JP7653053B2 - Urethane resin composition, laminate, and shaped object - Google Patents

Description

The present invention relates to a urethane resin composition that can be imparted with antiviral properties by containing a visible light responsive photocatalyst, and to a laminate and a molded object that have been imparted with antiviral properties.

In recent years, the spread of various viruses and bacteria, including the new coronavirus, has led to a growing demand throughout society for products with antibacterial and antiviral properties. There is a particularly high demand for these products in places that are touched by many people and for items that are used frequently, but because it is time-consuming and costly to change all existing equipment and items to ones that have antibacterial and antiviral properties, there is a demand for products that can impart these properties in a simple manner.

Conventionally used antibacterial and antiviral agents include various alcohols, quaternary ammonium salt compounds, silver-based compounds, and copper-based compounds, but these do not fully meet market requirements, such as skin irritation and reduced antibacterial and antiviral properties over time.

In contrast, photocatalysts that use titanium oxide are less irritating to the human body and maintain their antibacterial and antiviral properties for a long period of time, so there are high expectations for their practical use (see Patent Document 1).

JP 2013-166705 A

The object of the present invention is to provide a urethane resin composition capable of imparting antiviral properties, a laminate imparted with antiviral properties, and a molded object.

The present invention provides a urethane resin composition that can be imparted with antiviral properties by containing a visible light responsive photocatalyst, and synthetic leather and shaped objects that are imparted with antiviral properties by containing the urethane resin composition. The present invention includes the following.

[1] A urethane resin composition comprising a visible light responsive photocatalyst.
[2] The urethane resin composition according to [1], wherein the visible light responsive photocatalyst is a metal compound supported on titanium oxide (a).
[3] The urethane resin composition according to [2], wherein the titanium oxide (a) comprises rutile titanium oxide (a1).
[4] The urethane resin composition according to [2] or [3], wherein the metal compound is a divalent copper compound.
[5] The urethane resin composition according to any one of [1] to [4], wherein the content of the visible light responsive photocatalyst is 0.3 parts by mass or more and 67 parts by mass or less, based on 100 parts by mass of the resin solid content of the urethane resin composition.
[6] A laminate comprising a fibrous base material and a surface layer formed on at least one surface of the fibrous base material from the urethane resin composition according to any one of [1] to [5].
[7] The laminate according to [6], further comprising a surface treatment layer formed on the surface of the skin layer using a surface treatment agent.
[8] The laminate according to [6] or [7], wherein the form of the fibrous substrate is one selected from the group consisting of knitted fabrics, woven fabrics, and nonwoven fabrics.
[9] A shaped object made of the urethane resin composition according to any one of [1] to [4] above.
[10] The object according to [9], characterized in that it is produced by fused deposition modeling.

The urethane resin composition of the present invention can produce a coating and a molded object having antiviral properties. The laminate and the molded object having the coating have antiviral properties.

The urethane resin composition of the present invention contains a urethane resin and a visible light responsive photocatalyst.

The visible light responsive photocatalyst may be, for example, a composition containing titanium oxide (a), and preferably a composition in which a metal compound is supported on titanium oxide (a) because it provides even more excellent antiviral properties.

As the titanium oxide (a), for example, rutile type titanium oxide (a1), 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, it is preferable to include rutile type titanium oxide (a1) because it has excellent photocatalytic activity in the visible light region.

The content (rutilated rate) of the rutile-type titanium oxide (a1) is preferably 15 mol % or more, more preferably 50 mol % or more, and even more preferably 90 mol % or more, of the total titanium oxide (a), in order to obtain even better antiviral properties in bright and dark places and visible light responsiveness.

Generally, the liquid phase method and the gas phase method are known as methods for producing the titanium oxide (a). The liquid phase method is a method in which titanium oxide is obtained by hydrolyzing or neutralizing titanyl sulfate obtained from a liquid in which raw ore such as ilmenite ore is dissolved. The gas phase method is a method in which titanium oxide is obtained by a gas phase reaction between oxygen and titanium tetrachloride obtained by chlorinating raw ore such as rutile ore. In addition, a method for distinguishing between titanium oxides produced by both methods is to analyze the impurities. Titanium oxide produced by the liquid phase method contains zirconium, niobium, etc., which are derived from impurities in ilmenite ore. In contrast, the gas phase method includes a process of purifying titanium tetrachloride and removing impurities, so that these impurities are hardly contained in the titanium oxide.

Although titanium oxide produced by the gas phase method has the advantage of being able to produce uniform particle diameters, it is thought that secondary aggregates are difficult to produce, and therefore the apparent specific surface area is high, which increases the viscosity of the mixed liquid during the reaction process. In contrast, titanium oxide (a) produced by the liquid phase method is thought to produce gentle secondary aggregates in the firing process, and has low cohesive force compared to the specific surface area (BET value) caused by the primary particles, making it possible to suppress the viscosity of the mixed liquid. For these reasons, titanium oxide (a) produced by the liquid phase method is preferable because it can further improve the productivity of the self-cleaning agent.

The BET specific surface area of the titanium oxide (a) is preferably in the range of 1 to 200 m ² /g, more preferably in the range of 3 to 100 m ² /g, more preferably in the range of 4 to 70 m ² /g, and even more preferably in the range of 8 to 50 m ² /g, from the viewpoint of obtaining even better antiviral properties and visible light responsiveness, and is preferably in the range of 7.5 to 9.5 m ² /g from the viewpoint of further increasing the productivity of the antiviral agent. The method for measuring the BET specific surface area of the rutile titanium oxide (a1) will be described in the Examples described later.

The primary particle diameter of the titanium oxide (a) is preferably in the range of 0.01 to 0.5 μm, more preferably in the range of 0.06 to 0.35 μm, in order to obtain even better antiviral properties and visible light responsiveness. The primary particle diameter of the titanium oxide (a) is measured by a method in which a transmission electron microscope (TEM) is used to directly measure the size of the primary particles from an electron microscope photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of titanium oxide are measured, and the average is taken as the particle diameter of the primary particles. Next, the volume (weight) of each particle is calculated for 100 or more titanium oxide particles by approximating it to the cube of the calculated particle diameter, and the volume average particle diameter is taken 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 (a) in order to further improve the photocatalytic activity in the visible light region and to easily exhibit appropriate activity under practical indoor lighting.

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 preferred, and a divalent copper compound is more preferred, in that it provides even more excellent antibacterial and antiviral properties. A known method can be used to support the metal compound on the titanium oxide (a).

Next, we will explain the most preferred method of supporting a divalent copper compound on titanium oxide (a).

As an example of a method for supporting a divalent copper compound on the titanium oxide (a), there can be mentioned a method having a mixing step (i) of titanium oxide (a) including rutile-type titanium oxide (a1), a divalent copper compound raw material (b), water (c), and an alkaline substance (d).

The concentration of the titanium oxide (a) in the mixing step (i) is preferably in the range of 3 to 40% by mass. In the present invention, when titanium oxide (a) produced by a liquid phase method is used, the mixing step can be carried out with good handling even if the concentration of titanium oxide (a) is increased. Specifically, the mixing step can be carried out well even if the concentration of titanium oxide (a) is in the range of more than 25% by mass to 40% by mass or less.

As the divalent copper compound raw material (b), for example, a divalent copper inorganic compound, a divalent copper organic compound, etc. can be used.

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

Examples of the divalent copper organic compounds include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper caprate, copper myristic acid, 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 mellitic acid, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipic acid, copper fumarate, and glycol. Examples of compounds that can be used include copper ester, copper glycerate, copper gluconate, copper tartrate, copper acetylacetonate, copper ethylacetoacetate, copper isovalerate, copper β-resorcylate, copper diacetoacetate, copper formylsuccinate, copper salicylamine, copper bis(2-ethylhexanoate), copper sebacate, copper naphthenate, copper oxine, copper acetylacetonate, copper ethylacetoacetate, copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxide, copper isopropoxide, copper methoxide, and copper dimethyldithiocarbamate. These compounds may be used alone or in combination of two or more.

As the divalent copper compound raw material (b), among those mentioned above, it is preferable to use one represented by the following general formula (1).
_CuX2 (1)
(In formula (1), X represents a halogen atom, CH ₃ COO, NO ₃ , or (SO ₄ ) _1/2 .)

In the formula (1), X is more preferably a halogen atom, and even more preferably a chlorine atom.

The amount of the divalent copper compound raw material (b) 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, per 100 parts by mass of the titanium oxide (a).

The water (c) is a solvent in the mixing step (i), and although water alone is preferred, other solvents may be included as necessary. Examples of the other solvents that can be used 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, and the like. These solvents may be used alone or in combination of two or more.

Examples of the alkaline substance (d) that can be used include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, and basic surfactants, and it is preferable to use sodium hydroxide.

The alkaline substance (d) is preferably added as a solution in order to facilitate control of the reaction, and the concentration of the alkaline solution added is preferably in the range of 0.1 to 5 mol/L, more preferably in the range of 0.3 to 4 mol/L, and even more preferably in the range of 0.5 to 3 mol/L.

In the mixing step (i), the titanium oxide (a), the divalent copper compound raw material (b), the water (c), and the alkaline substance (d) may be mixed. For example, the titanium oxide (a) may be mixed with the water (c) and stirred as necessary, the divalent copper compound raw material (b) may then be mixed and stirred, and the alkaline substance (d) may then be added and stirred. By this mixing step (i), the divalent copper compound derived from the divalent copper compound raw material (b) is supported on the titanium oxide (a).

The total stirring time in the mixing step (i) is, for example, 5 to 120 minutes, and preferably 10 to 60 minutes. The temperature during the mixing step (i) is, for example, in the range of room temperature to 70°C.

In order to ensure good support of the divalent copper compound on the titanium oxide (a), the titanium oxide (a), the divalent copper compound raw material (b), and water (c) are mixed and stirred, and then the alkaline substance (d) is mixed and stirred to produce a mixture having a pH value preferably in the range of 8 to 11, and more preferably in the range of 9.0 to 10.5.

After the mixing step (i) is completed, the mixture can be separated as a solid content. Methods for the separation include, for example, filtration, sedimentation, centrifugation, and evaporation and drying, with filtration being preferred. The separated solid content may then be washed with water, crushed, classified, etc., as necessary.

After obtaining the solid content, it is preferable to heat treat the solid content in order to more firmly bond the divalent copper compound derived from the divalent copper compound raw material (b) supported on the titanium oxide (a). 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.

By the above method, a titanium oxide composition containing titanium oxide in which a divalent copper compound is supported on titanium oxide (a) can be obtained. From the viewpoint of photocatalytic activity including antiviral activity, it is preferable that the amount of the divalent copper compound supported on the titanium oxide (a) is in the range of 0.01 to 20 parts by mass per 100 parts by mass of titanium oxide (a). The amount of the divalent copper compound supported can be adjusted by the amount of the divalent copper compound raw material (b) used in the mixing step (i).

The content of the visible light responsive photocatalyst in the urethane resin composition is not particularly limited within the range in which the effects of the present invention can be obtained, but when the resin solid content of the urethane resin composition is 100 parts by mass, the lower limit is usually 0.3 parts by mass or more, preferably 3.3 parts by mass or more, and more preferably 10 parts by mass or more, and the upper limit is usually 67 parts by mass or less, preferably 50 parts by mass or less, and more preferably 33 parts by mass or less. Any combination of these upper and lower limits may be used. The content of the visible light responsive photocatalyst in the urethane resin composition is usually 0.3 parts by mass or more and 67 parts by mass or less, preferably 3.3 parts by mass or more and 50 parts by mass or less, and more preferably 10 parts by mass or more and 33 parts by mass or less, when the resin solid content of the urethane resin composition is 100 parts by mass.

The urethane resin used in the present invention includes, for example, polyether-based urethane resin, polycarbonate-based urethane resin, polyester-based urethane resin, resin and modified products thereof, and either thermosetting urethane resin or thermoplastic polyurethane resin can be used. Among these, polyether-based urethane resin is suitable when flexibility is required for sports shoes and clothing applications. Polycarbonate-based urethane resin is suitable when long-term durability is required for applications such as furniture and vehicles. The molecular weight of the urethane resin varies depending on the application and required performance, but may be appropriately selected from the number average molecular weight range of 5,000 to 50,000, preferably 5,000 to 15,000.

Examples of the polyol component that is the raw material of the urethane resin include polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, polyethylene adipate, polypropylene adipate, polyoxytetraethylene adipate, etc. These polyol components can be used alone or in combination of two or more types.

Examples of the isocyanate component that is a raw material for the urethane resin include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 2,2'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 1,5-naphthalene diisocyanate, 1,5-tetrahydronaphthalene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, etc. These polyisocyanates can be used alone or in combination of two or more kinds.

A crosslinking agent can be added to the urethane resin composition of the present invention as necessary. The crosslinking agent is not particularly limited as long as it can crosslink with the urethane resin used in the present invention. Examples of such crosslinking agents include compounds having two or more functional groups in one molecule that can react with functional groups such as active hydrogen atoms in the urethane resin, or cyclic compounds that react with functional groups such as active hydrogen atoms in the urethane resin by opening the ring to form bonds and crosslink the urethane resin. Specific examples include epoxy compounds, aziridine compounds, carbodiimide compounds, polyisocyanate compounds, oxazoline compounds, melamine formamide compounds, and urea methylol compounds. Among these, polyisocyanate compounds are preferred. These crosslinking agents can be used alone or in combination of two or more types.

An organic solvent can be added to the urethane resin composition of the present invention to impart coatability. The organic solvent is not particularly limited as long as it dissolves the urethane resin. Examples of such organic solvents include organic solvents such as N,N-dimethylformamide (hereinafter abbreviated as DMF). In addition, in order to improve the drying property after application of the resin solution, methanol, ethanol, isopropyl alcohol, toluene, methyl ethyl ketone, ethyl acetate, cyclohexanone, ethyl cellosolve, methyl cellosolve, propylene glycol methyl ether, propylene glycol methyl ether acetate, N-methylpyrrolidone, etc. can be used. Among these, cyclohexanone, ethyl acetate, methyl ethyl ketone, ethanol, methanol, isopropyl alcohol, etc., which have a boiling point of less than 100°C, are particularly preferred. These solvents used to improve drying property can be used alone or in combination of two or more types.

The total amount of the organic solvent and, if necessary, the solvent used to improve drying properties is preferably in a range such that the solids concentration of the resin composition is 5 to 60% by mass.

The urethane resin composition of the present invention can be suitably used for the surface layer, adhesive layer and intermediate layer of the fibrous substrate, as well as for the surface treatment layer on the surface of the surface layer.

The urethane resin composition of the present invention may further contain, as necessary, various additives such as crosslinking accelerators, colorants such as organic pigments, flame retardants, and antioxidants, and resins other than urethane resins.

Furthermore, when manufacturing objects using various molding methods, it is preferable to use a thermoplastic urethane resin. These thermoplastic polyurethanes are resins obtained by polymerizing a polyol and a polyisocyanate in the presence of a chain extender.

The polyol used as a raw material for the thermoplastic polyurethane resin is not particularly limited, and conventionally known polyols can be used. Examples of these polyols include polymer polyols such as polyester polyols, polyether polyols, polycarbonate polyols, and polylactone polyols. These polyols may be used alone or in combination of two or more.

The average molecular weight (number average molecular weight) of the polyol used as a raw material for the thermoplastic polyurethane resin may be appropriately selected, preferably within the range of 500 to 5,000, more preferably 700 to 4,000.

Specific examples of polyols used as raw materials for the thermoplastic urethane resin include polytetramethylene glycol, polyethylene glycol, polypropylene glycol, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, nonanediol, and 1,4-cyclohexanedimethanol, and polyols obtained by dealcoholization reaction of low molecular weight polyols with carbonate compounds such as diethylene carbonate, dipropylene carbonate, and diphenyl carbonate. These polyol components can be used alone or in combination of two or more types.

The polyisocyanate used as a raw material for the thermoplastic urethane resin is not particularly limited as long as it has two or more isocyanate groups, and conventionally known polyisocyanates can be used. For example, aliphatic isocyanates such as 1,6-hexamethylene diisocyanate (HDI), 2,2,4-trimethylhexamethylene diisocyanate, methylene diisocyanate, isopropylene diisocyanate, lysine diisocyanate, lysine diisocyanate methyl ester, and 1,5-octylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), and norbornene diisocyanate can be used. isocyanate, hydrogenated tolylene diisocyanate, methylcyclohexane diisocyanate, isopropylidene bis (4-cyclohexyl isocyanate), alicyclic isocyanates such as dimer acid diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, p- or m-xylylene diisocyanate (XDI), Examples of the isocyanates include aromatic isocyanates such as lysine diisocyanate, p-phenylene diisocyanate, diphenyl ether diisocyanate, diphenyl sulfone diisocyanate, dianisidine diisocyanate, and tetramethyl-m-xylylene diisocyanate; triphenylmethane triisocyanate, triisocyanate phenyl thiophosphate, polymethylene polyphenylene polyisocyanate (polymeric MDI), isocyanurate modified products and biuret modified products which are trimers of HDI and TDI; and polyols obtained by dealcoholization reaction between low molecular weight polyols such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, nonanediol, and 1,4-cyclohexanedimethanol and carbonate compounds such as diethylene carbonate, dipropylene carbonate, and diphenyl carbonate. These polyisocyanates can be used alone or in combination of two or more.

The chain extender used as a raw material for the thermoplastic urethane resin is not particularly limited, and any conventionally known one can be used. As the chain extender, for example, any conventionally known polyhydric alcohol or amine can be used, but low molecular weight polyols having 2 to 10 carbon atoms are preferred. Examples of these low molecular weight polyols include aliphatic polyols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpentanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, octanediol, nonanediol, decanediol, trimethylpropane, and glycerin, alicyclic polyols such as cyclohexanediol and cyclohexanedimethanol, and aromatic polyols such as bishydroxyethoxybenzene and xylene glycol. These chain extenders can be used alone or in combination of two or more types.

When using thermoplastic polyurethane in the present invention, additives such as silane coupling agents, fillers, thixotropic agents, tackifiers, waxes, plasticizers, heat stabilizers, antioxidants, UV absorbers, light resistance stabilizers, fillers, fiber-based reinforcing materials, pigments, fluorescent brighteners, foaming agents, thermoplastic resins, thermosetting resins, dyes, conductivity-imparting agents, antistatic agents, moisture permeability enhancers, water repellents, oil repellents, hollow foams, crystal water-containing compounds, flame retardants, water absorbents, moisture absorbents, deodorants, antibacterial agents, antifungal agents, blocking inhibitors, hydrolysis inhibitors, organic water-soluble compounds, and inorganic water-soluble compounds may be blended as necessary.

Next, we will explain specific aspects in which the urethane resin composition is used.

The urethane resin composition of the present invention can be used as a coating agent for fibrous substrates. A coating agent is an agent for obtaining a film formed on the surface of a substrate, and includes the concept of a surface treatment agent. By coating the surface of a fibrous substrate with a urethane resin composition, a laminate having a surface layer with excellent antiviral properties can be obtained. By further surface treating the surface of the surface layer with a urethane resin composition, a laminate having a surface layer and a surface treatment layer on the surface of the fibrous substrate can be obtained, and the antiviral properties can be further improved.

Examples of materials for fibrous substrates include natural fibers (plant and animal fibers) such as cotton, linen, and silk; and chemical fibers such as polyester, nylon, acrylic, and polyurethane.

Examples of the form of the fibrous substrate include knitted fabrics, woven fabrics, nonwoven fabrics, etc.

Specific examples of articles having the laminate of the present invention include synthetic leather, artificial leather, natural leather, automobile interior seats using polyvinyl chloride (PVC) leather, sports shoes, clothing, furniture, thermoplastic olefin (TPO) leather, dashboards, instrument panels, etc.

The laminate of the present invention can be manufactured by a known dry film-forming method. For example, the following method can be mentioned.

The resin composition for the skin layer is applied onto the release paper with a doctor knife and then dried. Next, the resin composition for the adhesive layer is applied onto the dried coating of the skin layer with a doctor knife and then pre-dried. It is then laminated with a nonwoven fabric and then dried. After aging, the release paper is peeled off to obtain a laminate.

The thickness of the layer made of the urethane resin composition is preferably in the range of 0.1 to 100 μm, for example.

The urethane resin composition of the present invention can be made into a shaped object by various shaping methods. These shaping methods include three-dimensional shaping methods such as fused deposition modeling, and well-known shaping methods such as vacuum molding and injection molding. However, it is preferable to use a three-dimensional shaping method such as fused deposition modeling, since the visible light responsive photocatalyst is uniformly distributed on the shaped object and the effects of the present invention can be optimally obtained.

When a three-dimensional modeling method such as fused deposition modeling is selected for producing the object of the present invention, the form of the urethane resin composition to be used may be powder, pellets, filaments, etc., and may be appropriately selected depending on the three-dimensional modeling device to be used.

Examples of objects formed by the three-dimensional modeling method include mechanical industrial parts such as belts, tubes, hoses, electric wire coating materials, cable coating materials, waterproof hoses, gears, casters, packings, and wind turbines for wind power generation; bumpers, side moldings, tail lamp seals, snow chains, ball joint seals, constant velocity joint boots, bellows, spring cover materials, ABS cables, ABS cable plugs, instrument panel skins, gear knobs, console boxes, door seal covers, seat materials, and car parts such as knobs; various types of seats, air mattresses, synthetic leather, films and sheets such as protective films, shoe soles, watch bands, camera grips, animal ear tags, smartphone cases, tablet cases, keyboard protective covers, and everyday items such as decorative items; medical products such as heart valves, bypass devices, artificial ventricles, dialysis tubes, thin films, connectors, catheters, medical tubes, and pacemaker insulators; building materials such as interior and exterior materials; and sporting goods such as skis, snowboards, surfboards, and rackets, and can be used in a wide range of fields both indoors and outdoors.

The present invention will now be described more specifically with reference to examples.
[Photocatalyst Preparation Example 1]
(1) Titanium oxide a) Crystalline rutile titanium oxide b) Manufacturing method: Liquid phase method (sulfuric acid method)
c) Physical properties: BET specific surface area: 9.0 m ² /g
- Rutile rate: 95.4%
・Primary particle size: 0.18μm

[Method for measuring the BET specific surface area of titanium oxide (a)]
The specific surface area was measured (BET single point method) using a fully automatic BET specific surface area measuring device "MacSORB HM model-1208" manufactured by Mountech Co., Ltd.

[Method for measuring the rutile content of titanium oxide (a)]
Using an X-ray diffractometer "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to rutile crystals was calculated from the peak heights corresponding to the entire titanium oxide crystals (rutile, brookite, and anatase types).

[Method for measuring primary particle size of titanium oxide (a)]
The size of the primary particles was measured directly from an electron microscope photograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of each titanium oxide primary particle were measured, and the average was taken as the particle diameter of the primary particles. Next, the volume (weight) of each of 100 or more titanium oxide particles was calculated by approximating it to a cube of the calculated particle diameter, and the volume average particle diameter was taken as the average primary particle diameter.

(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. The mixture was then stirred with a stirrer ("Robomix" manufactured by Tokushu Kika Kogyo Co., Ltd.), and 1 mol/L of aqueous sodium hydroxide solution was added dropwise until the pH of the mixture reached 10.
b) Dehydration step The mixture was filtered under reduced pressure using qualitative filter paper (5C) to separate the solid matter from the mixture, and then washed with ion-exchanged water. The washed solid matter was then dried at 120°C for 12 hours to remove moisture. After drying, a powdered titanium oxide composition was obtained using a mill (Iwatani Sangyo Co., Ltd.'s "Miller").
c) Heat Treatment Step Heat treatment was carried out at 450° C. for 3 hours in the presence of oxygen using a precision incubator (DH650 manufactured by Yamato Scientific Co., Ltd.) to obtain a titanium oxide composition containing titanium oxide carrying a divalent copper compound.

[Photocatalyst Preparation Example 2]
(1) Titanium oxide a) Crystalline rutile titanium oxide b) Manufacturing method: Gas phase method c) Physical properties: BET specific surface area: 13 m ² /g
- Rutile rate: 95.6%
・Primary particle size: 0.15μm

A titanium oxide composition was obtained in the same manner as in Preparation Example 1, except that the type of titanium oxide was changed to the titanium oxide described above and the amount of water used was changed from 900 parts by mass to 4,000 parts by mass.

[Method for measuring the amount of divalent copper compound supported on titanium oxide (a)]
The titanium oxide compositions obtained in Preparation Examples were completely dissolved in a hydrofluoric acid solution, and the extract was analyzed by an ICP atomic emission spectrometer 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)). As a result, in both Preparation Examples 1 and 2, the amount of copper ions was 0.5 parts by mass per 100 parts by mass of titanium oxide.

[Preparation of urethane resin composition]
<Materials for urethane resin composition>
Crisbon NB-130 (polyether-polyester-based yellowing-resistant urethane resin solution (DIC Corporation), one-component urethane resin, resin solids: 30% by weight, DMF: 70% by weight)
Dilac White L-6725 (colorant (manufactured by DIC Corporation), rutile-type pigment-grade titanium dioxide; 50%, DMF; 40%, urethane resin solids; 10%)
Crisbon TA-265 (polyether-based yellowing-resistant urethane resin solution (DIC Corporation), two-component urethane resin, resin solids: 65% by weight, DMF: 35% by weight)
Burnock DN-950 (polyisocyanate compound (manufactured by DIC Corporation, resin solids: 75% by weight, ethyl acetate: 25% by weight)
・Crisbon Accel T-81E: Crosslinking accelerator (manufactured by DIC Corporation)

<Composition of urethane resin composition>
A resin composition A for a surface layer was obtained by mixing the following materials in a homomixer.
(1) CRISBON NB-130 100 parts by weight (2) DMF 40 parts by weight (3) Dilac White L-6725 15 parts by weight (4) Preparation Example 1 or Preparation Example 2 0.5 to 15 parts by weight

A resin composition B for a surface layer was obtained by mixing the following materials in a homomixer.
(1) CRISBON NB-130 100 parts by weight (2) DMF 40 parts by weight (3) Dilac White L-6725 15 parts by weight

A resin composition for adhesive layers was obtained by mixing the following materials in a homomixer.
(1) 100 parts by weight of CRISBON TA-265 (2) 20 parts by weight of DMF (3) 20 parts by weight of MEK (4) 12 parts by weight of Burnock DN-950 (5) 3 parts by weight of CRISBON Axel T-81E

Surface treatment agent resin composition A was obtained by mixing the following materials in a homomixer.
(1) 100 parts by weight of CRISBON NB-130 (2) 100 parts by weight of DMF (3) 100 parts by weight of MEK (4) 5 parts by weight of Preparation Example 1 or Preparation Example 2

Surface treatment resin composition B was obtained by mixing the following materials in a homomixer.
(1) Crisbon NB-130 100 parts by mass (2) DMF 100 parts by mass (3) MEK 100 parts by mass

[Method of preparing evaluation samples]
An artificial leather for evaluation was prepared by the following dry film formation method.
On release paper (product name "Asahi Release AR-191" manufactured by Asahi Roll Co., Ltd.), the skin layer resin composition A or B was applied with a doctor knife to a thickness of 150 μm (film thickness when dried: about 30 μm), and then dried with hot air at 120° C. for 2 minutes. Next, on the dried coating film of the skin layer, the adhesive layer resin composition was applied with a doctor knife to a thickness of 150 μm (film thickness when dried: about 50 μm), and then pre-dried with hot air at 70° C. for 1 minute. Furthermore, the pre-dried adhesive layer was attached to a nonwoven fabric, and then dried with hot air at 120° C. for 2 minutes. After aging at 70° C. for 12 hours, the release paper was peeled off to produce an artificial leather for evaluation.
When further surface treatment was performed, the surface treatment resin composition A or B was applied to a thickness of 20 μm (7 μm thick when dried) using a gravure coater, and then dried with hot air at 80° C. for 2 minutes.

[Method for evaluating antiviral activity]
The artificial leather for evaluation obtained above was subjected to an anti-phage virus test (film adhesion method, see JIS R1756:2020).

1) The light irradiation conditions were as follows: white fluorescent light was filtered out with an N113 filter to cut out ultraviolet rays, and the illuminance was set to 1000 lux.
2) 100 μL of a Qβ phage solution of a known concentration was dropped onto a 5 cm×5 cm piece of artificial leather for evaluation, and then a 4 cm×4 cm adhesive film was placed over the piece to prepare a sample for evaluation.
3) The sample irradiated for 2 hours was collected in SCDLP solution, appropriately diluted, infected with E. coli, spread on an agar medium, and evaluated by counting the number of colonies after cultivation. Antiviral activity was evaluated by the degree of inactivation of Qβ phage, and an inactivation degree of -2 to -5 was evaluated as having antiviral activity.

The inactivation degree is a log(N/N ₀ ) value indicating the degree of reduction in the infectivity of the phage in a bright place, where N is the infectivity of the sample after the reaction (pfu/mm ² ), and N ₀ is the infectivity of the inoculated phage (pfu/mm ² ). Inactivation degree-1 indicates that 90% of the virus is inactivated, inactivation degree-2 indicates that 99% is inactivated, inactivation degree-3 indicates that 99.9% is inactivated, inactivation degree-4 indicates that 99.99% is inactivated, and inactivation degree-5 indicates that 99.999% of the virus is inactivated, indicating high antiviral activity.

Example 1
Resin composition A for surface layer: 5 parts by mass of Preparation Example 1 added No surface treatment agent (Evaluation results) Inertness: -3 → Antiviral

Example 2
Resin composition A for surface layer: 15 parts by mass of Preparation Example 1 added No surface treatment agent (Evaluation results) Inertness: -5 → Antiviral

Example 3
Resin composition A for surface layer: 5 parts by mass of Preparation Example 2 added No surface treatment agent (Evaluation results) Inertness: -3 → Antiviral

Example 4
Resin composition A for surface layer: 0.5 parts by mass of Preparation Example 1 added No surface treatment agent (Evaluation results) Inertness: -2 → Antiviral

Example 5
Resin composition B for surface layer: Neither Preparation Example 1 nor Preparation Example 2 was added. Surface treatment agent was added. 5 parts by mass of Preparation Example 1 was added to surface treatment resin composition A. (Evaluation results) Inactivity: -3 → Antiviral properties present

Example 6
Resin composition B for surface layer: Neither Preparation Example 1 nor Preparation Example 2 was added. Surface treatment agent was added. 5 parts by mass of Preparation Example 2 was added to surface treatment resin composition A. (Evaluation results) Inactivity: -3 → Antiviral properties present

Example 7
Resin composition A for surface layer: 5 parts by mass of Preparation Example 1 added Surface treatment agent included 5 parts by mass of Preparation Example 1 added to surface treatment agent composition A (Evaluation results) Inactivity: -4 → Antiviral properties present

<Comparative Example 1>
Resin composition B for surface layer: Neither Preparation Example 1 nor Preparation Example 2 was added. No surface treatment agent was added. (Evaluation results) Inertness: -0.2 → No antiviral properties

<Comparative Example 2>
・Surface layer resin composition B: Neither Preparation Example 1 nor Preparation Example 2 was added. ・Surface treatment agent was present. Surface treatment resin composition B: Neither Preparation Example 1 nor Preparation Example 2 was added. (Evaluation results) Inactivity: -0.2 → No antiviral properties

<Comparative Example 3>
Surface layer resin composition A: 5 parts by mass of Preparation Example 1 added Surface treatment agent included Surface treatment resin composition B: Neither Preparation Example 1 nor Preparation Example 2 added (Evaluation results) Inactivity: -0.2 → No antiviral properties

[Production of urethane resin molded objects]
Examples of the production of a shaped object using the urethane resin composition of the present invention will be described below.

[Preparation of urethane resin composition]
<Materials for urethane resin composition>
Pantex T-9290 (polycarbonate-based thermoplastic urethane (manufactured by DIC Covestro Polymers)), Irganox 1010 (phenol-based antioxidant (manufactured by BASF))

<Composition of urethane resin composition>
Composition A for shaping was prepared by kneading the following raw materials by melt kneading extrusion to obtain filaments.
(1) Pantex T-9290 100 parts by weight (2) Preparation Example 1 11 parts by weight (3) Irganox 1010 0.3 to 0.4 parts by weight

Composition B for shaping was prepared by kneading the following raw materials by melt kneading and extrusion to obtain filaments.
(1) Pantex T-9290 100 parts by weight (2) Preparation Example 1 25 parts by weight (3) Irganox 1010 0.3 to 0.4 parts by weight

[Method of preparing evaluation samples]
Preparation Example 1 An additive-free product (100 parts by weight of Pantex T-9290) and the above-mentioned shaped article compositions A and B were further processed into a filament shape by melt kneading and extrusion to obtain a filament having a diameter of 2.85 mmφ.

The filament was subjected to fusion deposition modeling using a three-dimensional modeling device (Ultimaker) to produce a model measuring 60 mm x 60 mm x 2 mm. The model was then adjusted to a size of 50 mm x 50 mm x 2 mm to obtain a sample for evaluation.

[Method for evaluating antiviral activity]
The evaluation samples obtained above were subjected to an antiviral test (see ISO21702 (JIS Z2801)).

1) Preparation Example 1 of Evaluation Sample 0.4 ml of virus liquid was dropped onto the additive-free product and the compositions A and B for molding, and covered with a film measuring 40 mm x 40 mm.
2) Leave at 25°C for 24 hours.
3) After leaving it to stand, the virus on the test piece is washed and collected, and then the virus infectivity is measured.

The virus used in the virus test was influenza A virus (H3N2), and the percentage of virus reduction (virus reduction rate %) was calculated using the following formula. A virus reduction rate of 95% or more was evaluated as having antiviral activity.
Formula) R=(Ut-At)/Ut×100
R: Virus reduction rate (%)
Ut: average value of viral infectivity (PFU/cm ² ) of the additive-free product of Preparation Example 1 after standing for 24 hours At: average value of viral infectivity (PFU/cm ² ) of compositions A and B for molding after standing for 24 hours

<Comparative Example 4>
Preparation Example 1 Additive-free product (Evaluation results)
・Influenza A virus (H3N2): Virus reduction rate 0% → no antiviral effect

Example 8
Composition A for molding
(Evaluation Results)
Influenza A virus (H3N2): Virus reduction rate of 97% → antiviral effect

<Example 9>
Composition for molding B
(Evaluation Results)
- Influenza A virus (H3N2): Virus reduction rate of 99% → antiviral properties

Claims (10)

A urethane resin composition comprising a visible light responsive photocatalyst ,
The visible light responsive photocatalyst is a titanium oxide including a rutile type titanium oxide having a divalent copper compound supported thereon,
The urethane resin composition, wherein the visible light responsive photocatalyst is a visible light responsive photocatalyst obtained by mixing titanium oxide including rutile type titanium oxide, a divalent copper compound raw material, water and an alkaline substance. The divalent copper compound raw material is CuX ₂ (X is a halogen atom, CH ₃ COO, NO ₃ Or (SO ₄ ) _1/2 The urethane resin composition according to claim 1, wherein the compound is represented by the formula (I). 3. The urethane resin composition according to claim 1, wherein the divalent copper compound raw material is used in an amount of 0.1 to 15 parts by mass per 100 parts by mass of the titanium oxide. The urethane resin composition according to any one of claims 1 to 3, wherein the alkaline substance is one or more selected from the group consisting of sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, and ammonia. The urethane resin composition according to any one of claims 1 to 4, wherein the content of the visible light responsive photocatalyst is 0.3 parts by mass or more and 67 parts by mass or less, based on 100 parts by mass of the resin solid content of the urethane resin composition. A laminate comprising a fibrous base material and a skin layer on at least one surface of the fibrous base material,
A laminate, wherein the surface layer is formed from the urethane resin composition according to any one of claims 1 to 5. A laminate comprising a fibrous base material, a surface layer on at least one surface of the fibrous base material, and a surface treatment layer on the surface layer,
A laminate, wherein the surface-treated layer is formed from the urethane resin composition according to any one of claims 1 to 5. The laminate according to claim 6 or 7, wherein the form of the fibrous substrate is one selected from the group consisting of nonwoven fabric, knitted fabric, and woven fabric. A shaped object made of the urethane resin composition according to any one of claims 1 to 4. The object according to claim 9, characterized in that it is produced by fused deposition modeling.