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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/282—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing two or more oxygen 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
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
• • 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
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/10—Esters
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
• • 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
• • 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
  • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
  • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
  • C09D161/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
  • C09D161/28—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds with melamine
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
  • C09D5/02—Emulsion paints including aerosols
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives

Definitions

• the present invention relates to a metal fine particle dispersant, a metal fine particle dispersion, a coating agent, a cured film, and a binder resin, and specifically, a metal fine particle dispersion, a metal fine particle dispersion in which metal fine particles are dispersed by a metal fine particle dispersant. Further, the present invention relates to a coating agent containing the metal fine particle dispersion, a cured film obtained by curing the coating agent, and a binder resin contained in the coating agent.
• the cured film obtained by applying and curing the coating agent for example, mechanical properties, chemical resistance, high refractive index, antistatic properties, ultraviolet / infrared shielding properties, scratch resistance, etc.
• Various metal fine particles are dispersed in order to impart the various physical properties described above and further as pigments.
• the metal fine particles may aggregate depending on the metal fine particles, the solvent, the binder resin, and the like. Therefore, in order to disperse the metal fine particles satisfactorily, it has been proposed to add a dispersant to the coating agent.
• the first reactive functional group, an ionic group for adsorbing to the metal fine particles, and a (meth) acrylic polymer containing a polyoxyalkylene side chain are bonded to the first reactive functional group.
• a metal fine particle dispersant obtained by reacting a compound (b) containing a second reactive functional group for curing with an active energy ray-curable group for curing with active energy rays has been proposed, It has been proposed to prepare a fine metal particle dispersion by blending the fine metal particle dispersant, fine metal particles, and a dispersion medium (see Patent Document 1).
• Such a metal fine particle dispersant can disperse metal fine particles satisfactorily and further improve various physical properties (chemical resistance, hardness, etc.) of a cured film obtained by curing the dispersion. Can do.
• the metal fine particle dispersant described in Patent Document 1 is usually produced in an organic solvent and added to the coating agent as a dispersion thereof. Therefore, when the metal fine particle dispersant described in Patent Document 1 is used as an aqueous coating agent, the storage stability and dispersion stability are not sufficient, and the metal fine particle dispersant aggregates and the metal fine particles cannot be dispersed. In some cases, the physical properties of the film cannot be improved.
• a metal fine particle dispersant that is excellent in storage stability and dispersion stability and can improve the physical properties of a cured film may be required even in an aqueous coating agent.
• aqueous coating agent for example, a hard coating agent that improves the scratch resistance and hardness of a substrate (a workpiece) is known.
• Hard coat agents are used in various industrial fields.
• a hard coating agent may be required to deform a substrate (object) after coating.
• hard coating agents are usually designed for the purpose of improving the scratch resistance and hardness of the substrate (the object to be coated), the flexibility and adhesion may not be sufficient. If the base material (the object to be coated) is deformed after the coating of the agent, the coating film may be peeled off or damaged. For this reason, a hard coat agent having excellent adhesion and flexibility may be required depending on applications.
• various physical properties are required for the coating film obtained by such a coating agent depending on the use, and for example, transparency and heat-and-moisture resistance may be required.
• An object of the present invention is a metal fine particle dispersant that is excellent in dispersibility of metal fine particles in an aqueous dispersion medium and that can improve various physical properties of a cured film, and metal fine particles are dispersed by a metal fine particle dispersant.
• An object of the present invention is to provide a metal fine particle dispersion, a coating agent containing the metal fine particle dispersion, a cured film obtained by curing the coating agent, and a binder resin contained in the coating agent.
• the present invention [1] comprises a (meth) acrylic polymer containing an ionic group, and the (meth) acrylic polymer has a glass transition point of ⁇ 30 ° C. or higher and 80 ° C. or lower, and an acid value of 80 mgKOH / g or higher. It contains a metal fine particle dispersant having a hydroxyl value of 200 mgKOH / g or less and a hydroxyl value of 20 mgKOH / g or more and 90 mgKOH / g or less.
• the present invention [2] includes a metal fine particle dispersion containing the metal fine particle dispersant described in [1] above, metal fine particles, and an aqueous dispersion medium.
• the present invention [3] includes a coating agent containing the metal fine particle dispersion described in [2] above.
• this invention [4] contains the coating agent as described in said [3] which contains a melamine resin and / or binder resin further.
• this invention [5] contains the coating agent as described in said [4] in which the said binder resin contains the same kind of resin as the said (meth) acryl polymer in the metal fine particle dispersing agent of said [1]. Yes.
• the present invention [6] includes a cured film that is a cured product of the coating agent according to any one of [3] to [5] above.
• the present invention [7] comprises a (meth) acrylic polymer containing an ionic group, and the glass transition point of the (meth) acrylic polymer is ⁇ 30 ° C. or higher and 80 ° C. or lower, and the acid value is 80 mgKOH / a binder resin having a hydroxyl value of 20 mgKOH / g to 90 mgKOH / g.
• the metal fine particle dispersant of the present invention is made of a (meth) acrylic polymer containing an ionic group, and all of the glass transition point, acid value and hydroxyl value are adjusted to a specific range. It is possible to improve the dispersibility of the metal fine particles therein and to improve various physical properties of the cured film.
• the metal fine particle dispersion of the present invention contains the metal fine particle dispersant of the present invention, the metal fine particle dispersion is excellent in the dispersibility of the metal fine particles in the aqueous dispersion medium and improves various physical properties of the cured film. Can do.
• the coating agent of the present invention contains the metal fine particle dispersion of the present invention, it is excellent in the dispersibility of the metal fine particles in the aqueous dispersion medium, and can improve various physical properties of the cured film. .
• the cured film of the present invention obtained by curing the coating agent of the present invention is excellent in various physical properties such as scratch resistance, hardness, adhesion, flexibility, transparency, and wet heat resistance.
• the binder resin of the present invention is made of a (meth) acrylic polymer containing an ionic group, and the glass transition point, acid value and hydroxyl value are all adjusted to a specific range, so that the cured film Various physical properties can be improved.
• the metal fine particle dispersant of the present invention is made of a (meth) acrylic polymer containing an ionic group, specifically, a (meth) acrylic polymer containing an ionic group and a hydroxyl group.
• (meth) acrylic polymer is defined as acrylic polymer and / or methacrylic polymer.
• (meth) acryl described below is also defined as “acryl” and / or “methacryl” as described above.
• the (meth) acrylic polymer which will be described in detail later, is a raw material mainly composed of an organic compound having one or more acryloyl groups and / or methacryloyl groups in one molecule (hereinafter referred to as (meth) acrylic monomer). Obtained as a monomer polymer.
• the ionic group is a functional group for adsorbing the metal fine particle dispersant to the metal fine particles (described later).
• the ionic group is not particularly limited and includes known ionic groups.
• the ionic group examples include an anionic group such as a carboxyl group and a phosphate group, and a cationic group such as a tertiary amino group and a quaternary ammonium group.
• the tertiary amino group is not particularly limited.
• Examples of the quaternary ammonium group include those obtained by allowing a quaternizing agent such as epihalohydrin, benzyl halide, or alkyl halide to act on the tertiary amino group.
• a quaternizing agent such as epihalohydrin, benzyl halide, or alkyl halide
• These ionic groups may be one kind or two or more kinds may be used in combination.
• an anionic group is preferable, and a carboxyl group is more preferable.
• the average content of the ionic group is appropriately set according to the purpose and application.
• an anionic group when employed as the ionic group, a part of the anionic group may be neutralized with a neutralizing agent (described later). If a part of the anionic group is neutralized by a neutralizing agent (described later), a salt of the anionic group is formed, so that the dispersibility in the aqueous dispersion medium can be improved.
• the (meth) acrylic polymer can have other groups (groups other than ionic groups and hydroxyl groups) as necessary.
• Examples of the other group include a polyoxyalkylene side chain, a saturated alicyclic group composed of two or more rings, and the like.
• the polyoxyalkylene side chain is formed by containing a polyoxyalkylene group having an oxyalkylene unit (C n H 2n O) as a repeating unit in the (meth) acrylic polymer as a side chain, and is hydrophilic. In order to improve, it is introduced into the (meth) acrylic polymer.
• the polyoxyalkylene group is represented, for example, by the following general formula (1).
• n represents an integer of 1 to 4
• m represents an integer of 2 or more
• X represents a hydrogen atom or an alkyl group.
• n is 1 or more, preferably 2 or more, and 4 or less, preferably 3 or less.
• m is the number of repeating units of the oxyalkylene unit and is 2 or more, preferably 3 or more, more preferably 4 or more, for example 40 or less, preferably 30 or less, more preferably 15 or less.
• the obtained metal fine particle dispersant effectively suppresses reaggregation of the metal fine particles, so that the storage stability of the metal fine particle dispersion containing the metal fine particle dispersant is improved.
• the transparency of the cured film obtained by curing the metal fine particle dispersion can be improved as the metal fine particles are refined.
• X is a terminal portion of the polyoxyalkylene group and represents a hydrogen atom or an alkyl group.
• alkyl group examples include alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, etc., and preferably the number of carbon atoms in the oxyalkylene unit.
• An alkyl group having the same carbon number as (the number of n in the general formula (1)) can be mentioned.
• the general formula (1) when X is a hydrogen atom, the general formula (1) is a polyoxyalkylene group having a hydroxyl group.
• the molecular weight of the polyoxyalkylene group is appropriately set according to the purpose and application.
• These polyoxyalkylene groups may be of one type, or two or more types may be used in combination.
• the average content of the polyoxyalkylene group is appropriately set according to the purpose and application.
• the saturated alicyclic group composed of two or more rings is, for example, a saturated alicyclic group in which a cyclic structure such as polycyclic, bridged cyclic, or spirocyclic is formed by two or more rings, In order to improve the dispersibility of the fine particles, it is introduced into the (meth) acrylic polymer.
• saturated alicyclic group composed of two or more rings examples include a bicyclo group, a tricyclo group, and a tetracyclo group, preferably a bicyclo group and a tricyclo group.
• bicyclo group examples include bornyl, isobornyl, dicyclopentanyl and the like.
• tricyclo group include adamantyl and dimethyladamantyl.
• saturated alicyclic groups composed of two or more rings may be of one type, or two or more types may be used in combination.
• the dispersibility can be improved, and further, a binder resin or the like is blended in the metal fine particle dispersion. The compatibility with them can be improved.
• the average content is appropriately set according to the purpose and application.
• the (meth) acrylic polymer includes, for example, an aliphatic group (for example, an alkyl group, a cycloalkyl group, etc.), an aromatic group (for example, various groups such as a phenyl group) can be contained.
• an aliphatic group for example, an alkyl group, a cycloalkyl group, etc.
• aromatic group for example, various groups such as a phenyl group
• Such a (meth) acrylic polymer can be produced by polymerizing raw material monomers mainly composed of (meth) acrylic monomers.
• the raw material monomer includes an ionic group-containing monomer (described later) and a hydroxyl group-containing monomer (described later), which will be described later in detail.
• (meth) acrylic monomers examples include (meth) acrylic acid esters and / or derivatives thereof.
• (meth) acrylic acid esters include (meth) acrylic acid alkyl esters.
• (meth) acrylic acid alkyl esters examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth).
• acrylic acid alkyl esters can be used alone or in combination of two or more.
• Preferred examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, n-butyl (meth) acrylate, and dodecyl (meth) acrylate.
• the (meth) acrylic acid ester for example, a polyoxyalkylene group-containing (meth) acrylate having one end that is an alkoxy group (X in the general formula (1) is an alkyl group)
• two Examples include saturated alicyclic group-containing (meth) acrylates containing saturated alicyclic groups composed of the above rings.
• Examples of the polyoxyalkylene group-containing (meth) acrylate whose one end is an alkoxy group include ethoxyethoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, propoxypropoxypropyl (meth) acrylate, ethoxypropoxypropyl (meta) ) Acrylate, methoxypropoxypropyl (meth) acrylate, butoxybutoxybutyl (meth) acrylate, propoxybutoxybutyl (meth) acrylate, ethoxybutoxybutyl (meth) acrylate, methoxybutoxybutyl (meth) acrylate, and the like.
• polyoxyalkylene group-containing (meth) acrylate whose one end is an alkoxy group
• examples of the polyoxyalkylene group-containing (meth) acrylate whose one end is an alkoxy group include, for example, methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, methoxytetraethylene glycol mono (meta) ) Acrylate, methoxypentaethylene glycol mono (meth) acrylate, methoxyhexaethylene glycol mono (meth) acrylate, methoxyheptaethylene glycol mono (meth) acrylate, methoxyoctaethylene glycol mono (meth) acrylate, methoxynonaethylene glycol mono (meta) ) Acrylate, Methoxydecaethylene glycol mono (meth) acrylate, Methoxyundecaethylene glycol mono (meth) acrylate DOO, methoxy dodeca ethylene glycol mono
• saturated alicyclic group-containing (meth) acrylate containing a saturated alicyclic group composed of two or more rings for example, a (meth) acrylate containing a bicyclo group, a (meth) acrylate containing a tricyclo group, a tetracyclo group (Meth) acrylate etc. containing are mentioned, Preferably, the (meth) acrylate containing a bicyclo group and the (meth) acrylate containing a tricyclo group are mentioned.
• Examples of the (meth) acrylate containing a bicyclo group include bornyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and the like. These (meth) acrylates containing a bicyclo group can be used alone or in combination of two or more.
• Examples of the (meth) acrylate containing a tricyclo group include adamantyl (meth) acrylate and dimethyladamantyl (meth) acrylate. These (meth) acrylates containing a tricyclo group can be used alone or in combination of two or more.
• saturated alicyclic group-containing (meth) acrylates having a saturated alicyclic group composed of two or more rings can be used alone or in combination of two or more.
• a saturated alicyclic group consisting of two or more rings can be introduced into the (meth) acrylic polymer, and metal fine particles.
• a binder resin or the like is added to the metal fine particle dispersion, compatibility with them can be improved.
• the saturated alicyclic group-containing (meth) acrylate having a saturated alicyclic group composed of two or more rings is preferably a (meth) acrylate containing a bicyclo group, more preferably isobornyl (meth) acrylate.
• the raw material monomer can contain a copolymerizable monomer copolymerizable with a (meth) acrylic monomer.
• Examples of the copolymerizable monomer include aromatic ethylenically unsaturated monomers.
• aromatic ethylenically unsaturated monomer examples include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-tert-butylstyrene and the like. If an aromatic ethylenically unsaturated monomer is used, the glass transition point of the (meth) acrylic polymer can be adjusted to a desired range, and when a binder resin or the like is blended in the metal fine particle dispersion, the phase with them can be adjusted. The solubility can be improved.
• examples of the copolymerizable monomer include itaconic acid esters such as dimethyl itaconate, maleic acid esters such as dimethyl maleate, fumaric acid esters such as dimethyl fumarate, acrylonitrile, methacrylonitrile, and vinyl acetate. .
• copolymerizable monomers can be used alone or in combination of two or more.
• the raw material monomer contains an ionic group-containing monomer containing an ionic group and a hydroxyl group-containing monomer containing a hydroxyl group as a (meth) acryl monomer and / or a copolymerizable monomer.
• the raw material monomer includes a (meth) acrylic monomer containing an ionic group and / or a copolymerizable monomer containing an ionic group, a (meth) acrylic monomer containing a hydroxyl group, and / or a hydroxyl group. Containing copolymerizable monomers.
• the monomer having an acryloyl group and / or a methacryloyl group is classified as a (meth) acryl monomer
• a monomer that has neither an acryloyl group nor a methacryloyl group and is copolymerizable with a (meth) acryl monomer is classified as a copolymerizable monomer.
• ionic group-containing monomers examples include anionic group-containing monomers such as carboxyl group-containing monomers and phosphate group-containing monomers, for example, cationic group-containing monomers such as tertiary amino group-containing monomers and quaternary ammonium group-containing monomers. Etc.
• carboxyl group-containing monomer examples include ⁇ , ⁇ -unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic acid and fumaric acid or salts thereof, such as hydroxyl group-containing (meth) acrylate (described later) and acid.
• carboxyl group-containing monomer examples include half-esterified products with anhydrides, preferably ⁇ , ⁇ -unsaturated carboxylic acids, and more preferably (meth) acrylic acid.
• Examples of the phosphoric acid group-containing monomer include phosphoric acid group-containing (meth) acrylates such as acid phosphooxyethyl (meth) acrylate and mono (2-hydroxyethyl (meth) acrylate) phosphate. (2-hydroxyethyl (meth) acrylate) phosphate.
• tertiary amino group-containing monomer examples include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N— N, N-dialkylaminoalkyl (meth) acrylates such as di-t-butylaminoethyl (meth) acrylate and N, N-dimethylaminobutyl (meth) acrylate, for example, N, N-dimethylaminoethyl (meth) acrylamide N, N-diethylaminoethyl (meth) acrylamide, N, N-dialkylaminoalkyl (meth) acrylamide such as N, N-dimethylaminopropyl (meth) acrylamide, and the like, preferably N, N-dialkylamino Alkyl (meth
• the quaternary ammonium group-containing monomer is, for example, a quaternizing agent (for example, epihalohydrin, benzyl halide, alkyl halide, etc.) acting on the above-mentioned tertiary amino group-containing monomer.
• a quaternizing agent for example, epihalohydrin, benzyl halide, alkyl halide, etc.
• (meth) acryloyloxyalkyltrialkylammonium salts such as 2- (methacryloyloxy) ethyltrimethylammonium chloride, 2- (methacryloyloxy) ethyltrimethylammonium bromide, 2- (methacryloyloxy) ethyltrimethylammonium dimethyl phosphate, (Meth) acryloylaminoalkyltrialkylamines such as methacryloylaminopropyltrimethylammonium chloride and methacryloylaminopropyltrimethylammonium bromide
• the metal salt include tetraalkyl (meth) acrylates such as tetrabutylammonium (meth) acrylate, and trialkylbenzylammonium (meth) acrylates such as trimethylbenzylammonium (meth) acrylate.
• Acryloyloxyalkyltrialkylammonium salt such as 2-
• ionic group-containing monomers can be used alone or in combination of two or more.
• the ionic group-containing monomer is preferably an anionic group-containing monomer, more preferably a carboxyl group-containing monomer.
• hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-methyl-2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl.
• hydroxyl group-containing (meth) acrylates such as (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
• hydroxyl-containing monomer for example, polyoxyethylene (meth) acrylate, polyoxypropylene (meth) acrylate, polyoxyalkylene (meth) acrylate such as polyoxyethylene polyoxypropylene (meth) acrylate, etc., one terminal And (meth) acrylates containing a polyoxyalkylene group in which X is a hydroxyl group (X in the above general formula (1) is a hydrogen atom).
• polyoxyethylene (meth) acrylate for example, diethylene glycol mono (meth) acrylate, triethylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, Hexaethylene glycol mono (meth) acrylate, heptaethylene glycol mono (meth) acrylate, octaethylene glycol mono (meth) acrylate, nonaethylene glycol mono (meth) acrylate, decaethylene glycol mono (meth) acrylate, undecaethylene glycol mono (Meth) acrylate, dodecaethylene glycol mono (meth) acrylate, tridecaethylene glycol mono (meth) acrylate, etc. It is below.
• polyoxypropylene (meth) acrylate examples include dipropylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetrapropylene glycol mono (meth) acrylate, and pentapropylene glycol mono (meth).
• hydroxyl group-containing monomers can be used alone or in combination of two or more.
• hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, tetraethylene glycol mono (meth) acrylate, pentaethylene glycol mono (meth) acrylate, and pentapropylene glycol mono (meth) acrylate, more preferably 2-hydroxyethyl (meth) acrylate.
• the blending ratio of each monomer in the raw material monomer is adjusted so that all of the glass transition point, acid value, and hydroxyl value of the (meth) acrylic polymer to be obtained are within a specific range described later.
• the mixing ratio of the ionic group-containing monomer is, for example, 10 parts by mass or more, preferably 12 parts by mass or more, more preferably 14 parts by mass or more, with respect to 100 parts by mass of the total amount of raw material monomers. Especially preferably, it is 17 mass parts or more, for example, 30 mass parts or less, Preferably, it is 25 mass parts or less.
• the mixture ratio of a hydroxyl-containing monomer is 5 mass parts or more, for example, Preferably, it is 10 mass parts or more, for example, is 50 mass parts or less, Preferably, it is 40 mass parts or less.
• the balance is other monomers (monomers (such as (meth) acrylic acid alkyl ester) excluding ionic group-containing monomers and hydroxyl group-containing monomers)).
• the blending ratio of the ionic group-containing monomer By setting the blending ratio of the ionic group-containing monomer to the above lower limit or more, the dispersibility with respect to the metal fine particles can be improved and the reaggregation of the metal fine particles can be suppressed.
• the blending ratio of the ionic group-containing monomer not more than the above upper limit value, it is possible to obtain excellent dispersion stability and coating solution stability, such as transparency of the cured film, scratch resistance, moisture heat resistance, etc. Various physical properties can be improved.
• the mixing ratio of the hydroxyl group-containing monomer to the above lower limit or more, the dispersibility with respect to the metal fine particles can be improved, and the reaggregation of the metal fine particles can be suppressed. Furthermore, excellent coating liquid stability can be obtained, and various physical properties such as hardness, adhesion, flexibility, scratch resistance, and wet heat properties of the cured film can be improved.
• the mixing ratio of other monomers is not particularly limited, and can be set as appropriate so as to satisfy the required characteristics as a metal fine particle dispersant.
• the blending ratio is, for example, 0.1 with respect to 100 parts by weight of the total amount of raw material monomers. It is not less than 3 parts by mass, preferably not less than 3 parts by mass, for example, not more than 50 parts by mass, preferably not more than 40 parts by mass.
• the blending ratio of the (meth) acrylate containing a saturated alicyclic group composed of two or more rings is within the above range, the amount of the saturated alicyclic group composed of two or more rings is adjusted to an appropriate ratio. Can do. Therefore, the dispersibility of the metal fine particles can be improved.
• the polymerization initiator is not particularly limited and is appropriately selected depending on the purpose and application. Specific examples of the polymerization initiator include radical polymerization initiators.
• radical polymerization initiator examples include azo compounds, peroxide compounds, sulfides, sulfines, sulfinic acids, diazo compounds, redox compounds, and preferably azo compounds and peroxide compounds. Can be mentioned.
• azo compound examples include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, 1,1′-azobis (1-acetoxy-1-phenylethane), dimethyl 2,2′-azo.
• examples thereof include bisisobutyrate and 4,4′-azobis-4-cyanovaleric acid.
• peroxide compounds examples include benzoyl peroxide, lauroyl peroxide, acetyl peroxide, capryel peroxide, 2,4-dichlorobenzoyl peroxide, isobutyl peroxide, acetylcyclohexylsulfonyl peroxide, and t-butyl peroxide.
• These polymerization initiators can be used alone or in combination of two or more.
• the blending ratio of the polymerization initiator is, for example, 0.1 parts by mass or more, preferably 2 parts by mass or more with respect to 100 parts by mass of the total amount of the ionic group-containing monomer, the hydroxyl group-containing monomer and the copolymerizable monomer. For example, it is 13 parts by mass or less, preferably 10 parts by mass or less.
• the solvent examples include aqueous solvents.
• water for example, alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol, such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether, are used.
• alcohol solvents such as methanol, ethanol, propanol, isopropanol, and butanol, such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether, are used.
• glycol ether solvents examples include glycol ether solvents.
• solvents can be used alone or in combination of two or more.
• solvent water and alcohol solvents are preferable, and alcohol solvents are more preferable.
• the mixing ratio of the solvent is not particularly limited, and is appropriately set according to the purpose and use.
• the polymerization conditions in the production of the (meth) acrylic polymer vary depending on the types of raw material monomer, polymerization initiator, solvent, etc., but the polymerization temperature is 30 ° C. or higher, preferably 60 ° C. or higher, for example, 150 ° C. or lower, Preferably, it is 120 degrees C or less.
• the polymerization time is, for example, 2 hours or more, preferably 4 hours or more, for example, 20 hours or less, preferably 8 hours or less.
• an anionic group-containing monomer is used as the ionic group-containing monomer, preferably, after the polymerization, a neutralizing agent is added to neutralize a part of the anionic group, A salt of the group is formed.
• Examples of the neutralizing agent include known basic compounds. Specific examples include amine compounds (monoamines such as ammonia, triethylamine, and diethylamine, 2-amino-2-methyl-1-propanol, N, N— Dimethylaminoethanol, N, N-diethylaminoethanol, 2-dimethylamino-2-methyl-1-propanol, monoisopropanolamine, diisopropanolamine, triisopropanolamine, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine , Alkanolamines such as N-methyldiethanolamine), hydroxides (sodium hydroxide, potassium hydroxide, etc.), morpholine, and the like.
• amine compounds such as ammonia, triethylamine, and diethylamine, 2-amino-2-methyl-1-propanol, N, N— Dimethylaminoethanol, N, N-diethylaminoethanol, 2-
• neutralizing agents can be used alone or in combination of two or more.
• the neutralizing agent is added so that at least a part of the anionic group is neutralized and the remainder remains without being neutralized.
• the neutralizing agent is 0.1 equivalent or more, preferably 0.2 equivalent or more per equivalent of anionic group, for example, 0.9 equivalent or less, preferably 0.8 equivalent or less. is there.
• a salt of the anionic group is formed, so that the dispersibility in the aqueous dispersion medium can be improved.
• a dispersion of (meth) acrylic polymer is obtained. That is, a dispersion of a metal fine particle dispersant is obtained. If necessary, the concentration of the (meth) acrylic polymer dispersion can be adjusted by adding or removing the aqueous solvent.
• the solid content concentration (nonvolatile content) of (meth) acrylic polymer is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 50% by mass or less, preferably Is 45 mass% or less.
• the glass transition point of the (meth) acrylic polymer determined by the Fox formula is ⁇ 30 ° C. or higher, preferably ⁇ 20 ° C. or higher, more preferably ⁇ 5 ° C. or higher, and 80 ° C. or lower, preferably 70 ° C. or lower, more preferably 60 ° C. or lower.
• the acid value of the (meth) acrylic polymer is 80 mgKOH / g or more, preferably 100 mgKOH / g or more, more preferably 110 mgKOH / g or more. 200 mgKOH / g or less, preferably 180 mgKOH / g or less, more preferably 150 mgKOH / g or less, and particularly preferably 135 mgKOH / g or less.
• the hydroxyl value of the (meth) acrylic polymer is 20 mgKOH / g or more, preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, and 90 mgKOH / g or less. , Preferably, it is 70 mgKOH / g or less, More preferably, it is 60 mgKOH / g or less.
• the weight average molecular weight (polystyrene conversion by GPC measurement) of the (meth) acrylic polymer is, for example, 2000 or more, preferably 3000 or more, more preferably 5000 or more, for example, 100,000 or less, preferably 50000 or less, More preferably, it is 20000 or less.
• the (meth) acrylic polymer can be obtained with good productivity, and the dispersibility of the metal fine particles can be improved.
• Various physical properties of a cured film obtained by curing a metal fine particle dispersion containing an agent can be improved.
• the measuring method of a weight average molecular weight is based on the Example mentioned later.
• Such a metal fine particle dispersant is made of a (meth) acrylic polymer containing an ionic group, and all of the glass transition point, acid value and hydroxyl value are adjusted to a specific range, so that it is water-based.
• the dispersibility of the metal fine particles in the dispersion medium can be improved, and various physical properties of the cured film can be improved.
• the glass transition point when the glass transition point is in the above range, the balance between the flexibility and adhesion of the cured film, the hardness and the scratch resistance can be improved. Further, when the acid value is in the above range, excellent dispersion stability and coating solution stability can be obtained, and a coating film excellent in transparency, moist heat resistance, scratch resistance and hardness can be obtained. . Furthermore, when the hydroxyl value is in the above range, excellent coating solution stability can be obtained, and a coating film excellent in scratch resistance, moist heat resistance, flexibility, adhesion and hardness can be obtained.
• Such a metal fine particle dispersant can be easily produced and is excellent in low cost.
• the fine metal particle dispersion contains the fine metal particle dispersant, the fine metal particles, and the aqueous dispersion medium.
• the metal fine particles are not particularly limited, but for example, metal oxide fine particles such as aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, tin oxide, yttrium oxide, bismuth oxide, antimony oxide, cerium oxide, indium oxide,
• metal oxide fine particles such as aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, tin oxide, yttrium oxide, bismuth oxide, antimony oxide, cerium oxide, indium oxide
• fine particles of different element-doped metal oxides obtained by doping these metal oxides with different elements such as gallium, antimony, tin, fluorine, phosphorus, aluminum, and the like can be given.
• the crystal structure of these metal oxides is not particularly limited, and for example, any of cubic, tetragonal, orthorhombic, monoclinic, triclinic, hexagonal, trigonal, etc. There may be.
• metal fine particles aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, gallium-doped zinc oxide, and antimony-doped tin oxide are preferable, and aluminum oxide is more preferable.
• the metal fine particles may be surface-treated by a known method if necessary.
• These metal fine particles can be used alone or in combination of two or more.
• the shape of the metal fine particle is not particularly limited, and examples thereof include a lump shape, a spherical shape, a hollow shape, a porous shape, a rod shape, a plate shape, a fiber shape, an indefinite shape, and a mixture thereof.
• the particle diameter of the metal fine particles is measured as the primary particle diameter of the metal fine particles themselves (distinguishable from the average particle diameter described later), and is, for example, 200 nm or less, preferably 90 nm or less, usually 1 nm or more, preferably 3 nm or more.
• the primary particle diameter of the metal fine particles is within the above range, the metal fine particles can be easily obtained, and the storage stability of the metal fine particle dispersion and the transparency of the cured film can be improved.
• the transparency of the cured film can be further improved by properly using the type of ionic group contained in the metal fine particle dispersant depending on the charge on the surface of the metal fine particle.
• zinc-based metal fine particles for example, zinc oxide, gallium-doped zinc oxide, etc.
• a tertiary amino group or a quaternary ammonium group is used as the ionic group.
• aluminum-based metal fine particles for example, aluminum oxide
• titanium-based metal fine particles for example, titanium oxide surface-treated with silicon, zirconium and titanium oxide surface-treated with aluminum
• zirconium-based metal fine particles zirconium oxide
• a carboxyl group or a phosphate group is preferably used as the ionic group.
• aqueous dispersion medium examples include aqueous solvents used in the synthesis of the (meth) acrylic polymer described above.
• aqueous solvents used in the synthesis of the (meth) acrylic polymer described above.
• water for example, alcohol solvents such as methanol, ethanol, propanol, isopropanol, butanol
• glycol ether solvents such as ethylene glycol monoethyl ether and propylene glycol monomethyl ether.
• aqueous dispersion media can be used alone or in combination of two or more.
• aqueous dispersion medium water and alcohol solvents are preferable, and water is more preferable.
• aqueous solvent used in the synthesis of the (meth) acrylic polymer described above can be used as an aqueous dispersion medium as it is.
• a metal fine particle dispersion the above-described components are blended, and the metal fine particles are dispersed by a known dispersion method.
• the compounding ratio of each component in the metal fine particle dispersion is such that the metal fine particle dispersant (nonvolatile content) is, for example, 1 part by mass or more, preferably 5 parts by mass or more with respect to 100 parts by mass of the metal fine particles. 200 parts by mass or less, preferably 100 parts by mass or less, and more preferably 70 parts by mass or less.
• the metal fine particles are, for example, 0.5 parts by mass or more, preferably 2.5 parts by mass or more, for example, 35 parts by mass or less, preferably 30 parts by mass with respect to 100 parts by mass of the metal fine particle dispersion. Or less.
• the blending ratio of the metal fine particle dispersant is a ratio excluding the blending amount as the binder resin described later.
• the particle size of the metal fine particles in the metal fine particle dispersion is measured as an average particle size (average particle size) of the metal fine particles as primary particles and secondary particles, and is, for example, 200 nm or less, preferably , 90 nm or less, usually 1 nm or more, preferably 3 nm or more.
• the measuring method of an average particle diameter is based on the Example mentioned later.
• the dispersion method is not particularly limited, and for example, a known disperser such as a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a bead mill, or an ultrasonic disperser can be used.
• a known disperser such as a paint shaker, a roll mill, a ball mill, an attritor, a sand mill, a bead mill, or an ultrasonic disperser can be used.
• ball mills and bead mills are preferable from the viewpoint of improving coatability, paint stability, and transparency of a cured film, and more preferably. And a bead mill.
• dispersion media such as zirconia beads and glass beads can be used.
• the bead diameter of the dispersion medium is not particularly limited, but is, for example, 10 ⁇ m or more, for example, 500 ⁇ m or less, preferably 100 ⁇ m or less. Note that the filling rate of the dispersion medium is appropriately set according to the purpose and application.
• the fine metal particles can be pulverized by the above-described dispersion medium, and the average particle diameter can be adjusted to the above range.
• metal fine particles having an average particle diameter larger than the above range can be introduced into the disperser.
• the metal fine particle dispersion includes, for example, a pigment, a desiccant, a rust inhibitor, a plasticizer, a coating film surface conditioner, an antioxidant, an ultraviolet absorber, and a dispersant excluding the metal fine particle dispersant described above.
• Various additives such as nonionic surfactants such as sorbitan fatty acid esters and polyethylene glycol fatty acid esters can be added.
• the mixture ratio of an additive is suitably set according to the objective and use.
• the nonvolatile content of the metal fine particle dispersion is, for example, 0.5% by mass or more, preferably 3% by mass or more, for example, 50% by mass or less, preferably 40% by mass or less.
• Such a metal fine particle dispersion contains the metal fine particle dispersant described above, it has excellent dispersibility of the metal fine particles in the aqueous dispersion medium, and can improve various physical properties of the cured film. it can.
• the above metal fine particle dispersion can be suitably used as a coating agent in various industrial fields.
• the coating agent contains the metal fine particle dispersion.
• the coating agent can further contain a melamine resin and / or a binder resin as a curing agent.
• the coating agent contains a melamine resin, it can be crosslinked and cured as described later, and a cured film can be obtained. Further, if the coating agent contains a binder resin, a cured film excellent in various physical properties can be obtained when dried and cured as described later.
• melamine resin a known melamine compound can be used. Specifically, for example, an alkylol or alkoxyalkylol-modified melamine compound can be mentioned, and more specifically, for example, methoxymethylated melamine, Examples include butoxymethylated melamine.
• melamine resin a compound obtained by co-condensing urea or the like with a part of the melamine compound can also be used.
• Melamine resin can be used alone or in combination of two or more.
• the blending ratio of the melamine resin in the coating agent is, for example, 30 parts by mass or more, preferably 50 parts by mass or more, for example, 120 parts by mass or less, preferably 110 parts by mass or less with respect to 100 parts by mass of the metal fine particles. More preferably, it is 100 parts by mass or less.
• the coating agent can further contain other curing agents (curing agents excluding melamine resin).
• curing agents are not particularly limited, and examples include epoxy curing agents, carbodiimide curing agents, aziridine curing agents, oxazoline curing agents, and isocyanate curing agents.
• the blending ratio is appropriately set according to the purpose and application.
• binder resin examples include polyester resin, epoxy resin, phenol resin, polyimide resin, (meth) acrylic resin, and the like.
• binder resins can be used alone or in combination of two or more.
• the binder resin is preferably a (meth) acrylic resin.
• the (meth) acrylic resin is not particularly limited, and a known (meth) acrylic resin can also be used.
• (meth) acrylic polymers as the metal fine particle dispersant described above are used.
• the coating agent preferably contains the same type of resin as the (meth) acrylic polymer in the metal fine particle dispersant described above as a binder resin.
• the binder resin is preferably a (meth) acrylic polymer in which the glass transition point, the acid value, and the hydroxyl value are all adjusted to a specific range.
• the (meth) acrylic polymer obtained above is blended more (excessively) than the blending ratio described above.
• the (meth) acrylic polymer is adsorbed on the metal fine particles via the ionic group, and the remaining part of the (meth) acrylic polymer is dispersed in water as a binder resin without adsorbing on the metal fine particles. Dispersed in the medium in a free state. In this way, the (meth) acrylic polymer is used as a metal fine particle dispersant and also as a binder resin.
• the (meth) acrylic polymer as the metal fine particle dispersant described above is used as the binder resin, the compatibility between the metal fine particle dispersant and the binder resin is excellent, and the dispersion stability of the coating agent is improved. In addition, a cured film having excellent various physical properties can be obtained.
• the binder resin is made of a (meth) acrylic polymer containing an ionic group, and the glass transition point, acid value, and hydroxyl value are all adjusted to a specific range, various physical properties of the cured film can be obtained. Improvements can be made.
• the blending ratio of the binder resin is appropriately set according to the purpose and application. For example, it is 10 parts by mass or more, preferably 20 parts by mass or more, for example, 80 parts by mass with respect to 100 parts by mass of the metal fine particles. It is 70 parts by mass or less, more preferably 60 parts by mass or less.
• the blending ratio of the (meth) acrylic polymer is the sum of the blending ratio of the metal fine particle dispersant and the blending ratio of the binder resin. Specifically, for example, 30 parts by mass or more, preferably 40 parts by mass or more, for example, 90 parts by mass or less, preferably 80 parts by mass or less, with respect to 100 parts by mass of the metal fine particles. Preferably, it is 70 parts by mass or less.
• the coating agent includes, for example, a pigment, a desiccant, a rust inhibitor, a plasticizer, a coating film surface conditioner, an antioxidant, an ultraviolet absorber, and a dispersant other than the above-described metal fine particle dispersant (for example, And various other additives such as nonionic surfactants such as sorbitan fatty acid ester and polyethylene glycol fatty acid ester can be added.
• the mixture ratio of an additive is suitably set according to the objective and use.
• the nonvolatile content of the coating agent is, for example, 0.5% by mass or more, preferably 3% by mass or more, for example, 50% by mass or less, preferably 40% by mass or less.
• Such a coating agent contains the above-mentioned metal fine particle dispersion liquid, it is excellent in the dispersibility of the metal fine particle in an aqueous dispersion medium, and can aim at the improvement of various physical properties of a cured film.
• the above coating agent can be suitably used as a coating agent in various industrial fields.
• the cured film composed of the above coating agent is excellent in various physical properties such as scratch resistance, hardness, adhesion, flexibility, transparency, moisture and heat resistance, and thus the above coating agent is suitable as a hard coating agent. Used.
• the coating agent is applied to a substrate by a known method, and then applied.
• the film is cured by heating (crosslinking curing).
• the substrate is not particularly limited.
• polycarbonate polymethyl methacrylate, polystyrene, polyester (polyethylene terephthalate, etc.), polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.
• plastics such as metal, wood, paper, glass, and slate.
• the coating method is not particularly limited. For example, roll coating, bar coating, doctor blade, Mayer bar, air knife, etc., coating using a commonly used device, screen printing, offset printing, etc.
• Known coating methods such as flexographic printing, brush coating, spray coating, gravure coating, and reverse gravure coating are employed.
• the heating temperature is, for example, 100 ° C. or more, preferably 110 ° C. or more, for example, 200 ° C. or less, preferably 180 ° C. or less
• the heating time is, for example, 1 minute or more, preferably Is 3 minutes or more, for example, 60 minutes or less, preferably 30 minutes or less.
• the curing of the coating film may be one-stage curing or multi-stage curing.
• the curing conditions at each stage may be the same or different from each other.
• the coating agent (including melamine resin) is crosslinked to form a three-dimensional cured film.
• the coating agent does not contain the melamine resin
• the coating agent is applied to the substrate by the above method, and then the coating film is dried and cured.
• the drying temperature is, for example, 100 ° C. or more, preferably 110 ° C. or more, for example, 200 ° C. or less, preferably 180 ° C. or less
• the drying time is, for example, 3 minutes or more, preferably Is 5 minutes or more, for example, 10 minutes or less, preferably 7 minutes or less.
• the aqueous dispersion medium is volatilized from the coating agent (excluding the melamine resin), and the metal fine particle dispersant (and the binder resin contained if necessary) is dried and cured to form a cured film. .
• the cured film thus obtained is obtained from the above-mentioned coating agent, it is excellent in various physical properties such as scratch resistance, hardness, adhesion, flexibility, transparency, and moisture and heat resistance.
• the cured film is suitably used in various industrial products, for example, for applications such as optical films and functional coatings such as plastic and metal.
• Tg the glass transition temperature of the copolymer (unit: K)
• ⁇ Hydroxyl value> Based on the titration method described in JIS K0070 (1992), the hydroxyl value (mgKOH / g) was measured. ⁇ Average particle size> Measurement was performed under the following conditions using a laser light diffraction / scattering particle size distribution analyzer Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.).
• Measurement solvent Dispersion medium CI value used in preparation of dispersion: 0.4 to 0.8
• Particle permeability Transmission sensitivity: Standard filter: Stand: Norm Nanorange correction: Invalid ⁇ weight average molecular weight (Mw) measurement by gel permeation chromatography> The sample was dissolved in tetrahydrofuran, the sample concentration was set to 1.0 g / L, and the sample was measured by gel permeation chromatograph (GPC) equipped with a differential refractive index detector (RID) to obtain the molecular weight distribution of the sample.
• GPC gel permeation chromatograph
• RID differential refractive index detector
• a dispersion of a metal fine particle dispersant made of a (meth) acrylic polymer having a weight average molecular weight of 7000, a glass transition point of ⁇ 5 ° C., an acid value of 130 mgKOH / g, and a hydroxyl value of 65 mgKOH / g was obtained.
• the non-volatile content of the dispersion was 40%.
• Examples 2 to 10 and Comparative Examples 1 to 8 A metal fine particle dispersant was obtained in the same manner as in Example 1 except that the formulations shown in Tables 1 to 4 were used. Tables 1 to 4 show the weight average molecular weight, glass transition point, acid value, hydroxyl value, and nonvolatile content of the dispersion of the metal fine particle dispersant.
• Example 11 15 parts of a dispersion of a metal fine particle dispersant obtained in Example 1 (non-volatile content 40%), 20 parts of aluminum oxide as a metal fine particle (trade name AEROXIDE AluC, primary particle size 13 nm, manufactured by EVONIK), as a solvent 65 parts of water and 150 parts of 50 ⁇ m zirconia beads as a dispersion medium are placed in a 300 mL bottle, and using a disperser (Rocking Shaker RS-05W manufactured by Seiwa Giken Co., Ltd.), metal fine particles are pulverized at 60 Hz for 10 hours. Dispersed. Thereafter, zirconia beads were removed by filtration to obtain a metal fine particle dispersion in which metal fine particles were dispersed.
• a disperser Rocking Shaker RS-05W manufactured by Seiwa Giken Co., Ltd.
• the nonvolatile content in the obtained metal fine particle dispersion was 26% by mass, and the average particle size of the metal fine particles was 50 nm.
• Examples 12 to 20 and Comparative Examples 9 to 16 A metal fine particle dispersion was obtained in the same manner as in Example 11 except that the metal fine particle dispersants obtained in Examples 2 to 10 and Comparative Examples 1 to 8 were used and the formulations were changed to the formulations shown in Tables 5 and 6. It was.
• Tables 5 and 6 show the nonvolatile content and the average particle size in the obtained metal fine particle dispersion.
• Example 21 63 parts of the metal fine particle dispersion (non-volatile content 26%) obtained in Example 11 and the dispersion of the metal fine particle dispersant obtained in Example 1 as a binder resin (dispersion of (meth) acrylic polymer, non-volatile) Mixing 9 parts of melamine resin (Nicarac MX-706, Nippon Carbide Industries, 70% non-volatile content) and 12 parts of diluting water and mixing at 30 ° C. An agent was obtained.
• the obtained coating agent was applied to a polyethylene terephthalate film (Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m) as a base material using a bar coater so that the film thickness after drying was 1.0 ⁇ m. Heat at 10 ° C. for 10 minutes to cure. Thereby, a cured film was obtained.
• a polyethylene terephthalate film Cosmo Shine A4300, manufactured by Toyobo Co., Ltd., thickness 100 ⁇ m
• Examples 22 to 30 and Comparative Examples 17 to 24 A cured film was obtained in the same manner as in Example 21 except that the metal fine particle dispersions obtained in Examples 12 to 20 and Comparative Examples 9 to 16 were used and the formulations were changed to the formulations shown in Tables 7 and 8.
• the criteria for evaluation are as follows. A: No precipitate was confirmed even after 2 months. ⁇ : No precipitate was confirmed after 1 month, but a small amount of precipitate was confirmed after 2 months. ⁇ : Sediment was not confirmed after 1 week, but a little sediment was confirmed after 1 month. X: Precipitate was confirmed after 1 week.
• the Haze value is 1.0 or less, the transparency is excellent.
• the hardness is excellent.
• the criteria for evaluation are as follows. (Double-circle): The coating-film crack exceeding 2 mm in diameter was not confirmed. ⁇ : A crack in the coating film having a diameter of 2 mm or more and less than 3 mm was confirmed. X: The crack of the coating film with a diameter of 3 mm or more was confirmed.
• the criteria for evaluation are as follows. A: No scratch was confirmed. ⁇ : 1 to 5 scratches were confirmed. ⁇ : There were 6 to 10 confirmed scratches. X: The number of confirmed scratches was 11 or more.
• the criteria for evaluation are as follows. A: The amount of change in the Haze value was 0.5 or less. ⁇ : The change amount of the Haze value exceeded 0.5 and was 1.0 or less. X: The amount of change in the Haze value was 1.0 or more.
• the metal fine particle dispersant, metal fine particle dispersion, coating agent, cured film and binder resin of the present invention are used as optical films, functional coatings and the like in various industrial products.

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