WO2024024866A1 - 紫外線吸収剤水性塗料組成物 - Google Patents

紫外線吸収剤水性塗料組成物 Download PDF

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WO2024024866A1
WO2024024866A1 PCT/JP2023/027470 JP2023027470W WO2024024866A1 WO 2024024866 A1 WO2024024866 A1 WO 2024024866A1 JP 2023027470 W JP2023027470 W JP 2023027470W WO 2024024866 A1 WO2024024866 A1 WO 2024024866A1
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group
carbon atoms
ultraviolet absorber
coating composition
dispersant
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French (fr)
Japanese (ja)
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康弘 井手
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Mikuni Color Ltd
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Mikuni Color Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/16—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms condensed with carbocyclic rings or ring systems
    • C07D249/18—Benzotriazoles
    • C07D249/20—Benzotriazoles with aryl radicals directly attached in position 2
    • 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
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • 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
    • C09D7/45—Anti-settling agents
    • 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
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • 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
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/52—Natural or synthetic resins or their salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere

Definitions

  • the present invention relates to an ultraviolet absorber aqueous coating composition and a method for producing the same.
  • Benzotriazole-based ultraviolet absorbers are known for their excellent properties such as ultraviolet absorption performance and photostability, and have been widely used.
  • 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] also known as bisoctrisol
  • a UV absorber that can absorb up to long wavelengths.
  • Patent Documents 1, 2, 3, 4, and 5 methods of dispersing the compound in water have been reported (Patent Documents 1, 2, 3, 4, and 5). Dispersing in water not only makes it possible to use aqueous solvents and eliminates the need for organic solvents, but also improves the light resistance of the UV absorber itself because it is in a dispersed state and is not dissolved. Since the absorption of UV absorbers in the solid state increases to longer wavelengths than in the dissolved state, the amount of UV absorber used can be reduced, so it is expected that the range of applicable products will expand to water-based paints, sol-gel coating liquids, in-line coating liquids, etc. can. Furthermore, by creating an aqueous dispersion, it can be processed into paint or film forms, etc. In particular, by creating a transparent dispersion, it can be used for textile materials, inks, cosmetics, food packaging, etc. that require light resistance and are transparent. It can be expected to be widely applied to products where performance is important.
  • Patent Documents 4 and 5 high transmittance is maintained through a long manufacturing process, and the production efficiency cannot be said to be high due to the long manufacturing process. Therefore, there has been a need for a dispersion composition and a coating composition that maintain high transmittance and have a short manufacturing process and high production efficiency.
  • the present inventor has made repeated studies to solve the above problems. As a result, it was found that the transmittance could be improved in a shorter time than before by using and dispersing a specific ultraviolet absorber. That is, it is a dispersion liquid in which a specific bisoctrizole analog compound is dispersed in water. It has also been found that aqueous dispersion compositions of bisoctrisol analogs can be easily mixed with various resins and emulsions and can be provided as aqueous coating compositions for applications requiring high transparency.
  • an aqueous coating composition in which at least an ultraviolet absorber, a dispersant, and a resin component are present in an aqueous medium, and the ultraviolet absorber is a compound represented by the following general formula (I).
  • a water-based paint composition containing an ultraviolet absorber, characterized by General formula (I) During the ceremony, R 1 and R 1' may be the same or different from each other and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R 3 SO- group, or R 3 It is an O 2 - group.
  • R 2 and R 2' may be the same or different from each other, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a CO 2 H group, a phenyl group, an alkyl group moiety is a phenylalkyl group containing 1 to 4 carbon atoms, or a cycloalkyl group containing 5 to 8 carbon atoms.
  • R 3 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; , substituted by one or two cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or alkyl groups having 1 to 4 carbon atoms; or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms).
  • R 1 and R 1' are chlorine, R 2 and R 2' are tert-octyl, the dispersant is one or more compounds selected from acrylic copolymers of controlled polymerization, and further a surfactant.
  • the ultraviolet absorber-containing aqueous coating composition according to (1) or (2) above, characterized in that it contains (8) An aqueous composition in which at least an ultraviolet absorber and a dispersant are present in an aqueous medium, the ultraviolet absorber being a compound represented by the following general formula (I), A method for producing an aqueous paint composition containing an ultraviolet absorber, the method comprising the step of blending a resin component; General formula (I) During the ceremony, R 1 and R 1' may be the same or different from each other and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R 3 SO- group, or R 3 It is an O 2 - group.
  • R 2 and R 2' may be the same or different from each other, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a CO 2 H group, a phenyl group, an alkyl group moiety is a phenylalkyl group containing 1 to 4 carbon atoms, or a cycloalkyl group containing 5 to 8 carbon atoms.
  • R 3 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; , substituted by one or two cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or alkyl groups having 1 to 4 carbon atoms; or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms).
  • the above (8) characterized in that the ultraviolet absorber in the aqueous composition in which at least the ultraviolet absorber and the dispersant are present in the aqueous medium is dispersed with an average dispersed particle size of 10 to 35 nm.
  • the method for producing the ultraviolet absorber-containing aqueous coating composition described above (10) The method for producing an aqueous coating composition containing an ultraviolet absorber as described in (8) above, wherein the dispersant is one or more compounds selected from acrylic copolymers of controlled polymerization.
  • an aqueous coating composition containing an ultraviolet absorber that can sufficiently block ultraviolet rays while improving visible light transmittance, and a method for producing the same.
  • FIG. 1 is a graph showing the transmittance versus wavelength of a glass plate coated with a resin coating using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 1.
  • FIG. 2 is a graph showing the transmittance versus wavelength of a glass plate coated with a resin coating using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 2.
  • FIG. 3 is a diagram showing a graph of transmittance versus wavelength of a glass plate coated with a resin coating using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 3.
  • FIG. 4 is a diagram showing a graph of transmittance versus wavelength of a resin-coated glass plate using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 4.
  • FIG. 1 is a graph showing the transmittance versus wavelength of a glass plate coated with a resin coating using the ultraviolet absorber aqueous coating composition of the present invention obtained in Example 1.
  • FIG. 2 is a graph showing the transmittance versus wavelength
  • FIG. 5 is a diagram showing a graph of transmittance versus wavelength of a resin-coated glass plate using the ultraviolet absorber aqueous coating composition obtained in Comparative Example 1.
  • FIG. 6 is a diagram showing a graph of transmittance versus wavelength of a resin-coated glass plate using the ultraviolet absorber aqueous coating composition obtained in Comparative Example 2.
  • FIG. 7 is a diagram showing a graph of transmittance versus wavelength of a resin-coated glass plate using the ultraviolet absorber aqueous coating composition obtained in Comparative Example 3.
  • FIG. 8 shows the wavelengths of the ultraviolet absorbent dispersions of the present invention obtained in Example 1, Example 2, Example 3, and Example 4 and the ultraviolet absorbent dispersions obtained in Comparative Example 1 and Comparative Example 2.
  • FIG. 9 shows the wavelengths of the ultraviolet absorbent dispersions of the present invention obtained in Example 1, Example 2, Example 3, and Example 4 and the ultraviolet absorbent dispersions obtained in Comparative Example 1 and Comparative Example 2. It is a figure which shows the graph of the transmittance
  • UV absorber 1. Structure of Ultraviolet Absorber
  • an ultraviolet absorber represented by the following general formula (1) is used.
  • R 1 and R 1' may be the same or different from each other and are a hydrogen atom, a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R 3 SO- group, or R 3 It is an O 2 - group.
  • Particularly preferred are a halogen atom, a nitro group, a cyano group, a perfluoroalkyl group having 1 to 12 carbon atoms, an R 3 SO- group or an R 3 O 2- group.
  • R 2 and R 2' may be the same or different from each other, and are an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms substituted with a CO 2 H group, a phenyl group, an alkyl group moiety is a phenylalkyl group containing 1 to 4 carbon atoms, or a cycloalkyl group containing 5 to 8 carbon atoms.
  • Preferred is an alkyl group having 1 to 12 carbon atoms.
  • R 3 is an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 20 carbon atoms, an alkyl group substituted with an alkoxycarbonyl group having 2 to 9 carbon atoms, an alkenyl group having 3 to 18 carbon atoms; , substituted by one or two cycloalkyl groups having 5 to 12 carbon atoms, phenylalkyl groups having 7 to 15 carbon atoms, aryl groups having 6 to 10 carbon atoms or alkyl groups having 1 to 4 carbon atoms; or a 1,1,2,2-tetrahydroperfluoroalkyl group (the perfluoroalkyl portion of this group consists of 6 to 16 carbon atoms).
  • R 1 and R 1' are preferably an alkyl group having 1 to 4 carbon atoms or a halogen group. More preferably, it is a halogen group. Most preferred is a chlorine atom.
  • R 2 and R 2' are preferably alkyl groups having 1 to 12 carbon atoms. Most preferably, both R 2 and R 2' are the following groups:
  • benzotriazole compounds themselves are known, and in addition to being able to use commercially available products, they can also be produced and used by various conventionally known production methods for benzotriazole compounds.
  • the benzotriazole is further dimerized with an aldehyde.
  • it can be produced by the methods described in Japanese Patent No. 3223377, German Patent No. 1,670,951, etc.
  • the ultraviolet absorber used in the present invention preferably has a glass transition point of 35°C or higher, more preferably 60°C or higher, and most preferably 67°C. If it is too low, the glass transition point will be exceeded due to dispersion heat during dispersion, making it impossible to maintain crystallinity and making it difficult to proceed with dispersion. For this reason, the particle size becomes large and the transparency decreases.
  • the ultraviolet absorber used in the present invention preferably has a melting point of 150°C or higher, more preferably 190°C or higher, and most preferably 205°C or higher. If the melting point is too low, the glass transition point also tends to be low, causing the above-mentioned problems.
  • the melting point and glass transition point are values measured by DSC. More specifically, the method described in JIS standard K-7121-1987 "Method for measuring transition temperature of plastics" is used.
  • the ultraviolet absorber used in the present invention preferably has a molecular weight of 400 to 2,500, more preferably 650 to 750, and most preferably 727.76.
  • the molecular weight is lower than 400, the melting point and glass transition point tend to be low, and when it is higher than 2500, it tends to become difficult to crystallize, causing a problem that it becomes impossible to disperse.
  • surfactant In the present invention, preferably a surfactant is contained.
  • Surfactants include, for example, ionic surfactants, nonionic surfactants, and cationic surfactants.
  • ionic surfactants include fatty acid salts, alkyl sulfate ester salts, alkylbenzenesulfone salts, alkylnaphthalene sulfonates, alkyl sulfosuccinates, alkyldiphenyl ether disulfonates, polyoxyethylene alkyl sulfate ester salts, and polyoxyethylene.
  • Examples include alkylaryl sulfate salts, alkanesulfonate salts, naphthalenesulfonic acid formalin condensates, polyoxyethylene alkyl phosphate salts, N-methyl-oleoyl taurate salts, and ⁇ -olefin sulfonate salts.
  • nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene derivatives, ethylene oxide-propylene oxide block copolymers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acids.
  • esters examples include esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkyl amines, acetylene glycols, and ethylene glycol adducts of acetylene glycols.
  • examples of the cationic surfactant and amphoteric surfactant include alkyl amine salts, quaternary ammonium salts, alkyl betaines, and amine oxides. These ionic surfactants may be used as dispersants, wetting agents, detergents, and surface tension modifiers, which will be described later.
  • Particularly preferred surfactants are polyoxyalkylene derivatives having an HLB of 9 to 16, preferably 11 to 15, most preferably 13.2, having 1 to 3 benzyl groups, and having a phenyl ether ring.
  • the hydrophilic group may be bonded to any part, and the hydrophilic group may contain ethylene oxide or propylene oxide . It may contain a sexual group.
  • a polymer dispersant may be used in combination.
  • Preferred polymer dispersants include controlled polymerization acrylic copolymers.
  • disperbyk-190, 2010, 2012, 2013, 2015, 2055, 2060, 2061, 2096 manufactured by BYK Chemie, ZETASPERSE 3800 manufactured by EVONIC, TEGO Dispers 750W, etc. can be used.
  • Disperbyk-190, 2015, most preferably Disperbyk-2015 is preferred because it has high compatibility with the surfactant used in combination and improves dispersibility compared to the case of a surfactant alone.
  • Dispersion medium In the present invention, at least each of the above components is dispersed in water. If a dispersion medium other than water is contained, the ultraviolet absorber may not be dissolved and the wavelength may shift to a shorter wavelength. Therefore, it is preferable to contain no dispersion medium other than water as much as possible. It is desirable to suppress the content to 1% by weight or less in the dispersion, and preferably the dispersion medium is 100% water.
  • the content of the ultraviolet absorber in the dispersion is preferably 5 to 20% by mass. If it is less than 5%, it will be difficult to apply shear and dispersion will be difficult to proceed, and if it exceeds 20% by mass, the viscosity will be high and it will be difficult to proceed to dispersion. Preferably it is 8-12% by weight, most preferably 10% by weight.
  • the content of the surfactant is preferably 1 to 100 parts by weight per 100 parts by weight of the ultraviolet absorber.
  • this activator is less than 1 part by mass, it will be difficult to proceed with fragmentation of 50 nm or less, and there will be problems such as a long dispersion time; if it exceeds 100 parts by mass, the viscosity will increase and dispersion will be difficult. It becomes difficult to proceed.
  • it is 50 to 90 parts by weight, most preferably 70 parts by weight.
  • a polymer dispersant When a polymer dispersant is used in combination with a surfactant, it is preferably used in an amount of 1 to 100 parts by weight per 100 parts by weight of the ultraviolet absorber within the above surfactant content range. If the amount is less than 1 part by mass, the effect of the combined use will be small, and if it exceeds 100 parts by mass, the viscosity will increase and dispersion will be difficult to proceed. Preferably it is 5 to 20 parts by weight, most preferably 10 parts by weight.
  • the method for producing the ultraviolet absorber aqueous coating composition of the present invention is not particularly limited, but includes first producing an ultraviolet absorber dispersion containing at least an ultraviolet absorber, an aqueous medium, and a dispersant, and further adding a resin component. is highly desirable. In particular, it is extremely desirable to produce an ultraviolet absorber dispersion containing at least an ultraviolet absorber, an aqueous medium, a dispersant, and a surfactant, and further add a resin component. By dispersing the ultraviolet absorber to a desired particle size at the stage of forming the ultraviolet absorber dispersion, the resulting coating composition will have excellent performance.
  • the method for producing the ultraviolet absorbent dispersion is not particularly limited, it can be produced using, for example, a device such as a media-type disperser or a collision-type disperser.
  • a media-type dispersing machine moves small-diameter media such as glass, alumina, zirconia, steel, and tungsten as media at high speed in a vessel, and disperses the slurry passing between them by grinding it with the shear force between the media.
  • This is a disperser that performs Specific examples of media-type dispersing machines include ball mills, sand mills, pearl mills, spike mills, agitator mills, Kobo mills, and Ultra Visco mills, and more specifically, for example, Ultra Apex mills manufactured by Hiroshima Metal & Machinery Co., Ltd., and wide separators. Mill, MAX Nano Getter manufactured by Ashizawa Finetech Co., Ltd., Mugen Flow MGF, Dyno Mill ECM type manufactured by Shinmaru Enterprises Co., Ltd., and the like.
  • a collision type dispersion machine is a dispersion machine that performs dispersion by pulverizing pigments and the like in the fluid by colliding a fluid against a single wall surface at high speed or by causing fluids to collide with each other at high speed.
  • collision-type dispersers include jet mills that accelerate and pulverize raw material particles using high-speed jet streams, and "Starburst" (registered trademark, manufactured by Sugino Machine Co., Ltd.), which is a wet atomization device. . It may also be produced using other known dispersion equipment, such as a roll mill or an ultrasonic dispersion machine.
  • any equipment and media that can obtain sufficient shearing force to obtain the target particle size may be used, and in general, various media type dispersion machines are suitable. be. These devices and media may be appropriately selected, the above-mentioned components may be added, and the process may be carried out until the ultraviolet absorber becomes fine particles having the above-described desired particle size.
  • the ultraviolet absorber dispersion containing the specific compound used in the present invention can have a transmittance of 75% or more at 600 nm as measured by the above measurement method. Furthermore, it can also be set to 80% or more. In addition, if the dispersion has a transmittance of 600 nm lower than 75% by the above measurement method, the turbidity will increase and the transparency will decrease, but as shown in the comparative example described later, in the conventional technology, the transmittance is 75% or higher. It is difficult to do so.
  • the coating composition of the present invention can maintain ultraviolet absorption performance over a long period of time. As a result, a coating film with excellent light resistance can be obtained.
  • the ultraviolet absorber dispersion containing the specific compound used in the present invention was diluted with water so that the ultraviolet absorber concentration was 0.002%, and the absorption spectrum was measured using an ultraviolet-visible spectrophotometer (Co., Ltd.).
  • the absorbance at 380 nm (A380) can be 0.50 to 0.70.
  • A380/A600 which is the result of calculating the ratio of the absorbance at 380 nm (A380) and the absorbance at 600 nm (A600) in the absorption spectrum when the UV absorber concentration of the UV absorber dispersion is 0.002%, is 200 or more.
  • a high value of A380/A600 means that the visible light range can be sufficiently transmitted and ultraviolet light can be sufficiently absorbed, and when A380/A600 is lower than 200, the ultraviolet light range can be sufficiently cut and the UV range can be sufficiently absorbed. tends to be difficult to maintain.
  • FIG. 9 shows the relationship between wavelength and transmittance of the ultraviolet absorber dispersion containing the specific compound used in the present invention, and FIG. 8 shows the relationship between wavelength and absorbance. As can be seen from these figures, this ultraviolet absorber dispersion has high transmittance in the visible region, excellent transparency, and maintains high transparency while sufficiently shielding the ultraviolet region.
  • the ultraviolet absorber-containing aqueous coating composition of the present invention has excellent transparency and light resistance. More specifically, a UV absorber dispersion with a 600 nm transmittance of 80% or more, particularly 82.8% to 88.2%, and an A380/A600 of 200 or more as determined by the above measurement method, and a transparent styrene-acrylic as a binder.
  • the 600 nm transmittance of the resulting coating film (when formed with bar coater #5 (approximately 1.5 ⁇ m)) is 80% or more, especially 89.9 to 90.8%, T380/T600 is 0.38 or less, and 0.37 or less, and even 0.36 or less (in other words, it can sufficiently absorb ultraviolet rays while transmitting visible light and has excellent transparency), and the transmittance change in the ultraviolet region by xenon fade meter test is 0 even after 70 hours.
  • the change is extremely small at -0.1 to -0.4, and it has high transmittance in the visible region, excellent transparency, and maintains high transparency for a long period of time while sufficiently blocking the ultraviolet region. It turns out that you can keep it.
  • the particle size of the ultraviolet absorber it is preferable to adjust the particle size of the ultraviolet absorber to a certain range.
  • the ultraviolet absorber concentration of the ultraviolet absorber dispersion of the present invention was diluted with water so that the loading index was in the range of 0.1 to 100, and a particle size distribution analyzer (manufactured by Nikkiso Co., Ltd., Micro
  • the particle size is 10 to 35 nm, preferably 10 to 30 nm, most preferably 13 to 20 nm. Within this range, the balance between the above-mentioned ultraviolet absorption performance and transparency is the best.
  • Viscosity The viscosity of the ultraviolet absorber dispersion is 2.0 to 4.5 mPa ⁇ s when measured at 25°C using a viscometer (manufactured by Toki Sangyo Co., Ltd., product number "VISCOMETER TV-22"). , particularly preferably 2.0 to 3.0 mPa ⁇ s. This range is particularly preferable because it is easy to mix with other materials such as resin components and easy to handle. By blending the aforementioned components in the aforementioned proportions, the viscosity can be easily adjusted to a preferred range.
  • pH of the ultraviolet absorber dispersion can be appropriately selected depending on the purpose and the pH of other components such as the resin to be blended.
  • the pH can be adjusted appropriately by selecting the functional group of the surfactant.
  • the ultraviolet absorber dispersion described above can be further mixed with a resin component to form a paint, and in particular can be made into an aqueous paint composition using an aqueous dispersion medium.
  • the aqueous coating composition of the present invention may be any aqueous composition as long as it can form a film on a substrate.
  • water-based paint compositions There are two types of water-based paint compositions: one-component type, in which the curing agent and cross-linking agent coexist in the same system, and two-component type, in which the main agent and curing agent are stored separately and mixed at the time of use.
  • any of them can be used in the present invention.
  • it can also be used for various purposes as described in WO2015/152057.
  • Coated products using the ultraviolet absorber aqueous coating composition of the present invention have particularly excellent weather resistance, maintain performance for a long period of time, and exhibit almost no increase in transmittance in the ultraviolet region and no decrease in transmittance in the visible region. can not see.
  • the ultraviolet absorber-containing aqueous coating composition of the present invention contains a resin component in addition to the ultraviolet absorber, dispersant, and dispersion medium described above.
  • the resin component is also not particularly limited, and various resins conventionally used in aqueous coating compositions can be used without limitation. Examples include various water-soluble resins, emulsion resins, disversion resins, etc., and acrylic resins, urethane resins, acrylic urethane resins, styrene acrylic resins, silicone resins, fluororesins, etc. can be used without limitation.
  • Bonron S-415 acrylic (or styrene acrylic) aqueous emulsion
  • Joncryl PDX-7630A styrene-acrylic acid resin emulsion
  • the ultraviolet absorber-containing aqueous coating composition of the present invention can be suitably used as a coating for various purposes in which it is desirable to have an ultraviolet absorbing function.
  • the base material to be coated is not limited at all, and examples thereof include glass, resin glass, metal, plastic, fiber, cloth, paper, wood, concrete, and the like. These base materials constitute, for example, components for window glass, interior and exterior materials, building materials such as architectural structures, containers for containing foods, medicines, cosmetics, chemicals, etc., signboards, signs, solar cells, etc. It may be a member. Further, by using the ultraviolet absorber-containing aqueous coating composition of the present invention using printed matter as a base material, it is possible to prevent ink from fading.
  • the ultraviolet absorber-containing aqueous coating composition of the present invention may be an ink, and in this case, it can, for example, prevent the ink from fading.
  • the ultraviolet absorber-containing aqueous coating composition of the present invention may be an adhesive, in which case it can prevent deterioration of the adhesive due to sunlight or ultraviolet light, for example.
  • a base material such as fiber
  • the ultraviolet absorber-containing aqueous coating composition of the present invention it is also possible to produce, for example, clothing, hats, umbrellas, etc. that have an ultraviolet shielding effect.
  • it is also possible to produce a film that protects foodstuffs such as grains, vegetables, and fruits from ultraviolet rays by coating a food packaging film with the ultraviolet absorber-containing aqueous coating composition of the present invention.
  • Example 1 A compound as an ultraviolet absorber in which R 1 and R 1 ' in general formula (I) are both chlorine atoms, and R 2 and R 2 ' are both 1,1,3,3-tetramethylbutyl groups.
  • the ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 1 was diluted with water to 0.0982%, and the transmission spectrum was measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850). As a result of measurement at room temperature, the transmittance at 600 nm was 82.1%.
  • As coating resin 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200 mgKOH/g, 34.1% by weight of active ingredient), 0.66 parts by weight of ultraviolet absorber dispersion 1, water 1 .77 parts by weight was stirred to form a coating composition.
  • the obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film.
  • the appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation).
  • UV-1850 ultraviolet-visible spectrophotometer
  • the transmittance was 30.6%, the transmittance at 450 nm was 88.7%, and the transmittance at 600 nm was 90.8%.
  • the resulting resin-coated glass plate was irradiated with ultraviolet rays using a xenon weather meter under the conditions of a wavelength of 300 to 400 nm, an illuminance of 42 W/m 2 , and a black panel temperature of 63°C.
  • the transmission spectrum was measured every 70 hours using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation) at room temperature, and changes in the spectrum were observed. Table 2 shows the change values.
  • Example 2 A compound as an ultraviolet absorber in which R 1 and R 1 ' in general formula (I) are both chlorine atoms, and R 2 and R 2 ' are both 1,1,3,3-tetramethylbutyl groups.
  • 1 (2,2'-methylenebis[6-(5-chloro-2H-benzotriazol-2-yl)-4-tert-octylphenol]) 4.0 parts by weight, a high molecular weight dispersant having an acid value as a dispersant (manufactured by BYK Chemie, disperbyk-2015, acid value 10mgKOH/g, active ingredient 40.0% by weight) 2.8 parts by weight and 33.2 parts by weight of water in a paint conditioner using zirconia beads with a diameter of 0.1 mm.
  • the mixture was mixed and pulverized for 20 hours to obtain an ultraviolet absorbent dispersion 2.
  • the ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 2 was diluted to 8.8%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 4° C. and 16,300 rpm. Centrifugation was performed under conditions of 1 hour and 30 minutes. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 3.
  • the transmittance of the obtained ultraviolet absorber dispersion 3 was measured in the same manner as in Example 1, and was found to be 82.3%.
  • styrene-acrylic acid resin emulsion manufactured by BASF, Joncryl PDX-7630A, 200mgKOH/g, 34.1% by weight of active ingredient
  • 0.92 parts by weight of ultraviolet absorber dispersion 3 1 part by weight of water .51 parts by weight was stirred to form a coating composition.
  • the obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film.
  • the appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850).
  • the transmittance was 31.8%, the transmittance at 450 nm was 88.8%, and the transmittance at 600 nm was 90.5%. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.
  • Example 3 A compound as an ultraviolet absorber in which R 1 and R 1 ' in general formula (I) are both hydrogen atoms, and R 2 and R 2 ' are both 1,1,3,3-tetramethylbutyl groups.
  • 2 (2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (“TINUVIN360” manufactured by BASF)) 17.0 parts by weight, a high acid value having an acid value as a dispersant 10.6 parts by weight of a molecular weight dispersant (manufactured by BYK Chemie, disperbyk-2015, acid value 10 mg KOH/g, active ingredient 40.0% by weight), polyoxyethylene tribenzyl phenyl ether (manufactured by Kao Corporation, "Emulgen”) as a surfactant.
  • TINUVIN360 manufactured by BASF
  • B-66'', HLB13.2) 4.5 parts by weight and 67.9 parts by weight of water were mixed and ground in a paint conditioner for 3 hours using zirconia beads with a diameter of 0.5 mm.
  • the mixture was mixed and ground using zirconia beads for 14 hours to obtain an ultraviolet absorbent dispersion 4.
  • the ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 4 was diluted to 5.6%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 35° C. and 16,300 rpm. Centrifugation was performed for 1 hour and 45 minutes. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 5.
  • the transmittance of the obtained ultraviolet absorber dispersion 5 was measured in the same manner as in Example 1, and was found to be 88.3%.
  • a coating resin 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200 mg KOH/g, 34.1% by weight of active ingredient), 2.25 parts by weight of ultraviolet absorber dispersion 5, 0 parts by weight of water. .18 parts by weight were stirred to form a coating composition.
  • the obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film.
  • the appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation).
  • UV-1850 ultraviolet-visible spectrophotometer
  • the transmittance was 31.9%, the transmittance at 450 nm was 89.2%, and the transmittance at 600 nm was 90.6%. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.
  • Example 4 A compound as an ultraviolet absorber in which R 1 and R 1 ' in general formula (I) are both hydrogen atoms, and R 2 and R 2 ' are both 1,1,3,3-tetramethylbutyl groups.
  • R 1 and R 1 ' in general formula (I) are both hydrogen atoms
  • R 2 and R 2 ' are both 1,1,3,3-tetramethylbutyl groups.
  • 2 (2,2′-methylenebis[6-(2H-benzotriazol-2-yl)-4-tert-octylphenol] (“TINUVIN360” manufactured by BASF)
  • TINUVIN360 manufactured by BASF
  • the ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 6 was diluted to 5.6%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 35° C. and 16,300 rpm. Centrifugation was performed under conditions of , 2 hours. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 7. The transmittance of the obtained ultraviolet absorber dispersion 7 was measured in the same manner as in Example 1, and was found to be 87.8%.
  • styrene-acrylic acid resin emulsion manufactured by BASF, Joncryl PDX-7630A, 200 mgKOH/g, 34.1% by weight of active ingredient
  • 2.13 parts by weight of ultraviolet absorber dispersion 7 0 parts by weight of water. .30 parts by weight were stirred to form a coating composition.
  • the obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film.
  • the appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation).
  • the transmittance was 34.6%, the transmittance at 450 nm was 87.2%, and the transmittance at 600 nm was 89.9. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.
  • Comparative example 1 4.0 parts by weight of compound 3 (2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol ("TINUVIN326" manufactured by BASF)) as a UV absorber, dispersant 2.8 parts by weight of a high molecular weight dispersant having an acid value (SOLSPERSE4600 manufactured by Lubrizol, nonionic, active ingredient 50.0% by weight) and 33.2 parts by weight of water were mixed for 23 hours using zirconia beads with a diameter of 0.1 mm. The mixture was mixed and pulverized to obtain an ultraviolet absorbent dispersion 8.
  • the ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 8 was diluted to 8.8%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 4° C. and 16,300 rpm. Centrifugation was performed under conditions of , 2 hours. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 9. The transmittance of the obtained ultraviolet absorber dispersion 9 was measured in the same manner as in Example 1, and was found to be 71.7%.
  • coating resin 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200 mgKOH/g, 34.1% by weight of active ingredient), 2.28 parts by weight of ultraviolet absorber dispersion 9, 0 parts by weight of water. .15 parts by weight were stirred to form a coating composition.
  • the obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film.
  • the appearance of the obtained resin-coated glass plate was slightly cloudy, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850).
  • the transmittance was 31.2%, the transmittance at 450 nm was 78.7%, and the transmittance at 600 nm was 79.1%. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.
  • Comparative example 2 10.0 parts by weight of compound 4 (2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one (manufactured by ChemiPro Kasei Co., Ltd., "KEMISORB500”) as a UV absorber) , 1.0 parts by weight of styrene acrylic resin (manufactured by BASF, Joncryl HPD-196, acid value 200 mg KOH/g, active ingredient 36.0% by weight) as a dispersant and 89.0 parts by weight of water in a paint conditioner, After mixing and pulverizing for 4 hours using zirconia beads having a diameter of 0.5 mm, the mixture was further mixed and pulverizing for 24 hours using zirconia beads having a diameter of 0.1 mm to obtain an ultraviolet absorber dispersion 10.
  • compound 4 2,2'-(1,4-phenylene)bis-4H-3,1-benzoxazin-4-one (manufactured by ChemiPro Kas
  • the ultraviolet absorber concentration of the obtained ultraviolet absorber dispersion 10 was diluted to 8.0%, and 34 g of the diluted solution was placed in a centrifuge tube using a centrifuge (Suprema 25, manufactured by TOMY) at 4° C. and 16,300 rpm. , centrifugation was performed for 10 minutes. After centrifugation, 25 g of the supernatant was collected to obtain ultraviolet absorbent dispersion 11. The transmittance of the obtained ultraviolet absorber dispersion 11 was measured in the same manner as in Example 1, and was found to be 63.9%.
  • styrene-acrylic acid resin emulsion manufactured by BASF, Joncryl PDX-7630A, 200 mg KOH/g, 34.1% by weight of active ingredient
  • 1.92 parts by weight of ultraviolet absorber dispersion 11 0 parts by weight of water. .51 parts by weight was stirred to form a coating composition.
  • the obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film.
  • the appearance of the resulting resin-coated glass plate was cloudy, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (UV-1850, manufactured by Shimadzu Corporation).
  • the transmittance was 6.8%, the transmittance at 450 nm was 56.6%, and the transmittance at 600 nm was 68.4. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.
  • Comparative example 3 As a coating resin, 1.76 parts by weight of styrene-acrylic acid resin emulsion (manufactured by BASF, Joncryl PDX-7630A, 200mgKOH/g, 34.1% by weight of active ingredient) and 1.66 parts by weight of water were stirred to form a coating composition. did. The obtained coating composition was coated on a glass plate using a bar coater #5, and then dried at 80° C. for 10 minutes to obtain a glass plate with a resin coating film. The appearance of the obtained resin-coated glass plate had good transparency, and the transmission spectrum was measured at room temperature using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, UV-1850). The transmittance at 450 nm was 90.1%, and the transmittance at 450 nm was 91.6%. Changes in the transmission spectrum of the obtained resin-coated glass plate were observed in the same manner as in Example 1.
  • Table 1 shows the ultraviolet absorber, activator, and dispersant contained, as well as the transmittance and absorbance of each dispersion obtained in each of the above Examples and Comparative Examples.
  • Table 2 shows the appearance transparency of the glass plate with the resin coating film obtained by applying the aqueous coating composition obtained in each of the above Examples and Comparative Examples, and the change in transmittance in the visible and ultraviolet regions upon irradiation with ultraviolet rays. The values are shown in Table 2.
  • an aqueous coating composition containing an ultraviolet absorber that has excellent transparency and sufficiently blocks ultraviolet rays, and a method for producing the same.

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JPH03233448A (ja) * 1990-02-08 1991-10-17 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH04340960A (ja) * 1991-05-17 1992-11-27 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JP2002201420A (ja) * 2000-12-28 2002-07-19 Asahi Glass Co Ltd 紫外線吸収剤を含有する水性塗料用組成物およびその製造方法
JP2009120638A (ja) * 2007-11-12 2009-06-04 Kose Corp 紫外線吸収剤水分散組成物
JP2013087228A (ja) * 2011-10-19 2013-05-13 Dainichiseika Color & Chem Mfg Co Ltd 紫外線・近赤外線遮断水性塗料、該塗料からなる塗膜が形成された遮熱処理ガラス及び該塗料を用いた窓ガラスの遮熱処理方法
JP2017095559A (ja) * 2015-11-20 2017-06-01 三菱鉛筆株式会社 紫外線吸収剤水分散組成物
JP2022115765A (ja) * 2021-01-28 2022-08-09 御国色素株式会社 紫外線吸収剤水性組成物
JP2022115764A (ja) * 2021-01-28 2022-08-09 御国色素株式会社 紫外線吸収剤水性組成物
JP2022115766A (ja) * 2021-01-28 2022-08-09 御国色素株式会社 紫外線吸収剤水性組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03233448A (ja) * 1990-02-08 1991-10-17 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JPH04340960A (ja) * 1991-05-17 1992-11-27 Fuji Photo Film Co Ltd ハロゲン化銀カラー写真感光材料
JP2002201420A (ja) * 2000-12-28 2002-07-19 Asahi Glass Co Ltd 紫外線吸収剤を含有する水性塗料用組成物およびその製造方法
JP2009120638A (ja) * 2007-11-12 2009-06-04 Kose Corp 紫外線吸収剤水分散組成物
JP2013087228A (ja) * 2011-10-19 2013-05-13 Dainichiseika Color & Chem Mfg Co Ltd 紫外線・近赤外線遮断水性塗料、該塗料からなる塗膜が形成された遮熱処理ガラス及び該塗料を用いた窓ガラスの遮熱処理方法
JP2017095559A (ja) * 2015-11-20 2017-06-01 三菱鉛筆株式会社 紫外線吸収剤水分散組成物
JP2022115765A (ja) * 2021-01-28 2022-08-09 御国色素株式会社 紫外線吸収剤水性組成物
JP2022115764A (ja) * 2021-01-28 2022-08-09 御国色素株式会社 紫外線吸収剤水性組成物
JP2022115766A (ja) * 2021-01-28 2022-08-09 御国色素株式会社 紫外線吸収剤水性組成物

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