Coating composition

Abstract

The present invention addresses the problem of providing a coating composition capable of providing, on various objects with a simple operation, a coating layer that exerts sustained antimicrobial and antiviral properties over a long period of time.　The present invention solves the problem by a coating composition characterized by containing a titanium oxide-containing photocatalyst. The present invention may also be characterized in that the titanium oxide-containing photocatalyst supports a metallic compound on the catalyst surface, that the metallic compound is a divalent copper compound, or that the coating composition additionally contains an actinic ray curable resin. The present invention pertains to a laminate obtained by coating the surface of a substrate with any one of such coating compositions and curing the same.

Description

Technical Field

[0001] The present invention relates to a coating composition characterized by containing a titanium oxide-containing photocatalyst. This application claims priority based on Japanese Patent Application No. 2020-166850 filed in Japan on October 1, 2020, and the contents thereof are incorporated herein by reference.

Background Art

[0002] In recent years, various viruses and bacteria such as the novel coronavirus have spread, and the demand for products with antibacterial and antiviral properties has increased throughout society. There is a particularly high demand for products that are touched by many people's hands or are used frequently, but it is time-consuming and costly to change all conventional facilities and articles to those with antibacterial and antiviral effects, so there is a need for products that can impart these properties in a simple manner. Conventionally used antibacterial and antiviral agents include various alcohol agents, quaternary ammonium salt compounds, silver-based compounds, copper-based compounds, etc. However, these do not fully meet the required characteristics of the market, such as irritation to the skin, reduction of antibacterial and antiviral properties over time, deterioration due to oxidation, etc., which damage the appearance, or impair the texture of the substrate when coating the surface (see, for example, Patent Document 1). On the other hand, photocatalysts using titanium oxide are less irritating to the human body and maintain antibacterial and antiviral performance over a long period, so expectations for practical application are increasing (see Patent Document 2).

[0003] However, photocatalysts using titanium oxide have not been sufficiently developed for their applications, and there has been a problem that their usefulness has not been demonstrated.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

[0005] The present invention relates to a coating composition containing a titanium oxide-containing photocatalyst.

[0006] The present invention further relates to the coating composition, wherein the titanium oxide-containing photocatalyst has a metal compound supported on the catalyst surface.

[0007] The present invention further relates to the coating composition, wherein the metal compound is a divalent copper compound in addition to the above features.

[0008] The present invention relates to an invention, wherein the coating composition contains an active energy ray-curable resin.

[0009] The present invention further relates to a laminate obtained by applying and curing the coating composition on the surface of a substrate. MEANS FOR SOLVING THE PROBLEMS

[0010] The present invention provides a coating composition containing a titanium oxide-containing photocatalyst having antibacterial and antiviral actions. EFFECTS OF THE INVENTION

[0011] According to the coating composition of the present invention, a coating layer that exhibits long-term and continuous antibacterial and antiviral properties can be imparted to various objects by a simple operation, and antibacterial and antiviral properties can be imparted to various substrates.

[0012] In addition, the coating composition of the present invention has a low haze value, so it does not impair the texture of the substrate, and further does not cause absorption into the human body, so it is a coating composition that is safe for the human body.

Mode for Carrying Out the Invention

[0013] The coating composition of the present invention may be any composition that can form a coating layer capable of protecting the surface of an object to be coated by performing active energy ray irradiation such as ultraviolet ray irradiation or electromagnetic ray irradiation, or other treatments such as drying.

[0014] The coating composition of the present invention contains a titanium oxide-containing catalyst, and its composition is not particularly limited as long as it can coat an object, but it preferably contains a curable raw material capable of forming a stable coating layer.

[0015] As the coating method of the coating composition of the present invention, it is not particularly limited as long as the effects of the present invention can be obtained, but various coating methods such as a spray method, a dip method, and other coating methods using various printing machines and coaters can be selected.

[0016] The coating composition in the present invention is not particularly limited as long as it is applied and cured by those skilled in the art for the purpose of imparting antibacterial and antiviral properties to an object to be coated, and it contains various raw materials according to desired properties such as high hardness, water repellency, oil repellency, slipperiness, and blue light cut, and various functions other than antibacterial and antiviral properties may be imparted.

[0017] 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 not particularly limited as long as it contains titanium oxide and has a photoreactivity that exhibits antibacterial and antiviral properties when irradiated with light such as visible light and ultraviolet light, but a titanium oxide-containing photocatalyst having a metal compound supported on its surface is preferred because more suitable antibacterial and antiviral properties can be obtained.

[0018] As the titanium oxide used in the present invention, for example, rutile-type titanium oxide, anatase-type titanium oxide, brookite-type titanium oxide, etc. can be used. These titanium oxides may be used alone or in combination of two or more. Among these, from the viewpoint of having excellent photocatalytic activity in the visible light region, it is preferable to contain rutile-type titanium oxide.

[0019] As the content rate (rutile ratio) of the rutile-type titanium oxide, from the viewpoint of obtaining more excellent antiviral properties in bright and dark places, decomposability of organic compounds in bright places, and photoreactivity, it is preferably 15 mol% or more, more preferably 50 mol% or more, and still more preferably 90 mol% or more.

[0020] As the method for producing the titanium oxide, generally, a liquid phase method and a gas phase method are known, and the present invention may use titanium oxide produced by any method. The liquid phase method is a method of obtaining titanium oxide by hydrolyzing or neutralizing and firing titanyl sulfate obtained from a solution in which raw ore such as ilmenite ore is dissolved. The gas phase method is a method of obtaining titanium oxide by a gas phase reaction between titanium tetrachloride obtained by chlorinating raw ore such as rutile ore and oxygen. As a method for distinguishing titanium oxide produced by both methods, analyzing its impurities can be mentioned. Titanium oxide produced by the liquid phase method contains zirconium, niobium, etc. derived from impurities in ilmenite ore in the product. On the other hand, in the gas phase method, since there is a step of purifying titanium tetrachloride to remove impurities, these impurities are hardly contained in the titanium oxide.

[0021] Although titanium oxide produced by the gas-phase method has the advantage of being able to generate a uniform particle size, since it is difficult to generate secondary aggregates, it is considered that the viscosity of the mixed solution during the reaction process increases due to the high apparent specific surface area. On the other hand, titanium oxide (a) produced by the liquid-phase method is considered to generate gentle secondary aggregates in the firing process, and the cohesive force is small with respect to the specific surface area (BET value) caused by primary particles, and it is possible to suppress the viscosity of the mixed solution. For the above reasons, as the titanium oxide, titanium oxide produced by the liquid-phase method is preferable from the viewpoint of further improving productivity.

[0022] As the BET specific surface area of the titanium oxide, from the viewpoint of obtaining more excellent antiviral properties and photoreactivity, the range of 1 to 200 m 2 / g is preferable, the range of 3 to 100 m 2 / g is more preferable, the range of 4 to 70 m 2 / g is more preferable, the range of 8 to 50 m 2 / g is further preferable, and from the viewpoint of further enhancing the productivity of the antiviral agent, the range of 7.5 to 9.5 m 2 / g is most preferable.

[0023] As the primary particle size of the titanium oxide, from the viewpoint of obtaining more suitable antiviral properties and photoreactivity, the range of 0.01 to 1.5 μm is preferable, and the range of 0.02 to 0.5 μm is more preferable. The measurement method of the primary particle size of the titanium oxide is a value measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each titanium oxide are measured, and the average is taken as the particle diameter of the primary particles. Next, for 100 or more titanium oxide particles, the cube of the particle diameter obtained by approximating the volume (weight) of each particle is obtained, and the volume average particle diameter is taken as the average primary particle diameter.

[0024] In addition, as the visible light-responsive photocatalyst, it is preferable to use a titanium oxide supported with a metal compound from the viewpoint of further improving the photocatalytic activity in the visible light region and easily exhibiting antiviral properties under practical indoor light.

[0025] As 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. As the metal compound to be supported on titanium oxide, for example, a copper compound, an iron compound, a tungsten compound, etc. can be used. Among these, a copper compound is preferable, and a divalent copper compound is more preferable from the viewpoint of obtaining more excellent antibacterial and antiviral properties. The method for supporting the metal compound on the titanium oxide is not particularly limited, and known methods can be used.

[0026] When the titanium oxide-containing photocatalyst supports a metal compound on the catalyst surface as described above (hereinafter referred to as "metal-supported titanium oxide-containing photocatalyst"), the primary particle size is preferably in the range of 0.01 to 1.5 μm, more preferably in the range of 0.02 to 0.5 μm, from the viewpoint of obtaining more suitable antiviral properties and handleability. The measurement method of the primary particle size of the metal-supported titanium oxide-containing photocatalyst is a value measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each metal-supported titanium oxide-containing photocatalyst are measured, and the average is taken as the particle size of the primary particles. Next, for 100 or more titanium oxide particles, the volume (weight) of each particle is approximated by the cube of the obtained particle size, and the volume average particle diameter is taken as the average primary particle size.

[0027] Next, a method for supporting a divalent copper compound on titanium oxide, which is the most preferable embodiment as the titanium oxide-containing photocatalyst, will be described.

[0028] Examples of the method for supporting a divalent copper compound on the titanium oxide include a method having a mixing step of titanium oxide containing rutile-type titanium oxide, a divalent copper compound raw material, water, and an alkaline substance.

[0029] As the concentration of the titanium oxide in the mixing step, a range of 3 to 40 parts by mass is preferable. In the present invention, when titanium oxide produced by a liquid phase method is used, even if the concentration of titanium oxide is increased, a mixing step with good handleability can be performed. Specifically, when the concentration of the titanium oxide is in the range exceeding 25 parts by mass and 40 parts by mass or less, the mixing step can be performed particularly well.

[0030] As the divalent copper compound raw material, for example, a divalent copper inorganic compound, a divalent copper organic compound, or the like can be used.

[0031] Examples of the divalent copper inorganic compound include inorganic acid salts of divalent copper such as copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate; halides of divalent copper such as copper chloride, copper fluoride, and copper bromide; copper oxide, copper sulfide, azurite, malachite, copper azide, and the like. These compounds may be used alone or in combination of two or more.

[0032] Examples of the divalent copper organic compound include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper myristate, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, copper mellitate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, copper acetylacetonate, copper ethyl acetoacetate, copper isovalerate, copper β -resorcylate, copper diacetate, copper formylsuccinate, copper salicylamine, copper bis(2-ethylhexanoate), copper sebacate, copper naphthenate, copper oxine, copper acetylacetonate, copper ethyl acetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, copper dimethyldithiocarbamate, etc. These compounds may be used alone or in combination of two or more kinds.

[0033] Among those described above, the divalent copper compound is preferably one represented by the following general formula (1). CuX2(1) (In formula (1), X represents a halogen atom, CH3COO, NO3, or (SO4) 1 / 2 .)

[0034] More preferably, X in the formula (1) is a halogen atom, and particularly preferably a chlorine atom.

[0035] 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, more preferably in the range of 0.1 to 15 parts by mass, and still more preferably in the range of 0.3 to 10 parts by mass with respect to 100 parts by mass of the titanium oxide.

[0036] The water is a solvent in the mixing step and is preferably used alone, but may contain other solvents as necessary. Examples of the other solvents include 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, tetrahydrofuran, etc. These solvents may be used alone or in combination of two or more.

[0037] Examples of the alkaline substance include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, basic surfactants, etc., and it is preferable to use sodium hydroxide.

[0038] From the viewpoint of easy reaction control, the alkaline substance is preferably added as a solution. The concentration of the alkaline solution to be added is preferably in the range of 0.1 to 5 mol / L, more preferably in the range of 0.3 to 4 mol / L, and even more preferably in the range of 0.5 to 3 mol / L.

[0039] In the mixing step, the titanium oxide, divalent copper compound raw material, water, and alkaline substance may be mixed. For example, first, titanium oxide is mixed with water and stirred as necessary, then the divalent copper compound raw material is mixed and stirred, and thereafter, an alkaline substance is added and stirred. By this mixing step, the divalent copper compound derived from the divalent copper compound raw material is supported on the titanium oxide.

[0040] The total stirring time in the mixing step is not particularly limited as long as the effects of the present invention can be obtained. For example, it may be 5 to 120 minutes, preferably 10 to 60 minutes. The temperature during the mixing step may be, for example, in the range of room temperature to 70°C.

[0041] The pH of the mixture after mixing and stirring the titanium oxide, divalent copper compound raw material, and water, and then mixing and stirring an alkaline substance is preferably in the range of 8 to 11, more preferably in the range of 9.0 to 10.5, from the viewpoint that the loading of the divalent copper compound on the titanium oxide is good.

[0042] After the mixing step is completed, the mixed liquid can be separated as a solid content. Examples of the method for performing the separation include filtration, sedimentation separation, centrifugal separation, evaporation to dryness, etc., but filtration is preferred. The separated solid content may then be washed with water, crushed, classified, etc. as necessary.

[0043] After obtaining the solid content, it is preferable to heat-treat the solid content from the viewpoint that the divalent copper compound derived from the divalent copper compound raw material supported on the titanium oxide can be more firmly bonded. 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.

[0044] By the above method, a titanium oxide composition containing titanium oxide supporting a divalent copper compound is obtained. The loading 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 the titanium oxide, from the viewpoints of antiviral properties and photocatalytic activity. The loading amount of the divalent copper compound can be adjusted by the amount of the divalent copper compound raw material used in the mixing step.

[0045] In the coating composition of the present invention, the content of the titanium oxide-containing catalyst is not particularly limited as long as the effects of the present invention can be obtained. However, since the antibacterial and antiviral effects can be preferably obtained, it is preferably contained in an amount of 0.01 part by mass or more based on the whole coating composition. Since the antibacterial and antiviral effects can be preferably obtained, it is more preferably contained in an amount of 0.02 to 5 parts by mass. Since the increase in the haze value is suppressed and the antiviral effect can be obtained, it is most preferably contained in an amount of 0.02 to 2 parts by mass.

[0046] The coating composition of the present invention can contain various resins, pastes, etc. within the range where the effects of the present invention can be obtained in order to improve the coating performance. As the resin, various resins such as thermoplastic resins, thermosetting resins, and active energy ray-curable resins can be used, but it is preferable to use an active energy ray-curable resin because a coating layer can be easily formed on various substrates.

[0047] The active energy ray-curable resin is not particularly limited within the range where the effects of the present invention can be obtained, and various active energy ray-curable resins such as ultraviolet-curable resins (hereinafter referred to as UV-curable resins), visible light-curable resins, and electron beam-curable resins can be used. When using a photoactive energy ray-curable resin in the present invention, it is preferable to use a UV-curable resin because the curing treatment can be easily performed.

[0048] The UV-curable resin used in the present invention is not particularly limited, but resins such as urethane acrylate, acrylic acrylate, and epoxy acrylate, and resins modified with various substituents on these resins can be used alone or in combination. As the UV-curable resin, an acrylic acrylate resin is preferable because the titanium oxide-containing photocatalyst of the present invention can be preferably dispersed therein and the haze value can be reduced.

[0049] When an active energy ray-curable resin is blended in the present invention, various photoinitiators may be blended to adjust the curing rate and the like. The photoinitiator may be appropriately selected according to the active energy ray-curable resin to be blended, and can be selected from alkylphenone-based photoinitiators, acylphosphine oxide-based photoinitiators, intramolecular hydrogen abstraction-type photoinitiators, oxime ester-based photoinitiators, cationic photoinitiators, etc.

[0050] The coating composition of the present invention can be made into a laminate having antibacterial and antiviral properties imparted to the surface by coating and curing on various substrates. The substrate is not particularly limited as long as the effects of the present invention can be obtained, but any substrate that requires antibacterial and antiviral properties such as touch panels, anti-droplet acrylic plates, face shields, handrails and doorknobs, and nails may be used. Also, as the material, plastics such as triacetyl cellulose (TAC), polyethylene terephthalate (PET), cycloolefin polymer (COP), acrylic (PMMA), polycarbonate (PC), metals, woods, papers, etc. can be appropriately used.

[0051] The coating composition of the present invention preferably has a haze value of 55 or less, more preferably 25 or less, still more preferably 10 or less, and most preferably 5 or less after film formation measured using a haze meter NDH4000 manufactured by Nippon Denshoku Industries Co., Ltd., so as not to impair the texture of the substrate. By adjusting the haze value to be within the above range, it is possible to maintain a suitable design without impairing the texture of the substrate even when the coating composition of the present invention is coated and cured on the substrate. Also, for substrates that require transparency such as the display surface, antibacterial and antiviral properties can be imparted without disturbing the display.

[0052] Next, specific embodiments of the coating composition according to the present invention will be described.

[0053] Examples of the form of the coating material according to the present invention include coating agents in the form of liquid agents, spray agents, etc., and these can be appropriately used according to the desired application.

[0054] In addition to the above-mentioned additive components, various additives can be incorporated into the coating composition within the scope where the effects of the present invention are achieved. Examples of these compounding components include solvents such as water and alcohol, and other antibacterial and antiviral agents. As the binder resin, for example, acrylic resin, urethane resin, phenol resin, polyester resin, epoxy resin, etc. can be used. These binder resins may be used alone or in combination of two or more.

[0055] As described above, according to the coating composition of the present invention, a coating layer that exhibits long-term and continuous antibacterial and antiviral properties can be imparted to various objects by a simple operation. Furthermore, antibacterial and antiviral properties that are safe for the human body can be imparted to various substrates without impairing the texture of the substrate.

Examples

[0056] Hereinafter, the present invention will be described in more detail using examples.

[0057] [Preparation Example 1]: (1) Titanium oxide a) Crystalline rutile-type titanium oxide b) Production method: Liquid phase method (sulfuric acid method) c) Physical property values · BET specific surface area: 9.0 m 2 / g · Rutile conversion rate: 95.4% · Primary particle size: 0.13 μm (2) Manufacturing process a) Mixing process (reaction process) 600 parts by mass of the 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. Next, the mixture was stirred with a stirrer ("Robomix" manufactured by Tokushu Kika Kogyo Co., Ltd.), and a 1 mol / L aqueous sodium hydroxide solution was added dropwise until the pH of the mixed solution reached 10. b) Dehydration process Qualitative filter paper (5C) was used for vacuum filtration to separate the solid content from the mixed solution, and further washing was carried out with ion-exchanged water. Subsequently, the washed solid was dried at 120 °C for 12 hours to remove moisture. After drying, a powdery titanium oxide composition was obtained using a mill ("Millcer" manufactured by Iwatani Sangyo Co., Ltd.). c) Heat treatment step Using a precision thermostat ("DH650" manufactured by Yamato Scientific Co., Ltd.), heat treatment was carried out at 450 °C for 3 hours in the presence of oxygen to obtain a titanium oxide composition (A) containing titanium oxide on which a divalent copper compound was supported.

[0058] [Preparation Example 2] As titanium oxide a) Crystalline rutile-type titanium oxide b) Production method: Liquid phase method (sulfuric acid method) c) Physical property values · BET specific surface area: 9.0 m 2 / g · Rutile conversion rate: 95.4% · Primary particle size: 0.4 μm The same operations as in Preparation Example 1 were carried out except that the titanium oxide was used, and a titanium oxide composition (B) containing titanium oxide on which a divalent copper compound was supported was obtained.

[0059] [Preparation Example 3] As titanium oxide a) Crystalline rutile-type titanium oxide b) Production method: Liquid phase method (sulfuric acid method) c) Physical property values · BET specific surface area: 9.0 m 2 / g · Rutile conversion rate: 95.4% · Primary particle size: 0.92 μm The same operations as in Preparation Example 1 were carried out except that the titanium oxide was used, and a titanium oxide composition (C) containing titanium oxide on which a divalent copper compound was supported was obtained.

[0060] [Preparation Example 4]: As titanium oxide a) Crystalline rutile-type titanium oxide b) Production method: Gas phase method c) Physical property values · BET specific surface area: 9.0 m 2 / g · Rutile ratio: 70.0% · Primary particle size: 0.13 μm The operation was carried out in the same manner as in Preparation Example 1 except that titanium oxide was used, and a titanium oxide composition (D) containing titanium oxide on which a divalent copper compound was supported was obtained.

[0061] [Preparation Example 5] In Preparation Example 1, the operation was carried out in the same manner as in Preparation Example 1 except that iron(II) chloride was used instead of copper(II) chloride dihydrate, and a titanium oxide composition (E) containing titanium oxide on which a divalent iron compound was supported was obtained.

[0062] [Preparation Example 6]: Photocatalytic titanium oxide (ST-41 manufactured by Ishihara Sangyo Co., Ltd. Primary particle size 0.14 μm) was used as the titanium oxide composition (F).

[0063] [Reference Preparation Example 1] Copper(I) oxide (primary particle size 0.15 μm) known to have an antiviral action described in WO2011 / 078203 was used as a reference control as a positive control.

[0064] The average particle diameters of the titanium oxide compositions (A) to (F) and the comparative control are described in Tables 1 to 2.

[0065] [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 (A).

[0066] As a coating material a, a coating material was produced by mixing 5 parts by mass of the dispersion (A), 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF SE), and 15 parts by mass of toluene.

[0067] As coating material b, a coating material was prepared by mixing 76 parts by mass of pentaerythritol triacrylate (e.g., "ARONIX M305" manufactured by Toagosei Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Corporation), and 20 parts by mass of toluene.

[0068] Coating material b was applied to a triacetyl cellulose film with a thickness of 60 μm so that the coating film thickness was 8 μm, dried at 60°C for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film. On this coating film, coating material a was further applied so that the coating film thickness was 0.1 μm, and cured in the same manner to obtain the coating film of Example 1.

[0069] [Example 2] The same operations as in Example 1 were performed except that titanium oxide composition (B) was used instead of titanium oxide composition (A) to obtain the coating film of Example 2.

[0070] [Example 3] In Example 1, coating material b was applied to a triacetyl cellulose film with a thickness of 60 μm so that the coating film thickness was 7.6 μm, and further coating material a was applied so that the coating film thickness was 0.5 μm, and then cured in the same manner as in Example 1 to obtain the coating film of Example 3.

[0071] [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 (A).

[0072] As coating material c, a coating material was prepared by mixing 5 parts by mass of the dispersion (A), 50 parts by mass of pentaerythritol triacrylate ("ARONIX M305" manufactured by Toagosei Co., Ltd.), 52 parts by mass of acrylic acrylate ("LUXYDIR 6840" manufactured by DIC Corporation), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Corporation), and 15 parts by mass of toluene.

[0073] As the coating material d, 50 parts by mass of pentaerythritol triacrylate (“ARONIX M305” manufactured by Toagosei Co., Ltd.), 52 parts by mass of acrylic acrylate (“LUXYDIR V6840” manufactured by DIC Corporation), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“RUNTECURE 1104” manufactured by BASF Corporation), and 20 parts by mass of toluene were mixed to produce a coating material.

[0074] The coating material d was applied to a 60 μm thick triacetyl cellulose film so that the coating film thickness was 8 μm, dried at 60° C. for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film. On this coating film, the coating material c was further applied so that the coating film thickness was 0.1 μm, and cured in the same manner to obtain the coating film of Example 4.

[0075] [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 (A).

[0076] As the coating material e, 5 parts by mass of the dispersion (A), 70 parts by mass of pentaerythritol triacrylate (for example, “ARONIX M305” manufactured by Toagosei Co., Ltd.), 13 parts by mass of a silica dispersion (for example, “MEK-AC-2140Z” manufactured by Nissan Chemical Industries, Ltd.), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“RUNTECURE 1104” manufactured by BASF Corporation), and 15 parts by mass of toluene were mixed to produce a coating material.

[0077] As the coating material f, 70 parts by mass of pentaerythritol triacrylate (“ARONIX M305” manufactured by Toagosei Co., Ltd.), 13 parts by mass of a silica dispersion (for example, “MEK-AC-2140Z” manufactured by Nissan Chemical Industries, Ltd.), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“RUNTECURE 1104” manufactured by BASF Corporation), and 20 parts by mass of toluene were mixed to produce a coating material.

[0078] A coating material f was applied to a 60-μm-thick triacetyl cellulose film to a coating film thickness of 8 μm, dried at 60°C for 60 seconds using a hot air dryer, and cured with a fusion lamp to obtain a coating film. On this coating film, a coating material e was further applied to a coating film thickness of 0.1 μm and cured in the same manner to obtain the coating film of Example 5.

[0079] [Example 6] The same operations as in Example 1 were carried out except that titanium oxide composition (C) was used instead of titanium oxide composition (A), and the coating film of Example 6 was obtained.

[0080] [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 (A2).

[0081] As coating material a, a coating material was produced by mixing 5 parts by mass of the dispersion (A2), 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Corporation), and 15 parts by mass of toluene.

[0082] Coating material a was applied to a 60-μm-thick triacetyl cellulose film to a coating film thickness of 8.1 μm and cured in the same manner to obtain the coating film of Example 1.

[0083] [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 (A2).

[0084] As the coating material a, a coating material was produced by mixing 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.), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Corporation), and 8 parts by mass of toluene. The coating material a was applied to a 60-μm-thick triacetyl cellulose film to a coating film thickness of 8.1 μm and cured in the same manner to obtain the coating film of Example 1.

[0085] Reference Example 9] The same operations as in Example 1 were carried out except that the titanium oxide composition (D) was used instead of the titanium oxide composition (A). Reference Example A coating film of 9 was obtained.

[0086] Reference Example 10] The same operations as in Example 1 were carried out except that the titanium oxide composition (E) was used instead of the titanium oxide composition (A). Reference Example A coating film of 10 was obtained.

[0087] Reference Example 11 The same operations as in Example 1 were carried out except that the titanium oxide composition (F) was used instead of the titanium oxide composition (A). Reference Example A coating film of 11 was obtained.

[0088] [Comparative Example 1] 1 part by mass of trimethoxysilylpropyl methacrylate and 99 parts by mass of methyl ethyl ketone were dispersed with a paint conditioner to obtain a comparative dispersion liquid.

[0089] As a comparative coating material, a coating material was produced by mixing 5 parts by mass of the comparative dispersion liquid, 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Corporation), and 15 parts by mass of toluene.

[0090] ​​​​ As a comparative coating material b, a coating material was prepared by mixing 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF SE), and 20 parts by mass of toluene.

[0091] The comparative coating material was applied to a 60-μm-thick triacetyl cellulose film so that the coating film thickness was 8 μm, dried at 60°C for 60 seconds using a hot air dryer, and cured using a fusion lamp to obtain a coating film. On this coating film, the comparative coating material was further applied so that the coating film thickness was 0.1 μm, and cured in the same manner to obtain the coating film of Comparative Example 1.

[0092] [Reference Example] The same operations as in Example 1 were performed except that a reference adjustment material was used instead of the titanium oxide composition (A), and a coating film of the reference example was obtained.

[0093] The prepared Examples 1 to 10, Comparative Example 1, and Reference Example , Reference Examples 9 to 11 were subjected to an antiviral property test, a haze value measurement test, and a scratch resistance test and evaluation by the following methods.

[0094] [Antiviral Property Test] An antiviral property test was conducted in accordance with JIS R 1756:2020. The antiviral property was evaluated by the value, inactivation degree, obtained by the following formula for the sample after 4-hour irradiation using a light source with a wavelength of 400 nm or less cut by an N-113 filter for the coating films obtained in the examples , Reference Example and comparative examples, and the antiviral property was evaluated according to the following criteria. Passing is defined as B or higher. Inactivation degree = log(N / N0) N = Infectious titer of the sample after the reaction N0 = Infectious titer of the inoculated phage A: Inactivation degree is 99.9% or higher B: Inactivation degree is 99% or higher and less than 99.9% C: Inactivation degree is 90% or lower

[0095] [Haze Value Measurement Test] Regarding the evaluation sample obtained above, in accordance with JIS test method K7136:2000, the haze value was measured using a haze meter ("NDH2000" manufactured by Nippon Denshoku Industries Co., Ltd.).

[0096] [Abrasion resistance test] The test piece film obtained above was cut into a rectangle of 30 cm × 2 cm, fixed to a plane friction tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) with a jig, and the damaged state of the test piece after performing 10 reciprocations at a load of 1 kg / cm2, a stroke of 10 cm, a speed of 20 cm / second using steel wool #0000 was visually observed, and the abrasion resistance (SW resistance) was evaluated according to the following criteria. A: No scratches B: A few scratches C: The entire test piece film is scratched but within the allowable range D: The entire test piece film is scratched and whitened.

[0097] Each example , Reference Example The evaluation results of the comparative examples are shown in Tables 1 to 2.

[0098]

Table 1

[0099]

Table 2

[0100] As described in Tables 1 to 2, according to the coating composition of the present invention, a coat layer that exhibits long-term continuous antibacterial and antiviral properties on various objects can be provided by a simple operation.

[0101] [Example 12] 19 parts by mass of a 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 (X).

[0102] 21.5 parts by mass of pentaerythritol triacrylate (“Aronix M305” manufactured by Toagosei Co., Ltd.), 21.5 parts by mass of aliphatic urethane acrylate (“Miramer PU610” manufactured by Toyo Chemicals Co., Ltd.), 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“RUNTECURE 1104” manufactured by BASF), and 55 parts by mass of MEK were mixed to produce coating material b-1.

[0103] Also, 0.5 part by mass of titanium oxide dispersion (X) was added to and mixed with 10 parts by mass of coating material b-1 to produce coating material a-1.

[0104] Coating material b-1 was applied to a 60-μm thick triacetyl cellulose film to a coating film thickness of 8 μm, dried at 60°C for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film. On this coating film, coating material a-1 was further applied to a coating film thickness of 0.1 μm and cured in the same manner to obtain the coating film of Example 12.

[0105] [Examples 13 to 15] Coating films of Examples 13 to 15 were obtained in the same manner as in Example 12, except that coating materials a-2 to a-4 in which the addition amounts of titanium oxide dispersion (X) were 1.5 parts by mass, 2.5 parts by mass, and 5.0 parts by mass, respectively, were used.

[0106] [Examples 16 to 19, Comparative Example 2] Coating films of Examples 16 to 19 were obtained in the same manner as in Examples 12 to 15, except that the coating order of any of coating materials a-1 to a-4 and coating material b-1 was reversed, and coating materials a-1 to a-4 were applied to the lower layer and coating material b-1 was applied to the upper layer. Also, a coating film of Comparative Example 2 was obtained in the same manner as in Example 12, except that coating material a-1 was not applied.

[0107] For the prepared Examples 12 to 19 and Comparative Example 2, antiviral tests, haze value measurements, and abrasion resistance (SW resistance) tests were carried out in the same manner as above. In addition, the transmittance was measured as follows. The results are also shown in Table 3.

[0108] [Transmittance measurement] For the evaluation samples obtained above, in accordance with JIS:K-7361-1(1997), the transmittance was measured using a haze meter.

[0109]

Table 3

[0110] [Example 20] 21.5 parts by mass of pentaerythritol triacrylate (“Aronix M305” manufactured by Toagosei Co., Ltd.), 21.5 parts by mass of bisphenol A epoxy diacrylate (“Miramer PE210” manufactured by Toyo Chemicals Co., Ltd.), 2 parts by mass of 1-hydroxycyclohexyl phenyl ketone (“RUNTECURE 1104” manufactured by BASF), and 55 parts by mass of MEK were mixed to produce Coating Material b-10.

[0111] In addition, 0.5 part by mass of titanium oxide dispersion (X) was added to and mixed with 10 parts by mass of Coating Material b-10 to produce Coating Material a-10.

[0112] Coating Material b-10 was applied to a 60-μm-thick triacetyl cellulose film to a coating film thickness of 8 μm, dried at 60°C for 60 seconds with a hot air dryer, and cured with a fusion lamp to obtain a coating film. On this coating film, Coating Material a-10 was further applied to a coating film thickness of 0.1 μm and cured in the same manner to obtain the coating film of Example 20.

[0113] [Examples 21 to 27, Comparative Example 3] Coating films of Examples 21 to 23 were obtained in the same manner as in Example 20, except that Coating Materials a-11 to a-13 with the addition amounts of titanium oxide dispersion (X) being 1.5 parts by mass, 2.5 parts by mass, and 5.0 parts by mass, respectively, were used. Further, coating films of Examples 24 to 27 were obtained in the same manner as in Examples 20 to 23, except that the layer of Coating Material b-10 was not provided. Furthermore, 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.

[0114] For the prepared Examples 20 to 27 and Comparative Example 3, antiviral property tests, haze value measurements, scratch resistance (SW resistance) tests, and transmittance measurements were carried out in the same manner as above. In addition, the transmittance was measured as follows. The results are also shown in Table 4.

[0115] [Table 4]

[0116] As is clear from the results shown in Tables 3 to 4, it was confirmed that the coating composition of the present invention can impart excellent antiviral properties even when the types of active energy ray-curable resins are different.

Claims

Claim 1 A coating composition comprising a titanium oxide-containing photocatalyst dispersion and an active energy ray-curable resin, wherein the titanium oxide-containing photocatalyst dispersion consists of a titanium oxide-containing photocatalyst, trimethoxysilylpropyl methacrylate, and an organic solvent, the titanium oxide-containing photocatalyst contains liquid-phase method titanium oxide and has a metal compound supported on the catalyst surface, and the metal compound is a divalent copper compound. Claim 2 The coating composition according to claim 1, wherein the active energy ray-curable resin is an acrylic acrylate resin. Claim 3 A laminate obtained by applying and curing the coating composition according to claim 1 or 2 on the surface of a substrate.

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