WO2010095665A1 - Composition aqueuse de résine de polyuréthane et articles de type films l'utilisant - Google Patents

Composition aqueuse de résine de polyuréthane et articles de type films l'utilisant Download PDF

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WO2010095665A1
WO2010095665A1 PCT/JP2010/052377 JP2010052377W WO2010095665A1 WO 2010095665 A1 WO2010095665 A1 WO 2010095665A1 JP 2010052377 W JP2010052377 W JP 2010052377W WO 2010095665 A1 WO2010095665 A1 WO 2010095665A1
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polyurethane resin
aqueous polyurethane
viscosity
mpa
resin composition
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PCT/JP2010/052377
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English (en)
Japanese (ja)
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誠司 前浜
隆夫 蒲原
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東ソー株式会社
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Priority claimed from JP2009035795A external-priority patent/JP5544724B2/ja
Application filed by 東ソー株式会社 filed Critical 東ソー株式会社
Publication of WO2010095665A1 publication Critical patent/WO2010095665A1/fr

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    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to an aqueous polyurethane resin composition and a film molded body using the same.
  • the film molded body is, for example, a glove, a finger sack, a condom or the like, and these are usually produced by a salt coagulation method (for example, Patent Documents 1 to 3).
  • a salt coagulation method the mold is immersed in a coagulation solution such as an aqueous calcium nitrate solution to form a coagulation solution layer, immersed in an emulsion to form a film, washed with water, and then dried.
  • the direct immersion molding method is advantageous in that the production cost is low because the film is obtained by immersing the aqueous polyurethane resin in a mold to form a film and drying.
  • the present invention has been made in view of the above problems, and an object thereof is to provide an aqueous polyurethane resin composition capable of obtaining a film molded body having a uniform film thickness without bubbles or bubbles even when molded at a high temperature.
  • the film molding manufactured using this is provided.
  • the present invention contains an aqueous polyurethane resin produced from a polyisocyanate and a polyhydroxy compound and a nonionic surfactant, a resin solid content concentration of 50% by weight or more, and a corrected viscosity of 100 to 2000 mPa.s. s, an aqueous polyurethane resin composition having a yield value of 200 mPa or more, wherein the aqueous polyurethane resin satisfies a specific condition, and a film molded body using the same.
  • the water-based polyurethane resin composition of the present invention can produce a film molded body having a uniform film thickness without bubbles or bubbles even when molded at a high temperature. Therefore, the film molded body can be produced by a simple method using a direct immersion molding method. Became possible.
  • the aqueous polyurethane resin composition of the present invention contains an aqueous polyurethane resin produced from a polyisocyanate and a polyhydroxy compound and a nonionic surfactant, and has a resin solid content concentration of 50% by weight or more, represented by the following formula (1).
  • the required corrected viscosity is 100 to 2000 mPa.s. s
  • the yield value obtained by the following formula (2) is 200 mPa or more
  • the aqueous polyurethane resin satisfies the following conditions (A) and (B).
  • V ′ 6 is a BM type viscometer, using a No. 3 spindle, a viscosity (mPa.s) at a liquid temperature of 30 ° C. and a rotation speed of 6 rpm
  • V ′ 12 is a BM type viscometer, No. 3 spindle is used, and the viscosity (mPa.s) at a liquid temperature of 30 ° C.
  • polyisocyanate is diphenylmethane diisocyanate.
  • hydrophilic group contained in the aqueous polyurethane resin is 0.03 to 0.30 mmol with respect to 1 g of the resin solid content.
  • the aqueous polyurethane resin composition of the present invention contains an aqueous polyurethane resin produced from a polyisocyanate and a polyhydroxy compound and a nonionic surfactant.
  • the aqueous polyurethane resin is obtained by reacting at least a polyisocyanate and a polyhydroxy compound to obtain a prepolymer, and then extending the chain before, during or after emulsification.
  • the nonionic surfactant contained in the aqueous polyurethane resin composition of the present invention include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether.
  • Polyoxyethylene alkyl phenyl ether, ethylene oxide adduct of acetylene diol, polyoxyethylene derivative, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyethylene glycol fatty acid ester, polyoxyethylene alkyl such as polyoxyethylene laurylamine An amine etc. are mentioned.
  • the content of the nonionic surfactant varies depending on the type of surfactant and the degree of hydrophobicity of the polymer, but is preferably 0.1 to 5% by weight, more preferably in the aqueous polyurethane resin composition of the present invention. 0.2 to 3% by weight.
  • the preferred HLB (Hydrophil Lipophil Balance) of the nonionic active agent is 12 to 20, more preferably 14 to 17.
  • the aqueous polyurethane resin composition of the present invention needs to have a resin solid content concentration of 50% by weight or more, preferably 55 to 80% by weight, more preferably 60 to 75% from the viewpoint of shortening the drying time and suppressing swelling. % By weight.
  • the resin solid content concentration is less than 50% by weight, a long drying time is required, and bulge is likely to occur due to evaporation of moisture, resulting in poor film appearance.
  • the resin solid content concentration is obtained by measuring the non-volatile content by volatilizing water or a solvent, obtained as a ratio to the original weight, and according to the test method for synthetic resin emulsions defined in JIS K 6828-1. It can be measured.
  • the water-based polyurethane resin composition of the present invention has a corrected viscosity of 100 to 2000 mPa.s determined by the above formula (1) measured at a liquid temperature of 30 ° C. s, the yield value obtained by the above formula (2) must be 200 mPa or more, and preferably the corrected viscosity is 200 to 2000 mPa.s. s, the yield value is 300 mPa or more.
  • the corrected viscosity is 100 mPa.s. If it is less than s, the basis weight of the aqueous polyurethane resin adhering to the surface of the mold is poor, and it becomes difficult to obtain a uniform film molding. On the other hand, the corrected viscosity is 2000 mPa.s.
  • aqueous polyurethane resin contained in the aqueous polyurethane resin composition of the present invention 50% by weight or more of the polyisocyanate needs to be diphenylmethane diisocyanate.
  • diphenylmethane diisocyanate is less than 50% by weight, the film appearance may be deteriorated or the physical properties may be deteriorated.
  • the amount is preferably 60 to 95% by weight in order to prevent the generation of aggregates and to prevent deterioration of physical properties and appearance when formed into a film.
  • diphenylmethane diisocyanate examples include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude MDI (mixture of diphenylmethane diisocyanate and polymethylene polyphenylene polyisocyanate), a mixture thereof, and the like.
  • the aqueous polyurethane resin needs to contain a hydrophilic group in order to improve the emulsion stability.
  • the hydrophilic group is an anionic group such as a carboxylic acid group or a sulfonic acid group, and an anionic group obtained by neutralizing these with a basic compound such as sodium hydroxide or tertiary amine.
  • the amount of the hydrophilic group contained in the aqueous polyurethane resin needs to be 0.03 to 0.30 mmol, preferably 0.05 to 0.15 mmol, with respect to 1 g of resin solid content. When the hydrophilic group is less than 0.03 mmol, the dispersion stability of the aqueous polyurethane resin is insufficient and phase separation tends to proceed.
  • the average particle diameter of the aqueous polyurethane resin is not particularly limited, but is 0.05 to 5.5 in order to increase the resin solid content concentration to ensure an appropriate viscosity and to maintain the stability of the aqueous polyurethane resin composition. 0 ⁇ m is preferable, more preferably 0.1 to 3.0 ⁇ m, and still more preferably 0.2 to 1.5 ⁇ m.
  • the aqueous polyurethane resin composition of the present invention can improve viscosity characteristics by containing a thickener.
  • the thickener examples include inorganic thickeners such as silicate, metal silicate, montmorillonite, organic montmorillonite, colloidal alumina, polyacrylic acid soda, polyacrylic acid- (meth) acrylic acid ester.
  • Polyacrylic acid thickeners such as copolymers, urethane associative thickeners, fiber derivative thickeners such as carboxymethylcellulose, methylcellulose, and hydroxyethylcellulose; protein systems such as casein, sodium caseinate, and ammonium caseinate Thickeners, alginic acid thickeners such as sodium alginate, polyvinyl thickeners such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinylbenzyl ether copolymers, pluronic polyethers, polyether dialkyl esters, polyether dialkyl ethers, polyethers Epo Polyether thickeners such as poly-modified products, maleic anhydride copolymer thickeners such as vinyl methyl ether-maleic anhydride
  • urethane associative thickeners are preferred because a high thickening effect can be expected with addition of a small amount.
  • examples of the urethane associative thickener include compounds having a urethane bond and a polyether chain in the molecule and a hydrophobic group at the terminal, and the urethane bonds are associated with each other in an aqueous medium. It is known to effectively increase the viscosity.
  • urethane associative thickeners include “UH-420”, “UH-450”, “UH-462”, “UH-472”, “UH-540”, “UH-752” ( All are products of ADEKA Corporation), “SN thickener 612”, “SN thickener 621N”, “SN thickener 625N”, “SN thickener 627N”, “SN thickener 660T” (all are products of San Nopco Corporation), etc. be able to.
  • the content of the thickener is not particularly limited, but is preferably 0.01 to 3.0% by weight, more preferably 0.05 to 1.0% by weight, based on the aqueous polyurethane resin composition. is there.
  • the aqueous polyurethane resin composition of the present invention can be imparted with a specific viscosity characteristic that is less likely to sag during molding by the inclusion of a thickener, and the viscosity ratio 1 calculated by the following formula (1) is 4. It is preferable that the viscosity ratio 2 obtained by the following formula (2) is 0 or more and 0.85 or more.
  • Viscosity ratio 1 V 30,6 / V 30,60 (1) (In the formula, V 30,6 uses a BM type viscometer, No. 3 spindle is used, the liquid temperature is 30 ° C., and the rotation speed is 6 rpm (mPa.s), V 30,60 is BM type. (The viscosity (mPa.s) when using a No.
  • Viscosity ratio 2 V 60,12 / V 30,12 ( 2)
  • V 60 and 12 are BM type viscometers, No. 3 spindle is used, liquid temperature is 60 ° C. and rotation speed is 12 rpm (mPa.s), V 30 and 12 are BM type)
  • Viscosity ratio 1 is generally called a thixotropy index (TI) and is an index that correlates with sagging difficulty. In order to prevent deposits from dripping when performing immersion molding and to prevent occurrence of uneven thickness, 4 It is preferably 0.0 or more, more preferably 5.0 or more. Viscosity ratio 2 is an index that correlates with the temperature dependency of viscosity, and the aqueous polyurethane resin composition adhered during heat drying is more difficult to sag, and prevents the occurrence of uneven thickness and tear during heat molding. It is preferably 85 or more, more preferably 1.00 or more.
  • the aqueous polyurethane resin composition of the present invention can also contain a crosslinking agent for the purpose of improving durability.
  • a crosslinking agent include amino resins, epoxy compounds, aziridine compounds, carbodiimide compounds, oxazoline compounds, polyisocyanate compounds, and the like.
  • the water-based polyurethane resin composition of the present invention contains additives that are usually used within a range that does not inhibit cohesion, such as plasticizers, tackifiers (rosin resin, rosin ester resin, terpene resin, terpene phenol resin petroleum Resin, coumarone resin, etc.), fillers, pigments, antifoaming agents, antioxidants, ultraviolet absorbers, flame retardants, preservatives, and the like.
  • additives that are usually used within a range that does not inhibit cohesion, such as plasticizers, tackifiers (rosin resin, rosin ester resin, terpene resin, terpene phenol resin petroleum Resin, coumarone resin, etc.), fillers, pigments, antifoaming agents, antioxidants, ultraviolet absorbers, flame retardants, preservatives, and the like.
  • Examples of the method for producing the aqueous polyurethane resin composition of the present invention include: (a) Prepolymer obtained by reacting a polyisocyanate, a polyhydroxy compound and a polyhydroxy compound having a hydrophilic group with the presence of a nonionic surfactant. A method of extending the chain after emulsification, (b) presence of a nonionic surfactant after extending the chain of a prepolymer obtained by reacting an organic polyisocyanate and a polyhydroxy compound with a polyamine compound having a hydrophilic group The emulsification method is used under these conditions.
  • a prepolymer having a hydrophilic group introduced is used, and in the presence of a nonionic surfactant.
  • the method (a) emulsified with is desirable.
  • Examples of the polyisocyanate used for producing the prepolymer include aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and araliphatic polyisocyanate.
  • Examples of the aliphatic polyisocyanate include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, And dimer acid diisocyanate.
  • alicyclic polyisocyanates examples include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (isophorone).
  • Diisocyanate bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), norbornane diisocyanate and the like.
  • aromatic polyisocyanate examples include 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, crude MDI, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and the like.
  • Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate, and the like.
  • the polyisocyanate used for producing the prepolymer needs to be 50% by weight or more of diphenylmethane diisocyanate.
  • diphenylmethane diisocyanate When diphenylmethane diisocyanate is less than 50% by weight, the film appearance may be deteriorated or the physical properties may be deteriorated.
  • the amount is preferably 60 to 95% by weight in order to prevent the generation of aggregates and to prevent deterioration of physical properties and appearance when formed into a film.
  • diphenylmethane diisocyanate include 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, crude MDI, and mixtures thereof.
  • the polyhydroxy compound used in the present invention is a compound containing two or more hydroxyl groups having reactivity with isocyanate groups.
  • Examples of the polymer polyhydroxy compound having a molecular weight of 400 or more include polyester polyol (a), polyether polyol (b), and a mixture of two or more thereof.
  • Examples of the polyester polyol (a) include condensed polyester polyol (a1), polycarbonate polyol (a2), polylactone polyol (a3) and the like.
  • Examples of the condensed polyester polyol (a1) include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1 , 6-hexanediol, neopentyl glycol, butyl ethyl propane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol and other diols and succinic acid, adipic acid, azelaic acid, sebacine Acid, dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene
  • Adipate-type condensed polyester diols such as adipate diol
  • azelate-type condensed polyester diols such as polyethylene azelate diol and polybutylene azelate diol.
  • Examples of the polycarbonate polyol (a2) include a reaction product of a dialkyl carbonate represented by the above diols and dimethyl carbonate, and the like. Specific examples include polytetramethylene carbonate diol, poly 3-methylpentamethylene. Examples thereof include carbonate diol and polyhexamethylene carbonate diol.
  • Examples of the polylactone polyol (a3) include ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and a ring-opening polymer of a mixture of two or more thereof. Specific examples include polycaprolactone diol and the like. It can be illustrated.
  • polyether polyol (b) examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, catechol, hydroquinone, and bisphenol A.
  • 1 type or 2 types of monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, cyclohexylene, etc., with one or more compounds having at least two active hydrogen atoms as initiators
  • a reaction product obtained by addition polymerization of the above can be mentioned.
  • reaction product obtained by addition polymerization of two or more monomers block addition, random addition, or a mixed system of both may be used.
  • Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like.
  • polyester polyols are preferred from the viewpoint of the physical properties of the film molding, and specific examples include polybutylene adipate diol, polyhexamethylene adipate diol, and polyhexamethylene carbonate diol. it can. From the viewpoint of water resistance of the molded film, polyether polyol is preferable, and specific examples include polypropylene glycol and polytetramethylene ether glycol.
  • the hydroxyl value of the polymer polyhydroxy compound is preferably 10 to 300 mgKOH / g, more preferably 20 to 250 mgKOH / g.
  • the hydroxyl value is determined by the method specified in JIS-K0070, that is, a sample solution prepared by adding acetic anhydride and pyridine to dissolve the sample, allowing to cool, and adding water and toluene after standing to cool is neutralized with a KOH ethanol solution. It can be measured by titration.
  • the hydroxyl value is represented by the number of mg of potassium hydroxide required to neutralize acetic acid consumed to acetylate the hydroxyl group contained in a 1 g sample.
  • Examples of the low molecular weight polyhydroxy compound having a molecular weight of less than 400 include ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentanediol.
  • 1,6-hexanediol 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, tripropylene glycol and other aliphatic diols, glycerin, trimethylolpropane, pentaerythritol and other polyfunctional aliphatic polyols, 1,4-cyclohexane Diols, 1,4-cyclohexanedimethanol, alicyclic diols such as hydrogenated bisphenol A, aromatic diols such as bisphenol A, hydroquinone, bishydroxyethoxybenzene, and addition of these alkylene oxides Polyols and the like of the like.
  • polyhydroxy compound having a hydrophilic group used in the present invention examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbutyric acid, and 2,2-dimethylolvaleric acid.
  • Carboxylic acid group-containing polyester polyols produced using these as part of the raw material can also be suitably used.
  • a polyester polyol having a sulfonic acid group introduced by 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid or the like may be used.
  • These polyhydroxy compounds introduced with hydrophilic groups are neutralized with at least one selected from organic amines such as ammonia and triethylamine and metal bases such as Na, K, Li and Ca, and then used as raw materials for prepolymers. You can also
  • polyamine compound having a hydrophilic group used in the present invention examples include sodium 2- (2-aminoethylamino) ethanesulfonate, sodium salt of an addition reaction product of 2-acrylamido-2-methylpropanesulfonic acid and ethylenediamine. Lysine, 1,3-propylenediamine- ⁇ -ethylsulfonic acid, and the like. Chain extension with these polyamine compounds having hydrophilic groups is carried out before emulsification.
  • the use amount of the polyhydroxy compound having a hydrophilic group or the polyamine compound having a hydrophilic group maintains the dispersion stability of the aqueous polyurethane resin and increases the resin solid content concentration to prevent the water resistance of the dried coating film from being lowered. Therefore, it is necessary to adjust the amount of the hydrophilic group contained in the aqueous polyurethane resin so as to be 0.03 to 0.30 mmol with respect to 1 g of the resin solid content, and preferably 0.05 to 0.15 mmol. It is.
  • the molar ratio of the total isocyanate groups derived from the polyisocyanate and the total hydroxyl groups derived from the polyhydroxy compound: NCO / OH is not particularly limited, but prevents poor dispersion and extends the chain with the polyamine compound. In order to prevent gelation, the range of 1.03 to 1.5 is preferable, and 1.05 to 1.4 is more preferable.
  • an organic solvent inert to an isocyanate group such as acetone, methyl ethyl ketone, acetonitrile, ethyl acetate, dioxane, tetrahydrofuran or the like is used before the reaction, during the reaction, or after the completion of the reaction so that the reaction proceeds uniformly. It may be added.
  • the temperature range for the synthesis of the prepolymer is not particularly limited, but is preferably 30 to 120 ° C., more preferably 40 to 100 ° C., particularly in order to prevent an increase in the viscosity of the prepolymer and to sufficiently promote urethanization. Preferably, it is 45 to 90 ° C.
  • the appropriate reaction time for obtaining the prepolymer depends on conditions such as the reaction temperature, but the prepolymer can usually be obtained by reacting for 0.1 to 10 hours.
  • the prepolymer contains a hydrophilic group capable of forming a salt such as a carboxylic acid group or a sulfonic acid group
  • basic compounds that can be used as the neutralizing agent include inorganic bases such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and tertiary compounds such as trimethylamine, triethylamine, triethylenediamine, dimethylaminoethanol, and N-methylmorpholine.
  • Examples include amines and aqueous ammonia.
  • hydrophilization neutralization
  • a method of reacting with a neutralizing agent before, during or after synthesis of the prepolymer (b) in water used for emulsification It can be carried out by a method of adding a compatibilizer.
  • nonionic surfactant used in the method for producing an aqueous polyurethane resin composition examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, and polyoxyethylene nonyl phenyl ether.
  • polyoxyethylene alkyl phenyl ether, ethylene oxide adduct of acetylenic diol, polyoxyethylene derivative, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid monoglyceride, polyethylene glycol fatty acid ester, polyoxyethylene alkyl such as polyoxyethylene laurylamine An amine etc. are mentioned.
  • the addition method of the nonionic surfactant is not particularly limited, and for example, (a) a method of adding before emulsification, (b) a method of adding with water used during emulsification, and the like can be carried out.
  • the amount of the nonionic surfactant used varies depending on the type of the surfactant and the hydrophobicity of the polymer, but is preferably 0.1 to 5% by weight, more preferably in the aqueous polyurethane resin composition of the present invention. 0.2 to 3% by weight.
  • the preferable HLB of the nonionic active agent is 12 to 20, more preferably 14 to 17.
  • the amount of water used for emulsification is not particularly limited, but is preferably 25 to 120 parts by weight, more preferably 40 to 90 parts by weight with respect to 100 parts by weight of resin solids. If the amount of water is less than 25 parts by weight relative to 100 parts by weight of the resin solid content, stirring may be difficult due to thickening, and if it exceeds 120 parts by weight, an appropriate resin solid content concentration is obtained. Therefore, it is necessary to distill off a large amount of water.
  • the aqueous polyurethane resin in the present invention is desirably made high molecular weight by adding a chain extender before, during or after emulsification.
  • the chain extender is a polyamine compound containing at least two primary or secondary amino groups, and can achieve a high molecular weight by extending the remaining isocyanate group of the prepolymer.
  • Specific examples of the polyamine compound include ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, xylylenediamine, metaphenylenediamine, piperazine, hydrazine, and adipic acid dihydrazide.
  • the amount of the polyamine compound used can be arbitrarily selected from 0.3 to 1.5 equivalents, preferably 0.4 to 1.2 equivalents, based on the terminal isocyanate group of the prepolymer.
  • the aqueous polyurethane resin composition contains a low-boiling organic solvent, it is desirable to distill off the solvent at 30 to 80 ° C. under reduced pressure. Moreover, it is also possible to adjust the resin solid content density
  • a thickener When a thickener is used in the method for producing the aqueous polyurethane resin composition of the present invention, for example, it is added to increase the film thickness and improve the smoothness of the surface of the molded film.
  • thickeners are the same as those described above.
  • the addition amount of the thickener is not particularly limited, but is preferably 0.015 to 6.0 parts by weight and more preferably 0.075 to 2.0 parts by weight with respect to 100 parts by weight of the resin solid content. .
  • the film molded body of the present invention is molded by a direct immersion molding method.
  • the direct immersion molding method is to immerse the mold in an aqueous polyurethane resin composition and pull it up to uniformly attach the aqueous polyurethane resin composition to the mold, dry it, and then peel it from the mold to form a film molding. It is a manufacturing method to obtain. Since a coagulant (for example, calcium nitrate) used in the salt coagulation method is not used, a cleaning process is unnecessary and the manufacturing process is simple.
  • mold used for manufacture of an immersion product is not specifically limited, For example, conventionally well-known various types
  • the preheating temperature and immersion time of the mold are set according to the composition of the aqueous polyurethane resin composition and the film thickness of the film, and are not particularly limited. Further, the molding temperature is not particularly limited, but is preferably from 100 to 200 ° C., more preferably from 110 to 200 ° C. in order to shorten the molding time.
  • the film thickness of the molded film of the present invention varies depending on the use and is not particularly limited, but is preferably 10 to 1000 ⁇ m, more preferably 20 to 1000 ⁇ m, and particularly preferably 100 to 500 ⁇ m.
  • the film molded product of the present invention exhibits excellent mechanical properties (elongation, tensile strength, low modulus) without using a crosslinking agent.
  • the breaking strength is 25 MPa or more, preferably 30 MPa or more, the breaking elongation is 400% or more, preferably 500% or more, and the 300% modulus is 10 MPa or less, preferably 5 MPa or less (measurement conditions: distance between chucks 20 mm, pulling speed 100 mm / Min).
  • the molded film of the present invention can be used as, for example, gloves, finger sack, condom, medical bag, leather-like sheet, catheter, O-ring and the like.
  • the water-based polyurethane resin composition of the present invention can produce a film molded body having a uniform film thickness without bubbles or bubbles even when molded at a high temperature. Therefore, the film molded body can be produced by a simple method using a direct immersion molding method. Became possible.
  • the measurement method and evaluation method regarding the aqueous polyurethane resin composition of the present invention are as follows.
  • ⁇ Measurement method of corrected viscosity and yield value> A 300 mL sample of the aqueous polyurethane resin composition was collected in a beaker, and after removing bubbles, the temperature was adjusted to 30 ° C. No. 1 on a single cylinder viscometer (BM type viscometer, BROOKFIELD, DV-E VISCOMETER). 3 spindles were attached and immersed in the sample solution up to the immersion liquid mark of the viscometer, taking care not to allow bubbles to adhere. After immersion, the spindle was rotated at 12 rpm for 1 minute, and the viscosity was read to obtain V′12.
  • BM type viscometer BROOKFIELD, DV-E VISCOMETER
  • ⁇ Measurement method of viscosity ratio> A 300 mL sample of the aqueous polyurethane resin composition was collected in a beaker, and after removing bubbles, the temperature was adjusted to 30 ° C. No. 1 on a single cylinder viscometer (BM type viscometer, BROOKFIELD, DV-E VISCOMETER). 3 spindles were attached and immersed in the sample solution up to the immersion liquid mark of the viscometer, taking care not to allow bubbles to adhere. Rpm 6 rpm, the viscosity was read by rotating one minute at 12rpm and 60rpm respectively, V 30,6, V 30,12, and the V 30, 60.
  • Part 1 Evaluation of film formability
  • Part 1 Evaluation of film formability
  • a strip-shaped (3 cm ⁇ 15 cm ⁇ 0.2 cm) alumina plate was immersed in the aqueous polyurethane resin composition and adhered to the mold surface.
  • the film was pulled up at a rate of 100 mm / min, allowed to stand at room temperature for 5 minutes, and then dried in an oven at a predetermined temperature for a predetermined time.
  • the film was peeled off from the alumina plate, and the film thickness at the center was measured.
  • PTMG2000 Polytetramethylene ether glycol (PTG2000, manufactured by Hodogaya Chemical Co., Ltd., molecular weight 2000, OH value 56.5 mgKOH / g)
  • PPG2000 Polypropylene glycol (Sanix PP-2000, manufactured by Sanyo Chemical Industries, Ltd., molecular weight 2000, OH value 54.8 mgKOH / g)
  • PBA2000 polybutylene adipate (Nippolan 4010, molecular weight 2000, OH value 55.5 mgKOH / g)
  • PEA2000 Polyethylene adipate (Nippolan 4040, molecular weight 2000, OH value 56.0 mgKOH / g) 2,2-dimethylolpropionic acid: manufactured by Tokyo Chemical Industry Co., Ltd.
  • Neopentyl glycol manufactured by Tokyo Chemical Industry Co., Ltd. trimethylolpropane: manufactured by Tokyo Chemical Industry Co., Ltd. 4,4′-diphenylmethane diisocyanate: Millionate MT, Nippon Polyurethane Industry Co., Ltd. Company-made isophorone diisocyanate: Tokyo Chemical Industry Co., Ltd. 1,6-hexamethylene diisocyanate: Tokyo Chemical Industry Co., Ltd.
  • nonionic surfactant Polyoxyethylene lauryl ether (Nonion K-220, NOF Corporation, HLB16 .5)
  • Thickener SN thickener 660T (urethane associative thickener, manufactured by San Nopco)
  • Example 1 [Prepolymer synthesis] 300 parts by weight of PTMG2000 was added to a reactor equipped with a stirring blade, a heating device and a reflux condenser, heated to 120 ° C., and dehydrated under reduced pressure for 60 minutes. After cooling to 80 ° C., 17.4 parts by weight of 1,6-hexamethylene diisocyanate was added and reacted for 3 hours. Subsequently, 7.2 parts by weight of 2,2-dimethylolpropionic acid, 22.0 parts by weight of neopentyl glycol, 103.7 parts by weight of 4,4′-diphenylmethane diisocyanate and 193.0 parts by weight of methyl ethyl ketone were added for 3 hours. Reaction, prepolymer no. 1 (PP No. 1) was synthesized. Table 1 shows the blending during prepolymer synthesis.
  • aqueous polyurethane resin composition As shown in Table 2, 2.8 parts by weight of triethylamine and 3.2 parts by weight of a nonionic surfactant were added to 143.2 parts by weight of deionized water, and this solution was synthesized by [Prepolymer Synthesis]. 300.0 parts by weight of prepolymer (PP No. 1) was added dropwise with stirring, and emulsified and dispersed. Subsequently, 20.0 parts by weight of a 10% piperazine aqueous solution (2.0 parts by weight as piperazine) was added, and the chain was extended by stirring at room temperature for 30 minutes to obtain an emulsion. Finally, the obtained emulsion was desolvated and adjusted with deionized water to obtain an aqueous polyurethane resin composition having a resin solid content concentration of 60.0% by weight.
  • Examples 2 to 9 In the same manner as in Example 1, prepolymers (PP Nos. 1 to 7) were synthesized according to the formulation described in Table 1. The obtained prepolymer was emulsified and chain-extended under the conditions described in Table 2, and the solvent was removed to obtain aqueous polyurethane resin compositions of Examples 2 to 9. The obtained aqueous polyurethane resin composition is shown in Table 2. About the obtained aqueous polyurethane resin composition, the corrected viscosity and the yield value were measured in the same manner as in Example 1, and the immersion moldability was evaluated under the conditions of drying temperature and drying time shown in Table 3 (Part 1: Film). Evaluation of film formability) was performed. The results are shown in Table 3 as Evaluation Examples 2 to 10.
  • Examples 10-13 In the same manner as in Example 1, prepolymers (PP No. 8 and No. 9) were synthesized according to the formulation described in Table 1. The obtained prepolymer was emulsified and chain-extended under the conditions described in Table 2, and then the solvent was removed and a thickener was added to obtain aqueous polyurethane resin compositions of Examples 10 to 13. The obtained aqueous polyurethane resin composition is shown in Table 2. About the obtained water-based polyurethane resin composition, it carried out similarly to Example 1, measured the corrected viscosity and the yield value, and also measured the viscosity ratio 1 and the viscosity ratio 2 according to the measuring method of a viscosity ratio. Subsequently, immersion moldability was evaluated (part 2) under the conditions of drying temperature and drying time shown in Table 4. The results are shown in Table 4 as Evaluation Examples 11 to 14.
  • Comparative Examples 1-7 In the same manner as in Example 1, prepolymers (PP Nos. 1, 3, 10 to 13) were synthesized according to the formulation shown in Table 1. The obtained prepolymer was emulsified and chain-extended under the conditions described in Table 5 to obtain aqueous polyurethane resin compositions of Comparative Examples 1 to 6. In Comparative Example 7, the aqueous polyurethane resin was used for thickening during emulsification. A composition could not be obtained. The obtained aqueous polyurethane resin composition is shown in Table 5.
  • Comparative Example 1 Comparative Example 2 and Comparative Example 4, the resin solids concentration was low with respect to the average particle size (depending on the amount of 2,2-dimethylolpropionic acid used), and as a result, the corrected viscosity was 100 mPa.s. It was as low as less than s, and a sufficient film thickness could not be obtained.
  • Comparative Example 3 the resin solid content concentration was higher than the average particle size (depending on the amount of 2,2-dimethylolpropionic acid used), and as a result, the corrected viscosity was 3330 mPa.s.
  • the water-based polyurethane resin composition of the present invention can produce a film molded body having a uniform film thickness without bubbles or bubbles even when molded at a high temperature. Therefore, the film molded body can be produced by a simple method using a direct immersion molding method. In particular, it is useful for the production of film moldings such as gloves, finger sack, condoms, medical bags, leather-like sheets, catheters, O-rings and the like. It should be noted that the entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2009-35795 and Japanese Patent Application No. 2009-35796 filed on February 18, 2009 are incorporated herein by reference. It shall be incorporated as disclosure.

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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)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

L'invention porte sur une composition aqueuse de résine de polyuréthane qui comprend à la fois une résine aqueuse de polyuréthane préparée à partir d'un polyisocyanate et d'un composé polyhydroxylé et un tensioactif non ionique et qui a une teneur en résine supérieure ou égale à 50 % en poids (en termes de teneur en matière solide), une viscosité corrigée de 100 à 2000 mPa.s telle que définie par la formule (1) et une limite apparente d'élasticité supérieure ou égale à 200 mPa telle que définie par la formule (2) : viscosité corrigée V9 = 2V'12 – V'6 (1) limite apparente d'élasticité Y = 12(V'6 – V'12) (2) [dans lesquelles V'6 est une viscosité (mPa.s) telle que déterminée à l'aide d'un viscosimètre de type BM avec un mobile N°3 à une température de liquide de 30°C et une vitesse de rotation de 6 tours/min; et V'12 est une viscosité (mPa.s) telle que déterminée à l'aide d'un viscosimètre de type BM avec un mobile n°3 à une température de liquide de 30°C et une vitesse de rotation de 12 tours/min]. En outre, la composition aqueuse de résine de polyuréthane est caractérisée en ce que la résine aqueuse de polyuréthane satisfait aux exigences (A) et (B) : (A) le diisocyanate de diphénylméthane représente au moins 50 % en poids du polyisocyanate et (B) la résine aqueuse de polyuréthane contient des groupes hydroxyles à hauteur de 0,03 à 0,30 mmol par g de la résine (en termes de matière solide).
PCT/JP2010/052377 2009-02-18 2010-02-17 Composition aqueuse de résine de polyuréthane et articles de type films l'utilisant WO2010095665A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010215897A (ja) * 2009-02-18 2010-09-30 Tosoh Corp 水性ポリウレタン樹脂組成物およびこれを用いたフィルム成型体
CN102424704A (zh) * 2011-08-30 2012-04-25 吴江市北厍盛源纺织品助剂厂 改性的水分散多异氰酸酯
JP2016117801A (ja) * 2014-12-19 2016-06-30 東洋インキＳｃホールディングス株式会社 接着剤組成物、積層体、および積層体の製造方法
CN111132570A (zh) * 2017-09-14 2020-05-08 Dic株式会社 手套的制造方法
EP3892144A4 (fr) * 2018-12-07 2022-01-26 DIC Corporation Gant

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JPS52155627A (en) * 1976-06-22 1977-12-24 Sanyo Chem Ind Ltd Film-forming urethane emulsion
JPH03160019A (ja) * 1989-11-20 1991-07-10 Dainippon Ink & Chem Inc ポリウレタンポリ尿素の製造方法
JPH05125349A (ja) * 1991-11-07 1993-05-21 Dai Ichi Kogyo Seiyaku Co Ltd 接着剤組成物
JP2000096457A (ja) * 1998-09-22 2000-04-04 Kuraray Co Ltd 感熱ゲル化性ポリウレタン系エマルジョンおよびその製造方法
JP2002256145A (ja) * 2001-03-01 2002-09-11 Okamoto Ind Inc コンドーム用アニオン性水系ポリウレタン樹脂組成物およびコンドームの製造方法
JP2005239841A (ja) * 2004-02-25 2005-09-08 Sanyo Chem Ind Ltd 水系ポリウレタン樹脂エマルション
JP2006096852A (ja) * 2004-09-29 2006-04-13 Sanyo Chem Ind Ltd 水系ポリウレタン樹脂エマルション
JP2007270036A (ja) * 2006-03-31 2007-10-18 Sanyo Chem Ind Ltd ポリウレタン樹脂水性分散体

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JPS52155627A (en) * 1976-06-22 1977-12-24 Sanyo Chem Ind Ltd Film-forming urethane emulsion
JPH03160019A (ja) * 1989-11-20 1991-07-10 Dainippon Ink & Chem Inc ポリウレタンポリ尿素の製造方法
JPH05125349A (ja) * 1991-11-07 1993-05-21 Dai Ichi Kogyo Seiyaku Co Ltd 接着剤組成物
JP2000096457A (ja) * 1998-09-22 2000-04-04 Kuraray Co Ltd 感熱ゲル化性ポリウレタン系エマルジョンおよびその製造方法
JP2002256145A (ja) * 2001-03-01 2002-09-11 Okamoto Ind Inc コンドーム用アニオン性水系ポリウレタン樹脂組成物およびコンドームの製造方法
JP2005239841A (ja) * 2004-02-25 2005-09-08 Sanyo Chem Ind Ltd 水系ポリウレタン樹脂エマルション
JP2006096852A (ja) * 2004-09-29 2006-04-13 Sanyo Chem Ind Ltd 水系ポリウレタン樹脂エマルション
JP2007270036A (ja) * 2006-03-31 2007-10-18 Sanyo Chem Ind Ltd ポリウレタン樹脂水性分散体

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010215897A (ja) * 2009-02-18 2010-09-30 Tosoh Corp 水性ポリウレタン樹脂組成物およびこれを用いたフィルム成型体
CN102424704A (zh) * 2011-08-30 2012-04-25 吴江市北厍盛源纺织品助剂厂 改性的水分散多异氰酸酯
JP2016117801A (ja) * 2014-12-19 2016-06-30 東洋インキＳｃホールディングス株式会社 接着剤組成物、積層体、および積層体の製造方法
CN111132570A (zh) * 2017-09-14 2020-05-08 Dic株式会社 手套的制造方法
EP3892144A4 (fr) * 2018-12-07 2022-01-26 DIC Corporation Gant
US12082634B2 (en) 2018-12-07 2024-09-10 Dic Corporation Glove

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