WO2013176256A1 - Aqueous polyurethane dispersing element - Google Patents

Aqueous polyurethane dispersing element Download PDF

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Publication number
WO2013176256A1
WO2013176256A1 PCT/JP2013/064490 JP2013064490W WO2013176256A1 WO 2013176256 A1 WO2013176256 A1 WO 2013176256A1 JP 2013064490 W JP2013064490 W JP 2013064490W WO 2013176256 A1 WO2013176256 A1 WO 2013176256A1
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Prior art keywords
water dispersion
component
polyurethane water
polyurethane
weight
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PCT/JP2013/064490
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French (fr)
Japanese (ja)
Inventor
充朗 後藤
謙次 清水
善夫 関
朋哉 厳本
智恵 一本杉
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トーヨーポリマー株式会社
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Priority to JP2014516865A priority Critical patent/JP6100770B2/en
Publication of WO2013176256A1 publication Critical patent/WO2013176256A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—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
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/3246—Polyamines heterocyclic, the heteroatom being oxygen or nitrogen in the form of an amino group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • 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
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group

Definitions

  • the present invention relates to a polyurethane water dispersion.
  • polyurethane water dispersions include self-emulsifying types having a carboxyl group in the polyurethane resin.
  • a polyurethane water dispersion that uses polycarbonate polyol as the polyol component, defines the content of carboxyl groups, urethane groups, and urea groups, and gives a dry film excellent in solvent resistance and flexibility (Reference 1), polyisocyanate
  • Reference 2 A polyurethane water dispersion (Reference 2) that gives a dry film having both toughness and flexibility by using a specific diphenylmethane diisocyanate and an alicyclic diisocyanate together has been proposed.
  • the main objective is to provide the polyurethane water dispersion which can form the film layer which has utility in the point of ethanol water resistance performance and moisture permeability. is there.
  • the present inventors have used diphenylmethane diisocyanate and alicyclic diisocyanate in combination as polyisocyanate, and among various polyols, a random copolymer of ethylene oxide and tetrahydrofuran The present inventors have found that a film obtained from a polyurethane water dispersion produced by using a polycarbonate polyol in combination has practicality with respect to ethanol water resistance and moisture permeability, and completed the present invention.
  • the gist of the present invention is as follows.
  • Polyisocyanate (A) composed of diphenylmethane diisocyanate (a1) and alicyclic diisocyanate (a2), random copolymer of ethylene oxide and tetrahydrofuran (B), polycarbonate polyol (C), number average molecular weight is 400 or less
  • the polyurethane water dispersion according to the above [4], wherein the content of 2,4′-diphenylmethane diisocyanate in the component (a1) is 70% by weight or more.
  • the film layer obtained from the water dispersion is practical in terms of both ethanol water resistance and moisture permeability.
  • the polyurethane water dispersion of the present invention has a polyisocyanate (A) composed of diphenylmethane diisocyanate (MDI) and an alicyclic diisocyanate, a random copolymer of ethylene oxide and tetrahydrofuran (B), a polycarbonate polyol (C), and a number average molecular weight. It was obtained by neutralizing an isocyanate group-terminated prepolymer obtained by reacting a polyhydric alcohol chain extender (D) of 400 or less, a diol compound (E) having a carboxyl group, and other components as necessary.
  • A polyisocyanate
  • D polyhydric alcohol chain extender
  • E diol compound having a carboxyl group
  • polyurethane water dispersion is suitably used, for example, as a paint, a coating agent, an adhesive or the like.
  • component (A) the polyisocyanate (hereinafter sometimes simply referred to as “component (A)”
  • MDI hereinafter sometimes simply referred to as “component (a1)”
  • component (a2) diisocyanate
  • component (a1) and component (a2) in combination, a film layer having practicality can be obtained in terms of ethanol water resistance and moisture permeability.
  • the “film layer” means a coating layer, a coating layer, or an adhesive formed when the polyurethane aqueous dispersion of the present invention is used as a paint, a coating agent, an adhesive, or the like.
  • the ethanol water resistance of the film layer is an index of the ethanol water resistance of the film layer formed when the polyurethane water dispersion of the present invention is used as a paint, a coating agent, an adhesive, or the like.
  • a film film thickness: about 100 ⁇ m
  • the breaking strength and the area swelling ratio is obtained for a film (film thickness: about 100 ⁇ m) produced by casting a polyurethane water dispersion on a glass plate. It is evaluated by measuring. The measurement of breaking strength is performed as follows. From the manufactured film, a test piece was cut out using a JIS No. 3 dumbbell, and the test piece taken out after being immersed in 70% water (23 ° C.
  • the area swelling rate is measured as follows. A 50 mm square test piece was cut out from the manufactured film, taken out after being immersed in 70% water (23 ° C. ⁇ 2 ° C.) of ethyl alcohol for 30 minutes, the area of the taken out test piece was measured, and the film area before immersion Is evaluated based on the area swelling ratio. As an evaluation standard, when the area swelling rate is 10% or more and less than 60%, it is judged to have practicality, and when the area swelling rate is less than 10%, it is judged to be excellent in practicality.
  • the “moisture permeability of the film layer” is an index of the moisture permeability of the film layer formed when the polyurethane water dispersion of the invention is used as a paint, a coating agent, an adhesive, or the like.
  • a film film thickness: about 100 ⁇ m
  • JIS L 1099A-1 method calcium chloride method
  • the moisture permeability is 500 g / m 2 -24hrs or more and less than 800 g / m 2 -24hrs, it is judged to be practical, and when the moisture permeability is 800 g / m 2 -24hrs or more. It is judged to be excellent in practical use.
  • MDI examples include 2,2′-diphenylmethane diisocyanate (2,2′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), and 4,4′-diphenylmethane diisocyanate (4,4 '-MDI).
  • the said compound can be used individually by 1 type, or can be used in combination of 2 or more type.
  • the alicyclic diisocyanate is not particularly limited.
  • isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (Isocyanatomethyl) cyclohexane, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, etc.
  • the said compound can be used individually by 1 type, or can be used in combination of 2 or more type.
  • the combination of MDI and alicyclic diisocyanate is not particularly limited, but the film layer obtained from the polyurethane water dispersion has practicality in terms of both ethanol water resistance and moisture permeability, MDI and IPDI, A combination of MDI and hydrogenated MDI is preferred.
  • the content ratio of the component (a1) and the component (a2) is not particularly limited, but the film layer obtained from the polyurethane water dispersion has practicality both in terms of ethanol water resistance and moisture permeability.
  • (A1) / (a2) 20/80 to 80/20 (molar ratio) is preferable.
  • a random copolymer (B) of ethylene oxide and tetrahydrofuran (hereinafter sometimes abbreviated as “component (B)”) and a polycarbonate polyol (C) (hereinafter referred to as “component (C)”) (It may be abbreviated in some cases).
  • component (C) ethylene oxide and tetrahydrofuran
  • component (C) polycarbonate polyol
  • the film layer obtained from the polyurethane water dispersion has practicality in terms of ethanol water resistance, but is not practical in terms of moisture permeability.
  • the component (B) and the component (C) in combination the film layer obtained from the polyurethane water dispersion has both practicality in terms of ethanol water resistance and moisture permeability.
  • Component (B) is a kind of polyether polyol, and the molar ratio (EO / THF) of ethylene oxide units (EO) to tetrahydrofuran units (THF) is preferably 80/20 to 10/90, and 70/30 to 20 / 80 is more preferable.
  • the number average molecular weight of the component (B) is preferably 800 to 4000, and more preferably 900 to 3500.
  • a component (B) can be used individually by 1 type, or can be used in combination of 2 or more type.
  • component (C) examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4- One or two or more polyols selected from cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, pentaerythritol, and the like; and diethylene carbonate, dimethyl carbonate, diethyl carbonate DOO, one or more carbonates selected from diphenyl carbonate
  • polyhydric alcohol chain extender (D) having a number average molecular weight of 400 or less examples include ethylene glycol, propylene glycol, and 1,3-propane.
  • Linear aliphatic glycols such as dipropylene glycol, tripropylene glycol, polyethylene glycol, 1,8-octanediol, 1,9-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, 2methyl 1,3-propanediol, 2-butyl-2-ethyl Aliphatic branched glycol
  • Dialkylol alkanoic acid having 6 to 24 carbon atoms can be used as the diol compound (E) having a carboxyl group (hereinafter sometimes abbreviated as “component (E)”), for example, 2,2-dimethylol.
  • component (E) examples include propionic acid (DMPA), 2,2-dimethylolbutanoic acid (DMBA), 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid and the like.
  • DMPA propionic acid
  • DMBA 2,2-dimethylolbutanoic acid
  • These salts such as salts of amines (triethylamine, alkanolamine, morpholine, etc.) and / or alkali metal salts (sodium salt, etc.) can also be used.
  • the said compound can be used individually by 1 type, or can be used in combination of 2 or more type.
  • amine chain extender (F) examples include ethylenediamine, propylenediamine, hexamethylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, 2 -Methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine, hydrazine and the like.
  • component (F) examples include ethylenediamine, propylenediamine, hexamethylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, 2 -Methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine, hydrazine and the like.
  • the said compound can be used individually by 1 type, or can be used in combination of 2 or more type.
  • Examples of other components include additives and auxiliaries commonly used in the aqueous system related to the polyurethane water dispersion of the present invention.
  • additives, auxiliaries and the like commonly used in the field of aqueous paint and aqueous coating agent can be blended as necessary.
  • known methods such as stirring and dispersion can be employed.
  • additives, auxiliaries and the like commonly used in the aqueous adhesive field can be blended as necessary.
  • pigments and dyes water for adjusting solid content and viscosity
  • organic solvents such as isopropanol and N-methylpyrrolidone for adjusting surface tension
  • antiblocking agents such as isopropanol and N-methylpyrrolidone for adjusting surface tension
  • antiblocking agents such as isopropanol and N-methylpyrrolidone for adjusting surface tension
  • dispersion stabilizers such as isopropanol and N-methylpyrrolidone for adjusting surface tension
  • antiblocking agents such as isopropanol and N-methylpyrrolidone for adjusting surface tension
  • antiblocking agents such as isopropanol and N-methylpyrrolidone for adjusting surface tension
  • dispersion stabilizers such as isopropanol and N-methylpyrrolidone for adjusting surface tension
  • antiblocking agents such as isopropan
  • the polyurethane water dispersion of the present invention is used by blending with other resin emulsions on the premise that the film layer obtained from the water dispersion satisfies practicality in terms of ethanol water resistance and moisture permeability.
  • other resin-based emulsions include acrylic emulsion, polyester emulsion, polyolefin emulsion, and latex.
  • the component (A1) is used as the component (A1) on the premise that the film layer obtained from the water dispersion satisfies practicality in terms of ethanol water resistance and moisture permeability.
  • polyisocyanates other than (a2) can be used together as necessary. Examples of polyisocyanates that can be used in combination include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetramethylxylene diisocyanate, and m-phenylene.
  • Aromatic diisocyanates such as diisocyanate and p-phenylene diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 3-methyl-1,5-pentane diisocyanate, pentane-1,5-diisocyanate lysine diisocyanate and the like It is done. Further, urethanized products, urea compounds, allophanates, biurets, carbodiimidides, uretoniminates, uretdiones, isocyanurates, and the like obtained by reacting with these polymeric substances and active hydrogen group-containing compounds are also included. Furthermore, the mixture which consists of 2 or more types of these series of isocyanate group containing compounds is also mentioned.
  • polyurethane water dispersion of the present invention other than the above components (B) and (C) on the premise that the film layer obtained from the water dispersion satisfies practicality in terms of ethanol water resistance and moisture permeability.
  • These polyols can be used in combination as required.
  • examples of the polyol that can be used in combination include polyether polyols and polyester polyols other than the component (B).
  • polyether polyols other than component (B) examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, catechol, and hydroquinone.
  • One or two or more kinds of monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, cyclohexylene, etc. using one or more kinds of compounds having at least two active hydrogen atoms such as bisphenol A as an initiator
  • Examples of the reaction product obtained by addition polymerization of the above are listed.
  • reaction product obtained by addition polymerization of two or more monomers block addition, random addition, or a mixture of both may be used.
  • Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • Polyether polyols other than the above component (B) can be used alone or in combination of two or more.
  • polyester polyol examples include 1 selected from phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, fumaric acid and the like.
  • examples thereof include those obtained by a polycondensation reaction between a seed or two or more dibasic acids and one or two or more polyols used for the synthesis of the aforementioned polycarbonate polyol.
  • the said polyester polyol can be used individually by 1 type, or can be used in combination of 2 or more type.
  • the polyurethane water dispersion of the present invention may be abbreviated as an isocyanate group-terminated prepolymer (hereinafter referred to as “prepolymer”) by reacting the above components (A) to (E) and, if necessary, other components. Then, the prepolymer is neutralized, and the resulting neutralized product is dispersed in water and then subjected to a chain extension reaction using an amine chain extender (F).
  • prepolymer isocyanate group-terminated prepolymer
  • the equivalent ratio of isocyanate group / hydroxyl group (NCO group / OH group) at the time of producing the prepolymer is not particularly limited and is usually 1.05 to 2, more preferably 1.05 to 1.5.
  • the reaction conditions for producing the prepolymer are not particularly limited, but are usually 30 to 120 ° C., preferably 40 to 100 ° C., more preferably 45 to 90 ° C., and usually 1 to 10 hours.
  • a reaction catalyst such as dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine can be added as necessary.
  • reaction catalysts can be used individually by 1 type, or can also be used in combination of 2 or more type.
  • an organic solvent that does not react with the isocyanate group can be added in the reaction step or after the reaction is completed.
  • examples of such an organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, N, N-dimethylformamide, N-methylpyrrolidone and the like.
  • the production method of the isocyanate group-terminated prepolymer is not particularly limited, and a conventionally known one-shot method (one-stage method) or a multi-stage isocyanate polyaddition reaction method is used.
  • the prepolymer usually has an isocyanate value of 0.1 to 5% (weight content of residual isocyanate groups with respect to resin solids).
  • the neutralizing agent used to neutralize the prepolymer is not particularly limited as long as it can neutralize the carboxyl group, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, and triethanolamine. Examples include amines, sodium hydroxide, potassium hydroxide, and ammonia.
  • prepolymer neutralized product When the prepolymer neutralized product is emulsified and dispersed in water, 50 to 500 parts by weight of water is used per 100 parts by weight of resin solids in the prepolymer so that phase inversion emulsification proceeds efficiently. Is used.
  • the polyurethane water dispersion is produced by adding the above component (F) during or after emulsification and causing a chain extension reaction.
  • the amount of component (F) used can be arbitrarily selected from 0.3 to 1.5 equivalents, preferably 0.4 to 1.2 equivalents, based on the terminal isocyanate group of the prepolymer.
  • the resin solid content (nonvolatile content) concentration in the polyurethane water dispersion is preferably in the range of 15 to 66%.
  • the resin solid content concentration in the polyurethane water dispersion can also be adjusted by adding or distilling off water.
  • the EO content derived from the ethylene oxide unit (EO) in the polyurethane water dispersion is not particularly limited, but the film layer obtained from the polyurethane water dispersion has practicality in terms of moisture permeability. It is preferable to set it as 1.5 weight% or more with respect to the polyurethane (namely, resin solid content) in a polyurethane water dispersion, and it is more preferable to set it as 7 weight% or more.
  • the EO content is preferably 1.5 to 18% by weight, preferably 7 to 18% by weight. % Is more preferable.
  • the raw materials charged so that the total weight of EO is the above content with respect to the total weight of the manufacturing raw materials constituting the polyurethane resin among the manufacturing raw materials of the polyurethane water dispersion. It can be adjusted by setting.
  • the content of 2,4′-MDI is preferably 40% by weight or more, more preferably 70% by weight. % Or more, and particularly preferably 80% by weight or more, the film layer obtained from the polyurethane water dispersion has excellent practicality in terms of flexibility, and has a breaking strength and an area in ethanol water resistance. The practicality is excellent in terms of swelling rate.
  • “flexibility of the film layer” is an index of flexibility for the film layer formed when the aqueous polyurethane dispersion of the present invention is used as a paint, coating agent, adhesive, or the like.
  • the EO content is described above. There is no particular need to set the range, but the above effect can be exhibited even when the EO content is lower than the above range.
  • the EO content is usually in the range of 1 to 18% by weight, preferably 1 to 8% by weight, more preferably 1 to 3% by weight.
  • the EO content is 1 to 18 % By weight is preferred, and 7 to 18% by weight is more preferred.
  • the polyurethane water dispersion of the present invention is suitably used as, for example, a paint, a coating agent or an adhesive. That is, the polyurethane water dispersion of the present invention can be used as a paint, coating agent, adhesive or the like containing the polyurethane water dispersion of the present invention.
  • the film thickness of the film layer obtained from the polyurethane water dispersion of the present invention varies depending on the use, and is not particularly limited, but is preferably 5 to 1000 ⁇ m, more preferably 20 to 1000 ⁇ m.
  • Component (D) Polyhydric alcohol chain extender 1,4-butanediol
  • DMPA 2,2-dimethylolpropionic acid
  • DMBA 2,2-dimethylolbutanoic acid
  • the criteria for determining 100% modulus are as follows. A: Less than 4.0 MPa (good) ⁇ : 4.0 MPa or more and less than 9.0 MPa (slightly good) X: 9.0 MPa or more (defect) * Among the above criteria, ⁇ and ⁇ are evaluated as having practicality.
  • Area swelling rate (%) ⁇ (area after immersion ⁇ initial area) / initial area ⁇ ⁇ 100 A: Less than 10% (good) ⁇ : 10% or more and less than 60% (slightly good) X: 60% or more (defect) * Among the above criteria, ⁇ and ⁇ are evaluated as having practicality.
  • Area swelling rate (%) ⁇ (area after immersion ⁇ initial area) / initial area ⁇ ⁇ 100 A: Less than 10% (good) ⁇ : 10% or more and less than 60% (slightly good) X: 60% or more (defect) * Among the above criteria, ⁇ and ⁇ are evaluated as having practicality.
  • Moisture permeability Measurement of moisture permeability According to JIS L 1099A-1 method (calcium chloride method), the moisture permeability of the film obtained above (thickness: about 100 ⁇ m) was measured, and moisture permeability was measured according to the following criteria. Evaluated. ⁇ : 800 g / m 2 -24hrs or more ⁇ : 500 g / m 2 -24hrs or more, less than 800 g / m 2 -24hrs ⁇ : 500 g / m 2 -24hrs or less * Of the above criteria, ⁇ and ⁇ are practical It is evaluated that it has sex.
  • Polyurethane water dispersions No. 2 to No. 10 were produced in the same manner as polyurethane water dispersion No. 1 using the raw materials and formulation shown in Table 1.
  • Table 2 shows the results.
  • the numerical values of the charged raw materials in Table 2 indicate the content (% by weight) of each component when the total weight of the components (A) to (F) is 100% of the manufactured raw material.
  • This test is particularly effective for films obtained from polyurethane aqueous dispersions produced by variously changing the types and combinations of components (A) on the premise that components (B) and (C) are used in combination as polyols.
  • the relationship between ethanol water performance and moisture permeability is examined. From Table 2, when only MDI (a1) is used as the polyisocyanate (No. 6), the polyurethane water dispersion itself cannot be produced, and when only H12MDI (a2) or IPDI (a2) is used as the polyisocyanate It was found that (No. 7, No. 9) has practicality in both moisture permeability, but ethanol water resistance is not practical in terms of breaking strength.
  • Polyurethane water dispersions No. 12 to No. 22 were produced in the same manner as polyurethane water dispersion No. 11, using the raw materials and formulation shown in Table 3.
  • Table 4 shows the results.
  • the numerical values of the charged raw materials in Table 4 indicate the content (% by weight) of each component when the total weight of the components (A) to (F) is 100% of the manufactured raw material.
  • the product of the present invention was compared with the products of the present invention (No.3, No.11, No.13 to No.15, No.17 to No.20) and comparative products (No.21, No.22). It can be said that a stable polyurethane water dispersion can be produced up to an EO content of about 20% by weight.
  • Polyurethane water dispersions No. 24 and No. 25 were produced in the same manner as polyurethane water dispersion No. 23, using the raw materials and formulation shown in Table 5.
  • Table 6 shows the results.
  • the numerical values of the charged raw materials in Table 6 indicate the content (% by weight) of each component when the total weight of the components (A) to (F) is 100% of the manufactured raw material.
  • the EO content in the polyurethane water dispersion was set to the same level (2.0%) as No. 1 to No. 10 used in Table 2, and the component (a1) was 2,4 as the isomer component.
  • the effect of using Millionate NM100 with a high content of -MDI was examined. From Table 6, when Millionate NM100 having a content of 2,4′-MDI of about 90% is used, the practicality of flexibility is improved, and the practicality of ethanol water resistance is both practical in terms of breaking strength and area swelling rate. was rated as improved.
  • the film layer obtained from the water dispersion has both practicality in terms of ethanol water resistance and moisture permeability, paints and coatings that require the above characteristics. It can be used for adhesives and adhesives.

Abstract

Provided is an aqueous polyurethane dispersing element with which it is possible to form a film layer exhibiting practicality in terms of ethanol water resistance and moisture permeability. An isocyanate-terminated prepolymer is obtained by reacting: a polyisocyanate (A) comprising a diphenylmethane diisocyanate (a1) and an alicyclic diisocyanate (a2); a random copolymer (B) of an ethylene oxide and a tetrahydrofuran; a polycarbonate polyol (C); a polyalcohol-based chain extender (D) having a number average molecular weight of 400 or less; and a diol compound (E) having a carboxyl group. The present invention is obtained by neutralizing said isocyanate-terminated prepolymer, dispersing the neutralized product thus obtained in water, and by subjecting the dispersed neutralized product to chain extension reaction by using an amine-based chain extender (F).

Description

ポリウレタン水分散体Polyurethane water dispersion
　本発明はポリウレタン水分散体に関するものである。 The present invention relates to a polyurethane water dispersion.
　従来、ポリウレタン水分散体には、ポリウレタン樹脂中にカルボキシル基を有する自己乳化型のものがある。例えば、ポリオール成分としてポリカーボネートポリオールを使用し、カルボキシル基、ウレタン基及びウレア基の含有量を規定して、耐溶剤性と柔軟性に優れる乾燥皮膜を与えるポリウレタン水分散体（文献１）、ポリイソシアネートとして特定のジフェニルメタンジイソシアネートと脂環族系ジイソシアネートを併用して、強靭さと柔軟性を併せ持つ乾燥皮膜を与えるポリウレタン水分散体（文献２）等が提案されている。
　しかし、ポリウレタン水分散体から得られる乾燥皮膜について、要求特性として耐エタノール水性能と透湿性能が求められることがあるが、文献１，２には、これらの特性を十分満足するポリウレタン水分散体は開示されていない。 Conventional polyurethane water dispersions include self-emulsifying types having a carboxyl group in the polyurethane resin. For example, a polyurethane water dispersion that uses polycarbonate polyol as the polyol component, defines the content of carboxyl groups, urethane groups, and urea groups, and gives a dry film excellent in solvent resistance and flexibility (Reference 1), polyisocyanate A polyurethane water dispersion (Reference 2) that gives a dry film having both toughness and flexibility by using a specific diphenylmethane diisocyanate and an alicyclic diisocyanate together has been proposed.
However, with respect to the dry film obtained from the polyurethane water dispersion, ethanol water resistance and moisture permeation performance may be required as required characteristics. In References 1 and 2, a polyurethane water dispersion that sufficiently satisfies these characteristics is required. Is not disclosed.
特開２０１１－１２２０３４号公報JP 2011-122034 A 特開２０１０－０５３１５９号公報JP 2010-053159 A
　本発明は上記事情に鑑みてなされたものであり、その主たる目的は、耐エタノール水性能と透湿性能の点で、実用性を有するフィルム層を形成し得るポリウレタン水分散体を提供することにある。 This invention is made | formed in view of the said situation, The main objective is to provide the polyurethane water dispersion which can form the film layer which has utility in the point of ethanol water resistance performance and moisture permeability. is there.
　本発明者らは、上記課題を解決するため、鋭意検討した結果、ポリイソシアネートとして、ジフェニルメタンジイソシアネートと脂環式ジイソシアネートとを併用し、かつ種々のポリオールのうち、エチレンオキシドとテトラヒドロフランのランダム共重合体とポリカーボネートポリオールとを併用して製造されたポリウレタン水分散体から得られたフィルムが耐エタノール水性能と透湿性能について実用性を有することを見出し、本発明を完成した。 As a result of diligent studies to solve the above problems, the present inventors have used diphenylmethane diisocyanate and alicyclic diisocyanate in combination as polyisocyanate, and among various polyols, a random copolymer of ethylene oxide and tetrahydrofuran The present inventors have found that a film obtained from a polyurethane water dispersion produced by using a polycarbonate polyol in combination has practicality with respect to ethanol water resistance and moisture permeability, and completed the present invention.
　すなわち、本発明の要旨は以下のとおりである。
〔１〕　ジフェニルメタンジイソシアネート（ａ１）と脂環式ジイソシアネート（ａ２）とからなるポリイソシアネート（Ａ）、エチレンオキシドとテトラヒドロフランのランダム共重合体（Ｂ）、ポリカーボネートポリオール（Ｃ）、数平均分子量が４００以下である多価アルコール系鎖延長剤（Ｄ）及びカルボキシル基を有するジオール化合物（Ｅ）を反応させて得られるイソシアネート基末端プレポリマーを中和し、得られた中和物を水中に分散させた後、アミン系鎖延長剤（Ｆ）を用いて鎖延長反応させて得られる、フィルム層を形成するために用いられるポリウレタン水分散体。
〔２〕　成分（ａ１）と成分（ａ２）のモル比が、（ａ１）／（ａ２）＝２０／８０～８０／２０である、前記〔１〕記載のポリウレタン水分散体。
〔３〕　成分（ａ２）が水素添加ジフェニルメタンジイソシアネート及びイソホロンジイソシアネートから選択される少なくとも１種である、前記〔２〕記載のポリウレタン水分散体。
〔４〕　成分（Ｂ）の数平均分子量が８００～４０００であり、エチレンオキシド単位（ＥＯ）とテトラヒドロフラン単位（ＴＨＦ）のモル比がＥＯ／ＴＨＦ＝８０／２０～１０／９０である、前記〔１〕～〔３〕のいずれか記載のポリウレタン水分散体。
〔５〕　ポリウレタン水分散体中のポリウレタンに対して、ＥＯ含有量が１．５重量％以上である、前記〔４〕記載のポリウレタン水分散体。
〔６〕　ＥＯ含有量が１．５～１８重量％である、前記〔５〕記載のポリウレタン水分散体。
〔７〕　成分（ａ１）中における２，４’－ジフェニルメタンジイソシアネートの含有量が７０重量％以上である、前記〔４〕記載のポリウレタン水分散体。 That is, the gist of the present invention is as follows.
[1] Polyisocyanate (A) composed of diphenylmethane diisocyanate (a1) and alicyclic diisocyanate (a2), random copolymer of ethylene oxide and tetrahydrofuran (B), polycarbonate polyol (C), number average molecular weight is 400 or less After neutralizing an isocyanate group-terminated prepolymer obtained by reacting a polyhydric alcohol chain extender (D) and a diol compound (E) having a carboxyl group, and dispersing the obtained neutralized product in water A polyurethane water dispersion used for forming a film layer, obtained by chain extension reaction using an amine chain extender (F).
[2] The polyurethane water dispersion according to [1], wherein the molar ratio of the component (a1) to the component (a2) is (a1) / (a2) = 20/80 to 80/20.
[3] The polyurethane water dispersion according to the above [2], wherein the component (a2) is at least one selected from hydrogenated diphenylmethane diisocyanate and isophorone diisocyanate.
[4] The number average molecular weight of component (B) is 800 to 4000, and the molar ratio of ethylene oxide unit (EO) to tetrahydrofuran unit (THF) is EO / THF = 80/20 to 10/90, ] The polyurethane water dispersion according to any one of [3] to [3].
[5] The polyurethane water dispersion according to the above [4], wherein the EO content is 1.5% by weight or more based on the polyurethane in the polyurethane water dispersion.
[6] The polyurethane water dispersion according to [5], wherein the EO content is 1.5 to 18% by weight.
[7] The polyurethane water dispersion according to the above [4], wherein the content of 2,4′-diphenylmethane diisocyanate in the component (a1) is 70% by weight or more.
　本発明のポリウレタン水分散体によれば、該水分散体から得られるフィルム層が、耐エタノール水性能と透湿性能の点で、ともに実用性を有するものとなる。 According to the polyurethane water dispersion of the present invention, the film layer obtained from the water dispersion is practical in terms of both ethanol water resistance and moisture permeability.
　本発明のポリウレタン水分散体は、ジフェニルメタンジイソシアネート（ＭＤＩ）と脂環式ジイソシアネートとからなるポリイソシアネート（Ａ）、エチレンオキシドとテトラヒドロフランのランダム共重合体（Ｂ）、ポリカーボネートポリオール（Ｃ）、数平均分子量が４００以下である多価アルコール系鎖延長剤（Ｄ）、カルボキシル基を有するジオール化合物（Ｅ）、及び必要によりその他の成分を反応させて得られるイソシアネート基末端プレポリマーを中和し、得られた中和物を水中に乳化分散させた後、アミン系鎖延長剤（Ｆ）を用いて鎖延長反応させて得られる。得られたポリウレタン水分散体は、例えば、塗料、コーティング剤、接着剤等として好適に用いられる。 The polyurethane water dispersion of the present invention has a polyisocyanate (A) composed of diphenylmethane diisocyanate (MDI) and an alicyclic diisocyanate, a random copolymer of ethylene oxide and tetrahydrofuran (B), a polycarbonate polyol (C), and a number average molecular weight. It was obtained by neutralizing an isocyanate group-terminated prepolymer obtained by reacting a polyhydric alcohol chain extender (D) of 400 or less, a diol compound (E) having a carboxyl group, and other components as necessary. It is obtained by emulsifying and dispersing the neutralized product in water and then subjecting it to a chain extension reaction using an amine chain extender (F). The obtained polyurethane water dispersion is suitably used, for example, as a paint, a coating agent, an adhesive or the like.
　本発明では、ポリイソシアネート（Ａ）（以下、単に「成分（Ａ）」と略記する場合がある）としては、ＭＤＩ（以下、「成分（ａ１）」と略記する場合がある）と脂環式ジイソシアネート（以下、「成分（ａ２）」と略記する場合がある）を併用する点に特徴がある。成分（ａ１）のみを用いた場合は、ポリウレタン水分散体が製造できず、成分（ａ２）のみを用いた場合は、ポリウレタン水分散体を用いて得られるフィルム層が耐エタノール水性能に劣るという問題点がある。成分（ａ１）と成分（ａ２）を併用することで、耐エタノール水性能と透湿性能の点で、実用性を有するフィルム層が得られる。ここで、本発明において「フィルム層」とは、本発明のポリウレタン水分散体を、塗料、コーティング剤、または接着剤等として用いた場合にそれぞれ形成される塗膜層、コーティング層、または接着剤層等を総称したものをいう。 In the present invention, as the polyisocyanate (A) (hereinafter sometimes simply referred to as “component (A)”), MDI (hereinafter sometimes simply referred to as “component (a1)”) and alicyclic It is characterized in that diisocyanate (hereinafter sometimes abbreviated as “component (a2)”) is used in combination. When only the component (a1) is used, a polyurethane water dispersion cannot be produced, and when only the component (a2) is used, the film layer obtained using the polyurethane water dispersion is inferior in ethanol water resistance. There is a problem. By using the component (a1) and the component (a2) in combination, a film layer having practicality can be obtained in terms of ethanol water resistance and moisture permeability. Here, in the present invention, the “film layer” means a coating layer, a coating layer, or an adhesive formed when the polyurethane aqueous dispersion of the present invention is used as a paint, a coating agent, an adhesive, or the like. A general term for layers.
　本発明において「フィルム層の耐エタノール水性能」は、本発明のポリウレタン水分散体を、塗料、コーティング剤、または接着剤等として用いた場合に形成されるフィルム層について、耐エタノール水性能の指標となるものであり、後述する実施例では、ポリウレタン水分散体をガラス板上にキャストして製造されたフィルム（膜厚：約１００μｍ）について、破断強度と面積膨潤率のうち、少なくとも１つを測定することで評価される。破断強度の測定は以下のように行われる。製造されたフィルムから、ＪＩＳ３号ダンベルを用い試験片を切り出し、エチルアルコール７０％水（２３℃±２℃）に３０分間浸漬させた後に取り出した試験片をＪＩＳ　Ｋ－６３０１に従い、破断強度試験を行い、得られた破断強度により評価される。評価基準として、破断強度が４ＭＰａ以上、１０ＭＰａ未満のときは、実用性を有すると判断され、破断強度が１０ＭＰａ以上のときは、実用性に優れると判断される。面積膨潤率の測定は以下のように行われる。製造されたフィルムから、５０mm角の試験片を切り出し、エチルアルコール７０％水（２３℃±２℃）に３０分間浸漬させた後に取り出し、取り出した試験片の面積を測定し、浸漬前のフィルム面積を基準とした面積膨潤率により評価される。評価基準として、面積膨潤率が１０％以上、６０％未満のときは、実用性を有すると判断され、面積膨潤率が１０％未満のときは、実用性に優れると判断される。 In the present invention, “the ethanol water resistance of the film layer” is an index of the ethanol water resistance of the film layer formed when the polyurethane water dispersion of the present invention is used as a paint, a coating agent, an adhesive, or the like. In the examples described later, for a film (film thickness: about 100 μm) produced by casting a polyurethane water dispersion on a glass plate, at least one of the breaking strength and the area swelling ratio is obtained. It is evaluated by measuring. The measurement of breaking strength is performed as follows. From the manufactured film, a test piece was cut out using a JIS No. 3 dumbbell, and the test piece taken out after being immersed in 70% water (23 ° C. ± 2 ° C.) for 30 minutes was subjected to a breaking strength test according to JIS K-6301. And evaluated by the obtained breaking strength. As an evaluation criterion, when the breaking strength is 4 MPa or more and less than 10 MPa, it is judged to have practicality, and when the breaking strength is 10 MPa or more, it is judged to be excellent in practicality. The area swelling rate is measured as follows. A 50 mm square test piece was cut out from the manufactured film, taken out after being immersed in 70% water (23 ° C. ± 2 ° C.) of ethyl alcohol for 30 minutes, the area of the taken out test piece was measured, and the film area before immersion Is evaluated based on the area swelling ratio. As an evaluation standard, when the area swelling rate is 10% or more and less than 60%, it is judged to have practicality, and when the area swelling rate is less than 10%, it is judged to be excellent in practicality.
　本発明において「フィルム層の透湿性能」は、本発明のポリウレタン水分散体を、塗料、コーティング剤、または接着剤等として用いた場合に形成されるフィルム層について、透湿性能の指標となるものであり、後述する実施例では、ポリウレタン水分散体をガラス板上にキャストして製造されたフィルム（膜厚：約１００μｍ）をＪＩＳ　Ｌ　１０９９Ａ－１法（塩化カルシウム法）に準じて測定された透湿度により評価される。評価基準として、透湿度が５００　g/m２－24hrs　以上、８００　g/m２－24hrs　未満のときは、実用性を有すると判断され、透湿度が８００　g/m２－24hrs　以上のときは実用性に優れると判断される。 In the present invention, the “moisture permeability of the film layer” is an index of the moisture permeability of the film layer formed when the polyurethane water dispersion of the invention is used as a paint, a coating agent, an adhesive, or the like. In Examples described later, a film (film thickness: about 100 μm) produced by casting a polyurethane water dispersion on a glass plate was measured according to JIS L 1099A-1 method (calcium chloride method). It is evaluated by the moisture permeability. As an evaluation standard, when the moisture permeability is 500 g / m 2 -24hrs or more and less than 800 g / m 2 -24hrs, it is judged to be practical, and when the moisture permeability is 800 g / m 2 -24hrs or more. It is judged to be excellent in practical use.
　ＭＤＩとしては、例えば、２，２’－ジフェニルメタンジイソシアネート（２，２’－ＭＤＩ）、２，４’－ジフェニルメタンジイソシアネート（２，４’－ＭＤＩ）、及び４，４’－ジフェニルメタンジイソシアネート（４，４’－ＭＤＩ）等が挙げられる。上記化合物は、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 Examples of MDI include 2,2′-diphenylmethane diisocyanate (2,2′-MDI), 2,4′-diphenylmethane diisocyanate (2,4′-MDI), and 4,4′-diphenylmethane diisocyanate (4,4 '-MDI). The said compound can be used individually by 1 type, or can be used in combination of 2 or more type.
　脂環式ジイソシアネートとしては特に限定されず、例えば、イソホロンジイソシアネート（ＩＰＤＩ）、４，４’－ジシクロヘキシルメタンジイソシアネート（水素添加ＭＤＩ）、１，４－ビス（イソシアナトメチル）シクロヘキサン、１，３－ビス（イソシアナトメチル）シクロヘキサン、メチルシクロヘキシレンジイソシアネート（水素添加ＴＤＩ）、ビス　（２－イソシアナトエチル）－４－シクロヘキセン－１，２－ジカルボキシレート、２，５－又は２，６－ノルボルナンジイソシアネート等が挙げられる。上記化合物は、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 The alicyclic diisocyanate is not particularly limited. For example, isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated MDI), 1,4-bis (isocyanatomethyl) cyclohexane, 1,3-bis (Isocyanatomethyl) cyclohexane, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, etc. Is mentioned. The said compound can be used individually by 1 type, or can be used in combination of 2 or more type.
　ＭＤＩと脂環式ジイソシアネートの組合せとしては特に限定されないが、ポリウレタン水分散体から得られるフィルム層が、耐エタノール水性能と透湿性能の点で、ともに実用性を有する点で、ＭＤＩとＩＰＤＩ、ＭＤＩと水素添加ＭＤＩの組合せが好ましい。 The combination of MDI and alicyclic diisocyanate is not particularly limited, but the film layer obtained from the polyurethane water dispersion has practicality in terms of both ethanol water resistance and moisture permeability, MDI and IPDI, A combination of MDI and hydrogenated MDI is preferred.
　本発明において成分（ａ１）と成分（ａ２）の含有比は特に限定されないが、ポリウレタン水分散体から得られるフィルム層が、耐エタノール水性能と透湿性能の点で、ともに実用性を有する点で（ａ１）／（ａ２）＝２０／８０～８０／２０（モル比）の範囲とすることが好ましい。 In the present invention, the content ratio of the component (a1) and the component (a2) is not particularly limited, but the film layer obtained from the polyurethane water dispersion has practicality both in terms of ethanol water resistance and moisture permeability. (A1) / (a2) = 20/80 to 80/20 (molar ratio) is preferable.
　本発明では、ポリオールとして、エチレンオキシドとテトラヒドロフランのランダム共重合体（Ｂ）（以下、「成分（Ｂ）」と略記する場合がある）とポリカーボネートポリオール（Ｃ）（以下、「成分（Ｃ）」と略記する場合がある）を併用する点に特徴がある。ポリオールとして成分（Ｃ）のみを用いた場合は、ポリウレタン水分散体から得られるフィルム層が、耐エタノール水性能の点で実用性を有するが、透湿性能の点で実用性を有しない。ポリオールとして成分（Ｂ）と成分（Ｃ）を併用することで、ポリウレタン水分散体から得られるフィルム層が、耐エタノール水性能と透湿性能の点で、ともに実用性を有するものとなる。 In the present invention, as the polyol, a random copolymer (B) of ethylene oxide and tetrahydrofuran (hereinafter sometimes abbreviated as “component (B)”) and a polycarbonate polyol (C) (hereinafter referred to as “component (C)”) (It may be abbreviated in some cases). When only the component (C) is used as the polyol, the film layer obtained from the polyurethane water dispersion has practicality in terms of ethanol water resistance, but is not practical in terms of moisture permeability. By using the component (B) and the component (C) in combination as the polyol, the film layer obtained from the polyurethane water dispersion has both practicality in terms of ethanol water resistance and moisture permeability.
　成分（Ｂ）はポリエーテルポリオールの一種であり、エチレンオキシド単位（ＥＯ）とテトラヒドロフラン単位（ＴＨＦ）のモル比（ＥＯ／ＴＨＦ）として、８０／２０～１０／９０が好ましく、７０／３０～２０／８０がより好ましい。成分（Ｂ）の数平均分子量としては、８００～４０００が好ましく、９００～３５００がより好ましい。成分（Ｂ）は、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 Component (B) is a kind of polyether polyol, and the molar ratio (EO / THF) of ethylene oxide units (EO) to tetrahydrofuran units (THF) is preferably 80/20 to 10/90, and 70/30 to 20 / 80 is more preferable. The number average molecular weight of the component (B) is preferably 800 to 4000, and more preferably 900 to 3500. A component (B) can be used individually by 1 type, or can be used in combination of 2 or more type.
　成分（Ｃ）としては、例えば、エチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、ネオペンチルグリコール、１，８－オクタンジオール、１，９－ノナンジオール、ジエチレングリコール、ジプロピレングリコール、１，４－シクロヘキサンジメタノール、あるいはビスフェノールＡのエチレンオキサイド又はプロピレンオキサイド付加物、トリメチロールプロパン、グリセリン、ペンタエリスリトール等から選ばれる１種または２種以上のポリオール類；と、ジエチレンカーボネート、ジメチルカーボネート、ジエチルカーボネート、ジフェニルカーボネート等から選ばれる１種または２種以上のカーボネート類；との脱アルコール反応、脱フェノール反応等で得られるものが挙げられる。成分（Ｃ）の数平均分子量としては、通常１０００～５０００、好ましくは１０００～４０００、より好ましくは１０００～３０００である。成分（Ｃ）は、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 Examples of the component (C) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, dipropylene glycol, 1,4- One or two or more polyols selected from cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, pentaerythritol, and the like; and diethylene carbonate, dimethyl carbonate, diethyl carbonate DOO, one or more carbonates selected from diphenyl carbonate; dealcoholization reaction with those obtained in dephenol reaction or the like. The number average molecular weight of the component (C) is usually 1000 to 5000, preferably 1000 to 4000, more preferably 1000 to 3000. A component (C) can be used individually by 1 type, or can be used in combination of 2 or more type.
　数平均分子量が４００以下である多価アルコール系鎖延長剤（Ｄ）（以下、「成分（Ｄ）」と略記する場合がある）としては、例えば、エチレングリコール、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、ポリエチレングリコール、１，８－オクタンジオール、１，９－ノナンジオール等の直鎖脂肪族グリコール；ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、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－メチル－１，８－オクタンジオール等の脂肪族分岐グリコール；１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール、水添加ビスフェノールＡ等の脂環族グリコール；グリセリン、トリメチロールプロパン、トリブチロールプロパン、ペンタエリスリトール、ソルビトール等の多官能グリコール；が挙げられる。成分（Ｄ）は、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 Examples of the polyhydric alcohol chain extender (D) having a number average molecular weight of 400 or less (hereinafter sometimes abbreviated as “component (D)”) include ethylene glycol, propylene glycol, and 1,3-propane. Diol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol Linear aliphatic glycols such as dipropylene glycol, tripropylene glycol, polyethylene glycol, 1,8-octanediol, 1,9-nonanediol; neopentyl glycol, 3-methyl-1,5-pentanediol, 2methyl 1,3-propanediol, 2-butyl-2-ethyl Aliphatic branched glycols such as ru-1,3-propanediol and 2-methyl-1,8-octanediol; alicyclic groups such as 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and water-added bisphenol A Glycol; multifunctional glycols such as glycerin, trimethylolpropane, tributyrolpropane, pentaerythritol, sorbitol; A component (D) can be used individually by 1 type, or can be used in combination of 2 or more type.
　カルボキシル基を有するジオール化合物（Ｅ）（以下、「成分（Ｅ）」と略記する場合がある）としては、炭素数６～２４のジアルキロールアルカン酸が使用でき、例えば２，２－ジメチロールプロピオン酸（ＤＭＰＡ）、２，２－ジメチロールブタン酸（ＤＭＢＡ）、２，２－ジメチロールヘプタン酸、２，２－ジメチロールオクタン酸等が挙げられる。これらの塩、例えばアミン類（トリエチルアミン、アルカノールアミン、モルホリン等）の塩及び／又はアルカリ金属塩（ナトリウム塩等）も使用できる。上記化合物は、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 Dialkylol alkanoic acid having 6 to 24 carbon atoms can be used as the diol compound (E) having a carboxyl group (hereinafter sometimes abbreviated as “component (E)”), for example, 2,2-dimethylol. Examples include propionic acid (DMPA), 2,2-dimethylolbutanoic acid (DMBA), 2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid and the like. These salts such as salts of amines (triethylamine, alkanolamine, morpholine, etc.) and / or alkali metal salts (sodium salt, etc.) can also be used. The said compound can be used individually by 1 type, or can be used in combination of 2 or more type.
　アミン系鎖延長剤（Ｆ）（以下、「成分（Ｆ）」と略記する場合がある）としては、例えば、エチレンジアミン、プロピレンジアミン、ヘキサメチレンジアミン、４,４'－ジアミノジシクロヘキシルメタン、ピペラジン、２－メチルピペラジン、イソホロンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ヒドラジン等が挙げられる。上記化合物は、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 Examples of the amine chain extender (F) (hereinafter sometimes abbreviated as “component (F)”) include ethylenediamine, propylenediamine, hexamethylenediamine, 4,4′-diaminodicyclohexylmethane, piperazine, 2 -Methylpiperazine, isophoronediamine, diethylenetriamine, triethylenetetramine, hydrazine and the like. The said compound can be used individually by 1 type, or can be used in combination of 2 or more type.
　その他の成分としては、本発明のポリウレタン水分散体に係る水系システムで慣用される添加剤、助剤等が挙げられる。 Examples of other components include additives and auxiliaries commonly used in the aqueous system related to the polyurethane water dispersion of the present invention.
　本発明のポリウレタン水分散体を水性塗料、水性コーティング剤として用いる場合は、水性塗料、水性コーティング剤の分野で慣用される添加剤、助剤等を必要に応じて配合することができる。例えば、顔料、溶剤、ブロッキング防止剤、乳化剤、分散安定剤、消泡剤、粘度調節剤、レベリング剤、ゲル化防止剤、光安定剤、酸化防止剤、紫外線吸収剤、耐熱性向上剤、抗菌剤、無機及び有機充填剤、可塑剤、滑剤、帯電防止剤、補強材、触媒等が挙げられる。配合方法としては、攪拌、分散等の公知の方法が採用できる。 When the polyurethane water dispersion of the present invention is used as an aqueous paint or aqueous coating agent, additives, auxiliaries and the like commonly used in the field of aqueous paint and aqueous coating agent can be blended as necessary. For example, pigments, solvents, antiblocking agents, emulsifiers, dispersion stabilizers, antifoaming agents, viscosity modifiers, leveling agents, antigelling agents, light stabilizers, antioxidants, UV absorbers, heat resistance improvers, antibacterial agents Agents, inorganic and organic fillers, plasticizers, lubricants, antistatic agents, reinforcing materials, catalysts and the like. As a blending method, known methods such as stirring and dispersion can be employed.
　本発明のポリウレタン水分散体を水性接着剤として用いる場合は、必要に応じて、水性接着剤分野で慣用される添加剤、助剤等を必要に応じて配合することができる。例えば、顔料や染料、固形分や粘度を調整するための水、表面張力を調整するためのイソプロパノールやＮ－メチルピロリドンのような有機溶剤、ブロッキング防止剤、分散安定剤、揺変剤、酸化防止剤、紫外線吸収剤、消泡剤、増粘剤、分散剤、界面活性剤、触媒、フィラー、滑剤、帯電防止剤、可塑剤等の添加剤を配合することができる。さらに、必要に応じて、接着剤の塗布直前に硬化剤を添加して使用することができる。 When using the aqueous polyurethane dispersion of the present invention as an aqueous adhesive, additives, auxiliaries and the like commonly used in the aqueous adhesive field can be blended as necessary. For example, pigments and dyes, water for adjusting solid content and viscosity, organic solvents such as isopropanol and N-methylpyrrolidone for adjusting surface tension, antiblocking agents, dispersion stabilizers, thixotropic agents, and antioxidants Additives such as agents, ultraviolet absorbers, antifoaming agents, thickeners, dispersants, surfactants, catalysts, fillers, lubricants, antistatic agents, and plasticizers can be blended. Furthermore, if necessary, a curing agent can be added and used immediately before application of the adhesive.
　本発明のポリウレタン水分散体には、該水分散体から得られるフィルム層が耐エタノール水性能と透湿性能の点で実用性を満たすことを前提として、他樹脂系のエマルジョンをブレンドして使用することもできる。このような他樹脂系のエマルジョンとしては、例えば、アクリルエマルジョン、ポリエステルエマルジョン、ポリオレフィンエマルジョン、ラテックス等が挙げられる。 The polyurethane water dispersion of the present invention is used by blending with other resin emulsions on the premise that the film layer obtained from the water dispersion satisfies practicality in terms of ethanol water resistance and moisture permeability. You can also Examples of such other resin-based emulsions include acrylic emulsion, polyester emulsion, polyolefin emulsion, and latex.
　本発明のポリウレタン水分散体には、該水分散体から得られるフィルム層が耐エタノール水性能と透湿性能の点で実用性を満たすことを前提として、成分（Ａ）として、上記成分（ａ１）と（ａ２）以外のポリイソシアネートを必要に応じて併用することができる。併用し得るポリイソシアネートとしては、例えば、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、キシレン－１，４－ジイソシアネート、キシレン－１，３－ジイソシアネート、テトラメチルキシレンジイソシアネート、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート等の芳香族ジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、３－メチル－１，５－ペンタンジイソシアネート、ペンタン－１，５－ジイシシアネートリジンジイソシアネート等の脂肪族ジイソシアネート等が挙げられる。また、これらのポリメリック体、活性水素基含有化合物と反応させて得られるウレタン化物、ウレア化物、アロファネート化物、ビウレット化物、カルボジイミド化物、ウレトンイミン化物、ウレトジオン化物、イソシアヌレート化物等も挙げられる。さらに、これら一連のイソシアネート基含有化合物の２種以上からなる混合物も挙げられる。 In the polyurethane water dispersion of the present invention, the component (A1) is used as the component (A1) on the premise that the film layer obtained from the water dispersion satisfies practicality in terms of ethanol water resistance and moisture permeability. ) And polyisocyanates other than (a2) can be used together as necessary. Examples of polyisocyanates that can be used in combination include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetramethylxylene diisocyanate, and m-phenylene. Aromatic diisocyanates such as diisocyanate and p-phenylene diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 3-methyl-1,5-pentane diisocyanate, pentane-1,5-diisocyanate lysine diisocyanate and the like It is done. Further, urethanized products, urea compounds, allophanates, biurets, carbodiimidides, uretoniminates, uretdiones, isocyanurates, and the like obtained by reacting with these polymeric substances and active hydrogen group-containing compounds are also included. Furthermore, the mixture which consists of 2 or more types of these series of isocyanate group containing compounds is also mentioned.
　本発明のポリウレタン水分散体には、該水分散体から得られるフィルム層が耐エタノール水性能と透湿性能の点で実用性を満たすことを前提として、上記成分（Ｂ）と（Ｃ）以外のポリオールを必要に応じて併用することができる。併用し得るポリオールとしては、例えば、成分（Ｂ）以外のポリエーテルポリオール、ポリエステルポリオール等が挙げられる。 In the polyurethane water dispersion of the present invention, other than the above components (B) and (C) on the premise that the film layer obtained from the water dispersion satisfies practicality in terms of ethanol water resistance and moisture permeability. These polyols can be used in combination as required. Examples of the polyol that can be used in combination include polyether polyols and polyester polyols other than the component (B).
　成分（Ｂ）以外のポリエーテルポリオールとしては、例えば、エチレングリコール、プロピレングリコール、１，３－ブチレングリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール、カテコール、ヒドロキノン、ビスフェノールＡ等の活性水素原子を少なくとも２個有する化合物の１種または２種以上を開始剤として、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、スチレンオキシド、エピクロルヒドリン、シクロヘキシレン等のモノマーの１種または２種以上を付加重合させた反応物が挙げられ、モノマーの２種以上を付加重合させた反応物の場合は、ブロック付加、ランダム付加または両者の混合系でも良い。具体的には、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコール等を例示できる。上記成分（Ｂ）以外のポリエーテルポリオールは、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 Examples of polyether polyols other than component (B) include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, catechol, and hydroquinone. , One or two or more kinds of monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, cyclohexylene, etc. using one or more kinds of compounds having at least two active hydrogen atoms such as bisphenol A as an initiator Examples of the reaction product obtained by addition polymerization of the above are listed. In the case of a reaction product obtained by addition polymerization of two or more monomers, block addition, random addition, or a mixture of both may be used. Specific examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Polyether polyols other than the above component (B) can be used alone or in combination of two or more.
　ポリエステルポリオールとしては、例えば、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸、コハク酸、マロン酸、アジピン酸、セバシン酸、１，４－シクロヘキシルジカルボン酸、マレイン酸、フマル酸等から選ばれる１種または２種以上の二塩基酸と、前述のポリカーボネートポリオールの合成に用いられる１種または２種以上のポリオール類との重縮合反応により得られるものが挙げられる。上記ポリエステルポリオールは、１種を単独で用いることができ、または２種以上を組み合わせて用いることができる。 Examples of the polyester polyol include 1 selected from phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, malonic acid, adipic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, maleic acid, fumaric acid and the like. Examples thereof include those obtained by a polycondensation reaction between a seed or two or more dibasic acids and one or two or more polyols used for the synthesis of the aforementioned polycarbonate polyol. The said polyester polyol can be used individually by 1 type, or can be used in combination of 2 or more type.
　本発明のポリウレタン水分散体は、上記成分（Ａ）～（Ｅ）、及び必要によりその他の成分を反応させることにより、イソシアネート基末端プレポリマー（以下、「プレポリマー」と略記する場合がある。）を製造し、次いで該プレポリマーを中和し、得られた中和物を水中に分散させた後、アミン系鎖延長剤（Ｆ）を用いて鎖延長反応させて製造される。 The polyurethane water dispersion of the present invention may be abbreviated as an isocyanate group-terminated prepolymer (hereinafter referred to as “prepolymer”) by reacting the above components (A) to (E) and, if necessary, other components. Then, the prepolymer is neutralized, and the resulting neutralized product is dispersed in water and then subjected to a chain extension reaction using an amine chain extender (F).
　プレポリマー製造時のイソシアネート基／水酸基の当量比（ＮＣＯ基／ＯＨ基）は特に限定されず、通常１．０５～２であり、１．０５～１．５がより好ましい。 The equivalent ratio of isocyanate group / hydroxyl group (NCO group / OH group) at the time of producing the prepolymer is not particularly limited and is usually 1.05 to 2, more preferably 1.05 to 1.5.
　プレポリマー製造時の反応条件は特に限定されないが、通常３０～１２０℃、好ましくは４０～１００℃、さらに好ましくは４５～９０℃で、通常１～１０時間の条件で行われる。この際、必要に応じて、ジブチル錫ジラウレート、ジオクチル錫ジラウレート、スタナスオクトエート、ジブチル錫－２－エチルへキソエート、トリエチルアミン、トリエチレンジアミン、Ｎ－メチルモルホリンなどの反応触媒を添加することができる。これらの反応触媒は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。 The reaction conditions for producing the prepolymer are not particularly limited, but are usually 30 to 120 ° C., preferably 40 to 100 ° C., more preferably 45 to 90 ° C., and usually 1 to 10 hours. At this time, a reaction catalyst such as dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dibutyltin-2-ethylhexoate, triethylamine, triethylenediamine, N-methylmorpholine can be added as necessary. These reaction catalysts can be used individually by 1 type, or can also be used in combination of 2 or more type.
　また、反応段階において、あるいは、反応終了後に、イソシアネート基と反応しない有機溶剤を添加することができる。このような有機溶剤としては、例えば、アセトン、メチルエチルケトン、トルエン、テトラヒドロフラン、ジオキサン、Ｎ,Ｎ－ジメチルホルムアミド、Ｎ－メチルピロリドンなどを挙げることができる。本発明においてイソシアネート基末端プレポリマーの製造方法は特に限定されず、従来公知のワンショット法（１段式）、または多段式のイソシアネート重付加反応法が用いられる。 Also, an organic solvent that does not react with the isocyanate group can be added in the reaction step or after the reaction is completed. Examples of such an organic solvent include acetone, methyl ethyl ketone, toluene, tetrahydrofuran, dioxane, N, N-dimethylformamide, N-methylpyrrolidone and the like. In the present invention, the production method of the isocyanate group-terminated prepolymer is not particularly limited, and a conventionally known one-shot method (one-stage method) or a multi-stage isocyanate polyaddition reaction method is used.
　プレポリマーは通常０．１～５％のイソシアネート値（樹脂固形分に対する残存イソシアネート基の重量含有量）を有する。 The prepolymer usually has an isocyanate value of 0.1 to 5% (weight content of residual isocyanate groups with respect to resin solids).
　プレポリマーを中和するのに用いられる中和剤はカルボキシル基を中和できるものであれば特に限定されず、例えば、トリメチルアミン、トリエチルアミン、トリ－ｎ－プロピルアミン、トリブチルアミン、トリエタノールアミン等のアミン類や、水酸化ナトリウム、水酸化カリウム、アンモニア等が挙げられる。 The neutralizing agent used to neutralize the prepolymer is not particularly limited as long as it can neutralize the carboxyl group, and examples thereof include trimethylamine, triethylamine, tri-n-propylamine, tributylamine, and triethanolamine. Examples include amines, sodium hydroxide, potassium hydroxide, and ammonia.
　プレポリマーの中和物を水中に乳化分散させる際には、転相乳化が効率よく進行するようにするため、プレポリマー中の樹脂固形分１００重量部に対して、５０～５００重量部の水が用いられる。 When the prepolymer neutralized product is emulsified and dispersed in water, 50 to 500 parts by weight of water is used per 100 parts by weight of resin solids in the prepolymer so that phase inversion emulsification proceeds efficiently. Is used.
　ポリウレタン水分散体は、乳化中または乳化後に上記成分（Ｆ）を添加し、鎖延長反応させることにより製造される。成分（Ｆ）の使用量はプレポリマーの末端イソシアネート基に対して０．３～１．５等量、好ましくは０．４～１．２等量で任意に選ぶことができる。 The polyurethane water dispersion is produced by adding the above component (F) during or after emulsification and causing a chain extension reaction. The amount of component (F) used can be arbitrarily selected from 0.3 to 1.5 equivalents, preferably 0.4 to 1.2 equivalents, based on the terminal isocyanate group of the prepolymer.
　ポリウレタン水分散体が有機溶剤を含有する場合は、減圧下、３０～８０℃で溶媒を留去することが望ましい。ポリウレタン水分散体中の樹脂固形分（不揮発分）濃度は１５～６６％の範囲が好ましい。ポリウレタン水分散体中の樹脂固形分濃度は、水を追加または留去することで調整することも可能である。 When the polyurethane water dispersion contains an organic solvent, it is desirable to distill off the solvent at 30 to 80 ° C. under reduced pressure. The resin solid content (nonvolatile content) concentration in the polyurethane water dispersion is preferably in the range of 15 to 66%. The resin solid content concentration in the polyurethane water dispersion can also be adjusted by adding or distilling off water.
　本発明では、ポリウレタン水分散体中のエチレンオキシド単位（ＥＯ）に由来するＥＯ含有量は特に限定されないが、ポリウレタン水分散体から得られるフィルム層が透湿性能の点で実用性を有する点で、ポリウレタン水分散体中のポリウレタン（すなわち、樹脂固形分）に対して、１．５重量％以上とすることが好ましく、７重量％以上とすることがより好ましい。 In the present invention, the EO content derived from the ethylene oxide unit (EO) in the polyurethane water dispersion is not particularly limited, but the film layer obtained from the polyurethane water dispersion has practicality in terms of moisture permeability. It is preferable to set it as 1.5 weight% or more with respect to the polyurethane (namely, resin solid content) in a polyurethane water dispersion, and it is more preferable to set it as 7 weight% or more.
　また、上記ＥＯ含有量を増やしすぎると、ポリウレタン水分散体から得られるフィルム層が耐エタノール水性能の点で実用性に劣ったものとなる。このため、ポリウレタン水分散体から得られるフィルム層が、耐エタノール水性能と透湿性能の点で実用性を満たすには、ＥＯ含有量として１．５～１８重量％が好ましく、７～１８重量％がより好ましい。 Further, if the EO content is increased too much, the film layer obtained from the polyurethane water dispersion becomes inferior in practicality in terms of ethanol water resistance. Therefore, in order that the film layer obtained from the polyurethane water dispersion satisfies practicality in terms of ethanol water resistance and moisture permeability, the EO content is preferably 1.5 to 18% by weight, preferably 7 to 18% by weight. % Is more preferable.
　ＥＯ含有量を上記範囲に設定するには、ポリウレタン水分散体の製造原料のうち、ポリウレタン樹脂を構成する製造原料の合計重量に対して、ＥＯの合計重量が上記含有量になるように仕込み原料を設定することで調整することができる。 In order to set the EO content within the above range, the raw materials charged so that the total weight of EO is the above content with respect to the total weight of the manufacturing raw materials constituting the polyurethane resin among the manufacturing raw materials of the polyurethane water dispersion. It can be adjusted by setting.
　さらに、本発明では、少なくとも２，４’－ＭＤＩと４，４’－ＭＤＩを含有するＭＤＩ中において、２，４’－ＭＤＩの含有量を、好ましくは４０重量％以上、さらに好ましくは７０重量％以上、特に好ましくは８０重量％以上に設定することで、ポリウレタン水分散体から得られるフィルム層が、柔軟性の点で実用性に優れたものになり、耐エタノール水性能における破断強度および面積膨潤率の点で実用性が優れたものになる。本発明において「フィルム層の柔軟性」は、本発明のポリウレタン水分散体を、塗料、コーティング剤、または接着剤等として用いた場合に形成されるフィルム層について、柔軟性の指標となるものであり、後述する実施例では、ポリウレタン水分散体をガラス板上にキャストして製造されたフィルム（膜厚：約１００μｍ）について、ＪＩＳ３号ダンベルを用いて試験片を切り出し、引張試験機を用い、ＪＩＳ　Ｋ６２５１に準拠して測定された１００％モジュラスにより評価される。評価基準として、１００％モジュラスが４．０ＭＰａ以上、７．０ＭＰａ未満のときは、実用性を有すると判断され、１００％モジュラスが４．０ＭＰａ未満のときは、実用性に優れると判断される。 Further, in the present invention, in the MDI containing at least 2,4′-MDI and 4,4′-MDI, the content of 2,4′-MDI is preferably 40% by weight or more, more preferably 70% by weight. % Or more, and particularly preferably 80% by weight or more, the film layer obtained from the polyurethane water dispersion has excellent practicality in terms of flexibility, and has a breaking strength and an area in ethanol water resistance. The practicality is excellent in terms of swelling rate. In the present invention, “flexibility of the film layer” is an index of flexibility for the film layer formed when the aqueous polyurethane dispersion of the present invention is used as a paint, coating agent, adhesive, or the like. Yes, in the examples described later, for a film manufactured by casting a polyurethane water dispersion on a glass plate (film thickness: about 100 μm), a test piece was cut out using a JIS No. 3 dumbbell, and a tensile tester was used. It is evaluated by 100% modulus measured according to JIS K6251. As an evaluation criterion, when the 100% modulus is 4.0 MPa or more and less than 7.0 MPa, it is judged to have practicality, and when the 100% modulus is less than 4.0 MPa, it is judged to be practical.
　２，４’－ＭＤＩの含有量を高めたＭＤＩを用いて、上述したとおり、フィルム層の柔軟性及び耐エタノール水性能の点で優れた実用性を発揮させる場合、上記ＥＯ含有量を上述した範囲に設定する必要は特になく、むしろ上記範囲よりもＥＯ含有量を低くした場合でも上記効果を発揮させることができる。この場合、ＥＯ含有量としては、１～１８重量％の範囲で通常使用され、好ましくは１～８重量％、さらに好ましくは１～３重量％である。また、フィルム層の柔軟性及び耐エタノール水性能の点で優れた実用性を発揮させるとともに、耐エタノール水性能と透湿性能の点で実用性を満たすには、ＥＯ含有量として、１～１８重量％が好ましく、７～１８重量％がより好ましい。 As described above, when MDI with an increased content of 2,4′-MDI is used to demonstrate the practicality of the film layer in terms of flexibility and ethanol water resistance, the EO content is described above. There is no particular need to set the range, but the above effect can be exhibited even when the EO content is lower than the above range. In this case, the EO content is usually in the range of 1 to 18% by weight, preferably 1 to 8% by weight, more preferably 1 to 3% by weight. In order to exhibit excellent practicality in terms of flexibility of the film layer and ethanol water resistance, and to satisfy practicality in terms of ethanol water resistance and moisture permeability, the EO content is 1 to 18 % By weight is preferred, and 7 to 18% by weight is more preferred.
　本発明のポリウレタン水分散体は、例えば、塗料、コーティング剤、接着剤等として好適に用いられる。すなわち本発明のポリウレタン水分散体は、本発明のポリウレタン水分散体を含有する塗料、コーティング剤、接着剤等として供することができる。 The polyurethane water dispersion of the present invention is suitably used as, for example, a paint, a coating agent or an adhesive. That is, the polyurethane water dispersion of the present invention can be used as a paint, coating agent, adhesive or the like containing the polyurethane water dispersion of the present invention.
　本発明のポリウレタン水分散体から得られるフィルム層の膜厚は、用途によって異なるため、特に制限はないが、５～１０００μｍが好ましく、２０～１０００μｍがさらに好ましい。 The film thickness of the film layer obtained from the polyurethane water dispersion of the present invention varies depending on the use, and is not particularly limited, but is preferably 5 to 1000 μm, more preferably 20 to 1000 μm.
　以下、本発明を試験例に基づいて具体的に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。なお、実施例中の「部」および「％」は、特に明示しない限り、それぞれ「重量部」および「重量％」を意味する。 Hereinafter, the present invention will be specifically described based on test examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively, unless otherwise specified.
　以下にポリウレタン水分散体の製造原料、ポリウレタン水分散体の製造例、該水分散体から製造したフィルムの評価方法について説明する。 Hereinafter, the production raw material of the polyurethane water dispersion, the production example of the polyurethane water dispersion, and the evaluation method of the film produced from the water dispersion will be described.
＜ポリウレタン水分散体の製造原料＞
成分（Ａ）：ポリイソシアネート
・ジフェニルメタンジイソシアネート（成分（ａ１））
　（商品名「ミリオネートＭＴ」、日本ポリウレタン工業社製、4,4’-MDIが99.5％以上で残りが2,4’-MDI、以下本製品と他の成分（ａ１）の製品とを特に区別する必要のない場合は「ＭＤＩ」と略記する。）
　（商品名「ミリオネートＮＭ１００」、日本ポリウレタン工業社製、4,4’-MDI：2,4’-MDI＝5～15％：95～85％）
・脂環式ジイソシアネート（成分（ａ２））
　（水素添加ジフェニルメタンジイソシアネート（商品名「デスモジュールＷ」、住化バイエルウレタン社製、以下「Ｈ１２ＭＤＩ」と略記）
　（イソホロンジイソシアネート（商品名「デスモジュールＩ」、住化バイエルウレタン社製、以下「ＩＰＤＩ」と略記） <Production raw material for polyurethane water dispersion>
Component (A): Polyisocyanate / diphenylmethane diisocyanate (component (a1))
(Trade name "Millionate MT", manufactured by Nippon Polyurethane Industry Co., Ltd., 4,4'-MDI is 99.5% or more and the remainder is 2,4'-MDI. The following is a distinction between this product and other components (a1). (If not necessary, abbreviated as “MDI”.)
(Product name "Millionate NM100", manufactured by Nippon Polyurethane Industry Co., Ltd., 4,4'-MDI: 2,4'-MDI = 5-15%: 95-85%)
・ Alicyclic diisocyanate (component (a2))
(Hydrogenated diphenylmethane diisocyanate (trade name “Desmodur W”, manufactured by Sumika Bayer Urethane Co., Ltd., hereinafter abbreviated as “H12MDI”)
(Isophorone diisocyanate (trade name “Desmodur I”, manufactured by Sumika Bayer Urethane Co., Ltd., hereinafter abbreviated as “IPDI”)
成分：ポリオール
・エチレンオキシドとテトラヒドロフランのランダム共重合体（成分（Ｂ））
　商品名「ポリセリンＤＣ３０００Ｅ」、モル比（ＥＯ／ＴＨＦ）＝５０／５０、数平均分子量３１００、日油社製、以下「ＤＣ３０００」と略記）
・ポリヘキサメチレンカーボネートジオール（成分（Ｃ））
　商品名「ＵＨ－３００」、数平均分子量３０００、宇部興産社製、以下「ＵＨ３００」と略記）
　商品名「ニッポラン９８０Ｎ」、数平均分子量２０００、日本ポリウレタン工業社製）
・ポリエチレングリコール
　商品名「ＰＥＧ２０００」、数平均分子量２０００、日油社製）
　商品名「ＰＥＧ４０００」、数平均分子量４０００、日油社製） Component: Random copolymer of polyol, ethylene oxide and tetrahydrofuran (component (B))
Trade name “Polyserine DC3000E”, molar ratio (EO / THF) = 50/50, number average molecular weight 3100, manufactured by NOF Corporation, hereinafter abbreviated as “DC3000”)
・ Polyhexamethylene carbonate diol (component (C))
(Product name “UH-300”, number average molecular weight 3000, manufactured by Ube Industries, Ltd., hereinafter abbreviated as “UH300”)
Product name “Nipporan 980N”, number average molecular weight 2000, manufactured by Nippon Polyurethane Industry Co., Ltd.)
-Polyethylene glycol product name "PEG2000", number average molecular weight 2000, manufactured by NOF Corporation)
(Product name "PEG4000", number average molecular weight 4000, manufactured by NOF Corporation)
成分（Ｄ）：多価アルコール系鎖延長剤
・１，４－ブタンジオール Component (D): Polyhydric alcohol chain extender 1,4-butanediol
成分（Ｅ）：カルボキシル基を有するジオール化合物
・２，２－ジメチロールプロピオン酸（以下、「ＤＭＰＡ」と略記）
・２，２－ジメチロールブタン酸（以下、「ＤＭＢＡ」と略記） Component (E): Diol compound having a carboxyl group, 2,2-dimethylolpropionic acid (hereinafter abbreviated as “DMPA”)
・ 2,2-dimethylolbutanoic acid (hereinafter abbreviated as “DMBA”)
成分（Ｆ）：アミン系鎖延長剤
・３０％　６水和ピペラジン Component (F): Amine chain extender, 30% hexahydrate piperazine
（その他の成分）
・水
・中和剤：トリエチルアミン
・溶剤：Ｎ－メチルピロリドン（ＮＭＰ）、メチルエチルケトン（ＭＥＫ）
・触媒：ジオクチル錫ジラウレート (Other ingredients)
・ Water ・ Neutralizer: Triethylamine ・ Solvent: N-methylpyrrolidone (NMP), methyl ethyl ketone (MEK)
・ Catalyst: Dioctyltin dilaurate
＜フィルムの評価方法＞
（フィルム作製方法）
　後述する方法により得られたポリウレタン水分散体をガラス板上にキャストし、室温で２４時間乾燥後、４５℃で１２時間および１２０℃で１２０分の熱処理を行い、約１００μｍの膜厚を有するフィルムを作製した。 <Evaluation method of film>
(Film production method)
A polyurethane water dispersion obtained by the method described later is cast on a glass plate, dried at room temperature for 24 hours, heat-treated at 45 ° C. for 12 hours and 120 ° C. for 120 minutes, and having a film thickness of about 100 μm Was made.
（柔軟性）：１００％モジュラスの測定
　上記で得られたフィルム（厚み：約１００μｍ）から、ＪＩＳ　３号のダンベルを用いて試験片を切り出し、島津製作所製オートグラフを用い、チャック間隔６０ｍｍ、標線２０ｍｍ、引張速度２００ｍｍ/分、温度２３±２℃で、ＪＩＳ　Ｋ６３０１に準拠して評価した。
　試験片が１００％伸びた時の引張荷重を測定し、下記式によって引張強度を求めた。
　１００％モジュラス（ＭＰａ）＝Ｆ１００％／Ａ
ただし、Ｆ１００％は１００％伸び時の引張荷重（Ｎ）、Ａは試験片の断面積（ｍｍ２）である。
　１００％モジュラスの判断基準は以下のとおりである。
◎:４．０ＭＰａ未満（良好）
○:４．０ＭＰａ以上、９．０ＭＰａ未満（やや良）
×:９．０ＭＰａ以上（不良）
　＊上記基準のうち、◎と○は実用性を有すると評価される。 (Flexibility): Measurement of 100% modulus From the film obtained above (thickness: about 100 μm), a test piece was cut out using a JIS No. 3 dumbbell and an autograph manufactured by Shimadzu Corporation was used. Evaluation was performed according to JIS K6301 at a line of 20 mm, a tensile speed of 200 mm / min, and a temperature of 23 ± 2 ° C.
The tensile load when the test piece was extended by 100% was measured, and the tensile strength was determined by the following formula.
100% modulus (MPa) = F 100% / A
However, F 100% is the tensile load (N) at 100% elongation, and A is the cross-sectional area (mm 2 ) of the test piece.
The criteria for determining 100% modulus are as follows.
A: Less than 4.0 MPa (good)
○: 4.0 MPa or more and less than 9.0 MPa (slightly good)
X: 9.0 MPa or more (defect)
* Among the above criteria, ◎ and ○ are evaluated as having practicality.
（耐エタノール水性能）：破断強度の測定
　上記で得られたフィルム（厚み：約１００μｍ）から、ＪＩＳ３号ダンベルを用いて試験片を切り出し、エチルアルコール７０％水（２３℃±２℃）に３０分間浸漬させた後に取り出した。取り出した試験片を軽く拭いてから９０秒後に、ＪＩＳ　Ｋ－６３０１に従い、破断強度試験を行い、以下の基準で耐エタノール水性能を評価した。
◎：破断強度が１０ＭＰａ以上（良好）
○：破断強度が４ＭＰａ以上、１０ＭＰａ未満（やや良）
×：破断強度が４ＭＰａ未満（不良）
　＊上記基準のうち、◎と○は実用性を有すると評価される。 (Ethanol water resistance): Measurement of breaking strength From the film obtained above (thickness: about 100 μm), a test piece was cut out using a JIS No. 3 dumbbell, and 30% ethyl alcohol in 70% water (23 ° C. ± 2 ° C.) It was taken out after being immersed for a minute. Ninety seconds after lightly wiping the removed test piece, a breaking strength test was conducted according to JIS K-6301, and the ethanol water resistance was evaluated according to the following criteria.
A: Breaking strength is 10 MPa or more (good)
○: Break strength is 4 MPa or more and less than 10 MPa (slightly good)
X: Breaking strength is less than 4 MPa (defect)
* Among the above criteria, ◎ and ○ are evaluated as having practicality.
（耐エタノール水性能）：面積膨潤率の測定
　上記で得られたフィルム（厚み：約１００μｍ）から５０ｍｍ×５０ｍｍの試験片を切り出し、エチルアルコール７０％水（２３℃±２℃）に３０分間浸漬させた後に取り出した。取り出した試験片を軽く拭いてから再度面積を測定し、下記式により面積膨潤率を求め、以下の基準で耐エタノール水性能を評価した。
　面積膨潤率（％）：{（浸漬後の面積－初期の面積）／初期の面積}×１００
◎：１０％未満（良好）
○：１０％以上、６０％未満（やや良）
×：６０％以上（不良）
　＊上記基準のうち、◎と○は実用性を有すると評価される。 (Ethanol-resistant performance): Measurement of area swelling rate A 50 mm × 50 mm test piece was cut out from the film obtained above (thickness: about 100 μm) and immersed in 70% ethyl alcohol (23 ° C. ± 2 ° C.) for 30 minutes. And then removed. The test piece taken out was lightly wiped, the area was measured again, the area swelling rate was determined by the following formula, and the ethanol water resistance performance was evaluated according to the following criteria.
Area swelling rate (%): {(area after immersion−initial area) / initial area} × 100
A: Less than 10% (good)
○: 10% or more and less than 60% (slightly good)
X: 60% or more (defect)
* Among the above criteria, ◎ and ○ are evaluated as having practicality.
（耐水性能）：破断強度の測定
　上記で得られたフィルム（厚み：約１００μｍ）から、ＪＩＳ３号ダンベルを試験片として切り出し、水道水（２３℃±２℃）に３０分間浸漬させた後に取り出した。取り出した試験片を軽く拭いてから９０秒後に、ＪＩＳ　Ｋ－６３０１に従い、破断強度試験を行い、以下の基準で耐エタノール水性能を評価した。
◎：破断強度が１０ＭＰａ以上（良好）
○：破断強度が４ＭＰａ以上、１０ＭＰａ未満（やや良）
×：破断強度が４ＭＰａ未満（不良）
　＊上記基準のうち、◎と○は実用性を有すると評価される。 (Water resistance performance): Measurement of breaking strength From the film obtained above (thickness: about 100 μm), a JIS No. 3 dumbbell was cut out as a test piece and taken out after being immersed in tap water (23 ° C. ± 2 ° C.) for 30 minutes. . Ninety seconds after lightly wiping the removed test piece, a breaking strength test was conducted according to JIS K-6301, and the ethanol water resistance was evaluated according to the following criteria.
A: Breaking strength is 10 MPa or more (good)
○: Break strength is 4 MPa or more and less than 10 MPa (slightly good)
X: Breaking strength is less than 4 MPa (defect)
* Among the above criteria, ◎ and ○ are evaluated as having practicality.
（耐水性能）：面積膨潤率の測定
　上記で得られたフィルム（厚み：約１００μｍ）から５０ｍｍ×５０ｍｍの試験片を切り出し、水道水（２３℃±２℃）に３０分間浸漬させた後に取り出した。取り出した試験片を軽く拭いてから再度面積を測定し、下記式により面積膨潤率を求め、以下の基準で耐エタノール水性能を評価した。
　面積膨潤率（％）：{（浸漬後の面積－初期の面積）／初期の面積}×１００
◎：１０％未満（良好）
○：１０％以上、６０％未満（やや良）
×：６０％以上（不良）
　＊上記基準のうち、◎と○は実用性を有すると評価される。 (Water resistance performance): Measurement of area swelling rate A test piece of 50 mm × 50 mm was cut out from the film obtained above (thickness: about 100 μm) and taken out after being immersed in tap water (23 ° C. ± 2 ° C.) for 30 minutes. . The test piece taken out was lightly wiped, the area was measured again, the area swelling rate was determined by the following formula, and the ethanol water resistance performance was evaluated according to the following criteria.
Area swelling rate (%): {(area after immersion−initial area) / initial area} × 100
A: Less than 10% (good)
○: 10% or more and less than 60% (slightly good)
X: 60% or more (defect)
* Among the above criteria, ◎ and ○ are evaluated as having practicality.
（透湿性能）：透湿度の測定
　ＪＩＳ　Ｌ　１０９９Ａ－１法（塩化カルシウム法）に準じ、上記で得られたフィルム（厚み：約１００μｍ）の透湿度を測定し、以下の基準で透湿性能を評価した。
◎：８００　g/m２－24hrs　以上
○：５００　g/m2-24hrs　以上、８００　g/m2-24hrs　未満
×：５００　g/m2-24hrs　未満
　＊上記基準のうち、◎と○は実用性を有すると評価される。 (Moisture permeability): Measurement of moisture permeability According to JIS L 1099A-1 method (calcium chloride method), the moisture permeability of the film obtained above (thickness: about 100 μm) was measured, and moisture permeability was measured according to the following criteria. Evaluated.
◎: 800 g / m 2 -24hrs or more ○: 500 g / m 2 -24hrs or more, less than 800 g / m 2 -24hrs ×: 500 g / m 2 -24hrs or less * Of the above criteria, ◎ and ○ are practical It is evaluated that it has sex.
１．ＭＤＩと脂環式ジイソシアネートを併用したポリウレタン水分散体の特徴
（ポリウレタン水分散体No.１の製造）
　反応器に、ＤＣ３０００（成分（Ｂ））　１２．８部、ＵＨ３００（成分（Ｃ））１７０．９部、ジオクチル錫ジラウレート　０．０１部を仕込み、十分撹拌溶解し、ＭＤＩ（成分（Ａ））　３３．６部、Ｈ１２ＭＤＩ（成分（Ａ））１７．６部を加えて８５℃で３時間反応させた。次に、６０℃まで冷却した後、ＤＭＰＡ（成分（Ｅ））５．０部、１，４－ブタンジオール（成分（Ｄ））５．３部、ＮＭＰ　６１．３部、ＭＥＫ　１８８．７部を加え、十分撹拌溶解し、ジオクチル錫ジラウレート　０．０４部を加え、８０℃で８時間反応させた。その後、イソシアネート値（固形分に対する残存イソシアネート基の重量含有量）が０．８％のプレポリマーを得た。このプレポリマーを５０℃まで冷却し、トリエチルアミン　３．７部を加えて中和し、次いで水４７０．９部を加えて転相乳化した。この乳化分散液に３０％　６水和ピペラジン（成分（Ｆ））１９．１部（残存イソシアネート基に対してアミン基として１００当量％）を加えて乳化分散した。得られた乳化液を脱溶剤することにより、不揮発分２５％、ｐＨ７．３のポリウレタン水分散体No.1を得た。得られた水分散体は、粒子径が０．０９μｍと微細で、安定していた。 1. Characteristics of polyurethane water dispersion using MDI and alicyclic diisocyanate together (Production of polyurethane water dispersion No. 1)
In a reactor, 13000 parts of DC3000 (component (B)), 170.9 parts of UH300 (component (C)) and 0.01 part of dioctyltin dilaurate are charged and dissolved with sufficient stirring. MDI (component (A)) 33.6 parts and 17.6 parts of H12MDI (component (A)) were added and reacted at 85 ° C. for 3 hours. Next, after cooling to 60 ° C., 5.0 parts of DMPA (component (E)), 5.3 parts of 1,4-butanediol (component (D)), 61.3 parts of NMP, 188.7 parts of MEK Was added and dissolved with sufficient stirring, and 0.04 part of dioctyltin dilaurate was added and reacted at 80 ° C. for 8 hours. Then, the prepolymer whose isocyanate value (weight content of the residual isocyanate group with respect to solid content) was 0.8% was obtained. The prepolymer was cooled to 50 ° C, neutralized by adding 3.7 parts of triethylamine, and then 470.9 parts of water was added for phase inversion emulsification. To this emulsified dispersion, 19.1 parts of 30% hexahydrated piperazine (component (F)) (100 equivalent% as an amine group with respect to the remaining isocyanate group) was added and emulsified and dispersed. By removing the solvent from the obtained emulsion, polyurethane water dispersion No. 1 having a nonvolatile content of 25% and a pH of 7.3 was obtained. The obtained aqueous dispersion had a fine particle size of 0.09 μm and was stable.
（ポリウレタン水分散体No.2～No.10の製造）
　表１に示す原材料、配合処方を用いてポリウレタン水分散体No.1と同様の方法でポリウレタン水分散体No.2～No.10を製造した。 (Manufacture of polyurethane water dispersion No.2 to No.10)
Polyurethane water dispersions No. 2 to No. 10 were produced in the same manner as polyurethane water dispersion No. 1 using the raw materials and formulation shown in Table 1.
　ポリウレタン水分散体No.1～No.10からフィルムを作製し、柔軟性、耐エタノール水性能、耐水性能および透湿性能を評価した。表２に結果を示す。なお、表２における仕込み原料の数値は、製造原料のうち、成分（Ａ）～（Ｆ）の合計重量を１００％としたときの各成分の含有量（重量％）を示したものである。 Films were prepared from polyurethane water dispersions No. 1 to No. 10, and their flexibility, ethanol water resistance, water resistance and moisture permeability were evaluated. Table 2 shows the results. The numerical values of the charged raw materials in Table 2 indicate the content (% by weight) of each component when the total weight of the components (A) to (F) is 100% of the manufactured raw material.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　本試験は、ポリオールとして成分（Ｂ）と成分（Ｃ）を併用することを前提として、成分（Ａ）の種類、組合せを種々変えて製造したポリウレタン水分散体から得られたフィルムについて、特に耐エタノール水性能と透湿性能の関係を検討したものである。
　表２より、ポリイソシアネートとしてＭＤＩ（ａ１）のみを用いた場合（No.6）は、ポリウレタン水分散体自体が製造できないこと、ポリイソシアネートとしてＨ１２ＭＤＩ（ａ２）またはＩＰＤＩ（ａ２）のみを用いた場合（No.7，No.9）は、透湿性能はともに実用性を有するが、耐エタノール水性能は破断強度の点で実用性を有さないことが分かった。一方、ポリイソシアネートとして成分（ａ１）と成分（ａ２）を併用すると、耐エタノール水性能と透湿性能はともに実用性を有することが分かった。成分（ａ１）と成分（ａ２）のモル比としては、本試験例で用いた範囲であれば、耐エタノール水性能と透湿性能はともに実用性を有し、フィルム評価として特に違いはないといえる。 This test is particularly effective for films obtained from polyurethane aqueous dispersions produced by variously changing the types and combinations of components (A) on the premise that components (B) and (C) are used in combination as polyols. The relationship between ethanol water performance and moisture permeability is examined.
From Table 2, when only MDI (a1) is used as the polyisocyanate (No. 6), the polyurethane water dispersion itself cannot be produced, and when only H12MDI (a2) or IPDI (a2) is used as the polyisocyanate It was found that (No. 7, No. 9) has practicality in both moisture permeability, but ethanol water resistance is not practical in terms of breaking strength. On the other hand, it was found that when the component (a1) and the component (a2) were used in combination as the polyisocyanate, both the ethanol water resistance performance and the moisture permeability performance were practical. As long as the molar ratio of the component (a1) and the component (a2) is within the range used in this test example, both the ethanol water resistance performance and the moisture permeability performance are practical, and there is no particular difference in film evaluation. I can say that.
２．耐エタノール水性能、透湿性能に優れた処方の検討
（ポリウレタン水分散体No.11の製造）
　反応器に、ＤＣ３０００（成分（Ｂ））　２４．９部、ＵＨ－３００（成分（Ｃ））１５８．４部、ジオクチル錫ジラウレート　０．０１部を仕込み、十分撹拌溶解し、ＭＤＩ（成分（Ａ））　２５．２部、Ｈ１２ＭＤＩ（成分（Ａ））２６．４部を加えて８５℃で３時間反応させた。次に、６０℃まで冷却した後、ＤＭＰＡ（成分（Ｅ））５．０部、１，４－ブタンジオール（成分（Ｄ））５．２部、ＮＭＰ　６１．３部、ＭＥＫ　１８８．７部を加え、十分撹拌溶解し、ジオクチル錫ジラウレート　０．０４部を加え、８０℃で８時間反応させた。その後、イソシアネート値（固形分に対する残存イソシアネート基の重量含有量）が０．８％のプレポリマーを得た。このプレポリマーを、５０℃まで冷却し、トリエチルアミン　３．８部を加えて中和し、次いで水４７０．８部を加えて転相乳化した。この乳化分散液に３０％　６水和ピペラジン（成分（Ｆ））１８．９部（残存イソシアネート基に対してアミン基として１００当量％）を加えて乳化分散した。得られた乳化液を脱溶剤することにより、不揮発分２５％、ｐＨ７．３のポリウレタン水分散体No.11を得た。 2. Examination of prescription with excellent ethanol water resistance and moisture permeability (Manufacture of polyurethane water dispersion No. 11)
A reactor was charged with 23,000 parts of DC3000 (component (B)), 158.4 parts of UH-300 (component (C)) and 0.01 part of dioctyltin dilaurate. )) 25.2 parts of H12MDI (component (A)) 26.4 parts were added and reacted at 85 ° C. for 3 hours. Next, after cooling to 60 ° C., 5.0 parts of DMPA (component (E)), 5.2 parts of 1,4-butanediol (component (D)), 61.3 parts of NMP, 188.7 parts of MEK Was added and dissolved with sufficient stirring, and 0.04 part of dioctyltin dilaurate was added and reacted at 80 ° C. for 8 hours. Then, the prepolymer whose isocyanate value (weight content of the residual isocyanate group with respect to solid content) was 0.8% was obtained. The prepolymer was cooled to 50 ° C., neutralized by adding 3.8 parts of triethylamine, and then 470.8 parts of water was added for phase inversion emulsification. To this emulsified dispersion, 18.9 parts of 30% hexahydrated piperazine (component (F)) (100 equivalent% as an amine group with respect to the remaining isocyanate group) was added and emulsified and dispersed. By removing the solvent from the obtained emulsion, polyurethane water dispersion No. 11 having a nonvolatile content of 25% and a pH of 7.3 was obtained.
（ポリウレタン水分散体No.12～No.22の製造）
　表３に示す原材料、配合処方を用いてポリウレタン水分散体No.11と同様の方法でポリウレタン水分散体No.12～No.22を製造した。 (Manufacture of polyurethane water dispersion No. 12 to No. 22)
Polyurethane water dispersions No. 12 to No. 22 were produced in the same manner as polyurethane water dispersion No. 11, using the raw materials and formulation shown in Table 3.
　ポリウレタン水分散体No.11～No.22からフィルムを作製し、柔軟性、耐エタノール水性能、耐水性能および透湿性能を評価した。表４に結果を示す。なお、表４における仕込み原料の数値は、製造原料のうち、成分（Ａ）～（Ｆ）の合計重量を１００％としたときの各成分の含有量（重量％）を示したものである。 Films were prepared from polyurethane water dispersions No. 11 to No. 22, and their flexibility, ethanol water resistance, water resistance and moisture permeability were evaluated. Table 4 shows the results. The numerical values of the charged raw materials in Table 4 indicate the content (% by weight) of each component when the total weight of the components (A) to (F) is 100% of the manufactured raw material.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本試験は、ポリウレタン水分散体中のポリウレタン（樹脂固形分）に対するエチレンオキシド単位（ＥＯ）の含有量（単位：重量％）（以下、単に「ＥＯ含有量」と略記）と、得られたフィルムについての特に耐エタノール水性能、透湿性能の関係を検討したものである。
　表４から、ＥＯ含有量がおよそ１．５重量％以上になると、透湿性能が実用性を有すると評価され、さらにＥＯ含有量が７重量％を超えると、実用性に優れた透湿性能を示すことが分かった。
　また、耐エタノール水性能は、通常は実用性を有すると評価されるが、ＥＯ含有量が増え過ぎて１８重量％を超えると、実用性を有しなくなることが分かった。
　さらに、本発明品（No.3，No.11，No.13～No.15，No.17～No.20）と比較品（No.21，No.22）との比較から、本発明品は、ＥＯ含有量が約２０重量％近くまでは、安定したポリウレタン水分散体を製造することができるといえる。 In this test, the content of ethylene oxide units (EO) (unit:% by weight) (hereinafter simply abbreviated as “EO content”) with respect to the polyurethane (resin solids) in the polyurethane water dispersion and the obtained film In particular, the relationship between ethanol water resistance and moisture permeability was examined.
From Table 4, when the EO content is about 1.5% by weight or more, the moisture permeability is evaluated as having practicality, and when the EO content exceeds 7% by weight, the moisture permeability having excellent practicality is obtained. It was found that
Moreover, although the ethanol water resistance performance is usually evaluated as having practicality, it has been found that when the EO content increases too much and exceeds 18% by weight, it has no practicality.
Furthermore, the product of the present invention was compared with the products of the present invention (No.3, No.11, No.13 to No.15, No.17 to No.20) and comparative products (No.21, No.22). It can be said that a stable polyurethane water dispersion can be produced up to an EO content of about 20% by weight.
３．柔軟性、耐エタノール水性能に優れた処方の検討
（ポリウレタン水分散体No.23の製造）
　反応器に、ＤＣ３０００（成分（Ｂ））１８０．５部、ＵＨ－３００（成分（Ｃ））１２．８部、ジオクチル錫ジラウレート　０．０１部を仕込み、十分撹拌溶解し、ミリオネートＮＭ１００（成分（Ａ））２９．０部、Ｈ１２ＭＤＩ（成分（Ａ））１５．３部を加えて８５℃で３時間反応させた。次に、６０℃まで冷却した後、ＤＭＰＡ（成分（Ｅ））５．０部、１，４－ブタンジオール（成分（Ｄ））３．１部、ＮＭＰ　６１．４部、ＭＥＫ　３１３．６部を加え、十分撹拌溶解し、ジオクチル錫ジラウレート　０．０４部を加え、８０℃で８時間反応させた。その後、イソシアネート値（固形分に対する残存イソシアネート基の重量含有量）が０．９％のプレポリマーを得た。このプレポリマーを、５０℃まで冷却し、トリエチルアミン　３．７部を加えて中和し、次いで水４７４．７部を加えて転相乳化した。この乳化分散液に３０％　６水和ピペラジン（成分（Ｆ））１９．９部（残存イソシアネート基に対してアミン基として１００当量％）を加えて乳化分散した。得られた乳化液を脱溶剤することにより、不揮発分２５％、ｐＨ７．３のポリウレタン水分散体No.23を得た。 3. Examination of prescription with excellent flexibility and ethanol water resistance (Manufacture of polyurethane water dispersion No. 23)
A reactor was charged with 180.5 parts of DC3000 (component (B)), 12.8 parts of UH-300 (component (C)) and 0.01 part of dioctyltin dilaurate, and sufficiently stirred and dissolved. Millionate NM100 (component ( A)) 29.0 parts and 15.3 parts of H12MDI (component (A)) were added and reacted at 85 ° C. for 3 hours. Next, after cooling to 60 ° C., 5.0 parts of DMPA (component (E)), 3.1 parts of 1,4-butanediol (component (D)), 61.4 parts of NMP, 313.6 parts of MEK Was added and dissolved with sufficient stirring, and 0.04 part of dioctyltin dilaurate was added and reacted at 80 ° C. for 8 hours. Then, the prepolymer whose isocyanate value (weight content of the residual isocyanate group with respect to solid content) is 0.9% was obtained. The prepolymer was cooled to 50 ° C., neutralized by adding 3.7 parts of triethylamine, and then 474.7 parts of water was added for phase inversion emulsification. To this emulsified dispersion, 19.9 parts of 30% hexahydrated piperazine (component (F)) (100 equivalent% as an amine group with respect to the remaining isocyanate group) was added and emulsified and dispersed. By removing the solvent from the obtained emulsion, polyurethane water dispersion No. 23 having a nonvolatile content of 25% and a pH of 7.3 was obtained.
（ポリウレタン水分散体No.24，No.25の製造）
　表５に示す原材料、配合処方を用いてポリウレタン水分散体No.23と同様の方法でポリウレタン水分散体No.24とNo.25を製造した。 (Manufacture of polyurethane water dispersion No.24 and No.25)
Polyurethane water dispersions No. 24 and No. 25 were produced in the same manner as polyurethane water dispersion No. 23, using the raw materials and formulation shown in Table 5.
　ポリウレタン水分散体No.23～No.25からフィルムを作製し、柔軟性、耐エタノール水性能、耐水性能および透湿性能を評価した。表６に結果を示す。なお、表６における仕込み原料の数値は、製造原料のうち、成分（Ａ）～（Ｆ）の合計重量を１００％としたときの各成分の含有量（重量％）を示したものである。 Films were prepared from polyurethane water dispersions No. 23 to No. 25 and evaluated for flexibility, ethanol water resistance, water resistance and moisture permeability. Table 6 shows the results. The numerical values of the charged raw materials in Table 6 indicate the content (% by weight) of each component when the total weight of the components (A) to (F) is 100% of the manufactured raw material.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
　本試験は、ポリウレタン水分散体中のＥＯ含有量を、表２で用いたNo.1～No.10と同程度（2.0％）にして、成分（ａ１）として、異性体成分として2,4’-MDIの含有量が多いミリオネートＮＭ１００を用いた場合の効果を検討したものである。表６から、2,4’-MDIの含有量が約９０％であるミリオネートＮＭ１００を用いた場合、柔軟性について実用性が向上し、耐エタノール水性能について、破断強度および面積膨潤率ともに実用性が向上すると評価された。 In this test, the EO content in the polyurethane water dispersion was set to the same level (2.0%) as No. 1 to No. 10 used in Table 2, and the component (a1) was 2,4 as the isomer component. 'The effect of using Millionate NM100 with a high content of -MDI was examined. From Table 6, when Millionate NM100 having a content of 2,4′-MDI of about 90% is used, the practicality of flexibility is improved, and the practicality of ethanol water resistance is both practical in terms of breaking strength and area swelling rate. Was rated as improved.
　本発明のポリウレタン水分散体によれば、該水分散体から得られるフィルム層が、耐エタノール水性能と透湿性能の点で、ともに実用性を有するので、上記特性が要求される塗料、コーティング剤、接着剤等に利用可能である。
  According to the polyurethane water dispersion of the present invention, since the film layer obtained from the water dispersion has both practicality in terms of ethanol water resistance and moisture permeability, paints and coatings that require the above characteristics. It can be used for adhesives and adhesives.

Claims (7)

  1. 　ジフェニルメタンジイソシアネート（ａ１）と脂環式ジイソシアネート（ａ２）とからなるポリイソシアネート（Ａ）、
    　エチレンオキシドとテトラヒドロフランのランダム共重合体（Ｂ）、
    　ポリカーボネートポリオール（Ｃ）、
    　数平均分子量が４００以下である多価アルコール系鎖延長剤（Ｄ）及びカルボキシル基を有するジオール化合物（Ｅ）を反応させて得られるイソシアネート基末端プレポリマーを中和し、得られた中和物を水中に分散させた後、アミン系鎖延長剤（Ｆ）を用いて鎖延長反応させて得られる、フィルム層を形成するために用いられるポリウレタン水分散体。     Polyisocyanate (A) comprising diphenylmethane diisocyanate (a1) and alicyclic diisocyanate (a2),
    A random copolymer of ethylene oxide and tetrahydrofuran (B),
    Polycarbonate polyol (C),
    A neutralized product obtained by neutralizing an isocyanate group-terminated prepolymer obtained by reacting a polyhydric alcohol chain extender (D) having a number average molecular weight of 400 or less and a diol compound (E) having a carboxyl group A polyurethane water dispersion used for forming a film layer, obtained by dispersing in water, followed by chain extension reaction using an amine chain extender (F).
  2. 　成分（ａ１）と成分（ａ２）のモル比が、（ａ１）／（ａ２）＝２０／８０～８０／２０である、請求項１記載のポリウレタン水分散体。 The polyurethane water dispersion according to claim 1, wherein the molar ratio of the component (a1) to the component (a2) is (a1) / (a2) = 20/80 to 80/20.
  3. 　成分（ａ２）が水素添加ジフェニルメタンジイソシアネート及びイソホロンジイソシアネートから選択される少なくとも１種である、請求項２記載のポリウレタン水分散体。 The polyurethane water dispersion according to claim 2, wherein the component (a2) is at least one selected from hydrogenated diphenylmethane diisocyanate and isophorone diisocyanate.
  4. 　成分（Ｂ）の数平均分子量が８００～４０００であり、エチレンオキシド単位（ＥＯ）とテトラヒドロフラン単位（ＴＨＦ）のモル比がＥＯ／ＴＨＦ＝８０／２０～１０／９０である、請求項１～３のいずれか記載のポリウレタン水分散体。 The number average molecular weight of component (B) is 800 to 4000, and the molar ratio of ethylene oxide units (EO) to tetrahydrofuran units (THF) is EO / THF = 80/20 to 10/90. Any polyurethane water dispersion.
  5. 　ポリウレタン水分散体中のポリウレタンに対して、ＥＯ含有量が１．５重量％以上である、請求項４記載のポリウレタン水分散体。 The polyurethane water dispersion according to claim 4, wherein the EO content is 1.5% by weight or more based on the polyurethane in the polyurethane water dispersion.
  6. 　ＥＯ含有量が１．５～１８重量％である、請求項５記載のポリウレタン水分散体。 The polyurethane water dispersion according to claim 5, wherein the EO content is 1.5 to 18% by weight.
  7. 　成分（ａ１）中における２，４’－ジフェニルメタンジイソシアネートの含有量が７０重量％以上である、請求項４記載のポリウレタン水分散体。
          The polyurethane water dispersion according to claim 4, wherein the content of 2,4'-diphenylmethane diisocyanate in component (a1) is 70% by weight or more.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62260811A (en) * 1986-05-07 1987-11-13 Dainippon Ink & Chem Inc Production of aqueous polyurethane dispersion
JPH03203920A (en) * 1989-12-29 1991-09-05 Dainichiseika Color & Chem Mfg Co Ltd Moisture-permeable polyurethane resin film
JP2010053159A (en) * 2008-08-26 2010-03-11 Nippon Polyurethane Ind Co Ltd Aqueous polyurethane dispersion and method for producing the same
WO2011125540A1 (en) * 2010-03-31 2011-10-13 三井化学株式会社 Thermoplastic polyurethane resin and molded article
JP2011213884A (en) * 2010-03-31 2011-10-27 Ube Industries Ltd Aqueous polyurethane resin dispersion and use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62260811A (en) * 1986-05-07 1987-11-13 Dainippon Ink & Chem Inc Production of aqueous polyurethane dispersion
JPH03203920A (en) * 1989-12-29 1991-09-05 Dainichiseika Color & Chem Mfg Co Ltd Moisture-permeable polyurethane resin film
JP2010053159A (en) * 2008-08-26 2010-03-11 Nippon Polyurethane Ind Co Ltd Aqueous polyurethane dispersion and method for producing the same
WO2011125540A1 (en) * 2010-03-31 2011-10-13 三井化学株式会社 Thermoplastic polyurethane resin and molded article
JP2011213884A (en) * 2010-03-31 2011-10-27 Ube Industries Ltd Aqueous polyurethane resin dispersion and use thereof

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