Handbag

Abstract

The present invention addresses the problem of providing a glove in which an urethane resin containing water is used and which has antiviral properties. The present invention provides a glove characterized by having a coating formed from an urethane resin composition containing a urethane resin (A), a visible-light-responsive photocatalyst (B), and water (C). The visible-light-responsive photocatalyst preferably has a metallic compound supported on titanium oxide (a). The titanium oxide (a) preferably contains a rutile-type titanium oxide (a1). The metallic compound is preferably a divalent copper compound. The glove according to the present invention can be suitably used as an industrial glove used in various fields, such as in the chemical industry field, the food product field, and the medical service field, and can be particularly suitably used as a medical glove.

Description

Technical Field

[0001] The present invention relates to gloves having a film made of a urethane resin composition containing a visible light-responsive photocatalyst.

Background Art

[0002] Generally, as rubbers used as materials having rubber elasticity, natural rubber, isoprene rubber, chloroprene rubber, nitrile rubber, etc. are utilized. When these are used for gloves, allergies due to proteins contained in natural rubber or allergies due to vulcanizing agents and vulcanization accelerators used for these rubbers in general may become problems.

[0003] Therefore, as alternative materials for these rubbers, it is promising to utilize urethane resins having rubber elasticity and not containing the above substances. Until now, rubber latex has been widely used in glove processing, and the substitution with urethane dispersion (a product in which a urethane resin is dispersed in water, etc.) that can be used with the same manufacturing equipment is particularly promising among them.

[0004] On the other hand, recently, due to the pandemic of the coronavirus, the interest in antiviral properties of gloves has increased, and it is required to further enhance the antiviral properties by wearing gloves while suppressing allergies.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0006] The problem to be solved by the present invention is to provide gloves having antiviral properties by using a urethane resin containing water.

Means for Solving the Problems

[0007] The present invention provides gloves characterized by having a film formed from a urethane resin composition containing a urethane resin (A), a visible light-responsive photocatalyst (B), and water (C).

Effects of the Invention

[0008] The gloves of the present invention are excellent in antiviral properties. Further, since a urethane resin composition containing water is used, the environmental load during glove production is also small. Therefore, the gloves of the present invention can be suitably used as industrial gloves used in various fields such as the chemical industry field, the food field, and the medical field, and can be particularly suitably used as medical gloves.

Modes for Carrying Out the Invention

[0009] The gloves of the present invention have a film formed from a urethane resin composition containing a urethane resin (A), a visible light-responsive photocatalyst (B), and water (C).

[0010] The urethane resin (A) can be dispersed in water (B) described later, for example, those having hydrophilic groups such as anionic groups, cationic groups, and nonionic groups; those forcibly dispersed in water (B) with an emulsifier, etc. can be used. These urethane resins (A) may be used alone or in combination of two or more. Among these, from the viewpoint of ease of emulsification, it is preferable to use a urethane resin having a hydrophilic group, and from the viewpoint of ease of glove processing, it is more preferable to use a urethane resin having an anionic group.

[0011] Examples of the method for obtaining the urethane resin having an anionic group include a method using at least one compound selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group as a raw material.

[0012] Examples of the compound having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, 2,2-valeric acid, etc. These compounds may be used alone or in combination of two or more.

[0013] Examples of the compound having a sulfonyl group include 3,4-diaminobutanesulfonic acid, 3,6-diamino-2-toluenesulfonic acid, 2,6-diaminobenzenesulfonic acid, N-(2-aminoethyl)-2-aminosulfonic acid, N-(2-aminoethyl)-2-aminoethylsulfonic acid, N-2-aminoethane-2-aminosulfonic acid, N-(2-aminoethyl)-β-alanine; and salts thereof can be used. These compounds may be used alone or in combination of two or more.

[0014] In the urethane resin composition, part or all of the carboxyl group and sulfonyl group may be neutralized with a basic compound. Examples of the basic compound include organic amines such as ammonia, triethylamine, pyridine, morpholine; alkanolamines such as monoethanolamine, dimethylethanolamine; metal base compounds containing sodium, potassium, lithium, calcium, etc.

[0015] Examples of the method for obtaining the urethane resin having a cationic group include a method using one or more compounds having an amino group as raw materials.

[0016] Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine, diethylenetriamine; compounds having a tertiary amino group such as N-methyldiethanolamine, N-ethyldiethanolamine and other N-alkyldialkanolamines, N-methyldiaminoethylamine, N-ethyldiaminoethylamine and other N-alkyldiaminoalkylamines. These compounds may be used alone or in combination of two or more.

[0017] As a method for obtaining the urethane resin having the nonionic group, for example, a method of using one or more compounds having an oxyethylene structure as raw materials can be mentioned.

[0018] As the compound having an oxyethylene structure, for example, polyether polyols having an oxyethylene structure such as polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol can be used. These compounds may be used alone or in combination of two or more.

[0019] As an emulsifier that can be used when obtaining the aqueous urethane resin that is forcibly dispersed in water (B), for example, nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene-polyoxypropylene copolymer; fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkanesulfonate sodium salts, and alkyl diphenyl ether sulfonate sodium salts; cationic emulsifiers such as alkylamine salts, alkyltrimethylammonium salts, and alkyldimethylbenzylammonium salts, etc. can be used. These emulsifiers may be used alone or in combination of two or more.

[0020] As the urethane resin (A), for example, polyol (a1), polyisocyanate (a2), chain extender (a3), and, if necessary, the reaction product of the raw materials used for producing the urethane resin having the hydrophilic group described above can be used.

[0021] As the polyol (a1), for example, polycarbonate polyol, polyether polyol, polyester polyol, polyacrylic polyol, etc. can be used. These polyols may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining further improved chemical resistance and flexibility, polycarbonate polyol and / or polyether polyol are preferable, and polycarbonate polyol and / or polytetramethylene glycol are more preferable.

[0022] Regarding the number average molecular weight of the polyol (a1), from the viewpoint of obtaining further excellent flexibility and chemical resistance, the range of 500 to 10,000 is preferable, and the range of 1,000 to 5,000 is more preferable. The number average molecular weight of the polyol (a1) indicates the value measured by the gel permeation chromatography (GPC) method.

[0023] As the polyisocyanate (a2), for example, aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, carbodiimidized diphenylmethane polyisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, etc. can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanate is preferable, and diphenylmethane diisocyanate is more preferable from the viewpoint of obtaining further excellent chemical resistance.

[0024] Examples of the chain extender (a3) include chain extenders having an amino group such as ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, hydrazine, diethylenetriamine, etc.; chain extenders having a hydroxyl group such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, sucrose, methylene glycol, glycerin, sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, trimethylolpropane, etc.; chain extenders having a branched structure such as 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-butanediol, 1,3-butanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,2-propanediol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-isopropyl-1,4-butanediol, 2,4-dimethyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2-ethyl-1,3-hexanediol, 2-ethyl-1,6-hexanediol, 3,5-heptanediol, 2-methyl-1,8-octanediol, trimethylolpropane, etc. These chain extenders may be used alone or in combination of two or more. Among these, from the viewpoint of obtaining even more excellent chemical resistance, it is preferable to use a chain extender having no branched structure, more preferably a chain extender having a hydroxyl group, and particularly preferably ethylene glycol.

[0025] Examples of the method for producing the urethane resin (A) include a method in which, in the absence of a solvent or in the presence of an organic solvent, the polyol (a1), the polyisocyanate (a2), the chain extender (a3), and the raw materials for producing the urethane resin having a hydrophilic group are mixed and reacted at 50 to 100°C for 3 to 20 hours; a method in which, in the absence of a solvent or in the presence of an organic solvent, the polyol (a1), the polyisocyanate (a2), and the raw materials for producing the urethane resin having a hydrophilic group are mixed and reacted at 50 to 100°C for 3 to 15 hours to obtain a urethane prepolymer having isocyanate groups, and then the urethane prepolymer and the chain extender (a3) are reacted. When an organic solvent is used in the reaction, it is preferably finally distilled off.

[0026] Examples of the organic solvent that can be used when producing the urethane resin (A) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetate ester solvents such as ethyl acetate and butyl acetate; nitrile solvents such as acetonitrile; and amide solvents such as dimethylformamide and N-methylpyrrolidone. The organic solvent may be used alone or in combination of two or more.

[0027] The average particle diameter of the urethane resin (A) is preferably in the range of 0.05 to 1 μm, more preferably in the range of 0.10 to 0.7 μm, from the viewpoint of obtaining more excellent dispersion stability and a relatively high concentration of the urethane resin. The method for measuring the average particle diameter of the urethane resin (A) is as follows: Using a laser diffraction / scattering particle size distribution measuring device ("Microtrac UPA-EX150" manufactured by Nikkiso Co., Ltd.), water is used as the dispersion liquid, and the average particle diameter is the value obtained by measuring the volume average diameter with a solvent refractive index of 1.33 and a particle refractive index of 1.51 for the urethane resin composition containing the urethane resin (A).

[0028] The content of the urethane resin (A) is preferably 10 to 95% by mass, more preferably 20 to 80% by mass in the urethane resin composition, from the viewpoint of improving storage stability and workability.

[0029] The visible light-responsive photocatalyst (B) is an essential component for obtaining excellent antiviral properties. Examples thereof include compositions containing titanium oxide (a). From the viewpoint of obtaining even more excellent antiviral properties, those in which a metal compound is supported on titanium oxide (a) are preferably mentioned.

[0030] 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 contain rutile-type titanium oxide (a1) from the viewpoint of having excellent photocatalytic activity in the visible light region.

[0031] The content ratio (rutile ratio) 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, from the viewpoint of obtaining even more excellent antiviral properties in bright and dark places, decomposability of organic compounds in bright places, and visible light responsiveness.

[0032] As the production method of the titanium oxide (a), 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 raw ore such as ilmenite ore is dissolved. The gas phase method is a method of obtaining titanium oxide by a gas phase reaction of titanium tetrachloride obtained by chlorinating raw ore such as rutile ore and oxygen. As a method for distinguishing titanium oxide produced by both methods, analyzing its impurities can be mentioned. Titanium oxide produced by the liquid phase method contains zirconium, niobium, etc. derived from impurities in ilmenite ore in the product. On the other hand, in the gas phase method, since there is a step of purifying titanium tetrachloride to remove impurities, these impurities are hardly contained in titanium oxide.

[0033] 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 solution during the reaction process increases due to the increase in the apparent specific surface area. On the other hand, the titanium oxide (a) produced by the liquid phase method is considered to generate gentle secondary aggregates in the firing process, and the cohesive force is small with respect to the specific surface area (BET value) caused by the primary particles, and it is possible to suppress the viscosity of the mixed solution. For the above reasons, as the titanium oxide (a), titanium oxide produced by the liquid phase method is preferable in terms of further improving the productivity of the visible light-responsive photocatalyst (B), the abrasion resistance, flexural resistance, flexibility, durability, and chemical resistance of the gloves.

[0034] As the BET specific surface area of the titanium oxide (a), in terms 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 still more preferable, and in terms of further enhancing the productivity of the visible light-responsive photocatalyst (B), it is preferably in the range of 7.5 to 9.5 m 2 / g. The method for measuring the BET specific surface area of the rutile-type titanium oxide (a1) will be described in the examples described later.

[0035] As the primary particle diameter of the titanium oxide (a), 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 even more excellent antiviral properties and visible light responsiveness. The measurement method of the primary particle diameter of the titanium oxide (a) shows 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 major axis diameter of each primary particle of titanium oxide are measured, and the average is taken as the particle diameter of the primary particle. 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.

[0036] In addition, as the visible light-responsive photocatalyst, from the viewpoint of further improving the photocatalytic activity in the visible light region and easily exhibiting appropriate activity capable of decomposing dirt components under practical indoor light, it is preferable to use one in which a metal compound is supported on titanium oxide (a).

[0037] 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 even more excellent antibacterial properties and antiviral properties. As the method for supporting the metal compound on the titanium oxide (a), a known method can be used.

[0038] Next, a method for supporting a divalent copper compound on titanium oxide (a), which is the most preferable embodiment, will be described.

[0039] As the method for supporting a divalent copper compound on the titanium oxide (a), for example, a method having a mixing step (i) of titanium oxide (a) containing rutile-type titanium oxide (a1), a divalent copper compound raw material (b), water (c), and an alkaline substance (d) can be mentioned.

[0040] 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 the titanium oxide (a) produced by the liquid phase method is used, even if the concentration of the titanium oxide (a) is increased, a mixing step with good handleability can be performed. Specifically, even when the concentration of the titanium oxide (a) is in the range exceeding 25% by mass and 40% by mass or less, a mixing step can be performed well.

[0041] As the divalent copper compound raw material (b), for example, a divalent copper inorganic compound, a divalent copper organic compound, or the like can be used.

[0042] 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.

[0043] 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.

[0044] Among those described above, as the divalent copper compound raw material (b), 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 .)

[0045] As X in the formula (1), a halogen atom is more preferable, and a chlorine atom is even more preferable.

[0046] 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 with respect to 100 parts by mass of the titanium oxide (a).

[0047] The water (c) 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.

[0048] Examples of the alkaline substance (d) include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, basic surfactants, etc., and it is preferable to use sodium hydroxide.

[0049] From the viewpoint of easy reaction control, the alkaline substance (d) is preferably added as a solution. The concentration of the alkaline solution to be added is preferably in the range of 0.1 to 5 mol / L, more preferably in the range of 0.3 to 4 mol / L, and still more preferably in the range of 0.5 to 3 mol / L.

[0050] 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, first, the titanium oxide (a) is mixed with the water (c) and stirred as necessary, then the divalent copper compound raw material (b) is mixed and stirred, and then the alkaline substance (d) is 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).

[0051] 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 from room temperature to 70°C.

[0052] From the viewpoint that the loading of the divalent copper compound on titanium oxide (a) is good, the pH of the mixture after mixing and stirring titanium oxide (a), divalent copper compound raw material (b), and water (c), and then mixing and stirring an alkaline substance (d) is preferably in the range of 8 to 11, more preferably in the range of 9.0 to 10.5.

[0053] After the mixing step (i) is completed, the mixed solution can be separated as a solid content. Examples of the method for separation include filtration, sedimentation separation, centrifugal separation, evaporation to dryness, etc., but filtration is preferred. The separated solid content may then be washed with water, crushed, classified, etc. as necessary.

[0054] After obtaining the solid content, it is preferable to heat-treat the solid content from the viewpoint that the divalent copper compound derived from the divalent copper compound raw material (b) supported on the titanium oxide (a) 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. Also, the heat treatment time is preferably 1 to 10 hours, more preferably 2 to 5 hours.

[0055] By the above method, a titanium oxide composition containing titanium oxide with a divalent copper compound supported on titanium oxide (a) is obtained. The loading amount of the divalent copper compound supported on the titanium oxide (a) is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (a) 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 (b) used in the mixing step (i).

[0056] The content of the visible light-responsive photocatalyst (B) is preferably 0.1 to 60% by mass, more preferably 0.3 to 60% by mass, still more preferably 1 to 40% by mass, and particularly preferably 1 to 20% by mass in the aqueous urethane resin composition from the viewpoints of improving antiviral properties and various physical properties of the gloves.

[0057] As the water (C), for example, distilled water, ion-exchanged water, etc. can be used. These waters may be used alone or in combination of two or more.

[0058] As the content of the water (C), from the viewpoint of improving storage stability and workability, 20 to 85% by mass in the aqueous urethane resin composition is preferable, and 30 to 75% by mass is more preferable.

[0059] The urethane resin composition used in the present invention contains the urethane resin (A), the visible light-responsive photocatalyst (B), and the water (C) as essential components, and may contain other additives as necessary.

[0060] Examples of the other additives include thickeners, defoamers, urethanization catalysts, silane coupling agents, fillers, thixotropy imparting agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent brighteners, foaming agents, foam stabilizers, pigments, dyes, conductivity imparting agents, antistatic agents, moisture permeability imparting agents, water repellents, oil repellents, blocking preventives, hydrolysis preventives, etc. These additives may be used alone or in combination of two or more.

[0061] Since the urethane resin composition used in the present invention requires different durability and flexibility depending on the intended use, for example, it may contain styrene-butadiene copolymer (SBR), butadiene copolymer (BR), isoprene copolymer (IR), ethylene-propylene-diene copolymer (EPDM), chloroprene polymer (CR), acrylonitrile-butadiene copolymer (NBR), butyl polymer (IIR), natural rubber (NR), etc.

[0062] The urethane resin composition used in the present invention can be used not only for gloves but also for medical tubes such as catheter tubes and contraceptives.

[0063] As a method for manufacturing gloves having a film made of the urethane resin composition, for example, first, a hand mold, a tubular mold, etc. are immersed in a coagulant described later, and then dried if necessary, so that metal salts, etc. in the coagulant adhere to the surface of the hand mold, etc. Next, the hand mold, etc. are immersed in the urethane resin composition, then the surface is washed with water and dried, whereby a glove having a film solidified on the surface of the hand mold, etc. is manufactured. At this time, the urethane resin composition may be further diluted with distilled water, ion-exchanged water, or the like.

[0064] As the coagulant, for example, metal salt solutions such as calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, sodium chloride; acid solutions such as formic acid and acetic acid can be used. As a solvent capable of dissolving the metal salt and acid, for example, water, methanol, ethanol, isopropanol, etc. can be used. The metal salt contained in the coagulant is preferably contained in the range of 1 to 50% by mass based on the total amount of the coagulant. Also, the time for immersing the coated object in the coagulant may be 1 to 10 minutes. Further, the coagulant can be used at a temperature of 5 to 60°C.

[0065] When the hand mold or tubular mold is immersed in the coagulant, it may be at room temperature or heated to 30 to 70°C.

[0066] Further, a glove-like or tubular object made of a knitted fabric such as nylon fiber may be preliminarily attached to the hand mold or tube mold. Specifically, first, after immersing the hand mold or the like with the glove-like object made of the knitted fabric in the coagulant, and drying it if necessary, the glove-like object or the like is impregnated with the coagulant. Next, after immersing the hand mold or the like in the urethane resin composition, washing the surface with water and drying it, a glove or the like made of a film solidified on the surface of the glove-like object or the like is formed, and by peeling the glove or the like from the hand mold and the glove-like object or the like, a glove or the like made of a solidified film having a shape corresponding to the hand mold or the like can be obtained. When manufacturing the tube, it can be manufactured by the same method as described above except that a tube mold and a tubular object made of a knitted fabric such as nylon fiber are used.

[0067] The knitted fabric is not limited to the nylon fiber, and for example, those made of polyester fiber, aramid fiber, polyethylene fiber, cotton, etc. can be used. Further, instead of the knitted fabric, a woven fabric made of the fiber can also be used. Further, instead of the knitted fabric, a glove-like or tubular object made of a resin material such as vinyl chloride, natural rubber, or synthetic rubber can also be used.

[0068] As described above, the glove of the present invention has excellent antiviral properties. In addition, since a urethane resin composition containing water is used, the environmental load during glove production is also small. Therefore, the glove of the present invention can be suitably used as an industrial glove used in various fields such as the chemical industry, food industry, and medical field, and can be particularly suitably used as a medical glove.

Example

[0069] Hereinafter, the present invention will be described in more detail using examples.

[0070] [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 ratio: 95.4% · Primary particle size: 0.18 μm

[0071] (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. Subsequently, the mixture was stirred with a stirrer ("Robomix" manufactured by Tokushu Kika Kogyo Co., Ltd.), and a 1 mol / L aqueous sodium hydroxide solution was added dropwise until the pH of the mixed solution reached 10. b) Dehydration process Vacuum filtration was performed using qualitative filter paper (5C) to separate the solid content from the mixed solution, and further washing was carried out with ion-exchanged water. Subsequently, the washed solid was dried at 120 °C for 12 hours to remove moisture. After drying, a powdery titanium oxide composition was obtained using a mill ("Millcer" manufactured by Iwatani Sangyo Co., Ltd.). c) Heat treatment process Heat treatment was performed at 450 °C for 3 hours in the presence of oxygen using a precision thermostat ("DH650" manufactured by Yamato Scientific Co., Ltd.) to obtain a titanium oxide composition containing titanium oxide supported with a divalent copper compound. In addition, the supported amount of the divalent copper compound in the titanium oxide supported with the divalent copper compound was 0.5% by mass based on the titanium oxide.

[0072] [Preparation Example 2] 25 parts of the titanium oxide composition obtained in Preparation Example 1, 75 parts of water, and 1 part of a dispersant ("SN Dispersant 5023" manufactured by San Nopco Ltd.) were mixed and stirred. After adding 100 parts of 1.0 mmφ ceramic beads, it was ground with a sand grinder for 4 hours. After completion of grinding, the beads and the dispersion liquid were separated to obtain a titanium oxide composition dispersion liquid.

[0073] [Preparation Example 3] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 600 parts by mass of a polycarbonate polyol (made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000), 33 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000), 181 parts by mass of polypropylene triol (an adduct of glycerin and propylene oxide, number average molecular weight: 6,000), 8.4 parts by mass of ethylene glycol, 15.8 parts by mass of 2,2-dimethylolpropionic acid, 154 parts by mass of 4,4'-diphenylmethane diisocyanate, and 991 parts by mass of methyl ethyl ketone were reacted at 70 °C. When the reactant reached the specified viscosity, 1.0 part by mass of methanol was added and stirred for 1 hour to terminate the reaction. Further, 498 parts by mass of methyl ethyl ketone was added as a diluting solvent to obtain an organic solvent solution of the urethane resin. Next, 9.6 parts by mass of a 48% by mass aqueous potassium hydroxide solution was added to the organic solvent solution of the urethane resin as a neutralizing agent to neutralize the carboxyl groups of the urethane resin. Further, 2,480 parts by mass of water was added and stirred to obtain an aqueous dispersion of the urethane resin. Then, the organic solvent of the aqueous dispersion of the urethane resin was removed to obtain a urethane resin (A1) composition having a non-volatile content of 45% by mass and an average particle diameter of 0.73 μm.

[0074] [Preparation Example 4] In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 895.3 parts by mass of polyoxytetramethylene glycol (number average molecular weight: 2,000), 18 parts by mass of ethylene glycol, 25.5 parts by mass of 2,2'-dimethylolpropionic acid, 224 parts by mass of diphenylmethane diisocyanate, and 487 parts by mass of methyl ethyl ketone were reacted at 70 °C. When the reactant reached the specified viscosity, 2.9 parts by mass of methanol was added and stirred for 1 hour to terminate the reaction. Further, 1,257 parts by mass of methyl ethyl ketone was added as a diluting solvent to obtain an organic solvent solution of the urethane. Next, 19.2 parts by mass of triethylamine as a neutralizing agent was added to the organic solvent solution of the anionic polyurethane and stirred, and then 3638 parts by mass of water was added and stirred to obtain an aqueous dispersion of anionic polyurethane. Then, by desolventizing this aqueous dispersion, a urethane resin (A2) composition with a non-volatile content of 40% by mass and an average particle diameter of 0.25 μm was obtained.

[0075] [Example 1] [Preparation of Urethane Resin Composition] A urethane resin composition was obtained by blending 1 part by mass of the titanium oxide composition dispersion obtained in Preparation Example 2 with 100 parts by mass of the urethane resin (A1) composition obtained in Preparation Example 3.

[0076] [Preparation of Gloves (Thin)] Gloves were prepared according to the following procedure. (1) A pottery hand mold was immersed in a 10% by mass aqueous calcium nitrate solution and then pulled out. (2) The hand mold in (1) was dried at 70 °C for 2 minutes. (3) The hand mold in (2) was immersed in the urethane resin composition for 5 seconds and then pulled out. (4) The hand mold in (3) was washed with water. (5) The hand mold in (4) was dried at 70 °C for 20 minutes and then at 120 °C for 30 minutes. (6) Baby powder was adhered to the hand mold in (5), and the urethane resin film was peeled off from the hand mold.

[0077] [Example 2] A urethane resin composition and gloves were obtained in the same manner as in Example 1, except that the blending amount of the titanium oxide composition dispersion obtained in Preparation Example 2 was changed to 20 parts by mass.

[0078] [Example 3] A urethane resin composition and gloves were obtained in the same manner as in Example 1, except that the blending amount of the titanium oxide composition dispersion obtained in Preparation Example 2 was changed to 80 parts by mass.

[0079] [Example 4] [Preparation of Urethane Resin Composition] 100 parts by mass of the urethane resin (A2) composition obtained in Preparation Example 4 was blended with 1 part by mass of the titanium oxide composition dispersion obtained in Preparation Example 2 to obtain a urethane resin composition.

[0080] <Production of Gloves (Thick)> Gloves were produced according to the following procedure. (1) A knitted glove made of nylon fiber was worn on an aluminum hand mold, immersed in a 5 mass% aqueous calcium nitrate solution for 10 seconds, and then pulled out. (2) The hand mold in (1) was immersed in the urethane resin composition for 2 seconds, and after forming a coagulation film of an anionic urethane resin on the surface of the knitted glove, it was pulled out. (3) The hand mold in (2) was immersed in water for 30 minutes and then pulled out. (4) The hand mold in (3) was dried at 70 °C for 20 minutes and then at 120 °C for 30 minutes. (5) The glove coated with the coagulation film was peeled off from the hand mold in (4).

[0081] [Example 5] A urethane resin composition and gloves were obtained in the same manner as in Example 4, except that the blending amount of the titanium oxide composition dispersion obtained in Preparation Example 2 was changed to 20 parts by mass.

[0082] [Example 6] A urethane resin composition and gloves were obtained in the same manner as in Example 4, except that the blending amount of the titanium oxide composition dispersion obtained in Preparation Example 2 was changed to 80 parts by mass.

[0083] [Comparative Example 1] A urethane resin composition and gloves were obtained in the same manner as in Example 1, except that the blending amount of the titanium oxide composition dispersion obtained in Preparation Example 2 was changed to 0 parts by mass.

[0084] [Comparative Example 2] A urethane resin composition and gloves were obtained in the same manner as in Example 4, except that the blending amount of the titanium oxide composition dispersion obtained in Preparation Example 2 was changed to 0 parts by mass.

[0085] [Measurement Method of Number-Average Molecular Weight] The number-average molecular weight of the polyol and the like used in the synthesis example is the value measured under the following conditions by the gel permeation chromatography (GPC) method.

[0086] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 piece Detector: RI (differential refractometer) Column temperature: 40 °C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was created using the following standard polystyrene.

[0087] (Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0088] [Method for Measuring the Loading Amount of Divalent Copper Compound on Titanium Oxide] The titanium oxide composition obtained in Preparation Example 1 was completely dissolved in a hydrofluoric acid solution, and the extract was analyzed by an ICP emission spectrometer to quantify the loading amount of the divalent copper compound with respect to titanium oxide (a) (loading amount of divalent copper compound (parts by mass) / titanium oxide (a) (parts by mass)).

[0089] [Evaluation of Antiviral Activity] Against the gloves obtained in the Examples and Comparative Examples, an anti-phage virus test (refer to JIS R1756:2020) was carried out.

[0090] 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) Cut out the palm of the thin gloves obtained in the Examples and Comparative Examples into 5 cm × 5 cm, place it on a 5 cm × 5 cm glass plate, drop 100 μL of a Qβ phage solution with a known concentration, and then sandwich it with a 5 cm × 5 cm glass plate to obtain a sample for evaluation. 3) Cut out the palm of the thick gloves obtained in the Examples and Comparative Examples into 5 cm × 5 cm, drop 100 μL of a Qβ phage solution with a known concentration on the urethane resin surface, and then cover it with a 4 cm × 4 cm close-fitting film to obtain a sample for evaluation. 4) The samples irradiated with light for 8 hours were collected with SCDLP solution, appropriately diluted, infected with Escherichia coli, spread on an agar medium, and evaluated by counting the number of colonies after culturing. The antiviral property was evaluated by the inactivation degree of Qβ phage, and inactivation degrees of -2 to -5 were evaluated as having antiviral property "〇".

[0091]

Table 1

[0092]

Table 2

[0093] Examples 1 to 6, which are the gloves of the present invention, were found to have excellent antiviral properties.

[0094] On the other hand, Comparative Examples 1 and 2 are modes without using the visible light-responsive photocatalyst (B), but their antiviral properties were poor.

Claims

1. A method for manufacturing gloves having a film formed from a urethane resin composition containing a urethane resin (A), a visible light-responsive photocatalyst (B), and water (C), wherein the visible light-responsive photocatalyst (B) is a titanium oxide composition containing titanium oxide (a) carrying a divalent copper compound, the titanium oxide carrying the divalent copper compound is obtained by a method having a mixing step (i) of titanium oxide (a), a divalent copper compound raw material (b), water (c), and an alkaline substance (d), the titanium oxide (a) contains rutile-type titanium oxide (a1), the titanium oxide (a) is produced by a liquid phase method, and the loading amount of the divalent copper compound ranges from 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (a). A method for manufacturing gloves, characterized thereby.

2. The method for manufacturing gloves according to claim 1, wherein the divalent copper compound raw material (b) is represented by the following general formula (1). CuX ２ (1) (In formula (1), X represents a halogen atom, CH ３ COO, NO ３ , or (SO ４ ) １／２ .)

3. The method for manufacturing gloves according to claim 1, wherein the content of the visible light-responsive photocatalyst (B) ranges from 1 to 60% by mass in the aqueous urethane resin composition.

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