm.
• Synthesis example 2 According to Table 1, an aqueous dispersion of composite polymer particles was synthesized. 975 g of an aqueous dispersion of fluoropolymer (A-1), 44.6 g of 28.0% by weight aqueous solution of anion 1 as a surfactant, 183 g of methyl methacrylate (MMA), 1.9 g of butyl acrylate (n-BA), acrylic An aqueous dispersion of composite polymer particles was obtained in the same manner as in Synthesis Example 1 except that 1.9 g of acid (AA) and 25.0 g of a 50 mass% solution of nonion 1 were used (solid content concentration 51.0). mass%). The average particle diameter of the obtained composite polymer particles was 170 nm.
• Synthesis example 3 According to Table 1, an aqueous dispersion of composite polymer particles was synthesized.
• the aqueous composite polymer particles were prepared in the same manner as in Synthesis Example 1 except that 250.8 g of methyl methacrylate (MMA), 58.0 g of 2-hydroxyethyl methacrylate (2-HEMA), and 3.1 g of acrylic acid (AA) were used.
• a dispersion was obtained (solid content concentration 51.0% by mass).
• the average particle diameter of the obtained composite polymer particles was 170 nm.
• Example 1 After adding water to the aqueous dispersion of composite polymer particles obtained in Synthesis Example 1 and adjusting the solid content concentration to 50% by mass, as a film-forming aid for 100 parts by mass of the solid content of the aqueous dispersion 10 parts by weight of diethyl adipate was added with stirring and mixed with a stirrer for 30 minutes, and 1 part by weight of 10% aqueous solution of Adecanol UH-420 (manufactured by ADEKA) as a viscosity modifier and BYK028 (manufactured by BYK Chemie) as a defoaming agent. ) 0.1 part by mass was added in order with stirring and mixed for 30 minutes with a stirrer.
• Adecanol UH-420 manufactured by ADEKA
• BYK028 manufactured by BYK Chemie
• Comparative Example 1 In the same manner as in Example 1, except that the aqueous dispersion of composite polymer particles obtained in Synthesis Example 2 was used instead of the aqueous dispersion of composite polymer particles obtained in Synthesis Example 1, a clear paint was obtained. Got. Using this clear paint, a solvent resistance test, a magic stain resistance test, an adhesion test and a transparency test were conducted in the same manner as in Example 1. The results are shown in Table 2.
• Comparative Example 2 In the same manner as in Example 1 except that the aqueous dispersion of composite polymer particles obtained in Synthesis Example 3 was used instead of the aqueous dispersion of composite polymer particles obtained in Synthesis Example 1, a clear paint was obtained. Got. Using this clear paint, a solvent resistance test, a magic stain resistance test, an adhesion test and a transparency test were conducted in the same manner as in Example 1. The results are shown in Table 2.
• Synthesis example 4 An aqueous dispersion of composite polymer particles was synthesized according to Table 3.
• a surfactant 22.3 g of anionic 1 28.0% by weight aqueous solution, 167 g of methyl methacrylate (MMA), 121 g of butyl acrylate (n-BA), 15.6 g of 2-hydroxyethyl methacrylate (2-HEMA), 3-methacrylic acid Roxypropyltriethoxysilane (SiMA) 3.1 g Acrylic acid (AA) 7.5 g
• Nonionic 1 50 mass% solution was the same as Synthesis Example 1 except that 12.5 g was used.
• a dispersion was obtained (solid content concentration 51.0% by mass). The average particle diameter of the obtained composite polymer particles was 190 nm.
• Synthesis example 5 An aqueous dispersion of composite polymer particles was synthesized according to Table 3.
• the surfactant 22.3 g of 28.0% by weight aqueous solution of anion 1, 245 g of methyl methacrylate (MMA), 44 g of butyl acrylate (n-BA), 15.6 g of 2-hydroxyethyl acrylate (2-HEA), 3-methacrylic acid
• the composite polymer particles were synthesized in the same manner as in Synthesis Example 1 except that 3.1 g of loxypropyltriethoxysilane (SiMA), 7.5 g of acrylic acid (AA), and 12.5 g of a 50 mass% solution of nonion 1 were used.
• An aqueous dispersion was obtained (solid content concentration 51.0% by mass).
• the average particle diameter of the obtained composite polymer particles was 190 nm.
• Synthesis Example 6 An aqueous dispersion of composite polymer particles was synthesized according to Table 3. 975 g of an aqueous dispersion of fluoropolymer (A-1), 22.3 g of 28.0% by weight aqueous solution of anion 1 as a surfactant, 154 g of methyl methacrylate (MMA), 15.5 g of butyl acrylate (n-BA), 2 -9.4 g of hydroxyethyl methacrylate (2-HEMA), 1.9 g of 3-methacryloxypropyltriethoxysilane (SiMA), 7.5 g of acrylic acid (AA), 12.5 g of 50% by mass solution of nonion 1 Except for the above, an aqueous dispersion of composite polymer particles was obtained in the same manner as in Synthesis Example 1 (solid content concentration 51.0% by mass). The average particle diameter of the obtained composite polymer particles was 190 nm.
• Example 2 The same operation as in Example 1 was conducted except that 10 parts by mass of diethyldiglycol (DEDG) was used as a film-forming aid. The results are shown in Table 4.
• DEDG diethyldiglycol
• Example 3-5 The same operation as in Example 1 was carried out except that the composite polymer particles shown in Table 4 were used.
• Tables 1 and 3 show calculated values of acid value (mgKOH / g) and hydroxyl value (mgKOH / g) of the composite polymer particles.
• Acid value ⁇ number of moles of acrylic acid (AA) used ⁇ ⁇ ⁇ ratio of acrylic acid (AA) in acrylic polymer (mass%) ⁇ ⁇ ⁇ molecular weight of KOH (56.1) ⁇ ⁇ 1000/100 ⁇ composite Ratio of acrylic polymer in polymer particles (mass%) ⁇
• Hydroxyl value ⁇ number of moles of 2-hydroxyethyl methacrylate (2-HEMA) and 2-hydroxyethyl acrylate (2-HEA) used ⁇ ⁇ ⁇ 2-hydroxyethyl methacrylate (2-HEMA) and 2- Hydroxyethyl acrylate (2-HEA) ratio (mass%) ⁇ ⁇ ⁇ KOH molecular weight (56.1) ⁇ ⁇ 1000/100 ⁇ ⁇ Acrylic polymer ratio in composite polymer particles (mass%) ⁇

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Medicinal Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Polymers & Plastics (AREA)
• Dispersion Chemistry (AREA)
• Paints Or Removers (AREA)
• Application Of Or Painting With Fluid Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polymerisation Methods In General (AREA)

Priority Applications (5)

Applications Claiming Priority (2)

Publications (1)

Family

ID=57144048

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (7)

Citations (6)

Family Cites Families (46)

• 2016
  • 2016-04-21 WO PCT/JP2016/062651 patent/WO2016171217A1/ja not_active Ceased
  • 2016-04-21 CN CN201911152795.7A patent/CN110951351A/zh active Pending
  • 2016-04-21 EP EP16783238.5A patent/EP3287491B1/en active Active
  • 2016-04-21 EP EP19170744.7A patent/EP3536744A1/en active Pending
  • 2016-04-21 US US15/568,300 patent/US10787587B2/en active Active
  • 2016-04-21 CN CN201680022720.5A patent/CN107531971A/zh active Pending
  • 2016-04-21 CN CN202310094600.8A patent/CN115948011A/zh active Pending
  • 2016-04-21 JP JP2016085307A patent/JP6103107B2/ja active Active
  • 2016-09-12 JP JP2016177962A patent/JP6249066B2/ja active Active

Patent Citations (6)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events