WO2013035461A1 - Polyurethane film and film processed article obtained using same - Google Patents

Polyurethane film and film processed article obtained using same Download PDF

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Publication number
WO2013035461A1
WO2013035461A1 PCT/JP2012/069573 JP2012069573W WO2013035461A1 WO 2013035461 A1 WO2013035461 A1 WO 2013035461A1 JP 2012069573 W JP2012069573 W JP 2012069573W WO 2013035461 A1 WO2013035461 A1 WO 2013035461A1
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WO
WIPO (PCT)
Prior art keywords
polyurethane
mass
parts
emulsifier
film
Prior art date
Application number
PCT/JP2012/069573
Other languages
French (fr)
Japanese (ja)
Inventor
定 永浜
北田　満
Original Assignee
Dic株式会社
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Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to CN201280043936.1A priority Critical patent/CN103781848B/en
Priority to JP2012552972A priority patent/JP5206912B1/en
Publication of WO2013035461A1 publication Critical patent/WO2013035461A1/en

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Classifications

    • 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
    • C08G18/08—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
    • C08G18/08—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
    • C08G18/28—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
    • C08G18/70—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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • 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

Definitions

  • the present invention relates to a polyurethane film that can be used in the manufacture of film processed products such as gloves, various tubes, and contraceptives.
  • Polyurethane is used in the manufacture of various molded articles such as gloves, for example, because it can form a cured product such as a film or sheet having relatively good flexibility.
  • gloves and medical tubes that are very flexible and excellent in texture are demanded by the industry as high-value-added products, and polyurethanes that can satisfy these characteristics are being developed.
  • polyurethane film examples include a polyurethane film obtained by using an aqueous polyurethane emulsion composition containing a predetermined amount of polyisocyanate, polyester polyol, ionic compound, chain extender, water, and solvent. It is known (for example, refer to Patent Document 1).
  • the polyurethane film obtained using the aqueous polyurethane emulsion composition has a hard texture, it may be difficult to use it for the production of gloves or the like that require a particularly soft texture.
  • a solvent-based polyurethane composition has been conventionally used for the production of the gloves and the like, but in recent years, the use of a water-based polyurethane composition has been studied from the viewpoint of reducing environmental burden.
  • polyurethane composition in which polyurethane is stably dispersed in the aqueous medium for example, a polyurethane composition having a hydrophilic group in an amount sufficient to impart water dispersibility, or a polyurethane having no hydrophilic group is used as an emulsifier.
  • a polyurethane composition stably dispersed in an aqueous medium is known.
  • a typical carboxyl group as the hydrophilic group can be a cross-linking point when forming a polyurethane film
  • a polyurethane film having a large number of hydrophilic groups such as the carboxyl group is combined with a crosslinking agent to form a polyurethane film.
  • the resulting polyurethane film has a high crosslink density, and as a result, it may cause a significant decrease in flexibility. .
  • the polyurethane can be stably added to the aqueous medium unless a certain amount of emulsifier is used. It is difficult to disperse, and when the amount of the emulsifier used is increased, the strength may be significantly reduced, such as tearing when the polyurethane film is rubbed.
  • the problem to be solved by the present invention is to provide a polyurethane film having a level of strength and a flexible texture that does not cause tearing due to, for example, rubbing.
  • the present inventors have used a polyurethane having a polyoxyethylene structure at the end and having a specific acid value, and combined a very small amount of an emulsifier with the polyurethane. It has been found that the above problem can be solved only when it is used.
  • the present invention comprises a polyurethane (A) having a polyoxyethylene structure at the terminal and having an acid value of 0.1 to 10, an emulsifier (B), and an aqueous medium (C), and the emulsifier (B).
  • the present invention relates to a polyurethane film obtained by using a polyurethane composition (D) having a ratio of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A), and a film processed product obtained by using the polyurethane film It is.
  • the polyurethane film of the present invention can achieve both high strength and excellent flexibility, it can produce various processed film products including, for example, gloves, tubes such as medical tubes, and contraceptives such as condoms. Can be used.
  • the polyurethane film of the present invention comprises a polyurethane (A) having a polyoxyethylene structure at the terminal and an acid value of 0.1 to 10, an emulsifier (B), an aqueous medium (C), and other additives as required. And a polyurethane composition (D) having a content of the emulsifier (B) of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A).
  • the polyurethane film of the present invention can be produced, for example, by coating the polyurethane composition (D) on the surface of a release film, and then immersing the coating in a coagulant containing a metal salt and drying.
  • the method of applying the polyurethane composition (D) to the release film examples include a knife coater method, a spray method, a curtain coater method, a flow coater method, a roll coater method, and a brush coating method.
  • the polyurethane composition (D) preferably has a viscosity in the range of 50 mPa ⁇ s to 10,000 mPa ⁇ s, and has a viscosity of 1,000 mPa ⁇ s to 3,000 mPa ⁇ s. More preferably.
  • the viscosity of the polyurethane composition (D) can be adjusted as appropriate depending on the amount of solvent used and the use of an associative thickener.
  • a coagulant used when producing the polyurethane film for example, a metal salt or an aqueous solution thereof can be preferably used.
  • metal salt for example, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, sodium chloride and the like can be used.
  • the metal salt previously dispersed in a solvent can also be used as a coagulant.
  • the solvent capable of dissolving the metal salt or acid for example, water, methanol, ethanol, isopropanol or the like can be used.
  • the metal salt contained in the coagulant is preferably contained in an amount of about 1% by mass to 50% by mass, and preferably in the range of 1% by mass to 20% by mass, with respect to the total amount of the coagulant. Washing the film is preferable because the metal salt remaining on the surface can be easily removed with water.
  • a coagulant containing conventionally known formic acid, acetic acid or the like together with the metal salt may be used.
  • the time for immersing the coated material in the coagulant containing the metal salt is preferably about 1 to 10 minutes.
  • the coagulant preferably has a temperature of about 5 ° C. to 60 ° C.
  • the coated material is dried at a temperature of 50 ° C. to 150 ° C. for about 1 minute to 1 hour, whereby a solidified polyurethane film can be formed on the surface of the release film.
  • polyurethane film of the present invention can also be produced by applying the polyurethane composition (D) to the surface of the release film and then drying, in addition to the method described above.
  • Examples of the method for drying the coated product of the polyurethane composition (D) include a method of drying at a temperature of 50 ° C. to 150 ° C. for about 1 minute to 1 hour.
  • the polyurethane film obtained by the above method preferably has a thickness of about 0.5 ⁇ m to 300 ⁇ m from the viewpoint of maintaining good flexibility. In order to achieve both the flexibility and particularly excellent strength, the thickness is more preferably about 40 ⁇ m to 200 ⁇ m.
  • the polyurethane film obtained by the above method has very excellent flexibility as described above, for example, manufacture of various gloves including medical use, manufacture of various tubes such as medical tubes, condoms, etc. It can be suitably used for the production of various film processed products including contraceptives.
  • Examples of a method for producing a film processed product having a predetermined shape, such as a glove or a tube made of the polyurethane film include the following methods.
  • the hand mold, the tube mold, etc. are first immersed in the coagulant containing the metal salt, and then dried as necessary. A metal salt contained in the coagulant is adhered to the surface of the material.
  • the surface is washed with water and dried to form a solidified polyurethane film on the surface of the hand mold or the like.
  • the hand mold or tube mold When the hand mold or tube mold is immersed in the coagulant, it may be at room temperature (about 25 ° C.), but may be heated to approximately 30 ° C. to 70 ° C. Further, the coagulant may be at room temperature (about 25 ° C.) as in the hand mold and the like, but when the hand mold or the like is warmed, it is heated to approximately 30 ° C. to 70 ° C. May be.
  • the hand shape or tube shape may be preliminarily equipped with a glove-like material or a tubular material made of knitted material such as nylon fiber.
  • the glove-like article is dried as necessary. Impregnation of the coagulant into an object or the like.
  • the surface is washed with water and dried, so that a glove made of a polyurethane film coagulated on the surface of the glove-like material or the like is obtained.
  • a glove made of a polyurethane film having a shape corresponding to the hand mold or the like can be obtained.
  • it can manufacture by the method similar to the above except using the tubular thing which consists of the said pipe
  • the knitted fabric is not limited to the nylon fiber, but may be made of polyester fiber, aramid fiber, cotton or the like. Moreover, the textile fabric which consists of the said fiber can also be used instead of the said knitting. Instead of the knitted fabric, a glove-like article or a tubular article made of a resin material such as vinyl chloride, natural rubber, or synthetic rubber can be used.
  • Examples of the polyurethane composition (D) used in the production of the polyurethane film and film processed products such as gloves made of the polyurethane film include polyurethane (A) having an acid value of 0.1 to 10 having a polyoxyethylene structure at the terminal. , Emulsifier (B), and aqueous medium (C), and the content of the emulsifier (B) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A). Is used.
  • polyurethane (A) contained in the polyurethane composition (D) one having a polyoxyethylene structure at the terminal and an acid value of 0.1 to 10 is used.
  • the polyurethane when a polyurethane having an acid value of 0.1 to 10 having no polyoxyethylene structure is used in place of the polyurethane (A), the polyurethane is stably dispersed in the aqueous medium (C). It may not be possible.
  • the polyurethane (A) the one having the polyoxyethylene structure at the molecular end in the range of 0.5% by mass to 10% by mass with respect to the total amount of the polyurethane (A) can be used. It is preferable for stable dispersion in the aqueous medium (C), and it is more preferable to use one having a range of 2% by mass to 8% by mass.
  • polyurethane (A) for example, when a polyurethane having a polyoxyethylene structure at the terminal but having an acid value of 15 is used, a polyurethane film having a flexible texture may not be produced.
  • the polyurethane (A) for example, when a polyurethane having a polyoxyethylene structure at the terminal but having an acid value of 0.05 is used, it can be stably dispersed in the aqueous medium (C). As a result, it may be impossible to produce a polyurethane film having excellent strength such as friction resistance.
  • the polyurethane (A) has an acid value of 0.1 to 6 in order to achieve both the excellent water dispersion stability of the polyurethane composition (D) and the flexible texture and high strength of the polyurethane film. It is preferable to use those having an acid value of 0.1 to 2.
  • the acid value referred to above is derived from the carboxyl group and carboxylate group.
  • the polyurethane (A) has a weight average molecular weight of 5,000 to 500,000 for forming a polyurethane film having both a soft texture and excellent strength such as abrasion resistance. It is preferable to use those having a weight average molecular weight of 20,000 to 300,000.
  • polyurethane (A) it is preferable to use what has another polyether structure other than the polyoxyethylene structure which exists in the said terminal in order to improve the flexible feel of the polyurethane film obtained.
  • the polyether structure is preferably present in a proportion of 70% by mass to 90% by mass with respect to the entire polyurethane (A) from the viewpoint of the balance between flexibility and strength of the polyurethane film.
  • the polyurethane (A) is preferably contained in the range of 10% by mass to 50% by mass with respect to the entire polyurethane composition (D), and is preferably contained in an amount of 20% by mass to 50% by mass.
  • a polyurethane film having a thickness of about 40 ⁇ m to 200 ⁇ m required for applications such as gloves can be produced, which is more preferable.
  • the present invention does not mean that the above-mentioned problem can be solved by simply using the specific polyurethane (A) described above, and is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A). It is important to use a very small amount of emulsifier (B) in the range.
  • the amount of the emulsifier (B) used is not usually an amount that can provide good water dispersion stability of the polyurethane aqueous medium (C).
  • the polyurethane composition (D) for example, when a polyurethane composition in which the amount of the emulsifier (B) used is 6 parts by mass with respect to 100 parts by mass of the polyurethane (A), Even when a specific polyurethane (A) is used, the strength may be lowered.
  • the emulsifier (B) in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A). It is preferable to use in the range of 2 parts by mass.
  • the polyurethane (A) used in the polyurethane composition (D) includes, for example, a polyol (a1) containing a polyol (a1-1) having an acid group, a polyisocyanate (a2), a polyisocyanate having one hydroxyl group at one end. It can be produced by reacting oxyethylene monoalcohol (a4) and, if necessary, a chain extender (a3).
  • the polyurethane (A) is produced by reacting the polyol (a1), the polyisocyanate (a2) and, if necessary, the chain extender (a3) to have a polyurethane having an isocyanate group at the terminal.
  • the polyurethane having an isocyanate group obtained in the above step with the polyoxyethylene monoalcohol (a4) having one hydroxyl group at one end. can do.
  • a polyol (a1-1) having an acid group is used for the purpose of imparting a predetermined acid value to the polyurethane (A).
  • Examples of the polyol (a1-1) having an acid group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylol. Valeric acid or the like can be used. Of these, 2,2'-dimethylolpropionic acid and 2,2'-dimethylolbutanoic acid are preferably used.
  • the carboxyl group may be partially or entirely neutralized with a basic compound to form a carboxylate group.
  • a basic compound examples include organic amines such as ammonia, triethylamine, pyridine, and morpholine, alkanolamines such as monoethanolamine, and metal base compounds including sodium, potassium, lithium, calcium, and the like.
  • the polyol (a1-1) having an acid group is a raw material used for the production of the polyurethane (A), specifically, a polyol (a1), a polyisocyanate (a2), and a polyhydroxy having one hydroxyl group at one end.
  • the oxyethylene monoalcohol (a4) and the chain extender can be used in the range of 0.01% by mass to 3% by mass.
  • a polyether polyol (a1-) can be used from the viewpoint of imparting an even more flexible texture by introducing an ether structure other than the polyoxyethylene structure at the terminal of the polyurethane (A). It is preferable to use 2) in combination.
  • polyether polyol (a1-2) for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
  • the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolethane, Trimethylolpropane and the like can be used.
  • alkylene oxide for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or the like can be used.
  • polyether polyol (a1-2) specifically, polyoxytetramethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, or the like can be used.
  • polyether polyol (a1-2) those having a hydroxyl value of 35 to 230 are preferably used from the viewpoint of imparting excellent strength to the polyurethane film in terms of wear resistance and the like.
  • the polyether polyol (a1-2) is a raw material used for the production of the polyurethane (A), specifically, the polyol (a1), the polyisocyanate (a2), and a polyoxyethylene having one hydroxyl group at one end.
  • the monoalcohol (a4) and the chain extender can be used in the range of 70 to 90% by mass with respect to the total mass.
  • polyol (a1) in addition to the polyol (a1-1) having an acid group and the polyether polyol (a1-2), other polyols can be used in combination as required.
  • Examples of the other polyols include 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-butyl-1,3-propanediol, and 2-methyl-1,3. -Propanediol, 2-butyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-pentyl-2-ethyl-1,3-propanediol, 2 , 2-dibutyl-1,3-propanediol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1, 4-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2-
  • polycarbonate polyol or polyester polyol may be used as long as the effects of the present invention are not impaired.
  • Examples of the polyisocyanate (a2) that can react with the polyol (a1) when producing the polyurethane (A) include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidization.
  • Aromatic polyisocyanates such as diphenylmethane polyisocyanate, aliphatics or fats such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer diisocyanate, norbornene diisocyanate
  • Aromatic cyclic structure Yu polyisocyanates can be used in combination singly used or two or more. Among these, it is preferable to use an aromatic polyisocyanate because a high-strength polyurethane film can be produced.
  • the polyol (a1) and the polyisocyanate (a2) are mixed in the absence of a solvent or in the presence of an organic solvent and reacted at 50 ° C. to 100 ° C. for about 3 to 10 hours. Can be done. Thereby, the polyurethane which has an isocyanate group at the terminal can be manufactured.
  • the reaction between the polyol (a1) and the polyisocyanate (a2) is equivalent to the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (a1) and the isocyanate group of the polyisocyanate (a2).
  • the range is preferably from 1 to 3.5, and more preferably from 1.1 to 2.5.
  • a polyurethane having a relatively high molecular weight and a urea bond can be used for producing a polyurethane film having a further excellent strength.
  • the urea bond can be imparted to the polyurethane by using a chain extender (a3) as necessary when the polyurethane is produced.
  • the polyol (a1) and the polyisocyanate (a2) are mixed in the absence of a solvent or in the presence of an organic solvent, and reacted at 50 ° C. to 100 ° C. for about 3 hours to 10 hours.
  • a polyurethane having an isocyanate group can be produced, and then the polyurethane and the chain extender (a3) can be reacted.
  • the polyurethane (A) it is preferable to use one having a urea bond of 50 mmol / kg to 1,000 mmol / kg from the viewpoint of imparting high strength without impairing the flexible texture of the polyurethane film. It is more preferable to use those in the range of kg to 700 mmol / kg.
  • chain extender (a3) for example, polyamine or the like can be used.
  • polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N A diamine containing one primary amino group and one secondary amino group such as methylaminopropylamine; a polyamine such as diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N Hydrazines such as dimethylhydrazine and 1,6-hexamethylenebishydrazine; dihydrazides such as
  • the chain extender (a3) introduces a urea bond into the polyurethane film, and from the viewpoint of imparting high strength without impairing the flexible texture, the chain extender (a3) is added to the total amount of raw materials used in the production of the polyurethane (A). On the other hand, it is preferably used in the range of 0.5 to 10% by mass.
  • the equivalent ratio [isocyanate group / amino group] of the isocyanate group of the polyurethane having an isocyanate group at the terminal and the amino group of the polyamine is preferably 0.3 to 1, and less than 0.5 to 1. It is more preferable.
  • the step [II] of reacting the polyurethane having an isocyanate group at the terminal obtained in the step [I] with the polyoxyethylene monoalcohol (a4) having one hydroxyl group at one terminal is, for example, an organic solvent for the polyurethane.
  • the solution and the polyoxyethylene monoalcohol (a4) can be mixed and reacted at a temperature of about 50 ° C. to 100 ° C. for about 1 to 5 hours.
  • polyoxyethylene monoalcohol (a4) having one hydroxyl group at one end for example, a part of the hydroxyl groups present at both ends of polyoxyethylene glycol is etherified using monoalcohol or the like, and sealed. It can be used.
  • the monoalcohol for example, methanol, ethanol, propanol, butanol and the like can be used.
  • the polyurethane composition (D) gives more excellent water dispersion stability and improves the flexibility of the polyurethane film.
  • those having a number average molecular weight of 500 to 5,000 are preferably used, and those having a number average molecular weight in the range of 2,000 to 5,000 are particularly preferably used.
  • the emulsifier (B) may be used in a very small amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A). It is important for imparting flexibility and flexibility such as a polyurethane film to be obtained.
  • the emulsifier (B) include fatty acid salts such as sodium oleate, alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, polyoxy Anionic emulsifiers such as ethylene phenyl ether sulfate, alkane sulfonate sodium salt, alkyl diphenyl ether sulfonic acid sodium salt; cationic emulsifiers such as alkyl amine salt, alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt; polyoxyethylene nonyl phenyl Ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene ⁇ Polyoxypropylene copolymer
  • the polyoxyethylene polycyclic phenyl ether sulfate ester salt is used as the anionic emulsifier
  • the polyoxyethylene / polyoxypropylene copolymer is used as the nonionic emulsifier.
  • an anionic emulsifier are more preferable because both an excellent strength and flexibility can be achieved.
  • the polyurethane composition (D) is obtained by dissolving or dispersing the polyurethane (A) and the emulsifier (B) in an aqueous medium (C).
  • Examples of the aqueous medium (C) include water, organic solvents miscible with water, and mixtures thereof.
  • the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycol; And lactams such as N-methyl-2-pyrrolidone.
  • only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
  • the aqueous medium (C) is preferably contained in the range of 5% by mass to 85% by mass to 85% by mass, and in the range of 45% by mass to 90% by mass with respect to the total amount of the polyurethane composition (D). More preferably, it is contained in the range of 45% by mass to 85% by mass.
  • the polyurethane composition (D) is prepared by mixing the polyurethane (A) obtained by the method or an organic solvent solution thereof, the emulsifier (B), and other additives as necessary, and then an aqueous medium.
  • the polyurethane composition (D) in which the polyurethane (A), the emulsifier (B) and the like are dissolved or dispersed in the aqueous medium (C) can be produced.
  • part or all of the acid groups of the polyurethane (A) may be neutralized with the basic compound.
  • the neutralization is preferably performed before supplying the aqueous medium (C).
  • aqueous medium (c1) made of alcohol, such as methanol, ethanol, isopropyl alcohol, or acetone, which is easily miscible with water.
  • the aqueous medium (c1) is preferably used in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the polyurethane (A) before supplying water or simultaneously with water.
  • a machine such as a homogenizer may be used as necessary.
  • the polyurethane composition (D) used in the present invention may contain various additives as necessary.
  • additives for example, associative thickeners and antifoaming agents, urethanization catalysts, silane coupling agents, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent whitening agents, foaming agents, etc.
  • thermoplastic resins thermosetting resins, pigments, dyes, conductivity imparting agents, antistatic agents, moisture permeability improvers, water repellents, oil repellents, hollow foams, crystal water-containing compounds, flame retardants, Water absorbents, moisture absorbents, deodorants, antifungal agents, antiseptics, algae inhibitors, pigment dispersants, antiblocking agents, antihydrolysis agents, vulcanizing agents, vulcanizing catalysts, and surfactants may be used in combination. it can.
  • the associative thickener can be suitably used for adjusting the viscosity of the polyurethane composition (D) and facilitating processing using a coagulant containing a metal salt, such as hydroxyethyl cellulose, methyl cellulose, Cellulose derivatives such as carboxymethyl cellulose, polyacrylate, polyvinyl pyrrolidone, urethane, polyether and the like can be used.
  • a coagulant containing a metal salt such as hydroxyethyl cellulose, methyl cellulose, Cellulose derivatives such as carboxymethyl cellulose, polyacrylate, polyvinyl pyrrolidone, urethane, polyether and the like
  • a urethane type thickener is preferably used in the range of 0.5% by mass to 5% by mass with respect to the total amount of the polyurethane (A).
  • an antifoaming agent such as silicone, mineral oil, polyglycol ether, fatty acid ester, metal soap, or fluorine compound can be used.
  • the polyurethane composition (X) used in the present invention requires durability and flexibility depending on the intended use, for example, a styrene-butadiene copolymer (SBR), a butadiene copolymer (BR) ), Isoprene copolymer (IR), ethylene-propylene-diene copolymer (EPDM), chloroprene polymer (CR), acrylonitrile-butadiene copolymer (NBR), butyl polymer (IIR), natural rubber (NR) ) And the like.
  • SBR styrene-butadiene copolymer
  • BR butadiene copolymer
  • IIR ethylene-propylene-diene copolymer
  • EPDM ethylene-propylene-diene copolymer
  • chloroprene polymer CR
  • NBR acrylonitrile-butadiene copolymer
  • IIR acrylonitrile-butadiene copolymer
  • acrylonitrile-butadiene copolymer for example, a polymer obtained by polymerizing acrylonitrile, butadiene and, if necessary, other vinyl polymers can be used.
  • the polyurethane composition (X) can be used for production of various film processed products such as the polyurethane film, gloves, tubes and contraceptives of the present invention having a soft texture.
  • Example 1 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 306.11 parts by mass, 2,2′- 1.41 parts by mass of dimethylolpropionic acid and 65.44 parts by mass of isophorone diisocyanate were reacted for 3 hours in the presence of 248.64 parts by mass of ethyl acetate.
  • polyether polyol manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • the NCO% is the ratio of the mass of isocyanate groups possessed by polyisocyanate to the total mass of raw materials used in the production of the polyurethane.
  • the coated product was immersed in a normal temperature (approximately 25 ° C.) calcium nitrate aqueous solution adjusted to a concentration of 20% by weight for 3 minutes and then immersed in water for 18 hours.
  • a normal temperature approximately 25 ° C.
  • the coated material was dried in an environment of 70 ° C. for 20 minutes, and further dried in an environment of 120 ° C. for 2 minutes to form a polyurethane film on the surface of the polypropylene film.
  • the polyurethane film was peeled off from the surface of the polypropylene film to obtain a polyurethane film (I-2) having a thickness of 50 ⁇ m.
  • a hand-shaped glove made of nylon fiber knitting was immersed in an aqueous solution of calcium nitrate at room temperature (approximately 25 ° C.) adjusted to a concentration of 20% by mass for 15 seconds. did.
  • the hand mold equipped with the glove-like material was immersed in the urethane resin composition (I-1) for 3 minutes, and further immersed in water for 30 minutes.
  • the immersion material was dried in an environment of 70 ° C. for 20 minutes, and further dried in an environment of 120 ° C. for 30 minutes, thereby forming a hand shape on the surface of the glove-like material to which the hand shape was attached.
  • a polyurethane film (gloves) was formed.
  • the glove (I-3) was obtained by removing the hand-shaped polyurethane film (glove) from the hand mold and glove-like material.
  • Example 2 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, polyether polyol (Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 294.90 parts by mass, 2,2′- 4.69 parts by mass of dimethylolpropionic acid and 72.99 parts by mass of isophorone diisocyanate were reacted in the presence of 248.39 parts by mass of ethyl acetate for 3 hours.
  • polyether polyol Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • a polyurethane film (II-2) and a glove (II-) were prepared in the same manner as in Example 1 except that the polyurethane composition (II-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • Example 3 In a container purged with nitrogen equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 307.62 parts by mass, 2,2′- 1.41 parts by mass of dimethylolpropionic acid and 65.77 parts by mass of isophorone diisocyanate were reacted in the presence of 249.87 parts by mass of ethyl acetate for 3 hours.
  • polyether polyol manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • a polyurethane film (III-2) and a glove (III-) were prepared in the same manner as in Example 1 except that the polyurethane composition (III-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • Example 4 Polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 288.51 parts by mass, 2,2′- in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer 6.56 parts by mass of dimethylolpropionic acid and 77.29 parts by mass of isophorone diisocyanate were reacted for 3 hours in the presence of 248.24 parts by mass of ethyl acetate.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • a polyurethane film (IV-2) and a glove (IV-) were prepared in the same manner as in Example 1 except that the polyurethane composition (IV-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • Example 5 In a container purged with nitrogen equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, polyether polyol (Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 301.67 parts by mass, 2,2′- 1.39 parts by mass of dimethylolpropionic acid and 64.49 parts by mass of isophorone diisocyanate were reacted in the presence of 245.04 parts by mass of ethyl acetate for 3 hours.
  • polyether polyol Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • a polyurethane film (V-2) and a glove (V-) were prepared in the same manner as in Example 1 except that the polyurethane composition (V-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • Example 6 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, polyether polyol (Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 306.11 parts by mass, 2, 2 1.41 parts by mass of '-dimethylolpropionic acid and 65.44 parts by mass of isophorone diisocyanate were reacted for 3 hours in the presence of 248.64 parts by mass of ethyl acetate.
  • polyether polyol Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • a nonionic emulsifier manufactured by Sanyo Chemical Industries, Newpol PE78, polyoxyethylene / polyoxypropylene copolymer, number average molecular weight 10,000, ratio of polyoxyethylene structure 20
  • mass% After adding 3.93 mass and 1.17 mass of triethylamine and mixing, 203.24 mass parts of isopropyl alcohol, 889.26 mass parts of water, and 6.79 mass parts of 80 mass% hydrazine hydrate were added.
  • an aqueous dispersion (A-6 ′) in which the polyurethane (A-6) and the emulsifier were mixed was obtained.
  • a polyurethane film (VI-2) and a glove (VI-) were prepared in the same manner as in Example 1 except that the polyurethane composition (VI-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • Example 7 In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 302.97 parts by mass, 2, 2 4.69 parts by mass of '-dimethylolpropionic acid and 74.60 parts by mass of isophorone diisocyanate were reacted in the presence of 254.84 parts by mass of ethyl acetate for 3 hours.
  • polyether polyol manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • an anionic emulsifier (Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) 3.92 mass and triethylamine 3.89 mass were added to the organic solvent solution of the urethane resin and mixed. Thereafter, 200.24 parts by mass of isopropyl alcohol, 889.46 parts by mass of water and 7.85 parts by mass of 80% by mass hydrated hydrazine were added, and the mixture was stirred to obtain a water dispersion in which polyurethane (A-7) and an emulsifier were mixed. A body (A-7 ′) was obtained.
  • a polyurethane film (VII-2) and a glove (VII-) were prepared in the same manner as in Example 1 except that the polyurethane composition (VII-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • Example 8 Polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 327.63 parts by mass, 2,2′- in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer 1.42 parts by mass of dimethylolpropionic acid and 46.52 parts by mass of isophorone diisocyanate were reacted in the presence of 250.38 parts by mass of ethyl acetate for 3 hours.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • an anionic emulsifier (Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) 3.95 mass and triethylamine 1.18 mass were added to the organic solvent solution of the polyurethane and mixed. Thereafter, 204.66 parts by mass of isopropyl alcohol, 888.22 parts by mass of water, and 1.38 parts by mass of 80% by mass of hydrazine hydrate are added, and the mixture is stirred to obtain an aqueous dispersion in which polyurethane (A-8) and an emulsifier are mixed. (A-8 ′) was obtained.
  • a polyurethane film (VIII-2) and a glove (VIII-) were prepared in the same manner as in Example 1 except that the polyurethane composition (VIII-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • aqueous dispersion (A-9 ′) is aged and desolvated to obtain a polyurethane composition (IX-1) having a nonvolatile content of 40% by mass and containing polyurethane (A-9) having an acid value of 14.8. Obtained.
  • polyurethane film (IX-2) and the gloves (IX-) were prepared in the same manner as in Example 1 except that the polyurethane composition (IX-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • aqueous dispersion (A-10 ′) was aged and removed to obtain a polyurethane composition (X-1) having a nonvolatile content of 40% by mass and containing polyurethane (A-10) having an acid value of 0. .
  • a polyurethane film (X-2) and a glove (X-) were prepared in the same manner as in Example 1 except that the polyurethane composition (X-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • a polyurethane film (XI-2) and a glove (XI-) were prepared in the same manner as in Example 1 except that the polyurethane composition (XI-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • a polyurethane composition (XII-1) having a nonvolatile content of 40% by mass containing polyurethane (A-12) having an acid value of 1.5 is obtained. Obtained.
  • the polyurethane composition (XII-1) was not sufficient in terms of water dispersion stability. Therefore, a polyurethane film (XII-2) or a glove (XII-3) could not be produced using the polyurethane composition (XII-1).
  • the reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
  • a polyurethane film (XIII-2) and a glove (XIII-) were produced in the same manner as in Example 1 except that the polyurethane composition (XIII-1) was used instead of the polyurethane composition (I-1). 3) was produced.
  • A The 300% modulus was less than 12 MPa, and the flexibility was excellent.
  • B 300% modulus was 12 MPa or more and less than 15 MPa, and was excellent in flexibility.
  • the 300% modulus was 15 MPa or more and less than 20 MPa and had good flexibility.
  • the 300% modulus was 20 MPa or more and less than 25 MPa, and it did not have sufficient flexibility.
  • A The number of wear was 4000 times or more and high strength.
  • the number of wears was 3500 times or more and less than 4000 times and had good strength.
  • C The number of wear was 3000 times or more and less than 3500 times and had good strength.
  • D The number of wear was 2500 or more and less than 3000 times, and the strength was not sufficient.
  • Emsifier content ratio indicates the content of the emulsifier with respect to 100 parts by mass of the polyurethane.
  • the “mass ratio of terminal polyoxyethylene structure” indicates the mass ratio of the terminal polyoxyethylene structure to the total amount of polyurethane.
  • the polyurethane films obtained in Examples 1 to 3 each had excellent strength such as flexibility and abrasion resistance. Further, the polyurethane film described in Example 4 in which the acid value of the polyurethane used was slightly higher was provided with excellent strength and good flexibility. Moreover, the polyurethane film of Example 5 in which the content of the emulsifier is slightly higher was provided with good strength and excellent flexibility. Further, the polyurethane film described in Example 6 using a nonionic emulsifier instead of an anionic emulsifier was provided with good strength and excellent flexibility. Further, the water dispersion stability of the polyurethane composition described in Example 7 in which the proportion of the terminal polyoxyethylene structure is 2.5% by mass is good, and the polyurethane film has excellent flexibility and wear resistance. It had strength. Moreover, the polyurethane film described in Example 9 having a slightly lower urea bond amount had good strength and excellent flexibility.
  • the polyurethane film described in Comparative Example 1 using a very high acid value polyurethane was not sufficient in terms of flexibility and strength.
  • the polyurethane film described in Comparative Example 2 using polyurethane having an acid value of 0 was not sufficient in terms of flexibility and strength.
  • the polyurethane film described in Comparative Example 3 using a relatively large amount of emulsifier was not sufficient in terms of flexibility and strength.
  • the polyurethane composition was insufficient in water dispersion stability, and thus a polyurethane film could not be produced using it.
  • the polyurethane film described in Comparative Example 6 using a polyurethane having a polyoxyethylene structure in the molecule, which does not have a polyoxyethylene structure at the terminal was not sufficient in terms of flexibility and strength.

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Abstract

The present invention addresses the problem of providing a polyurethane film that has soft texture and a level of strength sufficient for preventing, for example, rupture due to scratch or the like. The present invention is a polyurethane film which is characterized by being obtained using a polyurethane composition (D) that contains a polyurethane (A) which has a polyoxyethylene structure at an end and an acid value of 0.1-10, an emulsifier (B) and an aqueous medium (C), with the content ratio of the emulsifier (B) being 0.1-5 parts by mass par 100 parts by mass of the polyurethane (A).

Description

ポリウレタンフィルム及びそれを用いて得たフィルム加工品Polyurethane film and processed film product obtained using the same
　本発明は、例えば手袋や各種管、避妊具等のフィルム加工品の製造に使用可能なポリウレタンフィルムに関する。 The present invention relates to a polyurethane film that can be used in the manufacture of film processed products such as gloves, various tubes, and contraceptives.
　ポリウレタンは、比較的良好な柔軟性を備えたフィルムやシート等の硬化物を形成できることから、例えば手袋をはじめとする様々な成形品の製造に使用されている。 Polyurethane is used in the manufacture of various molded articles such as gloves, for example, because it can form a cured product such as a film or sheet having relatively good flexibility.
　特に、手袋や医療用チューブ等には、非常に柔軟で風合いに優れたものが、高付加価値製品として産業界から求められており、かかる特性を満足しうるポリウレタンの開発が進められている。 Especially, gloves and medical tubes that are very flexible and excellent in texture are demanded by the industry as high-value-added products, and polyurethanes that can satisfy these characteristics are being developed.
　前記手袋等の製造に使用可能なポリウレタンフィルムとしては、例えばポリイソシアネートとポリエステルポリオールとイオン性化合物と鎖伸長剤と水と溶剤とを所定量含む水性ポリウレタンエマルジョン組成物を用いて得られるポリウレタンフィルムが知られている（例えば特許文献１参照。）。 Examples of the polyurethane film that can be used in the production of the gloves include a polyurethane film obtained by using an aqueous polyurethane emulsion composition containing a predetermined amount of polyisocyanate, polyester polyol, ionic compound, chain extender, water, and solvent. It is known (for example, refer to Patent Document 1).
　しかし、前記水性ポリウレタンエマルジョン組成物を用いて得られたポリウレタンフィルムは、硬めの風合いを有するため、特に柔軟な風合いが求められる手袋等の製造に使用することは困難な場合があった。 However, since the polyurethane film obtained using the aqueous polyurethane emulsion composition has a hard texture, it may be difficult to use it for the production of gloves or the like that require a particularly soft texture.
　ところで、前記手袋等の製造には、従来、溶剤系ポリウレタン組成物が使用されていたが、近年、環境負荷低減の観点から、水系のポリウレタン組成物の使用が検討されている。 Incidentally, a solvent-based polyurethane composition has been conventionally used for the production of the gloves and the like, but in recent years, the use of a water-based polyurethane composition has been studied from the viewpoint of reducing environmental burden.
　前記水性媒体中にポリウレタンが安定分散したポリウレタン組成物としては、例えば水分散性を付与するに足りる量の親水性基を有するポリウレタン組成物や、親水性基を有さないポリウレタンを乳化剤等を用いて水性媒体中に安定分散したポリウレタン組成物等が知られている。 As the polyurethane composition in which polyurethane is stably dispersed in the aqueous medium, for example, a polyurethane composition having a hydrophilic group in an amount sufficient to impart water dispersibility, or a polyurethane having no hydrophilic group is used as an emulsifier. A polyurethane composition stably dispersed in an aqueous medium is known.
　しかし、前記親水性基として代表的なカルボキシル基等は、ポリウレタンフィルムを形成する際の架橋点となりうるため、前記カルボキシル基等の親水性基を多く有するポリウレタン組成物を架橋剤と組み合わせポリウレタンフィルムを製造する場合や、前記ポリウレタン組成物を金属塩によって凝固させることでポリウレタンフィルムを製造する場合に、得られるポリウレタンフィルムの架橋密度が高くなり、その結果、柔軟性の著しい低下を引き起こす場合があった。 However, since a typical carboxyl group as the hydrophilic group can be a cross-linking point when forming a polyurethane film, a polyurethane film having a large number of hydrophilic groups such as the carboxyl group is combined with a crosslinking agent to form a polyurethane film. When producing a polyurethane film by coagulating the polyurethane composition with a metal salt, the resulting polyurethane film has a high crosslink density, and as a result, it may cause a significant decrease in flexibility. .
　また、前記親水性基を有さないポリウレタンを、乳化剤等を用いて水性媒体中に分散するポリウレタン組成物については、やはり一定量以上の乳化剤を用いなければ、ポリウレタンを水性媒体中に安定的に分散することは難しく、また、前記乳化剤の使用量が増加すると、ポリウレタンフィルムが擦過された場合に破れを引き起こす等、強度の著しい低下を引き起こす場合があった。 In addition, regarding a polyurethane composition in which the polyurethane having no hydrophilic group is dispersed in an aqueous medium using an emulsifier or the like, the polyurethane can be stably added to the aqueous medium unless a certain amount of emulsifier is used. It is difficult to disperse, and when the amount of the emulsifier used is increased, the strength may be significantly reduced, such as tearing when the polyurethane film is rubbed.
　このように、ポリウレタン組成物の優れた水分散安定性とともに、得られるポリウレタンフィルム等の優れた柔軟性と強度とを両立することは、技術的に困難であり、未だ見出されていないのが実情である。 Thus, it is technically difficult to achieve both the excellent water dispersion stability of the polyurethane composition and the excellent flexibility and strength of the resulting polyurethane film, etc., and has not yet been found. It is a fact.
特表２００８－５０６８３０号公報Special table 2008-506830 gazette
　本発明が解決しようとする課題は、例えば擦過等によって破れ等を引き起こさないレベルの強度と柔軟な風合いとを備えたポリウレタンフィルムを提供することである。 The problem to be solved by the present invention is to provide a polyurethane film having a level of strength and a flexible texture that does not cause tearing due to, for example, rubbing.
　本発明者等は、上記課題を解決すべく検討した結果、末端にポリオキシエチレン構造を有し、かつ特定の酸価を有するポリウレタンを使用するとともに、前記ポリウレタンに対してごく微量の乳化剤を組み合わせ使用した場合に限り、上記課題を解決できることを見出した。 As a result of studies to solve the above problems, the present inventors have used a polyurethane having a polyoxyethylene structure at the end and having a specific acid value, and combined a very small amount of an emulsifier with the polyurethane. It has been found that the above problem can be solved only when it is used.
　すなわち、本発明は、末端にポリオキシエチレン構造を有する酸価０．１～１０のポリウレタン（Ａ）、乳化剤（Ｂ）、及び、水性媒体（Ｃ）を含有し、前記乳化剤（Ｂ）の含有割合が、前記ポリウレタン（Ａ）１００質量部に対して０．１質量部～５質量部であるポリウレタン組成物（Ｄ）を用いて得られるポリウレタンフィルム及びそれを用いて得られるフィルム加工品に関するものである。 That is, the present invention comprises a polyurethane (A) having a polyoxyethylene structure at the terminal and having an acid value of 0.1 to 10, an emulsifier (B), and an aqueous medium (C), and the emulsifier (B). The present invention relates to a polyurethane film obtained by using a polyurethane composition (D) having a ratio of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A), and a film processed product obtained by using the polyurethane film It is.
　本発明のポリウレタンフィルムであれば、高強度と優れた柔軟性とを両立できることから、例えば手袋をはじめ、医療用チューブ等の管、コンドーム等の避妊具をはじめとする様々なフィルム加工品の製造に使用することが可能である。 Since the polyurethane film of the present invention can achieve both high strength and excellent flexibility, it can produce various processed film products including, for example, gloves, tubes such as medical tubes, and contraceptives such as condoms. Can be used.
　本発明のポリウレタンフィルムは、末端にポリオキシエチレン構造を有する酸価０．１～１０のポリウレタン（Ａ）、乳化剤（Ｂ）、水性媒体（Ｃ）、及び、必要に応じてその他の添加剤を含有し、前記乳化剤（Ｂ）の含有割合が、前記ポリウレタン（Ａ）１００質量部に対して０．１質量部～５質量部であるポリウレタン組成物（Ｄ）を用いて得られるものである。 The polyurethane film of the present invention comprises a polyurethane (A) having a polyoxyethylene structure at the terminal and an acid value of 0.1 to 10, an emulsifier (B), an aqueous medium (C), and other additives as required. And a polyurethane composition (D) having a content of the emulsifier (B) of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A).
　本発明のポリウレタンフィルムは、例えば前記ポリウレタン組成物（Ｄ）を離型フィルムの表面に塗布し、次いで、その塗布物を金属塩を含む凝固剤に浸漬し乾燥することによって製造することができる。 The polyurethane film of the present invention can be produced, for example, by coating the polyurethane composition (D) on the surface of a release film, and then immersing the coating in a coagulant containing a metal salt and drying.
　前記ポリウレタン組成物（Ｄ）を離型フィルムに塗布する方法としては、例えばナイフコーター法、スプレー法、カーテンコーター法、フローコーター法、ロールコーター法、刷毛塗り法等が挙げられる。その際、前記ポリウレタン組成物（Ｄ）としては、５０ｍＰａ・ｓ～１０，０００ｍＰａ・ｓの範囲の粘度であることが好ましく、１，０００ｍＰａ・ｓ～３，０００ｍＰａ・ｓの粘度であるものを使用することがより好ましい。前記ポリウレタン組成物（Ｄ）の粘度は、溶媒の使用量や会合型増粘剤の使用などによって適宜調整できる。 Examples of the method of applying the polyurethane composition (D) to the release film include a knife coater method, a spray method, a curtain coater method, a flow coater method, a roll coater method, and a brush coating method. At that time, the polyurethane composition (D) preferably has a viscosity in the range of 50 mPa · s to 10,000 mPa · s, and has a viscosity of 1,000 mPa · s to 3,000 mPa · s. More preferably. The viscosity of the polyurethane composition (D) can be adjusted as appropriate depending on the amount of solvent used and the use of an associative thickener.
　前記ポリウレタンフィルムを製造する際に使用する凝固剤としては、例えば金属塩やその水溶液を好適に使用することができる。 As a coagulant used when producing the polyurethane film, for example, a metal salt or an aqueous solution thereof can be preferably used.
　前記金属塩としては、例えば硝酸カルシウムや塩化カルシウム、硝酸亜鉛、塩化亜鉛、酢酸マグネシウム、硫酸アルミニウム、塩化ナトリウム等を使用することができる。 As the metal salt, for example, calcium nitrate, calcium chloride, zinc nitrate, zinc chloride, magnesium acetate, aluminum sulfate, sodium chloride and the like can be used.
　また、前記金属塩は、予め溶媒に分散等したものを凝固剤として使用することもできる。 The metal salt previously dispersed in a solvent can also be used as a coagulant.
　前記金属塩や酸を溶解しうる溶媒としては、例えば水、メタノール、エタノール、イソプロパノール等を使用することができる。前記凝固剤中に含まれる金属塩は、前記凝固剤の全量に対して１質量％～５０質量％程度含まれることが好ましく、１質量％～２０質量％の範囲であることが、得られるポリウレタンフィルムを洗浄することによって、その表面に残存した前記金属塩等を水で除去しやすいため好ましい。 As the solvent capable of dissolving the metal salt or acid, for example, water, methanol, ethanol, isopropanol or the like can be used. The metal salt contained in the coagulant is preferably contained in an amount of about 1% by mass to 50% by mass, and preferably in the range of 1% by mass to 20% by mass, with respect to the total amount of the coagulant. Washing the film is preferable because the metal salt remaining on the surface can be easily removed with water.
　また、本発明では、凝固剤として前記金属塩とともに、従来知られる蟻酸や酢酸等を含有するものを使用してもよい。 Further, in the present invention, a coagulant containing conventionally known formic acid, acetic acid or the like together with the metal salt may be used.
　前記金属塩を含有する凝固剤中に前記塗布物を浸漬する時間は、概ね１分～１０分であることが好ましい。また、前記凝固剤は、概ね５℃～６０℃の温度であることが好ましい。 The time for immersing the coated material in the coagulant containing the metal salt is preferably about 1 to 10 minutes. The coagulant preferably has a temperature of about 5 ° C. to 60 ° C.
　前記浸漬後、前記塗布物を５０℃～１５０℃の温度で１分～１時間程度乾燥することによって、離型フィルム表面に凝固したポリウレタンフィルムが形成することができる。 After the immersion, the coated material is dried at a temperature of 50 ° C. to 150 ° C. for about 1 minute to 1 hour, whereby a solidified polyurethane film can be formed on the surface of the release film.
　また、本発明のポリウレタンフィルムは、前記した方法以外に、ポリウレタン組成物（Ｄ）を離型フィルムの表面に塗布し、次いで乾燥することによって製造することもできる。 Further, the polyurethane film of the present invention can also be produced by applying the polyurethane composition (D) to the surface of the release film and then drying, in addition to the method described above.
　前記ポリウレタン組成物（Ｄ）を離型フィルムに塗布する方法としては、前記した方法と同様の方法を採用することができる。 As the method for applying the polyurethane composition (D) to the release film, the same method as described above can be employed.
　前記ポリウレタン組成物（Ｄ）の塗布物を乾燥する方法としては、５０℃～１５０℃の温度で１分～１時間程度乾燥する方法が挙げられる。 Examples of the method for drying the coated product of the polyurethane composition (D) include a method of drying at a temperature of 50 ° C. to 150 ° C. for about 1 minute to 1 hour.
　前記方法で得たポリウレタンフィルムは、良好な柔軟性を維持する観点から、概ね０．５μｍ～３００μｍの厚さであることが好ましい。また、前記柔軟性と特に優れた強度とを両立する場合には、４０μｍ～２００μｍ程度の厚さであることがより好ましい。 The polyurethane film obtained by the above method preferably has a thickness of about 0.5 μm to 300 μm from the viewpoint of maintaining good flexibility. In order to achieve both the flexibility and particularly excellent strength, the thickness is more preferably about 40 μm to 200 μm.
　前記方法で得られたポリウレタンフィルムは、前記のとおり非常に優れた柔軟性を有することから、例えば医療用をはじめとする各種手袋の製造や、医療用チューブ等の各種管の製造、コンドーム等の避妊具をはじめとする各種フィルム加工品の製造に好適に使用することが可能である。 Since the polyurethane film obtained by the above method has very excellent flexibility as described above, for example, manufacture of various gloves including medical use, manufacture of various tubes such as medical tubes, condoms, etc. It can be suitably used for the production of various film processed products including contraceptives.
　前記ポリウレタンフィルムからなる手袋や管等のような、所定の形状を有するフィルム加工品を製造する方法としては、例えば以下の方法が挙げられる。 Examples of a method for producing a film processed product having a predetermined shape, such as a glove or a tube made of the polyurethane film, include the following methods.
　前記凝固剤を用いて手袋等を製造する場合であれば、はじめに手型、管型等を前記金属塩を含有する凝固剤中に浸漬した後、必要に応じて乾燥することで、前記手型等の表面に前記凝固剤中に含まれる金属塩を付着させる。 In the case of producing gloves using the coagulant, the hand mold, the tube mold, etc. are first immersed in the coagulant containing the metal salt, and then dried as necessary. A metal salt contained in the coagulant is adhered to the surface of the material.
　次いで、前記手型等を前記ポリウレタン組成物（Ｄ）中に浸漬した後、その表面を水で洗浄し、乾燥することで、前記手型等の表面に凝固したポリウレタンフィルムが形成される。 Next, after the hand mold or the like is immersed in the polyurethane composition (D), the surface is washed with water and dried to form a solidified polyurethane film on the surface of the hand mold or the like.
　次いで、前記手型等から前記ポリウレタンフィルムを剥離することで、前記手型等に応じた形状をしたポリウレタンフィルムからなる手袋等を得ることができる。前記管を製造する場合も、前記管型を使用すること以外は前記と同様の方法で製造することができる。 Next, by peeling off the polyurethane film from the hand mold or the like, a glove made of a polyurethane film having a shape corresponding to the hand mold or the like can be obtained. Also when manufacturing the said pipe | tube, it can manufacture by the method similar to the above except using the said pipe | tube type.
　前記手型や管型は、凝固剤中に浸漬する際に、常温（２５℃程度）であってもよいが、概ね３０℃～７０℃に加温されていてもよい。また、前記凝固剤も、前記手型等と同様に常温（２５℃程度）であってもよいが、前記手型等が加温されている場合には、概ね３０℃～７０℃に加温されていてもよい。 When the hand mold or tube mold is immersed in the coagulant, it may be at room temperature (about 25 ° C.), but may be heated to approximately 30 ° C. to 70 ° C. Further, the coagulant may be at room temperature (about 25 ° C.) as in the hand mold and the like, but when the hand mold or the like is warmed, it is heated to approximately 30 ° C. to 70 ° C. May be.
　また、前記手型や管型には、予めナイロン繊維等の編み物からなる手袋状物や管状物が装着されていてもよい。 Further, the hand shape or tube shape may be preliminarily equipped with a glove-like material or a tubular material made of knitted material such as nylon fiber.
　具体的には、はじめに、前記編み物からなる手袋状物等が装着された手型等を、前記金属塩を含有する凝固剤中に浸漬した後、必要に応じて乾燥することで、前記手袋状物等に前記凝固剤を含浸する。 Specifically, first, after immersing a hand mold or the like to which the glove-like article made of the knitted material is attached in a coagulant containing the metal salt, the glove-like article is dried as necessary. Impregnation of the coagulant into an object or the like.
　次いで、前記手型等を前記ポリウレタン組成物（Ｄ）中に浸漬した後、その表面を水で洗浄し、乾燥することで、前記手袋状物等の表面に凝固したポリウレタンフィルムからなる手袋等が形成し、前記手型及び手袋状物等から前記手袋等を剥離することで、前記手型等に応じた形状をしたポリウレタンフィルムからなる手袋等を得ることができる。前記管を製造する場合も、前記管型、及び、ナイロン繊維等の編み物からなる管状物を使用すること以外は、前記と同様の方法で製造することができる。 Next, after the hand mold or the like is immersed in the polyurethane composition (D), the surface is washed with water and dried, so that a glove made of a polyurethane film coagulated on the surface of the glove-like material or the like is obtained. By forming and peeling the glove from the hand mold and glove-like material, a glove made of a polyurethane film having a shape corresponding to the hand mold or the like can be obtained. Also when manufacturing the said pipe | tube, it can manufacture by the method similar to the above except using the tubular thing which consists of the said pipe | tube type and knitted materials, such as a nylon fiber.
　前記編み物は、前記ナイロン繊維に限らず、ポリエステル繊維やアラミド繊維、綿等によって構成されたものを使用することができる。また、前記編み物の代わりに、前記繊維からなる織物を使用することもできる。また、前記編み物の代わりに、塩化ビニル、天然ゴム、合成ゴム等の樹脂材料からなる手袋状物や管状物を使用することもできる。 The knitted fabric is not limited to the nylon fiber, but may be made of polyester fiber, aramid fiber, cotton or the like. Moreover, the textile fabric which consists of the said fiber can also be used instead of the said knitting. Instead of the knitted fabric, a glove-like article or a tubular article made of a resin material such as vinyl chloride, natural rubber, or synthetic rubber can be used.
　前記ポリウレタンフィルムや、該ポリウレタンフィルムからなる手袋等のフィルム加工品の製造に使用するポリウレタン組成物（Ｄ）としては、末端にポリオキシエチレン構造を有する酸価０．１～１０のポリウレタン（Ａ）、乳化剤（Ｂ）、及び、水性媒体（Ｃ）を含有し、前記乳化剤（Ｂ）の含有割合が、前記ポリウレタン（Ａ）１００質量部に対して０．１質量部～５質量部であるものを使用する。 Examples of the polyurethane composition (D) used in the production of the polyurethane film and film processed products such as gloves made of the polyurethane film include polyurethane (A) having an acid value of 0.1 to 10 having a polyoxyethylene structure at the terminal. , Emulsifier (B), and aqueous medium (C), and the content of the emulsifier (B) is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A). Is used.
　前記ポリウレタン組成物（Ｄ）に含まれるポリウレタン（Ａ）としては、末端にポリオキシエチレン構造を有し、酸価が０．１～１０であるものを使用する。 As the polyurethane (A) contained in the polyurethane composition (D), one having a polyoxyethylene structure at the terminal and an acid value of 0.1 to 10 is used.
　ここで、前記ポリウレタン（Ａ）の代わりに、末端にポリオキシエチレン構造を有さない酸価０．１～１０のポリウレタンを使用した場合、前記ポリウレタンを水性媒体（C）に安定して分散することができない場合がある。 Here, when a polyurethane having an acid value of 0.1 to 10 having no polyoxyethylene structure is used in place of the polyurethane (A), the polyurethane is stably dispersed in the aqueous medium (C). It may not be possible.
　前記ポリウレタン（Ａ）としては、前記ポリウレタン（Ａ）の全量に対して、前記ポリオキシエチレン構造を０．５質量％～１０質量％の範囲で、その分子末端に有するものを使用することが、水性媒体（Ｃ）中で安定して分散するうえで好ましく、２質量％～８質量％の範囲で有するものを使用することがより好ましい。 As the polyurethane (A), the one having the polyoxyethylene structure at the molecular end in the range of 0.5% by mass to 10% by mass with respect to the total amount of the polyurethane (A) can be used. It is preferable for stable dispersion in the aqueous medium (C), and it is more preferable to use one having a range of 2% by mass to 8% by mass.
　また、前記ポリウレタン（Ａ）の代わりに、例えば、末端にポリオキシエチレン構造を有するものの酸価が１５であるポリウレタンを使用した場合、柔軟な風合いを備えたポリウレタンフィルムを製造できない場合がある。 Further, in place of the polyurethane (A), for example, when a polyurethane having a polyoxyethylene structure at the terminal but having an acid value of 15 is used, a polyurethane film having a flexible texture may not be produced.
　また、前記ポリウレタン（Ａ）の代わりに、例えば、末端にポリオキシエチレン構造を有するものの酸価が０．０５のポリウレタンを使用した場合、前記水性媒体（Ｃ）中で安定して分散することができず、その結果、耐摩擦性等の優れた強度を備えたポリウレタンフィルムを製造できない場合がある。 Further, instead of the polyurethane (A), for example, when a polyurethane having a polyoxyethylene structure at the terminal but having an acid value of 0.05 is used, it can be stably dispersed in the aqueous medium (C). As a result, it may be impossible to produce a polyurethane film having excellent strength such as friction resistance.
　前記ポリウレタン（Ａ）としては、ポリウレタン組成物（Ｄ）の優れた水分散安定性とともに、ポリウレタンフィルムの柔軟な風合いと高強度とを両立するうえで、０．１～６の酸価を有するものを使用することが好ましく、０．１～２の酸価を有するものを使用することが特に好ましい。なお、前記でいう酸価は、前記カルボキシル基及びカルボキシレート基に由来するものである。 The polyurethane (A) has an acid value of 0.1 to 6 in order to achieve both the excellent water dispersion stability of the polyurethane composition (D) and the flexible texture and high strength of the polyurethane film. It is preferable to use those having an acid value of 0.1 to 2. The acid value referred to above is derived from the carboxyl group and carboxylate group.
　前記ポリウレタン（Ａ）としては、柔軟な風合いと、耐摩耗性等の優れた強度とを両立したポリウレタンフィルムを形成するうえで、５，０００～５００，０００の重量平均分子量を有するものであることが好ましく、２０，０００～３００，０００の重量平均分子量を有するものを使用することがより好ましい。 The polyurethane (A) has a weight average molecular weight of 5,000 to 500,000 for forming a polyurethane film having both a soft texture and excellent strength such as abrasion resistance. It is preferable to use those having a weight average molecular weight of 20,000 to 300,000.
　また、前記ポリウレタン（Ａ）としては、前記末端に存在するポリオキシエチレン構造以外に、その他のポリエーテル構造を有するものを使用することが、得られるポリウレタンフィルムの柔軟な風合いを向上するうえで好ましい。前記ポリエーテル構造は、ポリウレタンフィルムの柔軟性と強度のバランスの観点から、前記ポリウレタン（Ａ）全体に対して７０質量％～９０質量％の割合で存在することが好ましい。 Moreover, as said polyurethane (A), it is preferable to use what has another polyether structure other than the polyoxyethylene structure which exists in the said terminal in order to improve the flexible feel of the polyurethane film obtained. . The polyether structure is preferably present in a proportion of 70% by mass to 90% by mass with respect to the entire polyurethane (A) from the viewpoint of the balance between flexibility and strength of the polyurethane film.
　前記ポリウレタン（Ａ）は、前記ポリウレタン組成物（Ｄ）全体に対して、１０質量％～５０質量％の範囲で含有するものであること好ましく、２０質量％～５０質量％含有することが、例えば手袋等の用途で求められる４０μｍ～２００μｍ程度の厚さを備えたポリウレタンフィルムを製造できるためより好ましい。 The polyurethane (A) is preferably contained in the range of 10% by mass to 50% by mass with respect to the entire polyurethane composition (D), and is preferably contained in an amount of 20% by mass to 50% by mass. A polyurethane film having a thickness of about 40 μm to 200 μm required for applications such as gloves can be produced, which is more preferable.
　また、本発明は、単に前記した特定のポリウレタン（Ａ）を使用すれば前記課題を解決できるというものではなく、前記ポリウレタン（Ａ）１００質量部に対して０．１質量部～５質量部の範囲の、ごく微量の乳化剤（Ｂ）を使用することが重要である。 Further, the present invention does not mean that the above-mentioned problem can be solved by simply using the specific polyurethane (A) described above, and is 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A). It is important to use a very small amount of emulsifier (B) in the range.
　前記乳化剤（Ｂ）の使用量は、通常、ポリウレタンの水性媒体（Ｃ）に対する良好な水分散安定性を付与できる程度の量ではない。 The amount of the emulsifier (B) used is not usually an amount that can provide good water dispersion stability of the polyurethane aqueous medium (C).
　しかし、前記ごく微量の乳化剤（Ｂ）であっても、前記特定のポリウレタン（Ａ）と組み合わせ使用する場合には、前記ポリウレタン組成物（Ｄ）の水分散安定性を低下させることなく、得られるポリウレタンフィルムの耐摩擦性等の強度を向上させることができる。 However, even a very small amount of the emulsifier (B) can be obtained without reducing the water dispersion stability of the polyurethane composition (D) when used in combination with the specific polyurethane (A). Strength such as friction resistance of the polyurethane film can be improved.
　ここで、前記ポリウレタン組成物（Ｄ）の代わりに、例えば、前記乳化剤（Ｂ）の使用量が前記ポリウレタン（Ａ）１００質量部に対して６質量部であるポリウレタン組成物を用いた場合、前記特定のポリウレタン（Ａ）を使用した場合であっても前記強度の低下を引き起こす場合がある。 Here, instead of the polyurethane composition (D), for example, when a polyurethane composition in which the amount of the emulsifier (B) used is 6 parts by mass with respect to 100 parts by mass of the polyurethane (A), Even when a specific polyurethane (A) is used, the strength may be lowered.
　また、前記ポリウレタン組成物（Ｄ）の代わりに、例えば、前記乳化剤（Ｂ）の使用量が前記ポリウレタン（Ａ）１００質量部に対して０．０５質量部であるポリウレタン組成物を用いた場合には、水分散安定性の著しい低下や、ポリウレタンフィルムの柔軟性と強度の低下を引き起こす場合がある。 Moreover, when using the polyurethane composition whose usage-amount of the said emulsifier (B) is 0.05 mass part with respect to 100 mass parts of said polyurethane (A) instead of the said polyurethane composition (D), for example. May cause a significant decrease in water dispersion stability and a decrease in flexibility and strength of the polyurethane film.
　したがって、本発明では、前記乳化剤（Ｂ）を、前記ポリウレタン（Ａ）１００質量部に対して０．１質量部～５質量部の範囲で使用することが必須であり、０．１質量部～２質量部の範囲で使用することが好ましい。 Therefore, in the present invention, it is essential to use the emulsifier (B) in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A). It is preferable to use in the range of 2 parts by mass.
　前記ポリウレタン組成物（Ｄ）に使用するポリウレタン（Ａ）は、例えば酸基を有するポリオール（ａ１－１）を含むポリオール（ａ１）、ポリイソシアネート（ａ２）、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（ａ４）、及び、必要に応じて鎖伸長剤（ａ３）を反応させることによって製造することができる。 The polyurethane (A) used in the polyurethane composition (D) includes, for example, a polyol (a1) containing a polyol (a1-1) having an acid group, a polyisocyanate (a2), a polyisocyanate having one hydroxyl group at one end. It can be produced by reacting oxyethylene monoalcohol (a4) and, if necessary, a chain extender (a3).
　具体的には、前記ポリウレタン（Ａ）は、前記ポリオール（ａ１）とポリイソシアネート（ａ２）と必要に応じて鎖伸長剤（ａ３）とを反応させることによって末端にイソシアネート基を有するポリウレタンを製造する工程［Ｉ］、及び、前記工程で得たイソシアネート基を有するポリウレタンと、前記片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（ａ４）とを反応させる工程［ＩＩ］を経ることによって製造することができる。 Specifically, the polyurethane (A) is produced by reacting the polyol (a1), the polyisocyanate (a2) and, if necessary, the chain extender (a3) to have a polyurethane having an isocyanate group at the terminal. Produced by passing through the step [I] and the step [II] of reacting the polyurethane having an isocyanate group obtained in the above step with the polyoxyethylene monoalcohol (a4) having one hydroxyl group at one end. can do.
　前記工程［I］で使用可能なポリオール（ａ１）としては、ポリウレタン（Ａ）に所定の酸価を付与することを目的として、酸基を有するポリオール（ａ１－１）を使用する。 As the polyol (a1) that can be used in the step [I], a polyol (a1-1) having an acid group is used for the purpose of imparting a predetermined acid value to the polyurethane (A).
　前記酸基を有するポリオール（ａ１－１）としては、例えば、２，２’－ジメチロールプロピオン酸、２，２’－ジメチロールブタン酸、２，２’－ジメチロール酪酸、２，２’－ジメチロール吉草酸等を使用することができる。なかでも、２，２’－ジメチロールプロピオン酸、２，２’－ジメチロールブタン酸を使用することが好ましい。 Examples of the polyol (a1-1) having an acid group include 2,2′-dimethylolpropionic acid, 2,2′-dimethylolbutanoic acid, 2,2′-dimethylolbutyric acid, and 2,2′-dimethylol. Valeric acid or the like can be used. Of these, 2,2'-dimethylolpropionic acid and 2,2'-dimethylolbutanoic acid are preferably used.
　前記カルボキシル基は、その一部または全部が塩基性化合物に中和されカルボキシレート基を形成していてもよい。前記塩基性化合物としては、例えばアンモニア、トリエチルアミン、ピリジン、モルホリン等の有機アミンや、モノエタノールアミン等のアルカノールアミンや、ナトリウム、カリウム、リチウム、カルシウム等を含む金属塩基化合物を使用することができる。 The carboxyl group may be partially or entirely neutralized with a basic compound to form a carboxylate group. Examples of the basic compound that can be used include organic amines such as ammonia, triethylamine, pyridine, and morpholine, alkanolamines such as monoethanolamine, and metal base compounds including sodium, potassium, lithium, calcium, and the like.
　前記酸基を有するポリオール（ａ１－１）は、前記ポリウレタン（Ａ）の製造に使用する原料、具体的にはポリオール（ａ１）、ポリイソシアネート（ａ２）、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（ａ４）、及び、鎖伸長剤の合計質量に対して、０．０１質量％～３質量％の範囲で使用することができる。 The polyol (a1-1) having an acid group is a raw material used for the production of the polyurethane (A), specifically, a polyol (a1), a polyisocyanate (a2), and a polyhydroxy having one hydroxyl group at one end. The oxyethylene monoalcohol (a4) and the chain extender can be used in the range of 0.01% by mass to 3% by mass.
　また、前記ポリオール（ａ１）としては、ポリウレタン（Ａ）の末端のポリオキシエチレン構造以外のエーテル構造を導入することによって、より一層優れた柔軟な風合いを付与する観点から、ポリエーテルポリオール（ａ１－２）を組み合わせ使用することが好ましい。 In addition, as the polyol (a1), a polyether polyol (a1-) can be used from the viewpoint of imparting an even more flexible texture by introducing an ether structure other than the polyoxyethylene structure at the terminal of the polyurethane (A). It is preferable to use 2) in combination.
　前記ポリエーテルポリオール（ａ１－２）は、例えば活性水素原子を２個以上有する化合物の１種または２種以上を開始剤として、アルキレンオキサイドを付加重合させたものを使用することができる。 As the polyether polyol (a1-2), for example, one obtained by addition polymerization of alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator can be used.
　前記開始剤としては、例えばエチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、トリメチレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、グリセリン、トリメチロールエタン、トリメチロールプロパン等を使用することができる。 Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolethane, Trimethylolpropane and the like can be used.
　また、前記アルキレンオキサイドとしては、例えばエチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド、エピクロルヒドリン、テトラヒドロフラン等を使用することができる。 Further, as the alkylene oxide, for example, ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, or the like can be used.
　前記ポリエーテルポリオール（ａ１－２）としては、具体的には、ポリオキシテトラメチレングリコールや、ポリオキシエチレングリコール、ポリオキシプロピレングリコール等を使用することができる。 As the polyether polyol (a1-2), specifically, polyoxytetramethylene glycol, polyoxyethylene glycol, polyoxypropylene glycol, or the like can be used.
　また、前記ポリエーテルポリオール（ａ１－２）としては、ポリウレタンフィルムに耐摩耗性等の点で優れた強度を付与する観点から３５～２３０の水酸基価を有するものを使用することが好ましい。 As the polyether polyol (a1-2), those having a hydroxyl value of 35 to 230 are preferably used from the viewpoint of imparting excellent strength to the polyurethane film in terms of wear resistance and the like.
　前記ポリエーテルポリオール（ａ１－２）は、前記ポリウレタン（Ａ）の製造に使用する原料、具体的にはポリオール（ａ１）、ポリイソシアネート（ａ２）、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（ａ４）、及び、鎖伸長剤の合計質量に対して、７０質量％～９０質量％の範囲で使用することができる。 The polyether polyol (a1-2) is a raw material used for the production of the polyurethane (A), specifically, the polyol (a1), the polyisocyanate (a2), and a polyoxyethylene having one hydroxyl group at one end. The monoalcohol (a4) and the chain extender can be used in the range of 70 to 90% by mass with respect to the total mass.
　前記ポリオール（ａ１）としては、酸基を有するポリオール（ａ１－１）や前記ポリエーテルポリオール（ａ１－２）やの他に、必要に応じてその他のポリオールを組み合わせ使用することができる。 As the polyol (a1), in addition to the polyol (a1-1) having an acid group and the polyether polyol (a1-2), other polyols can be used in combination as required.
　前記その他のポリオールとしては、例えば２，２－ジメチル－１，３－プロパンジオール、３－メチル－１，５－ペンタンジオール、２－ブチル－１，３－プロパンジオール、２－メチル－１，３－プロパンジオール、２－ブチル－２－メチル－１，３－プロパンジオール、２－ブチル－２－エチル－１，３－プロパンジオール、２－ペンチル－２－エチル－１，３－プロパンジオール、２，２－ジブチル－１，３－プロパンジオール、１，２－プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、１，３－ブタンジオール、１，２－ブタンジオール、２，３－ブタンジオール、１，４－ヘキサンジオール、２，５－ヘキサンジオール、２－エチル－１，３－ヘキサンジオール、２－メチル－１，８－オクタンジオール等を使用することができる。 Examples of the other polyols include 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-butyl-1,3-propanediol, and 2-methyl-1,3. -Propanediol, 2-butyl-2-methyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-pentyl-2-ethyl-1,3-propanediol, 2 , 2-dibutyl-1,3-propanediol, 1,2-propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, 1, 4-hexanediol, 2,5-hexanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octane It can be used Lumpur like.
　前記その他のポリオールとしては、本発明の効果を損なわない範囲で、ポリカーボネートポリオールやポリエステルポリオールを使用してもよい。 As the other polyol, polycarbonate polyol or polyester polyol may be used as long as the effects of the present invention are not impaired.
　前記ポリウレタン（Ａ）を製造する際に前記ポリオール（ａ１）と反応しうるポリイソシアネート（ａ２）としては、例えばフェニレンジイソシアネート、トリレンジイソシアネート、ジフェニルメタンジイソシアネート、ナフタレンジイソシアネート、ポリメチレンポリフェニルポリイソシアネート、カルボジイミド化ジフェニルメタンポリイソシアネート等の芳香族ポリイソシアネートや、ヘキサメチレンジイソシアネート、リジンジイソシアネート、シクロヘキサンジイソシアネート、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート、ダイマー酸ジイソシアネート、ノルボルネンジイソシアネート等の脂肪族または脂肪族環式構造含有ポリイソシアネート等を、単独で使用または２種以上を併用して使用することができる。なかでも、芳香族ポリイソシアネートを使用することが、高強度のポリウレタンフィルムを製造できるため好ましい。 Examples of the polyisocyanate (a2) that can react with the polyol (a1) when producing the polyurethane (A) include phenylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and carbodiimidization. Aromatic polyisocyanates such as diphenylmethane polyisocyanate, aliphatics or fats such as hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, dimer diisocyanate, norbornene diisocyanate Aromatic cyclic structure Yu polyisocyanates can be used in combination singly used or two or more. Among these, it is preferable to use an aromatic polyisocyanate because a high-strength polyurethane film can be produced.
　前記工程［I］は、例えば無溶剤下または有機溶剤の存在下、前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）とを混合し、５０℃～１００℃で概ね３時間～１０時間程度反応させることによって行うことができる。これにより、イソシアネート基を末端に有するポリウレタンを製造することができる。 In the step [I], for example, the polyol (a1) and the polyisocyanate (a2) are mixed in the absence of a solvent or in the presence of an organic solvent and reacted at 50 ° C. to 100 ° C. for about 3 to 10 hours. Can be done. Thereby, the polyurethane which has an isocyanate group at the terminal can be manufactured.
　その際、前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）との反応は、前記ポリオール（ａ１）の有する水酸基と前記ポリイソシアネート（ａ２）の有するイソシアネート基との当量割合［イソシアネート基／水酸基］は、１～３．５の範囲であることが好ましく、１．１～２．５であることが好ましい。 At that time, the reaction between the polyol (a1) and the polyisocyanate (a2) is equivalent to the equivalent ratio [isocyanate group / hydroxyl group] of the hydroxyl group of the polyol (a1) and the isocyanate group of the polyisocyanate (a2). The range is preferably from 1 to 3.5, and more preferably from 1.1 to 2.5.
　また、前記工程［I］では、より一層優れた強度を備えたポリウレタンフィルムを製造するうえで、比較的高分子量でウレア結合を有するポリウレタンを使用することができる。前記ウレア結合は、前記ポリウレタンを製造する際に、必要に応じて鎖伸長剤（ａ３）を使用することによってポリウレタンに付与することができる。 In the step [I], a polyurethane having a relatively high molecular weight and a urea bond can be used for producing a polyurethane film having a further excellent strength. The urea bond can be imparted to the polyurethane by using a chain extender (a3) as necessary when the polyurethane is produced.
　具体的には、無溶剤下または有機溶剤の存在下、前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）とを混合し、５０℃～１００℃で概ね３時間～１０時間程度反応させることによって末端にイソシアネート基を有するポリウレタンを製造し、次いで、前記ポリウレタンと鎖伸長剤（ａ３）とを反応させることができる。 Specifically, the polyol (a1) and the polyisocyanate (a2) are mixed in the absence of a solvent or in the presence of an organic solvent, and reacted at 50 ° C. to 100 ° C. for about 3 hours to 10 hours. A polyurethane having an isocyanate group can be produced, and then the polyurethane and the chain extender (a3) can be reacted.
　前記ポリウレタン（Ａ）としては、ポリウレタンフィルムの柔軟な風合いを損なうことなく、高強度を付与する観点から、ウレア結合を５０ｍｍｏｌ／ｋｇ～１，０００ｍｍｏｌ／ｋｇ有するものを使用することが好ましく、１００ｍｍｏｌ／ｋｇ～７００ｍｍｏｌ／ｋｇの範囲であるものを使用することがより好ましい。 As the polyurethane (A), it is preferable to use one having a urea bond of 50 mmol / kg to 1,000 mmol / kg from the viewpoint of imparting high strength without impairing the flexible texture of the polyurethane film. It is more preferable to use those in the range of kg to 700 mmol / kg.
　前記鎖伸長剤（ａ３）としては、例えばポリアミン等を使用することができる。 As the chain extender (a3), for example, polyamine or the like can be used.
　前記ポリアミンとしては、例えば、エチレンジアミン、１，２－プロパンジアミン、１，６－ヘキサメチレンジアミン、ピペラジン、２，５－ジメチルピペラジン、イソホロンジアミン、４，４’－ジシクロヘキシルメタンジアミン、３，３’－ジメチル－４，４’－ジシクロヘキシルメタンジアミン、１，４－シクロヘキサンジアミン等のジアミン；Ｎ－ヒドロキシメチルアミノエチルアミン、Ｎ－ヒドロキシエチルアミノエチルアミン、Ｎ－ヒドロキシプロピルアミノプロピルアミン、Ｎ－エチルアミノエチルアミン、Ｎ－メチルアミノプロピルアミン等の１個の１級アミノ基と１個の２級アミノ基を含有するジアミン；ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン等のポリアミン；ヒドラジン、Ｎ，Ｎ’－ジメチルヒドラジン、１，６－ヘキサメチレンビスヒドラジン等のヒドラジン；コハク酸ジヒドラジッド、アジピン酸ジヒドラジド、グルタル酸ジヒドラジド、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド等のジヒドラジド；β－セミカルバジドプロピオン酸ヒドラジド、３－セミカルバジッド－プロピル－カルバジン酸エステル、セミカルバジッド－３－セミカルバジドメチル－３，５，５－トリメチルシクロヘキサン等のセミカルバジドを使用することができる。 Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N A diamine containing one primary amino group and one secondary amino group such as methylaminopropylamine; a polyamine such as diethylenetriamine, dipropylenetriamine, triethylenetetramine; hydrazine, N, N Hydrazines such as dimethylhydrazine and 1,6-hexamethylenebishydrazine; dihydrazides such as succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide propionic acid hydrazide, 3-semicarbadium Semicarbazides such as did-propyl-carbazate, semicarbazide-3-semicarbazide methyl-3,5,5-trimethylcyclohexane can be used.
　前記鎖伸長剤（ａ３）は、ポリウレタンフィルム中にウレア結合を導入することで、柔軟な風合いを損なうことなく、高強度を付与する観点から、ポリウレタン（Ａ）の製造に使用する原料の全量に対して０．５質量％～１０質量％の範囲で使用することが好ましい。 The chain extender (a3) introduces a urea bond into the polyurethane film, and from the viewpoint of imparting high strength without impairing the flexible texture, the chain extender (a3) is added to the total amount of raw materials used in the production of the polyurethane (A). On the other hand, it is preferably used in the range of 0.5 to 10% by mass.
　前記末端にイソシアネート基を有するポリウレタンのイソシアネート基と、前記ポリアミンのアミノ基との当量割合［イソシアネート基／アミノ基］は、０．３～１であることが好ましく、０．５～１未満であることがより好ましい。 The equivalent ratio [isocyanate group / amino group] of the isocyanate group of the polyurethane having an isocyanate group at the terminal and the amino group of the polyamine is preferably 0.3 to 1, and less than 0.5 to 1. It is more preferable.
　前記工程［I］で得たイソシアネート基を末端に有するポリウレタンと、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（ａ４）とを反応させる工程［II］は、例えば前記ポリウレタンの有機溶剤溶液と、前記ポリオキシエチレンモノアルコール（ａ４）とを混合し、５０℃～１００℃程度の温度で１～５時間程度反応させることによって行うことができる。 The step [II] of reacting the polyurethane having an isocyanate group at the terminal obtained in the step [I] with the polyoxyethylene monoalcohol (a4) having one hydroxyl group at one terminal is, for example, an organic solvent for the polyurethane. The solution and the polyoxyethylene monoalcohol (a4) can be mixed and reacted at a temperature of about 50 ° C. to 100 ° C. for about 1 to 5 hours.
　前記片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（ａ４）としては、例えばポリオキシエチレングリコールの両末端に存在する水酸基の一部を、モノアルコール等を用いてエーテル化反応し、封止したものを使用することができる。 As the polyoxyethylene monoalcohol (a4) having one hydroxyl group at one end, for example, a part of the hydroxyl groups present at both ends of polyoxyethylene glycol is etherified using monoalcohol or the like, and sealed. It can be used.
　前記モノアルコールとしては、例えばメタノール、エタノール、プロパノール、ブタノール等を使用することができる。 As the monoalcohol, for example, methanol, ethanol, propanol, butanol and the like can be used.
　前記片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（ａ４）としては、前記ポリウレタン組成物（Ｄ）により一層優れた水分散安定性を付与し、かつ、ポリウレタンフィルムの柔軟性を向上するうえで、５００～５，０００の数平均分子量を有するものを使用することが好ましく、２，０００～５，０００の範囲の数平均分子量を有するものを使用することが特に好ましい。 As the polyoxyethylene monoalcohol (a4) having one hydroxyl group at one end, the polyurethane composition (D) gives more excellent water dispersion stability and improves the flexibility of the polyurethane film. In addition, those having a number average molecular weight of 500 to 5,000 are preferably used, and those having a number average molecular weight in the range of 2,000 to 5,000 are particularly preferably used.
　次に、本発明のポリウレタンフィルムの製造に使用するポリウレタン組成物（Ｄ）に使用する乳化剤（Ｂ）について説明する。 Next, the emulsifier (B) used for the polyurethane composition (D) used for the production of the polyurethane film of the present invention will be described.
　前記乳化剤（Ｂ）は、前記したとおり、ポリウレタン（Ａ）１００質量部に対して０．１質量部～５質量部というごく少量を使用することが、前記ポリウレタン組成物（Ｄ）の水分散安定性と、得られるポリウレタンフィルム等の柔軟性とを付与するうえで重要である。 As described above, the emulsifier (B) may be used in a very small amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the polyurethane (A). It is important for imparting flexibility and flexibility such as a polyurethane film to be obtained.
　前記乳化剤（Ｂ）としては、具体的には、オレイン酸ナトリウム等の脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルフォン酸塩、アルキルスルホコハク酸塩、ナフタレンスルフォン酸塩、ポリオキシエチレンアルキル硫酸塩、ポリオキシエチレン フェニルエーテル硫酸塩、アルカンスルフォネートナトリウム塩、アルキルジフェニルエーテルスルフォン酸ナトリウム塩等のアニオン系乳化剤；アルキルアミン塩、アルキルトリメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩等のカチオン系乳化剤；ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビトールテトラオレエート、ポリオキシエチレン・ポリオキシプロピレン共重合体等のノニオン系乳化剤等を使用することができる。 Specific examples of the emulsifier (B) include fatty acid salts such as sodium oleate, alkyl sulfate esters, alkyl benzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, polyoxy Anionic emulsifiers such as ethylene phenyl ether sulfate, alkane sulfonate sodium salt, alkyl diphenyl ether sulfonic acid sodium salt; cationic emulsifiers such as alkyl amine salt, alkyl trimethyl ammonium salt, alkyl dimethyl benzyl ammonium salt; polyoxyethylene nonyl phenyl Ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, polyoxyethylene · Polyoxypropylene copolymer nonionic emulsifier, etc. may be used.
　なかでも、アニオン系乳化剤としては、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩、ノニオン系乳化剤としては、ポリオキシエチレン・ポリオキシプロピレン共重合体を使用することが、前記ポリウレタン組成物の水分散安定性と、得られるポリウレタンフィルム等の高強度とを付与するうえで好ましく、アニオン系乳化剤を使用することが、より一層優れた強度と柔軟性とを両立できるためより好ましい。 Among these, the polyoxyethylene polycyclic phenyl ether sulfate ester salt is used as the anionic emulsifier, and the polyoxyethylene / polyoxypropylene copolymer is used as the nonionic emulsifier. And an anionic emulsifier are more preferable because both an excellent strength and flexibility can be achieved.
　前記ポリウレタン組成物（Ｄ）は、前記ポリウレタン（Ａ）や前記乳化剤（Ｂ）が水性媒体（Ｃ）に溶解または分散したものである。 The polyurethane composition (D) is obtained by dissolving or dispersing the polyurethane (A) and the emulsifier (B) in an aqueous medium (C).
　前記水性媒体（Ｃ）としては、水、水と混和する有機溶剤、及び、これらの混合物が挙げられる。水と混和する有機溶剤としては、例えば、メタノール、エタノール、ｎ－及びイソプロパノール等のアルコール；アセトン、メチルエチルケトン等のケトン；エチレングリコール、ジエチレングリコール、プロピレングリコール等のポリアルキレングリコール；ポリアルキレングリコールのアルキルエーテル;Ｎ-メチル-２-ピロリドン等のラクタム等が挙げられる。本発明では、水のみを用いても良く、また水及び水と混和する有機溶剤との混合物を用いても良く、水と混和する有機溶剤のみを用いても良い。安全性や環境に対する負荷の点から、水のみ、又は、水及び水と混和する有機溶剤との混合物が好ましく、水のみが特に好ましい。 Examples of the aqueous medium (C) include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n- and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycol; And lactams such as N-methyl-2-pyrrolidone. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used. From the viewpoint of safety and load on the environment, water alone or a mixture of water and an organic solvent miscible with water is preferable, and only water is particularly preferable.
　前記水性媒体（Ｃ）は、前記ポリウレタン組成物（Ｄ）の全量に対して５質量％～８５質量％～８５質量の範囲で含まれることが好ましく、４５質量％～９０質量％の範囲で含まれることがより好ましく、４５質量％～８５質量％の範囲で含まれることがさらに好ましい。 The aqueous medium (C) is preferably contained in the range of 5% by mass to 85% by mass to 85% by mass, and in the range of 45% by mass to 90% by mass with respect to the total amount of the polyurethane composition (D). More preferably, it is contained in the range of 45% by mass to 85% by mass.
　前記ポリウレタン組成物（Ｄ）は、前記方法によって得られたポリウレタン（Ａ）またはその有機溶剤溶液と、前記乳化剤（Ｂ）と、必要に応じてその他の添加剤とを混合し、次いで、水性媒体（Ｃ）を供給することによって、前記水性媒体（Ｃ）中に前記ポリウレタン（Ａ）や乳化剤（Ｂ）等が溶解または分散したポリウレタン組成物（Ｄ）を製造することができる。 The polyurethane composition (D) is prepared by mixing the polyurethane (A) obtained by the method or an organic solvent solution thereof, the emulsifier (B), and other additives as necessary, and then an aqueous medium. By supplying (C), the polyurethane composition (D) in which the polyurethane (A), the emulsifier (B) and the like are dissolved or dispersed in the aqueous medium (C) can be produced.
　その際、前記ポリウレタン（Ａ）の有する酸基は、その一部または全部が、前記塩基性化合物によって中和されていてもよい。前記中和は、水性媒体（Ｃ）を供給する前に行うことが好ましい。 At that time, part or all of the acid groups of the polyurethane (A) may be neutralized with the basic compound. The neutralization is preferably performed before supplying the aqueous medium (C).
　前記水性媒体（Ｃ）の供給に際しては、水分散安定性に優れたポリウレタン（Ａ）からなる樹脂粒子を形成するうえで、前記水性媒体（Ｃ）としての水を供給する前、または、水と同時に、前記水と混和しやすいメタノールやエタノール、イソプロピルアルコールなどのアルコールやアセトン等からなる水性媒体（ｃ１）を供給することが好ましい。前記水性媒体（ｃ１）は、前記ポリウレタン（Ａ）１００質量部に対して５質量部～１００質量部を、水を供給する前、または、水と同時に使用することが好ましい。 In supplying the aqueous medium (C), before forming water particles as the aqueous medium (C), in order to form resin particles made of polyurethane (A) excellent in water dispersion stability, At the same time, it is preferable to supply an aqueous medium (c1) made of alcohol, such as methanol, ethanol, isopropyl alcohol, or acetone, which is easily miscible with water. The aqueous medium (c1) is preferably used in an amount of 5 to 100 parts by mass with respect to 100 parts by mass of the polyurethane (A) before supplying water or simultaneously with water.
　また、前記ポリウレタン（Ａ）等と水性媒体（Ｃ）とを混合する際には、必要に応じてホモジナイザー等の機械を使用してもよい。 Further, when mixing the polyurethane (A) or the like and the aqueous medium (C), a machine such as a homogenizer may be used as necessary.
　また、本発明で使用するポリウレタン組成物（Ｄ）は、必要に応じて、各種添加剤を含んでいても良い。例えば、会合型増粘剤や消泡剤、ウレタン化触媒、シランカップリング剤、充填剤、チキソ付与剤、粘着付与剤、ワックス、熱安定剤、耐光安定剤、蛍光増白剤、発泡剤等の添加剤、熱可塑性樹脂、熱硬化性樹脂、顔料、染料、導電性付与剤、帯電防止剤、透湿性向上剤、撥水剤、撥油剤、中空発泡体、結晶水含有化合物、難燃剤、吸水剤、吸湿剤、消臭剤、防黴剤、防腐剤、防藻剤、顔料分散剤、ブロッキング防止剤、加水分解防止剤、加硫剤、加硫触媒、界面活性剤を併用することができる。 Moreover, the polyurethane composition (D) used in the present invention may contain various additives as necessary. For example, associative thickeners and antifoaming agents, urethanization catalysts, silane coupling agents, fillers, thixotropic agents, tackifiers, waxes, heat stabilizers, light stabilizers, fluorescent whitening agents, foaming agents, etc. Additives, thermoplastic resins, thermosetting resins, pigments, dyes, conductivity imparting agents, antistatic agents, moisture permeability improvers, water repellents, oil repellents, hollow foams, crystal water-containing compounds, flame retardants, Water absorbents, moisture absorbents, deodorants, antifungal agents, antiseptics, algae inhibitors, pigment dispersants, antiblocking agents, antihydrolysis agents, vulcanizing agents, vulcanizing catalysts, and surfactants may be used in combination. it can.
　前記会合型増粘剤は、ポリウレタン組成物（Ｄ）の粘度を調整し、金属塩を含む凝固剤を用いた加工を容易にするうえで好適に使用することができ、例えばヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース等のセルロース誘導体や、ポリアクリル酸塩、ポリビニルピロリドン、ウレタン、ポリエーテル等を使用することができる。なかでも、前記ポリウレタン（Ａ）と良好な相溶性を有することから、ウレタン系増粘剤を使用することが好ましい。前記会合型増粘剤は、前記ポリウレタン（Ａ）の全量に対して０．５質量％～５質量％の範囲で使用することが好ましい。 The associative thickener can be suitably used for adjusting the viscosity of the polyurethane composition (D) and facilitating processing using a coagulant containing a metal salt, such as hydroxyethyl cellulose, methyl cellulose, Cellulose derivatives such as carboxymethyl cellulose, polyacrylate, polyvinyl pyrrolidone, urethane, polyether and the like can be used. Especially, since it has favorable compatibility with the said polyurethane (A), it is preferable to use a urethane type thickener. The associative thickener is preferably used in the range of 0.5% by mass to 5% by mass with respect to the total amount of the polyurethane (A).
　前記消泡剤としては、例えばシリコーン、ミネラルオイル、ポリグリコールエーテル、脂肪酸エステル、金属石ケン、フッ素化合物等の消泡剤を使用することができる。 As the antifoaming agent, for example, an antifoaming agent such as silicone, mineral oil, polyglycol ether, fatty acid ester, metal soap, or fluorine compound can be used.
　また、本発明で使用するポリウレタン組成物（Ｘ）は、使用用途によってことなる耐久性や柔軟性が必要とされることから、例えばスチレン－ブタジエン共重合体（ＳＢＲ）、ブタジエン共重合体（ＢＲ）、イソプレン共重合体（ＩＲ）、エチレン－プロピレン－ジエン共重合体（ＥＰＤＭ）、クロロプレン重合体（ＣＲ）、アクリロニトリル－ブタジエン共重合体（ＮＢＲ）、ブチル重合体（ＩＩＲ）、天然ゴム（ＮＲ）等を含有してもよい。なかでも、アクリロニトリル－ブタジエン共重合体（ＮＢＲ）を使用することが、より一層優れた柔軟性と強度とを両立するうえで好ましい。 Further, since the polyurethane composition (X) used in the present invention requires durability and flexibility depending on the intended use, for example, a styrene-butadiene copolymer (SBR), a butadiene copolymer (BR) ), Isoprene copolymer (IR), ethylene-propylene-diene copolymer (EPDM), chloroprene polymer (CR), acrylonitrile-butadiene copolymer (NBR), butyl polymer (IIR), natural rubber (NR) ) And the like. Among these, the use of acrylonitrile-butadiene copolymer (NBR) is preferable in order to achieve both excellent flexibility and strength.
　前記アクリロニトリル－ブタジエン共重合体としては、例えばアクリロニトリルとブタジエンと必要に応じてその他のビニル重合体とを重合することによって得られるものを使用することができる。 As the acrylonitrile-butadiene copolymer, for example, a polymer obtained by polymerizing acrylonitrile, butadiene and, if necessary, other vinyl polymers can be used.
　前記ポリウレタン組成物（Ｘ）であれば、柔軟な風合いを備えた本発明のポリウレタンフィルムや手袋、管、避妊具等の様々なフィルム加工品の製造に使用することが可能である。 The polyurethane composition (X) can be used for production of various film processed products such as the polyurethane film, gloves, tubes and contraceptives of the present invention having a soft texture.
　以下、本発明を、実施例及び比較例により具体的に説明する。 Hereinafter, the present invention will be specifically described with reference to examples and comparative examples.
　［実施例１］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３０６．１１質量部、２，２’－ジメチロールプロピオン酸１．４１質量部、及びイソホロンジイソシアネート６５．４４質量部を、酢酸エチル２４８．６４質量部の存在下で３時間反応させた。 [Example 1]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 306.11 parts by mass, 2,2′- 1.41 parts by mass of dimethylolpropionic acid and 65.44 parts by mass of isophorone diisocyanate were reacted for 3 hours in the presence of 248.64 parts by mass of ethyl acetate.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．６３質量部と酢酸エチル７２．５７質量部を加え、さらに３時間反応させた。 Next, 19.63 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF CORPORATION) and 72.57 parts by mass of ethyl acetate were added, and further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。なお、前記ＮＣＯ％は、前記ポリウレタンの製造に使用した原料の合計質量に対する、そのうちポリイソシアネートが有するイソシアネート基の質量の割合である。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained. The NCO% is the ratio of the mass of isocyanate groups possessed by polyisocyanate to the total mass of raw materials used in the production of the polyurethane.
　次いで、前記ポリウレタンの有機溶剤溶液に、アニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）３．９３質量とトリエチルアミン１．１７質量とを加えて混合を行った後、イソプロピルアルコール２０３．２４質量部と水８８９．２６質量部、８０質量％水加ヒドラジン６．７９質量部を加え、攪拌することによりポリウレタン（Ａ－１）と乳化剤が混在する水分散体（Ａ－1’）を得た。 Next, 3.93 masses of anionic emulsifier (manufactured by Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) and 1.17 mass of triethylamine are added to the organic solvent solution of polyurethane and mixed. Then, 203.24 parts by mass of isopropyl alcohol, 889.26 parts by mass of water and 6.79 parts by mass of 80% by mass of hydrazine hydrate are added, and the mixture is stirred to give water in which the polyurethane (A-1) and the emulsifier are mixed. Dispersion (A-1 ′) was obtained.
　次いで、前記水分散体（Ａ－1’）をエージング及び脱溶剤することによって、酸価１．５のポリウレタン（Ａ－１）を含む不揮発分４０質量％のポリウレタン組成物（I－１）を得た。 Next, by aging and removing the water dispersion (A-1 ′), a polyurethane composition (I-1) having a nonvolatile content of 40% by mass containing polyurethane (A-1) having an acid value of 1.5 is obtained. Obtained.
　前記ポリウレタン組成物（I－１）１００質量部と、ハイドラン　アシスターＴ１０（会合型増粘剤、ＤＩＣ（株）製）１．５質量部とを混合し、それらの混合物の粘度が１０００～３０００ｍＰａ・ｓとなるように調整した後、離型処理の施した常温（概ね２５℃）のポリプロピレンフィルムの表面に、前記混合物をナイフコーター法により１５０ｇ／ｃｍ２塗布した。 100 parts by mass of the polyurethane composition (I-1) and 1.5 parts by mass of Hydran Assistor T10 (associative thickener, manufactured by DIC Corporation) are mixed, and the viscosity of the mixture is 1000 to 3000 mPa · After adjusting so as to be s, 150 g / cm 2 of the mixture was applied to the surface of a polypropylene film at room temperature (approximately 25 ° C.) subjected to release treatment by a knife coater method.
　前記塗布物を、２０質量％の濃度に調整した常温（概ね２５℃）の硝酸カルシウム水溶液に３分間浸漬した後、水中に１８時間浸漬した。 The coated product was immersed in a normal temperature (approximately 25 ° C.) calcium nitrate aqueous solution adjusted to a concentration of 20% by weight for 3 minutes and then immersed in water for 18 hours.
　次いで、前記塗布物を７０℃の環境下で２０分間乾燥し、更に、１２０℃の環境下で２分間乾燥することによって、前記ポリプロピレンフィルムの表面にポリウレタンフィルムを形成した。 Next, the coated material was dried in an environment of 70 ° C. for 20 minutes, and further dried in an environment of 120 ° C. for 2 minutes to form a polyurethane film on the surface of the polypropylene film.
　前記乾燥後、前記ポリプロピレンフィルムの表面から、ポリウレタンフィルムを剥離することによって、厚さ５０μｍのポリウレタンフィルム（I－２）を得た。 After the drying, the polyurethane film was peeled off from the surface of the polypropylene film to obtain a polyurethane film (I-2) having a thickness of 50 μm.
　また、手袋の作製にあたっては、はじめに、手型にナイロン繊維の編み物からなる手袋状物を装着したものを、２０質量％の濃度に調整した常温（概ね２５℃）の硝酸カルシウム水溶液に１５秒間浸漬した。 Also, when making gloves, first, a hand-shaped glove made of nylon fiber knitting was immersed in an aqueous solution of calcium nitrate at room temperature (approximately 25 ° C.) adjusted to a concentration of 20% by mass for 15 seconds. did.
　次いで、前記ウレタン樹脂組成物（I－１）中に、前記手袋状物を装着した手型を３分間浸漬した後、更に水中に３０分間浸漬した。 Subsequently, the hand mold equipped with the glove-like material was immersed in the urethane resin composition (I-1) for 3 minutes, and further immersed in water for 30 minutes.
　次いで、前記浸漬物を７０℃の環境下で２０分間乾燥し、更に、１２０℃の環境下で３０分間乾燥することによって、前記手型の装着した手袋状物の表面に、手型形状をしたポリウレタンフィルム（手袋）を形成した。 Next, the immersion material was dried in an environment of 70 ° C. for 20 minutes, and further dried in an environment of 120 ° C. for 30 minutes, thereby forming a hand shape on the surface of the glove-like material to which the hand shape was attached. A polyurethane film (gloves) was formed.
　前記手型及び手袋状物から、手型形状をしたポリウレタンフィルム（手袋）をとりはずしたものを、手袋（I－３）とした。 The glove (I-3) was obtained by removing the hand-shaped polyurethane film (glove) from the hand mold and glove-like material.
　［実施例２］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）２９４．９０質量部、２，２’－ジメチロールプロピオン酸４．６９質量部、及びイソホロンジイソシアネート７２．９９質量部を、酢酸エチル２４８．３９質量部の存在下で３時間反応させた。 [Example 2]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, polyether polyol (Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 294.90 parts by mass, 2,2′- 4.69 parts by mass of dimethylolpropionic acid and 72.99 parts by mass of isophorone diisocyanate were reacted in the presence of 248.39 parts by mass of ethyl acetate for 3 hours.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．６１質量部と酢酸エチル７２．５０質量部を加え、さらに３時間反応させた。 Next, 19.61 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF CORPORATION) and 72.50 parts by mass of ethyl acetate were added, and further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）３．９２質量とトリエチルアミン３．８９質量を加えて混合を行った後、イソプロピルアルコール２００．３０質量部と水８８９．４１質量部、８０質量％水加ヒドラジン７．５９質量部を加え、攪拌することによりウレタン樹脂（Ａ－２）と乳化剤が混在する水分散体（Ａ－２’）を得た。 Next, 3.92 masses of anionic emulsifier (Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) and 3.89 masses of triethylamine were added to the organic solvent solution of polyurethane and mixed. Thereafter, 200.30 parts by mass of isopropyl alcohol, 889.41 parts by mass of water, and 7.59 parts by mass of 80% by mass of hydrazine hydrate are added, and the mixture is stirred to disperse the urethane resin (A-2) and the emulsifier together. A body (A-2 ′) was obtained.
　次いで、前記水分散体（Ａ－２’）をエージング及び脱溶剤することによって、酸価５．０のポリウレタン（Ａ－２）を含む不揮発分４０質量％のポリウレタン組成物（II－１）を得た。 Next, by aging and removing the solvent from the aqueous dispersion (A-2 ′), a polyurethane composition (II-1) having a nonvolatile content of 40% by mass containing polyurethane (A-2) having an acid value of 5.0 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（II－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（II－２）及び手袋（II－３）を作製した。 Further, a polyurethane film (II-2) and a glove (II-) were prepared in the same manner as in Example 1 except that the polyurethane composition (II-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［実施例３］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３０７．６２質量部、２，２’－ジメチロールプロピオン酸１．４１質量部、及びイソホロンジイソシアネート６５．７７質量部を、酢酸エチル２４９．８７質量部の存在下で３時間反応させた。 [Example 3]
In a container purged with nitrogen equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 307.62 parts by mass, 2,2′- 1.41 parts by mass of dimethylolpropionic acid and 65.77 parts by mass of isophorone diisocyanate were reacted in the presence of 249.87 parts by mass of ethyl acetate for 3 hours.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．７３質量部と酢酸エチル７２．９３質量部を加え、さらに３時間反応させた。 Next, 19.73 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF Corporation) and 72.93 parts by mass of ethyl acetate were added, and further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）１．９７質量とトリエチルアミン１．１７質量を加えて混合を行った後、イソプロピルアルコール２０１．６３質量部と水８８９．２６質量部、８０質量％水加ヒドラジン６．８２質量部を加え、攪拌することによりポリウレタン（Ａ－３）と乳化剤が混在する水分散体（Ａ－３’）を得た。 Next, 1.97 masses of an anionic emulsifier (manufactured by Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate salt) and 1.17 mass of triethylamine were added to the organic solvent solution of the polyurethane and mixed. Thereafter, 201.63 parts by mass of isopropyl alcohol, 889.26 parts by mass of water and 6.82 parts by mass of 80% by mass of hydrazine hydrate are added, and the aqueous dispersion in which the polyurethane (A-3) and the emulsifier are mixed is stirred. (A-3 ′) was obtained.
　次いで、前記水分散体（Ａ－３’）をエージング及び脱溶剤することによって、酸価１．５のポリウレタン（Ａ－３）を含む不揮発分４０質量％のポリウレタン組成物（III－１）を得た。 Next, by aging and removing the water dispersion (A-3 ′), a polyurethane composition (III-1) having a nonvolatile content of 40% by mass containing polyurethane (A-3) having an acid value of 1.5 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（III－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（III－２）及び手袋（III－３）を作製した。 Further, a polyurethane film (III-2) and a glove (III-) were prepared in the same manner as in Example 1 except that the polyurethane composition (III-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［実施例４］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）２８８．５１質量部、２，２’－ジメチロールプロピオン酸６．５６質量部、及びイソホロンジイソシアネート７７．２９質量部を、酢酸エチル２４８．２４質量部の存在下で３時間反応させた。 [Example 4]
Polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 288.51 parts by mass, 2,2′- in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer 6.56 parts by mass of dimethylolpropionic acid and 77.29 parts by mass of isophorone diisocyanate were reacted for 3 hours in the presence of 248.24 parts by mass of ethyl acetate.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．６０質量部と酢酸エチル７２．４５質量部を加え、さらに３時間反応させた。 Next, 19.60 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF Corporation) and 72.45 parts by mass of ethyl acetate were added, and further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ）３．９２質量とトリエチルアミン５．４４質量を加えて混合を行った後、イソプロピルアルコール１９８．６３質量部と水８８９．５０質量部、８０％水加ヒドラジン８．０５質量部を加え、攪拌することによりポリウレタン（Ａ－４）と乳化剤が混在する水分散体（Ａ－４’）を得た。 Next, after adding 3.92 masses of an anionic emulsifier (manufactured by Nippon Emulsifier Co., Ltd., New Coal 707 SFC) and 5.44 masses of triethylamine to the organic solvent solution of polyurethane, 198.63 parts by mass of isopropyl alcohol, By adding 889.50 parts by mass of water and 8.05 parts by mass of 80% hydrazine, and stirring, an aqueous dispersion (A-4 ′) in which polyurethane (A-4) and an emulsifier are mixed is obtained.
　次いで、前記水分散体（Ａ－４’）をエージング及び脱溶剤することによって、酸価６．９のポリウレタン（Ａ－４）を含む不揮発分４０質量％のポリウレタン組成物（IV－１）を得た。 Next, by aging and removing the water dispersion (A-4 ′), a polyurethane composition (IV-1) having a nonvolatile content of 40% by mass containing polyurethane (A-4) having an acid value of 6.9 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（IV－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（IV－２）及び手袋（IV－３）を作製した。 Further, a polyurethane film (IV-2) and a glove (IV-) were prepared in the same manner as in Example 1 except that the polyurethane composition (IV-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［実施例５］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３０１．６７質量部、２，２’－ジメチロールプロピオン酸１．３９質量部、及びイソホロンジイソシアネート６４．４９質量部を、酢酸エチル２４５．０４質量部の存在下で３時間反応させた。 [Example 5]
In a container purged with nitrogen equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, polyether polyol (Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 301.67 parts by mass, 2,2′- 1.39 parts by mass of dimethylolpropionic acid and 64.49 parts by mass of isophorone diisocyanate were reacted in the presence of 245.04 parts by mass of ethyl acetate for 3 hours.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．３４質量部と酢酸エチル７１．５２質量部を加え、さらに３時間反応させた。 Next, 19.34 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF CORPORATION) and 71.52 parts by mass of ethyl acetate were added, and the reaction was further continued for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）９．６７質量とトリエチルアミン１．１５質量を加えて混合を行った後、イソプロピルアルコール２０７．９８質量部と水８８９．２４質量部、８０質量％水加ヒドラジン６．６９質量部を加え、攪拌することによりポリウレタン（Ａ－５）と乳化剤が混在する水分散体（Ａ－５’）を得た。 Then, 9.67 mass of anionic emulsifier (Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) and 1.15 mass of triethylamine were added to the organic solvent solution of polyurethane and mixed. Then, 207.98 parts by mass of isopropyl alcohol, 889.24 parts by mass of water, 6.69 parts by mass of 80% by mass hydrated hydrazine are added, and the mixture is stirred to obtain an aqueous dispersion in which polyurethane (A-5) and an emulsifier are mixed. (A-5 ′) was obtained.
　次いで、前記水分散体（Ａ－５’）をエージング及び脱溶剤することによって、酸価１．５のポリウレタン（Ａ－５）を含む不揮発分４０質量％のポリウレタン組成物（V－１）を得た。 Next, by aging and removing the water dispersion (A-5 ′), a polyurethane composition (V-1) having a nonvolatile content of 40% by mass containing polyurethane (A-5) having an acid value of 1.5 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（Ｖ－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（Ｖ－２）及び手袋（Ｖ－３）を作製した。 Further, a polyurethane film (V-2) and a glove (V-) were prepared in the same manner as in Example 1 except that the polyurethane composition (V-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［実施例６］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３０６．１１質量部、２，２’－ジメチロールプロピオン酸１．４１質量部、及びイソホロンジイソシアネート６５．４４質量部を、酢酸エチル２４8．6４質量部の存在下で３時間反応させた。 [Example 6]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, polyether polyol (Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 306.11 parts by mass, 2, 2 1.41 parts by mass of '-dimethylolpropionic acid and 65.44 parts by mass of isophorone diisocyanate were reacted for 3 hours in the presence of 248.64 parts by mass of ethyl acetate.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会株式会社製、ユニオックスＭ３０００）１９．６３質量部と酢酸エチル７２．５７質量部を加え、さらに３時間反応させた。 Next, 19.63 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (manufactured by NOF CO., LTD., UNIOX M3000) and 72.57 parts by mass of ethyl acetate are added, and further reacted for 3 hours. It was.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液に、ノニオン性乳化剤（三洋化成工業株式会社製、ニューポールＰＥ７８、ポリオキシエチレン・ポリオキシプロピレン共重合体、数平均分子量 １０，０００、ポリオキシエチレン構造の割合 ２０質量％）３．９３質量とトリエチルアミン１．１７質量を加えて混合を行った後、イソプロピルアルコール２０３．２４質量部と水８８９．２６質量部、８０質量％水加ヒドラジン６．７９質量部を加え、攪拌することによりポリウレタン（Ａ－６）と乳化剤が混在する水分散体（Ａ－６’）を得た。 Next, a nonionic emulsifier (manufactured by Sanyo Chemical Industries, Newpol PE78, polyoxyethylene / polyoxypropylene copolymer, number average molecular weight 10,000, ratio of polyoxyethylene structure 20) is added to the polyurethane organic solvent solution. (Mass%) After adding 3.93 mass and 1.17 mass of triethylamine and mixing, 203.24 mass parts of isopropyl alcohol, 889.26 mass parts of water, and 6.79 mass parts of 80 mass% hydrazine hydrate were added. By stirring, an aqueous dispersion (A-6 ′) in which the polyurethane (A-6) and the emulsifier were mixed was obtained.
　次いで、前記水分散体（Ａ－６’）をエージング及び脱溶剤することによって、酸価１．５のポリウレタン（Ａ－６）を含む不揮発分４０質量％のポリウレタン組成物（VI－１）を得た。 Next, by aging and removing the solvent from the aqueous dispersion (A-6 ′), a polyurethane composition (VI-1) having a nonvolatile content of 40% by mass containing polyurethane (A-6) having an acid value of 1.5 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（VI－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（VI－２）及び手袋（VI－３）を作製した。 Further, a polyurethane film (VI-2) and a glove (VI-) were prepared in the same manner as in Example 1 except that the polyurethane composition (VI-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［実施例７］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３０２．９７質量部、２，２’－ジメチロールプロピオン酸４．６９質量部、及びイソホロンジイソシアネート７４．６０質量部を、酢酸エチル２５４．８４質量部の存在下で３時間反応させた。 [Example 7]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 302.97 parts by mass, 2, 2 4.69 parts by mass of '-dimethylolpropionic acid and 74.60 parts by mass of isophorone diisocyanate were reacted in the presence of 254.84 parts by mass of ethyl acetate for 3 hours.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会株式会社製、ユニオックスＭ３０００）９．８０質量部と酢酸エチル６５．９４質量部を加え、さらに３時間反応させた。 Next, 9.80 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (manufactured by NOF CO., LTD., UNIOX M3000) and 65.94 parts by mass of ethyl acetate are added, and further reacted for 3 hours. It was.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ウレタン樹脂の有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）３．９２質量とトリエチルアミン３．８９質量を加えて混合を行った後、イソプロピルアルコール２００．２４質量部と水８８９．４６質量部、８０質量％水加ヒドラジン７．８５質量部を加え、攪拌することによりポリウレタン（Ａ－７）と乳化剤が混在する水分散体（Ａ－７’）を得た。 Subsequently, an anionic emulsifier (Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) 3.92 mass and triethylamine 3.89 mass were added to the organic solvent solution of the urethane resin and mixed. Thereafter, 200.24 parts by mass of isopropyl alcohol, 889.46 parts by mass of water and 7.85 parts by mass of 80% by mass hydrated hydrazine were added, and the mixture was stirred to obtain a water dispersion in which polyurethane (A-7) and an emulsifier were mixed. A body (A-7 ′) was obtained.
　次いで、前記水分散体（Ａ－７’）をエージング及び脱溶剤することによって、酸価５．０のポリウレタン（Ａ－７）を含む不揮発分４０質量％のポリウレタン組成物（VII－１）を得た。 Next, by aging and removing the solvent from the aqueous dispersion (A-7 ′), a polyurethane composition (VII-1) having a nonvolatile content of 40% by mass containing polyurethane (A-7) having an acid value of 5.0 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（VII－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（VII－２）及び手袋（VII－３）を作製した。 Further, a polyurethane film (VII-2) and a glove (VII-) were prepared in the same manner as in Example 1 except that the polyurethane composition (VII-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［実施例８］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３２７．６３質量部、２，２’－ジメチロールプロピオン酸１．４２質量部、及びイソホロンジイソシアネート４６．５２質量部を、酢酸エチル２５０．３８質量部の存在下で３時間反応させた。 [Example 8]
Polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 327.63 parts by mass, 2,2′- in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer 1.42 parts by mass of dimethylolpropionic acid and 46.52 parts by mass of isophorone diisocyanate were reacted in the presence of 250.38 parts by mass of ethyl acetate for 3 hours.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．７７質量部と酢酸エチル７３．０８量部を加え、さらに３時間反応させた。 Next, 19.77 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF Corporation) and 73.08 parts by mass of ethyl acetate were added, and further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）３．９５質量とトリエチルアミン１．１８質量を加えて混合を行った後、イソプロピルアルコール２０４．６６質量部と水８８８．２２質量部、８０質量％水加ヒドラジン１．３８質量部を加え、攪拌することによりポリウレタン（Ａ－８）と乳化剤が混在する水分散体（Ａ－８’）を得た。 Subsequently, an anionic emulsifier (Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) 3.95 mass and triethylamine 1.18 mass were added to the organic solvent solution of the polyurethane and mixed. Thereafter, 204.66 parts by mass of isopropyl alcohol, 888.22 parts by mass of water, and 1.38 parts by mass of 80% by mass of hydrazine hydrate are added, and the mixture is stirred to obtain an aqueous dispersion in which polyurethane (A-8) and an emulsifier are mixed. (A-8 ′) was obtained.
　次いで、前記水分散体（Ａ－８’）をエージング及び脱溶剤することによって、酸価１．５のポリウレタン（Ａ－８）を含む不揮発分４０質量％のポリウレタン組成物（VIII－１）を得た。 Next, by aging and removing the solvent from the aqueous dispersion (A-8 ′), a polyurethane composition (VIII-1) having a nonvolatile content of 40% by mass containing polyurethane (A-8) having an acid value of 1.5 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（VIII－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（VIII－２）及び手袋（VIII－３）を作製した。 Further, a polyurethane film (VIII-2) and a glove (VIII-) were prepared in the same manner as in Example 1 except that the polyurethane composition (VIII-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［比較例１］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）２６３．００質量部、２，２’－ジメチロールプロピオン酸１４．０２質量部、及びイソホロンジイソシアネート９４．４５質量部を、酢酸エチル２４７．６５質量部の存在下で３時間反応させた。 [Comparative Example 1]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 263.00 parts by mass, 2,2′- 14.02 parts by mass of dimethylolpropionic acid and 94.45 parts by mass of isophorone diisocyanate were reacted in the presence of 247.65 parts by mass of ethyl acetate for 3 hours.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．５５質量部と酢酸エチル７２．２８量部を加え、さらに３時間反応させた。 Next, 19.55 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF CORPORATION) and 72.28 parts by mass of ethyl acetate were added, and the mixture was further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）３．９１質量とトリエチルアミン１１．６４質量を加えて混合を行った後、イソプロピルアルコール１９１．９５質量部と水８８９．８５質量部、８０質量％水加ヒドラジン９．８７質量部を加え、攪拌することによりウレタン樹脂（Ａ－９）と乳化剤が混在する水分散体（Ａ－９’）を得た。 Next, 3.91 masses of anionic emulsifier (manufactured by Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) and 11.64 masses of triethylamine were added to the organic solvent solution of polyurethane and mixed. Then, 191.95 parts by mass of isopropyl alcohol, 889.85 parts by mass of water, 9.87 parts by mass of 80% by mass hydrated hydrazine are added, and the mixture is stirred to obtain a water dispersion in which the urethane resin (A-9) and the emulsifier are mixed. A body (A-9 ′) was obtained.
　次いで、前記水分散体（Ａ－９’）をエージング及び脱溶剤することによって、酸価１４．８のポリウレタン（Ａ－９）を含む不揮発分４０質量％のポリウレタン組成物（IX－１）を得た。 Next, the aqueous dispersion (A-9 ′) is aged and desolvated to obtain a polyurethane composition (IX-1) having a nonvolatile content of 40% by mass and containing polyurethane (A-9) having an acid value of 14.8. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（IX－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（IX－２）及び手袋（IX－３）を作製した。 Further, the polyurethane film (IX-2) and the gloves (IX-) were prepared in the same manner as in Example 1 except that the polyurethane composition (IX-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［比較例２］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３１０．９２質量部、及びイソホロンジイソシアネート６２．２１質量部を、酢酸エチル２４８．７５質量部の存在下で３時間反応させた。 [Comparative Example 2]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Co., Ltd., PTMG2000, hydroxyl value 56.1) 310.92 parts by mass, and isophorone diisocyanate 62. 21 parts by mass were reacted for 3 hours in the presence of 248.75 parts by mass of ethyl acetate.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．6４質量部と酢酸エチル７２．６０量部を加え、さらに３時間反応させた。 Next, 19.64 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (manufactured by NOF Corporation, UNIOX M3000) and 72.60 parts by mass of ethyl acetate were added and further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）３．９３質量を加えて混合を行った後、イソプロピルアルコール２０４．５０質量部と水８８９．1９質量部、８０質量％水加ヒドラジン６．４４質量部を加え、攪拌することによりポリウレタン（Ａ－１０）と乳化剤が混在する水分散体（Ａ－１０’）を得た。 Subsequently, after adding 3.93 mass of an anionic emulsifier (Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) to the organic solvent solution of the polyurethane, the isopropyl alcohol 204 was mixed. Water dispersion (A-10 ′) in which polyurethane (A-10) and emulsifier are mixed by adding 50 parts by weight, 88.19 parts by weight of water and 6.44 parts by weight of 80% by weight hydrazine hydrate and stirring Got.
　次いで、前記水分散体（Ａ－１０’）をエージング及び脱溶剤することによって、酸価０のポリウレタン（Ａ－１０）を含む不揮発分４０質量％のポリウレタン組成物（Ｘ－１）を得た。 Next, the aqueous dispersion (A-10 ′) was aged and removed to obtain a polyurethane composition (X-1) having a nonvolatile content of 40% by mass and containing polyurethane (A-10) having an acid value of 0. .
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（Ｘ－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（Ｘ－２）及び手袋（Ｘ－３）を作製した。 Further, a polyurethane film (X-2) and a glove (X-) were prepared in the same manner as in Example 1 except that the polyurethane composition (X-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［比較例３］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）２９１．７９質量部、２，２’－ジメチロールプロピオン酸１．３４質量部、及びイソホロンジイソシアネート６２．３８質量部を、酢酸エチル２３７．０１質量部の存在下で３時間反応させた。 [Comparative Example 3]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 291.79 parts by mass, 2,2′- 1.34 parts by mass of dimethylolpropionic acid and 62.38 parts by mass of isophorone diisocyanate were reacted for 3 hours in the presence of 237.001 parts by mass of ethyl acetate.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１８．７１質量部と酢酸エチル６９．１８量部を加え、さらに３時間反応させた。 Next, 18.71 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF CORPORATION) and 69.18 parts by mass of ethyl acetate were added, and further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にアニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）２２．４５質量とトリエチルアミン１．１１質量を加えて混合を行った後、イソプロピルアルコール２１８．５３質量部と水８８９．１９質量部、８０質量％水加ヒドラジン６．４７質量部を加え、攪拌することによりポリウレタン（Ａ－１１）と乳化剤が混在する水分散体（Ａ－１１’）を得た。 Next, 22.45 masses of an anionic emulsifier (manufactured by Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) and 1.11 mass of triethylamine were added to the organic solvent solution of polyurethane and mixed. After that, 218.53 parts by mass of isopropyl alcohol, 889.19 parts by mass of water and 6.47 parts by mass of 80% by mass of hydrazine hydrate are added and stirred to obtain an aqueous dispersion in which polyurethane (A-11) and an emulsifier are mixed. (A-11 ′) was obtained.
　次いで、前記水分散体（Ａ－１１’）をエージング及び脱溶剤することによって、酸価１．５のポリウレタン（Ａ－１１）を含む不揮発分４０質量％のポリウレタン組成物（XI－１）を得た。 Next, by aging and removing the solvent from the aqueous dispersion (A-11 ′), a polyurethane composition (XI-1) having a nonvolatile content of 40% by mass containing polyurethane (A-11) having an acid value of 1.5 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（XI－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（XI－２）及び手袋（XI－３）を作製した。 Further, a polyurethane film (XI-2) and a glove (XI-) were prepared in the same manner as in Example 1 except that the polyurethane composition (XI-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　［比較例４］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３０９．１５量部、２，２’－ジメチロールプロピオン酸１．４２質量部、及びイソホロンジイソシアネート６６．０９質量部を、酢酸エチル２５１．１１質量部の存在下で３時間反応させた。 [Comparative Example 4]
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 309.15 parts by weight of polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG 2000, hydroxyl value 56.1), 2,2′- 1.42 parts by mass of dimethylolpropionic acid and 66.09 parts by mass of isophorone diisocyanate were reacted in the presence of 251.11 parts by mass of ethyl acetate for 3 hours.
　次いで、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（日油株式会社製、ユニオックスＭ３０００）１９．８２質量部と酢酸エチル７３．２９量部を加え、さらに３時間反応させた。 Next, 19.82 parts by mass of polyoxyethylene monoalcohol having one hydroxyl group at one end (Niox M3000, manufactured by NOF CORPORATION) and 73.29 parts by mass of ethyl acetate were added and further reacted for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液にトリエチルアミン１．１８質量を加えて混合を行った後、イソプロピルアルコール２００．００質量部と水８８９．２７質量部、８０質量％水加ヒドラジン６．８５質量部を加え、攪拌することによりポリウレタン（Ａ－１２）と水性媒体とを含む水分散体（Ａ－１２’）を得た。 Subsequently, after adding 1.18 mass of triethylamine to the organic solvent solution of the polyurethane and mixing, 200.00 mass parts of isopropyl alcohol, 889.27 mass parts of water, 6.85 mass parts of 80 mass% hydrazine hydrate. In addition, by stirring, an aqueous dispersion (A-12 ′) containing polyurethane (A-12) and an aqueous medium was obtained.
　次いで、前記水分散体（Ａ－１２’）をエージング及び脱溶剤することによって、酸価１．５のポリウレタン（Ａ－１２）を含む不揮発分４０質量％のポリウレタン組成物（XII－１）を得た。しかし、前記ポリウレタン組成物(XII－１)は、水分散安定性の点で十分でないものであった。そのため、前記ポリウレタン組成物（XII－１）を用いてポリウレタンフィルム（XII－２）や手袋（XII－３）を作製することができなかった。 Next, by aging and removing the water dispersion (A-12 ′), a polyurethane composition (XII-1) having a nonvolatile content of 40% by mass containing polyurethane (A-12) having an acid value of 1.5 is obtained. Obtained. However, the polyurethane composition (XII-1) was not sufficient in terms of water dispersion stability. Therefore, a polyurethane film (XII-2) or a glove (XII-3) could not be produced using the polyurethane composition (XII-1).
　［比較例５］
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、ポリエーテルポリオール（三菱化学株式会株式会社製、ＰＴＭＧ２０００、水酸基価５６．１）３３６．３７質量部、２，２’－ジメチロールプロピオン酸１．３９質量部、及びイソホロンジイソシアネート４９．６１質量部を、酢酸エチル２５８．２５質量部の存在下で３時間反応させた。 [Comparative Example 5]
Polyether polyol (manufactured by Mitsubishi Chemical Corporation, PTMG2000, hydroxyl value 56.1) 336.37 parts by mass, 2, 2 in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer 1.39 parts by mass of '-dimethylolpropionic acid and 49.61 parts by mass of isophorone diisocyanate were reacted in the presence of 258.25 parts by mass of ethyl acetate for 3 hours.
　反応物の規定のＮＣＯ％に達した時点で反応を終了し、ポリウレタンの有機溶剤溶液を得た。 The reaction was terminated when the prescribed NCO% of the reaction product was reached, and a polyurethane organic solvent solution was obtained.
　次いで、前記ポリウレタンの有機溶剤溶液に、酢酸エチル５８．６９質量部、アニオン性乳化剤（日本乳化剤株式会社製、ニューコール７０７ＳＦＣ、ポリオキシエチレン多環フェニルエーテル硫酸エステル塩）１１．６２質量とトリエチルアミン１．１５質量を加えて混合を行った後、イソプロピルアルコール２１０．８１質量部と水８８８．３３質量部、８０％水加ヒドラジン１．９６質量部を加え、攪拌することによりポリウレタン（Ａ－１５）と乳化剤が混在する水分散体（Ａ－１３’）を得た。 Next, 58.69 parts by mass of ethyl acetate, 11.62 parts by mass of an anionic emulsifier (manufactured by Nippon Emulsifier Co., Ltd., New Coal 707 SFC, polyoxyethylene polycyclic phenyl ether sulfate ester salt) After mixing by adding .15 parts by mass, 210.81 parts by mass of isopropyl alcohol, 88.33 parts by mass of water and 1.96 parts by mass of 80% hydrazine hydrate were added to the polyurethane (A-15) by stirring. An aqueous dispersion (A-13 ′) in which an emulsifier and an emulsifier were mixed was obtained.
　次いで、前記水分散体（Ａ－１３’）をエージング及び脱溶剤することによって、酸価１．５のポリウレタン（Ａ－１３）を含む不揮発分４０質量％のポリウレタン組成物（XIII－１）を得た。 Next, by aging and removing the solvent from the aqueous dispersion (A-13 ′), a polyurethane composition (XIII-1) having a nonvolatile content of 40% by mass containing polyurethane (A-13) having an acid value of 1.5 is obtained. Obtained.
　また、前記ポリウレタン組成物（I－１）の代わりにポリウレタン組成物（XIII－１）を使用すること以外は、実施例１と同様の方法によって、ポリウレタンフィルム（XIII－２）及び手袋（XIII－３）を作製した。 Further, a polyurethane film (XIII-2) and a glove (XIII-) were produced in the same manner as in Example 1 except that the polyurethane composition (XIII-1) was used instead of the polyurethane composition (I-1). 3) was produced.
　〔ポリウレタン組成物の水分散安定性の評価方法〕
　前記ポリウレタン組成物中の経時における沈降の程度に基づいて評価した。具体的には、前記ポリウレタン組成物をスクリュー管等のガラス容器に密栓し、室温（２５℃）での静置後、２週間、１ヶ月後の沈降物の有無を目視で確認することで、ポリウレタン組成物の水分散安定性を評価した。 [Evaluation method of water dispersion stability of polyurethane composition]
Evaluation was made based on the degree of sedimentation over time in the polyurethane composition. Specifically, the polyurethane composition is sealed in a glass container such as a screw tube, and after standing at room temperature (25 ° C.), visually confirming the presence or absence of precipitates after 2 weeks and 1 month, The water dispersion stability of the polyurethane composition was evaluated.
　[判定基準]
　Ａ：　室温（２５℃）で１ヶ月静置した後に、沈降物が全く確認できなかった。 [Criteria]
A: No sediment was confirmed after standing at room temperature (25 ° C.) for 1 month.
　Ｂ：　室温（２５℃）で２週間静置した後には、沈降物が全く確認できなかったものの、室温（２５℃）１ヶ月静置した後には、ごく僅かに沈降物の発生が確認できた。 B: Although the sediment was not confirmed at all after standing at room temperature (25 ° C.) for 2 weeks, the occurrence of the sediment was confirmed slightly after standing at room temperature (25 ° C.) for 1 month. .
　Ｃ：　室温（２５℃）で２週間静置した後には、沈降物が全く確認できなかったものの、室温（２５℃）３週間静置した後には、ごく僅かに沈降物の発生が確認できた。 C: After standing at room temperature (25 ° C.) for 2 weeks, no sediment was confirmed, but after standing at room temperature (25 ° C.) for 3 weeks, the occurrence of sediment was confirmed only slightly. .
　Ｄ：　室温（２５℃）で２週間静置した後に、沈降物の発生が確認できた。 D: Generation of sediment was confirmed after standing at room temperature (25 ° C.) for 2 weeks.
　Ｅ：　室温（２５℃）で１週間静置した後に、沈降物の発生が確認できた。 E: Generation of sediment was confirmed after standing at room temperature (25 ° C.) for 1 week.
　［ポリウレタンフィルムの柔軟性の評価方法］
　柔軟性は、前記実施例及び比較例で得たポリウレタンフィルムの３００％モジュラスに基づいて評価した。前記で得たポリウレタンフィルムの３００％モジュラスは、オートグラフＡＧ－Ｉ（（株）島津製作所製、引張り速度３００ｍｍ／分）を用いて測定した。前記で得た測定値と下記評価基準に基づいて、ポリウレタンフィルムの柔軟性を評価した。具体的には、前記測定値が小さいほど、柔軟性に優れるものと評価した。なお、ポリウレタンフィルムを作製できなかったものは、「フィルム化不可」と評価した。 [Method for evaluating flexibility of polyurethane film]
Flexibility was evaluated based on the 300% modulus of the polyurethane films obtained in the above examples and comparative examples. The 300% modulus of the polyurethane film obtained above was measured using Autograph AG-I (manufactured by Shimadzu Corporation, tensile speed 300 mm / min). Based on the measured value obtained above and the following evaluation criteria, the flexibility of the polyurethane film was evaluated. Specifically, the smaller the measured value, the better the flexibility. In addition, the thing which was not able to produce a polyurethane film was evaluated as "it cannot be made into a film."
　Ａ：　３００％モジュラスが１２ＭＰａ未満であり柔軟性に優れるものであった。 A: The 300% modulus was less than 12 MPa, and the flexibility was excellent.
　Ｂ：３００％モジュラスが１２ＭＰａ以上１５ＭＰａ未満であり柔軟性に優れるものであった。 B: 300% modulus was 12 MPa or more and less than 15 MPa, and was excellent in flexibility.
　Ｃ：　３００％モジュラスが１５ＭＰａ以上２０ＭＰａ未満であり良好な柔軟性を備えたものであった。 C: The 300% modulus was 15 MPa or more and less than 20 MPa and had good flexibility.
　Ｄ：　３００％モジュラスが２０ＭＰａ以上２５ＭＰａ未満であり十分な柔軟性を備えたものではなかった。 D: The 300% modulus was 20 MPa or more and less than 25 MPa, and it did not have sufficient flexibility.
　Ｅ：　３００％モジュラスが２５ＭＰａ以上であり十分な柔軟性を備えたものではなかった。 E: The 300% modulus was 25 MPa or more, and it did not have sufficient flexibility.
　［手袋の強度（耐摩耗性）の評価方法］
　強度（耐摩耗性）は、前記実施例及び比較例で得た手袋を用いて評価した。具体的には、前記手袋の手のひら部分の強度を、試験規格ＥＮ３８８：２００４（マーチンデール磨耗試験機；インテック（株）製）に準拠して行った。前記試験の結果、手袋の手のひら部分が破れるまでの磨耗回数が大きいほど、高強度であると評価した。なお、ポリウレタンフィルムを作製できなかったものは、「フィルム化不可」と評価した。 [Gloves strength (wear resistance) evaluation method]
The strength (wear resistance) was evaluated using the gloves obtained in the examples and comparative examples. Specifically, the strength of the palm part of the glove was measured in accordance with test standard EN388: 2004 (Martindale abrasion tester; manufactured by Intec Corporation). As a result of the test, the larger the number of wear until the palm of the glove was torn, the higher the strength. In addition, the thing which was not able to produce a polyurethane film was evaluated as "it cannot be made into a film."
　Ａ：　磨耗回数が４０００回以上であり高強度なものであった。 A: The number of wear was 4000 times or more and high strength.
　Ｂ：磨耗回数が３５００回以上４０００回未満であり良好な強度を備えたものであった。 B: The number of wears was 3500 times or more and less than 4000 times and had good strength.
　Ｃ：　磨耗回数が３０００回以上３５００回未満であり良好な強度を備えたものであった
　Ｄ：　磨耗回数が２５００回以上３０００回未満であり十分な強度を備えたものではなかった。 C: The number of wear was 3000 times or more and less than 3500 times and had good strength. D: The number of wear was 2500 or more and less than 3000 times, and the strength was not sufficient.
　Ｅ：　磨耗回数が２５００回未満であり十分な強度を備えたものではなかった。 E: The number of wear was less than 2500, and it was not equipped with sufficient strength.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表１～３中の「乳化剤の含有割合」は、ポリウレタン１００質量部に対する乳化剤の含有量を示す。また、「末端ポリオキシエチレン構造の質量割合」は、ポリウレタンの全量に対し、その末端のポリオキシエチレン構造の質量割合を示す。 In Tables 1 to 3, “Emulsifier content ratio” indicates the content of the emulsifier with respect to 100 parts by mass of the polyurethane. The “mass ratio of terminal polyoxyethylene structure” indicates the mass ratio of the terminal polyoxyethylene structure to the total amount of polyurethane.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　実施例１～３で得たポリウレタンフィルムは、いずれも優れた柔軟性と耐摩耗性等の強度を有するものであった。また、使用するポリウレタンの酸価が若干高めである実施例４記載のポリウレタンフィルムは、優れた強度と良好な柔軟性とを備えたものであった。また、乳化剤の含有割合が若干高めである実施例５記載のポリウレタンフィルムは、良好な強度と優れた柔軟性とを備えたものであった。また、アニオン系乳化剤の代わりにノニオン系乳化剤を使用した実施例６記載のポリウレタンフィルムは、良好な強度と優れた柔軟性とを備えたものであった。また、末端のポリオキシエチレン構造の割合が２．５質量％である実施例７記載のポリウレタン組成物の水分散安定性は良好であり、そのポリウレタンフィルムは優れた柔軟性と耐摩耗性等の強度を有するものであった。また、ウレア結合量が若干低めである実施例９記載のポリウレタンフィルムは、良好な強度と優れた柔軟性とを備えたものであった。 The polyurethane films obtained in Examples 1 to 3 each had excellent strength such as flexibility and abrasion resistance. Further, the polyurethane film described in Example 4 in which the acid value of the polyurethane used was slightly higher was provided with excellent strength and good flexibility. Moreover, the polyurethane film of Example 5 in which the content of the emulsifier is slightly higher was provided with good strength and excellent flexibility. Further, the polyurethane film described in Example 6 using a nonionic emulsifier instead of an anionic emulsifier was provided with good strength and excellent flexibility. Further, the water dispersion stability of the polyurethane composition described in Example 7 in which the proportion of the terminal polyoxyethylene structure is 2.5% by mass is good, and the polyurethane film has excellent flexibility and wear resistance. It had strength. Moreover, the polyurethane film described in Example 9 having a slightly lower urea bond amount had good strength and excellent flexibility.
　一方、非常に高酸価のポリウレタンを用いた比較例１記載のポリウレタンフィルムは、柔軟性及び強度の点で十分でなかった。また、酸価が０であるポリウレタンを用いた比較例２記載のポリウレタンフィルムは、柔軟性及び強度の点で十分でなかった。また、乳化剤を比較的多く使用した比較例３記載のポリウレタンフィルムは、柔軟性及び強度の点で十分でなかった。また、乳化剤を使用しない比較例４では、ポリウレタン組成物の水分散安定性が不十分であるため、それを用いポリウレタンフィルムを製造することができなかった。また、末端にポリオキシエチレン構造を有さないが、その分子中にポリオキシエチレン構造を有するポリウレタンを用いた比較例６記載のポリウレタンフィルムは、柔軟性及び強度の点で十分でなかった。 On the other hand, the polyurethane film described in Comparative Example 1 using a very high acid value polyurethane was not sufficient in terms of flexibility and strength. Moreover, the polyurethane film described in Comparative Example 2 using polyurethane having an acid value of 0 was not sufficient in terms of flexibility and strength. Moreover, the polyurethane film described in Comparative Example 3 using a relatively large amount of emulsifier was not sufficient in terms of flexibility and strength. Further, in Comparative Example 4 where no emulsifier was used, the polyurethane composition was insufficient in water dispersion stability, and thus a polyurethane film could not be produced using it. In addition, the polyurethane film described in Comparative Example 6 using a polyurethane having a polyoxyethylene structure in the molecule, which does not have a polyoxyethylene structure at the terminal, was not sufficient in terms of flexibility and strength.

Claims (5)

  1. 末端にポリオキシエチレン構造を有する酸価０．１～１０のポリウレタン（Ａ）、乳化剤（Ｂ）、及び、水性媒体（Ｃ）を含有し、前記乳化剤（Ｂ）の含有割合が、前記ポリウレタン（Ａ）１００質量部に対して０．１質量部～５質量部であるポリウレタン組成物（Ｄ）を用いて得られることを特徴とするポリウレタンフィルム。 It contains a polyurethane (A) having a polyoxyethylene structure at the terminal and an acid value of 0.1 to 10, an emulsifier (B), and an aqueous medium (C), and the content of the emulsifier (B) is the polyurethane ( A) A polyurethane film obtained by using a polyurethane composition (D) in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass.
  2. 前記ポリウレタン（Ａ）が、酸基を有するポリオール（ａ１－１）とポリエーテルポリオール（ａ１－２）とを含有するポリオール（ａ１）、ポリイソシアネート（ａ２）、及び、片末端に１個の水酸基を有するポリオキシエチレンモノアルコール（ａ４）を反応させることによって得られるものである請求項１に記載のポリウレタンフィルム。 The polyurethane (A) is a polyol (a1) containing a polyol (a1-1) having an acid group and a polyether polyol (a1-2), a polyisocyanate (a2), and one hydroxyl group at one end. The polyurethane film according to claim 1, which is obtained by reacting polyoxyethylene monoalcohol (a4) with
  3. 前記ポリウレタン（Ａ）が、前記ポリウレタン（Ａ）の全量に対して、末端にポリオキシエチレン構造を０．５質量％～１０質量％の範囲で有するものである請求項１に記載のポリウレタンフィルム。 The polyurethane film according to claim 1, wherein the polyurethane (A) has a polyoxyethylene structure in the range of 0.5 mass% to 10 mass% with respect to the total amount of the polyurethane (A).
  4. 前記乳化剤（Ｂ）がアニオン性乳化剤である請求項１に記載のポリウレタンフィルム。 The polyurethane film according to claim 1, wherein the emulsifier (B) is an anionic emulsifier.
  5. 請求項１～４のいずれか１項に記載のポリウレタンフィルムを用いて得られることを特徴とするフィルム加工品。 A film processed product obtained by using the polyurethane film according to any one of claims 1 to 4.
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