Compositions and laminates for coating

Abstract

The problem to be solved by this invention is to provide a coating composition that can impart a long-lasting antibacterial and antiviral coating to various objects through simple operation. This invention solves the aforementioned problem by using a coating composition characterized by containing a titanium dioxide-containing photocatalyst. Furthermore, this invention is also characterized by the titanium dioxide-containing photocatalyst having a metal compound supported on its surface, said metal compound being a divalent copper compound, and containing an active energy line curing resin, and relates to a laminate formed by applying these coating compositions to a substrate surface and then curing them.

Description

Technical Field

[0001] The present invention relates to a coating composition, which is 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 incorporates its content herein. Prior 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 effects in society as a whole is increasing. As such products, there are high requirements especially for places touched by a large number of people's hands or items with high usage frequencies. However, it is time-consuming and costly to change all previous equipment or items into those with antibacterial and antiviral effects. Therefore, there is a demand for products that can impart such properties by a simple method.

[0003] As previously used antibacterial and antiviral agents, there are various alcohol agents, quaternary ammonium salt compounds, silver-based compounds, copper-based compounds, etc. However, these cannot fully meet the required characteristics of the market due to their irritation to the skin, reduction of antibacterial and antiviral properties due to time-dependent changes, or damage to the appearance due to deterioration caused by oxidation, etc., and damage to the feel of the substrate during surface coating (for example, refer to Patent Document 1).

[0004] On the other hand, photocatalysts using titanium oxide are expected to be more practically applicable because they cause less irritation to the human body and maintain antibacterial and antiviral performance for a long time (refer to Patent Document 2).

[0005] However, photocatalysts using titanium oxide have not been fully developed for this application, and there is a problem that their usefulness has not been fully demonstrated.

[0006] [Prior Art Documents]

[0007] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2007-507407

[0009] [Patent Document 2] Japanese Patent Laid-Open No. 2013-166705 Summary of the Invention Problems to be Solved by the Invention

[0010] The present invention relates to a composition for coating, characterized in that it contains a titanium oxide-containing photocatalyst.

[0011] The present invention further relates to the composition for coating, characterized in that the titanium oxide-containing photocatalyst carries a metal compound on the catalyst surface.

[0012] The present invention relates to the composition for coating, which is further characterized in that, in addition to the previous features, the metal compound is a divalent copper compound.

[0013] The present invention relates to an invention, characterized in that the composition for coating contains an energy ray-curable resin.

[0014] The present invention further relates to a laminate formed by applying the composition for coating to the surface of a substrate and curing it. Means for Solving the Problems

[0015] The present invention provides a composition for coating, characterized in that it contains a titanium oxide-containing photocatalyst having antibacterial and antiviral effects. Advantages of the Invention

[0016] With the composition for coating according to the present invention, a coating layer that exhibits continuous antibacterial and antiviral properties over a long period can be imparted to various objects by a simple operation, and antibacterial and antiviral properties can be imparted to various substrates.

[0017] In addition, since the composition for coating of the present invention has a low haze value, it does not damage the feel of the substrate and does not cause absorption into the human body, so it is a composition for coating that is safe for the human body. Embodiments

[0018] The composition for coating of the present invention only needs to be subjected to energy ray irradiation such as ultraviolet irradiation or electron beam irradiation, or other drying treatments to form a coating layer that can protect the surface of the coated object.

[0019] If the composition for coating of the present invention contains a titanium oxide-containing photocatalyst and can be applied to an object, its composition is not particularly limited, but it preferably contains a curable raw material that can form a stable coating layer.

[0020] The coating method for the coating composition of the present invention is not particularly limited to the scope of achieving the effects of the present invention, and various coating methods such as spraying, dipping, and coating using various printing presses or coating machines can be selected.

[0021] The coating composition in this invention is not particularly limited if it is coated and hardened by those skilled in the art for the purpose of imparting antibacterial and antiviral properties to the object to be coated. It can contain various raw materials according to the desired properties such as high hardness, water repellency, oil repellency, lubricity, and blue light cut, thereby imparting various functions other than antibacterial and antiviral properties.

[0022] The coating composition of the present invention is characterized by containing a titanium oxide-containing photocatalyst. There is no particular limitation on the titanium oxide-containing photocatalyst used in the present invention, which contains titanium oxide and exhibits photoresponsiveness by receiving light such as visible light or ultraviolet light to exert antibacterial and antiviral properties. However, since more suitable antibacterial and antiviral properties can be obtained, it is preferable that a metal compound is supported on the surface of the titanium oxide-containing photocatalyst.

[0023] The titanium dioxide used in this invention may be, for example, rutile titanium dioxide, anatase titanium dioxide, brookite titanium dioxide, etc. These titanium dioxides may be used alone or in combination of two or more. Among these, rutile titanium dioxide is preferred in terms of exhibiting excellent photocatalytic activity in the visible light region.

[0024] The content of the rutile titanium dioxide (rutile content) is preferably 15 mol% or more, more preferably 50 mol% or more, and even more preferably 90 mol% or more, in order to obtain better antiviral properties in both light and dark, decomposition of organic compounds in light, and photosensitivity.

[0025] As methods for manufacturing titanium oxide, liquid-phase and gas-phase methods are generally known, and the present invention can use titanium oxide obtained by either method. The liquid-phase method involves hydrolyzing or neutralizing titanium oxysulfate obtained from a liquid containing raw materials such as ilmenite ore, followed by calcination to obtain titanium oxide. The gas-phase method refers to obtaining titanium oxide by reacting titanium tetrachloride, obtained by chlorinating raw materials such as rutile ore, with oxygen in a gas phase. Furthermore, as a way to distinguish titanium oxide produced by the two methods, methods for analyzing its impurities can be listed. Titanium oxide produced by the liquid-phase method contains impurities such as zirconium and niobium originating from ilmenite ore. In contrast, since the gas-phase method includes a step of refining titanium tetrachloride to remove impurities, titanium oxide contains almost none of these impurities.

[0026] While titanium oxide produced using the gas-phase method has the advantage of generating uniform particle size, it is difficult to form secondary agglomerates. Therefore, it is believed that the viscosity of the mixture during the reaction step increases due to the increased apparent specific surface area. In contrast, titanium oxide (a) produced using the liquid-phase method is believed to generate loose secondary agglomerates during the calcination step. Compared to the specific surface area (Brunauer-Emmett-Teller, BET value) caused by primary particles, it has low cohesion and can suppress the viscosity of the mixture. Based on the above reasons, titanium oxide produced using the liquid-phase method is preferred in terms of further improving productivity.

[0027] The BET specific surface area of ​​the titanium oxide is preferably in the range of 1 m² / g to 200 m² / g, more preferably in the range of 3 m² / g to 100 m² / g, more preferably in the range of 4 m² / g to 70 m² / g, and even more preferably in the range of 8 m² / g to 50 m² / g, in order to obtain better antiviral properties and photosensitivity. In order to further improve the productivity of the antiviral agent, the range of 7.5 m² / g to 9.5 m² / g is preferred.

[0028] The primary particle size of the titanium dioxide is preferably in the range of 0.01 μm to 1.5 μm, and more preferably in the range of 0.02 μm to 0.5 μm, to obtain more suitable antiviral properties and photosensitivity. Furthermore, the primary particle size of the titanium dioxide is a value determined by a method using a transmission electron microscope (TEM) to directly measure the size of the primary particles based on electron microscope images. Specifically, the minor axis and major axis of each primary particle of titanium dioxide are measured, and the average value is set as the particle size of that primary particle. Then, for more than 100 titanium dioxide particles, the volume (weight) of each particle is approximated by a cube of the calculated particle size, and the volume average particle size is set as the average primary particle size.

[0029] Furthermore, as the visible light responsive photocatalyst, it is preferable to use one that has a metal compound supported on titanium oxide to further improve the photocatalytic activity in the visible light region and easily exhibit antiviral properties under indoor light in practical applications.

[0030] The titanium dioxide-containing photocatalyst used in this invention is preferably one on which a metal compound is supported on the surface of the catalyst as described above. Examples of metal compounds supported on the titanium dioxide include copper compounds, iron compounds, and tungsten compounds. Among these, copper compounds are preferred, and more preferably divalent copper compounds, for better antibacterial and antiviral properties. There are no particular limitations on the method of supporting the metal compound on the titanium dioxide; known methods can be used.

[0031] As described above, when a metal compound is supported on the surface of a titanium oxide photocatalyst (hereinafter referred to as "metal-supported titanium oxide photocatalyst"), the primary particle size can obtain more suitable antiviral and treatment properties, preferably in the range of 0.01 μm to 1.5 μm, and more preferably in the range of 0.02 μm to 0.5 μm. Furthermore, the primary particle size of the metal-supported titanium oxide photocatalyst is a value determined by a transmission electron microscope (TEM) to directly measure the size of the primary particles based on electron microscope images. Specifically, the minor axis diameter and major axis diameter of the primary particles of each metal-supported titanium oxide photocatalyst are measured, and the average value is set as the particle size of that primary particle. Then, for more than 100 metal-supported titanium oxide photocatalyst particles, the volume (weight) of each particle is approximated by a cube of the calculated particle size, and the volume average particle size is set as the average primary particle size.

[0032] Next, the optimal state for a titanium oxide-containing photocatalyst, namely, the method of loading divalent copper compounds onto titanium oxide, will be explained.

[0033] As a method for loading the titanium oxide with a divalent copper compound, a method comprising mixing titanium oxide containing rutile titanium oxide, a divalent copper compound raw material, water, and an alkaline substance can be cited as an example.

[0034] The concentration of titanium oxide in the mixing step is preferably in the range of 3 parts by mass to 40 parts by mass. Furthermore, in the present invention, when using titanium oxide manufactured by liquid phase method, even if the concentration of titanium oxide is increased, the mixing step can be performed well. Specifically, the mixing step can be performed particularly well when the concentration of titanium oxide is in the range of more than 25 parts by mass and less than 40 parts by mass.

[0035] As raw materials for the divalent copper compound, divalent copper inorganic compounds, divalent copper organic compounds, etc., can be used, for example.

[0036] Examples of divalent copper inorganic compounds that can be used include: copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, ammonium copper sulfate, acetamiprid copper sulfate, ammonium copper chloride, copper pyrophosphate, copper carbonate, and other divalent copper inorganic acid salts; copper chloride, copper fluoride, copper bromide, and other divalent copper halides; copper oxide, copper sulfide, azurite, malachite, copper azide, etc. These compounds can be used alone or in combination of two or more.

[0037] Examples of divalent copper organic compounds that may be used include: copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper hexanoate, copper heptanoate, copper octanoate, nonanoate, copper decanoate, copper myristate, copper palmitate, copper pearlate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, and melamine acid. Copper, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipic acid, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, copper acetone, copper ethyl acetate, copper isovalerate, copper β-resorcinate, copper diacetate, copper methyl succinate, copper salicylamide, copper bis(2-ethylhexanoate), copper sebacic acid, copper naphthenate, oxine copper, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, methanol ketone, copper dimethyl dithiocarbamate, etc. These compounds can be used alone or in combination of two or more.

[0038] As the divalent copper compound, the compound is preferably represented by the following general formula (1).

[0039] CuX2 (1)

[0040] (In formula (1), X represents a halogen atom, CH3COO, NO3, or (SO4)1 / 2)

[0041] X in the above formula (1) is preferably a halogen atom, and more preferably a chlorine atom.

[0042] The amount of divalent copper compound raw material used in the mixing step is preferably in the range of 0.01 parts by mass to 20 parts by mass relative to 100 parts by mass of titanium oxide, more preferably in the range of 0.1 parts by mass to 15 parts by mass, and even more preferably in the range of 0.3 parts by mass to 10 parts by mass.

[0043] The water is the solvent in the mixing step and is preferably used alone, but other solvents may be included as needed. Examples of 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; and solvents such as dimethylformamide and tetrahydrofuran. These solvents may be used alone or in combination of two or more.

[0044] As the alkaline substance, for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, alkaline surfactants, etc. can be used, with sodium hydroxide being preferred.

[0045] In terms of ease of reaction control, the alkaline substance is preferably added in the form of a solution, and the concentration of the added alkaline solution is preferably in the range of 0.1 mol / L to 5 mol / L, more preferably in the range of 0.3 mol / L to 4 mol / L, and even more preferably in the range of 0.5 mol / L to 3 mol / L.

[0046] The mixing step simply involves mixing the titanium dioxide, the divalent copper compound raw material, water, and an alkaline substance. For example, the following method can be used: First, mix the titanium dioxide in water while stirring as needed; then mix the divalent copper compound raw material and stir; finally, add the alkaline substance and stir. Through this mixing step, the divalent copper compound derived from the divalent copper compound raw material is loaded onto the titanium dioxide.

[0047] The overall stirring time in the mixing step is not particularly limited within the range that yields the effects of the present invention; for example, 5 minutes to 120 minutes can be listed, with 10 minutes to 60 minutes being preferred. The temperature during the mixing step can be, for example, in the range of room temperature to 70°C.

[0048] The pH value of the mixture obtained by mixing and stirring the titanium oxide, divalent copper compound raw material, and water, followed by mixing and stirring an alkaline substance, is preferably in the range of 8 to 11, and more preferably in the range of 9.0 to 10.5, in terms of good loading of the divalent copper compound on the titanium oxide.

[0049] After the mixing step is completed, the mixture can be separated into solid components. Methods for this separation include, for example, filtration, sedimentation, centrifugation, and evaporation drying, with filtration being preferred. The separated solid components can also be subsequently washed, broken down, or classified as needed.

[0050] To more firmly bond the divalent copper compound derived from the divalent copper compound raw material supported on the titanium oxide after obtaining the solid component, it is preferable to heat-treat the solid component. The heat treatment temperature is preferably in the range of 150°C to 600°C, more preferably in the range of 250°C to 450°C. Furthermore, the heat treatment time is preferably 1 hour to 10 hours, more preferably 2 hours to 5 hours.

[0051] By means of the above method, a titanium oxide composition containing titanium oxide supported on a divalent copper compound can be obtained. Regarding antiviral properties and photocatalytic activity, the loading amount of the divalent copper compound on the titanium oxide is preferably in the range of 0.01 parts by weight to 20 parts by weight relative to 100 parts by weight of titanium oxide. 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.

[0052] In the coating composition of the present invention, the content of the titanium dioxide-containing photocatalyst is not particularly limited within the range that can obtain the effects of the present invention. In terms of obtaining antibacterial and antiviral effects, it is preferable to contain 0.01 parts by mass or more relative to the total coating composition. In terms of obtaining antibacterial and antiviral effects, it is even more preferable to contain 0.02 parts by mass to 5 parts by mass. In terms of suppressing the increase of haze value and obtaining antiviral effects, it is most preferably contained to contain 0.02 parts by mass to 2 parts by mass.

[0053] Within the scope of achieving the effects of the present invention, in order to improve coating performance, the coating composition of the present invention may contain various resins, pastes, etc. As the resin, various resins such as thermoplastic resins, thermosetting resins, and active energy line curing resins can be used. For ease of forming coating layers on various substrates, active energy line curing resins are preferred.

[0054] As for the photoactive energy line curing resin, there are no particular limitations within the scope of obtaining the effects of the present invention, and various photoactive energy line curing resins such as ultraviolet (UV) curing resins, visible light curing resins, and electron beam curing resins can be used. In terms of the ease of curing processing when using a photoactive energy line curing resin in the present invention, it is preferable to use a UV curing resin.

[0055] There are no particular limitations on the UV-curing resin used in this invention. Resins such as urethane acrylate, acrylic acrylate, and epoxy acrylate, as well as resins modified with various substituents, can be used alone or in combination. Acrylic acrylate resin is preferred as the UV-curing resin in terms of its suitability for dispersing the titanium dioxide-containing photocatalyst of this invention and reducing haze.

[0056] In the case of formulating the active energy line curing resin in this invention, various photopolymerization initiators can be formulated to adjust the curing speed, etc. The photopolymerization initiator can be appropriately selected according to the formulated active energy line curing resin, and can be selected from benzyl ketone-based photopolymerization initiators, phosphine oxide-based photopolymerization initiators, intramolecular hydrogen abstraction photopolymerization initiators, oxime ester-based photopolymerization initiators, cationic photopolymerization initiators, etc.

[0057] The coating composition of the present invention can be applied to various substrates and cured to form a laminate with antibacterial and antiviral properties on the surface. The substrate is not particularly limited to any material within the scope of achieving the effects of the present invention; it can be any substrate requiring antibacterial and antiviral properties, such as touch panels, droplet-proof acrylic sheets, protective face shields, handrails / door handles, or nails. Furthermore, suitable materials include triacetyl cellulose (TAC), polyethylene terephthalate (PET), cycloolefin polymer (COP), acrylic (polymethyl methacrylate (PMMA)), polycarbonate (PC), as well as plastics, metals, wood, paper, etc.

[0058] To avoid damaging the feel of the substrate, the haze value of the coating composition of the present invention, measured using a haze meter NDH4000 manufactured by Nippon Denshoku Co., Ltd., after coating film formation, is preferably 55 or less, more preferably 25 or less, further preferably 10 or less, and most preferably 5 or less. By adjusting the haze value to fall within the aforementioned range, even when the coating composition of the present invention is applied to the substrate and allowed to harden, suitable design properties can be maintained without damaging the feel of the substrate. Furthermore, for substrates where transparency is desired, such as display surfaces, antibacterial and antiviral properties can be imparted without hindering display.

[0059] Next, the specific form of the coating composition of the present invention will be described.

[0060] Examples of coating agents according to the present invention include liquids, sprays, and other forms of coating agents, and these forms can be used appropriately according to the desired application.

[0061] In addition to the aforementioned additives, various additives can be formulated into the coating composition within the scope of achieving the effects of the present invention. Examples of such formulations include solvents such as water and alcohols, as well as other antibacterial and antiviral agents. Examples of adhesive resins include acrylic resins, urethane resins, phenolic resins, polyester resins, and epoxy resins. These adhesive resins can be used alone or in combination of two or more.

[0062] As described above, the coating composition according to the present invention can impart a coating layer with long-lasting antibacterial and antiviral properties to various objects through simple operation. Furthermore, it can impart antibacterial and antiviral properties that are safe for human use to various substrates without damaging the feel of the substrate.

[0063] [Example]

[0064] The present invention will be described in more detail below using examples.

[0065] [Preparation Example 1]:

[0066] (1) Titanium oxide

[0067] a) Crystalline rutile titanium dioxide

[0068] b) Preparation method: Liquid phase method (sulfuric acid process)

[0069] c) Physical property values

[0070] BET specific surface area: 9.0 m² / g

[0071] Rutile conversion rate: 95.4%

[0072] Primary particle diameter: 0.13 μm

[0073] (2) Manufacturing steps

[0074] a) Mixing step (reaction step)

[0075] 600 parts by weight of titanium oxide, 8 parts by weight of copper(ii) dihydrate, and 900 parts by weight of water were mixed in a stainless steel container. The mixture was then stirred using a stirrer (Robomix manufactured by Special Chemical Industries Co., Ltd.), and 1 mol / L sodium hydroxide aqueous solution was added dropwise until the pH of the mixture reached 10.

[0076] b) Dehydration step

[0077] Solid components were separated from the mixture by vacuum filtration using qualitative filter paper (5C), and then washed with deionized water. The washed solids were then dried at 120°C for 12 hours to remove moisture. After drying, powdered titanium dioxide was obtained using a mill (Millser manufactured by Iwatani Corporation).

[0078] c) Heat treatment steps

[0079] Using a precision thermostat (DH650 manufactured by Daiwa Scientific Co., Ltd.), the titanium oxide composition (A) containing titanium oxide loaded with divalent copper compounds was obtained by heat treatment at 450°C for 3 hours in the presence of oxygen.

[0080] [Preparation Example 2]

[0081] As titanium oxide, used

[0082] a) Crystalline rutile titanium dioxide

[0083] b) Preparation method: Liquid phase method (sulfuric acid process)

[0084] c) Physical property values

[0085] BET specific surface area: 9.0 m² / g

[0086] Rutile conversion rate: 95.4%

[0087] Primary particle diameter: 0.4 μm

[0088] Titanium oxide was prepared in the same manner as in Preparation Example 1, except that titanium oxide was prepared to obtain a titanium oxide composition (B) containing titanium oxide supported on a divalent copper compound.

[0089] [Preparation Example 3]

[0090] As titanium oxide, used

[0091] a) Crystalline rutile titanium dioxide

[0092] b) Preparation method: Liquid phase method (sulfuric acid process)

[0093] c) Physical property values

[0094] BET specific surface area: 9.0 m² / g

[0095] Rutile conversion rate: 95.4%

[0096] Primary particle diameter: 0.92 μm

[0097] Titanium oxide was prepared in the same manner as in Preparation Example 1, except that titanium oxide was prepared to obtain a titanium oxide composition (C) containing titanium oxide supported on a divalent copper compound.

[0098] [Preparation Example 4]:

[0099] As titanium oxide, used

[0100] a) Crystalline rutile titanium dioxide

[0101] b) Preparation method: Vapor phase method

[0102] c) Physical property values

[0103] BET specific surface area: 9.0 m² / g

[0104] Rutile conversion rate: 70.0%

[0105] Primary particle diameter: 0.13 μm

[0106] The titanium oxide was prepared in the same manner as in Preparation Example 1, except that a titanium oxide composition (D) containing titanium oxide supported on a divalent copper compound was obtained.

[0107] [Preparation Example 5]

[0108] In Preparation Example 1, ferric chloride (ii) was used instead of copper chloride (ii) dihydrate. Otherwise, the same procedure as in Preparation Example 1 was performed to obtain a titanium oxide composition (E) containing titanium oxide supported on a divalent iron compound.

[0109] [Preparation Example 6]:

[0110] Photocatalytic titanium dioxide (ST-41 manufactured by Ishihara Sangyo Co., Ltd.; primary particle size 0.14 μm) is used as the titanium dioxide composition (F).

[0111] [Reference Preparation Example 1]

[0112] As a positive control, copper oxide (I) (primary particle diameter 0.15 μm), which is known to have antiviral activity as described in WO2011 / 078203, was used as a reference preparation.

[0113] The average particle size of the titanium oxide compositions (A) to (F) and the comparative preparations are described in Tables 1 and 2.

[0114] [Example 1]

[0115] A titanium dioxide dispersion (A) was obtained by dispersing 19 parts by mass of the obtained titanium dioxide composition (A), 1 part by mass of trimethoxysilyl propyl methacrylate, and 80 parts by mass of methyl ethyl ketone using a paint conditioner.

[0116] As coating material a, a coating material is manufactured by mixing 5 parts by mass of the dispersion (A), 76 parts by mass of pentaerythritol triacrylate (e.g., Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Corporation), and 15 parts by mass of toluene.

[0117] As coating material b, a coating material is manufactured by mixing 76 parts by weight of pentaerythritol triacrylate (e.g., Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 4 parts by weight of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Corporation), and 20 parts by weight of toluene.

[0118] Coating material b was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 8 μm. The membrane was dried at 60°C for 60 seconds using a hot air dryer and then cured using a fusion lamp to obtain a coating film. Coating material a was then applied to this coating film with a coating thickness of 0.1 μm, and the same curing process was performed to obtain the coating film of Example 1.

[0119] [Example 2]

[0120] Except for using titanium oxide composition (B) instead of titanium oxide composition (A), the same operation as in Example 1 was performed to obtain the coating film of Example 2.

[0121] [Example 3]

[0122] In Example 1, coating material b was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 7.6 μm, and then coating material a was applied with a coating thickness of 0.5 μm. Otherwise, the membrane was cured in the same manner as in Example 1 to obtain the coating membrane of Example 3.

[0123] [Example 4]

[0124] A titanium dioxide dispersion (A) was obtained by dispersing 19 parts by mass of the obtained titanium dioxide composition (A), 1 part by mass of trimethoxysilyl propyl methacrylate, and 80 parts by mass of methyl ethyl ketone using a coating conditioner.

[0125] As coating material c, a coating material is manufactured by mixing 5 parts by mass of the dispersion (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 manufactured by DIC Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Co., Ltd.), and 15 parts by mass of toluene.

[0126] As coating material d, a coating material is manufactured by mixing 50 parts by weight of pentaerythritol triacrylate (Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 52 parts by weight of acrylic acrylate (LUXYDIR V6840 manufactured by DIC Co., Ltd.), 4 parts by weight of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Co., Ltd.), and 20 parts by weight of toluene.

[0127] Coating material d was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 8 μm. The membrane was dried at 60°C for 60 seconds using a hot air dryer and then cured using a fusion lamp to obtain a coating film. Coating material c was then applied to this coating film with a coating thickness of 0.1 μm, and the same curing process was performed to obtain the coating film of Example 4.

[0128] [Example 5]

[0129] A titanium dioxide dispersion (A) was obtained by dispersing 19 parts by mass of the obtained titanium dioxide composition (A), 1 part by mass of trimethoxysilyl propyl methacrylate, and 80 parts by mass of methyl ethyl ketone using a coating conditioner.

[0130] As coating material e, a coating material is manufactured by mixing 5 parts by mass of the dispersion (A), 70 parts by mass of pentaerythritol triacrylate (e.g., Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 13 parts by mass of silica dispersion (e.g., MEK-AC-2140Z manufactured by Nissan Chemical Industries, Ltd.), 4 parts by mass of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Corporation), and 15 parts by mass of toluene.

[0131] As a coating material f, a coating material is manufactured by mixing 70 parts by weight of pentaerythritol triacrylate (Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 13 parts by weight of silica dispersion (such as MEK-AC-2140Z manufactured by Nissan Chemical Industries, Ltd.), 4 parts by weight of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Corporation), and 20 parts by weight of toluene.

[0132] Coating material f was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 8 μm. The membrane was dried at 60°C for 60 seconds using a hot air dryer and then cured using a fusion lamp to obtain a coating film. Coating material e was then applied to this coating film with a coating thickness of 0.1 μm, and the same curing process was performed to obtain the coating film of Example 5.

[0133] [Example 6]

[0134] Except for using titanium oxide composition (C) instead of titanium oxide composition (A), the same operation as in Example 1 was performed to obtain the coating film of Example 6.

[0135] [Example 7]

[0136] The obtained titanium dioxide composition (A) was dispersed in 19 parts by mass, trimethoxysilyl propyl methacrylate, and 60 parts by mass of methyl ethyl ketone using a coating conditioner to obtain a titanium dioxide dispersion (A2).

[0137] As coating material a, a coating material is manufactured by mixing 5 parts by mass of the dispersion (A2), 76 parts by mass of pentaerythritol triacrylate (e.g., Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Corporation), and 15 parts by mass of toluene.

[0138] Coating material a was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 8.1 μm, and then cured in the same manner to obtain the coated film of Example 7.

[0139] [Example 8]

[0140] The obtained titanium dioxide composition (A) was dispersed in 19 parts by mass, trimethoxysilyl propyl methacrylate, and 60 parts by mass of methyl ethyl ketone using a coating conditioner to obtain a titanium dioxide dispersion (A2).

[0141] As coating material a, a coating material is manufactured by mixing 12 parts by mass of the dispersion (A2), 76 parts by mass of pentaerythritol triacrylate (e.g., "Aronix M305" manufactured by Toa Synthetic Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexylphenyl ketone ("RUNTECURE 1104" manufactured by BASF Corporation), and 8 parts by mass of toluene.

[0142] Coating material a was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 8.1 μm, and then cured in the same manner to obtain the coated film of Example 8.

[0143] [Example 9]

[0144] Except for using titanium oxide composition (D) instead of titanium oxide composition (A), the same operation as in Example 1 was performed to obtain the coating film of Example 9.

[0145] [Example 10]

[0146] Except for using titanium oxide composition (E) instead of titanium oxide composition (A), the same operation as in Example 1 was performed to obtain the coating film of Example 10.

[0147] [Example 11]

[0148] Except for using titanium oxide composition (F) instead of titanium oxide composition (A), the same operation as in Example 1 was performed to obtain the coating film of Example 11.

[0149] [Comparative Example 1]

[0150] A comparative dispersion was obtained by dispersing 1 part by mass of trimethoxysilylpropyl methacrylate and 99 parts by mass of methyl ethyl ketone using a coating conditioner.

[0151] As a comparative coating material, a coating material was prepared by mixing 5 parts by mass of the comparative dispersion, 76 parts by mass of pentaerythritol triacrylate (e.g., Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 4 parts by mass of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Corporation), and 15 parts by mass of toluene.

[0152] As a comparative coating material b, a coating material was prepared by mixing 76 parts by weight of pentaerythritol triacrylate (e.g., Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 4 parts by weight of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Corporation), and 20 parts by weight of toluene.

[0153] A comparative coating material was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 8 μm. The membrane was dried at 60°C for 60 seconds using a hot air dryer and then cured using a fusion lamp to obtain a coating film. The comparative coating material was then applied to this coating film with a coating thickness of 0.1 μm, and the same curing process was performed to obtain the coating film of Comparative Example 1.

[0154] [Reference Example]

[0155] Except for using the reference preparation instead of the titanium oxide composition (A), the same operation as in Example 1 was performed to obtain the coating film of the reference example.

[0156] For Examples 1 to 10, Comparative Example 1, and Reference Example 1, antiviral tests, haze value determination tests, and abrasion resistance tests and evaluations were conducted using the following methods.

[0157] [Antiviral test]

[0158] Antiviral testing was conducted according to Japanese Industrial Standard (JIS) R 1756:2020. Regarding antiviral performance, the coatings obtained in the examples and comparative examples were irradiated for 4 hours using a light source with wavelengths cut off below 400 nm using an N-113 filter. The resulting samples were evaluated using the values ​​and inactivation rates calculated according to the following formulas. Antiviral performance was assessed according to the following criteria. A value of B or higher was considered acceptable.

[0159] Inactivation rate = log(N / N0)

[0160] N = Infect titer of the sample after reaction

[0161] N0 = Infection titer of phage inoculation

[0162] A: Inactivation rate is above 99.9%.

[0163] B: Inactivation rate is 99% or higher but less than 99.9%.

[0164] C: Inactivation rate below 90%

[0165] [Haze Value Measurement Test]

[0166] For the obtained evaluation samples, the haze value was measured using a haze meter (NDH2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) in accordance with JIS test method K7136:2000.

[0167] [Abrasion Resistance Test]

[0168] The obtained test film was cut into a rectangle of 30cm×2cm and fixed on a plane friction testing machine (manufactured by Toyo Seiki Co., Ltd.) using a clamp. Steel wool #0000 was used to conduct the test with a load of 1kg / cm2, a stroke of 10cm, a speed of 20cm / second, and 10 round trips. The scratch condition of the test film after the test was observed visually, and the scratch resistance (SW resistance) was evaluated according to the following criteria.

[0169] A: No scratches

[0170] B: There are several scratches.

[0171] C: The test film has scratches all over its surface, but these are within the acceptable range.

[0172] D: The test film has scratches and whitening throughout.

[0173] The evaluation results of each embodiment and comparative example are shown in Tables 1 and 2.

[0174]

[0175]

[0176] As described in Tables 1 and 2, the coating composition according to the present invention can impart a coating with long-lasting antibacterial and antiviral properties to various objects through simple operation.

[0177] [Example 12]

[0178] Titanium oxide dispersion (X) was obtained by dispersing 19 parts by mass of titanium oxide composition (A), 1 part by mass of trimethoxysilyl propyl methacrylate, and 80 parts by mass of methyl ethyl ketone using a coating conditioner.

[0179] Coating material b-1 is prepared by mixing 21.5 parts by weight of pentaerythritol triacrylate (Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 21.5 parts by weight of aliphatic aminocarbamate acrylate (Miramer PU610 manufactured by Toyo Chemicals Co., Ltd.), 2 parts by weight of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Co., Ltd.), and 55 parts by weight of MEK.

[0180] In addition, 0.5 parts by mass of titanium dioxide dispersion (X) were added to 10 parts by mass of coating material b-1 and mixed to produce coating material a-1.

[0181] Coating material b-1 was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 8 μm. The membrane was dried at 60°C for 60 seconds using a hot air dryer and then cured using a fusion lamp to obtain the coating film. Coating material a-1 was then applied to this coating film with a thickness of 0.1 μm, and the same curing process was performed to obtain the coating film of Example 12.

[0182] [Examples 13-15]

[0183] Except for using coating materials a-2 to a-4 with the amount of titanium dioxide dispersion (X) added set to 1.5 parts by mass, 2.5 parts by mass, and 5.0 parts by mass respectively, the same procedure as in Example 12 was performed to obtain the coating films of Examples 13 to 15.

[0184] [Examples 16-19, Comparative Example 2]

[0185] In Examples 12 to 15, the application order of any one of the coating materials a-1 to a-4 was reversed compared to that of the coating material b-1. Coating materials a-1 to a-4 were applied to the lower layer, and coating material b-1 was applied to the upper layer. Otherwise, the same procedure was performed to obtain the coating films of Examples 16 to 19.

[0186] In addition, except that coating material a-1 was not applied, the same procedure as in Example 12 was performed to obtain the coating film of Comparative Example 2.

[0187] For Examples 12 to 19 and Comparative Example 2, antiviral tests, haze value measurements, and abrasion resistance (SW resistance) tests were performed in the same manner as described above. Furthermore, transmittance was measured as follows. The results are recorded in Table 3.

[0188] [Transmittance Measurement]

[0189] For the obtained evaluation samples, the transmittance was determined using a haze meter according to JIS:K-7361-1 (1997).

[0190]

[0191] [Example 20]

[0192] Coating material b-10 is prepared by mixing 21.5 parts by weight of pentaerythritol triacrylate (Aronix M305 manufactured by Toa Synthetic Co., Ltd.), 21.5 parts by weight of bisphenol A epoxy diacrylate (Miramer PE210 manufactured by Toyo Chemicals Co., Ltd.), 2 parts by weight of 1-hydroxycyclohexylphenyl ketone (RUNTECURE 1104 manufactured by BASF Co., Ltd.), and 55 parts by weight of MEK.

[0193] In addition, 0.5 parts by mass of titanium dioxide dispersion (X) are added to 10 parts by mass of coating material b-10 and mixed to produce coating material a-10.

[0194] Coating material b-10 was applied to a 60 μm thick triacetyl cellulose membrane with a coating thickness of 8 μm. The membrane was dried at 60°C for 60 seconds using a hot air dryer and then cured using a fusion lamp to obtain a coating film. Coating material a-10 was then applied to this coating film with a thickness of 0.1 μm, and the same curing process was performed to obtain the coating film of Example 20.

[0195] [Examples 21-27, Comparative Example 3]

[0196] Except for using coating materials a-11 to a-13 with the amount of titanium dioxide dispersion (X) added set to 1.5 parts by mass, 2.5 parts by mass, and 5.0 parts by mass respectively, the same procedure as in Example 20 was performed to obtain the coating films of Examples 21 to 23.

[0197] In addition, except that the layer formed using coating material b-10 is not provided, the same procedures as in Examples 20 to 23 were performed to obtain the coating films of Examples 24 to 27.

[0198] Furthermore, except that b-10 was used as the coating material, the same procedure as in Example 24 was followed to obtain the coating film of Comparative Example 3.

[0199] For Examples 20 to 27 and Comparative Example 3, the antiviral test, haze value measurement, abrasion resistance (SW resistance) test, and transmittance measurement were performed in the same manner as described above. Furthermore, transmittance was measured as described later. The results are recorded in Table 4.

[0200]

[0201] As can be clearly seen from the results shown in Tables 3 and 4, it can be confirmed that even with different types of active energy line curing resins, the coating composition of the present invention can impart excellent antiviral properties.

Claims

1. A coating composition, characterized in that it comprises a titanium dioxide-containing photocatalyst, an active energy line-curing resin, and trimethoxysilyl propyl methacrylate, wherein the titanium dioxide-containing photocatalyst contains liquid-phase titanium dioxide, the active energy line-curing resin is an acrylic acrylate resin, the titanium dioxide-containing photocatalyst has a metal compound supported on its surface, the metal compound being copper chloride, and the primary particle size of the titanium dioxide-containing photocatalyst with the metal compound supported on its surface is in the range of 0.02 μm to 0.5 μm.

2. A laminate formed by applying a coating composition as described in claim 1 to a substrate surface and then curing it.

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