Composition and gloves

Abstract

The present invention provides a composition which contains a urethane resin (A), water (B) and an emulsifying agent (C), wherein: the urethane resin (A) is a reaction product of a polyol (a1) and a polyisocyanate (a2); the polyol (a1) contains a polycarbonate polyol and a nonionic polyol; the emulsifying agent (C) contains an anionic emulsifying agent; and the 500% modulus of a solidified film of this composition is 7 MPa or less. The present invention also provides a composition which contains a urethane resin (A), water (B) and an emulsifying agent (C), wherein: the urethane resin (A) is a reaction product of a polyol (a1) and a polyisocyanate (a2); the polyol (a1) contains a polycarbonate polyol; the emulsifying agent (C) contains an anionic emulsifying agent and a nonionic emulsifying agent; and the 500% modulus of a solidified film of this composition is 7 MPa or less. This composition is capable of forming highly flexible gloves.

Description

[Technical Field]

[0001] The present invention relates to a composition and a glove. [Background technology]

[0002] Generally, rubbers used as materials with rubber elasticity include natural rubber, isoprene rubber, chloroprene rubber, nitrile rubber, etc. When these materials are used for gloves, there are cases where allergies due to proteins contained in natural rubber, or vulcanizing agents and vulcanization accelerators used in these rubbers in general, can cause problems.

[0003] Therefore, as an alternative material to these rubbers, the use of urethane resins that have rubber elasticity and do not contain the above substances is promising. Rubber latex has been widely used in glove processing up until now, and the replacement with urethane dispersions (urethane resins dispersed in water, etc.) that can be used in the same manufacturing facilities is particularly promising. (See, for example, Patent Document 1.)

[0004] In particular, medical gloves are required to be resistant to alcohol (alcohol resistance). For example, the introduction of polyester polyol or polycarbonate polyol into urethane dispersions is an effective method of improving alcohol resistance. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Special Publication No. 2005-526889 Summary of the Invention [Problem to be solved by the invention]

[0006] The above-mentioned medical gloves are required to have high flexibility in addition to alcohol resistance. More specifically, a highly flexible glove is, for example, a glove having a 500% modulus of 7 MPa or less. However, according to the study by the present inventors, it has been found that when an attempt is made to produce a glove having a 500% modulus of 7 MPa or less using a urethane resin made from polycarbonate polyol, the alcohol resistance of the glove may be impaired.

[0007] Therefore, an object of the present invention is to improve a composition containing a urethane resin capable of forming a highly flexible glove so as to impart excellent alcohol resistance to the glove. [Means for solving the problem]

[0008] As a result of investigation, the present inventors have found that by using a nonionic component (nonionic polyol as a raw material of urethane resin, or a nonionic emulsifier for emulsifying (dispersing) urethane resin) in a composition containing urethane resin made from polycarbonate polyol as a raw material, when a gloves having 500% modulus of 7 MPa or less is prepared, excellent alcohol resistance can be imparted to the gloves.

[0009] The present invention includes the following aspects. [1] A composition containing a urethane resin (A), water (B), and an emulsifier (C), wherein the urethane resin (A) is a reaction product of a polyol (a1) and a polyisocyanate (a2), the polyol (a1) contains a polycarbonate polyol and a nonionic polyol, the emulsifier (C) contains an anionic emulsifier, and the 500% modulus of a solidified film of the composition is 7 MPa or less. [2] A composition containing a urethane resin (A), water (B), and an emulsifier (C), wherein the urethane resin (A) is a reaction product of a polyol (a1) and a polyisocyanate (a2), the polyol (a1) contains a polycarbonate polyol, the emulsifier (C) contains an anionic emulsifier and a nonionic emulsifier, and the 500% modulus of a solidified film of the composition is 7 MPa or less. [3] The composition according to [1], wherein the content of structural units derived from nonionic polyol in the urethane resin (A) is 2.0 to 5.0 mass %. [4] The composition according to [2], wherein the content of the nonionic emulsifier is 0.3 to 4.0 parts by mass per 100 parts by mass of the urethane resin (A). [5] The composition according to any one of [1] to [4], wherein the polyol does not contain an anionic polyol. [6] A glove comprising a solidified film of the composition according to any one of [1] to [5]. [Effects of the Invention]

[0010] According to one aspect of the present invention, a composition containing a urethane resin capable of forming a highly flexible glove can be improved so as to impart excellent alcohol resistance to the glove. DETAILED DESCRIPTION OF THE INVENTION

[0011] One embodiment of the present invention is a composition (X) containing a urethane resin (A), water (B), and an emulsifier (C). This composition (X) may be a dispersion (emulsion) in which the urethane resin (A) is dispersed in the water (B).

[0012] The composition (X) contains a nonionic component. The composition (X1) according to the first embodiment contains a nonionic polyol as the polyol (a1) described below, which is a raw material for the urethane resin (A). The composition (X2) according to the second embodiment contains a nonionic emulsifier as the emulsifier (C). Unless otherwise specified, the content described below is common to the composition (X1) according to the first embodiment and the composition (X2) according to the second embodiment.

[0013] The urethane resin (A) is a reaction product of polyol (a1) and polyisocyanate (a2). The urethane resin (A) may be a reaction product of only polyol (a1) and polyisocyanate (a2), or may be a reaction product of polyol (a1), polyisocyanate (a2), and other component (a3). In other words, the urethane resin (A) is made from polyol (a1) and polyisocyanate (a2) as raw materials (essential raw materials), or may be made from only polyol (a1) and polyisocyanate (a2) as raw materials (essential raw materials), or may be made from polyol (a1), polyisocyanate (a2), and other component (a3) as raw materials (essential raw materials).

[0014] The polyol (a1) includes a polycarbonate polyol. The polycarbonate polyol may be a polycarbonate diol. The polycarbonate polyol (polycarbonate diol) may be, for example, a reaction product of a diol with at least one selected from the group consisting of a carbonate ester and phosgene. The polycarbonate polyol is preferably an amorphous polycarbonate polyol, from the viewpoint of facilitating the production of a coagulated film having high flexibility.

[0015] The diol may be an aliphatic diol or an alicyclic diol. The aliphatic diol may be, for example, an aliphatic diol having 1 to 12 carbon atoms. Examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,5-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,8-nonanediol, 1,10-decanediol, 2-ethyl-2-butyl-1,3-propanediol, and 1,12-dodecanediol. Alicyclic diols include 1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol.

[0016] The diol may contain one or more aliphatic diols, and preferably contains at least one selected from the group consisting of 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, since this provides even better alcohol resistance, and more preferably contains 1,5-pentanediol and 1,6-hexanediol.

[0017] Examples of carbonate esters include dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, and propylene carbonate. These carbonate esters may be used alone or in combination of two or more.

[0018] The number average molecular weight of the polycarbonate polyol may be 500 or more, 700 or more, or 1,000 or more, and may be 100,000 or less, 10,000 or less, or 4,000 or less. The number average molecular weight of the polycarbonate polyol is measured by gel permeation chromatography (GPC).

[0019] In composition (X1), the polyol (a1) further contains a nonionic polyol in addition to the polycarbonate polyol. Examples of nonionic polyols include polyols having an oxyethylene structure (polyether polyols). Examples of polyols having an oxyethylene structure include polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, and polyoxyethylene polyoxytetramethylene glycol. These compounds may be used alone or in combination of two or more.

[0020] In the composition (X1), the urethane resin (A) contains structural units derived from a polycarbonate polyol and structural units derived from a nonionic polyol. In this urethane resin (A), the content of structural units derived from a polycarbonate polyol is preferably 60 to 90 mass% from the viewpoint of imparting even better alcohol resistance, and the content of structural units derived from a nonionic polyol is preferably 2.0 to 5.0 mass% from the viewpoint of imparting excellent emulsifiability and salt coagulation properties.

[0021] The lower limit of the content of structural units derived from polycarbonate polyol in the urethane resin (A) in the composition (X1) may be 65% by mass or 70% by mass, and the upper limit of the content may be 85% by mass or 80% by mass.

[0022] The lower limit of the content of structural units derived from nonionic polyol in the urethane resin (A) in the composition (X1) may be 2.5% by mass or 3.0% by mass, and the upper limit of the content may be 4.5% by mass or 4.0% by mass.

[0023] Examples of the polyisocyanate (a2) that can be used include aromatic polyisocyanates such as phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidized diphenylmethane polyisocyanate; and aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer acid diisocyanate, and norbornene diisocyanate. These polyisocyanates may be used alone or in combination of two or more.

[0024] The content of polyisocyanate (a2) is preferably 15% by mass or less, more preferably 13% by mass or less, based on the total of polyol (a1), polyisocyanate (a2), and other component (a3) used as raw materials for urethane resin (A) (also referred to as the total of polymerization components), from the viewpoint of facilitating the production of a coagulated film having high flexibility. The content of polyisocyanate (a2) may be 5% by mass or more, or 10% by mass or more, based on the total of polymerization components of urethane resin (A).

[0025] Other components (a3) used as raw materials as needed include, for example, chain extenders. The chain extenders are preferably polyamine chain extenders, more preferably polyamine chain extenders having three or more amino groups, from the viewpoint of easily obtaining the permanent elongation required for gloves. Examples of polyamine chain extenders include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3'-dimethyl-4,4'-dicyclohexylmethanediamine, hydrazine, diethylenetriamine, polyoxyalkylenetriamine (e.g., polyoxypropylenetriamine), and the like. These polyamine chain extenders may be used alone or in combination of two or more.

[0026] The urethane resin (A) may or may not have an anionic group. The anionic group is derived, for example, from a polyol (anionic polyol) having an anionic group. That is, the polyol (a1) may or may not contain an anionic polyol, and the urethane resin (A) may or may not contain a structural unit derived from an anionic polyol. Examples of anionic polyols include polyols having a carboxyl group. Examples of polyols having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid.

[0027] When the urethane resin (A) contains structural units derived from an anionic polyol, the content of the structural units derived from anionic polyol in the urethane resin (A) is preferably 0.20 to 0.70% by mass, from the viewpoint of enabling the urethane resin (A) to be suitably emulsified and achieving even better alcohol resistance. The lower limit of the content may be 0.30% by mass or 0.35% by mass. The upper limit of the content may be 0.60% by mass or less or 0.50% by mass or less.

[0028] The urethane resin (A) preferably does not have an anionic group from the viewpoint of easily obtaining a glove having even better alcohol resistance, that is, from the viewpoint of easily obtaining a glove having even better alcohol resistance, the polyol (a1) preferably does not contain an anionic polyol, and the urethane resin (A) preferably does not contain a structural unit derived from an anionic polyol.

[0029] The content of the urethane resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, based on the total amount of the composition (X), in order to improve storage stability and workability.

[0030] As the water (B), for example, distilled water, ion-exchanged water, etc. These waters may be used alone or in combination of two or more kinds.

[0031] The content of water (B) is preferably 30% by mass or more, more preferably 45% by mass or more, based on the total amount of composition (X), from the viewpoint of improving storage stability and workability, and is preferably 85% by mass or less, more preferably 75% by mass or less.

[0032] The emulsifier (C) includes an anionic emulsifier (c1). Examples of the anionic emulsifier (c1) include fatty acid salts such as sodium oleate, alkyl sulfate ester salts, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, sodium alkanesulfonates, and sodium alkyldiphenyl ether sulfonates. These anionic emulsifiers may be used alone or in combination of two or more.

[0033] The content of the anionic emulsifier (c1) is preferably 1 to 10 parts by mass relative to 100 parts by mass of the urethane resin (A) from the viewpoints of imparting emulsifying properties and suppressing foaming. The lower limit of the content may more preferably be 2 parts by mass or 4 parts by mass. The upper limit of the content may more preferably be 8 parts by mass or 6 parts by mass.

[0034] In composition (X2), the emulsifier (C) further contains a nonionic emulsifier (c2) in addition to the anionic emulsifier (c1). Examples of the nonionic emulsifier (c2) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene stearyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene-polyoxypropylene copolymer. These nonionic emulsifiers may be used alone or in combination of two or more.

[0035] The content of the nonionic emulsifier (c2) is preferably 0.3 to 4.0 parts by mass relative to 100 parts by mass of the urethane resin (A) from the viewpoint of imparting emulsifying properties and salt coagulation properties. The lower limit of the content may more preferably be 0.5 parts by mass or 1.0 part by mass. The upper limit of the content may more preferably be 3.0 parts by mass or 2.0 parts by mass.

[0036] Composition (X) may further contain other additives as necessary. Examples of other additives include thickeners, antifoaming agents, urethane catalysts, silane coupling agents, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light resistance stabilizers, fluorescent brighteners, foaming agents, foam stabilizers, pigments, dyes, conductivity-imparting agents, antistatic agents, moisture permeability-imparting agents, water repellents, oil repellents, antiblocking agents, and hydrolysis inhibitors. These additives may be used alone or in combination of two or more.

[0037] The composition (X) may further contain other polymers in addition to the urethane resin (A) depending on the durability required for the intended use, etc. Examples of other polymers include styrene-butadiene copolymer (SBR), butadiene copolymer (BR), isoprene copolymer (IR), ethylene-propylene-diene copolymer (EPDM), chloroprene polymer (CR), acrylonitrile-butadiene copolymer (NBR), butyl polymer (IIR), and natural rubber (NR).

[0038] The composition (X) can be obtained, for example, by synthesizing a urethane resin (A) by reacting a polyol (a1) with a polyisocyanate (a2), and then mixing the urethane resin (A) with an aqueous emulsifier solution containing water (B) and an emulsifier (C).

[0039] When a chain extender is used as the other component (a3), composition (X) can be obtained, for example, by reacting polyol (a1) with polyisocyanate (a2) to synthesize a urethane prepolymer, mixing the urethane prepolymer with an aqueous emulsifier solution containing water (B) and emulsifier (C), and then adding the chain extender to synthesize urethane resin (A). In this case, the urethane prepolymer is a urethane prepolymer having an isocyanate group (preferably a non-yellowing isocyanate group) at its terminal.

[0040] As described above, the composition (X) can be a dispersion (emulsion) in which the urethane resin (A) is suitably dispersed in the water (B) without using an organic solvent, i.e., the composition (X) does not need to contain an organic solvent.

[0041] By solidifying the composition (X) described above, a solidified film (coating) having high flexibility can be obtained. Specifically, the 500% modulus of the solidified film of the composition (X) is 7 MPa or less. In this specification, the 500% modulus of the solidified film of the composition (X) means the 500% modulus measured by the method described in the Examples.

[0042] The solidified film of composition (X) is suitable for use in gloves, and particularly suitable for use in medical gloves (surgical gloves). That is, another embodiment of the present invention is a glove comprising a solidified film of composition (X), preferably a medical glove (surgical glove) comprising a solidified film of composition (X). A method for producing the glove will be described below.

[0043] For example, a method for producing gloves includes first immersing a hand mold in a coagulant and then drying it as necessary to adhere metal salts and the like in the coagulant to the surface of the hand mold, then immersing the hand mold in composition (X), washing the surface with water, and drying to obtain a coagulated film (coagulated film) layer on the surface of the hand mold, and peeling this film layer from the hand mold to produce a film-formed glove. In this case, composition (X) may be further diluted with distilled water, ion-exchanged water, etc.

[0044] Examples of coagulants that can be used include solutions of metal salts such as calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, and sodium chloride; and solutions of acids such as formic acid and acetic acid. Examples of solvents that can dissolve metal salts and acids include water, methanol, ethanol, and isopropanol. The metal salt contained in the coagulant is preferably contained in an amount ranging from 1 to 50% by mass relative to the total amount of the coagulant. The time for immersing the hand mold in the coagulant can be 5 to 60 seconds. The coagulant can be used at a temperature of 5 to 60°C. The temperature of the hand mold when immersed in the coagulant may be room temperature, or it may be heated to 30 to 80°C.

[0045] A glove-like article made of knitted nylon fibers or the like may be attached to the hand mold in advance. Specifically, first, the hand mold with the knitted glove-like article attached is immersed in a coagulant, and then dried as necessary, thereby impregnating the glove-like article with the coagulant. Next, the hand mold is immersed in composition (X), and the surface is washed with water and dried, whereby a coagulated film (coagulated film) layer is formed on the surface of the glove-like article. The glove-like article is then peeled off from the hand mold, yielding a glove with a film layer formed on its surface. [Example]

[0046] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples.

[0047] Example 1 In the presence of 0.1 part by mass of bismuth tris(2-ethylhexanoate), 850 parts by mass of polycarbonate polyol (made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000), 38 parts by mass of polyethylene glycol (NOF Corporation's "PEG1540", number average molecular weight: 1540) as a nonionic polyol, and 113 parts by mass of isophorone diisocyanate (IPDI) were reacted at 180°C until the NCO% reached 0.47% by mass, to obtain urethane prepolymer A.

[0048] An emulsion was obtained by feeding and mixing urethane prepolymer A heated to 180°C, a 20% by weight aqueous solution of sodium dodecylbenzenesulfonate ("Neogen S-20F" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier, and water into a twin-screw extruder (TEM-18SS manufactured by Shibaura Machine Co., Ltd.). The flow rates of the respective feed solutions were urethane prepolymer A: 10 kg / h, emulsifier aqueous solution: 2.5 kg / h, and water: 8.5 kg / h. The twin-screw extruder was operated at 50°C and 260 rpm. Immediately thereafter, a water-diluted solution of a polyamine chain extender ("Jeffamine T-403" manufactured by HUNTSMAN) with an amino group content equivalent to 95% of the NCO groups was added to extend the chain, ultimately obtaining a composition (emulsion) with a urethane resin content of 40% by weight. In Example 1, the content of structural units derived from nonionic polyol in the urethane resin was 3.6% by weight.

[0049] Example 2 In the presence of 0.1 part by mass of bismuth tris(2-ethylhexanoate), 765 parts by mass of polycarbonate polyol (made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000), 85 parts by mass of polyester polyol ("PRIPLAST 1838" manufactured by Croda Japan), 38 parts by mass of polyethylene glycol ("PEG1540" manufactured by NOF Corporation, number average molecular weight: 1540) as a nonionic polyol, and 113 parts by mass of IPDI were reacted at 180°C until the NCO% reached 0.47% by mass, to obtain urethane prepolymer B.

[0050] An emulsion was obtained by simultaneously feeding and mixing urethane prepolymer B heated to 180°C, a 20% by weight aqueous solution of sodium dodecylbenzenesulfonate ("Neogen S-20F" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier, and water into a twin-screw extruder (TEM-18SS, manufactured by Shibaura Machine Co., Ltd.). The flow rates of the respective feed solutions were urethane prepolymer B: 10 kg / h, emulsifier aqueous solution: 2.5 kg / h, and water: 8.5 kg / h. The twin-screw extruder was operated at 50°C and 260 rpm. Immediately thereafter, a water-diluted solution of a polyamine chain extender ("Jeffamine T-403" manufactured by HUNTSMAN) with an amino group content equivalent to 95% of the NCO groups was added to extend the chain, ultimately obtaining a composition (emulsion) with a urethane resin content of 40% by weight. In Example 2, the content of structural units derived from nonionic polyol in the urethane resin was 3.6% by weight.

[0051] Example 3 In the presence of 0.1 part by mass of bismuth tris(2-ethylhexanoate), 850 parts by mass of polycarbonate polyol (made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000), 21 parts by mass of polyethylene glycol (NOF Corporation's "PEG1540", number average molecular weight: 1540) as a nonionic polyol, and 110 parts by mass of isophorone diisocyanate (IPDI) were reacted at 180°C until the NCO% reached 0.47% by mass, thereby obtaining urethane prepolymer C.

[0052] Urethane prepolymer C heated to 180°C, a 20% by weight aqueous solution of sodium dodecylbenzenesulfonate ("Neogen S-20F" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier, and polyoxyethylene stearyl ether ("Newcol 1807" manufactured by Nippon Nyukazai Co., Ltd.) as a nonionic emulsifier were mixed in a 2.5:1.0 (weight ratio). The aqueous emulsifier solution and water were fed into a twin-screw extruder (TEM-18SS manufactured by Shibaura Machine Co., Ltd.) and mixed to obtain an emulsion. The flow rates of the respective feed liquids were 10 kg / h of urethane prepolymer C, 3.5 kg / h of the aqueous emulsifier, and 6.9 kg / h of water. The twin-screw extruder was operated at 50°C and 260 rpm. Immediately thereafter, a water-diluted solution of a polyamine chain extender ("Jeffamine T-403" manufactured by HUNTSMAN) with an amino group content corresponding to 95% of the NCO groups was added to extend the chain, finally obtaining a composition (emulsion) with a urethane resin content of 40% by mass. In Example 3, the content of structural units derived from nonionic polyol in the urethane resin was 2.1% by mass, and the content of nonionic emulsifier per 100 parts by mass of urethane resin was 1.9 parts by mass.

[0053] Example 4 In the presence of 0.1 part by mass of bismuth tris(2-ethylhexanoate), 850 parts by mass of polycarbonate polyol (made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000), 3.8 parts by mass of 2,2-dimethylolpropionic acid as an anionic polyol, and 113 parts by mass of isophorone diisocyanate (IPDI) were reacted at 180°C until the NCO% reached 0.47% by mass, thereby obtaining urethane prepolymer D.

[0054] Urethane prepolymer D heated to 180°C, a 10% by weight aqueous solution of potassium hydroxide as a neutralizing agent, a 20% by weight aqueous solution of sodium dodecylbenzenesulfonate ("Neogen S-20F" manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier, and a polyoxyethylene stearyl ether ("Newcol 1807" manufactured by Nippon Nyukazai Co., Ltd.) as a nonionic emulsifier were mixed in a weight ratio of 0.13:2.5:1.0. The aqueous emulsifier solution and water were fed into a twin-screw extruder (TEM-18SS manufactured by Shibaura Machine Co., Ltd.) and mixed to obtain an emulsion. The flow rates of the respective feed solutions were 10 kg / h of urethane prepolymer D, 3.63 kg / h of the aqueous emulsifier solution, and 6.9 kg / h of water. The twin-screw extruder was operated at 50°C and 260 rpm. Immediately thereafter, a water-diluted solution of a polyamine chain extender (HUNTSMAN's "JEFFAMINE T-403") with an amino group content equivalent to 95% of the NCO groups was added to extend the chain, finally obtaining a composition (emulsion) with a urethane resin content of 40% by mass. In Example 4, the content of structural units derived from anionic polyol in the urethane resin was 0.39% by mass, and the content of nonionic emulsifier per 100 parts by mass of urethane resin was 1.8 parts by mass.

[0055] (Comparative Example 1) In a nitrogen-substituted vessel equipped with a thermometer, nitrogen gas inlet tube, and stirrer, 600 parts by weight of polycarbonate polyol (made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000), 33 parts by weight of polytetramethylene glycol (number average molecular weight: 2,000), 181 parts by weight of polypropylene triol (an adduct of glycerin and propylene oxide, number average molecular weight: 6,000), 8.4 parts by weight of ethylene glycol, 15.8 parts by weight of 2,2-dimethylolpropionic acid, 154 parts by weight of 4,4'-diphenylmethane diisocyanate, and 991 parts by weight of methyl ethyl ketone were reacted at 70 ° C. When the reaction mixture reached the specified viscosity, 1.0 part by weight of methanol was added, and the mixture was stirred for 1 hour to terminate the reaction. 498 parts by weight of methyl ethyl ketone was then added as a diluent to obtain an organic solvent solution of urethane resin.

[0056] Next, 9.6 parts by mass of a 48% by mass potassium hydroxide aqueous solution was added as a neutralizing agent to the urethane resin organic solvent solution to neutralize the carboxyl groups of the urethane resin, and 2,480 parts by mass of water was further added and stirred to obtain an aqueous dispersion of the urethane resin. Next, the solvent was removed from the aqueous dispersion of the urethane resin to obtain a composition (emulsion) with a urethane resin content of 40% by mass.

[0057] (Comparative Example 2) In a nitrogen-purged vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 800 parts by mass of polycarbonate polyol (made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000), 15.4 parts by mass of 3-methyl-1,5-pentanediol, 14.8 parts by mass of 2,2-dimethylolpropionic acid, 160 parts by mass of 4,4'-diphenylmethane diisocyanate, and 990 parts by mass of methyl ethyl ketone were reacted at 70°C. When the reaction mixture reached a specified viscosity, 1.2 parts by mass of methanol was added, and the mixture was stirred for 1 hour to terminate the reaction. 498 parts by mass of methyl ethyl ketone was then added as a diluent to obtain an organic solvent solution of a urethane resin.

[0058] Next, 9.0 parts by mass of a 48% by mass potassium hydroxide aqueous solution was added as a neutralizing agent to the urethane resin organic solvent solution to neutralize the carboxyl groups of the urethane resin, and 4,970 parts by mass of water was further added and stirred to obtain an aqueous dispersion of the urethane resin. Next, the solvent was removed from the aqueous dispersion of the urethane resin to obtain a composition (emulsion) with a urethane resin content of 40% by mass.

[0059] (Comparative Example 3) In the presence of 0.1 part by mass of stannous octoate, 1,000 parts by mass of polytetramethylene glycol (number average molecular weight: 2,000), 18 parts by mass of polyethylene glycol ("PEG600" manufactured by NOF Corporation, number average molecular weight: 600), and 262 parts by mass of 1,6-hexamethylene diisocyanate were reacted at 100°C until the NCO% reached 3.1% by mass, thereby obtaining urethane prepolymer E.

[0060] Urethane prepolymer E heated to 70°C, a polyoxyethylene polyoxypropylene copolymer ("Pluronic® L-64" manufactured by ADEKA Corporation) as a nonionic emulsifier, and water were fed into a twin-screw extruder (TEM-18SS, manufactured by Toshiba Machine Co., Ltd.) and mixed to obtain an emulsion. The flow rates of the respective feed liquids were urethane prepolymer E: 10 kg / h, emulsifier: 0.5 kg / h, and water: 5.8 kg / h. The twin-screw extruder was operated at 50°C and 260 rpm. Immediately thereafter, a water-diluted solution of isophorone diamine (IPDA) with an amino group content equivalent to 95% of the NCO groups was added to extend the chain, ultimately obtaining a composition (emulsion) with a urethane resin content of 60% by mass. In Comparative Example 3, the content of structural units derived from nonionic polyol in the urethane resin was 1.2% by mass, and the content of nonionic emulsifier per 100 parts by mass of urethane resin was 4.2 parts by mass.

[0061] <500% modulus measurement> First, a solidified film of each composition of the Examples and Comparative Examples was prepared according to the following procedures (1) to (6). (1) A ceramic hand mold was immersed in a 10% aqueous solution of calcium nitrate for 10 seconds and then removed. (2) The hand mold from (1) was dried at 70°C for 2 minutes. (3) The hand mold from (2) was immersed in the composition (emulsion) for 20 seconds and then removed. (4) The handprint from (3) was washed with water at 20 to 30°C for 10 minutes. (5) The hand mold from (4) was dried at 70°C for 20 minutes and then at 120°C for 30 minutes. (6) Baby powder was applied to the hand mold (5) and the solidified urethane resin film was peeled off from the mold.

[0062] Next, each of the resulting coagulated films was cut into "dumbbell TYPE D" shapes as specified in ASTM D412 to obtain test pieces. Both ends of the test piece were clamped with chucks, and the test piece was pulled at a crosshead speed of 500 mm / min using a tensile tester "Autograph AG-I" (Shimadzu Corporation) at a temperature of 23±2°C and a humidity of 60±10%, and the 500% modulus (MPa) of the test piece was measured. The gauge length was 20 mm, and the initial distance between the chucks was 40 mm. The results are shown below. When the composition of Comparative Example 3 was used, a coagulated film could not be prepared, and therefore the 500% modulus could not be measured. A 500% modulus value of 7.0 MPa or less was determined to be excellent in flexibility. Example 1: 2.9 MPa Example 2: 2.5 MPa Example 3: 2.9 MPa Example 4: 4.0 MPa Comparative Example 1: 6.5 MPa Comparative Example 2: 2.5 MPa Comparative Example 3: Unmeasurable

[0063] <Evaluation of alcohol resistance> A test piece obtained in the same manner as in the measurement of the 500% modulus was immersed in 2-propanol for 24 hours. The test piece was then removed, sandwiched between paper towels, and the alcohol on the surface was gently removed. The tensile strength (MPa) of the test piece was immediately measured using a tensile tester "Autograph AG-I" (Shimadzu Corporation) under the same conditions as in the measurement of the 500% modulus. The results are shown below. When the composition of Comparative Example 3 was used, a solidified film could not be formed, and therefore evaluation of alcohol resistance (measurement of tensile strength) could not be performed. Furthermore, a tensile strength of 5.0 MPa or more was determined to be excellent in alcohol resistance. Example 1: 7.0 MPa Example 2: 8.0 MPa Example 3: 7.5 MPa Example 4: 6.5 MPa Comparative Example 1: 1.1 MPa Comparative Example 2: 0.5 MPa Comparative Example 3: Unmeasurable

Claims

1. A composition containing a urethane resin (A), water (B), and an emulsifier (C), the urethane resin (A) is a reaction product of a polyol (a1) and a polyisocyanate (a2), the polyol (a1) comprises a polycarbonate polyol and a nonionic polyol, the content of structural units derived from the polycarbonate polyol in the urethane resin (A) is in the range of 60 to 90 mass%; the emulsifier (C) contains an anionic emulsifier (c1), the 500% modulus of a solidified film of the composition is 7 MPa or less; A composition, wherein the tensile strength of a solidified film of the composition is 5.0 MPa or more.

2. The composition described in claim 1, wherein the emulsifier (C) further contains a nonionic emulsifier (c2).

3. The composition according to claim 1, wherein the content of the structural unit derived from the nonionic polyol in the urethane resin (A) is 2.0 to 5.0 mass%.

4. The composition according to claim 2, wherein the content of the nonionic emulsifier (c2) is 0.3 to 4.0 parts by mass per 100 parts by mass of the urethane resin (A).

5. The composition of any one of claims 1 to 4, wherein the polyol does not comprise an anionic polyol.

6. A glove comprising a solidified film of the composition of any one of claims 1 to 4.