WO2022091547A1

WO2022091547A1 - Glove

Info

Publication number: WO2022091547A1
Application number: PCT/JP2021/031296
Authority: WO
Inventors: 寛樹田中; 俊介河中; 幸介藤田
Original assignee: Dic株式会社
Priority date: 2020-10-29
Filing date: 2021-08-26
Publication date: 2022-05-05
Also published as: JPWO2022091547A1; CN116194007A

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

gloves

The present invention relates to a glove having a film made of a urethane resin composition containing a visible light responsive photocatalyst.

As rubber generally used as a material having rubber elasticity, natural rubber, isoprene rubber, chloroprene rubber, nitrile rubber and the like are used. When these are used for gloves, allergies due to proteins contained in natural rubber and allergies due to vulcanizing agents and vulcanization accelerators used for these rubbers in general may become a problem.

Therefore, as a substitute material for these rubbers, the use of urethane resin having rubber elasticity that does not contain the above substances is promising. Until now, rubber latex has been widely used in glove processing, and an alternative to urethane dispersion (a urethane resin dispersed in water, etc.) that can be used in the same manufacturing equipment is particularly promising.

On the other hand, recently, due to the coronavirus pandemic, there is increasing interest in antiviral properties for gloves, and it is required to suppress allergies and further enhance antiviral properties by wearing gloves.

Special Table 2005-526889

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

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

The glove of the present invention has excellent antiviral properties. Further, since the urethane resin composition containing water is used, the environmental load at the time of manufacturing gloves is 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 field, the food field, and the medical field, and can be particularly preferably used as a medical glove. ..

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

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

Examples of the method for obtaining the urethane resin having an anionic group include a method using one or more compounds selected from the group consisting of a compound having a carboxyl group and a compound having a sulfonyl group as a raw material.

As the compound having a carboxyl group, for example, 2,2-dimethylol propionic acid, 2,2-dimethylol butyric acid, 2,2-dimethylol butyric acid, 2,2-valeric acid and the like can be used. These compounds may be used alone or in combination of two or more.

Examples of the compound having a sulfonyl group include 3,4-diaminobutane sulfonic acid, 3,6-diamino-2-toluene sulfonic acid, 2,6-diaminobenzene sulfonic acid, and N- (2-aminoethyl)-. 2-aminosulfonic acid, N- (2-aminoethyl) -2-aminoethylsulfonic acid, N-2-aminoethane-2-aminosulfonic acid, N- (2-aminoethyl) -β-alanine; salts thereof Can be used. These compounds may be used alone or in combination of two or more.

The carboxyl group and the sulfonyl group may be partially or completely neutralized with a basic compound in the urethane resin composition. As the basic compound, for example, organic amines such as ammonia, triethylamine, pyridine, and morpholine; alkanolamines such as monoethanolamine and dimethylethanolamine; and metal base compounds containing sodium, potassium, lithium, calcium and the like are used. Can be done.

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 a raw material.

Examples of the compound having an amino group include compounds having primary and secondary amino groups such as triethylenetetramine and diethylenetriamine; N-alkyldialkanolamines such as N-methyldiethanolamine and N-ethyldiethanolamine, and N-methyl. Compounds having a tertiary amino group such as N-alkyldiaminoalkylamine such as diaminoethylamine and N-ethyldiaminoethylamine can be used. These compounds may be used alone or in combination of two or more.

Examples of the method for obtaining the urethane resin having a nonionic group include a method using one or more compounds having an oxyethylene structure as a raw material.

As the compound having an oxyethylene structure, for example, a polyether polyol 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.

Examples of the emulsifier that can be used to obtain the aqueous urethane resin that is forcibly dispersed in water (B) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styrylphenyl ether, and poly. Nonionic emulsifiers such as oxyethylene sorbitol tetraoleate and polyoxyethylene / polyoxypropylene copolymer; fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalensulfonates. , Polyoxyethylene alkyl sulfate, alkan sulphonate sodium salt, alkyl diphenyl ether sulphonic acid sodium salt and other anionic emulsifiers; alkylamine salt, alkyltrimethylammonium salt, alkyldimethylbenzylammonium salt and other cationic emulsifiers Can be done. These emulsifiers may be used alone or in combination of two or more.

The urethane resin (A) is, for example, a polyol (a1), a polyisocyanate (a2), a chain extender (a3), and, if necessary, a raw material used for producing the urethane resin having the above-mentioned hydrophilic group. Reactants can be used.

As the polyol (a1), for example, a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyacrylic polyol, or the like can be used. These polyols may be used alone or in combination of two or more. Among these, a polycarbonate polyol and / or a polyether polyol is preferable, and a polycarbonate polyol and / or a polytetramethylene glycol is more preferable because further improved chemical resistance and flexibility can be obtained.

The number average molecular weight of the polyol (a1) is preferably in the range of 500 to 10,000, more preferably in the range of 1,000 to 5,000, from the viewpoint of obtaining even more excellent flexibility and chemical resistance. .. The number average molecular weight of the polyol (a1) indicates a value measured by a gel permeation chromatography (GPC) method.

Examples of the polyisocyanate (a2) include aromatic polyisocyanates such as phenylenediocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidated diphenylmethane polyisocyanate; hexamethylene diisocyanate, lysine diisocyanate, and the like. An aliphatic or alicyclic polyisocyanate such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimerate diisocyanate, norbornene diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferable, and diphenylmethane diisocyanates are more preferable, because even more excellent chemical resistance can be obtained.

Examples of the chain extender (a3) include ethylenediamine, 1,2-propanedidiol, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, and 1, Chain extender having an amino group such as 3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, hydrazine, diethylenetriamine, etc. Ethylene glycol, diethylene recall, triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, methylene glycol, glycerin, Chain extenders with hydroxyl groups such as sorbitol, bisphenol A, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenyl ether, trimethylolpropane; 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, neopentylglycol, 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, trimethylpropane A chain extender having a branched structure such as the above can be used. These chain extenders may be used alone or in combination of two or more. Among these, a chain extender having no branched structure is preferably used, a chain extender having a hydroxyl group is more preferable, and ethylene glycol is particularly preferable, from the viewpoint of obtaining even more excellent chemical resistance.

As a method for producing the urethane resin (A), for example, the polyol (a1), the polyisocyanate (a2), the chain extender (a3), and the hydrophilic group are used in the absence of a solvent or in the presence of an organic solvent. A method of mixing raw materials for producing a urethane resin having a urethane resin and reacting them in a range of 50 to 100 ° C. for 3 to 20 hours; with the polyol (a1) in the absence of a solvent or in the presence of an organic solvent. The polyisocyanate (a2) and the raw material 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 an isocyanate group. Then, a method of producing by reacting the urethane prepolymer with the chain extender (a3) and the like can be mentioned. When an organic solvent is used in the reaction, it is preferably distilled off in the end.

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

The average particle size of the urethane resin (A) is preferably in the range of 0.05 to 1 μm, preferably 0.10, from the viewpoint of obtaining even better dispersion stability and a relatively high concentration urethane resin. A range of ~ 0.7 μm is more preferable. The method for measuring the average particle size of the urethane resin (A) is a laser diffraction / scattering type particle size distribution measuring device (Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd.) using a urethane resin composition containing the urethane resin (A). ”), Water is used as the dispersion liquid, the solvent refractive index is 1.33, the particle refractive index is 1.51, and the average particle diameter indicates the measured value of the volume average diameter.

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.

The visible light responsive photocatalyst (B) is an essential component for obtaining excellent antiviral properties, and examples thereof include compositions containing titanium oxide (a), and even more excellent antiviral properties can be obtained. From this point of view, a titanium oxide (a) in which a metal compound is supported is preferably used.

As the titanium oxide (a), for example, rutile-type titanium oxide (a1), anatase-type titanium oxide, brookite-type titanium oxide, or the like can be used. These titanium oxides may be used alone or in combination of two or more. Among these, rutile-type titanium oxide (a1) is preferably contained because it has excellent photocatalytic activity in the visible light region.

As the content rate (rutileization rate) of the rutile-type titanium oxide (a1), further excellent antiviral property in bright and dark places, organic compound decomposability in bright place, and visible light responsiveness can be obtained. From this point of view, it is preferably 15 mol% or more, more preferably 50 mol% or more, still more preferably 90 mol% or more.

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

Titanium oxide produced by the vapor phase method has the advantage of being able to generate a uniform particle size, but it is difficult to form secondary aggregates, so the apparent specific surface area is high, and the mixed solution during the reaction step. It is considered that the viscosity of is high. On the other hand, the titanium oxide (a) produced by the liquid phase method is considered to generate loose secondary aggregates in the firing step, and has a specific surface area (BET value) due to the primary particles. The cohesive force is small and the viscosity of the mixed solution can be suppressed. For the above reasons, as the titanium oxide (a), the productivity of the visible light responsive photocatalyst (B), the wear resistance of gloves, the bending resistance, the flexibility, the durability, and the chemical resistance are further improved. Titanium oxide produced by the liquid phase method is preferable because it can be produced.

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

The primary particle size of the titanium oxide (a) is preferably in the range of 0.01 to 0.5 μm, preferably 0.06 to 0.5 μm, from the viewpoint of obtaining even more excellent antiviral properties and visible light responsiveness. A range of 0.35 μm is more preferred. The method for measuring the primary particle size of the titanium oxide (a) is a value measured by a method of directly measuring the size of the primary particle from an electron micrograph using a transmission electron microscope (TEM). .. Specifically, the minor axis diameter and the major axis diameter of each titanium oxide primary particle are measured, the average is taken as the particle diameter of the primary particle, and then each particle is obtained for 100 or more titanium oxide particles. The volume (weight) of was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was taken as the average primary particle size. The

Further, the visible light responsive photocatalyst further improves the photocatalytic activity in the visible light region, and easily develops an appropriate activity capable of decomposing dirt components under practical indoor light, and thus titanium oxide (a). ), It is preferable to use one in which a metal compound is supported.

As the metal compound, for example, a copper compound, an iron compound, a tungsten compound, or the like 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 and antiviral properties. As a method for supporting the metal compound on the titanium oxide (a), a known method can be used.

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

Examples of the method for supporting the divalent copper compound on the titanium oxide (a) include titanium oxide (a) containing rutyl-type titanium oxide (a1), a raw material for the divalent copper compound (b), water (c), and water (c). , A method having a mixing step (i) of the alkaline substance (d) can be mentioned.

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, a mixing step with good handling can be performed even if the concentration of the titanium oxide (a) is increased. In particular, the mixing step can be performed satisfactorily even when the concentration of the titanium oxide (a) is in the range of more than 25% by mass and 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, or the like can be used.

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

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 capricate, and mistinic acid. Copper, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, melitonic acid Copper, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, acetylacetone copper, ethylacetate acetate, isokichi Copper herbate, β-resorcylate copper, diacetoacetate copper, formyl succinate copper, salicylamine acid copper, bis (2-ethylhexanoic acid) copper, sebacate copper, naphthenate copper, oxine copper, acetylacetone copper, ethylacetate acetate , Trifluoromethanesulfonate copper, phthalocyanine copper, copper ethoxydo, copper isopropoxide, copper methoxyd, copper dimethyldithiocarbamate and the like can be used. These compounds may be used alone or in combination of two or more.

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

The X in the formula (1) 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 with respect to 100 parts by mass of the titanium oxide (a). The range of 0.1 to 15 parts by mass is more preferable, and the range of 0.3 to 10 parts by mass is further preferable.

The water (c) is the solvent in the mixing step (i), and water alone is preferable, but other solvents may be contained if necessary. As the other solvent, for example, alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide and tetrahydrofuran can be used. These solvents may be used alone or in combination of two or more.

As the alkaline substance (d), for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, a basic surfactant and the like can be used, and water can be used. It is preferable to use sodium oxide.

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

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 water (c) may be mixed. Examples thereof include a method in which titanium oxide (a) is mixed and stirred as necessary, then a divalent copper compound raw material (b) is mixed and stirred, and then an 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).

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

Since the support of the divalent copper compound on the titanium oxide (a) is good, the titanium oxide (a), the divalent copper compound raw material (b) and the water (c) are mixed and stirred, and then alkaline. The pH of the mixture after mixing and stirring the substance (d) is 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 mixed liquid can be separated as a solid content. Examples of the method for performing the separation include filtration, sedimentation separation, centrifugation, evaporation and drying, and the like, but filtration is preferable. The separated solid content may be subsequently washed with water, crushed, classified, or the like, if necessary.

After obtaining the solid content, the solid content can be more firmly bonded to the divalent copper compound derived from the divalent copper compound raw material (b) supported on the titanium oxide (a). Is preferably heat-treated. 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. 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 with respect to 100 parts by mass of the titanium oxide (a), which provides antiviral properties. It is preferable from the viewpoint of the photocatalytic activity including. 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 (B) is preferably 0.1 to 60% by mass, preferably 0.3 to 60% by mass, based on the aqueous urethane resin composition, from the viewpoint of improving antiviral properties and various physical properties of gloves. 60% by mass is more preferable, 1 to 40% by mass is further preferable, and 1 to 20% by mass is particularly preferable.

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

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

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, but other additives as necessary. May be contained.

Examples of the other additives include a thickener, a defoaming agent, a urethanization catalyst, a silane coupling agent, a filler, a texo property-imparting agent, an antistatic agent, a wax, a heat stabilizer, a light-resistant stabilizer, and fluorescence. Whitening agents, foaming agents, foam stabilizers, pigments, dyes, conductivity-imparting agents, antistatic agents, moisture-permeable agents, water-repellent agents, oil-repellent agents, blocking inhibitors, hydrolysis inhibitors and the like can be used. .. These additives may be used alone or in combination of two or more.

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

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.

As a method for producing a glove having a film made of the urethane resin composition, for example, the hand mold, the tube mold, etc. are first immersed in a coagulant described later and then dried as necessary to obtain the hand mold, etc. By adhering the metal salt or the like in the coagulant to the surface of the body, then immersing the hand mold or the like in the urethane resin composition, and then washing the surface with water and drying the hand mold or the like. A method of manufacturing a glove having a solidified film on the surface of the glove can be mentioned. At this time, the urethane resin composition may be further diluted with distilled water, ion-exchanged water, or the like.

As the coagulant, for example, a metal salt solution of calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, sodium chloride or the like; an acid solution of formic acid, acetic acid or the like can be used. As the solvent capable of dissolving the metal salt or acid, for example, water, methanol, ethanol, isopropanol or the like can be used. The metal salt contained in the coagulant is preferably contained in the range of 1 to 50% by mass with respect to the total amount of the coagulant. The time for immersing the coating material in the coagulant may be 1 to 10 minutes. Further, the coagulant can be used at a temperature of 5 to 60 ° C.

The hand mold or tube mold may be at room temperature or may be heated to 30 to 70 ° C. when immersed in the coagulant.

Further, the hand mold or the tube mold may be preliminarily attached with a glove-like object or a tubular object made of knitted material such as nylon fiber. Specifically, first, a hand mold or the like to which a glove-like material made of the knitted material is attached is immersed in the coagulant and then dried as necessary to coagulate the glove-like material or the like. Impregnate the agent. Next, after immersing the hand mold or the like in the urethane resin composition, the surface thereof is washed with water and dried to form gloves or the like made of a solidified film on the surface of the glove-like material or the like. By peeling the glove or the like from the hand mold or the glove-like object, a glove or the like made of a solidified film having a shape corresponding to the hand mold or the like can be obtained. Also in the case of producing the tube, it can be produced by the same method as described above except that the tube type and the tubular material made of knitted fabric such as nylon fiber are used.

The knitting is not limited to the nylon fiber, and for example, a knit made of polyester fiber, aramid fiber, polyethylene fiber, cotton or the like can be used. Further, instead of the knitting, a woven fabric made of the fibers can be used. Further, instead of the knitting, a glove-like material or a tubular material made of a resin material such as vinyl chloride, natural rubber or synthetic rubber can be used.

As described above, the glove of the present invention has excellent antiviral properties. Further, since the urethane resin composition containing water is used, the environmental load at the time of manufacturing gloves is 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 field, the food field, and the medical field, and can be particularly preferably used as a medical glove. ..

Hereinafter, the present invention will be described in more detail with reference to examples.

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

(2) Manufacturing process a) Mixing process (reaction process)
600 parts by mass of 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. Then, the mixture was stirred with a stirrer (“Robomics” manufactured by Tokushu Kagaku Kogyo Co., Ltd.), and a 1 mol / L sodium hydroxide aqueous solution was added dropwise until the pH of the mixture reached 10.
b) Dehydration step Vacuum filtration was performed under reduced pressure using a qualitative filter paper (5C), solid content was separated from the mixed solution, and further washing was carried out with ion-exchanged water. Then, the washed solid was dried at 120 ° C. for 12 hours to remove water. After drying, a powdery titanium oxide composition was obtained by a mill (“Miller” manufactured by Iwatani Corporation).
c) Heat treatment step A titanium oxide composition containing titanium oxide carrying a divalent copper compound is heat-treated at 450 ° C. for 3 hours in the presence of oxygen using a precision thermostat (“DH650” manufactured by Yamato Kagaku Co., Ltd.). Obtained.
The amount of the divalent copper compound supported on the titanium oxide on which the divalent copper compound was supported was 0.5% by mass with respect to the titanium oxide.

[Preparation Example 2]
After mixing and stirring 25 parts of the titanium oxide composition obtained in Adjustment Example 1, 75 parts of water, and 1 part of a dispersant (“SN Dispersant 5023” manufactured by San Nopco Ltd.), 100 parts of 1.0 mmφ ceramic beads were added. , Grinded with a sand grinder for 4 hours. After completion of grinding, the beads and the dispersion were separated to obtain a titanium oxide composition dispersion.

[Preparation Example 3]
Polypolypolyols (based on 1,5-pentanediol and 1,6-hexanediol, number average molecular weight; 2,000 in nitrogen-substituted containers equipped with thermometers, nitrogen gas inlet tubes and stirrers. ) By 600 parts by mass, polytetramethylene glycol (number average molecular weight; 2,000) by 33 parts by mass, polypropylene triol (additive of glycerin and propylene oxide, number average molecular weight; 6,000) by 181 parts by mass, ethylene. Glycol) at 8.4 parts by mass, 2,2-dimethylolpropionic acid by 15.8 parts by mass, 4,4'-diphenylmethanediisocyanate by 154 parts by mass, and methyl ethyl ketone in the presence of 991 parts by mass at 70 ° C. It was reacted.
When the reaction product reaches the specified viscosity, 1.0 part by mass of methanol is added and stirred for 1 hour to complete the reaction, and 498 parts by mass of methyl ethyl ketone is added as a diluting solvent to obtain an organic solvent solution of urethane resin. rice field.
Next, 9.6 parts by mass of a 48 mass% potassium hydroxide aqueous solution as a neutralizing agent was added to the organic solvent solution of the urethane resin to neutralize the carboxyl group of the urethane resin, and 2,480 parts by mass of water was further added. By further stirring, an aqueous dispersion of urethane resin was obtained. Then, by removing the solvent from the aqueous dispersion of the urethane resin, a urethane resin (A1) composition having a non-volatile content of 45% by mass and an average particle size of 0.73 μm was obtained.

[Preparation Example 4]
In a nitrogen-substituted container equipped with a thermometer, nitrogen gas, introduction tube, and stirrer, polyoxytetramethylene glycol (number average molecular weight; 2,000) was 895.3 parts by mass and ethylene glycol was 18 parts by mass. , 2,2'-Dimethylolpropionic acid was reacted at 70 ° C. in the presence of 25.5 parts by mass, diphenylmethane diisocyanate in an amount of 224 parts by mass, and methyl ethyl ketone in the presence of 487 parts by mass.
When the reaction product reached the specified viscosity, 2.9 parts by mass of methanol was added and stirred for 1 hour to complete the reaction, and 1257 parts by mass of methyl ethyl ketone was further added as a diluting solvent to obtain an organic solvent solution of 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 removing the solvent from this aqueous dispersion, a urethane resin (A2) composition having a non-volatile content of 40% by mass and an average particle size of 0.25 μm was obtained.

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

<Making gloves (thin)>
Gloves were produced by the following procedure.
(1) Immerse the pottery bill in a 10% by mass calcium nitrate aqueous solution and pull it up.
(2) Dry the hand mold of (1) at 70 ° C. for 2 minutes.
(3) The hand mold of (2) is immersed in the urethane resin composition for 5 seconds and pulled up.
(4) Wash the hand mold of (3) with water.
(5) The hand mold of (4) is dried at 70 ° C. for 20 minutes and then at 120 ° C. for 30 minutes.
(6) The baby powder is attached to the hand mold of (5), and the urethane resin film is peeled off from the hand mold.

[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.

[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.

[Example 4]
<Preparation of urethane resin composition>
A urethane resin composition was obtained by blending 100 parts by mass of the urethane resin (A2) composition obtained in Preparation Example 4 with 1 part by mass of the titanium oxide composition dispersion liquid obtained in Preparation Example 2.

<Making gloves (thick)>
Gloves were produced by the following procedure.
(1) Attach a knitted glove made of nylon fiber to an aluminum hand mold, immerse it in a 5 mass% calcium nitrate aqueous solution for 10 seconds, and pull it up.
(2) The hand mold of (1) is immersed in the urethane resin composition for 2 seconds to form a solidified film of anionic urethane resin on the surface of knitted gloves, and then pulled up.
(3) Immerse the hand mold of (2) in water for 30 minutes and then pull it up.
(4) The hand mold of (3) is dried at 70 ° C. for 20 minutes and then at 120 ° C. for 30 minutes.
(5) Remove the gloves coated with the coagulation film from the hand mold of (4).

[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.

[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.

[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.

[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.

[Measurement method of number average molecular weight]
The number average molecular weight of the polyol or the like used in the synthesis example shows the value measured under the following conditions by the gel permeation chromatography (GPC) method.

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 ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(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

[Method for measuring the amount of divalent copper compound supported 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 spectrophotometer to carry an amount of the divalent copper compound on titanium oxide (a) (divalent). The amount of copper compound carried (parts by mass) / titanium oxide (a) (parts by mass)) was quantified.

[Evaluation of antiviral property]
Anti-phage virus tests (see JIS R1756: 2020) were performed on the gloves obtained in Examples and Comparative Examples.

1) As for the light irradiation condition, the light of the white fluorescent lamp was cut off from ultraviolet rays by the N113 filter, and the illuminance was set to 500 lux.
2) Cut the palms of the gloves (thin) obtained in Examples and Comparative Examples into 5 cm × 5 cm pieces, place them on a 5 cm × 5 cm glass plate, drop a 100 μL Qβ phage solution of known concentration, and then drop 5 cm ×.
It was sandwiched between 5 cm glass plates to prepare a sample for evaluation.
3) Cut the palms of the gloves (thick) obtained in Examples and Comparative Examples into 5 cm × 5 cm, hang a 100 μL Qβ phage solution of known concentration on the urethane resin surface, and then cover with a 4 cm × 4 cm adhesive film. , As a sample for evaluation.
4) Samples irradiated with light for 8 hours were collected with SCDLP solution, appropriately diluted, infected with Escherichia coli, applied to an agar medium, and evaluated by counting the number of colonies after culturing. The antiviral property was evaluated by the degree of inactivation of Qβ phage, and the inactivation degree -2 to -5 was evaluated as having antiviral property "○".

It was found that Examples 1 to 6, which are the gloves of the present invention, have excellent antiviral properties.

On the other hand, in Comparative Examples 1 and 2, although the visible light responsive photocatalyst (B) was not used, the antiviral property was poor.

Claims

A glove having a film formed of a urethane resin composition containing a urethane resin (A), a visible light responsive photocatalyst (B), and water (C).
The glove according to claim 1, wherein the visible light responsive photocatalyst (B) is a titanium oxide (a) on which a metal compound is supported.
The glove according to claim 2, wherein the titanium oxide (a) contains rutile-type titanium oxide (a1).
The glove according to claim 2 or 3, wherein the metal compound is a divalent copper compound.