TW202214787A - Coating composition - Google Patents

Abstract

The problem to be solved by the present invention is to provide a coating composition capable of imparting a coating layer that exhibits long-lasting antibacterial and antiviral properties to various objects by a simple operation. The present invention solves the above-mentioned problems by a coating composition characterized by containing a titanium oxide-containing photocatalyst. Furthermore, the present invention may also be characterized in that the titanium oxide-containing photocatalyst supports a metal compound on the surface of the catalyst, the metal compound is a divalent copper compound, and contains an active energy ray curable resin, and relates to a kind of these A layered product in which a coating composition is applied to the surface of a substrate and cured.

Description

Composition for coating

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 for which it applied in Japan on October 1, 2020, and the content is incorporated herein by reference.

In recent years, various viruses and bacteria, including the new coronavirus, have spread, and the demand for antibacterial and antiviral products in the whole society is increasing. These products are particularly required in places touched by a large number of people's hands or in frequently used articles, but all the previous equipment or articles have been changed to those with antibacterial and antiviral effects, or Articles are labor-intensive and expensive, and therefore products capable of imparting these properties by a simple method are required. There are various alcohols, quaternary ammonium salt compounds, silver-based compounds, copper-based compounds, etc. as the antibacterial and antiviral agents that have been used in the past. , reduction of antiviral properties, deterioration of appearance due to oxidation, etc., damage to the feel of the substrate when coating the surface, etc., and the characteristics required by the market cannot be sufficiently satisfied (for example, refer to Patent Document 1). On the other hand, the photocatalyst using titanium oxide is less irritating to the human body and maintains antibacterial and antiviral properties for a long period of time, so expectations for practical use are increasing (refer to Patent Document 2).

However, the photocatalyst using titanium oxide has not been sufficiently developed for this application, and there is a problem that its usefulness is not exhibited. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2007-507407 [Patent Document 2] Japanese Patent Laid-Open No. 2013-166705

[The problem to be solved by the invention]

The present invention relates to a coating composition, which is characterized by containing a titanium oxide-containing photocatalyst.

The present invention further relates to the coating composition, wherein the titanium oxide-containing photocatalyst supports a metal compound on the surface of the catalyst.

The present invention relates to the coating composition, wherein, in addition to the previous features, the metal compound is a divalent copper compound.

The present invention relates to an invention characterized in that the coating composition contains an active energy ray curable resin.

The present invention further relates to a layered product obtained by applying the coating composition to the surface of a base material and curing it. [Means of Solving Problems]

The present invention provides a coating composition, which is characterized by comprising a titanium oxide-containing photocatalyst with antibacterial and antiviral effects. [Effect of invention]

According to the coating composition of the present invention, a coating layer that exhibits long-lasting 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.

In addition, since the coating composition of the present invention has a low haze value, it does not impair the feel of the base material, and also does not absorb into the human body, so it is a coating composition that is safe for the human body.

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

As long as the coating composition of the present invention contains a titanium oxide-containing catalyst and can be coated on an object, its composition is not particularly limited, but it preferably contains a hardenable coating layer capable of forming a stable coating layer. raw materials.

The coating method of the coating composition of the present invention is not particularly limited as long as the effects of the present invention can be obtained, and a spray method, a dipping method, other various printing machines, or a coating method using a coater can be selected. and other coating methods.

The coating composition in the present invention is not particularly limited as long as it is coated and cured by those skilled in the art for the purpose of imparting antibacterial and antiviral properties to the object to be coated, and may be selected according to high hardness and water repellency. , oil repellency, sliding properties, blue light cut (blue light cut) and other desired properties contain various raw materials to impart various functions other than antibacterial and antiviral.

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 photoresponsivity that exhibits antibacterial and antiviral properties by receiving light irradiation such as visible light or ultraviolet rays, but it can be Since more suitable antibacterial and antiviral properties are obtained, it is preferable that a metal compound is supported on the surface of the titanium oxide-containing photocatalyst.

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

As the content ratio (rutileization ratio) of the rutile-type titanium oxide, in terms of obtaining more excellent antiviral properties in bright places and dark places, organic compound decomposition properties in bright places, and light responsiveness, It is preferably 15 mol% or more, more preferably 50 mol% or more, and still more preferably 90 mol% or more.

As a method for producing the titanium oxide, a liquid phase method and a gas phase method are generally known, and titanium oxide obtained by either method can be used in the present invention. The liquid phase method is a method for obtaining titanium oxide by hydrolyzing or neutralizing and sintering titanyl sulfate obtained from a liquid in which raw material ore such as ilmenite ore is dissolved. In addition, the gas-phase method refers to a method of obtaining titanium oxide by gas-phase reaction of titanium tetrachloride obtained by chlorinating raw material ore such as rutile ore, and oxygen. In addition, as a method of distinguishing the titanium oxide produced by the two methods, the method of analyzing the impurity is mentioned. The titanium oxide produced by the liquid phase method contains zirconium, niobium and the like derived from impurities in ilmenite ore in its product. On the other hand, since the vapor phase method includes a step of purifying titanium tetrachloride to remove impurities, these impurities are hardly contained in titanium oxide.

Titanium oxide produced by the gas phase method has the advantage of being able to generate uniform particle diameters, but it is difficult to generate secondary aggregates. Therefore, it is considered that the viscosity of the mixed solution at the time of the reaction step is increased by increasing the apparent specific surface area. high. On the other hand, it is considered that the titanium oxide (a) produced by the liquid phase method generates loose secondary agglomerates in the calcination step, and the specific surface area (Brunauer-Emmett-Teller, BET) due to the primary particles is considered to be relatively loose. ) value), the cohesion is small, and the viscosity of the mixture can be suppressed. From the above-mentioned reasons, the titanium oxide produced by the liquid phase method is preferable in that the productivity can be further improved.

The BET specific surface area of the titanium oxide is preferably in the range of 1 m ² /g to 200 m ² /g, more preferably 3 m, in terms of obtaining more excellent antiviral properties and photoresponsivity. The range of ² /g to 100 m ² /g, more preferably the range of 4 m ² /g to 70 m ² /g, and still more preferably the range of 8 m ² /g to 50 m ² /g, can be further improved. From the viewpoint of the productivity of the antiviral agent, the optimum range is 7.5 m ² /g to 9.5 m ² /g.

The primary particle size of the titanium oxide is preferably in the range of 0.01 μm to 1.5 μm, more preferably in the range of 0.02 μm to 0.5 μm, in terms of obtaining more suitable antiviral properties and photoresponsivity . In addition, the method for measuring the primary particle diameter of titanium oxide refers to a value measured by a method using a transmission electron microscope (TEM) to directly measure the size of primary particles from an electron microscope photograph. . Specifically, the short-axis diameter and long-axis diameter of each primary particle of titanium oxide are measured, and the average value is taken as the particle diameter of the primary particle. Next, for 100 or more titanium oxide particles, the volume (weight ) was obtained by approximating the cube of the obtained particle diameter, and the volume average particle diameter was defined as the average primary particle diameter.

In addition, as the visible light responsive photocatalyst, it is preferable to use a metal compound supported on titanium oxide in terms of further improving the photocatalytic activity in the visible light region and easily showing antiviral properties under practical indoor light. By.

The titanium oxide-containing photocatalyst used in the present invention is preferably one that supports a metal compound on the surface of the catalyst as described above. As a metal compound supported on titanium oxide, a copper compound, an iron compound, a tungsten compound etc. can be used, for example. Among these, a copper compound is preferable, and a bivalent copper compound is more preferable from the viewpoint of obtaining more excellent antibacterial property and antiviral property. The method for supporting the metal compound on the titanium oxide is not particularly limited, and a known method can be used.

As described above, the primary particle size of the titanium oxide-containing photocatalyst when a metal compound is supported on the surface of the catalyst (hereinafter, referred to as "metal-supported titanium oxide-containing photocatalyst") can obtain a more suitable anti-oxidant. In terms of virality and handling properties, the range is preferably 0.01 μm to 1.5 μm, and more preferably the range of 0.02 μm to 0.5 μm. In addition, the method for measuring the primary particle diameter of the metal-supported titanium oxide-containing photocatalyst represents the value measured by the method using a transmission electron microscope (TEM) to directly measure the primary particle size from an electron microscope photograph. particle size. Specifically, the short-axis diameter and the long-axis diameter of the primary particles of each metal-supported titanium oxide-containing photocatalyst were measured, and the average value was taken as the particle diameter of the primary particle. Then, for 100 or more titanium oxide particles, The volume (weight) of each particle was obtained by approximating the cube of the obtained particle diameter, and the volume average particle diameter was defined as the average primary particle diameter.

Next, an optimum aspect as a titanium oxide-containing photocatalyst, that is, a method of supporting a divalent copper compound on titanium oxide will be described.

As a method of carrying a divalent copper compound on the titanium oxide, for example, a method having a mixing step of titanium oxide containing rutile-type titanium oxide, a raw material of a divalent copper compound, water, and an alkaline substance is exemplified.

The concentration of the 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, in the case of using titanium oxide produced by a liquid phase method, even if the concentration of titanium oxide is increased, a well-operated mixing step can be performed. In the range of 25 parts by mass and 40 parts by mass or less, the mixing step can be performed particularly well.

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

As the divalent copper inorganic compound, for example, copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amide sulfate, copper ammonium chloride, coke Inorganic acid salts of divalent copper such as copper phosphate and copper carbonate; halides of divalent copper such as copper chloride, copper fluoride and copper bromide; copper oxide, copper sulfide, azurite, malachite ), copper azide, etc. These compounds may be used alone or in combination of two or more.

As the divalent copper organic compound, for example, copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper hexanoate, copper heptanoate, copper octoate, nonanoic acid ketone, copper decanoate, Copper myristate, copper palmitate, copper bead photonic acid, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, Copper terephthalate, copper salicylate, copper beeslate, 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-lethanoate, copper diacetate, copper formyl succinate, salicylic acid Copper, copper bis(2-ethylhexanoate), copper sebacate, copper naphthenate, copper 8-hydroxyquinoline (oxine copper), copper acetylacetonate, copper ethylacetate, trifluoromethanesulfonate Copper acid, copper phthalocyanine, copper ethoxide, copper isopropoxide, methyl alcohol ketone, copper dimethyl dithiocarbamate, etc. These compounds may be used alone or in combination of two or more.

As the divalent copper compound, among the compounds, a compound represented by the following general formula (1) is preferably used. CuX ₂ (1) (in formula (1), X represents a halogen atom, CH ₃ COO, NO ₃ , or (SO ₄ ) _1/2 )

As X in the said formula (1), a halogen atom is more preferable, and a chlorine atom is especially preferable.

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 0.1 to 15 parts by mass relative to 100 parts by mass of the titanium oxide. range, more preferably in the range of 0.3 parts by mass to 10 parts by mass.

The water is the vehicle in the mixing step and is preferably used alone, but other vehicles may be included as needed. As the other solvent, for example, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; dimethyl ketone can be used; Carboxamide, tetrahydrofuran, etc. These solvents may be used alone or in combination of two or more.

As the alkaline substance, for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, an alkaline surfactant, etc. can be used , preferably using sodium hydroxide.

In terms of easy control of the reaction, 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 It is in the range of 0.3 mol/L to 4 mol/L, and more preferably in the range of 0.5 mol/L to 3 mol/L.

The mixing step only needs to mix the titanium oxide, the divalent copper compound raw material, water, and an alkaline substance. For example, the following method can be mentioned: first, mixing titanium oxide in water, stirring if necessary, and then mixing The divalent copper compound raw material was stirred, and then an alkaline substance was 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.

The entire stirring time in the mixing step is not particularly limited as long as the effects of the present invention can be obtained, and examples thereof include 5 minutes to 120 minutes, preferably 10 minutes to 60 minutes. As temperature at the time of a mixing process, the range of room temperature - 70 degreeC is mentioned, for example.

The pH value of the mixture obtained by mixing and stirring the raw materials of the titanium oxide and the divalent copper compound, and water, and then mixing and stirring the basic substance, is favorable in terms of supporting the divalent copper compound on the titanium oxide. In other words, the range of 8 to 11 is preferable, and the range of 9.0 to 10.5 is more preferable.

After the mixing step is completed, the mixed solution can be separated in the form of solid components. As a method for performing the separation, for example, filtration, sedimentation separation, centrifugal separation, evaporative drying, etc. are mentioned, and filtration is preferable. The separated solid content can also be washed with water, disintegrated, classified, etc. as necessary.

After the solid content is obtained, the solid content is preferably heat-treated in that the divalent copper compound derived from the divalent copper compound raw material carried on the titanium oxide can be more firmly bound. The heat treatment temperature is preferably in the range of 150°C to 600°C, and more preferably in the range of 250°C to 450°C. In addition, the heat treatment time is preferably 1 hour to 10 hours, more preferably 2 hours to 5 hours.

By the above method, the titanium oxide composition containing the titanium oxide supported with a divalent copper compound can be obtained. In terms of antiviral properties and photocatalytic activity, the supported amount of the divalent copper compound supported on the titanium oxide is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of the titanium oxide. scope. The supported amount of the divalent copper compound can be adjusted by the amount of the divalent copper compound raw material used in the mixing step.

In the coating composition of the present invention, the content of the catalyst containing titanium oxide is not particularly limited as long as the effects of the present invention can be obtained. It is preferable to contain 0.01 mass part or more with respect to the whole coating composition, from the viewpoint that the antibacterial and antiviral effects can be suitably obtained, and it is more preferable to contain 0.02 mass parts to 5 mass parts, from the viewpoint of suppressing the increase of the haze value. . In terms of obtaining an antiviral effect, it is optimal to contain 0.02 to 2 parts by mass.

The coating composition of the present invention may contain various resins, pastes, and the like within a range in which the effects of the present invention can be obtained, in order to achieve improvement in coating performance. As the resin, various resins such as thermoplastic resins, thermosetting resins, and active energy ray hardening resins can be used, and active energy ray hardening is preferably used in that the coating layer can be easily formed on various substrates resin.

The active energy ray-curable resin is not particularly limited as long as the effects of the present invention can be obtained, and various types of ultraviolet-curable resins (hereinafter, UV (Ultraviolet)-curable resins), visible light-curable resins, and electron beam-curable resins can be used. Active energy ray hardening resin. In the case where a photoactive energy ray-curable resin is used in the present invention, it is preferable to use a UV-curable resin in that the curing process can be easily performed.

The UV curable resin used in the present invention is not particularly limited, and resins such as urethane acrylate, acrylate acrylate, epoxy acrylate, and the like, and various substitutions based on these resins can be used alone or in combination. based modified resins. As the UV curable resin, an acrylic acrylate resin is preferable in that the titanium oxide-containing photocatalyst of the present invention can be suitably dispersed and the haze value can be reduced.

When the active energy ray curable resin is prepared in the present invention, various photopolymerization initiators can be prepared to adjust the curing speed and the like. The photopolymerization initiator may be appropriately selected according to the prepared active energy ray hardening resin, and may be selected from phenylalkyl ketone-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, and intramolecular hydrogen abstraction initiators. Type photopolymerization initiator, oxime ester photopolymerization agent, cationic photopolymerization initiator, etc.

The coating composition of the present invention can be applied to various substrates and cured to obtain a laminate having antibacterial and antiviral properties on the surface. The base material is not particularly limited as long as the effects of the present invention can be obtained, as long as antibacterial, Antiviral substrates are sufficient. In addition, its material can also be suitably used triacetyl cellulose (triacetyl cellulose, TAC), polyethylene terephthalate (polyethylene terephthalate, PET), cycloolefin polymer (cycloolefin polymer, COP), acrylic acid (polyethylene Methyl methacrylate (polymethyl methacrylate, PMMA), polycarbonate (polycarbonate, PC) and other plastics, metal, wood, paper, etc.

In order not to damage the feel of the substrate, the coating composition of the present invention preferably has a haze value of 55 or less, more preferably 25 or less, as measured by a haze meter NDH4000 manufactured by Nippon Denshoku Co., Ltd. after the coating film is formed. , more preferably 10 or less, and most preferably 5 or less. By adjusting the haze value so that the haze value falls within the above-mentioned range, even when the coating composition of the present invention is applied to a substrate and hardened, an appropriate design can be maintained without damaging the texture of the substrate. sex. In addition, antibacterial and antiviral properties can also be imparted to substrates where transparency is desired, such as display surfaces, without hindering display.

Next, the specific aspect of the coating composition of this invention is demonstrated.

Examples of the aspect of the coating material of the present invention include coating agents in the form of liquids and sprays, and these aspects can be appropriately used according to the intended use.

In the coating composition, in addition to the aforementioned additive components, various additives may be blended within a range having the effects of the present invention. As these preparation components, solvents, such as water and alcohol, and other antibacterial and antiviral agents, etc. are mentioned, for example. 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.

As described above, according to the coating composition of the present invention, a coating layer that exhibits long-lasting antibacterial and antiviral properties can be provided 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. [Example]

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

[Preparation Example 1]: (1) Titanium oxide a) Crystalline rutile titanium oxide b) Production method: liquid phase method (sulfuric acid method) c) Physical property value · BET specific surface area: 9.0 m ² /g · Rutile conversion rate : 95.4% Primary particle diameter: 0.13 μm (2) Production step a) Mixing step (reaction step) 600 parts by mass of the titanium oxide, 8 parts by mass of copper chloride (ii) dihydrate, and 900 parts by mass of water were added to Mix in stainless steel container. Next, the mixture was stirred with a stirrer (“Robomix” manufactured by Special Machinery Co., Ltd.), and a 1 mol/L aqueous sodium hydroxide solution was added dropwise until the pH value of the mixture was 10. b) In the dehydration step, a qualitative filter paper (5C) is used to filter under reduced pressure, and the solid content is separated from the mixed solution, and then the ion-exchanged water is used for cleaning. Next, 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 (“millser” manufactured by Iwatani Sangyo Co., Ltd.). c) Heat treatment step Using a precision thermostat (“DH650” manufactured by Daiwa Science Co., Ltd.), heat treatment at 450° C. for 3 hours in the presence of oxygen to obtain a titanium oxide composition containing a divalent copper compound-supported titanium oxide Object (A).

[Preparation Example 2] As titanium oxide, a) Crystalline rutile titanium oxide was used b) Production method: liquid phase method (sulfuric acid method) c) Physical property value · BET specific surface area: 9.0 m ² /g · Rutile conversion rate: A titanium oxide composition (B) containing a divalent copper compound-supported titanium oxide was obtained in the same manner as in Adjustment Example 1 except that the titanium oxide was 95.4% primary particle diameter: 0.4 μm.

[Preparation Example 3] As titanium oxide, a) Crystalline rutile titanium oxide was used b) Production method: liquid phase method (sulfuric acid method) c) Physical property value · BET specific surface area: 9.0 m ² /g · Rutile conversion rate: A titanium oxide composition (C) containing a divalent copper compound-supported titanium oxide was obtained in the same manner as in Adjustment Example 1 except that the titanium oxide was 95.4% primary particle diameter: 0.92 μm.

[Preparation Example 4]: As titanium oxide, a) Crystalline rutile titanium oxide was used b) Production method: gas phase method c) Physical property value · BET specific surface area: 9.0 m ² /g · Rutile conversion rate: 70.0% · A titanium oxide composition (D) containing a divalent copper compound-supported titanium oxide was obtained in the same manner as in Adjustment Example 1 except that the primary particle size was titanium oxide of 0.13 μm.

[Adjustment example 5] In Adjustment Example 1, except that iron chloride (ii) was used instead of copper chloride (ii) dihydrate, it was carried out in the same manner as in Adjustment Example 1 to obtain a titanium oxide containing a divalent iron compound supported. Titanium oxide composition (E).

[Preparation Example 6]: Photocatalyst titanium oxide (ST-41 manufactured by Ishihara Sangyo Co., Ltd.; primary particle diameter: 0.14 μm) was used as the titanium oxide composition (F).

[Reference adjustment example 1] As a positive control, copper (I) oxide (primary particle diameter: 0.15 μm) known to have an antiviral effect described in WO2011/078203 was used as a reference regulator.

The average particle diameters of the titanium oxide composition (A) to titanium oxide composition (F) and the comparative adjustment products are described in Tables 1 to 2.

[Example 1] Using a paint conditioner, 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 to obtain titanium oxide. Dispersion (A).

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

As the coating material b, 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone (BASF) Coating material prepared by mixing 4 parts by mass of "RUNTECURE 1104") and 20 parts by mass of toluene.

Coating material b was applied to a 60 μm-thick triacetate cellulose film so as to have a coating film thickness of 8 μm, dried at 60° C. for 60 seconds with a hot air dryer, and hardened with a fusion lamp to obtain coating. On this coating film, the coating material a was further coated so that the coating film thickness might be 0.1 μm, and it was cured in the same manner to obtain the coating film of Example 1.

[Example 2] Except having used the titanium oxide composition (B) instead of the titanium oxide composition (A), the same operation as Example 1 was performed, and the coating film of Example 2 was obtained.

[Example 3] In Example 1, the coating material b was applied to a 60 μm-thick triacetate cellulose film so that the coating film thickness would be 7.6 μm, and the coating material a was further coated so that the coating film thickness would be 0.5 μm. Other than that, it hardened like Example 1, and the coating film of Example 3 was obtained.

[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 in a paint conditioner to obtain a titanium oxide dispersion liquid (A ).

As the coating material c, 50 parts by mass of the dispersion liquid (A), 50 parts by mass of pentaerythritol triacrylate (“Aronix M305” manufactured by Toagosei Co., Ltd.), acrylic acrylate (Di DIC Co., Ltd. "LUXYDIR 6840") 52 parts by mass, 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Co., Ltd.) A coating material prepared by mixing 4 parts by mass and 15 parts by mass of toluene.

As the coating material d, 50 parts by mass of pentaerythritol triacrylate (“Aronix M305” manufactured by Toagosei Co., Ltd.), acrylic acrylate (“Rukia” of DIC Co., Ltd. 52 parts by mass of LUXYDIR V6840"), 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Co., Ltd.), and 20 parts by mass of toluene of coating material.

The coating material d was coated on 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 hardened with a fusion lamp to obtain coating. On this coating film, the coating material c was further coated so that the coating film thickness might be 0.1 μm, and the coating film of Example 4 was obtained by curing in the same manner.

[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 in a paint conditioner to obtain a titanium oxide dispersion liquid (A ).

As the coating material e, 5 parts by mass of the dispersion liquid (A), 70 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), and 70 parts by mass of silica dispersion liquid were produced. (For example, Nissan Chemical Industry Co., Ltd. "MEK-AC-2140Z") 13 parts by mass, 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Co., Ltd.) 4 mass parts and 15 parts by mass of toluene.

As the coating material f, 70 parts by mass of pentaerythritol triacrylate ("Aronix M305" manufactured by Toa Gosei Co., Ltd.), a silica dispersion (for example, Nissan Chemical Industry Co., Ltd. "MEK-AC") was prepared. -2140Z") 13 parts by mass, 1-hydroxycyclohexyl phenyl ketone ("RUNTECURE 1104" manufactured by BASF Co., Ltd.) 4 parts by mass, and 20 parts by mass of toluene. .

The coating material f was applied on a triacetate cellulose film having a thickness of 60 μm so that the film thickness would be 8 μm, dried at 60° C. for 60 seconds with a hot air dryer, and hardened with a fusion lamp to obtain coating. On this coating film, the coating material e was further coated so that the coating film thickness might be 0.1 μm, and the coating film of Example 5 was obtained by curing in the same manner.

[Example 6] Except having used the titanium oxide composition (C) instead of the titanium oxide composition (A), the same operation as Example 1 was performed, and the coating film of Example 6 was obtained.

[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 in a paint conditioner to obtain a titanium oxide dispersion liquid (A2 ).

As the coating material a, 5 parts by mass of the dispersion liquid (A2), 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), 1-hydroxycyclohexyl A coating material obtained by mixing 4 parts by mass of phenyl ketone (“RUNTECURE 1104” manufactured by BASF Co., Ltd.) and 15 parts by mass of toluene.

The coating material a was coated on a 60 μm-thick triacetoxycellulose film so that the coating film thickness would be 8.1 μm, and was similarly cured to obtain the coating film of Example 1.

[Example 8] 19 parts by mass of the obtained titanium oxide composition (A), 1 part by mass of trimethoxysilylpropyl methacrylate, and 60 parts by mass of methyl ethyl ketone were dispersed in a paint conditioner to obtain a titanium oxide dispersion liquid (A2 ).

As the coating material a, 12 parts by mass of the dispersion (A2), 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), 1-hydroxycyclohexyl A coating material obtained by mixing 4 parts by mass of phenyl ketone (“RUNTECURE 1104” manufactured by BASF Co., Ltd.) and 8 parts by mass of toluene. The coating material a was coated on a 60 μm-thick triacetoxycellulose film so that the coating film thickness would be 8.1 μm, and was similarly cured to obtain the coating film of Example 1.

[Example 9] Except having used the titanium oxide composition (D) instead of the titanium oxide composition (A), the same operation as Example 1 was performed, and the coating film of Example 9 was obtained.

[Example 10] Except having used the titanium oxide composition (E) instead of the titanium oxide composition (A), the same operation as Example 1 was performed, and the coating film of Example 10 was obtained.

[Example 10] Except having used the titanium oxide composition (F) instead of the titanium oxide composition (A), the same operation as Example 1 was performed, and the coating film of Example 11 was obtained.

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

As a comparative coating material, 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.), 1-hydroxycyclohexylphenyl A coating material obtained by mixing 4 parts by mass of ketone (“RUNTECURE 1104” manufactured by BASF Co., Ltd.) and 15 parts by mass of toluene.

As a comparative coating material b, 76 parts by mass of pentaerythritol triacrylate (for example, "Aronix M305" manufactured by Toagosei Co., Ltd.), 1-hydroxycyclohexyl phenyl ketone (BASF Co., Ltd. Coating material obtained by mixing 4 parts by mass of "RUNTECURE 1104" manufactured by the company and 20 parts by mass of toluene.

The comparative coating material was applied on a triacetate cellulose film having a thickness of 60 μm so that the film thickness would be 8 μm, dried at 60° C. for 60 seconds with a hot air dryer, and hardened with a fusion lamp to obtain the obtained coating. On this coating film, a comparative coating material was further applied so that the coating film thickness might be 0.1 μm, and the coating film of Comparative Example 1 was obtained by curing in the same manner.

[Reference example] The same operation as in Example 1 was carried out, except that the titanium oxide composition (A) was replaced by the reference adjusted product, and the coating film of the reference example was obtained.

With respect to the produced Examples 1 to 10, Comparative Example 1, and Reference Example 1, an antiviral test, a haze value measurement test, and a scratch resistance test and evaluation were performed by the following methods.

[Antiviral Test] The antiviral test was conducted according to Japanese Industrial Standard (JIS) R 1756:2020. Regarding the antiviral properties, the coating films obtained in Examples and Comparative Examples were irradiated for 4 hours using a light source with a wavelength of 400 nm or less cut off by an N-113 filter. The evaluation was performed on the basis of the value obtained by the following formula and the degree of inactivation, and the antiviral property was evaluated according to the following criteria. B or more was considered pass. Degree of inactivation=log(N/N ₀ ) N=infectious titer of the reacted sample N ₀ =infectious titer of inoculated phage A: degree of inactivation is 99.9% or more B: degree of inactivation is 99% or more and less than 99.9% C: The inactivation degree is below 90%

[Haze value measurement test] The haze value of the obtained sample for evaluation was measured according to JIS test method K7136:2000 using a haze meter (“NDH2000” manufactured by Nippon Denshoku Kogyo Co., Ltd.).

[Scratching resistance test] The obtained test piece film was cut out in a rectangle of 30 cm×2 cm, fixed on a plane friction tester (manufactured by Toyo Seiki Co., Ltd.) with a jig, and steel wool #0000 was used. The test was carried out with a load of 1 kg/cm ² , a stroke of 10 cm, a speed of 20 cm/sec, and 10 reciprocations. The scratched state of the test piece after the test was visually observed, and the scratch resistance (SW resistance) was evaluated according to the following criteria. . A: No scratches B: Several scratches C: The entire test piece film is scratched, but within the allowable range D: The entire test piece film is scratched and whitened

The evaluation results of the respective Examples and Comparative Examples are shown in Tables 1 to 2.

[Table 1] Two-layer coating example Two-layer coating example Two-layer coating example Two-layer coating example Two-layer coating example Two-layer coating example 1 2 3 4 5 6 Titanium oxide surface treatment copper copper copper copper copper copper Production method liquid phase method liquid phase method liquid phase method liquid phase method liquid phase method liquid phase method The average particle size μm 0.18 0.51 0.18 0.18 0.18 1.02 Titanium oxide content wt% 0.01 0.01 0.05 0.01 0.01 0.01 resin PETA PETA PETA PETA/AcAc PETA/Silica PETA Film thickness μm 8.1 8.1 8.1 8.1 8.1 8.1 haze value 1.6 2.6 1.8 0.9 2.0 5.1 antiviral A A A A A A SW resistance A A A A A B viscosity mPa s 5 5 5 5 5 5

[Table 2] Single layer coating example Single layer coating example Two-layer coating example Two-layer coating example Two-layer coating example Comparative example Reference example 7 8 9 10 11 1 1 Titanium oxide surface treatment copper copper copper iron none - copper only Production method liquid phase method liquid phase method gas phase method liquid phase method none - The average particle size μm 0.2 0.2 0.18 0.18 0.18 - 0.2 Titanium oxide content wt% 1.20 3.00 0.01 0.01 0.01 0.00 0.01 resin PETA PETA PETA PETA PETA PETA PETA Film thickness μm 8.1 8.1 8.1 8.1 8.1 8.1 8.1 haze value 23.2 50.0 2.0 2.1 1.6 0.1 5.0 antiviral A A B B B C C SW resistance B C A C C A C viscosity mPa s 5 50 120 67 5 5 5

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

[Example 12] Using a paint conditioner, 19 parts by mass of the titanium oxide composition (A), 1 part by mass of trimethoxysilylpropyl methacrylate, and 80 parts by mass of methyl ethyl ketone were dispersed to obtain a titanium oxide dispersion liquid (X).

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

Moreover, 0.5 mass part of titanium oxide dispersion liquid (X) was added and mixed with respect to 10 mass parts of coating material b-1, and coating material a-1 was manufactured.

Coating material b-1 was applied on a 60 μm-thick triacetate cellulose film so that the film thickness would be 8 μm, dried at 60°C for 60 seconds with a hot air dryer, and hardened with a fusion lamp. , to obtain a coating film. On this coating film, the coating material a-1 was further applied so that the coating film thickness might be 0.1 μm, and the coating material a-1 was cured in the same manner to obtain the coating film of Example 12.

[Example 13 to Example 15] Except having used the coating materials a-2 to a-4 in which the addition amounts of the titanium oxide dispersion liquid (X) were 1.5 parts by mass, 2.5 parts by mass, and 5.0 parts by mass, respectively, it was carried out in the same manner as in Example 12 to obtain The coating films of Examples 13 to 15.

[Example 16 to Example 19, Comparative Example 2] In Examples 12 to 15, the coating order of any one of the coating materials a-1 to a-4 and the coating material b-1 was reversed, and the coating materials a-1 to a-4 were applied. Except applying to the lower layer and applying the coating material b-1 to the upper layer, the same procedure was carried out, respectively, to obtain the coating films of Examples 16 to 19. Moreover, it carried out similarly to Example 12 except that the coating of the coating material a-1 was not performed, and the coating film of the comparative example 2 was obtained.

With respect to the produced Examples 12 to 19 and Comparative Example 2, the antiviral test, the haze value measurement, and the scratch resistance (SW resistance) test were carried out in the same manner as described above by the following methods. In addition, transmittance was measured as follows. The results are collectively described in Table 3.

[Transmittance measurement] The transmittance of the obtained sample for evaluation was measured using a haze meter in accordance with JIS: K-7361-1 (1997).

[table 3] Example Comparative example 12 13 14 15 16 17 18 19 2 upper layer a-1 a-2 a-3 a-4 b-1 b-1 b-1 b-1 - Titanium oxide 0.5 1.5 2.5 5.0 0 0 0 0 - lower level b-1 b-1 b-1 b-1 a-1 a-2 a-3 a-4 b-1 Titanium oxide 0 0 0 0 0.5 1.5 2.5 5.0 0 Haze value% 1.2 3.1 4.3 5.8 13.5 34.7 41.5 53.0 0.1 Transmittance% 89 89 88 88 85 77 74 69 90 SW resistance B B B B B B B B A antiviral B B A A A A A A C

[Example 20] 21.5 parts by mass of pentaerythritol triacrylate (“Aronix M305” manufactured by Toyo Chemical Co., Ltd.) and bisphenol A epoxy diacrylate (“Miramer” manufactured by Toyo Chemicals Co., Ltd.) A coating material b- 10.

Moreover, 0.5 mass part of titanium oxide dispersion liquid (X) was added and mixed with respect to 10 mass parts of coating material b-10, and coating material a-10 was manufactured.

Coating material b-10 was applied to a 60 μm-thick triacetate cellulose film so as to have a film thickness of 8 μm, dried at 60°C for 60 seconds with a hot air dryer, and hardened with a fusion lamp. , to obtain a coating film. On this coating film, the coating material a-10 was further coated so that the coating film thickness might be 0.1 μm, and it was cured in the same manner to obtain the coating film of Example 20.

[Example 21 to Example 27, Comparative Example 3] Except having used the coating materials a-11 to a-13 in which the addition amounts of the titanium oxide dispersion liquid (X) were 1.5 parts by mass, 2.5 parts by mass, and 5.0 parts by mass, respectively, it was carried out in the same manner as in Example 20 to obtain The coating films of Examples 21 to 23. Moreover, except not providing the layer formed with the coating material b-10, it carried out similarly to Example 20 - Example 23, and obtained the coating film of Example 24 - Example 27, respectively. Furthermore, except having used b-10 as a coating material, it carried out similarly to Example 24, and obtained the coating film of the comparative example 3.

With respect to the produced Examples 20 to 27 and Comparative Example 3, the virus resistance test, haze value measurement, scratch resistance (SW resistance) test, and transmittance measurement were carried out in the same manner as described above by the following methods. . In addition, transmittance was measured as follows. The results are collectively described in Table 4.

[Table 4] Example Comparative example 20 twenty one twenty two twenty three twenty four 25 26 27 3 upper layer a-10 a-11 a-12 a-13 - - - - - Titanium oxide 0.5 1.5 2.5 5.0 - - - - - lower level b-10 b-10 b-10 b-10 a-10 a-11 a-12 a-13 b-10 Titanium oxide 0 0 0 0 0.5 1.5 2.5 5.0 0 Haze value% 1.2 3.2 4.4 5.1 13.9 29.7 40.4 47.0 0.2 Transmittance% 90 89 88 88 87 85 79 74 90 SW resistance B B B B B B B B A antiviral B A A A B A A A C

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

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Claims (5)

A coating composition is characterized in that it contains a titanium oxide-containing photocatalyst. The coating composition according to claim 1, wherein the titanium oxide-containing photocatalyst supports a metal compound on the surface of the catalyst. The coating composition according to claim 2, wherein the metal compound is a divalent copper compound. The coating composition according to any one of Claims 1 to 3, comprising an active energy ray curable resin. A layered product obtained by applying the coating composition according to any one of Claims 1 to 4 on the surface of a base material and curing it.