Coating resin composition and coating layer

Abstract

To provide a coating resin composition that can give antiviral properties, and a coating layer having antiviral properties given thereto.SOLUTION: The inventive coating resin composition contains a hydrophilic resin (A), a visible photoresponsive photocatalyst (B), and an aqueous medium (C).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a coating resin composition and a coating layer.

Background Art

[0002] In recent years, various viruses and bacteria such as the novel coronavirus have spread, and the demand for products with antibacterial and antiviral properties has increased throughout society. There is a high demand for these products, especially for places where many people's hands touch and frequently used items. However, since it is time-consuming and costly to change all conventional facilities and items to those with antibacterial and antiviral effects, there is a need for products that can impart these properties in a simple way.

[0003] Conventionally used antibacterial and antiviral agents include various alcohol agents, quaternary ammonium salt compounds, silver-based compounds, copper-based compounds, etc. However, these have not been able to fully meet the required characteristics of the market, such as irritation to the skin and reduction of antibacterial and antiviral properties over time.

[0004] On the other hand, photocatalysts using titanium oxide have little stimulation to the human body and maintain antibacterial and antiviral performance over a long period, so expectations for practical application are increasing (see Patent Document 1).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] An object of the present invention is to provide a coating resin composition capable of imparting antiviral properties and a coating layer imparted with antiviral properties.

Means for Solving the Problems

[0007] The present invention provides a coating resin composition capable of imparting antiviral properties by containing a visible light-responsive photocatalyst, and a coating layer imparted with antiviral properties by using the coating resin composition. The present invention includes the following inventions.

[0008] [1] A coating resin composition comprising a hydrophilic resin (A), a visible light-responsive photocatalyst (B), and an aqueous medium (C). [2] The coating resin composition according to [1], wherein the visible light-responsive photocatalyst (B) is one in which a metal compound is supported on titanium oxide (b1). [3] The coating resin composition according to claim 2, wherein the titanium oxide (b1) contains rutile-type titanium oxide (b1-1). [4] The coating resin composition according to [2] or [3], wherein the metal compound is a divalent copper compound. [5] A coating layer formed from the coating resin composition according to any one of [1] to [4].

Effects of the Invention

[0009] According to the present invention, antiviral properties can be imparted to the coating resin composition and the coating layer.

Modes for Carrying Out the Invention

[0010] The coating resin composition of the present invention contains a hydrophilic resin (A), a visible light-responsive photocatalyst (B), and an aqueous medium (C).

[0011] Examples of the hydrophilic resin (A) include urethane resins and acrylic resins, and urethane resins are preferred.

[0012] Examples of the urethane resin include reaction products of a polyol (a1), a polyisocyanate (a2), and a chain extender (a3) used as necessary.

[0013] As the polyol (a1), from the viewpoint of water dispersion stability, it preferably contains at least one polymer polyol (a1-1) selected from polyether polyols, polyester polyols, and polycarbonate polyols, and a polyol (a1-2) having a hydrophilic group.

[0014] The number average molecular weight of the polymer polyol (a1-1) is preferably 500 or more and 3,000 or less. In the present invention, the number average molecular weight and the weight average molecular weight represent conversion values measured by gel permeation chromatography (GPC) using polystyrene as a standard sample.

[0015] Examples of the polyether polyol include those obtained by addition polymerization of an alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator; those obtained by ring-opening polymerization of a cyclic ether, and the like.

[0016] One or more of the above can be used as the initiator. For example, linear diols such as ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol; branched-chain diols such as neopentyl glycol; triols such as glycerin, trimethylolethane, trimethylolpropane, pyrogallol; polyols such as sorbitol, sucrose, and aconitic sugar; tricarboxylic acids such as aconitic acid, trimellitic acid, and hemimellitic acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine; phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2,3-propanetrithiol, and the like.

[0017] As the alkylene oxide, one kind or two or more kinds can be used. For example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, etc. can be mentioned. As the cyclic ether, tetrahydrofuran, etc. can be mentioned.

[0018] As the polyether polyol, it is preferable to use polyoxytetramethylene glycol obtained by addition polymerization (ring-opening polymerization) of tetrahydrofuran to the initiator.

[0019] Since the number average molecular weight of the polyether polyol can further improve the substrate adhesion, it is preferably 500 or more and 3,000 or less.

[0020] When including a polyether polyol, in the polyol (a), the content of the polyether polyol is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and the upper limit is 100% by mass.

[0021] As the polyester polyol, for example, a polyester polyol obtained by an esterification reaction of a low molecular weight polyol (for example, a polyol having a molecular weight of 50 or more and 500 or less) and a polycarboxylic acid; a polyester polyol obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone; these copolymer polyester polyols, etc. can be mentioned.

[0022] As the low molecular weight polyol, a polyol having a molecular weight of about 50 or more and less than 500 can be used. For example, aliphatic polyols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1,3-butanediol; alicyclic structure-containing polyols such as 1,4-cyclohexanediol and cyclohexanedimethanol; aromatic structure-containing polyols such as bisphenol compounds such as bisphenol A and bisphenol F and their alkylene oxide adducts, and the like can be mentioned.

[0023] As the polycarboxylic acid, aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid; and anhydrides or ester-forming derivatives of the aliphatic polycarboxylic acids and aromatic polycarboxylic acids, and the like can be mentioned.

[0024] Since the number average molecular weight of the polyester polyol can further improve the adhesion to the substrate, it is preferably 500 or more and 3,000 or less.

[0025] When the polyester polyol is included, in the polyol (a1), the content of the polyester polyol is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and the upper limit is 100% by mass.

[0026] Examples of the polycarbonate polyol include reaction products of a carbonic acid ester and a polyol; reaction products of phosgene and bisphenol A or the like.

[0027] Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclo carbonate, diphenyl carbonate and the like.

[0028] Examples of the polyol capable of reacting with the carbonic ester include, for example, the polyols exemplified as the above low-molecular-weight polyols; high-molecular-weight polyols (weight-average molecular weight of 500 or more and 5,000 or less) such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.), polyester polyols (polyhexamethylene adipate, etc.).

[0029] Since the number-average molecular weight of the polycarbonate polyol can further improve the substrate adhesion, it is preferably 500 to 3,000 in number-average molecular weight.

[0030] Examples of the polyolefin polyol include, for example, polyethylene polyol, polypropylene polyol, polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, hydrogenated (hydrogenated) polyisoprene polyol, and the like.

[0031] When an olefin polyol is included, in the polyol (a1), the content of the olefin polyol is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, and the upper limit is 100% by mass.

[0032] In the polyol (a1), the total content of the polymer polyol (a1-1) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and the upper limit is 100% by mass.

[0033] In addition, examples of the hydrophilic group in the polyol (a1-2) having the hydrophilic group include an anionic group, a cationic group, a nonionic group, etc. As the polyol (a1-2) having the hydrophilic group, for example, a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group other than the above-mentioned polyol (a1-1) can be used. Among these, it is preferable to use a polyol having an anionic group or a polyol having a cationic group, and it is more preferable to use a polyol having a cationic group.

[0034] Examples of the anionic group include a carboxy group, a sulfonic acid group, a phosphoric acid group, etc. Examples of the polyol having the anionic group include a polyol having a carboxy group, a polyol having a sulfonic acid group, a polyol having a phosphoric acid group, etc.

[0035] Examples of the polyol having the carboxy group include hydroxy acids such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-dimethylolvaleric acid; and reaction products of the polyol having the carboxy group and the polycarboxylic acid. As the hydroxy acid, 2,2-dimethylolpropionic acid is preferable. In addition, a polyester polyol having a carboxyl group obtained by reacting the polyol having a carboxyl group with various polycarboxylic acids can also be used.

[0036] Examples of the polyol having the sulfonic acid group include polyester polyols obtained by reacting dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5-[4-sulfophenoxy]isophthalic acid or their salts with the low molecular weight polyols exemplified as those usable for the production of the polyester polyol having the aromatic structure.

[0037] It is preferable that some or all of the anionic groups are neutralized by a basic compound or the like in order to exhibit good water dispersibility.

[0038] Examples of the basic compound that can be used when neutralizing the anionic group include organic amines having a boiling point of 200 °C or higher such as ammonia, triethylamine, morpholine, monoethanolamine, and diethylethanolamine, and metal hydroxides including sodium hydroxide, potassium hydroxide, and lithium hydroxide. From the viewpoint of improving the water dispersion stability of the coating resin composition, the molar ratio (basic group / anionic group) of the basic compound to the anionic group is preferably 0.5 or more and 3.0 or less, more preferably 0.8 or more and 2.0 or less.

[0039] Examples of the cationic group include a tertiary amino group, and examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specifically, N-methyl-diethanolamine, a polyol obtained by reacting a compound having two epoxies in one molecule with a secondary amine, and the like can be mentioned.

[0040] It is preferable that some or all of the cationic groups are neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, and adipic acid.

[0041] Moreover, it is preferable that some or all of the tertiary amino groups as the cationic groups are quaternized. Examples of the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride, and ethyl chloride. Among these, it is preferable to use dimethyl sulfate.

[0042] Examples of the nonionic group include a group having a polyoxyethylene structure, and examples of the polyol having a nonionic group include a polyol having a polyoxyethylene structure.

[0043] The content rate of the polyol (a1-2) having the hydrophilic group is preferably 0.3% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and preferably 30% by mass or less, more preferably 20% by mass or less, still more preferably 10% by mass or less in the polyol (a1).

[0044] As the polyol (a1), in addition to the above-described polyols, other polyols can be used as necessary.

[0045] Examples of the other polyols include low molecular weight polyols (for example, diols, triols, etc. having a molecular weight of 500 or less), such as alkylene glycol compounds such as methylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, hexamethylene glycol; triol compounds such as glycerin; alicyclic polyols such as hydrogenated bisphenol A; saccharides such as sucrose; sugar alcohols such as sorbitol; phenolic hydroxyl group-containing compounds such as bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, hydroquinone, and the like. These polyols may be used alone or in combination of two or more.

[0046] Examples of the polyisocyanate (a2) include aromatic diisocyanates such as xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,2-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane, and tetramethylxylylene diisocyanate. These polyisocyanates may be used alone or in combination of two or more. Among these, aliphatic or alicyclic diisocyanates are preferably used because they are less likely to cause yellowing.

[0047] The molar ratio [NCO / OH] of the isocyanate groups contained in the polyisocyanate (a2) to the hydroxy groups contained in the polyol (a1) is preferably 0.9 or more, preferably 3 or less, and more preferably 2 or less.

[0048] In addition, when producing the urethane resin, a chain extender (a3) may be used as necessary for the purpose of imparting various physical properties such as mechanical properties and thermal properties, specifically, increasing the hardness and toughness of the coating film.

[0049] As the chain extender (a3), one or more than two kinds can be used. For example, diamine compounds such as ethylenediamine, 1,3-propanediamine, 1,3-butanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane, hydrazine, o-tolylenediamine, m-tolylenediamine, p-tolylenediamine; triamine compounds such as diethylenetriamine; polyamine compounds having 4 or more amino groups such as triethylenetetramine and tetraethylenepentamine; etc. can be mentioned. The low molecular weight polyol (for example, a polyol having a molecular weight of 500 or less) may be used. These chain extenders may be used alone or in combination of two or more. It can also be used within the range where the storage stability of the aqueous resin composition of the present invention is not deteriorated.

[0050] When the urethane resin has an anionic group, the acid value of the urethane resin is preferably 1 mgKOH / g or more, more preferably 2 mgKOH / g or more, still more preferably 5 mgKOH / g or more, even more preferably 10 mgKOH / g or more, and preferably 70 mgKOH / g or less, more preferably 45 mgKOH / g or less, even more preferably 30 mgKOH / g or less, because the water dispersion stability is further improved. The acid value referred to in the present invention is a theoretical value calculated as the number of mg of potassium hydroxide required to neutralize 1 g of the urethane resin based on the amount of use of acid group-containing compounds such as polyols having a carboxy group or a sulfonic acid group used in the production of the urethane resin.

[0051] Also, when the urethane resin has a cationic group, the amine value of the urethane resin is preferably 2 mgKOH / g or more, more preferably 5 mgKOH / g or more, preferably 50 mgKOH / g or less, and more preferably 30 mgKOH / g or less. The amine value referred to in the present invention is a theoretical value calculated as the product of the number of moles (mmol) of hydrogen chloride required to neutralize 1 g of the urethane resin and the formula weight (56.1 g / mol) of potassium hydroxide, based on the amount of a tertiary amino group-containing compound such as a polyol having a tertiary amino group used in the production of the urethane resin.

[0052] The urethane resin can be produced by reacting the polyol (a1), the polyisocyanate (a2), and, if necessary, the chain extender (a3) in the absence of a solvent or in the presence of an organic solvent. The reaction can usually be carried out in a temperature range of 50 to 150°C.

[0053] Examples of the organic solvent that can be used in the production of the urethane resin include alcohol compounds such as methanol, ethanol, and isopropanol; ketone compounds such as acetone and methyl ethyl ketone; polyalkylene glycol compounds such as ethylene glycol, diethylene glycol, and propylene glycol; alkyl ether compounds of polyalkylene glycol; lactam compounds such as N-methyl-2-pyrrolidone, and the like. These organic solvents can be used alone or in combination of two or more.

[0054] The aqueous dispersion of the urethane resin is obtained by mixing the reaction solution and water after the production of the urethane resin and, if necessary, removing the solvent.

[0055] The content of the urethane resin is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, preferably 99% by mass or less, and more preferably 98% by mass or less in the non-volatile matter of the aqueous resin composition.

[0056] Since the content ratio of the urethane resin in the aqueous resin composition can maintain dispersion stability, it is preferably 5% by mass or more, more preferably 10% by mass or more, preferably 60% by mass or less, and more preferably 50% by mass or less.

[0057] The visible light-responsive photocatalyst (B) is an essential component for obtaining excellent antiviral properties. Examples thereof include compositions containing titanium oxide (b1). From the viewpoint of obtaining even more excellent antiviral properties, those in which a metal compound is supported on titanium oxide (b1) are preferably mentioned.

[0058] As the titanium oxide (b1), for example, rutile-type titanium oxide (b1-1), anatase-type titanium oxide, brookite-type titanium oxide, etc. can be used. These titanium oxides may be used alone or in combination of two or more. Among these, from the viewpoint of having excellent photocatalytic activity in the visible light region, it is preferable to contain rutile-type titanium oxide (b1-1).

[0059] The content ratio (rutile ratio) of the rutile-type titanium oxide (b1-1) is preferably 15 mol% or more, more preferably 50 mol% or more, and still more preferably 90 mol% or more with respect to the whole titanium oxide (b1) from the viewpoint of obtaining even more excellent antiviral properties in bright and dark places and visible light responsiveness.

[0060] As a method for producing the titanium oxide (b1), generally, a liquid phase method and a gas phase method are known. The liquid phase method is a method of obtaining titanium oxide by hydrolyzing or neutralizing titanyl sulfate obtained from a solution in which a raw ore such as ilmenite ore is dissolved. The gas phase method is a method of obtaining titanium oxide by a gas phase reaction between titanium tetrachloride obtained by chlorinating a raw ore such as rutile ore and oxygen. As a method for distinguishing titanium oxides produced by both methods, analyzing their impurities can be mentioned. The titanium oxide produced by the liquid phase method contains zirconium, niobium, etc. derived from impurities in the ilmenite ore in the product. On the other hand, in the gas phase method, since there is a step of purifying titanium tetrachloride to remove impurities, these impurities are hardly contained in the titanium oxide.

[0061] Although the titanium oxide produced by the gas phase method has the advantage of being able to generate a uniform particle size, since it is difficult to generate secondary aggregates, it is considered that the viscosity of the mixed liquid during the reaction process increases due to the increase in the apparent specific surface area. In contrast, the titanium oxide (b1) produced by the liquid phase method is considered to generate gentle secondary aggregates in the firing process, and the cohesive force is small with respect to the specific surface area (BET value) caused by primary particles, and it is possible to suppress the viscosity of the mixed liquid. For the above reasons, as the titanium oxide (b1), from the viewpoint of further improving the productivity of the visible light-responsive photocatalyst, the titanium oxide produced by the liquid phase method is preferable.

[0062] As the BET specific surface area of the titanium oxide (b1), from the viewpoint of obtaining more excellent antiviral properties and visible light responsiveness, the range of 1 to 200 m 2 / g is preferable, the range of 3 to 100 m 2 / g is more preferable, the range of 4 to 70 m 2 / g is more preferable, the range of 8 to 50 m 2 / g is even more preferable, and from the viewpoint of further enhancing the productivity of the antiviral agent, the range of 7.5 to 9.5 m 2 / g is preferably in this range. The method for measuring the BET specific surface area of the titanium oxide (b1) will be described in the examples described later.

[0063] As for the primary particle diameter of the titanium oxide (b1), a range of 0.01 to 0.5 μm is preferable, and a range of 0.06 to 0.35 μm is more preferable, from the viewpoint of obtaining more excellent antiviral properties and visible light responsiveness. The measurement method of the primary particle diameter of the titanium oxide (b1) is the value measured by a method of directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and the major axis diameter of the primary particles of each titanium oxide are measured, and the average is taken as the particle diameter of the primary particles. Next, for 100 or more titanium oxide particles, the volume (weight) of each particle is approximated by the cube of the obtained particle diameter, and the volume average particle diameter is taken as the average primary particle diameter.

[0064] Further, as the visible light-responsive photocatalyst, it is preferable to use one in which a metal compound is supported on titanium oxide (b1) from the viewpoint of further improving the photocatalytic activity in the visible light region and easily exhibiting appropriate activity under practical indoor light.

[0065] As the metal compound, for example, a copper compound, an iron compound, a tungsten compound, etc. can be used. Among these, a copper compound is preferable, and a divalent copper compound is more preferable, from the viewpoint of obtaining more excellent antibacterial properties and antiviral properties. As the method for supporting the metal compound on the titanium oxide (b1), a known method can be used.

[0066] Next, a method for supporting a divalent copper compound on titanium oxide (b1), which is the most preferable embodiment, will be described.

[0067] Examples of the method for supporting a divalent copper compound on the titanium oxide (b1) include a method having a mixing step (i) of titanium oxide (b1) containing rutile-type titanium oxide (b1-1), a divalent copper compound raw material (b2), water (b3), and an alkaline substance (b4).

[0068] The concentration of the titanium oxide (b1) in the mixing step (i) is preferably in the range of 3 to 40% by mass. In the present invention, when the titanium oxide (b1) produced by the liquid phase method is used, even if the concentration of the titanium oxide (b1) is increased, a mixing step with good handleability can be performed. Specifically, even when the concentration of the titanium oxide (b1) is in the range exceeding 25% by mass and 40% by mass or less, a mixing step can be performed well.

[0069] As the divalent copper compound raw material (b2), for example, a divalent copper inorganic compound, a divalent copper organic compound, or the like can be used.

[0070] Examples of the divalent copper inorganic compound include inorganic acid salts of divalent copper such as copper sulfate, copper nitrate, copper iodate, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amidosulfate, copper ammonium chloride, copper pyrophosphate, and copper carbonate; halides of divalent copper such as copper chloride, copper fluoride, and copper bromide; copper oxide, copper sulfide, azurite, malachite, copper azide, and the like. These compounds may be used alone or in combination of two or more.

[0071] Examples of the divalent copper organic compound include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper myristate, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, copper mellitate, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, copper acetylacetonate, copper ethyl acetoacetate, copper isovalerate, copper β-resorcylate, copper diacetoacetate, copper formylsuccinate, copper salicylamine, copper bis(2-ethylhexanoate), copper sebacate, copper naphthenate, copper oxine, copper acetylacetonate, copper ethyl acetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, copper dimethyldithiocarbamate, etc. These compounds may be used alone or in combination of two or more kinds.

[0072] Among the above-mentioned ones, as the divalent copper compound raw material (b2), those represented by the following general formula (1) are preferably used. CuX2(1) (In formula (1), X represents a halogen atom, CH3COO, NO3, or (SO4). 1 / 2 (It is shown.))

[0073] As X in the formula (1), a halogen atom is more preferable, and a chlorine atom is even more preferable.

[0074] The amount of the divalent copper compound raw material (b2) used in the mixing step (i) is preferably in the range of 0.01 to 20 parts by mass, more preferably in the range of 0.1 to 15 parts by mass, and even more preferably in the range of 0.3 to 10 parts by mass with respect to 100 parts by mass of the titanium oxide (b1).

[0075] The water (b3) is a solvent in the mixing step (i), and water alone is preferred, but other solvents may be included as necessary. Examples of the other solvents include alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide, tetrahydrofuran, etc. These solvents may be used alone or in combination of two or more.

[0076] Examples of the alkaline substance (b4) include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, basic surfactants, etc., and it is preferable to use sodium hydroxide.

[0077] From the viewpoint of easy reaction control, the alkaline substance (b4) is preferably added as a solution, and the concentration of the alkaline solution to be added is preferably in the range of 0.1 to 5 mol / L, more preferably in the range of 0.3 to 4 mol / L, and still more preferably in the range of 0.5 to 3 mol / L.

[0078] In the mixing step (i), the titanium oxide (b1), the divalent copper compound raw material (b2), the water (b3), and the alkaline substance (b4) may be mixed. For example, first, the titanium oxide (b1) is mixed with the water (b3) and stirred as necessary, then the divalent copper compound raw material (b2) is mixed and stirred, and thereafter, the alkaline substance (b4) is added and stirred. By this mixing step (i), the divalent copper compound derived from the divalent copper compound raw material (b2) is supported on the titanium oxide (b1).

[0079] Examples of the total stirring time in the mixing step (i) include 5 to 120 minutes, preferably 10 to 60 minutes. Examples of the temperature during the mixing step (i) include the range of room temperature to 70°C.

[0080] From the viewpoint that the loading of the divalent copper compound on titanium oxide (b1) is good, the pH of the mixture after mixing and stirring titanium oxide (b1), a divalent copper compound raw material (b2), and water (b3), and then mixing and stirring an alkaline substance (b4) is preferably in the range of 8 to 11, more preferably in the range of 9.0 to 10.5.

[0081] After the mixing step (i) is completed, the mixed solution can be separated into solid components. Examples of the method for performing the separation include filtration, sedimentation separation, centrifugal separation, evaporation to dryness, etc., and filtration is preferred. The separated solid components may then be washed with water, crushed, classified, etc. as necessary.

[0082] After obtaining the solid components, it is preferable to heat-treat the solid components from the viewpoint that the divalent copper compound derived from the divalent copper compound raw material (b2) supported on the titanium oxide (b1) can be more firmly bonded. The heat treatment temperature is preferably in the range of 150 to 600 °C, more preferably in the range of 250 to 450 °C. The heat treatment time is preferably 1 to 10 hours, more preferably 2 to 5 hours.

[0083] By the above method, a titanium oxide composition containing titanium oxide on which a divalent copper compound is supported on titanium oxide (b1) can be obtained. The loading amount of the divalent copper compound supported on the titanium oxide (b1) is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (b1) from the viewpoint of photocatalytic activity including antiviral properties. The loading amount of the divalent copper compound can be adjusted by the amount of the divalent copper compound raw material (b2) used in the mixing step (i).

[0084] When the resin solid content of the coating resin composition is 100 parts by mass, the content of the visible light-responsive photocatalyst in the coating resin composition is usually at least 0.3 part by mass, preferably at least 2 parts by mass, more preferably at least 3 parts by mass, and the upper limit is usually at most 100 parts by mass, preferably at most 50 parts by mass, more preferably at most 33 parts by mass. Any combination of these upper and lower limit values may be used. When the resin solid content of the coating resin composition is 100 parts by mass, the content of the visible light-responsive photocatalyst in the coating resin composition is usually from 0.3 part by mass to 100 parts by mass, preferably from 2 parts by mass to 50 parts by mass, more preferably from 3 parts by mass to 33 parts by mass.

[0085] Examples of the aqueous medium (C) include water, an organic solvent miscible with water, and a mixture thereof. Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol, isopropyl alcohol, 1,2-propylene glycol, and 1,3-butylene glycol; ketone solvents such as acetone and methyl ethyl ketone; glycol ether solvents such as ethylene glycol-n-butyl ether, diethylene glycol-n-butyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol-n-butyl ether, and tripropylene glycol methyl ether; lactam solvents such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; and amide solvents such as N,N-dimethylformamide. These organic solvents miscible with water can be used alone or in combination of two or more.

[0086] In consideration of safety and reduction of environmental load, the aqueous medium (C) is preferably water only or a mixture of water and an organic solvent miscible with water, more preferably water only.

[0087] The content ratio of the aqueous medium (C) is preferably 30 to 80% by mass, more preferably 50 to 70% by mass, based on the total amount of the aqueous resin composition.

[0088] In addition to the aqueous resin (A), the visible light-responsive photocatalyst (B), and the aqueous medium (C), the coating resin composition may contain, as necessary, crosslinking agents, plasticizers, antistatic agents, waxes, surfactants, light stabilizers, flow regulators, dyes, leveling agents, rheology control agents, ultraviolet absorbers, antioxidants, photocatalytic compounds, inorganic pigments, organic pigments, extender pigments, and other additives.

[0089] Examples of the crosslinking agent include amino resins, aziridine compounds, melamine compounds, epoxy compounds, oxazoline compounds, carbodiimide compounds, isocyanate compounds, and the like.

[0090] In addition, by using the surfactant, the blending stability of the urethane resin composition of the present invention can be further improved. When using a surfactant, since the adhesion of the obtained coating film to the substrate can be maintained, it is preferably used in a range of 20 parts by mass or less with respect to 100 parts by mass of the aqueous resin (A), and it is preferably not used as much as possible.

[0091] The content ratio of the other additives is, for example, 30% by mass or less, for example, 20% by mass or less, based on the nonvolatile content of the aqueous resin composition, and the lower limit is 0% by mass, and it may be 0.1% by mass or more.

[0092] Examples of the substrate of the coating resin composition include metals, various plastics and their films, glass, paper, wood, and the like.

[0093] Examples of the metal substrate include galvanized steel sheets, aluminum-zinc alloy galvanized steel sheets, aluminum plates, aluminum alloy plates, electromagnetic steel sheets, copper plates, stainless steel sheets, etc. used in applications such as automobiles, home appliances, and building materials.

[0094] As the plastic base material, generally, as materials adopted for plastic molded products such as mobile phones, home appliances, interior and exterior automotive trim materials, and OA equipment, there are acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS / PC resin, polystyrene resin (PS resin), polymethyl methacrylate resin (PMMA resin), acrylic resin, polypropylene resin, polyethylene resin, etc. As the plastic film base material, polyethylene terephthalate film, polyester film, polyethylene film, polypropylene film, TAC (triacetyl cellulose) film, polycarbonate film, polyvinyl chloride film, etc. can be used.

[0095] The coating agent can be suitably used, for example, for surface coating of various articles such as aluminum fins; building members such as outer walls and roofs; civil engineering members such as guardrails, soundproof walls, and drainage ditches; home appliances; industrial machinery; automotive exterior trim materials; goggles; anti-fogging materials such as anti-fogging film sheets and anti-fogging glass; mirrors; and medical instruments. Articles having a coating film of these coating agents are also included in the technical scope of the present invention.

Examples

[0096] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, and it is of course possible to appropriately modify and implement within the range that can conform to the gist of the foregoing and following descriptions, and all of them are included in the technical scope of the present invention.

[0097] [Preparation Example 1] (1) Titanium oxide a) Crystalline rutile-type titanium oxide b) Production method: Liquid phase method (sulfuric acid method) c) Physical property values · BET specific surface area: 9.0 m 2 / g · Rutile conversion rate: 95.4% · Primary particle size: 0.18 μm

[0098] [Measurement Method of BET Specific Surface Area of Titanium Oxide (a)] Using the fully automatic BET specific surface area measuring device "MacSORB HM model-1208" manufactured by Mount Tech Co., Ltd., the measurement was carried out by the specific surface area measurement (BET one-point method).

[0099] [Measurement Method of Rutile Ratio of Titanium Oxide (a)] Using the X-ray diffractometer "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to the rutile-type crystal was calculated from the peak heights corresponding to the crystals of the whole titanium oxide (rutile type, brookite type, anatase type).

[0100] [Measurement Method of Primary Particle Size of Titanium Oxide (a)] Using a transmission electron microscope (TEM), the measurement was carried out by a method of directly measuring the size of primary particles from electron micrographs. Specifically, the minor axis diameter and major axis diameter of the primary particles of each titanium oxide were measured, and the average was taken as the particle diameter of the primary particles. Next, for more than 100 titanium oxide particles, the volume (weight) of each particle was approximated by the cube of the obtained particle diameter, and the volume average particle diameter was taken as the average primary particle diameter.

[0101] (2) Manufacturing Process a) Mixing Process (Reaction Process) 600 parts by mass of the titanium oxide, 8 parts by mass of copper(II) chloride dihydrate, and 900 parts by mass of water were mixed in a stainless steel container. Next, the mixture was stirred with a stirrer ("Robomix" manufactured by Tokushu Kika Kogyo Co., Ltd.), and a 1 mol / L aqueous sodium hydroxide solution was added dropwise until the pH of the mixed solution reached 10.[[ID=Z3]]

[0102] b) Dehydration Process Vacuum filtration was carried out using qualitative filter paper (5C) to separate the solid content from the mixed solution, and further washing was carried out with ion-exchanged water. Next, the washed solid was dried at 120°C for 12 hours to remove moisture. After drying, a powdery titanium oxide composition was obtained with a coffee mill ("Millser" manufactured by Iwatani Sangyo Co., Ltd.).

[0103] c) Heat Treatment Process Using a precision thermostat ("DH650" manufactured by Yamato Scientific Co., Ltd.), heat treatment was carried out at 450 °C for 3 hours in the presence of oxygen to obtain a titanium oxide composition (antiviral agent 1) containing titanium oxide supported with copper(II) oxide as a visible light-responsive photocatalyst.

[0104] [Preparation Example 2] (1) Titanium Oxide a) Crystalline rutile-type titanium oxide b) Production method: vapor phase method c) Physical property values · BET specific surface area: 13 m 2 / g · Rutile conversion rate: 95.6% · Primary particle size: 0.15 μm

[0105] In Preparation Example 1, except that the type of titanium oxide was changed to the above titanium oxide and the amount of water used was changed from 900 parts by mass to 4,000 parts by mass, a titanium oxide composition (antiviral agent 2) as a visible light-responsive photocatalyst was obtained in the same manner as in Preparation Example 1.

[0106] [Measurement method for the amount of divalent copper compound supported on titanium oxide (a)] The titanium oxide composition obtained in the preparation example was completely dissolved in a hydrofluoric acid solution, and the extract was analyzed by an ICP emission spectroscopic analyzer to quantify the amount of divalent copper compound supported on titanium oxide (a) (amount of divalent copper compound supported (parts by mass) / titanium oxide (a) (parts by mass)). The amount of copper(II) oxide supported in the antiviral agents (photocatalysts) obtained in Preparation Examples 1 and 2 was 0.5 parts by mass with respect to 100 parts by mass of titanium oxide.

[0107] (Synthesis Example 1: Synthesis method of aqueous resin 1) 155.4 parts by mass of 1,6 - hexanediol (molecular weight 118), 137.0 parts by mass of neopentyl glycol (molecular weight 104), and 423.9 parts by mass of adipic acid (molecular weight 146) were added to a 3.0 - liter flask and melted at 120°C. Then, while stirring, the temperature was raised to 220°C over 3 to 4 hours and held for 5 hours, and then cooled to 150°C. After that, 88.2 parts by mass of 2,2’ - dimethylolpropionic acid (molecular weight 134) was added, and the mixture was held at 150°C with stirring for 5 to 10 hours. Then, 300.0 parts by mass of methyl ethyl ketone was added to prepare a methyl ethyl ketone solution of polyester polyol (a1 - 1A) having a carboxyl group with a non - volatile content of 70.0% by mass (acid value 52.9 mgKOH / g, hydroxyl value 62.3 mgKOH / g). Next, in a nitrogen - purged container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 198.3 parts by mass of the methyl ethyl ketone solution of the polyester polyol (a1 - 1A) having a carboxyl group, 159.8 parts by mass of the polyester polyol (a1 - 2A), 19.1 parts by mass of 1,6 - hexanediol, and 74.7 parts by mass of tolylene diisocyanate were reacted for 3 hours in the presence of 151.8 parts by mass of methyl ethyl ketone.

[0108] The reaction was terminated when the specified NCO% of the reactant was reached to obtain an organic solvent solution of polyurethane (A - 1). Then, 17.2 parts by mass of triethylamine, 652.6 parts by mass of water, and 7.7 parts by mass of piperazine were added to the organic solvent solution of the polyurethane (A - 1) and stirred to obtain an aqueous dispersion of polyurethane (A - 1). Then, by aging and desolventizing the aqueous dispersion of the polyurethane (A - 1), a polyurethane composition (I - 1) with a non - volatile content of 40% by mass (urea bond content of polyurethane (A - 1) was 445 mmol / kg) was obtained. The urea bond content was calculated based on the amount of piperazine used.

[0109] (Synthesis Example 2: Method for synthesizing aqueous resin 2) Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 590 parts by mass of polypropylene glycol diglycidyl ether (epoxy equivalent: 201 g / equivalent) was charged, and then the inside of the flask was purged with nitrogen. Next, after heating the inside of the flask to 70 °C using an oil bath, 380 parts by mass of di-n-butylamine was added dropwise over 30 minutes using the dropping device. After completion of the addition, the reaction was carried out at 90 °C for 10 hours. After completion of the reaction, using an infrared spectrophotometer (FT / IR-460Plus, manufactured by JASCO Corporation), it was confirmed that the absorption peak near 842 cm-1 due to the epoxy group of the reaction product had disappeared, and a tertiary amino group-containing polyol (amine equivalent: 339 g / equivalent, hydroxyl equivalent: 339 g / equivalent) was prepared.

[0110] Into a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser, and a dropping device, 705 parts by mass of "Nipporan 980R" [a polycarbonate polyol obtained by reacting 1,6-hexanediol and dimethyl carbonate, hydroxyl equivalent 986 g / equivalent, manufactured by Nippon Polyurethane Industry Co., Ltd.] and 352 parts by mass of a polyester (hydroxyl equivalent 951 g / equivalent) obtained by reacting neopentyl glycol, 1,4-butanediol, terephthalic acid, and adipic acid were added, and dehydration was carried out at 120 to 130 °C under a reduced pressure of 0.095 MPa. After dehydration, it was cooled to 70 °C, 666 parts by mass of ethyl acetate was added, and it was sufficiently stirred and mixed while cooling to 50 °C. After stirring and mixing, 280 parts by mass of 4,4'-dicyclohexylmethane diisocyanate (4,4-H-MDI) and 0.3 parts by mass of stannous octylate were added, and the reaction was carried out at 70 °C for 2 hours. After completion of the reaction, 84 parts by mass of the tertiary amino group-containing polyol was added, and after reacting for 4 hours, it was cooled to 55 °C, and 47 parts by mass of "Aminosilane A1100" [γ-aminopropyltriethoxysilane, manufactured by Nippon Unicar Co., Ltd.] was added and reacted for 1 hour to prepare a urethane prepolymer solution having terminal isocyanate groups. Next, 15 parts by mass of hydrazine hydrate was added to the urethane prepolymer solution, and a chain extension reaction was carried out for 1 hour. Next, 1954 parts by mass of ethyl acetate and 16 parts by mass of acetic acid were added, and after holding at 55 °C for 1 hour, it was cooled to 40 °C, and 3300 parts by mass of ion-exchanged water was added to prepare an aqueous dispersion. By subjecting this aqueous dispersion to vacuum distillation, a cationic polyurethane resin aqueous dispersion (I) having a non-volatile content of 35% by mass and a pH of 4.1 was prepared. The pH is a value measured using a pH meter (M-12, manufactured by Horiba, Ltd.) under an environment of 25 °C.

[0111] (Examples 1 to 4, Comparative Examples 1 to 4) 100 parts by mass of the aqueous resins 1 and 2 obtained in Synthesis Examples 1 and 2 and the photocatalysts 1 and 2 or titanium oxide ("Ti-Pure R-706" manufactured by Kemers) obtained in Preparation Examples 1 and 2 were blended as shown in Table 1, gradually added at 2000 rpm using a high-speed disperser, and then stirred for 30 minutes to obtain antiviral coating agents 1 to 4 and comparative coating agents 1 to 4.

[0112] [Antiviral performance evaluation] The coating agents obtained in the examples and comparative examples (1 g / m 2 ) were applied to corona-treated PET (Lumirror manufactured by Toray Industries, Inc. (50 μm thick)) to a dry weight of 10 g / m 2 and dried at 80°C for 2 minutes to prepare samples. Next, the obtained samples were subjected to an anti-phage virus test (JIS R1756:2020). 1) For the light irradiation conditions, the light of a white fluorescent lamp was cut off from ultraviolet rays by an N113 filter, and the illuminance was set to 500 lux. 2) The samples obtained in the examples and comparative examples were cut into 50 mm × 50 mm, and after dropping 100 μL of a Qβ phage solution with a known concentration onto the coating surface, a 4 cm × 4 cm contact film was placed on it to obtain a sample for evaluation. 3) The samples irradiated with light for 8 hours were collected with SCDLP solution, appropriately diluted, infected with Escherichia coli, applied to an agar medium, and evaluated by counting the number of colonies after culturing. The antiviral property was evaluated according to the following criteria based on the inactivation degree of Qβ phage. 〇: Inactivation degree is -2 or less ×: Inactivation degree is greater than -2

[0113] The results are shown in Table 1.

[0114] [Table 1]

[0115] Examples 1 to 4 are examples of the present invention and were able to impart antiviral properties. On the other hand, Comparative Examples 1 to 4 are examples that do not contain a visible light-responsive photocatalyst and had poor antiviral properties.

Claims

1. A coating resin composition comprising a hydrophilic resin (A), a visible light-responsive photocatalyst (B), and an aqueous medium (C), wherein the hydrophilic resin (A) is a urethane resin which is a reaction product containing a polyol (a1) and a polyisocyanate (a2), the polyol (a1) at least contains a polyol (a1-2) having a hydrophilic group, the polyol (a1-2) having a hydrophilic group contains a polyol having a cationic group, the cationic group is a tertiary amino group and / or a group in which a part or all of the tertiary amino group is quaternized, the coating resin composition, wherein the content of the visible light-responsive photocatalyst is 0.3 parts by mass or more and 33 parts by mass or less when the resin solid content of the coating resin composition is 100 parts by mass.

2. The coating resin composition according to claim 1, wherein the visible light-responsive photocatalyst (B) is a titanium oxide (b1) on which a metal compound is supported.

3. The coating resin composition according to claim 2, wherein the titanium oxide (b1) contains rutile-type titanium oxide (b1-1).

4. The coating resin composition according to claim 2 or 3, wherein the metal compound is a divalent copper compound.

5. A coating layer formed from the coating resin composition according to any one of claims 1 to 4.

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