WO2024158024A1 - Composition et gants - Google Patents

Composition et gants Download PDF

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Publication number
WO2024158024A1
WO2024158024A1 PCT/JP2024/002131 JP2024002131W WO2024158024A1 WO 2024158024 A1 WO2024158024 A1 WO 2024158024A1 JP 2024002131 W JP2024002131 W JP 2024002131W WO 2024158024 A1 WO2024158024 A1 WO 2024158024A1
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WO
WIPO (PCT)
Prior art keywords
mass
polyol
composition
urethane resin
emulsifier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2024/002131
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English (en)
Japanese (ja)
Inventor
寛樹 田中
智博 鉄井
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DIC Corp
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DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Priority to JP2024573220A priority Critical patent/JP7718612B2/ja
Publication of WO2024158024A1 publication Critical patent/WO2024158024A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to a composition and a glove.
  • rubbers that are used as materials with rubber elasticity include natural rubber, isoprene rubber, chloroprene rubber, and nitrile rubber.
  • isoprene rubber When these materials are used for gloves, there may be problems with allergies caused by the proteins contained in natural rubber, or by the vulcanizing agents and vulcanization accelerators that are generally used in these rubbers.
  • the above-mentioned medical gloves are required to have high flexibility in addition to alcohol resistance. More specifically, highly flexible gloves are gloves with a 500% modulus of 7 MPa or less. However, according to the inventors' research, it was found that when attempting to produce gloves with a 500% modulus of 7 MPa or less using urethane resin made from polycarbonate polyol, the alcohol resistance of the gloves may be impaired.
  • the problem that the present invention aims to solve is to improve a composition containing a urethane resin capable of forming gloves with high flexibility so that the gloves also have excellent alcohol resistance.
  • a nonionic component a nonionic polyol as a raw material for the urethane resin, or a nonionic emulsifier for emulsifying (dispersing) the urethane resin
  • a composition containing a urethane resin made from polycarbonate polyol when gloves are produced with a 500% modulus of 7 MPa or less, the gloves are also endowed with excellent alcohol resistance.
  • 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
  • the 500% modulus of a solidified film of the composition is 7 MPa or less.
  • the content of the structural unit derived from a nonionic polyol in the urethane resin (A) is 2.0 to 5.0 mass%.
  • 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).
  • a glove comprising a solidified film of the composition according to any one of [1] to [5].
  • 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.
  • 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).
  • composition (X) contains a nonionic component.
  • a nonionic polyol is contained as polyol (a1) described below, which is a raw material for urethane resin (A).
  • a nonionic emulsifier is contained as emulsifier (C). Unless otherwise specified, the contents explained below are common to composition (X1) according to the first embodiment and composition (X2) according to the second embodiment.
  • 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).
  • the urethane resin (A) is made of polyol (a1) and polyisocyanate (a2) as raw materials (essential raw materials), may be made of only polyol (a1) and polyisocyanate (a2) as raw materials (essential raw materials), or may be made of polyol (a1), polyisocyanate (a2), and other component (a3) as raw materials (essential raw materials).
  • 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 making it easier to obtain a coagulated film having high flexibility.
  • the diol may be an aliphatic diol or a cycloaliphatic 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,
  • 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.
  • carbonate esters examples 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.
  • 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).
  • polyol (a1) further contains a nonionic polyol in addition to the polycarbonate polyol.
  • nonionic polyols include polyols having an oxyethylene structure (polyether polyols).
  • polyols having an oxyethylene structure include polyoxyethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, etc. These compounds may be used alone or in combination of two or more.
  • the urethane resin (A) contains structural units derived from a polycarbonate polyol and structural units derived from a nonionic polyol.
  • this urethane resin (A) from the viewpoint of being able to impart even better alcohol resistance, it is preferable that the content of structural units derived from a polycarbonate polyol is 60 to 90 mass %, and from the viewpoint of being able to impart excellent emulsifiability and salt coagulation properties, the content of structural units derived from a nonionic polyol is 2.0 to 5.0 mass %.
  • 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.
  • the upper limit of the content may be 85% by mass or 80% by mass.
  • 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.
  • the upper limit of the content may be 4.5% by mass or 4.0% by mass.
  • polyisocyanates that can be used as polyisocyanates (a2) 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.
  • the content of polyisocyanate (a2) is preferably 15% by mass or less, and more preferably 13% by mass or less, based on the total of polyol (a1), polyisocyanate (a2), and other components (a3) used as raw materials for urethane resin (A) (also referred to as the total of polymerization components), from the viewpoint of making it easier to obtain a coagulated film with 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).
  • chain extenders used as raw materials as required include, for example, chain extenders.
  • the chain extender is preferably a polyamine chain extender, more preferably a polyamine chain extender having three or more amino groups.
  • polyamine chain extenders examples 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 (polyoxypropylenetriamine, etc.), and the like. These polyamine chain extenders may be used alone or in combination of two or more.
  • 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.
  • 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.
  • the content of structural units derived from anionic polyol in the urethane resin (A) is preferably 0.20 to 0.70 mass% from the viewpoint of being able to suitably emulsify the urethane resin (A) and obtain even better alcohol resistance.
  • the lower limit of the content may be 0.30 mass% or 0.35 mass%.
  • the upper limit of the content may be 0.60 mass% or less or 0.50 mass% or less.
  • the urethane resin (A) preferably does not have an anionic group, from the viewpoint of making it easier to obtain gloves with even better alcohol resistance.
  • the polyol (a1) preferably does not contain an anionic polyol
  • the urethane resin (A) preferably does not contain a structural unit derived from an anionic polyol.
  • the content of urethane resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total amount of composition (X), from the viewpoint of improving storage stability and workability, and is preferably 60% by mass or less, more preferably 50% by mass or less.
  • water (B) for example, distilled water, ion-exchanged water, etc. can be used. These waters can be used alone or in combination of two or more kinds.
  • 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.
  • the emulsifier (C) includes an anionic emulsifier (c1).
  • 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 alkyldiphenylethersulfonates. These anionic emulsifiers may be used alone or in combination of two or more.
  • the content of the anionic emulsifier (c1) is preferably 1 to 10 parts by mass per 100 parts by mass of the urethane resin (A) from the viewpoint 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.
  • the emulsifier (C) further contains a nonionic emulsifier (c2) in addition to the anionic emulsifier (c1).
  • the nonionic emulsifier (c2) include polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene stearyl ether, polyoxyethylene styrylphenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene-polyoxypropylene copolymer, and the like. These nonionic emulsifiers may be used alone or in combination of two or more.
  • the content of the nonionic emulsifier (c2) is preferably 0.3 to 4.0 parts by mass per 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 parts by mass.
  • the upper limit of the content may more preferably be 3.0 parts by mass or 2.0 parts by mass.
  • Composition (X) may further contain other additives as necessary.
  • additives include thickeners, defoamers, urethane catalysts, silane coupling agents, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light resistance stabilizers, fluorescent brighteners, foaming agents, foam stabilizers, pigments, dyes, conductivity agents, antistatic agents, moisture permeability agents, water repellents, oil repellents, antiblocking agents, hydrolysis inhibitors, etc. These additives may be used alone or in combination of two or more.
  • the composition (X) may further contain other polymers besides the urethane resin (A) depending on the durability required for the intended use.
  • 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), natural rubber (NR), etc.
  • Composition (X) can be obtained, for example, by synthesizing urethane resin (A) by reacting polyol (a1) with polyisocyanate (a2), and then mixing the urethane resin (A) with an aqueous emulsifier solution containing water (B) and emulsifier (C).
  • the composition (X) can be obtained, for example, by synthesizing a urethane prepolymer by reacting a polyol (a1) with a polyisocyanate (a2), mixing the urethane prepolymer with an aqueous emulsifier solution containing water (B) and an emulsifier (C), and then adding the chain extender to synthesize the urethane resin (A).
  • the urethane prepolymer is a urethane prepolymer having an isocyanate group (preferably a non-yellowing isocyanate group) at the end.
  • composition (X) can be a dispersion (emulsion) in which urethane resin (A) is suitably dispersed in water (B) without using an organic solvent.
  • composition (X) does not need to contain an organic solvent.
  • the 500% modulus of the solidified film of composition (X) is 7 MPa or less.
  • the 500% modulus of the solidified film of composition (X) means the 500% modulus measured by the method described in the Examples.
  • the solidified film of composition (X) is suitable for use in gloves, and is particularly suitable for use in medical gloves (surgical gloves). That is, another embodiment of the present invention is a glove containing a solidified film of composition (X), and preferably a medical glove (surgical glove) containing a solidified film of composition (X). A method for producing the glove will be described below.
  • One method for producing gloves is, for example, to first immerse a hand mold in a coagulant and then dry it as necessary to adhere metal salts and the like in the coagulant to the surface of the hand mold, then immerse the hand mold in composition (X), wash the surface with water, and dry it to obtain a coagulated film (coagulated film) layer on the surface of the hand mold, and peel off this film layer from the hand mold to produce gloves formed from the film.
  • composition (X) may be further diluted with distilled water, ion-exchanged water, etc.
  • the coagulant may be, for example, a solution of a metal salt such as calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, or sodium chloride; or an acid solution such as formic acid or acetic acid.
  • Solvents capable of dissolving metal salts or acids may be, for example, water, methanol, ethanol, or isopropanol.
  • the metal salt contained in the coagulant is preferably contained in a range of 1 to 50 mass% based on the total amount of the coagulant.
  • the time for immersing the hand mold in the coagulant may be 5 to 60 seconds.
  • the coagulant may 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.
  • the hand mold may be fitted with a glove-like article made of knitted nylon fibers or the like in advance. Specifically, the hand mold fitted with the knitted glove-like article is first immersed in a coagulant and then dried as necessary to impregnate 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 to form a coagulated film (coagulated film) layer on the surface of the glove-like article. The glove-like article can be peeled off from the hand mold to obtain a glove with a film layer formed on its surface.
  • 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 ("PEG1540" manufactured by NOF Corporation, 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 a urethane prepolymer A.
  • polycarbonate polyol made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000
  • PEG1540 polyethylene glycol
  • IPDI isophorone diisocyanate
  • the urethane prepolymer A heated to 180°C, a 20% by mass aqueous solution of sodium dodecylbenzenesulfonate as an anionic emulsifier ("Neogen S-20F” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and water were fed to a twin-screw extruder (TEM-18SS: manufactured by Shibaura Machine Co., Ltd.) and mixed to obtain an emulsion.
  • TEM-18SS manufactured by Shibaura Machine Co., Ltd.
  • the flow rates of the respective feed liquids were urethane prepolymer A: 10 kg/h, emulsifier aqueous solution: 2.5 kg/h, and water: 8.5 kg/h, and the twin-screw extruder operating conditions were 50°C and 260 rpm.
  • a water-diluted solution of a polyamine-based chain extender ("Jeffamine T-403" manufactured by HUNTSMAN Co., Ltd.) with an amino group content equivalent to 95% of the NCO groups was added to extend the chains, and a composition (emulsion) with a urethane resin content of 40% by mass was finally obtained.
  • the content of structural units derived from nonionic polyol in the urethane resin was 3.6% by mass.
  • 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 a urethane prepolymer B.
  • polycarbonate polyol made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000
  • polyester polyol (“PRIPLAST 1838” manufactured by Croda Japan)
  • PEG1540
  • the urethane prepolymer B heated to 180°C, a 20% by weight aqueous solution of sodium dodecylbenzenesulfonate as an anionic emulsifier ("Neogen S-20F” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and water were simultaneously fed and mixed into a twin-screw extruder (TEM-18SS: manufactured by Shibaura Machine Co., Ltd.) to obtain an emulsion.
  • TEM-18SS manufactured by Shibaura Machine Co., Ltd.
  • the flow rates of the respective feed liquids were urethane prepolymer B: 10 kg/h, emulsifier aqueous solution: 2.5 kg/h, and water: 8.5 kg/h, and the twin-screw extruder operating conditions were 50°C and 260 rpm.
  • a water-diluted solution of a polyamine-based chain extender ("Jeffamine T-403" manufactured by HUNTSMAN Co., Ltd.) with an amino group content equivalent to 95% of the NCO groups was added to extend the chains, and a composition (emulsion) with a urethane resin content of 40% by weight was finally obtained.
  • the content of structural units derived from nonionic polyol in the urethane resin was 3.6% by weight.
  • 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 ("PEG1540" manufactured by NOF Corporation, 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, to obtain a urethane prepolymer C.
  • polycarbonate polyol made from 1,5-pentanediol and 1,6-hexanediol, number average molecular weight: 2,000
  • PEG1540 polyethylene glycol
  • IPDI isophorone diisocyanate
  • TEM-18SS manufactured by Shibaura Machine Co., Ltd. twin-screw extruder
  • the flow rates of the respective feed liquids were urethane prepolymer C: 10 kg/h, aqueous solution of the emulsifier: 3.5 kg/h, and water: 6.9 kg/h, and the twin-screw extruder operating conditions were 50°C and 260 rpm.
  • 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.
  • 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.
  • 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, to obtain a urethane prepolymer D.
  • IPDI isophorone diisocyanate
  • the aqueous solution of the emulsifier and water were then fed to 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 urethane prepolymer D: 10 kg/h, aqueous solution of the emulsifier: 3.63 kg/h, and water: 6.9 kg/h, and the twin-screw extruder was operated at 50°C and 260 rpm.
  • 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.
  • reaction product reached a specified viscosity
  • 1.0 part by mass of methanol was added, the reaction was terminated by stirring for 1 hour, and 498 parts by mass of methyl ethyl ketone was added as a diluting solvent to obtain an organic solvent solution of a urethane resin.
  • reaction product reached a specified viscosity
  • 1.2 parts by mass of methanol was added, the reaction was terminated by stirring for 1 hour, and 498 parts by mass of methyl ethyl ketone was further added as a diluting solvent to obtain an organic solvent solution of a urethane resin.
  • the flow rates of the feed liquids were urethane prepolymer E: 10 kg/h, emulsifier: 0.5 kg/h, and water: 5.8 kg/h, and the twin-screw extruder operating conditions were 50°C and 260 rpm.
  • 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 calcium nitrate solution for 10 seconds and then removed.
  • 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 hand mold from (3) was washed with water at 20 to 30°C for 10 minutes.
  • the hand mold from (4) was dried at 70°C for 20 minutes and then dried at 120°C for 30 minutes.
  • Baby powder was applied to the hand mold from (5) and the solidified urethane resin film was peeled off from the hand mold.
  • each solidified film obtained was cut into a "dumbbell TYPE D" as specified in ASTM D412 to obtain a test piece. Both ends of the test piece were clamped with a chuck, and the test piece was pulled at a crosshead speed of 500 mm/min under an atmosphere of 23 ⁇ 2°C and 60 ⁇ 10% humidity using a tensile tester "Autograph AG-I” (manufactured by Shimadzu Corporation), and the 500% modulus (MPa) of the test piece was measured. The distance between the gauge lines at this time was 20 mm, and the initial distance between the chucks was 40 mm. The results are shown below.
  • 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
  • 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: 0.5MPa Comparative Example 3: Unmeasurable

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention concerne une composition qui contient une résine d'uréthane (A), de l'eau (B) et un agent émulsifiant (C), la résine d'uréthane (A) étant un produit de réaction d'un polyol (a1) et d'un polyisocyanate (a2) ; le polyol (a1) contenant un polycarbonate polyol et un polyol non ionique ; l'agent émulsifiant (C) contenant un agent émulsifiant anionique ; et le module à 500 % d'un film solidifié de cette composition étant inférieur ou égal à 7 MPa. La présente invention concerne également une composition qui contient une résine d'uréthane (A), de l'eau (B) et un agent émulsifiant (C), la résine d'uréthane (A) étant un produit de réaction d'un polyol (a1) et d'un polyisocyanate (a2) ; le polyol (a1) contenant un polycarbonate polyol ; l'agent émulsifiant (C) contenant un agent émulsifiant anionique et un agent émulsifiant non ionique; et le module à 500 % d'un film solidifié de cette composition étant inférieur ou égal à 7 MPa. Cette composition est capable de former des gants hautement souples.
PCT/JP2024/002131 2023-01-26 2024-01-25 Composition et gants Ceased WO2024158024A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002179759A (ja) * 2000-12-13 2002-06-26 Asahi Kasei Corp ポリウレタンエマルジョン
WO2018186142A1 (fr) * 2017-04-04 2018-10-11 Dic株式会社 Procédés de production de corps poreux, de gant et de cuir synthétique
WO2020217813A1 (fr) * 2019-04-23 2020-10-29 Dic株式会社 Composition de résine uréthanique, feuille d'uréthane expansée et cuir synthétique
WO2022045245A1 (fr) * 2020-08-27 2022-03-03 三井化学株式会社 Résine de polyuréthane, cuir synthétique et encre

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6616685B2 (ja) 2015-12-28 2019-12-04 日華化学株式会社 水分散型ポリカーボネート系ポリウレタン樹脂組成物、それを用いて処理した繊維製品、及び水分散型ポリカーボネート系ポリウレタン樹脂組成物の製造方法
NL2022103B1 (en) 2018-11-30 2020-06-26 Stahl Int B V Composite structure with polyurethane layers, which is substantially free of volatile organic compounds
EP3892144B1 (fr) 2018-12-07 2023-10-04 DIC Corporation Gant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002179759A (ja) * 2000-12-13 2002-06-26 Asahi Kasei Corp ポリウレタンエマルジョン
WO2018186142A1 (fr) * 2017-04-04 2018-10-11 Dic株式会社 Procédés de production de corps poreux, de gant et de cuir synthétique
WO2020217813A1 (fr) * 2019-04-23 2020-10-29 Dic株式会社 Composition de résine uréthanique, feuille d'uréthane expansée et cuir synthétique
WO2022045245A1 (fr) * 2020-08-27 2022-03-03 三井化学株式会社 Résine de polyuréthane, cuir synthétique et encre

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