Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/063—Titanium; Oxides or hydroxides thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/72—Copper
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/39—Photocatalytic properties
• • 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
  • 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
  • C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
• • 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
  • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds

Definitions

• the present invention relates to a coating composition comprising a titanium oxide-containing photocatalyst.
• antibacterial / antiviral agents include various alcohol agents, quaternary ammonium salt compounds, silver compounds, copper compounds, etc., which are irritating to the skin and antibacterial due to changes over time.
• Patent Documents It has not been able to sufficiently satisfy the market-required characteristics such as reduction of antiviral property, deterioration due to oxidation, etc., which impairs the appearance, and impairs the texture of the base material when the surface is coated (for example, Patent Documents). 1). On the other hand, photocatalysts using titanium oxide are less irritating to the human body and maintain antibacterial and antiviral performance for a long period of time, so expectations for practical use are increasing (see Patent Document 2).
• the present invention relates to a coating composition comprising a titanium oxide-containing photocatalyst.
• the present invention further relates to the coating composition, wherein the titanium oxide-containing photocatalyst carries a metal compound on the catalyst surface.
• the present invention relates to the coating composition, which is characterized in that the metal compound is a divalent copper compound in addition to the above-mentioned characteristics.
• the present invention relates to an invention characterized in that the coating composition contains an active energy ray-curable resin.
• the present invention further relates to a laminate obtained by applying and curing the coating composition on the surface of a substrate.
• the present invention provides a coating composition comprising a titanium oxide-containing photocatalyst having antibacterial and antiviral effects.
• a coat layer exhibiting long-lasting antibacterial and antiviral properties can be imparted to various objects by a simple operation, and various antibacterial and antiviral properties can be obtained as a base material. Can be given to.
• the coating composition of the present invention has a low haze value, so that the texture of the base material is not impaired, and further, absorption into the human body does not occur, so that the coating composition is safe for the human body.
• the coating composition of the present invention may form a coating layer capable of protecting the surface of the object to be coated by subjecting it to active energy ray irradiation such as ultraviolet irradiation or electromagnetic ray irradiation, or other treatments such as drying. It's fine.
• the coating composition of the present invention contains a titanium oxide-containing catalyst, and the composition is not particularly limited as long as it can coat the object, but includes a curable raw material capable of forming a stable coating layer. Is preferable.
• the method for applying the coating composition of the present invention is not particularly limited as long as the effects of the present invention can be obtained, but a spray method, a dip method, and other coating methods using various printing machines and coaters can be used. Various coating methods can be selected.
• the coating composition in the present invention is not particularly limited as long as it is applied and cured by a person skilled in the art for the purpose of imparting antibacterial and antiviral properties to the object to be coated, and is not particularly limited, and has high hardness, water repellency, and water repellency.
• Various raw materials may be contained according to desired performance such as oiliness, slip property, and blue light cut, and various functions other than antibacterial and antiviral properties may be imparted.
• the coating composition of the present invention is characterized by containing a titanium oxide-containing photocatalyst.
• the titanium oxide-containing photocatalyst used in the present invention is particularly limited as long as it contains titanium oxide and has photoresponsiveness that exhibits antibacterial and antiviral properties when exposed to light such as visible light or ultraviolet rays.
• the metal compound is supported on the surface of the titanium oxide-containing photocatalyst because more suitable antibacterial and antiviral properties can be obtained.
• titanium oxide used in the present invention for example, rutile-type titanium oxide, anatase-type titanium oxide, brookite-type titanium oxide and the like can be used. These titanium oxides may be used alone or in combination of two or more. Among these, rutile-type titanium oxide is preferably contained because it has excellent photocatalytic activity in the visible light region.
• the content of rutile-type titanium oxide is 15 from the viewpoint that even more excellent antiviral property in bright and dark places, organic compound decomposition property in bright place, and photoresponsiveness can be obtained. It is preferably mol% or more, more preferably 50 mol% or more, still more preferably 90 mol% or more.
• a liquid phase method and a gas phase method are generally known, and the present invention may use titanium oxide by any method.
• the liquid phase method is a method for obtaining titanium oxide by hydrolyzing, neutralizing and calcining titanyl sulfate obtained from a liquid in which a raw material ore such as ilmenite ore is dissolved.
• the vapor phase method is a method for obtaining titanium oxide by a vapor phase reaction between titanium tetrachloride obtained by chlorinating a raw material ore such as rutile ore and oxygen.
• analysis of the impurities can be mentioned.
• the titanium oxide produced by the liquid phase method contains zirconium, niobium and the like derived from impurities in the ilmenite ore in its product.
• the vapor phase method has a step of purifying titanium tetrachloride to remove impurities, titanium oxide hardly contains these impurities.
• Titanium oxide produced by the vapor phase method has the advantage of being able to generate a uniform particle size, but it is difficult to form secondary aggregates. It is considered that the viscosity of is high.
• the titanium oxide (a) produced by the liquid phase method is considered to generate loose secondary aggregates in the firing step, and has a specific surface area (BET value) due to the primary particles. The cohesive force is small and the viscosity of the mixed solution can be suppressed.
• titanium oxide produced by the liquid phase method is preferable from the viewpoint of further improving productivity.
• the BET specific surface area of the titanium oxide is preferably in the range of 1 to 200 m 2 / g, more preferably in the range of 3 to 100 m 2 / g, from the viewpoint of obtaining further excellent antiviral property and photoresponsiveness.
• the range of 4 to 70 m 2 / g is more preferable, the range of 8 to 50 m 2 / g is more preferable, and the productivity of the antiviral agent can be further increased. Most preferably, it is in the range of / g.
• the primary particle size of the titanium oxide is preferably in the range of 0.01 to 1.5 ⁇ m, preferably in the range of 0.02 to 0.5 ⁇ m, from the viewpoint of obtaining more suitable antiviral property and photoresponsiveness. Is more preferable.
• the method for measuring the primary particle size of titanium oxide shows the value measured by a method of directly measuring the size of the primary particle from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of each titanium oxide primary particle are measured, the average is taken as the particle diameter of the primary particle, and then each particle is obtained for 100 or more titanium oxide particles. The volume (weight) of the above was obtained by approximating it to a cube having a obtained particle size, and the volume average particle size was taken as the average primary particle size.
• a metal compound was supported on titanium oxide because the photocatalytic activity in the visible light region was further improved and antiviral properties were easily exhibited under practical indoor light. It is preferable to use one.
• the titanium oxide-containing photocatalyst used in the present invention it is preferable to use one in which a metal compound is supported on the surface of the catalyst as described above.
• a metal compound supported on titanium oxide for example, a copper compound, an iron compound, a tungsten compound and the like can be used.
• a copper compound is preferable, and a divalent copper compound is more preferable, from the viewpoint of obtaining even more excellent antibacterial and antiviral properties.
• the method for supporting the metal compound on titanium oxide is not particularly limited, and a known method can be used.
• the primary particle size of the metal-supported titanium oxide-containing photocatalyst is measured by directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM). show.
• TEM transmission electron microscope
• the minor axis diameter and the major axis diameter of the primary particles of each metal-supported titanium oxide-containing photocatalyst are measured, the average is taken as the particle diameter of the primary particles, and then 100 or more titanium oxide particles are used.
• the volume (weight) of each particle was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was taken as the average primary particle size.
• Examples of the method of supporting the divalent copper compound on the titanium oxide include a method having a step of mixing titanium oxide containing rutyl-type titanium oxide, a raw material for the divalent copper compound, water, and an alkaline substance.
• the concentration of the titanium oxide in the mixing step is preferably in the range of 3 to 40 parts by mass.
• a mixing step with good handling can be performed even if the concentration of titanium oxide is increased, and specifically, the above-mentioned oxidation can be performed.
• the mixing step can be carried out particularly well in the range where the concentration of titanium exceeds 25 parts by mass and is 40 parts by mass or less.
• divalent copper compound raw material for example, a divalent copper inorganic compound, a divalent copper organic compound, or the like can be used.
• divalent copper inorganic compound examples include copper sulfate, copper nitrate, copper iodide, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amide sulfate, copper ammonium chloride, and copper pyrophosphate.
• Inorganic acid salts of divalent copper such as copper carbonate; halides of divalent copper such as copper chloride, copper fluoride and copper bromide; copper oxide, copper sulfide, azurite, malakite, copper azide and the like can be used. .. These compounds may be used alone or in combination of two or more.
• divalent copper organic compound examples include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper capricate, and mistinic acid.
• divalent copper compound among the above-mentioned compounds, those represented by the following general formula (1) are preferably used.
• CuX 2 (1) (In formula (1), X represents a halogen atom, CH 3 COO, NO 3 or (SO 4 ) 1/2 .)
• the X in the formula (1) is more preferably a halogen atom, and particularly preferably a chlorine atom.
• the amount of the divalent copper compound raw material used in the mixing step is preferably in the range of 0.01 to 20 parts by mass, preferably in the range of 0.1 to 15 parts by mass with respect to 100 parts by mass of the titanium oxide. More preferably, the range of 0.3 to 10 parts by mass is further preferable.
• the water is a solvent in the mixing step and is preferably used alone, but may contain other solvents as needed.
• the other solvent for example, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide and tetrahydrofuran can be used. These solvents may be used alone or in combination of two or more.
• sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, a basic surfactant and the like can be used, and sodium hydroxide can be used. It is preferable to use it.
• the alkaline substance is preferably added as a solution from the viewpoint of easy control of the reaction, and the concentration of the alkaline solution to be added is preferably in the range of 0.1 to 5 mol / L, preferably 0.3 to 4 mol.
• the range of / L is more preferable, and the range of 0.5 to 3 mol / L is even more preferable.
• the titanium oxide divalent copper compound raw material, water, and an alkaline substance may be mixed.
• titanium oxide is first mixed with water and stirred as necessary, and then divalent copper is used.
• examples thereof include a method of mixing the compound raw materials, stirring the mixture, and then adding an alkaline substance and stirring the mixture.
• the total stirring time in the mixing step is not particularly limited as long as the effect of the present invention can be obtained, but examples thereof include 5 to 120 minutes, preferably 10 to 60 minutes.
• Examples of the temperature in the mixing step include a range of room temperature to 70 ° C.
• the pH of the mixture after mixing and stirring the titanium oxide divalent copper compound raw material and water and then mixing and stirring the alkaline substance is such that the support of the divalent copper compound on titanium oxide is good. From a certain point, the range of 8 to 11 is preferable, and the range of 9.0 to 10.5 is more preferable.
• the mixed liquid can be separated as a solid content.
• the method for performing the separation include filtration, sedimentation separation, centrifugation, evaporation and drying, and the like, but filtration is preferable.
• the separated solid content may be subsequently washed with water, crushed, classified, or the like, if necessary.
• the heat treatment temperature is preferably in the range of 150 to 600 ° C, more preferably in the range of 250 to 450 ° C.
• the heat treatment time is preferably 1 to 10 hours, more preferably 2 to 5 hours.
• a titanium oxide composition containing titanium oxide carrying a divalent copper compound can be obtained.
• the amount of the divalent copper compound supported on the titanium oxide is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of titanium oxide from the viewpoint of antiviral property and photocatalytic activity. ..
• the amount of the divalent copper compound carried can be adjusted by adjusting the amount of the divalent copper compound raw material used in the mixing step.
• the content of the titanium oxide-containing catalyst is not particularly limited as long as the effect of the present invention can be obtained, but since the antibacterial and antiviral effects can be preferably obtained, the entire coating composition. It is preferably contained in an amount of 0.01 part by mass or more, and more preferably 0.02 part by mass to 5 parts by mass because an antibacterial / antiviral effect is preferably obtained, and an increase in haze value is suppressed and an antiviral effect is obtained. Is most preferably contained in an amount of 0.02 to 2 parts by mass.
• the coating composition of the present invention can contain various resins, adhesives and the like in order to improve the coating performance within the range where the effect of the present invention can be obtained.
• the resin various resins such as a thermoplastic resin, a thermosetting resin, and an active energy ray-curable resin can be used, but since a coating layer can be easily formed on various substrates, an active energy ray-curable resin can be used. It is preferable to use.
• the active energy ray-curable resin is not particularly limited as long as the effect of the present invention can be obtained, and various active energies such as an ultraviolet curable resin (hereinafter referred to as UV curable resin), a visible light curable resin, and an electron beam curable resin are used.
• a linear curable resin can be used.
• a photoactive energy ray-curable resin it is preferable to use a UV curable resin because the curing process can be easily performed.
• the UV curable resin used in the present invention is not particularly limited, but a resin such as urethane acrylate, acrylic acrylate, or epoxy acrylate, and a resin modified with various substituents may be used alone or mixed. Can be used.
• a resin such as urethane acrylate, acrylic acrylate, or epoxy acrylate, and a resin modified with various substituents may be used alone or mixed.
• an acrylic acrylate resin is preferable because the titanium oxide-containing photocatalyst of the present invention can be suitably dispersed and the haze value can be lowered.
• various photopolymerization initiators may be blended to adjust the curing rate and the like.
• the photopolymerization initiator may be appropriately selected according to the active energy ray-curable resin to be blended, and is an alkylphenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an intramolecular hydrogen abstraction type photopolymerization initiator. , Oxyme ester-based photopolymerization agent, cationic photopolymerization initiator, and the like can be selected.
• the coating composition of the present invention can be coated on various substrates and cured to form a laminated body having antibacterial and antiviral properties on the surface.
• the base material is not particularly limited as long as the effects of the present invention can be obtained, but is a group that is required to have antibacterial and antiviral properties such as a touch panel, a splash prevention acrylic plate, a face shield, a handrail / doorknob, and a nail. It may be a material. Further, as the material thereof, plastics such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), cycloolefin polymer (COP), acrylic (PMMA), polycarbonate (PC), metals, wood, paper and the like can be appropriately used. ..
• TAC triacetyl cellulose
• PET polyethylene terephthalate
• COP cycloolefin polymer
• acrylic PMMA
• PC polycarbonate
• the coating composition of the present invention preferably has a haze value of 55 or less after coating film formation measured using a haze meter NDH4000 manufactured by Nippon Denshoku Co., Ltd. so as not to impair the texture of the base material. It is more preferably 10 or less, more preferably 5 or less, and most preferably 5 or less.
• a haze value is more preferably 10 or less, more preferably 5 or less, and most preferably 5 or less.
• coating material according to the present invention examples include coating agents in the form of liquids, sprays and the like, and these can be appropriately used according to desired uses.
• additives can be added to the coating composition within the range having the effect of the present invention.
• these compounding components include solvents such as water and alcohol, and other antibacterial / antiviral agents.
• the binder resin for example, acrylic resin, urethane resin, phenol resin, polyester resin, epoxy resin and the like can be used. These binder resins may be used alone or in combination of two or more.
• the coating composition of the present invention it is possible to impart a coating layer exhibiting long-lasting antibacterial and antiviral properties to various objects by a simple operation. Furthermore, it is possible to impart antibacterial and antiviral properties that are safe for the human body to various base materials without impairing the texture of the base material.
• Preparation Example 1 (1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method (sulfuric acid method) c) Physical properties / BET specific surface area: 9.0 m 2 / g -Rutilation rate: 95.4% -Primary particle diameter: 0.13 ⁇ m (2) Manufacturing process a) Mixing process (reaction process) 600 parts by mass of titanium oxide, 8 parts by mass of copper (ii) chloride dihydrate, and 900 parts by mass of water were mixed in a stainless steel container.
• Preparation Example 2 As titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method (sulfuric acid method) c) Physical properties / BET specific surface area: 9.0 m 2 / g -Rutilation rate: 95.4% ⁇ Primary particle diameter: 0.4 ⁇ m The same operation as in Preparation Example 1 was carried out except that titanium oxide was used, to obtain a titanium oxide composition (B) containing titanium oxide on which a divalent copper compound was supported.
• Preparation Example 3 As titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method (sulfuric acid method) c) Physical properties / BET specific surface area: 9.0 m 2 / g -Rutilation rate: 95.4% -Primary particle size: 0.92 ⁇ m The same operation as in Preparation Example 1 was carried out except that titanium oxide was used, to obtain a titanium oxide composition (C) containing titanium oxide on which a divalent copper compound was supported.
• Preparation Example 4 As titanium oxide a) Crystalline rutile type titanium oxide b) Manufacturing method: Gas phase method c) Physical characteristics / BET specific surface area: 9.0 m 2 / g ⁇ Rutileization rate: 70.0% -Primary particle diameter: 0.13 ⁇ m The same operation as in Preparation Example 1 was carried out except that titanium oxide was used, to obtain a titanium oxide composition (D) containing titanium oxide on which a divalent copper compound was supported.
• Adjustment example 5 In Adjustment Example 1, the same operation as in Adjustment Example 1 was carried out except that iron (ii) chloride was used instead of copper (ii) dihydrate, and the titanium oxide carrying the divalent iron compound was contained. A titanium oxide composition (E) was obtained.
• Preparation Example 6 A photocatalytic titanium oxide (ST-41 manufactured by Ishihara Sangyo Co., Ltd., primary particle diameter 0.14 ⁇ m) was used as the titanium oxide composition (F).
• Tables 1 and 2 show the average particle sizes of the titanium oxide compositions (A) to (F) and the comparatively adjusted product.
• Example 1 19 parts by mass of the obtained titanium oxide composition (A), 1 part by mass of trimethoxysilylpropyl methacrylate and 80 parts by mass of methyl ethyl ketone were dispersed with a paint conditioner to obtain a titanium oxide dispersion liquid (A).
• the coating material a 5 parts by mass of the dispersion liquid (A), 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305” manufactured by Toagosei Co., Ltd.), 1-hydroxycyclohexylphenyl ketone ("RUNECURE 1104" manufactured by BASF Japan Ltd.) A coating material was produced by mixing 4 parts by mass and 15 parts by mass of toluene.
• the coating material b 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305” manufactured by Toagosei Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexylphenylketone ("RUNTECURE 1104" manufactured by BASF Japan, Ltd.), 20 parts by mass of toluene. was mixed to produce a coating material.
• pentaerythritol triacrylate for example, "Aronix M305” manufactured by Toagosei Co., Ltd.
• RUNTECURE 1104" 1-hydroxycyclohexylphenylketone manufactured by BASF Japan, Ltd.
• a coating material b was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 8 ⁇ m, dried at 60 ° C. for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film.
• a coating material a was further applied onto this coating film so as to have a coating film thickness of 0.1 ⁇ m, and cured in the same manner to obtain a coating film of Example 1.
• Example 2 The same operation as in Example 1 was performed except that the titanium oxide composition (B) was used instead of the titanium oxide composition (A) to obtain a coating film of Example 2.
• Example 3 In Example 1, the coating material b was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 7.6 ⁇ m, and the coating material a was further applied to have a coating film thickness of 0.5 ⁇ m.
• the coating film of Example 3 was obtained by curing in the same manner as in Example 1.
• Example 4 19 parts by mass of the obtained titanium oxide composition (A), 1 part by mass of trimethoxysilylpropyl methacrylate and 80 parts by mass of methyl ethyl ketone were dispersed with a paint conditioner to obtain a titanium oxide dispersion liquid (A).
• the coating material c 5 parts by mass of the dispersion liquid (A), 50 parts by mass of pentaerythritol triacrylate (“Aronix M305” manufactured by Toa Synthetic Co., Ltd.), 52 parts by mass of acrylic acrylate (“LUXYDIR 6840”, DIC Corporation), A coating material was produced by mixing 4 parts by mass of 1-hydroxycyclohexylphenyl ketone (“RUNTECURE 1104” manufactured by BASF Corporation) and 15 parts by mass of toluene.
• a coating material was produced by mixing 4 parts by mass of 1-hydroxycyclohexylphenyl ketone (“RUNTECURE 1104” manufactured by BASF Corporation) and 15 parts by mass of toluene.
• the coating material d 50 parts by mass of pentaerythritol triacrylate (“Aronix M305” manufactured by Toagosei Corporation), 52 parts by mass of acrylic acrylate (“LUXYDIRV6840” manufactured by DIC Corporation), 1-hydroxycyclohexylphenylketone (manufactured by BASF Corporation). "RUNTECURE 1104") A coating material in which 4 parts by mass and 20 parts by mass of toluene were mixed was manufactured.
• a coating material d was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 8 ⁇ m, dried at 60 ° C. for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film.
• a coating material c was further applied onto this coating film so as to have a coating film thickness of 0.1 ⁇ m, and cured in the same manner to obtain a coating film of Example 4.
• Example 5 19 parts by mass of the obtained titanium oxide composition (A), 1 part by mass of trimethoxysilylpropyl methacrylate and 80 parts by mass of methyl ethyl ketone were dispersed with a paint conditioner to obtain a titanium oxide dispersion liquid (A).
• the coating material e 5 parts by mass of the dispersion liquid (A), 70 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305” manufactured by Toa Synthetic Co., Ltd.), and a silica dispersion liquid (for example, “MEK-AC” of Nissan Chemical Industry Co., Ltd.) -2140Z ") 13 parts by mass, 1-hydroxycyclohexylphenylketone (“RUNTECURE 1104" manufactured by BASF Corporation) 4 parts by mass, and 15 parts by mass of toluene were mixed to produce a coating material.
• pentaerythritol triacrylate for example, "Aronix M305" manufactured by Toa Synthetic Co., Ltd.
• a silica dispersion liquid for example, "MEK-AC” of Nissan Chemical Industry Co., Ltd.) -2140Z
• the coating material f 70 parts by mass of pentaerythritol triacrylate (“Aronix M305” manufactured by Toa Synthetic Co., Ltd.), 13 parts by mass of silica dispersion (for example, “MEK-AC-2140Z”, Nissan Chemical Industries, Ltd.), 1-hydroxycyclohexyl A coating material was produced by mixing 4 parts by mass of phenylketone (“RUNECURE 1104” manufactured by BASF Corporation) and 20 parts by mass of toluene.
• a coating material f was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 8 ⁇ m, dried at 60 ° C. for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film.
• a coating material e was further applied onto this coating film so as to have a coating film thickness of 0.1 ⁇ m, and cured in the same manner to obtain a coating film of Example 5.
• Example 6 The same operation as in Example 1 was performed except that the titanium oxide composition (C) was used instead of the titanium oxide composition (A) to obtain the coating film of Example 6.
• Example 7 19 parts by mass of the obtained titanium oxide composition (A), 1 part by mass of trimethoxysilylpropyl methacrylate and 60 parts by mass of methyl ethyl ketone were dispersed with a paint conditioner to obtain a titanium oxide dispersion liquid (A2).
• the coating material a 5 parts by mass of the dispersion liquid (A2), 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305” manufactured by Toagosei Co., Ltd.), 1-hydroxycyclohexylphenylketone ("RUNTECURE 1104" manufactured by BASF Japan Ltd.) A coating material was produced by mixing 4 parts by mass and 15 parts by mass of toluene.
• the coating material a was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 8.1 ⁇ m, and cured in the same manner to obtain the coating film of Example 1.
• Example 8 19 parts by mass of the obtained titanium oxide composition (A), 1 part by mass of trimethoxysilylpropyl methacrylate and 60 parts by mass of methyl ethyl ketone were dispersed with a paint conditioner to obtain a titanium oxide dispersion liquid (A2).
• the coating material a 12 parts by mass of the dispersion liquid (A2), 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305” manufactured by Toagosei Co., Ltd.), 1-hydroxycyclohexylphenylketone ("RUNTECURE 1104" manufactured by BASF Japan Ltd.)
• a coating material was produced by mixing 4 parts by mass and 8 parts by mass of toluene.
• a coating material a was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 8.1 ⁇ m, and cured in the same manner to obtain a coating film of Example 1.
• Example 9 The same operation as in Example 1 was performed except that the titanium oxide composition (D) was used instead of the titanium oxide composition (A) to obtain a coating film of Example 9.
• Example 10 The same operation as in Example 1 was performed except that the titanium oxide composition (E) was used instead of the titanium oxide composition (A) to obtain a coating film of Example 10.
• Example 10 The same operation as in Example 1 was performed except that the titanium oxide composition (F) was used instead of the titanium oxide composition (A) to obtain the coating film of Example 11.
• a comparative coating material 5 parts by mass of the comparative dispersion, 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305” manufactured by Toagosei Co., Ltd.), 1-hydroxycyclohexylphenyl ketone ("RUNTECURE 1104" manufactured by BASF Japan Ltd.) A coating material in which 4 parts by mass and 15 parts by mass of toluene were mixed was produced.
• the comparative coating material b 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305” manufactured by Toagosei Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexylphenylketone ("RUNTECURE 1104" manufactured by BASF Japan, Ltd.), 20 parts by mass of toluene. A coating material in which parts were mixed was manufactured.
• pentaerythritol triacrylate for example, "Aronix M305” manufactured by Toagosei Co., Ltd.
• RUNTECURE 1104" 1-hydroxycyclohexylphenylketone manufactured by BASF Japan, Ltd.
• a comparative coating material was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 8 ⁇ m, dried at 60 ° C. for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film.
• a comparative coating material was further applied onto this coating film so as to have a coating film thickness of 0.1 ⁇ m, and cured in the same manner to obtain a coating film of Comparative Example 1.
• the prepared Examples 1 to 10, Comparative Example 1, and Reference Example 1 were subjected to an antiviral test, a haze value measurement test, and a scratch resistance test and evaluation by the following methods.
• Antiviral tests were performed in accordance with JIS R 1756: 2020.
• the antiviral property was inactivated by the value obtained by the following formula for the sample after irradiation for 4 hours using a light source obtained by cutting the wavelength of 400 nm or less with an N-113 filter on the coating films obtained in Examples and Comparative Examples.
• Titanium oxide composition (A) 19 parts by mass, 1 part by mass of trimethoxysilylpropyl methacrylate and 80 parts by mass of methyl ethyl ketone were dispersed with a paint conditioner to obtain a titanium oxide dispersion liquid (X).
• Pentaerythritol triacrylate (“Aronix M305” manufactured by Toagosei Co., Ltd.) 21.5 parts by mass, aliphatic urethane acrylate (“Miramer PU610” manufactured by Toyo Chemicals Co., Ltd.) 21.5 parts by mass, 1-hydroxycyclohexylphenyl ketone (BASF)
• the coating material b-1 was manufactured by mixing 2 parts by mass and 55 parts by mass of MEK (“RUNECURE 1104”) manufactured by the company.
• titanium oxide dispersion liquid (X) was added to 10 parts by mass of the coating material b-1 and mixed to produce the coating material a-1.
• a coating material b-1 was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 8 ⁇ m, dried at 60 ° C. for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film.
• a coating material a-1 was further applied onto this coating film so as to have a coating film thickness of 0.1 ⁇ m, and cured in the same manner to obtain a coating film of Example 12.
• Example 13 to 15 Same as Example 12 except that the coating materials a-2 to a-4 in which the amount of the titanium oxide dispersion (X) added was 1.5 parts by mass, 2.5 parts by mass, and 5.0 parts by mass, respectively, were used. Then, the coating films of Examples 13 to 15 were obtained.
• Example 16 to 19 Comparative Example 2
• the coating materials a-1 to a-4 are coated on the lower layer by reversing the coating order of any of the coating materials a-1 to a-4 and the coating material b-1.
• the coating films of Examples 16 to 19 were obtained in the same manner except that the material b-1 was applied to the upper layer. Further, the coating film of Comparative Example 2 was obtained in the same manner as in Example 12 except that the coating material a-1 was not applied.
• the prepared Examples 12 to 19 and Comparative Example 2 were subjected to an anti-virus test, a haze value measurement, and a scratch resistance (SW resistance) test by the following methods in the same manner as described above.
• the transmittance was measured as follows. The results are also shown in Table 3.
• titanium oxide dispersion liquid (X) was added to 10 parts by mass of the coating material b-10 and mixed to produce the coating material a-10.
• a coating material b-10 was applied to a triacetyl cellulose film having a thickness of 60 ⁇ m so as to have a coating film thickness of 8 ⁇ m, dried at 60 ° C. for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film.
• a coating material a-10 was further applied onto this coating film so as to have a coating film thickness of 0.1 ⁇ m, and cured in the same manner to obtain a coating film of Example 20.
• Example 21 to 27, Comparative Example 3 Same as in Example 20 except that the coating materials a-11 to a-13 in which the amount of the titanium oxide dispersion (X) added was 1.5 parts by mass, 2.5 parts by mass, and 5.0 parts by mass, respectively, were used.
• the coating films of Examples 21 to 23 were obtained.
• the coating films of Examples 24 to 27 were obtained in the same manner as in Examples 20 to 23 except that the layer made of the coating material b-10 was not provided.
• a coating film of Comparative Example 3 was obtained in the same manner as in Example 24 except that b-10 was used as the coating material.
• the coating composition of the present invention can impart excellent antiviral properties even when the types of the active energy ray-curable resins are different. ..

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