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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
  • C09D133/04—Homopolymers or copolymers of esters
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • 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
  • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; 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
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
  • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
  • C09D7/40—Additives
  • C09D7/60—Additives non-macromolecular
  • C09D7/61—Additives non-macromolecular inorganic

Definitions

• the present invention relates to a coating agent and a coating film, and specifically relates to a coating agent in which metal fine particles are dispersed by a metal fine particle dispersant, and a coating film obtained by curing the coating agent.
• coating properties 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 to be blended, the solvent, the type of 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.
• a composition obtained by reacting a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (containing 67 mol% of dipentaerythritol pentaacrylate) and pyromellitic dianhydride It has been proposed to prepare an active energy ray-curable coating composition by mixing I), a copolymer of methyl methacrylate and hydroxyethyl acrylate, and colloidal silica using isopropyl alcohol as a dispersion medium (patent) Reference 1 (Example 10)).
• the coating film of the coating resin composition as described above is required to have adhesiveness with a base material, and is required to have hardness and durability (alkali resistance, light resistance).
• the coating resin composition is required to further improve dispersibility and dispersion stability, and the coating film is required to have excellent transparency depending on the application.
• An object of the present invention is a coating agent that is excellent in dispersibility and dispersion stability of metal fine particles, and that can improve the transparency, adhesion, hardness and durability (alkali resistance, light resistance) of the coating film, And it is providing the coating film obtained by hardening
• the present invention is a coating agent containing metal fine particles, a dispersion medium, a metal fine particle dispersant, and a binder, wherein the metal fine particle dispersant comprises two or more active energy curing groups, and It contains a monomer or oligomer having at least one carboxyl group, the binder contains a (meth) acrylic resin binder having a (meth) acryloyl group in the side chain, and the (meth) acrylic resin binder comprises an anionic group
• the coating agent which is the reaction material of the monomer component which does not contain a containing monomer or contains an anionic group containing monomer in the ratio of less than 5 mass% is included.
• the metal fine particle dispersant further contains a (meth) acrylic resin dispersant having a (meth) acryloyl group in a side chain, and the (meth) acrylic resin dispersant is 5% by mass.
• a (meth) acrylic resin dispersant having a (meth) acryloyl group in a side chain
• the (meth) acrylic resin dispersant is 5% by mass.
• the present invention [4] includes the coating agent according to any one of the above [1] to [3], wherein the anionic group of the anionic group-containing monomer is a carboxyl group or a phosphate group. .
• the present invention [5] provides the coating agent according to any one of the above [1] to [4], wherein the (meth) acrylic resin binder is a reaction product of a monomer component containing an aromatic ring-containing monomer. Contains.
• the present invention [6] is the coating according to the above [5], wherein in the (meth) acrylic resin binder, the content of the aromatic ring-containing monomer is 20% by mass or more based on the total amount of the monomer components. Contains agents.
• the present invention includes the coating agent according to any one of [1] to [6] above, wherein the (meth) acrylic resin binder has a weight average molecular weight of 3000 or more and 50000 or less.
• the present invention [8] is the coating agent according to any one of the above [2] to [7], wherein the (meth) acrylic resin dispersant is a reaction product of a monomer component containing an aromatic ring-containing monomer. Is included.
• This invention is the said (meth) acrylic resin dispersing agent,
• the content rate of the said aromatic ring containing monomer is 20 mass% or more with respect to the total amount of the said monomer component,
• the said [8] description. Contains a coating agent.
• the present invention [10] includes the coating agent according to any one of the above [2] to [9], wherein the (meth) acrylic resin dispersant has a weight average molecular weight of 3,000 to 50,000. .
• the invention [11] is any one of the above [2] to [10], wherein the fine metal particle dispersant further contains a caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
• the coating agent described in 1 is included.
• the present invention includes a coating film, which is a cured product of the coating agent according to any one of [1] to [11].
• the coating agent of the present invention is excellent in dispersibility and dispersion stability of metal fine particles, and can provide a coating film excellent in transparency, adhesion, hardness and durability (alkali resistance, light resistance).
• the coating film of the present invention is excellent in transparency, adhesion, hardness and durability (alkali resistance, light resistance).
• the coating agent of the present invention comprises a metal fine particle dispersion in which metal fine particles are dispersed in a dispersion medium.
• the coating agent contains metal fine particles, a dispersion medium, a metal fine particle dispersant, and a binder.
• metal fine particles For example, aluminum oxide (alumina), titanium oxide (titania), zinc oxide, zirconium oxide (zirconia), tin oxide, yttrium oxide (yttria), bismuth oxide, antimony oxide, cerium oxide , Metal oxide fine particles such as indium oxide and silicon oxide (silicon dioxide, silica, etc.), for example, these metal oxides are doped with different elements such as gallium, antimony, tin, fluorine, phosphorus, aluminum, etc. And foreign element-doped metal oxide fine particles.
• 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.
• Preferred examples of the metal fine particles include aluminum oxide, titanium oxide, and zirconium oxide.
• 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, and is, for example, 200 nm or less, preferably 90 nm or less, more preferably 50 nm or less, and usually 1 nm or more, preferably 3 nm or more. It is.
• the primary particle diameter of the metal fine particles is in the above range, the metal fine particles can be easily obtained, and the storage stability of the coating agent and the transparency of the coating film (described later) can be improved.
• a dispersion medium for example, petroleum hydrocarbon solvents, such as hexane and a mineral spirit, for example, aromatic hydrocarbon solvents, such as benzene, toluene, xylene, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, Ketone solvents such as diisobutyl ketone and cyclohexanone, for example, ester solvents such as methyl acetate, ethyl acetate, butyl acetate, ⁇ -butyrolactone, propylene glycol monomethyl ether acetate, such as N, N-dimethylformamide, N, N-dimethyl Examples thereof include organic solvents such as aprotic polar solvents such as acetamide, dimethyl sulfoxide, N-methylpyrrolidone and pyridine.
• aromatic hydrocarbon solvents such as benzene, toluene, xylene
• Ketone solvents
• an aqueous solvent such as water
• an alcohol solvent such as methanol, ethanol, propanol, isopropanol, or butanol
• a glycol ether solvent such as ethylene glycol monoethyl ether or propylene glycol monomethyl ether
• the dispersion medium is also available as a commercial product.
• examples of petroleum hydrocarbon solvents include AF Solvent Nos. 4 to 7 (above, Shin Nippon Oil Co., Ltd.) and the like.
• examples of the group hydrocarbon solvent include Ink Solvent No. 0, Solvesso 100, 150, and 200 (manufactured by Shin Nippon Oil Co., Ltd.) manufactured by Exxon Chemical.
• These dispersion media can be used alone or in combination of two or more.
• the metal fine particle dispersant is an additive for improving the dispersibility of the metal fine particles in the dispersion medium, and is a monomer having two or more active energy curing groups and at least one carboxyl group as essential components.
• oligomers hereinafter, monomers and oligomers may be collectively referred to as compounds).
• the active energy curing group is a group that forms a crosslinked structure by irradiation with active energy rays (described later) and cures, and examples thereof include a (meth) acryloyl group and a glycidyl group.
• a (meth) acryloyl group is preferable.
• the “(meth) acryloyl group” is defined as “acryloyl group” and / or “methacryloyl group”.
• (meth) acryl described below is also defined as “acryl” and / or “methacryl”
• “(meth) acrylate” is also defined as “acrylate” and / or “methacrylate”. Is done.
• the compound having two or more (meth) acryloyl groups and at least one carboxyl group for example, a compound having two or more (meth) acryloyl groups and at least one hydroxyl group is converted into an acid anhydride.
• denatured by is mentioned.
• a modified body for example, a polyfunctional (meth) acrylic compound having two or more (meth) acryloyl groups and at least one hydroxyl group (hereinafter referred to as “(meth) acrylic compound”)) (hereinafter, it may be abbreviated as “an acid anhydride modified product of (A) polyfunctional (meth) acrylic compound”).
• hydroxyl group-containing polyfunctional May be abbreviated as “(meth) acrylic compound”
• an acid anhydride modified product of (A) polyfunctional (meth) acrylic compound hereinafter, it may be abbreviated as “an acid anhydride modified product of (A) polyfunctional (meth) acrylic compound”.
• Hydroxyl group-containing polyfunctional (meth) acrylic compounds include, for example, polyols (for example, glycerin (hydroxyl group number 3), trimethylolpropane (hydroxyl group number 3), tris (2-hydroxyethyl) isocyanurate (hydroxyl group number 3), Known polyfunctional alcohols such as diglycerin (hydroxyl group number 4), ditrimethylolpropane (hydroxyl group number 4), pentaerythritol (hydroxyl group number 4), dipentaerythritol (hydroxyl group number 6), and tripentaerythritol (hydroxyl group number 8)) And adduct bodies (adducts) in which less than an equimolar amount of (meth) acrylic acid is added to the number of hydroxyl groups of the polyol.
• polyols for example, glycerin (hydroxyl group number 3), trimethylolpropane (hydroxyl group number 3), tris (2-hydroxyethyl) isocyanur
• Examples of the hydroxyl group-containing polyfunctional (meth) acrylic compound include pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Trimethylolpropane di (meth) acrylate, ditrimethylolpropane di (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, tris-2-hydroxyethylisocyanurate di (meth) acrylate, glycerin di (meth) acrylate, diglycerin di ( (Meth) acrylate, diglycerin tri (meth) acrylate, and adducts of these alkylene oxides (ethylene oxide, propylene oxide, etc.) Random adduct includes a block adduct.), And mixtures thereof.
• hydroxyl group-containing polyfunctional (meth) acrylic compounds can be used alone or in combination of two or more.
• Preferred examples of the hydroxyl group-containing polyfunctional (meth) acrylic compound include dipentaerythritol pentaacrylate and pentaerythritol tri (meth) acrylate. From the viewpoint of the hardness of the coating film (described later), more preferably dipentaerythritol.
• An example is erythritol pentaacrylate.
• the hydroxyl group-containing polyfunctional (meth) acrylic compound can be used in an appropriate ratio with the hydroxyl group-free polyfunctional (meth) acrylic compound described later.
• Examples of the acid anhydride include dicarboxylic acid monoanhydride, tricarboxylic acid monoanhydride, and tetracarboxylic acid dianhydride.
• dicarboxylic acid monoanhydride examples include oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12 to C18) succinic anhydride, tetrahydrophthalic anhydride, hymic anhydride, hexahydra Examples include phthalic anhydride, tetraprom phthalic anhydride, and tetrachlorophthalic anhydride.
• tricarboxylic acid monoanhydride examples include trimellitic anhydride, cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride, and the like.
• tetracarboxylic dianhydrides include pyromellitic anhydride, benzophenotetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 5- (2,5-oxotetrahydrofuryl) ) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride.
• the acid anhydride examples include dicarboxylic acid monoanhydride and tetracarboxylic acid dianhydride, and more preferred examples include succinic anhydride, phthalic anhydride, and pyromellitic anhydride.
• the acid anhydride is preferably dicarboxylic acid monoanhydride, and more preferably succinic anhydride or phthalic anhydride from the viewpoint of the hardness of the coating film (described later), and particularly preferably anhydrous. Examples include phthalic acid.
• a hydroxyl group-containing polyfunctional (meth) acrylic acid anhydride modified product for example, a hydroxyl group-containing polyfunctional (meth) acrylic compound and an acid anhydride are blended, and if necessary, in a solvent. And react by heating.
• the blending ratio of hydroxyl group-containing polyfunctional (meth) acrylic compound and acid anhydride is, for example, equivalent ratio of hydroxyl group-containing polyfunctional (meth) acrylic acid anhydride to carboxylic anhydride group relative to hydroxyl group (Carboxylic anhydride group / hydroxyl group) is, for example, 0.5 or more, preferably 0.67 or more, for example, 1 or less, preferably 0.91 or less.
• the solvent examples include the above-described organic solvent (the above-described organic solvent as a dispersion medium), the above-described aqueous solvent (the above-described aqueous solvent as a dispersion medium), and the like. These solvents can be used alone or in combination of two or more.
• the solvent is preferably an organic solvent, more preferably a ketone solvent, and still more preferably methyl isobutyl ketone.
• Examples of the catalyst include metals, organometallic compounds, metal halides, and amine compounds.
• Examples of the metal include alkali metals such as sodium and potassium.
• organometallic compound examples include the alkali metal alkoxides (alkali metal alkoxides) and derivatives thereof, such as alkylaluminum compounds such as triethylaluminum and derivatives thereof, such as alkoxytitanium compounds such as tetrabutyl titanate, 2-ethyl Examples thereof include organic tin compounds such as tin hexanoate, tin octylate, and dibutyltin laurate.
• alkali metal alkoxides alkali metal alkoxides
• derivatives thereof such as alkylaluminum compounds such as triethylaluminum and derivatives thereof, such as alkoxytitanium compounds such as tetrabutyl titanate, 2-ethyl
• organic tin compounds such as tin hexanoate, tin octylate, and dibutyltin laurate.
• metal halide examples include tin halides such as tin chloride (specifically, tin dichloride: SnCl 2 ).
• amine compound examples include N, N-dimethylbenzylamine, triethylamine, tributylamine, triethylenediamine, benzyltrimethylammonium chloride, benzyltriethylammonium bromide, tetramethylammonium bromide, cetyltrimethylammonium bromide and the like.
• These catalysts can be used alone or in combination of two or more.
• the catalyst is preferably an amine compound, more preferably N, N-dimethylbenzylamine, triethylamine, or tributylamine, and still more preferably triethylamine.
• the mixing ratio of the catalyst is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of the hydroxyl group-containing polyfunctional (meth) acrylic compound and the acid anhydride. Yes, for example, 5 parts by mass or less, preferably 0.5 parts by mass or less.
• a polymerization inhibitor can be added if necessary.
• polymerization inhibitor examples include p-methoxyphenol, hydroquinone, hydroquinone monomethyl ether, catechol, tert-butylcatechol, 2,6-di-tert-butyl-hydroxytoluene, 4-tert-butyl-1,2-dihydroxy Phenolic compounds such as benzene and 2,2′-methylene-bis (4-methyl-6-tert-butylcatechol) such as phenothiazine, diphenylphenylenediamine, dinaphthylphenylenediamine, p-aminodiphenylamine, N-alkyl-N Aromatic amines such as' -phenylenediamine, such as 4-hydroxy-2,2,6,6-tetramethylpiperidine, 4-acetoxy-1-oxy-2,2,6,6-tetramethylpiperidine, 4 -Benzoyloxy-1 Oxy-2,2,6,6-tetramethylpiperidine, 4-alkoxy-1-oxy-2,2,2,
• polymerization inhibitors can be used alone or in combination of two or more.
• the polymerization inhibitor is preferably p-methoxyphenol.
• the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass with respect to 100 parts by mass in total of the hydroxyl group-containing polyfunctional (meth) acrylic compound and the acid anhydride.
• Part or more for example, 1.0 part by weight or less, preferably 0.1 part by weight or less.
• the heating temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 140 ° C. or lower, Preferably, it is 110 degrees C or less.
• the heating time is, for example, 4 hours or more, preferably 8 hours or more, for example, 20 hours or less, preferably 12 hours or less.
• the hydroxyl group-containing polyfunctional (meth) acrylic compound can be modified with an acid anhydride, and (A) an acid anhydride modified product of the polyfunctional (meth) acrylic compound is obtained.
• (A) As an acid anhydride modified body of a polyfunctional (meth) acryl compound more specifically, for example, phthalic acid modified product of dipentaerythritol pentaacrylate, phthalic acid modified product of pentaerythritol triacrylate, dipentaerythritol Examples thereof include succinic acid-modified products of pentaacrylate and succinic acid-modified products of pentaerythritol triacrylate.
• the acid value of the acid anhydride modified product of the polyfunctional (meth) acrylic compound is, for example, 20 mgKOH / g or more, preferably 73 mgKOH / g or more, more preferably 80 mgKOH / g or more, for example, 500 mgKOH. / G or less, preferably 300 mgKOH / g or less.
• the hydroxyl value of the acid anhydride modified product of the polyfunctional (meth) acrylic compound (A) exceeds, for example, 0 mgKOH / g, preferably 1 mgKOH / g or more, for example, 350 mgKOH / g or less, preferably Is 230 mg KOH / g or less.
• the compound having two or more (meth) acryloyl groups and at least one carboxyl group is not limited to the acid anhydride-modified product of the above-mentioned (A) polyfunctional (meth) acrylic compound. Polyester (meth) acrylate or the like can also be used.
• the compound having two or more (meth) acryloyl groups and at least one carboxyl group is preferably (A) a polyfunctional (meth) acrylic compound.
• An acid anhydride modified body is mentioned.
• the compounding ratio of the compound having two or more (meth) acryloyl groups and at least one carboxyl group is 100
• 1 part by mass or more preferably 5 parts by mass or more, more preferably 7 parts by mass or more, for example, 200 parts by mass or less, preferably 100 parts by mass or less, more preferably with respect to parts by mass.
• 70 parts by mass or less and particularly preferably 50 parts by mass or less.
• the metal fine particle dispersant may further contain (B) a monofunctional (meth) acrylic compound.
• the monofunctional (meth) acryl compound is specifically a compound having one (meth) acryloyl group, and contains at least one of the compounds represented by the following (b1) to (b3). ing.
• (B1) A caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
• the compound represented by (b1) is a caprolactone adduct of (meth) acrylic acid represented by the following formula (1).
• R 1 represents a hydrogen atom or a methyl group, and n represents 1 to 10.
• R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
• n is the average number of moles of caprolactone added per mole of (meth) acrylic acid, and is 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. Preferably, it is 3 or less.
• Such a caprolactone adduct of (meth) acrylic acid can be obtained by subjecting (meth) acrylic acid to an addition reaction (ring-opening addition) with ⁇ -caprolactone.
• (Meth) acrylic acid is acrylic acid and / or methacrylic acid, preferably acrylic acid.
• ⁇ -caprolactone is not particularly limited, and a commercially available product can be used as it is.
• the method of reacting (meth) acrylic acid and ⁇ -caprolactone (ring-opening addition) is not particularly limited, and is a known method (for example, those described in JP-A-62-135521, JP-A-60-67446, etc.). Method).
• (meth) acrylic acid and ⁇ -caprolactone are blended, and if necessary, heated and stirred in the presence of a catalyst and a solvent.
• the blending ratio of (meth) acrylic acid and ⁇ -caprolactone depends on the molecular weight of the target product (compound represented by the above formula (1)), that is, the average addition mole number n of ⁇ -caprolactone to (meth) acrylic acid. Is set as appropriate.
• ⁇ -caprolactone is, for example, 1 mol or more, preferably 2 mol or more, for example, 10 mol or less, preferably 5 mol or less, more preferably 3 mol or less.
• ⁇ -caprolactone is, for example, 50 parts by mass or more, preferably 150 parts by mass or more, for example, 10000 parts by mass or less, preferably 2000 parts by mass. Or less.
• the reaction temperature is, for example, 80 ° C. or higher, preferably 120 ° C. or higher, for example, 240 ° C. or lower, in an inert gas or an inert gas-oxygen gas mixed atmosphere. Preferably, it is 200 degrees C or less.
• the reaction time is, for example, 4 hours or more, preferably 6 hours or more, for example, 20 hours or less, preferably 12 hours or less.
• the catalyst examples include Lewis acids such as aluminum chloride and stannic chloride, and acid catalysts such as Bronsted acid such as sulfuric acid, paratoluenesulfonic acid, benzenesulfonic acid, and sulfonic acid type ion exchange resin. .
• These catalysts can be used alone or in combination of two or more.
• the catalyst is preferably sulfuric acid, paratoluenesulfonic acid, or benzenesulfonic acid from the viewpoint of solubility in the reaction solution.
• the mixing ratio of the catalyst is, for example, 0.1 parts by mass or more, preferably 1 part by mass or more, for example, 50 parts by mass or less, preferably 20 parts by mass with respect to 100 parts by mass of (meth) acrylic acid. It is as follows.
• solvent examples include aromatic hydrocarbons such as benzene, toluene and xylene.
• the mixing ratio of the solvent is not particularly limited, and is appropriately set according to the purpose and application.
• the ⁇ -caprolactone adduct of (meth) acrylic acid can be produced without a solvent.
• the above-described polymerization inhibitor can be added as necessary.
• the polymerization inhibitor is preferably p-methoxyphenol.
• the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of (meth) acrylic acid and ⁇ -caprolactone. 1.0 parts by mass or less, preferably 0.1 parts by mass or less.
• the caprolactone adduct of (meth) acrylic acid can be obtained, for example, by an esterification reaction (condensation polymerization) between (meth) acrylic acid and ⁇ -oxycaproic acid in which caprolactone is ring-opened.
• the caprolactone adduct of (meth) acrylic acid can also be obtained as a commercial product.
• examples of such commercially available products include Aronix M-5300 ( ⁇ -carboxyl caprolactone monoacrylate, manufactured by Toagosei Co., Ltd.).
• the acid value of the caprolactone adduct of (meth) acrylic acid represented by the above formula (1) is, for example, 45 mgKOH / g or more, preferably 135 mgKOH / g or more, for example, 310 mgKOH / g or less. .
• the compound represented by (b2) is an acid anhydride modified product of a caprolactone adduct of hydroxylalkyl (meth) acrylate represented by the following formula (2).
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents at least one selected from the group consisting of an ethylene group, a propylene group, and a tetramethylene group
• n represents 1 to 10 is shown.
• R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
• R 2 is an ethylene group, at least one member selected from the group consisting of propylene and tetramethylene groups, preferably exhibit an ethylene group.
• n is the average number of moles of caprolactone added per mole of hydroxylalkyl (meth) acrylate, 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. is there.
• hydroxylalkyl (meth) acrylate and ⁇ -caprolactone are reacted (ring-opening addition) to obtain hydroxylalkyl (meth) acrylate represented by the above formula (2).
• hydroxylalkyl (meth) acrylate represented by the above formula (2) is reacted with an acid anhydride.
• hydroxyalkyl (meth) acrylate examples include hydroxyalkyl (meth) acrylates having a hydroxyalkyl group having 2 to 4 carbon atoms. Specific examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxy Examples thereof include propyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
• hydroxyalkyl (meth) acrylates can be used alone or in combination of two or more.
• the hydroxyalkyl (meth) acrylate is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl group having 2 carbon atoms, more preferably 2-hydroxyethyl (meth) acrylate.
• ⁇ -caprolactone is not particularly limited, and a commercially available product can be used as it is.
• the method for reacting (ring-opening addition) hydroxylalkyl (meth) acrylate with ⁇ -caprolactone is not particularly limited, and a known method (for example, the method described in JP-A-10-7774 or the like) should be adopted. Can do.
• hydroxylalkyl (meth) acrylate and ⁇ -caprolactone are blended, and if necessary, heated and stirred in the presence of the above catalyst and the above solvent.
• the blending ratio of hydroxylalkyl (meth) acrylate and ⁇ -caprolactone is the molecular weight of the target product (compound represented by the above formula (2)), that is, the average addition mole number n of ⁇ -caprolactone to hydroxylalkyl (meth) acrylate. It is set accordingly.
• ⁇ -caprolactone is, for example, 1 mol or more, preferably 2 mol or more, for example, 10 mol or less, preferably 5 mol or less.
• ⁇ -caprolactone is, for example, 90 parts by mass or more, preferably 190 parts by mass or more, for example, 1000 parts by mass or less, preferably 500 parts by mass with respect to 100 parts by mass of hydroxylalkyl (meth) acrylate. It is below mass parts.
• reaction temperature is, for example, 60 ° C. or higher, preferably 90 ° C. or higher, for example, 140 ° C. or lower, preferably oxygen gas or an inert gas-oxygen gas mixture atmosphere. 120 ° C. or lower.
• reaction time is 4 hours or more, for example, Preferably, it is 8 hours or more, for example, is 20 hours or less, Preferably, it is 12 hours or less.
• the above-described polymerization inhibitor can be added as necessary.
• the polymerization inhibitor is preferably p-methoxyphenol.
• the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.01 parts by mass or more with respect to 100 parts by mass of the total amount of hydroxylalkyl (meth) acrylate and ⁇ -caprolactone. 1.0 parts by mass or less, preferably 0.1 parts by mass or less.
• the caprolactone adduct of hydroxylalkyl (meth) acrylate can also be obtained as a commercial product.
• commercially available products include Plaxel FA-1, Plaxel FA-2, Plaxel FA-2D, Plaxel FA-3, Plaxel FA-4, Plaxel FA-5, Plaxel FA-10L, Plaxel FM-1, Plaxel FM-2, Plaxel FM-2D, Plaxel FM-3, Plaxel FM-4, Plaxel FM-5 (all manufactured by Daicel Chemical Industries, Ltd.) (PLACCEL is a registered trademark) and the like.
• caprolactone adducts of hydroxyl alkyl (meth) acrylate can be used alone or in combination of two or more.
• the acid anhydride examples include the acid anhydrides described above ((A) acid anhydrides used in the production of acid anhydride-modified products of polyfunctional (meth) acrylic compounds).
• dicarboxylic acid monoanhydrides are used.
• succinic anhydride and phthalic anhydride are more preferable, and succinic anhydride is more preferable.
• the hydroxylalkyl (meth) acrylate caprolactone adduct and the acid anhydride for example, the hydroxylalkyl (meth) acrylate caprolactone adduct and acid anhydride are blended, and if necessary, a solvent, Heating is performed in the presence of a catalyst or the like.
• the solvent examples include the above-described organic solvent (the above-described organic solvent as a dispersion medium), the above-described aqueous solvent (the above-described aqueous solvent as a dispersion medium), and the like. These solvents can be used alone or in combination of two or more.
• the solvent is preferably an organic solvent, more preferably a ketone solvent, and still more preferably methyl isobutyl ketone.
• the catalyst examples include the above-mentioned catalyst ((A) a catalyst used in the production of an acid anhydride-modified product of a polyfunctional (meth) acrylic compound). These catalysts can be used alone or in combination of two or more.
• the catalyst is preferably an amine compound, more preferably N, N-dimethylbenzylamine, triethylamine or tributylamine, and still more preferably triethylamine.
• the blending ratio of the caprolactone adduct of hydroxylalkyl (meth) acrylate and the acid anhydride is, for example, the equivalent ratio of the carboxylic anhydride group in the acid anhydride to the hydroxyl group in the caprolactone adduct of hydroxylalkyl (meth) acrylate.
• Carboxylic anhydride group / hydroxyl group is, for example, 0.5 or more, preferably 0.67 or more, for example, 1 or less, preferably 0.91 or less.
• the heating temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 140 ° C. or lower, preferably Is 110 ° C. or lower.
• the heating time is, for example, 4 hours or more, preferably 8 hours or more, for example, 20 hours or less, preferably 12 hours or less.
• the acid value of the acid anhydride modified product of the caprolactone adduct of hydroxylalkyl (meth) acrylate represented by the above formula (2) is, for example, 40 mgKOH / g or more, preferably 60 mgKOH / g or more. It is 280 mgKOH / g or less, preferably 150 mgKOH / g or less.
• the compound represented by (b3) is an acid anhydride modified product of an alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3).
• R 1 represents a hydrogen atom or a methyl group, m represents 2 to 4, and n represents 1 to 10.
• R 1 represents a hydrogen atom and / or a methyl group, preferably a hydrogen atom.
• m is 2 or more, 4 or less, preferably 3 or less.
• the alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) has oxyalkylene (C m H 2m O) having 2 to 4 carbon atoms.
• Examples of the oxyalkylene having 2 to 4 carbon atoms include oxyethylene (—CH 2 CH 2 O—), oxytrimethylene (—CH 2 CH 2 CH 2 O—), and oxytetramethylene (—CH 2 CH 2 CH 2 CH Linear oxyalkylene such as 2 O—), for example, oxypropylene (—CH 2 CH (CH 3 ) O—), oxybutylene (—CH 2 CH (CH 2 CH 3 ) O—, —CH (CH 3 And branched oxyalkylene such as CH (CH 3 ) O—), preferably linear oxyalkylene, and more preferably oxyethylene.
• oxyethylene —CH 2 CH 2 O—
• oxytrimethylene —CH 2 CH 2 CH 2 O—
• oxytetramethylene —CH 2 CH 2 CH 2 CH Linear oxyalkylene such as 2 O—
• oxypropylene —CH 2 CH (CH 3 ) O—
• oxybutylene —CH 2 CH (CH 2 CH
• n is the average number of moles of alkylene oxide added per mole of (meth) acrylic acid, and is 1 or more, preferably 2 or more, 10 or less, preferably 5 or less. is there.
• (Meth) acrylic acid is acrylic acid and / or methacrylic acid, preferably acrylic acid.
• alkylene oxide examples include alkylene oxides having 2 to 4 carbon atoms, and specific examples include cyclic ether compounds having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, trimethylene oxide (oxetane) and butylene oxide. It is done.
• alkylene oxides can be used alone or in combination of two or more.
• addition form is not particularly limited, and may be, for example, random addition or block addition.
• the alkylene oxide is preferably ethylene oxide or propylene oxide, and more preferably ethylene oxide.
• the method for adding alkylene oxide to (meth) acrylic acid is not particularly limited, and a known method can be employed.
• (meth) acrylic acid and alkylene oxide are blended, and if necessary, heated and stirred in the presence of the above catalyst and the above solvent.
• the blending ratio of (meth) acrylic acid and alkylene oxide is appropriately determined according to the molecular weight of the target product (compound represented by the above formula (3)), that is, the average addition mole number n of alkylene oxide to (meth) acrylic acid. Is set.
• alkylene oxide is, for example, 1 mole or more, preferably 2 moles or more, for example, 10 moles or less, preferably 5 moles or less.
• the alkylene oxide is, for example, 50 parts by mass or more, preferably 100 parts by mass or more, for example, 5000 parts by mass or less, preferably 1500 parts by mass. It is as follows.
• the reaction temperature is, for example, 40 ° C. or higher, preferably 100 ° C. or higher, for example, 240 ° C. or lower, preferably 200 ° C. or lower, in an inert gas-oxygen gas mixture atmosphere. It is.
• the reaction time is, for example, 1 hour or more, preferably 3 hours or more, for example, 20 hours or less, preferably 12 hours or less.
• alkylene oxide adduct of (meth) acrylic acid polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytrimethylene glycol mono (meth) acrylate, polybutylene glycol mono (meta) ) Acrylate, polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) ) Hydroxyl-terminated polyalkylene glycol mono (meth) acrylates such as mono (meth) acrylate, for example, (mono) ethylene glycol mono (meth) Hydroxyl groups such as acrylate, (mono) propylene glycol mono (meth) acrylate, (mono) trimethylene glycol mono (meth) acrylate, (mono)
• alkylene oxide adducts of (meth) acrylic acid can be used alone or in combination of two or more.
• alkylene oxide adduct of (meth) acrylic acid examples include hydroxyl-terminated polyalkylene glycol mono (meth) acrylate, and more preferred is polyethylene glycol mono (meth) acrylate.
• alkylene oxide adduct of (meth) acrylic acid can also be obtained as a commercial item.
• commercially available products include Blemmer PE series, Blemmer AE series, Blemmer PP series, Blemmer AP series, Blemmer PEP series, Blemmer AEP series, Blemmer PET series, Blemmer AET series, Blemmer PPT series, Blemmer APT series ( All of them are made from Japanese fats and oils). These can be used alone or in combination of two or more.
• the acid anhydride examples include the acid anhydrides described above ((A) acid anhydrides used in the production of acid anhydride-modified products of polyfunctional (meth) acrylic compounds).
• dicarboxylic acid monoanhydrides are used.
• succinic anhydride and phthalic anhydride are more preferable, and succinic anhydride is more preferable.
• an alkylene oxide adduct of (meth) acrylic acid and an acid anhydride are blended, and if necessary, a solvent, Heating is performed in the presence of a catalyst or the like.
• the solvent examples include the above-described organic solvent (the above-described organic solvent as a dispersion medium), the above-described aqueous solvent (the above-described aqueous solvent as a dispersion medium), and the like. These solvents can be used alone or in combination of two or more.
• the solvent is preferably an organic solvent, more preferably a ketone solvent, and still more preferably methyl isobutyl ketone.
• the catalyst examples include the above-mentioned catalyst ((A) a catalyst used in the production of an acid anhydride-modified product of a polyfunctional (meth) acrylic compound). These catalysts can be used alone or in combination of two or more.
• the catalyst is preferably an amine compound, more preferably N, N-dimethylbenzylamine, triethylamine or tributylamine, and still more preferably triethylamine.
• the blending ratio of the caprolactone adduct and the acid anhydride of the alkylene oxide adduct of (meth) acrylic acid is, for example, a carboxylic anhydride group in the acid anhydride to a hydroxyl group in the alkylene oxide adduct of (meth) acrylic acid.
• Equivalent ratio (carboxylic anhydride group / hydroxyl group) is, for example, 0.5 or more, preferably 0.67 or more, for example, 1 or less, preferably 0.91 or less.
• the heating temperature is, for example, 60 ° C. or higher, preferably 80 ° C. or higher, for example, 140 ° C. or lower, Preferably, it is 110 degrees C or less.
• the heating time is, for example, 4 hours or more, preferably 8 hours or more, for example, 20 hours or less, preferably 12 hours or less.
• the acid value of the acid anhydride modified product of the alkylene oxide adduct of (meth) acrylic acid represented by the above formula (3) is, for example, 55 mgKOH / g or more, preferably 95 mgKOH / g or more. 400 mg KOH / g or less, preferably 300 mg KOH / g or less.
• the compound represented by (b1) is preferably used, and more preferably (B) the monofunctional ( It is mentioned that the (meth) acrylic compound contains a caprolactone adduct of (meth) acrylic acid represented by the above formula (1), wherein n is 1 to 3.
• the content ratio is, for example, 2% by mass or more, preferably 5% by mass or more, based on the total amount of the metal fine particle dispersant. For example, it is 60% by mass or less, preferably 40% by mass or less.
• the metal fine particle dispersant preferably further contains a (meth) acrylic resin dispersant having a (meth) acryloyl group in the side chain (C).
• the (meth) acrylic resin dispersant having a (meth) acryloyl group in the side chain is a reaction product obtained by reacting a monomer component containing an anionic group-containing monomer by the method described below.
• An anionic group-containing monomer is a monomer having one or more anionic groups and one or more polymerizable unsaturated groups.
• the anionic group examples include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, and these can be used alone or in combination. From the viewpoint of the hardness of the coating film (described later), the anionic group is preferably a carboxyl group or a phosphate group, and more preferably a carboxyl group.
• the polymerizable unsaturated group is a group having a polymerizable unsaturated bond, and examples thereof include an ethylenically unsaturated group. Specifically, for example, a (meth) acryloyl group, a vinylaryl group, a vinyloxy group And allyl groups, and these may be used alone or in combination.
• the polymerizable unsaturated group is preferably a (meth) acryloyl group from the viewpoint of availability.
• anionic group-containing monomer examples include, for example, carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid and other ⁇ , ⁇ -unsaturated carboxylic acids or salts thereof, for example, Phosphoric acid group-containing (meth) acrylates such as acid phosphooxypolyoxypropylene glycol mono (meth) acrylate, acid phosphooxyethyl (meth) acrylate, mono (2-hydroxyethyl (meth) acrylate) phosphate Monomers, for example, sulfonic acid group-containing monomers such as 2-acrylamido-2-methylpropanesulfonic acid.
• carboxyl group-containing monomers such as (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid and other ⁇ , ⁇ -unsaturated carboxylic acids or salts thereof
• Phosphoric acid group-containing (meth) acrylates such as acid phosphooxypoly
• anionic group-containing monomers can be used alone or in combination of two or more.
• the anionic group-containing monomer is preferably a carboxyl group-containing monomer or a phosphate group-containing monomer, more preferably a carboxyl group-containing monomer, still more preferably.
• ⁇ , ⁇ -unsaturated carboxylic acid, and (meth) acrylic acid is particularly preferable.
• the monomer component contains an anionic group-containing monomer
• a (meth) acrylic resin containing an anionic group is obtained as the (meth) acrylic resin.
• the monomer component can contain other monomers copolymerizable with the anionic group-containing monomer.
• alkyl (meth) acrylates examples include alkyl (meth) acrylates, aromatic ring-containing monomers, hydroxyl group-containing monomers, and isocyanate group-containing monomers.
• alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) ) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate
• aromatic ring-containing monomer examples include phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, o-phenylphenoxyethyl (meth) acrylate, phenoxybenzyl (meth) )
• Aromatic ring-containing (meth) acrylates such as acrylate, and styrene monomers such as styrene and ⁇ -methylstyrene.
• the (meth) acrylic resin containing an aromatic ring is obtained as a (meth) acrylic resin.
• hydroxyl group-containing monomer examples include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 1-methyl-2-hydroxyethyl (meth) acrylate, 2-hydroxy
• hydroxyl group-containing (meth) acrylates such as propyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, preferably 2-hydroxyethyl (meth) acrylate.
• the monomer component contains a hydroxyl group-containing monomer
• a (meth) acrylic resin containing a hydroxyl group is obtained as the (meth) acrylic resin.
• isocyanate group-containing monomers examples include isocyanatomethyl (meth) acrylate, 2-isocyanatoethyl (meth) acrylate, 3-isocyanatopropyl (meth) acrylate, and 1-methyl-2-isocyanatoethyl (meth) acrylate.
• isocyanate group-containing (meth) acrylic monomers such as 2-isocyanatopropyl (meth) acrylate and 4-isocyanatobutyl (meth) acrylate.
• the (meth) acrylic resin containing an isocyanate group is obtained as a (meth) acrylic resin.
• examples of other monomers include glycidyl group-containing monomers such as glycidyl (meth) acrylate and allyl glycidyl ether, and vinyl ester monomers such as vinyl acetate and vinyl propionate.
• Other monomers are preferably alkyl (meth) acrylates, aromatic ring-containing monomers, hydroxyl group-containing monomers, isocyanate group-containing monomers, more preferably alkyl (meth) acrylates, aromatic ring-containing monomers, hydroxyl group-containing. Including all of the monomer and the isocyanate group-containing monomer.
• the monomer component contains an aromatic ring-containing monomer (that is, if the (meth) acrylic resin is a (meth) acrylic resin containing an aromatic ring), the adhesion of the coating film (described later) is improved. be able to.
• the monomer component contains a hydroxyl group-containing monomer and an isocyanate group-containing monomer
• a (meth) acryloyl group can be easily introduced into the side chain of the (meth) acrylic resin by the method described later, The adhesion of the coating film (described later) can be improved.
• the content ratio is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 90% by mass or less, based on the total amount of the monomer components. Preferably, it is 80 mass% or less.
• the content rate is 10 mass% or more with respect to the total amount of a monomer component from an adhesive viewpoint of a coating film (after-mentioned), Preferably, it is 20 It is 90 mass% or less, for example, Preferably, it is 80 mass% or less.
• the content ratio is, for example, 0.1% by mass or more, preferably 1% by mass or more, for example, 50% by mass with respect to the total amount of the monomer components. % Or less, preferably 30% by mass or less.
• the content rate is 0.1 mass% or more with respect to the total amount of a monomer component, Preferably, it is 1 mass% or more, for example, 20 mass. % Or less, preferably 10% by mass or less.
• the content ratio of the anionic group-containing monomer in the monomer component is 5% by mass or more based on the total amount of the monomer components. Preferably, it is 10 mass% or more, for example, 40 mass% or less, preferably 20 mass% or less.
• the (meth) acrylic resin dispersant obtained by the reaction of the monomer component can favorably disperse the metal fine particles.
• the (meth) acrylic resin dispersant obtained by polymerization of the monomer component improves the dispersibility and dispersion stability of the metal fine particles. Can be achieved.
• the (meth) acrylic resin obtained by the reaction of the monomer component is used as the (meth) acrylic resin dispersant.
• the (meth) acrylic resin binder ((meth) acrylic resin binder ( (To be described later). This distinguishes a (meth) acrylic resin dispersant from a (meth) acrylic resin binder (described later).
• a (meth) acrylic resin dispersant having a (meth) acryloyl group in the side chain is synthesized by the following reaction.
• a part of the monomer component is polymerized to obtain a (meth) acrylic resin having no (meth) acryloyl group in the side chain.
• the obtained (meth) acrylic resin and the remainder of the monomer component are reacted to introduce a (meth) acryloyl group into the side chain of the polymer.
• the monomer component include anionic group-containing monomers, alkyl (meth) acrylates, aromatic ring-containing monomers, and hydroxyl group-containing monomers (specifically, monomers other than isocyanate group-containing monomers).
• the content ratio of the anionic group-containing monomer is 5% by mass or more, preferably 10% by mass or more, for example, 40% by mass or less, preferably, based on the total amount of the monomer components. It is 20 mass% or less.
• the content rate is 10 mass% or more with respect to the total amount of a monomer component, Preferably, it is 20 mass% or more, for example, It is 90 mass% or less, Preferably, it is 80 mass% or less.
• the content rate is 10 mass% or more with respect to the total amount of a monomer component from an adhesive viewpoint of a coating film (after-mentioned), for example, Preferably Is 20% by mass or more, for example, 90% by mass or less, and preferably 80% by mass or less.
• the content rate is 0.1 mass% or more with respect to the total amount of a monomer component, Preferably it is 1 mass% or more, for example, , 50% by mass or less, preferably 30% by mass or less.
• the method for polymerizing a part of the monomer component is not particularly limited.
• a part of the monomer component preferably an anionic group-containing monomer, alkyl (meth) acrylate, aromatic ring-containing) Monomers and hydroxyl group-containing monomers
• a known radical polymerization initiator for example, an azo compound, a peroxide compound, etc.
• the polymerization conditions vary depending on the monomer component prescription and the type of radical polymerization initiator.
• the polymerization temperature is 30 ° C or higher, preferably 60 ° C or higher, for example, 150 ° C or lower, preferably 120 ° C. It is as follows.
• 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.
• the weight average molecular weight (GPC measurement: polystyrene conversion) of the (meth) acrylic resin for obtaining the dispersant is, for example, 2000 or more, preferably 3000 or more, for example, 100000 or less, preferably 50000 or less, more preferably. Is 15000 or less.
• weight average molecular weight is in the above range, a coating film (described later) excellent in transparency, adhesion, hardness and durability (alkali resistance, light resistance) can be obtained.
• the (meth) acrylic resin obtained by the above polymerization has a hydroxyl group.
• the polymer obtained above that is, the (meth) acrylic resin having a hydroxyl group
• the remainder of the monomer component is reacted with the remainder of the monomer component.
• the remainder of the monomer component examples include isocyanate group-containing monomers, and preferably, isocyanate group-containing (meth) acrylic monomers. More preferably, the remainder of the monomer component consists of an isocyanate group-containing (meth) acrylic monomer.
• the (meth) acrylic resin having a hydroxyl group is reacted with the remainder of the monomer component as follows, and the side chain of the (meth) acrylic resin A (meth) acryloyl group can be introduced into.
• the (meth) acrylic resin which has a hydroxyl group reacts with an isocyanate group containing (meth) acryl monomer
• the (meth) acrylic resin which has a hydroxyl group, and isocyanate group containing (meth) An acrylic monomer is blended, and if necessary, heated in the presence of a known catalyst and solvent.
• the blending ratio of the (meth) acrylic resin having a hydroxyl group and the isocyanate group-containing (meth) acrylic monomer is an isocyanate group-containing (meth) acrylic with respect to 1 mol of the hydroxyl group of the (meth) acrylic resin having a hydroxyl group.
• the isocyanate group of a monomer is 0.1 mol or more, for example, Preferably, it is 0.8 mol or more, for example, 2.0 mol or less, Preferably, it is 1.2 mol or less.
• the reaction conditions are, for example, in an air atmosphere, the reaction temperature is, for example, 40 ° C or higher, preferably 60 ° C or higher, for example, 200 ° C or lower, preferably 150 ° C or lower.
• the reaction time is, for example, 1 hour or more, preferably 2 hours or more, for example, 20 hours or less, preferably 12 hours or less.
• the above-described polymerization inhibitor can be added as necessary.
• the polymerization inhibitor is preferably p-methoxyphenol.
• the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.000 parts by mass with respect to 100 parts by mass as a total of the (meth) acrylic resin having a hydroxyl group and the isocyanate group-containing (meth) acrylic monomer.
• it is 1.0 part by mass or less, preferably 0.1 part by mass or less.
• the hydroxyl group of the (meth) acrylic resin having a hydroxyl group and the isocyanate group of the isocyanate group-containing (meth) acrylic monomer undergo urethane reaction.
• an isocyanate group-containing (meth) acrylic monomer is bonded to the side chain of the (meth) acrylic resin, and a (meth) acryloyl group is introduced to the end of the side chain.
• the method of introducing the (meth) acryloyl group into the side chain of the (meth) acrylic resin is not limited to the above method, and a known method can be adopted.
• the (meth) acrylic resin when the monomer component contains an isocyanate group-containing monomer, the (meth) acrylic resin has an isocyanate group. Therefore, a (meth) acryloyl group can also be introduced into the side chain of the (meth) acrylic resin by subjecting a (meth) acrylic resin having an isocyanate group to a urethane reaction with a hydroxyl group-containing (meth) acrylate.
• the (meth) acrylic resin when the monomer component contains an anionic group-containing monomer (for example, a carboxyl group-containing monomer), the (meth) acrylic resin has an anionic group (for example, a carboxyl group). Therefore, the (meth) acryloyl group can be introduced into the side chain of the (meth) acrylic resin by esterifying the (meth) acrylic resin having an anionic group and the glycidyl group-containing (meth) acrylate. .
• an anionic group-containing monomer for example, a carboxyl group-containing monomer
• the (meth) acrylic resin has an anionic group (for example, a carboxyl group). Therefore, the (meth) acryloyl group can be introduced into the side chain of the (meth) acrylic resin by esterifying the (meth) acrylic resin having an anionic group and the glycidyl group-containing (meth) acrylate. .
• the (meth) acrylic resin when the monomer component contains a glycidyl group-containing monomer, the (meth) acrylic resin has a glycidyl group. Therefore, the side chain of the (meth) acrylic resin is obtained by esterifying a (meth) acrylic resin having a glycidyl group and an anionic group-containing (meth) acrylate (for example, a carboxyl group-containing (meth) acrylate). A (meth) acryloyl group can also be introduced into.
• the adhesion of the coating film (described later) can be improved.
• the weight average molecular weight (GPC measurement: polystyrene conversion) of the (meth) acrylic resin dispersant having a (meth) acryloyl group in the side chain is, for example, 2000 or more, preferably 3000 or more, for example, 100000 or less. , Preferably, it is 50000 or less, More preferably, it is 15000 or less.
• weight average molecular weight is in the above range, a coating film (described later) excellent in transparency, adhesion, hardness and durability (alkali resistance, light resistance) can be obtained.
• the (meth) acryloyl group equivalent of the (meth) acrylic resin dispersant having a (meth) acryloyl group in the (C) side chain is, for example, 400 or more, preferably 800 or more, for example, 30000 or less, Preferably, it is 10,000 or less.
• the (meth) acrylic group equivalent is defined as the polymer mass per 1 mol of double bond (double bond equivalent) (the same applies hereinafter).
• the dispersibility and dispersion stability of the metal fine particles should be improved.
• a coating film (described later) having excellent transparency, adhesion, hardness, and durability (alkali resistance, light resistance) can be obtained.
• the content ratio of the (meth) acrylic resin dispersant having a (meth) acryloyl group in the side chain is, for example, 5% by mass or more, preferably 10% by mass or more with respect to the total amount of the metal fine particle dispersant. Yes, for example, 80% by mass or less, preferably 50% by mass or less.
• the binder is an additive for improving various physical properties such as hardness, adhesion, and durability (alkali resistance, light resistance) of the coating film (described later).
• a (meth) acryloyl group is added to the side chain. (Meth) acrylic resin binder having
• the (meth) acrylic resin binder having a (meth) acryloyl group in the side chain is a reaction product obtained by reacting the monomer components shown below by the method described below.
• examples of the monomer contained in the monomer component include an alkyl (meth) acrylate, an aromatic ring-containing monomer, a hydroxyl group-containing monomer, and an isocyanate group-containing monomer.
• alkyl (meth) acrylate examples include the same alkyl (meth) acrylate as the alkyl (meth) acrylate exemplified as the raw material of the (meth) acrylic resin dispersant.
• aromatic ring-containing monomer examples include the same aromatic ring-containing monomer as the aromatic ring-containing monomer exemplified as the raw material for the (meth) acrylic resin dispersant.
• the (meth) acrylic resin containing an aromatic ring is obtained as a (meth) acrylic resin.
• hydroxyl group-containing monomer examples include the same hydroxyl group-containing monomers as the hydroxyl group-containing monomers exemplified as the raw material for the (meth) acrylic resin dispersant.
• a monomer component contains a hydroxyl group containing monomer
• the (meth) acrylic resin containing a hydroxyl group is obtained as a (meth) acrylic resin.
• Examples of the isocyanate group-containing monomer include the same isocyanate group-containing monomers as the isocyanate group-containing monomers exemplified as the raw material for the (meth) acrylic resin dispersant.
• the (meth) acrylic resin containing an isocyanate group is obtained as a (meth) acrylic resin.
• examples of the monomer contained in the monomer component include the above-described glycidyl group-containing monomers, vinyl ester monomers, and the like.
• These monomers can be used alone or in combination of two or more.
• the monomer examples include alkyl (meth) acrylates, aromatic ring-containing monomers, hydroxyl group-containing monomers, and isocyanate group-containing monomers, and more preferred are alkyl (meth) acrylates, aromatic ring-containing monomers, hydroxyl group-containing monomers, and It may include all of the isocyanate group-containing monomers.
• the monomer component contains an aromatic ring-containing monomer (that is, if the (meth) acrylic resin is a (meth) acrylic resin containing an aromatic ring), the adhesion of the coating film (described later) is improved. be able to.
• the monomer component contains a hydroxyl group-containing monomer and an isocyanate group-containing (meth) acrylic monomer
• a (meth) acryloyl group is easily introduced into the side chain of the (meth) acrylic resin by the method described later. It is possible to improve the adhesion of the coating film (described later).
• the content ratio is, for example, 10% by mass or more, preferably 20% by mass or more, for example, 90% by mass or less, based on the total amount of the monomer components. Preferably, it is 80 mass% or less.
• the content rate is 10 mass% or more with respect to the total amount of a monomer component from a viewpoint of the hardness of a coating film (after-mentioned), Preferably, it is 20 mass. %, For example, 95% by mass or less, preferably 80% by mass or less.
• the content ratio is, for example, 0.1% by mass or more, preferably 1% by mass or more, for example, 50% by mass with respect to the total amount of the monomer components. % Or less, preferably 30% by mass or less.
• the content rate is 0.1 mass% or more with respect to the total amount of a monomer component, Preferably, it is 1 mass% or more, for example, 20 mass%. Hereinafter, it is preferably 10% by mass or less.
• the monomer component does not contain an anionic group-containing monomer, or contains an anionic group-containing monomer in a proportion of less than 5% by mass with respect to the total amount of the monomer components.
• examples of such an anionic group-containing monomer include the same anionic group-containing monomer as the anionic group-containing monomer in the (meth) acrylic resin dispersant described above.
• anionic group-containing monomers can be used alone or in combination of two or more.
• the anionic group-containing monomer is preferably a carboxyl group-containing monomer, more preferably an ⁇ , ⁇ -unsaturated carboxylic acid, and still more preferably ( And (meth) acrylic acid.
• the monomer component may not contain the above anionic group-containing monomer, but preferably contains the anionic group-containing monomer in a proportion of less than 5% by mass with respect to the total amount. .
• the (meth) acrylic resin binder obtained by the reaction of the monomer component can improve the adhesion of the coating film (described later).
• the content of the anionic group-containing monomer in the monomer component is, for example, 1% by mass or more, preferably 2% by mass or more, based on the total amount of the monomer components And less than 5% by mass, preferably 4.5% by mass or less.
• the (meth) acrylic resin obtained by the reaction of the monomer components is converted into (meth) acrylic.
• a resin binder is used. Further, as described above, when the content ratio of the anionic group-containing monomer with respect to the total amount of the monomer component is 5% by mass or more, the (meth) acrylic resin obtained by the reaction of the monomer component is dispersed in the (meth) acrylic resin. Use as an agent. Thereby, a (meth) acrylic resin binder and an above-described (meth) acrylic resin dispersing agent are distinguished.
• the (meth) acrylic resin binder having a (meth) acryloyl group in the side chain is synthesized by the following reaction.
• a part of the monomer component is polymerized to obtain a (meth) acrylic resin having no (meth) acryloyl group in the side chain.
• the obtained (meth) acrylic resin and the remainder of the monomer component are reacted to introduce a (meth) acryloyl group into the side chain of the polymer.
• Preferred examples of the monomer component include an anionic group-containing monomer, alkyl (meth) acrylate, aromatic ring-containing monomer, and hydroxyl group-containing monomer.
• the content ratio is less than 5% by mass, preferably 4.5% by mass or less with respect to the total amount of the monomer component. % By mass or more, preferably 2% by mass or more.
• the content rate is 10 mass% or more with respect to the total amount of a monomer component, Preferably, it is 20 mass% or more, for example, It is 90 mass% or less, Preferably, it is 80 mass% or less.
• the content rate is 10 mass% or more with respect to the total amount of a monomer component from an adhesive viewpoint of a coating film (after-mentioned), for example, Preferably Is 20 mass% or more, for example, 95 mass% or less, preferably 80 mass% or less.
• the content rate is 0.1 mass% or more with respect to the total amount of a monomer component, Preferably it is 1 mass% or more, for example, , 50% by mass or less, preferably 30% by mass or less.
• the method for polymerizing a part of the monomer component is not particularly limited.
• a part of the monomer component preferably an anionic group-containing monomer, alkyl (meth) acrylate, aromatic ring-containing) Monomers and hydroxyl group-containing monomers
• a known radical polymerization initiator for example, an azo compound, a peroxide compound, etc.
• the polymerization conditions vary depending on the monomer component prescription and the type of radical polymerization initiator.
• the polymerization temperature is 30 ° C or higher, preferably 60 ° C or higher, for example, 150 ° C or lower, preferably 120 ° C. It is as follows.
• 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.
• the weight average molecular weight (GPC measurement: polystyrene conversion) of the (meth) acrylic resin for obtaining the binder is, for example, 2000 or more, preferably 3000 or more, for example, 100,000 or less, preferably 50,000 or less, more preferably. 15000 or less.
• weight average molecular weight is in the above range, a coating film (described later) excellent in transparency, adhesion, hardness and durability (alkali resistance, light resistance) can be obtained.
• the (meth) acrylic resin obtained by the above polymerization has a hydroxyl group.
• the polymer obtained above that is, the (meth) acrylic resin having a hydroxyl group
• the polymer obtained above that is, the (meth) acrylic resin having a hydroxyl group
• the remainder of the monomer component examples include isocyanate group-containing monomers, and preferably, isocyanate group-containing (meth) acrylic monomers. More preferably, the remainder of the monomer component consists of an isocyanate group-containing (meth) acrylic monomer.
• the (meth) acrylic resin having a hydroxyl group is reacted with the remainder of the monomer component as follows, and the side chain of the (meth) acrylic resin A (meth) acryloyl group can be introduced into.
• the (meth) acrylic resin which has a hydroxyl group reacts with an isocyanate group containing (meth) acryl monomer
• the (meth) acrylic resin which has a hydroxyl group, and isocyanate group containing (meth) An acrylic monomer is blended, and if necessary, heated in the presence of a known catalyst and solvent.
• the blending ratio of the (meth) acrylic resin having a hydroxyl group and the isocyanate group-containing (meth) acrylic monomer is an isocyanate group-containing (meth) acrylic with respect to 1 mol of the hydroxyl group of the (meth) acrylic resin having a hydroxyl group.
• the isocyanate group of a monomer is 0.1 mol or more, for example, Preferably, it is 0.8 mol or more, for example, 2.0 mol or less, Preferably, it is 1.2 mol or less.
• the reaction conditions are, for example, in an air atmosphere, the reaction temperature is, for example, 40 ° C or higher, preferably 60 ° C or higher, for example, 200 ° C or lower, preferably 150 ° C or lower.
• the reaction time is, for example, 1 hour or more, preferably 2 hours or more, for example, 20 hours or less, preferably 12 hours or less.
• the above-described polymerization inhibitor can be added as necessary.
• the polymerization inhibitor is preferably p-methoxyphenol.
• the blending ratio of the polymerization inhibitor is, for example, 0.0001 parts by mass or more, preferably 0.000 parts by mass with respect to 100 parts by mass as a total of the (meth) acrylic resin having a hydroxyl group and the isocyanate group-containing (meth) acrylic monomer.
• it is 1.0 part by mass or less, preferably 0.1 part by mass or less.
• the hydroxyl group of the (meth) acrylic resin having a hydroxyl group and the isocyanate group of the isocyanate group-containing (meth) acrylic monomer undergo urethane reaction.
• an isocyanate group-containing (meth) acrylic monomer is bonded to the side chain of the (meth) acrylic resin, and a (meth) acryloyl group is introduced to the end of the side chain.
• the method of introducing the (meth) acryloyl group into the side chain of the (meth) acrylic resin is not limited to the above method, and a known method can be adopted.
• the (meth) acrylic resin when the monomer component contains an isocyanate group-containing monomer, the (meth) acrylic resin has an isocyanate group. Therefore, a (meth) acryloyl group can also be introduced into the side chain of the (meth) acrylic resin by subjecting a (meth) acrylic resin having an isocyanate group to a urethane reaction with a hydroxyl group-containing (meth) acrylate.
• the (meth) acrylic resin when the monomer component contains an anionic group-containing monomer (for example, a carboxyl group-containing monomer), the (meth) acrylic resin has an anionic group (for example, a carboxyl group). Therefore, the (meth) acryloyl group can be introduced into the side chain of the (meth) acrylic resin by esterifying the (meth) acrylic resin having an anionic group and the glycidyl group-containing (meth) acrylate. .
• an anionic group-containing monomer for example, a carboxyl group-containing monomer
• the (meth) acrylic resin has an anionic group (for example, a carboxyl group). Therefore, the (meth) acryloyl group can be introduced into the side chain of the (meth) acrylic resin by esterifying the (meth) acrylic resin having an anionic group and the glycidyl group-containing (meth) acrylate. .
• the (meth) acrylic resin when the monomer component contains a glycidyl group-containing monomer, the (meth) acrylic resin has a glycidyl group. Therefore, the side chain of the (meth) acrylic resin is obtained by esterifying a (meth) acrylic resin having a glycidyl group and an anionic group-containing (meth) acrylate (for example, a carboxyl group-containing (meth) acrylate). A (meth) acryloyl group can also be introduced into.
• the adhesion of the coating film (described later) can be improved.
• the weight average molecular weight (GPC measurement: polystyrene conversion) of the (meth) acrylic resin binder having a (meth) acryloyl group in the side chain is, for example, 2000 or more, preferably 3000 or more, for example, 100000 or less, preferably It is 50000 or less, More preferably, it is 15000 or less.
• weight average molecular weight is in the above range, a coating film (described later) excellent in transparency, adhesion, hardness and durability (alkali resistance, light resistance) can be obtained.
• the (meth) acryloyl group equivalent of the (meth) acrylic resin binder having a (meth) acryloyl group in the side chain is, for example, 400 or more, preferably 800 or more, for example, 30000 or less, preferably 10,000. It is as follows.
• binder other binders can be contained.
• binders examples include synthetic resins such as polyvinyl butyral resin, polyvinyl alcohol resin, vinyl acetate resin, and urethane resin.
• synthetic resins such as polyvinyl butyral resin, polyvinyl alcohol resin, vinyl acetate resin, and urethane resin.
• the (meth) acrylic resin except the above-mentioned (meth) acrylic resin binder is also mentioned as another binder.
• binders can be used alone or in combination of two or more.
• the above-mentioned metal fine particles, the above-mentioned dispersion medium, the above-mentioned metal fine-particle dispersant, and the above-mentioned binder are mixed together or sequentially and mixed to obtain a coating agent.
• the mixing ratio of each component in the coating agent is such that the metal fine particle dispersant is 1 part by mass or more, preferably 5 parts by mass or more, for example, 200 parts by mass or less, preferably 100 parts by mass of the metal fine particles. Is 100 parts by mass or less, 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, 50 parts by mass or less, preferably 40 parts by mass or less, with respect to 100 parts by mass of the coating agent.
• the binder is, for example, 1 part by mass or more, preferably 5 parts by mass or more, for example, 50 parts by mass or less, preferably 30 parts by mass or less with respect to 100 parts by mass of the coating agent.
• the mixing ratio of the dispersion medium is appropriately set according to the purpose and application.
• 100 parts by mass of the metal fine particles for example, 100 parts by mass or more, preferably 200 parts by mass or more, For example, it is 2000 parts by mass or less, preferably 1000 parts by mass or less.
• the coating agent can further contain a crosslinking agent.
• crosslinking agent examples include polyfunctional (meth) acrylate (polyfunctional (meth) acrylate not modified with acid anhydride).
• the polyfunctional (meth) acrylate is a compound having two or more (meth) acryloyl groups in one molecule, and includes, for example, a hydroxyl group-containing polyfunctional (meth) acrylic compound, a hydroxyl group-free-multifunctional ( And a (meth) acrylic compound.
• the hydroxyl group-containing polyfunctional (meth) acrylic compound is a polyfunctional (meth) acrylic compound having two or more (meth) acryloyl groups and at least one hydroxyl group as described above.
• the above hydroxyl group-containing polyfunctional (meth) acrylic compound ((A) hydroxyl used in the production of an acid anhydride modified product of the polyfunctional (meth) acrylic compound) Group-containing polyfunctional (meth) acrylic compound).
• the hydroxyl group-free polyfunctional (meth) acrylic compound is a polyfunctional (meth) acrylic compound having two or more (meth) acryloyl groups and no hydroxyl group.
• the hydroxyl group-free polyfunctional (meth) acrylic compound is, for example, a polyol (for example, 1,3-butanediol (hydroxyl group number 2), 1,6-hexanediol (hydroxyl group number 2), Ethylene glycol (2 hydroxyl groups), diethylene glycol (2 hydroxyl groups), neopentyl glycol (2 hydroxyl groups), triethylene glycol (2 hydroxyl groups), tetraethylene glycol (2 hydroxyl groups), polyethylene glycol (2 hydroxyl groups), Glycerin (3 hydroxyl groups), trimethylolpropane (3 hydroxyl groups), tris (2-hydroxyethyl) isocyanurate (3 hydroxyl groups), diglycerol (4 hydroxyl groups), ditrimethylol Lopan (hydroxyl group number 4), pentaerythritol (hydroxyl group number 4), dipentaerythritol (hydroxyl group number 6), tripentaerythritol (hydroxyl group number 8) and other
• hydroxyl group-free polyfunctional (meth) acrylic compounds include dipentaerythritol hexa (meth) acrylate, pentaerythritol tetra (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ditrimethylolpropane tetra (meth). An acrylate etc. are mentioned.
• examples of the crosslinking agent include monofunctional (meth) acrylic compounds (monofunctional (meth) acrylic compounds excluding the (B) monofunctional (meth) acrylic compounds).
• examples of such a monofunctional (meth) acrylic compound include the above-described alkyl (meth) acrylate, the above-described aromatic ring-containing monomer, the above-described hydroxyl group-containing monomer, and the above-described anionic group-containing monomer.
• crosslinking agents can be used alone or in combination of two or more.
• the blending ratio of the crosslinking agent is appropriately set according to the purpose and application.
• the blending method of the crosslinking agent is not particularly limited.
• it may be added separately from the metal fine particle dispersant, and for example, the acid anhydride modification of the (A) polyfunctional (meth) acryl compound.
• the hydroxyl group-containing polyfunctional (meth) acrylic compound is used in excess to leave the hydroxyl group-containing polyfunctional (meth) acrylic compound unmodified with an acid anhydride.
• Containing-polyfunctional (meth) acrylic compounds may be used as a crosslinking agent.
• a mixture of a hydroxyl group-containing polyfunctional (meth) acrylic compound and a hydroxyl group-free polyfunctional (meth) acrylic compound is, for example, a polyol (for example, glycerin, trimethylolpropane, diglycerin, ditrimethylolpropane, penta It can be obtained by reacting (meth) acrylic acid with less than equimolar amount with respect to the number of hydroxyl groups of the polyol to known polyfunctional alcohols such as erythritol and dipentaerythritol.
• an equimolar amount of (meth) acrylic acid is usually added to a part of the polyol with respect to the number of hydroxyl groups of the polyol, and the hydroxyl group-free polyfunctional (meth) acrylic is added.
• a compound is formed.
• a mixture of such a hydroxyl group-containing polyfunctional (meth) acrylic compound and a hydroxyl group-free polyfunctional (meth) acrylic compound is converted into (A) an acid anhydride modified product of the polyfunctional (meth) acrylic compound.
• the hydroxyl group-free polyfunctional (meth) acrylic compound remains unmodified by the acid anhydride.
• the remaining hydroxyl group-free polyfunctional (meth) acrylic compound can be used as a crosslinking agent as it is.
• the blending ratio of the crosslinking agent is, for example, 1 part by mass or more, preferably 5 parts by mass or more, for example, 1500 parts by mass or less, preferably 1000 parts by mass with respect to 100 parts by mass of the total amount of the metal fine particle dispersant.
• the coating agent can contain a polymerization initiator as required.
• polymerization initiator examples include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 1-cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl- Propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl ] -2-Morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,4,6-trimethylbenzoyl) -phenylphosphine Oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 4-methylbenzophenone, Zofenon, 2-hydroxy-1- ⁇ 4- [4- (2-hydroxy-2-methyl-propionyl) -
• These polymerization initiators can be used alone or in combination of two or more.
• the blending ratio of the polymerization initiator is, for example, 1 part by mass or more, preferably 3 parts by mass or more with respect to 100 parts by mass of the total amount of the metal fine particle dispersant (and the crosslinking agent blended as necessary). It is 10 parts by mass or less, preferably 7 parts by mass or less.
• the timing of blending the crosslinking agent and the polymerization initiator is not particularly limited, and may be blended at the same time when, for example, the metal fine particles, the solvent, the metal fine particle dispersant and the binder are mixed, or the metal fine particles, the solvent, Separately from the metal fine particle dispersant and the binder, a crosslinking agent and a polymerization initiator may be blended together or sequentially.
• the preparation of the coating agent is not particularly limited, and when mixing the metal fine particles, the solvent, and the metal fine particle dispersant (further, a binder, a crosslinking agent and a polymerization initiator blended as necessary), for example, a paint shaker, Known dispersing machines such as a roll mill, a ball mill, an attritor, a sand mill, a bead mill, and an ultrasonic dispersing machine can be used.
• a ball mill and a bead mill are preferable, and a bead mill is more preferable.
• 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 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, 70% by mass or less, preferably 50% by mass or less.
• the particle size of the metal fine particles is measured as an average particle size (average particle size) since the metal fine particles exist as primary particles or secondary particles, and is preferably, for example, 200 nm or less. Is 90 nm or less, more preferably 50 nm or less, and usually 1 nm or more, preferably 3 nm or more.
• Such a coating agent contains said metal fine particle dispersing agent, it is excellent in the dispersibility and dispersion stability of a metal fine particle, and transparency, adhesiveness, hardness, and durability (alkali resistance, light resistance) A coating film having excellent resistance can be obtained.
• a coating agent is used as a coating agent, applied to a substrate by a known method and dried, and then irradiated with active energy rays to be cured.
• 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 drying temperature is, for example, 40 ° C. or more, preferably 60 ° C. or more, for example, 180 ° C. or less, preferably 140 ° C. or less
• the drying time is, for example, 1 minute or more, preferably Is 2 minutes or more, for example, 60 minutes or less, preferably 30 minutes or less.
• the film thickness after drying is, for example, 50 nm or more, preferably 500 nm or more, for example, 10 ⁇ m or less, preferably 7 ⁇ m or less.
• active energy rays examples include ultraviolet rays and electron beams.
• an ultraviolet irradiation device having a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, or the like as a light source is used.
• the amount of ultraviolet irradiation, the amount of light of the ultraviolet irradiation device, the arrangement of the light source, etc. are adjusted as necessary.
• a high-pressure mercury lamp for example, a base material coated with a coating agent is conveyed at a conveyance speed of 5 to 50 m / min with respect to one lamp having a luminous intensity of about 80 to 1000 mW / cm 2. To do.
• the irradiation amount of ultraviolet rays is, for example, 100 to 10,000 mJ / cm 2 .
• the base material coated with the coating agent is transported at a transport speed of 5 to 50 m / min by an electron beam accelerator having an acceleration voltage of 10 to 300 kV, for example.
• the obtained coating film is obtained using said coating agent, it is excellent in transparency, adhesiveness, hardness, and durability (alkali resistance, light resistance).
• the coating film is suitable for various industrial products, for example, as an optical component such as a light emitting diode (LED), a lens, and an optical device, such as a fine ceramic, for example, a functional film such as a conductive film and an optical film. Used.
• an optical component such as a light emitting diode (LED), a lens
• an optical device such as a fine ceramic
• a functional film such as a conductive film and an optical film. Used.
• ⁇ Weight average molecular weight> The sample was dissolved in tetrahydrofuran and measured by gel permeation chromatography (GPC) at a sample concentration of 3.5 g / L to obtain a molecular weight distribution of the sample.
• the monomer mixture was dropped into the flask containing methyl isobutyl ketone over 3 hours, and then aged for 3 hours.
• reaction temperature was set to 80 ° C.
• atmospheric condition was switched from a nitrogen atmosphere to an air atmosphere, 2 parts of 2-isocyanatoethyl acrylate (Karenz AOI, Showa Denko) as the remainder of the monomer component, and methyl isobutyl ketone 5 parts and 0.1 part of p-methoxyphenol as a polymerization inhibitor were added and reacted for 4 hours.
• the weight average molecular weight of the obtained (meth) acrylic resin binder was 6500.
• Synthesis Examples 3-7 and Comparative Synthesis Examples 1-2 A solution of a (meth) acrylic resin binder having a (meth) acryloyl group in the side chain was obtained in the same manner as in Synthesis Example 2 except that the formulation was changed to the formulation shown in Table 1.
• the monomer mixture was dropped into the flask containing methyl isobutyl ketone over 3 hours, and then aged for 3 hours.
• reaction temperature was set to 80 ° C.
• atmospheric condition was switched from a nitrogen atmosphere to an air atmosphere, 2 parts of 2-isocyanatoethyl acrylate (Karenz AOI, Showa Denko) as the remainder of the monomer component, and methyl isobutyl ketone 5 parts and 0.1 part of p-methoxyphenol as a polymerization inhibitor were added and reacted for 4 hours.
• the weight average molecular weight of the obtained (meth) acrylic resin dispersant was 6700.
• Synthesis Examples 9-13 A solution of a (meth) acrylic resin dispersant having a (meth) acryloyl group in the side chain was obtained in the same manner as in Synthesis Example 8 except that the formulation was changed to the formulation shown in Table 2.
• Example 1 The non-volatile content (solid content) of the acid anhydride-modified product (metal fine particle dispersant) of the polyfunctional (meth) acrylic compound obtained in Synthesis Example 1 was 9 parts, and the (meth) acrylic resin obtained in Synthesis Example 2
• the binder has a non-volatile content (solid content) of 9 parts, and the non-volatile content (solid content) of zirconium oxide as a metal fine particle (UEP-100, manufactured by 1st rare element, average primary particle size of 15 nm) is 25 parts.
• methyl isobutyl ketone was 56.1 parts, and IRGACURE907 (BASF 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one) as a polymerization initiator was 0.9 parts. Each component was mixed so that a coating agent was obtained.
• the obtained coating agent was applied to a polyethylene terephthalate (PET) film (UH-13, thickness 125 ⁇ m, manufactured by Toray) as a substrate so that the film thickness after drying with a bar coater was 1 ⁇ m. Dry at 80 ° C. for 2 minutes.
• PET polyethylene terephthalate
• Examples 2 to 23 and Comparative Examples 1 to 7 A coating agent and a laminate of a substrate and a coating film were obtained in the same manner as in Example 1 except that the formulation was changed to the formulation shown in Tables 3 to 5.
• the average particle size of the coating agent was measured with a dynamic light scattering particle size distribution measuring device (product name “nanotrac wave” manufactured by Microtrack Bell). The criteria for evaluation are as follows. A: Average particle diameter is less than 30 nm. B: Average particle diameter of 30 nm or more and less than 70 nm. C: The average particle diameter is 70 nm or more.
• Dispersion stability The coating agent was allowed to stand at 23 ° C for 1 week to 6 months, and the dispersion stability was confirmed by visual observation and particle size measurement.
• the criteria for evaluation are as follows. A +: There was no sediment after 6 months, and there was no change in the average particle size. A: No sediment was observed after 3 months, and there was no change in the average particle size. B: There was no sediment after 3 months, but the average particle size increased. C: A sediment was confirmed within 3 months.
• Adhesiveness was evaluated according to the cross cut test (old standard) of JIS K5400. In addition, the peeling test was carried out at the same location up to 5 times. The criteria for evaluation are as follows. A ++: The adhesion test was performed 5 times, and no peeling occurred. A +: The film was peeled off at the fourth to fifth times. A: The coating film was peeled off at the second to third times. A-: There is slight peeling in the lattice portion of the grid. B: Peeling area is less than 5% of squares. C: The peeled area is 5% or more of the square.
• the surface of the coating film was subjected to 10 reciprocating wear with steel wool # 0000 with a load described below so that the width was 40 mm or more. Thereafter, a black tape was attached to the back surface of the substrate (PET film), and the presence or absence of scratches was confirmed under a three-wavelength fluorescent lamp.
• the criteria for evaluation are as follows. A ++: No scratch was observed at a load of 200 g / cm 2 . A +: 1 to 5 scratches were confirmed at a load of 200 g / cm 2 . A: Scratches were not confirmed at 100 g / cm 2 load. Six or more scratches were confirmed at a load of 200 g / cm 2 . B: 1 to 5 scratches were confirmed at a load of 100 g / cm 2 . C: Six or more scratches were confirmed at 100 g / cm 2 load.
• the film thickness of the coating film in the laminate was measured in advance, and immersed in a 4 mass% NaOH aqueous solution at 40 ° C for 5 minutes. After the film was taken out, the film was rinsed with distilled water and dried, and then the film thickness was measured again to confirm the change in film thickness before and after the test.
• the evaluation criteria are as follows. A: The film thickness reduction rate was less than 15%. B: The film thickness reduction rate was 15% or more and less than 30%. C: The film thickness reduction rate was 30% or more.
• the coating film in the laminate was irradiated with ultraviolet rays of 500 mJ / cm 2 and 400 mW / cm 2 using a high-pressure mercury lamp of an ultraviolet irradiation device (device name: CSOT-40, manufactured by Nihon Battery Co., Ltd.). Thereafter, it was confirmed whether the coating film was peeled off from the substrate.
• an ultraviolet irradiation device device name: CSOT-40, manufactured by Nihon Battery Co., Ltd.
• the ultraviolet ray was further irradiated as described above until the coating film peeled from the substrate, and the number of irradiations was measured. This was set as a light resistance test.
• the evaluation criteria are as follows. A +: UV irradiation 10 times, no peeling. A: Peeled when irradiated with ultraviolet rays for the 6th to 10th times. B: Peeled when irradiated with UV rays for 3 to 5 times. C: Stripped when irradiated with UV light for the first or second time.
• Zirconium oxide UEP-100, a first rare element, average primary particle size 15 nm Titanium oxide: Ishihara Sangyo TTO-51, average primary particle size 20nm Aluminum oxide: TM-300 manufactured by Daimei Chemical Industry, average primary particle size 10 nm NK ester CBX-0: Shin-Nakamura Chemical Co., Ltd.
• Disparon DA7301 Trade name Disparon DA-7301, Enomoto Kasei Co., Ltd., High-molecular-weight polyester acid alkylcyclohexane Aronix M-5300 -Carboxyl caprolactone monoacrylate DPHA: cross-linking agent, dipentaerythritol hexaacrylate (content of 95% or more)
• Irgacure 907 trade name, manufactured by BASF, polymerization initiator, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one
• the coating agent and coating film of the present invention are suitably used as a functional film in various industrial products such as light-emitting diodes (LEDs), lenses, optical devices, fine ceramics, conductive films, and optical films.
• LEDs light-emitting diodes
• lenses optical devices
• fine ceramics fine ceramics
• conductive films fine ceramics
• optical films optical films

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Inorganic Chemistry (AREA)
• Macromonomer-Based Addition Polymer (AREA)
• Paints Or Removers (AREA)
• Laminated Bodies (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=59678202

Family Applications (1)

Country Status (5)

Families Citing this family (5)

Citations (6)

Family Cites Families (5)

• 2016
  • 2016-03-31 JP JP2016071534A patent/JP6186032B1/ja active Active
• 2017
  • 2017-02-22 WO PCT/JP2017/006648 patent/WO2017169334A1/ja active Application Filing
  • 2017-02-22 CN CN201780000850.3A patent/CN107429104B/zh active Active
  • 2017-02-22 KR KR1020177017646A patent/KR101852314B1/ko active IP Right Grant
  • 2017-03-24 TW TW106109947A patent/TWI722152B/zh active

Patent Citations (6)

Also Published As

Similar Documents

Legal Events