Aqueous resin composition and glove

Abstract

Aqueous resin composition, comprising: an anionic polyurethane (A) having an aromatic ring, wherein the aromatic ring content in the anionic polyurethane (A) is 550 to 2,500 mmol / kg; wherein the aromatic ring content in the anionic polyurethane (A) represents the aromatic ring content occupying the starting material, based on the total mass of each starting material forming the anionic polyurethane (A); an acrylonitrile butadiene rubber (B); an aqueous medium (C); a vulcanizing agent (D) and a vulcanization accelerator (E), wherein the mass ratio (ratio of solids content) of the anionic polyurethane (A) and the acrylonitrile butadiene rubber (B) is in a range of 20 / 80 to 95 / 5, the vulcanizing agent (D) sulfur is and the vulcanization accelerator (E) zinc oxide and zinc diethyldithiocarbamate.

Description

Technical field

[0001] The present invention relates to an aqueous resin composition which has excellent storage stability. State of the art

[0002] In the relevant state of the art, natural rubber, synthetic rubber latex, and the like are used for gloves. The production of a glove coating film with an aqueous resin composition mixed with aqueous polyurethane has also been investigated for modifying these rubbers (see, for example, PTL 1).

[0003] More recently, the addition of aqueous polyurethane can be used to improve the flexibility and wear resistance of acrylonitrile butadiene rubber. It is common practice to add a vulcanizing agent or accelerator at this time; however, it has been observed that when these are added to a mixture of aqueous polyurethane and acrylonitrile butadiene rubber, thickening or hardening occurs over time, and storage stability deteriorates.

[0004] WO 2013 / 035461 A1 addresses the problem of providing a polyurethane film that has a soft texture and sufficient strength to prevent, for example, tearing due to scratches or similar causes. The document describes a polyurethane film characterized in that it is obtained using a polyurethane composition (D) comprising a polyurethane (A) having a polyoxyethylene structure at one end and an acid number of 0.1 to 10, an emulsifier (B), and an aqueous medium (C), wherein the mass ratio of the emulsifier (B) is 0.1 to 5 parts per 100 parts by mass of the polyurethane (A). List of literature on patent literature

[0005] [PTL 1] JP H08-209415 A Summary of the invention: Technical problem

[0006] One object of the invention is to provide a mixture of aqueous polyurethane and acrylonitrile butadiene rubber that has excellent storage stability, even in the case where a vulcanizing agent and a vulcanization accelerator are added. Solution to the problem

[0007] To solve the aforementioned problem, the invention provides the aqueous resin composition according to claim 1. Preferred embodiments thereof are specified in claims 2 and 3.

[0008] The invention further provides a glove comprising a coating film produced by solidifying the aqueous resin composition. Advantageous effects of the invention

[0009] The aqueous resin composition of the invention exhibits excellent storage stability. Furthermore, when using anionic polyurethane (A) with a specific composition, excellent wear resistance and flexibility are achieved in addition to the storage stability that is the object of the invention. Therefore, the aqueous resin composition of the invention can be suitablely used to manufacture a glove, a medical tube (e.g., a catheter), or a contraceptive (e.g., a condom), and is particularly suitable for manufacturing a glove. Description of embodiments

[0010] An aqueous resin composition of the invention is defined in claim 1 and comprises an anionic polyurethane (A) having an aromatic ring, an acrylonitrile butadiene rubber (B), an aqueous medium (C), a vulcanizing agent (D) and a vulcanization accelerator (E).

[0011] Anionic polyurethane (A) necessarily has an aromatic ring to achieve excellent storage stability. Because anionic polyurethane (A) has an aromatic ring, excellent storage stability can be achieved even when acrylonitrile butadiene rubber (B), aqueous medium (C), vulcanizing agent (D), and vulcanization accelerator (E) are added to the anionic polyurethane (A) and aqueous medium (C). If, for example, an aliphatic anionic polyurethane is used instead of anionic polyurethane (A), thickening or hardening may occur over time. The reason for the excellent storage stability achieved with anionic polyurethane (A) that has an aromatic ring is, for example, the following.Preventing the aggregation of dispersing elements due to electrostatic repulsion contributes to a stable dispersion of the dispersing elements dispersed in the aqueous medium (C). It is assumed that, according to the invention, as a result of the increased electrostatic repulsion due to the effect of π-electrons of the aromatic ring on the charge state of the dispersing elements comprising the anionic polyurethane (A), the dispersing elements comprising the anionic polyurethane (A) hardly aggregate with other components in the aqueous resin composition, thus improving the storage stability of the aqueous resin composition.

[0012] The aromatic ring content in the anionic polyurethane (A) is 550 to 2,500 mmol / kg, preferably 800 to 2,400 mmol / kg, and more preferably 1,000 to 2,300 mmol / kg, to achieve excellent storage stability and wear resistance. The aromatic ring content in the anionic polyurethane (A) represents the content of the aromatic ring occupying the starting material, based on the total mass of each starting material forming the anionic polyurethane (A). In a numerical example, the molecular weight of a benzene ring or a naphthalene ring, excluding any organic group, is used as the molecular weight of the aromatic ring.In the case of toluene, for example, the molecular weight of a benzene ring having five hydrogen atoms, excluding a methyl group, is used; in the case of diphenylmethane diisocyanate, the molecular weight of a benzene ring with four hydrogen atoms, excluding an isocyanate group and a methylene group, is used; and in the case of tolylene diisocyanate, the molecular weight of a benzene ring having four hydrogen atoms, excluding two methyl groups, is used.

[0013] Specifically, the anionic polyurethane (A) can be a reaction product of polyol, a carboxyl group-containing glycol, polyisocyanate and a chain extender.

[0014] Examples of polyols include polyoxyalkylene polyol, polyester polyol, polycarbonate polyol, and polyacrylic polyol. These polyols can be used alone or in combination with two or more types. Among these, polyoxyalkylene polyol is preferred, and polyoxytetramethylene glycol is preferred, for the purpose of achieving excellent flexibility with high polymer chain mobility.

[0015] The number-average molecular weight of the polyol is preferably 500 to 5,000 and more preferably 700 to 4,000, considering manufacturing stability and flexibility. The number-average molecular weight of the polyol is determined by gel permeation chromatography (GPC) under the following conditions.

[0016] Measuring device: fast GPC device (“HLC-8220 GPC”, manufactured by Tosoh Corporation) Column: the following columns, manufactured by Tosoh Corporation, were connected in series and used. "TSKgel G5000" (7.8 mm ID×30 cm)×1 piece "TSKgel G4000" (7.8 mm ID×30 cm)×1 piece "TSKgel G3000" (7.8 mm ID×30 cm)×1 piece "TSKgel G2000" (7.8 mm ID×30 cm)×1 piece

[0017] Detector: RI (Differential Refractometer) Column temperature: 40°C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Injected amount: 100 µl (tetrahydrofuran solution with a sample concentration of 0.4 wt%) Reference sample: A calibration curve was plotted using the following reference polystyrene. (Reference polystyrene) “TSKgel Reference Polystyrene A-500”, manufactured by Tosoh Corporation “TSKgel Reference Polystyrene A-1000”, manufactured by Tosoh Corporation “TSKgel Reference Polystyrene A-2500”, manufactured by Tosoh Corporation “TSKgel Reference Polystyrene A-5000”, manufactured by Tosoh Corporation “TSKgel Reference Polystyrene F-1”, manufactured by Tosoh Corporation “TSKgel Reference Polystyrene F-2”, manufactured by Tosoh Corporation “TSKgel Reference Polystyrene F-4”, manufactured by Tosoh Corporation “TSKgel reference polystyrene F-10”, manufactured by Tosoh Corporation “TSKgel reference polystyrene F-20”, manufactured by Tosoh Corporation “TSKgel reference polystyrene F-40”, manufactured by Tosoh Corporation “TSKgel reference polystyrene F-80”, manufactured by Tosoh Corporation “TSKgel Reference Polystyrene F-128”, manufactured by Tosoh Corporation “TSKgel reference polystyrene F-288”, manufactured by Tosoh Corporation “TSKgel reference polystyrene F-550”, manufactured by Tosoh Corporation

[0018] The content of an oxyalkylene group in the anionic polyurethane (A) is preferably 4 to 12 mol / kg, more preferably 5 to 11.5 mol / kg and more preferably 6 to 11 mol / kg, with the viewpoint of achieving excellent wear resistance and flexibility.

[0019] The oxyalkylene group is supplied when polyoxyalkylene polyol is used as the starting material for the anionic polyurethane (A). Accordingly, the content of the oxyalkylene group in the anionic polyurethane (A) indicates the content of an oxyalkylene group supplied by the polyoxyalkylene polyol, based on the total mass of each starting material forming the anionic polyurethane (A).

[0020] The carboxyl-containing glycol provides an anionic group. Examples that can be used include 2,2'-dimethylolpropionic acid, 2,2'-dimethylolbutanoic acid, 2,2'-dimethylolbutyric acid, and 2,2'-valeric acid. These compounds can be used alone or as a combination of two or more types.

[0021] In the aqueous resin composition, some or all of the carboxyl groups can be neutralized with a basic compound. Examples of basic compounds include organic amines, such as ammonia, triethylamine, pyridine, or morpholine; alkanolamines, such as monoethanolamine; and basic metal compounds, such as sodium, potassium, lithium, or calcium.

[0022] Examples of polyisocyanates include aromatic polyisocyanates, such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, or carbodiimidated diphenylmethane polyisocyanate; and aliphatic or alicyclic polyisocyanates, such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimeric acid diisocyanate, or norbornene diisocyanate. These polyisocyanates can be used alone or in combination with two or more types.Among these, the aromatic polyisocyanate is preferably used from the point of view of the simple introduction of an aromatic ring into the anionic polyurethane (A), and diphenylmethane diisocyanate or toluene diisocyanate is more preferably used from the point of view of the formation of a hard segment having a suitable chain length to obtain excellent wear resistance and flexibility.

[0023] The number-average molecular weight of the chain extender is 50 to 450, and examples include a chain extender containing an amino group, for example, 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, 1,4-cyclohexanediamine, or hydrazine; and a chain extender containing a hydroxyl group, for example, ethylene glycol, recycled diethylene, 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, or trimethylolpropane. These chain extenders can be used alone or in combination with two or more of them.Among these, the chain extender comprising a hydroxyl group is preferably used with regard to preventing hardening of a solidified coating film and achieving excellent wear resistance and flexibility, and one or more types of chain extenders selected from the group consisting of ethylene glycol, butanediol, trimethylolpropane and neopentyl glycol are more preferably used, and ethylene glycol or butanediol is even more preferably used with regard to forming a hard segment having a suitable wavelength to obtain excellent wear resistance and flexibility.

[0024] As described above, the anionic polyurethane (A) can be a reaction product of polyoxytetramethylene glycol, the carboxyl group-containing glycol, diphenylmethane diisocyanate or toluene diisocyanate, and ethylene glycol or butanediol. In this case, excellent wear resistance and flexibility are obtained in addition to storage stability, which is the object of the present invention.

[0025] The anionic polyurethane (A) can be produced, for example, by mixing the polyol, the carboxyl group-containing glycol, the polyisocyanate and the chain extender together in the absence of solvents or in the presence of an organic solvent and causing a urethanization reaction, for example, at a reaction temperature of 50°C to 100°C for 3 to 10 hours.

[0026] Furthermore, the anionic polyurethane (A) can also be produced, for example, by mixing the polyol, the carboxyl group-containing glycol, and the polyisocyanate together in the absence of solvents or in the presence of an organic solvent, causing a reaction, for example, at a reaction temperature of 50°C to 100°C for 3 to 10 hours, to produce a urethane prepolymer comprising an isocyanate group at one end of the molecule, and causing a reaction between the urethane prepolymer and the chain extender.

[0027] In the reaction of the polyol, the carboxyl group-containing glycol, the polyisocyanate and the chain extension agent, the [isocyanate group / hydroxyl group] (molar ratio) is preferably 0.9 to 1.1 and more preferably 0.93 to 1.05.

[0028] Examples of organic solvents that can be used in the manufacture of anionic polyurethane (A) include a ketone solvent, for example, acetone or methyl ethyl ketone; an ether solvent, for example, tetrahydrofuran or dioxane; an acetic acid ester solvent, for example, ethyl acetate or butyl acetate; a nitrile solvent, for example, acetonitrile; and an amide solvent, for example, dimethylformamide or N-methylpyrrolidone. The organic solvent can be used alone or as a combination of two or more types.

[0029] The average particle diameter of the anionic polyurethane (A) is preferably 0.01 to 1 µm and more preferably 0.05 to 0.9 µm, from the perspective of easily preventing the formation of precipitates. A method for measuring the average particle diameter of the anionic polyurethane (A), as described in the examples, will be described later.

[0030] The weight-average molecular weight of the anionic polyurethane (A) is preferably 10,000 to 100,000 and more preferably 30,000 to 500,000, from the perspective of achieving excellent flexibility and wear resistance. The weight-average molecular weight of the anionic polyurethane (A) is a value obtained by performing the measurement in the same manner as the measurement of the number-average molecular weight of the polyol.

[0031] The amount of urethane bonding in the anionic polyurethane (A) is preferably 500 to 3,500 mmol / kg and more preferably 700 to 3,000 mmol / kg, based on the total anionic polyurethane (A), with the aim of maintaining excellent flexibility and wear resistance. The amount of urethane bonding in the anionic polyurethane (A) indicates the proportion of a urethane bonding structure occupying the starting material, based on the total mass of each starting material that forms the anionic polyurethane (A).

[0032] The content of a urethane bond in the anionic polyurethane (A) is preferably 0.2 mol / kg and more preferably 0.15 mol / kg, from the point of view of preventing hardening of a solidified coating film as a result of hydrogen bonding and achieving excellent wear resistance and flexibility.

[0033] Examples of urea bonding include bonding generated by a reaction with polyisocyanate when using a chain-extending agent containing an amino group as the starting material for the anionic polyurethane (A), and bonding generated by a reaction between an amino group (generated by a reaction between an isocyanate group and water) and polyisocyanate. Accordingly, the urea bonding content in the anionic polyurethane (A) can be adjusted by modifying the amount of the chain-extending agent containing an amino group and by urethanizing all the isocyanate prior to emulsification. The urea bonding content is calculated using the general formula (1). Urea content (mol / kg) = (Number of moles of amino group) + (Number of moles of isocyanate group − Number of moles of hydroxyl group − Number of moles of amino group) / 2 Mass of polyol + Mass of glycol containing a carboxyl group + Mass of polyisocyanate + Mass of chain extender

[0034] The content of anionic polyurethane (A) in the aqueous resin composition is preferably 2 to 60 wt% and more preferably 5 to 50 wt%, based on the aqueous resin composition, from the point of view of maintaining excellent storage stability and coating processability.

[0035] As acrylonitrile butadiene rubber (B), well-known acrylonitrile butadiene rubber can be used, and examples include acrylonitrile butadiene rubber in which the content of an acrylonitrile segment is 10 wt% to 70 wt%, and acrylonitrile butadiene rubber in which the content of a butadiene segment is 30 wt% to 90 wt%. Methacrylic acid can be included as a starting material in the production of acrylonitrile butadiene rubber (B), if required.

[0036] The mass ratio (ratio of solids content) of anionic polyurethane (A) and NBR (B) is 20 / 80 to 95 / 5 from the point of view of achieving excellent storage stability.

[0037] Examples of the aqueous medium (C) include water, an organic solvent mixed with water, and a mixture thereof. Examples of the organic solvent mixed with water include an alcohol solvent, for example, methanol, ethanol, n-propanol, or isopropanol; a ketone solvent, for example, acetone or methyl ethyl ketone; a polyalkylene glycol solvent, for example, ethylene glycol, diethylene glycol, or propylene glycol; an alkyl ether solvent, for example, polyalkylene polyol; and a lactam solvent, for example, N-methyl-2-pyrrolidone. Of these, water is preferred from an environmental point of view.

[0038] The content of the aqueous medium (C) is preferably 10 wt% to 90 wt% and more preferably 30 wt% to 80 wt%, based on the aqueous resin composition, from the point of view of the coating properties.

[0039] The vulcanizing agent (D) vulcanizes with a double bond resulting from butadiene in the acrylonitrile-butadiene rubber (B) and imparts durability, for example, water or oil resistance. It is sulfur, which can be used alone or in combination with morpholine disulfide and dithiodicaprolactam, an alkylphenol disulfide. Sulfur is used for its excellent vulcanizing properties. The vulcanizing agent (D) is preferably used in a state where it is dispersed in an aqueous medium, for example, water.

[0040] The content of the vulcanizing agent (D) is preferably 0.2 to 20 wt% and more preferably 0.5 to 10 wt% as a ratio of solid content, based on 100 wt parts of the acrylonitrile butadiene rubber (B), from the point of view of the equilibrium between the vulcanization effect and the storage stability.

[0041] The vulcanization accelerator (E) accelerates the vulcanization of the vulcanizing agent (D) and consists of zinc diethyldithiocarbamate and zinc oxide. Zinc oxide and zinc diethyldithiocarbamate are used to vulcanize the acrylonitrile butadiene rubber (B) and the vulcanizing agent (D). The vulcanization accelerator (E) is preferably used in a state where it is dispersed in an aqueous medium, for example, water.

[0042] The content of the vulcanization accelerator (E) is preferably 0.1 to 20 wt% and more preferably 0.3 to 10 wt% as a ratio of solid contents based on 100 wt parts of the acrylonitrile butadiene rubber (B) with regard to a balance between the vulcanization effect and the storage stability.

[0043] For example, a method for producing the aqueous resin composition is a method for producing an aqueous resin composition by preparing the anionic polyurethane (A) in the absence of solvents or in the presence of an organic solvent, neutralizing a carboxyl group in the anionic polyurethane (A) if necessary, supplying the aqueous medium (C), dispersing the anionic polyurethane (A) in the aqueous medium (C) and mixing and stirring in the NBR (B), the vulcanizing agent (D) and the vulcanization accelerator (E).

[0044] In the case of the production of the aqueous resin composition, an emulsifier can be used from the point of view of improving the dispersion stability of the anionic polyurethane (A) in the aqueous medium (C).

[0045] Examples of emulsifiers include a nonionic emulsifier, such as polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, or a polyoxyethylene-polyoxypropylene copolymer; a fatty acid salt, such as sodium oleate; an anionic emulsifier, such as alkyl sulfate ester salt, alkylbenzenesulfonate salt, alkyl sulfosuccinate salt, naphthalenesulfonate, polyoxyethylene alkyl sulfate, sodium alkanesulfonate salt, or sodium alkyl diphenyl ethersulfonate; and a cationic emulsifier, such as alkylamine salt, alkyl trimethylammonium salt, or alkyl dimethylbenzylammonium salt. These emulsifiers can be used individually or in combination with two or more types.

[0046] The aqueous resin composition of the invention comprises the anionic polyurethane (A), the NBR (B), the aqueous medium (C), the vulcanizing agent (D) and the vulcanization accelerator (E) and may, if necessary, include other additives.

[0047] Examples of additives include a thickener, a defoaming agent, a urethanization catalyst, a silane coupling agent, a filler, a thixotropic agent, a tackifier, a wax, a heat stabilizer, a light stabilizer, a fluorescent whitening agent, a foaming agent, a pigment, a dye, an antistatic agent, a moisture permeability improver, a water repellent, an oil repellent, a flame retardant, an antiblocking agent, and a hydrolysis inhibitor. These additives can be used alone or in combinations of two or more types.

[0048] The thickening agent can be conveniently used to adjust the viscosity of the aqueous resin composition and to simplify a salt coagulation process. Examples include a cellulose derivative, such as hydroxyethylcellulose, methylcellulose, or carboxymethylcellulose; polyacrylate; polyvinylpyrrolidone; a urethane compound; and a polyether compound. The amount used when employing the thickening agent is, for example, 0.1 to 5 parts by weight, based on 100 parts by weight of the total anionic polyurethane (A) and acrylonitrile butadiene rubber (B).

[0049] Examples of defoaming agents include silicone compounds, mineral oil compounds, polyglycol ether compounds, fatty acid ester compounds, metallic soaps, and fluorine compounds. These defoaming agents can be used individually or in combinations of two or more types.

[0050] The acid value of the aqueous resin composition is preferably 5 to 19 mg KOH / g and more preferably 7 to 14 mg KOH / g, from the perspective of achieving excellent manufacturing stability. A method for measuring the acid value of the aqueous resin composition is described in the examples that follow.

[0051] As a method for obtaining a solidified coating film by using the aqueous resin composition of the invention, for example a method is used for applying the aqueous resin composition to a surface of a release film and immersing the applied material in a predetermined coagulant and drying the applied material.

[0052] For applying the aqueous resin composition to a release film or the like, a method using a doctor blade applicator, a spraying process, a curtain applicator, a flow applicator, a roller applicator, or a brush coating process is used, for example. In this case, the viscosity of the aqueous resin composition is preferably 50 to 10,000 mPa·s and more preferably 1,000 to 3,000 mPa·s. The viscosity of the aqueous resin composition is a value measured with a B-type viscometer (40P cone) at 25°C.

[0053] Examples of the coagulant into which the aqueous resin-based coating material is immersed include a metal salt solution, such as calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, or sodium chloride, and an acid solution, such as formic acid or acetic acid. Examples of solvents in which the metal salt or acid can dissolve include water, methanol, ethanol, and isopropanol. The metal salt content of the coagulant is preferably 1 to 50% by mass, based on the total amount of the coagulant. Furthermore, the immersion time of the applied material in the coagulant is preferably 1 to 10 minutes. The coagulant is also preferably used at a temperature of 5°C to 60°C.

[0054] After immersion, the applied material is dried, for example at a temperature of 50°C to 150°C for 1 minute to 1 hour, and a coating film is formed that has solidified on the surface of a release film.

[0055] The 100% modulus of the solidified coating film, obtained by a tensile test under conditions of a crosshead speed of 300 mm / min, is preferably equal to or less than 6 MPa and more preferably 0.1 to 4 MPa, from the point of view of excellent flexibility.

[0056] Furthermore, the 300% modulus of the solidified coating film, obtained by a tensile test under conditions of a crosshead speed of 300 mm / min, is preferably equal to or less than 14 MPa and preferably 0.1 to 12 MPa from the point of view of excellent flexibility.

[0057] In the case of manufacturing a glove using the solidified coating film, a glove mold or tube mold is first immersed in the coagulant and dried if necessary. Metal salts or similar substances in the coagulant are then bound to the surface of the glove mold or mold. The glove mold is then immersed in the aqueous resin composition, the surface is washed with water and dried, and a coating film is formed on the surface of the glove mold or mold. The solidified coating film is then removed from the glove mold or mold, and a glove, enclosing the solidified coating film within a mold corresponding to the glove mold or mold, can thus be obtained.Even in the case of manufacturing a hose, the hose can be produced using the same procedure as described above, except that the hose mold is used.

[0058] In the case of immersion in the coagulant, the glove or tube mold can be at room temperature or heated to, for example, 30°C to 70°C. Alternatively, the coagulant can also be at room temperature, as in the case of the glove mold, and if the glove mold is heated, the coagulant can also be heated to, for example, 30°C to 70°C.

[0059] Furthermore, a glove-shaped or tubular material, formed from a knitted fabric, for example from nylon fiber, can be pre-mounted onto the glove mold or tubular form. Specifically, the glove mold, onto which the glove-shaped material formed from the knitted fabric is mounted, is first immersed in the coagulant and dried if necessary, and the glove-shaped material is then impregnated with the coagulant.Then the glove mold or similar is immersed in the aqueous resin composition, its surface is washed with water and dried, a glove or similar formed from a solidified coating film is formed on the surface of the glove-shaped material, the glove or similar is separated from the glove mold and glove-shaped material, and accordingly, a glove or similar formed from the solidified coating film, having a shape corresponding to the glove or similar, can be obtained. Even in the case of hose production, the hose can be produced by the same procedure as described above, except that the hose mold and hose-shaped material are formed from knitted fabric, for example, nylon fiber.

[0060] The knitted fabric is not limited to nylon fiber; a knitted fabric made from polyester, aramid, or cotton fibers can be used. Alternatively, a woven fabric made from the same fiber can be used. Furthermore, a glove-shaped or tubular material formed from a resinous material, such as vinyl chloride, natural rubber, or synthetic rubber, can also be used instead of the knitted fabric.

[0061] The number of friction cycles of the glove, carried out on the basis of EN388:2004, is preferably equal to or greater than 2,000 times, more preferably equal to or greater than 5,000 times and even more preferably 8,000 times to 50,000 times, with regard to excellent wear resistance.

[0062] As described above, the glove of the invention has excellent wear resistance and flexibility and can therefore be used in various fields, for example in the chemical industry or in the food industry. Examples

[0063] The invention will be described in more detail below using examples. [Production Example 1] Production of aqueous urethane composition (X-1)

[0064] In a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 895.3 parts by mass of polyoxytetramethylene glycol (numerical mean molecular weight: 2,000, hereinafter referred to as "PTMG 2000"), 18 parts by mass of ethylene glycol (hereinafter referred to as "EG"), 25.5 parts by mass of 2,2'-dimethylolpropionic acid (hereinafter referred to as "DMPA"), and 224 parts by mass of diphenylmethane diisocyanate (hereinafter referred to as "MDI") were allowed to react at 70°C in the presence of 487 parts by mass of methyl ethyl ketone.

[0065] When the viscosity of the reaction product reached a specified value, 2.9 parts by mass of methanol were added, and the mixture was stirred for 1 hour to complete the reaction. Additionally, 1.257 parts by mass of methyl ethyl ketone were added as a diluent, resulting in a solution of anionic polyurethane in organic solvent.

[0066] Subsequently, 19.2 parts by mass of triethylamine were added to the solution of anionic polyurethane in organic solvent as a neutralizing agent and stirred in. In addition, 3,638 parts by mass of water were added and stirred in, resulting in an aqueous dispersion of anionic polyurethane. This aqueous dispersion was then subjected to solvent removal, resulting in an aqueous urethane composition (X-1) with a non-volatile component content of 40% by mass and an acid number of 9.2 mg KOH / g. Regarding the anionic polyurethane, the oxyalkylene group content was 10.7 mol / kg, the aromatic ring content was 1,300 mmol / kg, and the average particle diameter was 0.25 µm. [Production Example 2] Production of aqueous urethane composition (X-2)

[0067] In a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 764.5 parts by mass of PTMG 2000, 18.9 parts by mass of butanediol (hereinafter abbreviated as "BG"), 23.1 parts by mass of DMPA and 190.8 parts by mass of MDI were allowed to react at 70°C in the presence of 417.5 parts by mass of methyl ethyl ketone.

[0068] When the viscosity of the reaction product reached a specific viscosity, 2.5 parts by mass of methanol were added, and the mixture was stirred for 1 hour to complete the reaction. Additionally, 1,078.4 parts by mass of methyl ethyl ketone were added as a diluent, resulting in a solution of anionic polyurethane in organic solvent.

[0069] Subsequently, 17.4 parts by mass of triethylamine were added to the solution of anionic polyurethane in organic solvent as a neutralizing agent and the mixture was stirred. Additionally, 3,200 parts by mass of water were added and stirred, resulting in an aqueous dispersion of anionic polyurethane. This aqueous dispersion was then subjected to solvent removal, yielding an aqueous urethane composition (X-2) with a non-volatile component content of 40% by mass and an acid number of 9.7 mg KOH / g. The anionic polyurethane had an oxyalkylene group content of 10.6 mol / kg, an aromatic ring content of 1,290 mmol / kg, and an average particle diameter of 0.14 µm. [Production Example 3] Production of aqueous urethane composition (X-3)

[0070] In a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 354.3 parts by mass of polyoxytetramethylene glycol (numerical mean molecular weight: 700; hereinafter abbreviated as "PTMG 700"), 8.6 parts by mass of EG, 16.7 parts by mass of DMPA and 190.8 parts by mass of MDI were allowed to react at 70°C in the presence of 237.3 parts by mass of methyl ethyl ketone.

[0071] When the viscosity of the reaction product reached a specific viscosity, 2.7 parts by mass of methanol were added, and the mixture was then stirred for 1 hour to complete the reaction. Additionally, 618 parts by mass of methyl ethyl ketone were added as a diluent, thus obtaining a solution of anionic polyurethane in organic solvent.

[0072] Subsequently, 12.6 parts by mass of triethylamine were added to the solution of anionic polyurethane in organic solvent as a neutralizing agent and stirred. Then, 1,785 parts by mass of water were added and stirred, yielding an aqueous dispersion of anionic polyurethane. This aqueous dispersion was then subjected to solvent removal, resulting in an aqueous urethane composition (X-3) with a non-volatile component content of 40% by mass and an acid number of 12.3 mg KOH / g. The anionic polyurethane had an oxyalkylene group content of 8.6 mol / kg, an aromatic ring content of 2,260 mmol / kg, and an average particle diameter of 0.39 µm. [Production Example 4] Production of aqueous urethane composition (X-4)

[0073] In a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 1,127.3 parts by mass of polyoxytetramethylene glycol (numerical mean molecular weight: 4,000; hereinafter abbreviated as "PTMG 4000"), 10.3 parts by mass of EG, 44.5 parts by mass of DMPA and 190.8 parts by mass of MDI were allowed to react at 70°C in the presence of 569 parts by mass of methyl ethyl ketone.

[0074] When the viscosity of the reaction product reached a specific viscosity, 2.6 parts by mass of methanol were added, and the mixture was stirred for 1 hour to complete the reaction. Additionally, 1,490 parts by mass of methyl ethyl ketone were added as a diluent, resulting in a solution of anionic polyurethane in an organic solvent.

[0075] Subsequently, 33.5 parts by mass of triethylamine were added to the solution of anionic polyurethane in organic solvent as a neutralizing agent and the mixture was stirred. In addition, 4,293 parts by mass of water were added and stirred, thus obtaining an aqueous dispersion of anionic polyurethane. This aqueous dispersion was then subjected to solvent removal, yielding an aqueous urethane composition (X-4) with a non-volatile component content of 40% by mass and an acid number of 13.5 mg KOH / g. The anionic polyurethane had an oxyalkylene group content of 11.4 mol / kg, an aromatic ring content of 940 mmol / kg, and an average particle diameter of 0.43 µm. [Production Example 5] Production of aqueous urethane composition (X-5)

[0076] In a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 391.1 parts by mass of PTMG 2000, 26.7 parts by mass of EG, 15.7 parts by mass of DMPA and 190.8 parts by mass of MDI were allowed to react at 70°C in the presence of 261 parts by mass of methyl ethyl ketone.

[0077] When the viscosity of the reaction product reached a specific viscosity, 2.1 parts by mass of methanol were added and the mixture was stirred for 1 hour to complete the reaction. Additionally, 675.6 parts by mass of methyl ethyl ketone were added as a diluent, resulting in a solution of anionic polyurethane in an organic solvent.

[0078] Subsequently, 11.8 parts by mass of triethylamine were added to the solution of anionic polyurethane in organic solvent as a neutralizing agent and the mixture was stirred. Additionally, 1953.4 parts by mass of water were added and stirred, thus obtaining an aqueous dispersion of anionic polyurethane. This aqueous dispersion was then subjected to solvent removal, yielding an aqueous urethane composition (X-5) with a non-volatile component content of 40% by mass and an acid number of 10.5 mg KOH / g. The anionic polyurethane had an oxyalkylene group content of 8.7 mol / kg, an aromatic ring content of 2070 mmol / kg, and an average particle diameter of 0.42 µm. [Production Example 6] Production of aqueous urethane composition (X-6)

[0079] In a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 1,151 parts by mass of PTMG 2000, 17.8 parts by mass of EG, 42.4 parts by mass of DMPA and 200 parts by mass of toluene diisocyanate (hereinafter abbreviated as "TDI") were allowed to react at 70°C in the presence of 586.6 parts by mass of methyl ethyl ketone.

[0080] When the viscosity of the reaction product reached a specific viscosity, 3.9 parts by mass of methanol were added, and the mixture was then stirred for 1 hour to complete the reaction. Additionally, 1,530.3 parts by mass of methyl ethyl ketone were added as a diluent, resulting in a solution of anionic polyurethane in an organic solvent.

[0081] Subsequently, 32 parts by mass of triethylamine were added to the solution of anionic polyurethane in organic solvent as a neutralizing agent and the mixture was stirred. In addition, 4,415 parts by mass of water were added and stirred, thus obtaining an aqueous dispersion of anionic polyurethane. Next, this aqueous dispersion was subjected to solvent removal, resulting in an aqueous urethane composition (X-6) with a non-volatile component content of 40% by mass and an acid number of 12.6 mg KOH / g. The anionic polyurethane had an oxyalkylene group content of 11.3 mol / kg, an aromatic ring content of 960 mmol / kg, and an average particle diameter of 0.19 µm. [Manufacturing Example 7] Production of Acrylonitrile-Butadiene Rubber Composition (B-1)

[0082] Based on 100 parts by mass of the monomer, 145 parts of ion-exchanged water were mixed with 0.05 parts by mass of ethylenediaminetetraacetic acid, 0.25 parts by mass of sodium salt of condensed naphthalenesulfonic acid, 1.5 parts by mass of sodium dodecylbenzenesulfonate, and 0.6 parts by mass of tert-dodecyl mercaptan. The mixture was further combined with 60% butadiene, 35% acrylonitrile, and 5% methacrylic acid in a reactor equipped with a stirred mixer. The mixture was heated to 45°C, 0.05 parts by mass of potassium persulfate catalyst were injected, and emulsion polymerization was carried out. When a maximum polymerization temperature of 65°C was reached and the conversion rate of polymer from monomer reached 90% to 92%, the polymerization was stopped with ammonia. Cooling was carried out to atmospheric temperature and the pH was also adjusted to 7.2 to 7.5 using ammonia.Stripping and condensation were then carried out until the non-volatile component content reached 44%. An acrylonitrile-butadiene rubber composition (B-1) of carboxylated acrylonitrile-butadiene copolymer, having a non-volatile component content of 44% by mass and a pH of 8.2, was obtained. [Comparative Production Example 1] Production of aqueous urethane composition (X'-1)

[0083] In a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 735 parts by mass of PTMG 2000, 31.5 parts by mass of DMPA, and 205.8 parts by mass of dicyclohexylmethane-4,4'-diisocyanate (hereinafter referred to as "H") were added. 12 MDI (abbreviated) was allowed to react at 70°C for 4 hours in the presence of 243 parts by mass of methyl ethyl ketone and 0.2 parts by mass of dioctyltin dilaurate.

[0084] Then 729 parts by mass of methyl ethyl ketone were added and the mixture was stirred for 1 hour, and a solution of anionic polyurethane in organic solvent was obtained.

[0085] Subsequently, 23.8 parts by mass of triethylamine were added to the solution of anionic polyurethane in organic solvent as a neutralizing agent and stirred. Then, 2,917 parts by mass of water were added and stirred. Finally, 29 parts by mass of isophorone diamine (hereinafter abbreviated as "IPDA") were added and stirred, yielding an aqueous dispersion of anionic polyurethane. This aqueous dispersion was then subjected to solvent removal, resulting in an aqueous urethane composition (X'-1) with a solids content of 33% by mass. The anionic polyurethane had an oxyalkylene group content of 10.2 mol / kg, an aromatic ring content of 0 mol / kg, and an average particle diameter of 0.25 µm. [Comparative Production Example 2] Production of aqueous urethane composition (X'-2)

[0086] In a nitrogen-purged container equipped with a thermometer, a nitrogen gas inlet tube and a stirrer, 805 parts by mass of PTMG 2000, 34.5 parts by mass of DMPA and 144.6 parts by mass of hexamethylene diisocyanate (hereinafter abbreviated as "HDI") were allowed to react at 70°C for 4 hours in the presence of 246 parts by mass of methyl ethyl ketone and 0.2 parts by mass of dioctyltin dilaurate.

[0087] Then 738 parts by mass of methyl ethyl ketone were added and the mixture was stirred for 1 hour, and a solution of anionic polyurethane in organic solvent was obtained.

[0088] Subsequently, 26.0 parts by mass of triethylamine were added to the solution of anionic polyurethane in organic solvent as a neutralizing agent and stirred. 2.952 parts by mass of water were also added and stirred. 32 parts by mass of IPDA were added and stirred, thus obtaining an aqueous dispersion of anionic polyurethane. This aqueous dispersion was then subjected to solvent removal, resulting in an aqueous urethane composition (X'-2) with a solids content of 30% by mass. The anionic polyurethane had an oxyalkylene group content of 10.2 mol / kg, an aromatic ring content of 0 mol / kg, and an average particle diameter of 0.20 µm. [Example 1]

[0089] The aqueous urethane composition (X-1) and the acrylonitrile butadiene rubber composition (B-1) were mixed together in the amounts shown in Table 1, and the pH was adjusted to 8.5 to 9 with an aqueous potassium hydroxide solution. Then, sulfur, zinc oxide, and zinc diethyldithiocarbamate were mixed together in the amounts shown in Table 1 to obtain an aqueous resin composition. [Examples 2 to 7 and comparison examples 1 and 2]

[0090] An aqueous resin composition was obtained in the same manner as in Example 1, except that the types and / or amounts of the aqueous urethane composition, the acrylonitrile butadiene rubber composition, sulfur, zinc oxide and zinc diethyldithiocarbamate used were changed, as shown in Tables 1 and 2. [Evaluation method for storage stability]

[0091] In the examples and comparison examples, the time when the aqueous resin composition was prepared was set as the reference point, and the fluidity of a mixed solution was visually determined after 1, 6 and 24 hours and evaluated as follows. “A”: Fluidity was confirmed even after 24 hours. “B”: No fluidity was observed between the time after 6 hours and the time before 24 hours. “C”: No fluidity was observed between the time after 1 hour and the time before 6 hours have elapsed. “D”: No fluidity was observed until the end of 1 hour. [Measurement method for average particle diameter of anionic polyurethane (A)]

[0092] The average particle diameter of the aqueous urethane composition obtained in the synthesis examples was measured using a laser diffraction / scattering particle size distribution measuring device (“LA-910”, manufactured by Horiba, Ltd.) and using water as the dispersion liquid, when the relative refractive index was 1.10 and a particle diameter basis was the area. [Measurement method for the acid value of aqueous resin composition]

[0093] The aqueous resin composition obtained in the examples and the comparative examples was dried, 0.05 g to 0.5 g of the dried and solidified resin particles were weighed into a 300 ml Erlenmeyer flask, about 80 ml of a mixed solvent having a mass ratio of tetrahydrofuran and ion-exchanged water [tetrahydrofuran / ion-exchanged water] of 80 / 20 was added and a mixed solution was obtained.

[0094] Subsequently, a phenolphthalein indicator was mixed with the mixed solution, a titration was carried out with 0.1 mol / l aqueous potassium hydroxide solution that had been standardized beforehand, and the acid number (mgKOH / g) of the aqueous resin composition was obtained from the amount of aqueous potassium hydroxide solution consumed for the titration according to calculation expression (1). Calculation expression A=(B×f×5.611) / s

[0095] In the expression, A represents an acid number (mgKOH / g) of the solids content of the resin, B represents the amount (ml) of an aqueous 0.1 mol / l potassium hydroxide solution used for the titration, f represents a factor of aqueous 0.1 mol / l potassium hydroxide solution, s represents the mass (g) of the resin particles, and 5.611 represents the formula weight (56.11 / 10) of potassium hydroxide. [Evaluation method of flexibility]

[0096] An associative thickening agent “HYDRAN ASSISTER T10” (manufactured by DIC Corporation) was mixed with 100 parts by mass of the aqueous resin composition obtained in the examples and comparison examples. The viscosity of the mixture was adjusted to 5,000 to 3,000 mPa·s, and the mixture was applied at room temperature to a surface of a polypropylene film that had undergone a release treatment using a doctor blade coating method to achieve a density of 150 g / cm². 2 was received.

[0097] The coated material was immersed for 3 minutes in an aqueous calcium nitrate solution at room temperature, adjusted to a concentration of 20 wt%, and then immersed in water for 18 hours. The coated material was then dried in an environment of 70°C for 20 minutes and subsequently in an environment of 120°C for 2 minutes, forming a solidified coating film on the surface of the polypropylene film. After drying, the solidified coating film was peeled from the surface of the polypropylene film, resulting in a solidified coating film with a thickness of 50 µm.

[0098] The resulting solidified coating film was selected as a test piece, cut to a length of 100 mm and a width of 5 mm. Both ends of this test sample were inserted into chucks and pulled using an Autograph AG-I tensile tester (manufactured by Shimadzu Corporation) in an environment of 23°C and 60% humidity at a crosshead speed of 300 mm / min. The 100% and 300% moduli (MPa) of the test piece were measured. The gauge length in this case was 20 mm, and the initial distance between the chucks was 20 mm.

[0099] The flexibility was evaluated as follows from the obtained 100% module value and the 300% module value. “A”: The 100% module was 6 MPa and the 300% module was 14 MPa. “B”: The standard was not met. [Evaluation method of wear resistance]

[0100] A knitted glove, formed from nylon fiber, was mounted on a glove mold and immersed for 10 seconds in an aqueous calcium nitrate solution at room temperature, adjusted to a concentration of 5 wt%. The glove mold was then dried for 4 minutes at room temperature. Next, the glove mold was immersed for 2 seconds in the aqueous resin composition obtained in the examples and comparison examples. A solidified coating film formed on the surface of the knitted glove, and the glove mold was removed and dried for 10 minutes at room temperature. Finally, the glove mold was immersed in water for 180 minutes and then removed.Furthermore, the glove mold was dried in an environment of 70°C for 20 minutes and then further dried in an environment of 120°C for 30 minutes. The knitted glove was removed from the glove mold, resulting in a glove coated with the solidified coating film.

[0101] Based on EN388:2004, a friction test was carried out on a part of the palm of the received glove using a Martindale friction test device manufactured by Intec Co., Ltd., and the evaluation was carried out as follows. “A”: The number of friction events is equal to or greater than 5,000. “B”: The number of friction events is equal to or greater than 2,000 and less than 5,000. “C”: The number of friction events is less than 2,000. [Table 1] Table 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Anionic polyurethane (A) (X-1) (X-2) (X-3) (X-4) (X-5) (X-6) composition PTMG2000 PTMG2000 PTMG700 PTMG4000 PTMG2000 PTMG2000 DMPA DMPA DMPA DMPA DMPA DMPA EC BG EC EC EC EC MDI MDI MDI MDI MDI TDI Amount mixed in (parts by mass) (solids content conversion) 20 20 20 20 20 20 NBR(B) (B-1) (B-1) (B-1) (B-1) (B-1) (B-1) Amount mixed in (parts by mass) (solids content conversion) 80 80 80 80 80 80 Aqueous medium (C) Water Water Water Water Water Water Vulcanizing agent (D) sulfur sulfur sulfur sulfur sulfur sulfur Amount mixed in (parts by mass) 1,2 1,2 1,2 1,2 1,2 1,2 Vulcanization accelerator (E) (1) Art zinc oxide zinc oxide zinc oxide zinc oxide zinc oxide zinc oxide Amount mixed in (parts by mass) 0.8 0.8 0.8 0.8 0.8 0.8 (2) Art D-Zn D-Zn D-Zn D-Zn D-Zn D-Zn Amount mixed in (parts by mass) 0,4 0,4 0,4 0,4 0,4 0,4 Storage stability A A A A A A Evaluation of wear resistance A A A B A B Evaluation of flexibility A A A A A A [Table 2] Table 2 Example 7 Example 8 Example 9 Comparative example 1 Comparative example 2 Anionic polyurethane (A) (X-1) (X-1) (X-1) (X'-1) (X'-2) composition PTMG2000 PTMG2000 PTMG2000 PTMG2000 PTMG2000 DMPA DMPA DMPA DMPA DMPA EC EC EC IPDA IPDA MDI MDI MDI H 12 MDI HDI Amount mixed in (parts by mass) (solids content conversion) 80 20 20 20 20 NBR(B) (B-1) (B-1) (B-1) (B-1) (B-1) Amount mixed in (parts by mass) (solids content conversion) 20 80 80 80 80 Aqueous medium (C) Water Water Water Water Water Vulcanizing agent (D) sulfur sulfur sulfur sulfur sulfur Amount mixed in (parts by mass) 0,3 4,8 1,2 1,2 1,2 Vulcanization accelerator (E) (1) Art zinc oxide zinc oxide zinc oxide zinc oxide zinc oxide Amount mixed in (parts by mass) 0.2 0.8 2.4 0.8 0.8 (2) Art D-Zn D-Zn D-Zn D-Zn D-Zn Amount mixed in (parts by mass) 0,1 0,4 0,8 0,4 0,4 Storage stability A A A B B Evaluation of wear resistance A A A A A Evaluation of flexibility A A A B B

[0102] The aqueous resin composition of the invention was found to have excellent storage stability. Furthermore, the hardened coating film obtained using the aqueous resin compositions of Examples 1 to 9 was found to have excellent wear resistance and flexibility.

[0103] Meanwhile, in comparison examples 1 and 2, aliphatic anionic polyurethane was used instead of anionic polyurethane (A), and storage stability was deteriorated.

Claims

[1] Aqueous resin composition, comprising: an anionic polyurethane (A) having an aromatic ring, wherein the aromatic ring content in the anionic polyurethane (A) is 550 to 2,500 mmol / kg; wherein the aromatic ring content in the anionic polyurethane (A) represents the aromatic ring content occupying the starting material, based on the total mass of each starting material forming the anionic polyurethane (A); an acrylonitrile butadiene rubber (B); an aqueous medium (C); a vulcanizing agent (D) and a vulcanization accelerator (E), wherein the mass ratio (ratio of solids content) of the anionic polyurethane (A) and the acrylonitrile butadiene rubber (B) is in a range of 20 / 80 to 95 / 5, the vulcanizing agent (D) sulfur is and the vulcanization accelerator (E) zinc oxide and zinc diethyldithiocarbamate. [2] Aqueous resin composition according to claim 1, wherein the anionic polyurethane (A) is produced using an aromatic polyisocyanate as a starting material. [3] Aqueous resin composition according to claim 1 or 2, wherein the anionic polyurethane (A) is a reaction product of polyoxytetramethylene glycol, a carboxyl group-containing glycol, diphenylmethane diisocyanate or toluene diisocyanate and ethylene glycol or butanediol. [4] Glove, encompassing: a coating film produced by solidifying the aqueous resin composition according to one of claims 1 to 3.