WO2021172485A1 - Dispersion aqueuse de résine de polyuréthane - Google Patents

Dispersion aqueuse de résine de polyuréthane Download PDF

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Publication number
WO2021172485A1
WO2021172485A1 PCT/JP2021/007240 JP2021007240W WO2021172485A1 WO 2021172485 A1 WO2021172485 A1 WO 2021172485A1 JP 2021007240 W JP2021007240 W JP 2021007240W WO 2021172485 A1 WO2021172485 A1 WO 2021172485A1
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Prior art keywords
polyurethane resin
weight
aqueous dispersion
group
active hydrogen
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PCT/JP2021/007240
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English (en)
Japanese (ja)
Inventor
拓紀 牧野
増美 山根
将浩 渡辺
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三洋化成工業株式会社
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Priority to JP2022503733A priority Critical patent/JPWO2021172485A1/ja
Publication of WO2021172485A1 publication Critical patent/WO2021172485A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • 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
    • C08G18/80—Masked 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
    • C08G18/83—Chemically modified polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to a polyurethane resin aqueous dispersion.
  • Polyurethane resin aqueous dispersions are used as highly functional aqueous dispersions in paints, adhesives, fiber processing agents, paper processing agents, inks, etc. because they have excellent film properties obtained by drying.
  • solvent-based urethane dissolved in an organic solvent has been used in these applications, but due to the drawbacks of organic solvent toxicity, fire risk, environmental pollution, etc., in recent years, solvent-based urethane to polyurethane resin water-based Switching to dispersion is accelerating.
  • the painting is applied to the base material by a painting gun or the like.
  • a paint containing a polyurethane resin aqueous dispersion which generally has strong cohesiveness and is easy to form a film, is painted with a painting gun, the paint containing the polyurethane resin aqueous dispersion remaining in the painting gun after using the painting gun is washed and removed. It could be difficult to do.
  • An object of the present invention is to provide a polyurethane resin aqueous dispersion which is excellent in storage stability and detergency after using a coating gun, and can obtain a film having excellent appearance after coating, water resistance and water adhesion. There is.
  • the present inventors have found a polyurethane resin aqueous dispersion that can solve the above-mentioned problems. That is, in the present invention, the polyurethane resin (U) having an acidic group containing the active hydrogen component (A) and the organic polyisocyanate component (B) as essential constituent monomers and / or the acidic group contained in the polyurethane resin (U).
  • the polyurethane resin (U) has a hydroxyl group and has
  • the polyurethane resin (U) has an acid value of 5 to 18 mgKOH / g.
  • a polyurethane resin aqueous dispersion (Q) having a viscosity of the polyurethane resin (U) of 100 to 1,000,000 Pa ⁇ s at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer. be.
  • the polyurethane resin aqueous dispersion of the present invention is excellent in storage stability and detergency after using a painting gun, and can obtain a film having excellent appearance after painting, water resistance and water resistance.
  • the polyurethane resin aqueous dispersion (Q) of the present invention is a polyurethane resin (U) having an acidic group containing an active hydrogen component (A) and an organic polyisocyanate component (B) as essential constituent monomers, and / or the polyurethane resin. It contains a polyurethane resin (U1) obtained by neutralizing the acidic group of (U) and an aqueous medium. Further, the polyurethane resin (U) has a hydroxyl group.
  • the acid value of the polyurethane resin (U) is 5 to 18 mgKOH / g.
  • the viscosity of the polyurethane resin (U) at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer is 100 to 1,000,000 Pa ⁇ s.
  • the polyurethane resin aqueous dispersion (Q) of the present invention contains the polyurethane resin (U) and the polyurethane resin (U1), the polyurethane resin (U) or the polyurethane resin (U1) which is a precursor of the polyurethane resin (U1) ( It suffices that at least one of U) satisfies the mode to be satisfied by the following polyurethane resin (U) (preferably the preferred mode of the polyurethane resin (U)), and is a precursor of the polyurethane resin (U) and the polyurethane resin (U1).
  • the polyurethane resin (U) may be used alone or in combination of two or more.
  • the polyurethane resin (U1) may be used alone or in combination of two or more. At least one kind of polyurethane resin (U) and at least one kind of polyurethane resin (U1) may be used in combination.
  • the polyurethane resin (U) is a resin containing the active hydrogen component (A) and the organic polyisocyanate component (B) as essential constituent monomers. Each component will be described below.
  • the active hydrogen component (A) is a compound containing an active hydrogen-containing group.
  • the active hydrogen-containing group means a group having an active hydrogen atom.
  • the active hydrogen atom means a hydrogen atom that is bonded to an oxygen atom, a nitrogen atom, a sulfur atom, etc. and has a high reactivity with an isocyanate group, and as a group having this active hydrogen atom (active hydrogen-containing group), Examples thereof include a hydroxyl group, a primary amino group, a secondary amino group and a thiol group.
  • the carboxyl group and the sulfo group are not included in the active hydrogen-containing group.
  • the active hydrogen component (A) includes a high molecular weight polyol (A1), a low molecular weight polyol (A2), a compound having a hydrophilic group and an active hydrogen atom (A3), a chain extender (A4), and a reaction terminator (A4).
  • A5 and the like can be mentioned.
  • Examples of the polymer polyol (A1) include polymer polyols having a number average molecular weight of 300 or more.
  • the number average molecular weight of the polymer polyol (A1) is preferably 500 or more, and more preferably 500 to 2,000.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • polymer polyol (A1) examples include polyether polyols, polyester polyols, polycarbonate polyols and the like.
  • polyether polyol examples include an aliphatic polyether polyol and an aromatic ring-containing polyether polyol.
  • the polyether polyol does not include the polyester polyol and the polycarbonate polyol described later.
  • aliphatic polyether polyol examples include an alkylene oxide adduct having 2 to 4 carbon atoms to an aliphatic polyhydric alcohol having 2 to 20 carbon atoms (ethylene glycol, propylene glycol, butanediol, dodecanediol, glycerin, etc.). Be done. Specific examples thereof include polyoxyethylene polyol [polyethylene glycol (hereinafter abbreviated as PEG) and the like], polyoxypropylene polyol [polypropylene glycol and the like], polyoxyethylene / propylene polyol, polytetramethylene ether glycol and the like.
  • PEG polyethylene glycol
  • PTMG1800 [Mn] 1,800 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.]
  • PTMG3000 [Mn 3,000 poly Tetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.]
  • PTMG4000 [Mn 4,000 polytetramethylene ether glycol, manufactured by Mitsubishi Chemical Co., Ltd.]
  • PTGL3000 [Mn 3,000 modified PTMG, Hodoya Chemical Industry Co., Ltd.] Manufactured by Sanyo Kasei Kogyo Co., Ltd.] and Sanniks
  • polytetramethylene ether glycol having a Mn of 300 to 1300 and polytetramethylene ether glycol having an Mn of 1500 to 4000 is preferable from the viewpoint of water adhesion and heat resistant water adhesion.
  • PTMG polytetramethylene ether glycol
  • THF tetrahydrofuran
  • aromatic ring-containing polyether polyol examples include an alkylene oxide adduct having 2 to 4 carbon atoms added to an aromatic ring and a compound having 6 to 20 carbon atoms (bisphenol, resorcin, etc.) having two or more hydroxyl groups.
  • bisphenol A ethylene oxide (hereinafter abbreviated as EO) adduct bisphenol A EO 2 mol adduct, bisphenol A EO 4 mol adduct, bisphenol A EO 6 mol adduct, bisphenol A EO 8 mol adduct.
  • PO bisphenol A propylene oxide
  • the number average molecular weight of the polyether polyol contained in the active hydrogen component (A) is preferably 500 or more, and more preferably 500 to 2,000.
  • polyester polyol examples include condensed polyester polyol, polylactone polyol, castor oil-based polyol and the like.
  • the polyester polyol does not include the polycarbonate polyol described later.
  • the condensed polyester polyol is a polyester polyol obtained by a low molecular weight (less than Mn300) polyhydric alcohol and a polyvalent carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.
  • Low molecular weight polyhydric alcohols include aliphatic polyhydric alcohols of less than Mn300 and divalent to octavalent or higher, and alkylene oxides of phenols of less than Mn300 of divalent to 8 or higher (EO, PO, 1, 2). -, 1,3-, 2,3- or 1,4-butylene oxide, etc., hereinafter abbreviated as AO)
  • Low molecular weight adducts can be used.
  • low molecular weight polyhydric alcohols that can be used in condensed polyester polyols, preferred are ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexaneglycol, and EO or PO low molars of bisphenol A. Additives and combinations thereof.
  • polyvalent carboxylic acids having 2 to 10 carbon atoms or ester-forming derivatives thereof that can be used in condensed polyester polyols are aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.).
  • Alicyclic dicarboxylic acid (dimeric acid, etc.), aromatic dicarboxylic acid (terephthalic acid, isophthalic acid, phthalic acid, etc.), trivalent or higher polycarboxylic acid (trimellitic acid, pyromellitic acid, etc.), these Anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), their acid halides (dichloroide adipic acid, etc.), and these low molecular weight alkyl esters (dimethyl succinate, dimethyl phthalate, etc.) In addition, the combined use of these can be mentioned.
  • condensed polyester polyol examples include polyethylene adipatediol, polybutylene adipatediol, polyhexamethylene adipatediol, polyhexamethyleneisophthalatediol, polyneopentyl adipatediol, polyethylenepropylene adipatediol, polyethylenebutylene adipatediol, and polybutylene.
  • Hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene comprise Examples thereof include catediol and polyneopentyl terephthalate diol.
  • the polylactone polyol is a heavy adduct of a lactone to the low molecular weight polyhydric alcohol, and examples of the lactone include lactones having 4 to 12 carbon atoms ( ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -caprolactone, etc.). Be done.
  • Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, polycaprolactone triol and the like.
  • Castor oil-based polyol includes castor oil and modified castor oil modified with polyol or AO.
  • Modified castor oil can be produced by transesterification of castor oil and polyol and / or addition of AO.
  • Examples of castor oil-based polyols include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, and EO (4 to 30 mol) adducts of castor oil.
  • polycarbonate polyol examples include the low molecular weight polyhydric alcohol, a low molecular weight carbonate compound (for example, a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and a polycarbonate polyol having 6 to 9 carbon atoms.
  • polycarbonate polyol examples include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol and poly (tetramethylene / hexamethylene) carbonate diol (for example, 1,4-butanediol and 1,6-hexane).
  • Diol) and the like obtained by condensing a diol while dealcoholizing it with a dialkyl carbonate.
  • T4672 2,000 poly (tetramethylene / hexamethylene) carbonate diol, Asahi Kasei Chemicals Co., Ltd. ) Made] and the like.
  • the active hydrogen component (A) is a polytetramethylene ether which is a high molecular weight polyol (A1) from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the range described in detail later and from the viewpoint of water adhesion and heat resistance. It is preferable that glycol is contained as an essential constituent monomer.
  • the Mn of the polytetramethylene ether glycol is preferably 500 to 2,000 from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the range described in detail later.
  • Examples of the small molecule polyol (A2) include small molecule polyols having a number average molecular weight (hereinafter abbreviated as Mn) of less than 300.
  • Mn number average molecular weight
  • the Mn of the small molecule polyol is a calculated value from the chemical formula.
  • Examples of the low molecular weight polyol (A2) having a Mn of less than 300 include aliphatic dihydric alcohols, aliphatic trihydric alcohols, and tetrahydric or higher aliphatic alcohols.
  • a dihydric aliphatic alcohol is preferable from the viewpoint of water resistance and heat-resistant yellowing, and the aliphatic dihydric alcohol includes ethylene glycol and propylene glycol.
  • 1,4-Butanediol, neopentyl glycol and 1,6-hexanediol are particularly preferable, and trimethylolpropane is particularly preferable as the aliphatic trihydric alcohol.
  • examples of the hydrophilic group of the compound (A3) having a hydrophilic group and an active hydrogen atom include a carboxyl group, a carboxylate group, a sulfo group and a sulfonat group. Further, as described above, the active hydrogen atom does not include a hydrogen atom derived from a carboxyl group and a sulfo group.
  • examples of the compound (A3) having a hydrophilic group and an active hydrogen atom include a compound having a carboxyl group and having 2 to 10 carbon atoms [dialkylol alkanoic acid (2,2-dimethylolpropionic acid, 2,2-dimethylol).
  • the active hydrogen component (A) may contain a compound (A31) having an acidic group (carboxyl group, etc.) as an essential constituent monomer among the compounds (A3) having a hydrophilic group and an active hydrogen atom. preferable.
  • an acidic group can be introduced into the polyurethane resin (U).
  • the compound (A31) is used in an amount that allows the acid value of the polyurethane resin (U) to be within the range described in detail later.
  • Examples of the chain extender (A4) include compounds having two or more active hydrogen atoms other than (A1) to (A3), and specific examples thereof include water and diamines having 2 to 10 carbon atoms (ethylenediamine, propylene). Diamine, hexamethylenediamine, isophoronediamine, toluenediamine, piperazine, etc.), polyalkylene polyamines having 2 to 10 carbon atoms (diethylenetriamine, triethylenetetramine, etc.), hydrazine or a derivative thereof (dibasic acid dihydrazide, for example, adipic acid dihydrazide, etc.) ) And amino alcohols having 2 to 10 carbon atoms (ethanolamine, diethanolamine, 2-amino-2-methylpropanol, triethanolamine, etc.) and the like.
  • reaction terminator (A5) examples include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.) and monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, mono).
  • Mono or dialkylamines such as butylamines, dibutylamines and monooctylamines; mono- or dialkanolamines such as monoethanolamines, diethanolamines, propanolamines and diisopropanolamines) and the like.
  • the active hydrogen component (A) contains a reaction terminator (A5).
  • the chain extender (A4) and the reaction terminator (A5) affect the urea group content described later and also the viscosity of the polyurethane resin (U), they are used in an amount within a range that does not impair the effects of the present invention. There is a need to. Specifically, it is necessary to use the amount in the range in which the viscosity of the polyurethane resin (U) becomes a value described in detail later. Therefore, it is preferable to use the chain extender (A4) and the reaction terminator (A5) in an amount such that the urea group content in the polyurethane resin (U) becomes a value described later.
  • the active hydrogen component (A) may be used alone or in combination of two or more.
  • the organic polyisocyanate component (B) which is an essential constituent monomer of the polyurethane resin (U), is a compound having 2 to 3 or more isocyanate groups, and those conventionally used in polyurethane resin production and the like are used. Can be used.
  • the organic polyisocyanate component (B) includes an aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms, an alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms, and an aromatic aliphatic polyisocyanate having 10 to 17 carbon atoms. (B3), aromatic polyisocyanates (b4) having 8 to 22 carbon atoms and derivatives of (b1) to (b4) (for example, isocyanurates) and the like can be mentioned.
  • Examples of the aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2-. Isocyanatoethyl-2,6-diisocyanatohexanoate and the like can be mentioned.
  • Examples of the alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms include isophorone diisocyanate (IPDI), dicyclohexylmethane 4,4'-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate (hydrogenated TDI). , Bis (2-isosianatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornene diisocyanate and the like.
  • IPDI isophorone diisocyanate
  • MDI dicyclohexylmethane 4,4'-diisocyanate
  • TDI methylcyclohexylene diisocyanate
  • aromatic aliphatic polyisocyanate (b3) having 10 to 17 carbon atoms examples include m- and / or p-xylene diisocyanate (XDI), ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylene diisocyanate (TMXDI) and the like. Can be mentioned.
  • aromatic polyisocyanate (b4) having 8 to 22 carbon atoms examples include 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4'-or. 2,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 4,4', 4 ′′ -triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, crude MDI and the like. Be done.
  • organic polyisocyanate components (B), (b1) and (b2) are preferable from the viewpoint of mechanical properties and weather resistance of the obtained film, and (b2) is more preferable, and (b2) is particularly preferable. IPDI and hydrogenated MDI.
  • the organic polyisocyanate component (B) may be used alone or in combination of two or more. Among them, the organic polyisocyanate component (B) preferably contains a chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms and / or an alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms.
  • the type of the organic polyisocyanate component (B) affects the urethane group content described later and also affects the viscosity of the polyurethane resin (U) described in detail later, it is necessary to use the organic polyisocyanate component (B) within a range that does not impair the effects of the present invention. There is. Specifically, it is necessary to use the polyurethane resin (U) in a range in which the viscosity becomes a value described later. Therefore, as the type of the organic polyisocyanate component (B), it is preferable to use an amount in which the urethane group content in the polyurethane resin (U) becomes a value described later.
  • the polyurethane resin (U) may have a constituent monomer other than the active hydrogen component (A) and the organic polyisocyanate component (B).
  • the constituent monomers other than the active hydrogen component (A) and the organic polyisocyanate component (B) include polyepoxy compounds having 2 to 30 carbon atoms (1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, etc.). ) Etc. can be mentioned.
  • the viscosity of the polyurethane resin (U) at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer is 100 to 1,000,000 Pa ⁇ s.
  • the viscosity of the polyurethane resin (U) at 25 ° C. measured at a shear rate of 0.1 / s using a rheometer is 100 to 150,000 Pa from the viewpoint of cleanability and appearance after using a painting gun.
  • -It is preferably s. Further, from the viewpoint of water resistance and heat resistant water adhesion, it is more preferably 3,500 to 13,000 Pa ⁇ s, further preferably 3,500 to 9,000 Pa ⁇ s, and 3,500 to 3,500 to s.
  • the viscosity using a rheometer can be measured under the following conditions using, for example, "MCR-302" manufactured by AntonioPaar. (Measurement condition) Measuring jig: Parallel plate “PP-08" (diameter 8 mm) Distance between plates: 0.5 mm Measurement temperature: 25 ° C Measurement mode: Rotational shear rate: 0.1 / sec
  • polytetramethylene ether glycol which is a high molecular weight polyol (A1), is used as the active hydrogen component (A), and the urethane group content and The urethane group content is set to a preferable value described later, and the equivalent ratio of isocyanate groups / active hydrogen atoms is set to a preferable value described later for the active hydrogen component (A) and the organic polyisocyanate component (B) constituting the polyurethane resin (U).
  • the molecular weight of the polyurethane resin (U) is set to a preferable value described later, and the acid value is set to a value described later, and the like can be mentioned.
  • the molecular weight of the polyurethane resin (U) can be increased by increasing the equivalent ratio of isocyanate groups / active hydrogen atoms within a preferable range described later to increase the molecular weight of the polyurethane resin (U). The viscosity of can be increased.
  • the viscosity of the polyurethane resin (U) can be increased by increasing the urethane group content, the urea group content, and the acid value within the range of the values described later. Further, for example, when the viscosity of the polyurethane resin (U) is high, the molecular weight of the polyurethane resin (U) can be lowered by reducing the equivalent ratio of isocyanate groups / active hydrogen atoms within a preferable range described later, and the polyurethane resin (U) can be reduced. The viscosity of U) can be reduced. Further, the viscosity of the polyurethane resin (U) can be reduced by lowering the urethane group content, the urea group content, and the acid value within the range of the values described later.
  • the polyurethane resin (U) [including the polyurethane resin (U) which is a precursor of the polyurethane resin (U1)] for measuring the viscosity from the polyurethane resin aqueous dispersion (Q), the following methods and the like are used. Can be mentioned.
  • the component other than the polyurethane resin (U) contained in the polyurethane resin aqueous dispersion (Q) [including the neutralizing agent of the polyurethane resin (U) described later] is a volatile component
  • the polyurethane resin (containing a neutralizing agent for the polyurethane resin (U) described later) is heated or the like.
  • Polyurethane resin (U) can be obtained by volatilizing components other than U).
  • the polyurethane resin (U) is purified by known chromatography using a volatile solvent as a mobile phase, and then heated or the like.
  • the polyurethane resin (U) can be obtained by removing the volatile solvent and the like.
  • the neutralizing agent for the polyurethane resin (U) described later is non-volatile, the components other than the polyurethane resin (U) are removed by the above method after performing a salt exchange reaction with a volatile base. Then, the polyurethane resin (U) can be obtained.
  • the urethane group content of the polyurethane resin (U) is 1.0 to 3.5 mmol / g based on the weight of the polyurethane resin (U) from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the above-mentioned viscosity. It is preferably 1.0 to 1.5 mmol / g, more preferably 1.0 to 1.2 mmol / g, and particularly preferably 1.1 to 1.2 mmol / g. preferable.
  • the urea group content of the polyurethane resin (U) is preferably 0.8 mmol / g or less based on the weight of the polyurethane resin (U) from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the above-mentioned viscosity. ..
  • the urea group content is preferably 0.05 mmol / g or more, preferably 0.5 mmol / g or more, based on the weight of the polyurethane resin (U). It is more preferable to have.
  • the ratio of the urea group content to the urethane group content is preferably 0.45 or more from the viewpoint of water adhesion and heat resistant water adhesion, and is preferably 0. It is more preferably 47 to 0.80.
  • the ratio of the urea group to the urethane group content can be quantified by 1 1 H-NMR.
  • the amounts of the active hydrogen component (A) and the organic polyisocyanate component (B) may be appropriately adjusted.
  • the urethane group content can be calculated from the N atom content quantified by the nitrogen analyzer, the ratio of the urea group to the urethane group content, and the alohanate group and burette group content.
  • the total amount of N atoms derived from “urethane group” and “urea group” is calculated by subtracting the amount of N atoms derived from "alohaneate group” and "buret group” from “N atom content”. do.
  • the amounts of N atoms derived from the "urethane group” and the "urea group” are calculated from the ratio of the urethane group and the urea group, respectively. From this value, the urethane group concentration is calculated.
  • the amino group content, the water content and the isocyanate group content in the raw material of the polyurethane resin (U) may be appropriately adjusted.
  • the urea group content can be calculated from the N atom content quantified by a nitrogen analyzer, the ratio of the urea group to urethane group contents, and the alohanate group and burette group contents.
  • the total amount of N atoms derived from “urethane group” and “urea group” is calculated by subtracting the amount of N atoms derived from "alohaneate group” and “buret group” from "N atom content”. do.
  • the amounts of N atoms derived from the "urethane group” and the "urea group” are calculated from the ratio of the urethane group and the urea group, respectively. From this value, the urea group concentration is calculated.
  • the total content of the alohanate group and the burette group in the polyurethane resin (U) is 0 based on the weight of the polyurethane resin (U) from the viewpoint of film forming property and water resistance of the obtained film. It is preferably 0.1 mmol / g or less, more preferably 0.03 mmol / g or less, particularly preferably 0.01 mmol / g or less, particularly preferably 0.003 mmol / g or less, and most preferably 0.001 mmol / g or less. Is.
  • the amino group content in the raw material of the polyurethane resin (U) and the isocyanate group with respect to the equivalent of the hydroxyl group and the amino group may be appropriately adjusted.
  • the reaction temperature can be set to 120 ° C. or lower or 180 ° C. or higher to suppress the formation of alohanate groups and burette groups.
  • the content of alohanate group and burette group is measured by gas chromatography.
  • the Mn of the polyurethane resin (U) is preferably 1,500 to 8,000, more preferably 2,000 to 7,500, particularly 2,000 to 7,500, from the viewpoint of adjusting the viscosity of the polyurethane resin (U) to the above-mentioned viscosity. It is preferably 2,000 to 6,000, particularly preferably 2,000 to 5,500, and most preferably 2,000 to 5,000.
  • the Mn of the polyurethane resin (U) can be set in a desired range.
  • the Mw of the polyurethane resin (U) is preferably 4,000 to 20,000, more preferably 5,000 to 18,000, and even more preferably 5,000 to 18,000, from the viewpoint of adjusting the viscosity of (U) to the above-mentioned viscosity. It is 6,500 to 15,000, particularly preferably 7,000 to 9,800, and most preferably 7,000 to 7,600.
  • Mn and Mw are values measured by the above-mentioned gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the polyurethane resin (U) has a hydroxyl group.
  • the hydroxyl value of the polyurethane resin (U) is preferably 15 to 100 mgKOH / g from the viewpoint of paint gun detergency and appearance.
  • Examples of the hydroxyl group of the polyurethane resin (U) include a hydroxyl group derived from the active hydrogen component (A), and the hydroxyl value can be adjusted by adjusting the amounts of the active hydrogen component (A) and the organic polyisocyanate component (B). Can be adjusted to the above-mentioned preferable range.
  • the hydroxyl value of the polyurethane resin (U) is a value measured according to JIS K0070 (1992).
  • the polyurethane resin (U) has an acidic group.
  • the acid value of the polyurethane resin (U) is 5 to 18 mgKOH / g, preferably 5 to 15 mgKOH / g, and more preferably 5 to 10 mgKOH / g from the viewpoint of water resistance and adhesion.
  • Examples of the acidic group contained in the polyurethane resin (U) include an acidic group derived from the compound (A31) having an acidic group, and a carboxyl group and a sulfo group.
  • the acid value can be adjusted to the above-mentioned preferable range by adjusting the amount of the compound (A31) having an acidic group or the like.
  • the acid value of the polyurethane resin (U) is a value measured according to JIS K0070 (1992).
  • the weight ratio of the insoluble component generated when the polyurethane resin (U) and acetone (such as 25 ° C. acetone) having a weight 10 times that of the polyurethane resin (U) are stirred at 80 ° C. for 180 minutes in a sealed state is used for painting gun cleaning. From the viewpoint of properties, it is preferably 5% by weight or less based on the weight of the added polyurethane resin (U).
  • the following method can be used as a method for measuring the weight ratio of the insoluble component.
  • Wg of polyurethane resin (U) is placed in a pressure-resistant airtight container with an inner diameter of 6 cm and a depth of 12 cm together with a stirrer chip having a length of 3 cm. (Acetone at ° C., etc.) is added, and the mixture is stirred at 80 ° C. for 180 minutes in a hermetically sealed manner to obtain a mixed solution.
  • the obtained mixed solution is filtered through a SUS mesh (opening 75 ⁇ m) whose weight (W1) has been measured in advance, and then filtered with acetone (the same weight as acetone charged in a pressure-resistant airtight container such as 25 ° C. acetone). To wash.
  • Weight ratio of insoluble component (%) ⁇ (W2-W1) / W ⁇ x 100
  • polyurethane resin (U) for measuring the viscosity is used as a method for obtaining the polyurethane resin (U) for measuring the weight ratio of the insoluble component from the polyurethane resin aqueous dispersion (Q)
  • a method of obtaining from the polyurethane resin aqueous dispersion (Q) ”and the like can be used.
  • polytetramethylene ether glycol which is a high molecular weight polyol (A1)
  • A1 a high molecular weight polyol
  • the amount is set to the above-mentioned preferable value, and the equivalent ratio of the isocyanate group / active hydrogen atom is set to the above-mentioned preferable value (0.6) with respect to the active hydrogen component (A) and the organic polyisocyanate component (B) constituting the polyurethane resin (U).
  • the molecular weight of the urethane resin (U) is set to the above-mentioned preferable value
  • the acid value is set to the above-mentioned value.
  • the weight ratio of the insoluble component of the polyurethane resin (U) when the weight ratio of the insoluble component of the polyurethane resin (U) is high, the molecular weight of the polyurethane resin (U) can be lowered by reducing the equivalent ratio of the isocyanate group / active hydrogen atom within a preferable range described later. The weight ratio of the insoluble component can be reduced. Further, by lowering the urethane group content, the urea group content, and the acid value within the above-mentioned range, the weight ratio of the insoluble component can be reduced.
  • the polyurethane resin (U1) in the present invention is a polyurethane resin obtained by neutralizing the acidic group of the polyurethane resin (U).
  • the acidic group of the polyurethane resin (U) is preferably an acidic group derived from the compound (A31) having an acidic group (carboxyl group or the like).
  • Examples of the neutralizing agent used for neutralizing the acidic group derived from the compound (A31) include ammonia, amine compounds having 1 to 20 carbon atoms, and hydroxides of alkali metals (sodium, potassium, lithium, etc.). ..
  • Examples of amine compounds having 1 to 20 carbon atoms include primary amines (monomethylamine, monoethylamine, monobutylamine, monoethanolamine, 2-amino-2-methyl-1-propanol, etc.) and secondary amines (dimethylamine, diethylamine). , Dibutylamine, diethanolamine, N-methyldiethanolamine, etc.) and tertiary amines (trimethylamine, triethylamine, dimethylethylamine, N, N-dimethylaminoethanol, triethanolamine, etc.) and the like.
  • amine compounds having a low vapor pressure at 25 ° C. are preferable from the viewpoint of the odor of the aqueous dispersion and the water resistance of the obtained film, and more preferable are triethylamine, monoethanolamine, diethanolamine and N-methyl. Diethanolamine, N, N-dimethylaminoethanol.
  • the aqueous dispersion (Q) of the polyurethane resin (U) in the present invention can be produced by dispersing the polyurethane resin (U) and / or the polyurethane resin (U1) in water.
  • the polyurethane resin aqueous dispersion (Q) of the present invention may be used as an antioxidant, an antioxidant, a weathering stabilizer, a plasticizer, a mold release agent, etc., if necessary.
  • Additives can be included.
  • the amount of these additives used is preferably 10% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less, based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1). ..
  • the polyurethane resin aqueous dispersion (Q) of the present invention is produced by producing the polyurethane resin (U) and / or the polyurethane resin (U1) by the following methods (1), (2), (3) or (4). It can be manufactured with.
  • (1) A method in which an active hydrogen component (A) and an organic polyisocyanate component (B) are collectively mixed, and after a urethanization reaction, the above-mentioned neutralizing agent is mixed if necessary and dispersed in an aqueous medium.
  • a urethane prepolymer (P) having an isocyanate group at the terminal obtained by reacting an active hydrogen component (A) [(A1) to (A3), etc.] with an organic polyisocyanate component (B) is produced.
  • an extension reaction is carried out with a chain extender (A4), and then a stop reaction is carried out with a reaction terminator (A5).
  • the neutralizing agent is mixed in a predetermined weight ratio and dispersed in an aqueous medium.
  • the aqueous medium include water (pure water and the like) and a mixture of water and an organic solvent described later.
  • the active hydrogen component (A) contains a compound (A3) containing a hydrophilic group and an active hydrogen atom. ..
  • the polyurethane resin aqueous dispersion (Q) in the present invention includes, if necessary, a urethane prepolymer (P) and a polyurethane resin from the viewpoint of dispersibility of the polyurethane resin (U) and the polyurethane resin (U1) and the stability of the aqueous dispersion. (U) and / or the polyurethane resin (U1) may be dispersed in water in the presence of the dispersant (g).
  • Dispersants (g) include nonionic surfactants (g1), anionic surfactants (g2), cationic surfactants (g3), amphoteric surfactants (g4) and other emulsified surfactants (g5). ).
  • the dispersant (g) may be used alone or in combination of two or more.
  • nonionic surfactant (g1) examples include an AO-added nonionic surfactant and a polyhydric alcohol-based nonionic surfactant.
  • the AO addition type includes EO addition of an aliphatic alcohol having 10 to 20 carbon atoms, EO addition of phenol, EO addition of nonylphenol, EO addition of alkylamine having 8 to 22 carbon atoms, and EO addition of polypropylene glycol.
  • Examples of the polyhydric alcohol type include fatty acid (8 to 24 carbon atoms) esters of polyhydric (3 to 8 or higher) alcohols (2 to 30 carbon atoms) (for example, glycerin monostearate and glycerin). Monooleate, sorbitan monolaurate, sorbitan monooleate, etc.) and alkyl (4 to 24 carbon atoms) poly (polymerization degree 1 to 10) glycoside and the like can be mentioned.
  • anionic surfactant (g2) examples include ether carboxylic acid having a hydrocarbon group having 8 to 24 carbon atoms or a salt thereof [lauryl ether sodium acetate and (poly) oxyethylene (additional molars 1 to 100) lauryl ether.
  • Sulfate or ether sulfate having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof [sodium lauryl sulfate, (poly) oxyethylene (additional moles 1 to 100) sodium lauryl sulfate, (poly) ) Oxyethylene (additional moles 1 to 100) triethanolamine lauryl sulfate and (poly) oxyethylene (additional moles 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; Hydrocarbon groups having 8 to 24 carbon atoms Sulfate having (sodium dodecylbenzene sulfonate, etc.); sulfosuccinate having one or two hydrocarbon groups having 8 to 24 carbon atoms; phosphate ester or ether having a hydrocarbon group having 8 to 24 carbon atoms.
  • Phosphate esters and their salts [sodium lauryl phosphate and (poly) oxyethylene (additional moles 1 to 100) sodium lauryl ether phosphate, etc.]; fatty acid salts having hydrocarbon groups with 8 to 24 carbon atoms [lauric acid] Sodium and triethanolamine laurate, etc.]; and acylated amino acid salts having a hydrocarbon group having 8 to 24 carbon atoms [sodium coconut oil fatty acid methyl taurine, sodium coconut oil fatty acid sarcosin sodium, coconut oil fatty acid sarcosin triethanolamine, N- Palm oil fatty acid acyl-L-glutamate triethanolamine, N-coconut oil fatty acid acyl-L-sodium glutamate, sodium lauroylmethyl- ⁇ -alanine, etc.] can be mentioned.
  • Examples of the cationic surfactant (g3) include quaternary ammonium salt type [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride and lanolin fatty acid ethyl sulfate aminopropylethyldimethylammonium, etc.] and amine salt type. [Diethylaminoethylamide stearate, dilaurylamine hydrochloride, oleylamine hydrochloride, etc.] can be mentioned.
  • amphoteric tenside agent (g4) examples include betaine-type amphoteric tenside agents [coconut oil fatty acid amidopropyldimethylaminoacetate betaine, lauryldimethylaminoacetate betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium. Betaine, laurylhydroxysulfobetaine, lauroylamide ethylhydroxyethylcarboxymethylbetaine sodium hydroxypropyl phosphate, etc.] and amino acid amphoteric tenside [ ⁇ -laurylaminopropionate, etc.] can be mentioned.
  • emulsifying dispersants (g5) include, for example, polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethyl cellulose, methyl cellulose and hydroxyethyl cellulose, carboxyl group-containing (co) polymers such as sodium polyacrylate, and US Patent No. Examples thereof include the emulsion dispersant having a urethane group or an ester group described in 5906704 (for example, a polycaprolactone polyol and a polyether diol linked with a polyisocyanate).
  • the dispersant (g) may be used before the urethanization reaction of the polyurethane resin (U), during the urethanization reaction, after the urethanization reaction, before the water dispersion step of the polyurethane resin (U), during the water dispersion step, or after the water dispersion. Although it may be added at the appropriate time, it is preferable to add it before the water dispersion step or during the water dispersion step from the viewpoint of the dispersibility of the polyurethane resin (U) and the stability of the aqueous dispersion.
  • the content of the dispersant (g) is preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, particularly preferably 0.01 to 10% by weight, based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1). Is 0.1 to 5% by weight.
  • the total weight of the constituent unit derived from the compound (A3) and the dispersant (g) in the polyurethane resin (U) and the polyurethane resin (U1) is based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1). It is preferably 0.01 to 20% by weight, more preferably 0.1 to 15% by weight, and particularly preferably 0.6 to 10% by weight.
  • the polyurethane resin aqueous dispersion (Q) in the present invention is an organic solvent [ketone solvent (eg acetone and methyl ethyl ketone), ester solvent (eg ethyl acetate), ether solvent (eg tetrahydrofuran), amide solvent (eg N, N-dimethylformamide and N-methylpyrrolidone), alcohol solvents (eg isopropyl alcohol) and aromatic hydrocarbon solvents (eg toluene)] may be included.
  • organic solvent ketone solvent (eg acetone and methyl ethyl ketone), ester solvent (eg ethyl acetate), ether solvent (eg tetrahydrofuran), amide solvent (eg N, N-dimethylformamide and N-methylpyrrolidone), alcohol solvents (eg isopropyl alcohol) and aromatic hydrocarbon solvents (eg toluene)
  • the polyurethane resin (U) and the urethane prepolymer (P) are obtained by heating the active hydrogen component (A) and the organic polyisocyanate component (B) in a heatable facility and reacting them.
  • Kolben a uniaxial or biaxial kneader, a plastic mill, a universal kneader, or the like, and a method of heating and reacting while stirring or kneading can be mentioned.
  • the method of heating and reacting while stirring or kneading increases the homogeneity of the obtained polyurethane resin (U), and the mechanical properties, durability, chemical resistance, abrasion resistance, etc. of the obtained film are increased. Is preferred because it tends to be better.
  • the polyurethane resin (U) is preferably reacted at a ratio of an isocyanate group / active hydrogen atom equivalent ratio of 0.6 to 0.95. Further, when the polyurethane resin (U) is produced by reacting the active hydrogen component (A) and the organic polyisocyanate component (B), the weight ratio of water in the reaction system is such that the urea group content is the above-mentioned preferable value. From the viewpoint of adjusting to 1.45% by weight or less based on the weight of the polyurethane resin (U), it is preferable.
  • the reaction temperature at the time of producing the polyurethane resin (U) and the urethane prepolymer (P) is 60 to 120 ° C. or 180 to 250 ° C. from the viewpoint of the content of the alohanate group and the burette group of the polyurethane resin (U). It is preferable, more preferably 60 to 110 ° C. or 180 to 240 ° C., and most preferably 60 to 100 ° C. or 180 to 230 ° C.
  • the time for producing the polyurethane resin (U) and the urethane prepolymer (P) can be appropriately selected depending on the equipment used, but is preferably 1 minute to 100 hours, more preferably 3 minutes to 30 hours. It is particularly preferably 5 minutes to 20 hours. Within this range, a polyurethane resin (U) capable of fully exerting the effects of the present invention can be obtained.
  • reaction catalysts titanium octylate, bismuth octylate, etc.
  • reaction retarders phosphoric acid, etc.
  • the amount of these catalysts or reaction retardants added is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, and particularly preferably 0.01 to, based on the weight of the polyurethane resin (U). 1% by weight.
  • any device having a dispersing ability can be used, but temperature control, supply of granular or block-shaped resin, dispersion ability, etc. From the viewpoint, it is preferable to use a rotary dispersion / mixing device, an ultrasonic dispersion / kneader, and a rotary dispersion / mixing device having a particularly excellent dispersion ability is more preferable.
  • the main dispersion principle of the rotary dispersion mixing device is that a shearing force is applied to the processed material from the outside by the rotation of the drive unit or the like to make the processed material into fine particles and disperse the particles.
  • the rotary dispersion mixing device can be operated under normal pressure, reduced pressure or pressurization.
  • rotary dispersion mixer examples include a mixer having general stirring blades such as Max Blend and helical blades, TK homomixer [manufactured by Primix Corporation], Clairemix [manufactured by M-Technique Co., Ltd.], and fill mix.
  • TK homomixer manufactured by Primix Corporation
  • Clairemix manufactured by M-Technique Co., Ltd.
  • fill mix [Primix Corporation], Ultra Turlux [IKA Co., Ltd.], Ebara Milder [Ebara Corporation], Cavitron (Eurotech Co., Ltd.) and Biomixer [Nippon Seiki Co., Ltd.], etc. Is exemplified.
  • the number of rotations when the polyurethane resin (U) or urethane prepolymer (P) is dispersed using the rotary dispersion mixing device is preferably 10 to 30,000 rpm, more preferably 20,000 to 20,000 rpm, and particularly. It is preferably 30 to 10000 rpm.
  • the main dispersion principle of the ultrasonic dispersion device is to apply energy from the outside to the processed material by the vibration of the drive unit to make it fine particles and disperse it.
  • the ultrasonic disperser can be operated under normal pressure, reduced pressure or pressurization.
  • an ultrasonic disperser commercially available from Ikemoto Rika Kogyo Co., Ltd., Cosmo Bio Co., Ltd., Ginsen Co., Ltd., etc. can be used.
  • the frequency at which the polyurethane resin (U) or urethane prepolymer (P) is dispersed using the ultrasonic disperser is preferably 1 to 100 kHz, more preferably 3 to 60 kHz, particularly from the viewpoint of dispersion ability. It is preferably 10 to 30 kHz.
  • the main dispersion principle of the kneader is to knead the processed material in the rotating part of the kneader to give energy to make it into fine particles and disperse it. Further, the kneader can be operated under normal pressure, reduced pressure or pressurization.
  • a twin-screw extruder [PCM-30 manufactured by Ikegai Corp.]
  • a kneader [KRC kneader manufactured by Kurimoto, Ltd., etc.]
  • a universal mixer [Hibismix manufactured by Primix Corporation, etc.]
  • Plast mills [Lab plast mills manufactured by Toyo Seiki Seisakusho Co., Ltd., etc.]
  • the number of rotations when the polyurethane resin (U) or urethane prepolymer (P) is dispersed using a kneader is preferably 1 to 1000 rpm, more preferably 3 to 500 rpm, and particularly preferably 10. ⁇ 200 rpm.
  • the time for treating the polyurethane resin (U) or urethane prepolymer (P) and water in the disperser is preferably 10 seconds to 10 hours, more preferably 1 minute to 3 hours, most preferably from the viewpoint of dispersibility. Is 10 to 60 minutes.
  • one kind of additive selected from pH adjusters, defoamers, antifoaming agents, antioxidants, anticoloring agents, plasticizers, mold release agents, etc. is used as necessary. The above can be added. Further, if necessary, solvent removal, concentration, dilution and the like may be performed after dispersion.
  • the device for reacting the chain extender (A4) and the reaction terminator (A5) after dispersing the urethane prepolymer (P) is not particularly limited, but the reaction is carried out while mixing with the disperser or a static mixer or the like. It is preferable to let it.
  • the polyurethane resin aqueous dispersion (Q) of the present invention is a polyurethane resin (U') other than the polyurethane resin (U) and the polyurethane resin (U1) as long as the effects of the present invention are not impaired, and a rheometer is used. It may contain a polyurethane resin (U'1) having a viscosity of more than 1,000,000 Pa ⁇ s at 25 ° C. measured at a shear rate of 0.1 / s. From the viewpoint of paint gun cleaning property, the weight ratio of the polyurethane resin (U'1) is preferably 40% by weight or less based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1). It is preferably 10% by weight or less, particularly preferably 5% by weight or less, and most preferably 1% by weight or less.
  • the polyurethane resin aqueous dispersion (Q) of the present invention contains a reactive group capable of reacting with an active hydrogen-containing group (hydroxyl group or the like) contained in the polyurethane resin (U). It is preferable to contain a cross-linking agent (C) having two or more of them.
  • the mixture of the polyurethane resin (U) and the cross-linking agent (C) may form one particle, and the polyurethane resin (U) and the cross-linking agent (C) may be formed. ) May exist in the state of separate particles.
  • the cross-linking agent (C) can also be cross-linked with the acidic group of the polyurethane resin (U).
  • the cross-linking agent (C) is selected from the group consisting of a blocked isocyanate compound (c1), a melamine compound (c2), an oxazoline compound (c3), a carbodiimide compound (c4), an aziridine compound (c5) and an epoxy compound (c6). At least one cross-linking agent can be mentioned.
  • the blocked isocyanate compound (c1) is not particularly limited as long as it has two or more blocked isocyanate groups in the molecule, and for example, the polyisocyanate compound exemplified as the organic polyisocyanate component (B) is known as a blocking agent [ Phenols, secondary or tertiary alcohols, oximes, aliphatic or aromatic secondary amines, phthalate imides, lactams, active methylene compounds (malonic acid dialkyl esters, etc.), pyrazole compounds (Pyrazole and 3,5-dimethylpyrazole, etc.) and acidic sodium sulfite, etc.] and the like are blocked.
  • a blocking agent Phenols, secondary or tertiary alcohols, oximes, aliphatic or aromatic secondary amines, phthalate imides, lactams, active methylene compounds (malonic acid dialkyl esters, etc.), pyrazole compounds (Pyrazole and 3,5-di
  • blocked isocyanate compounds (c1) include Duranate series (Duranate 17B-60P, TPA-B80E, MF-B60B, MF-K60B, SBB-70P, SBN-70D, SBF-" manufactured by Asahi Kasei Chemicals Co., Ltd. 70E, E402-B80B, WM44-L70G, etc.) and the like.
  • the melamine compound (c2) is not particularly limited as long as it is a methylolated melamine compound or a methoxymethylolated melamine compound having two or more methylol groups or methoxymethylol groups in the molecule, and is, for example, the Uban series manufactured by Mitsui Chemicals Co., Ltd. [Uban 120, 20HS, 2021, 2028, 228, 2860, 22R, etc.], Cymel series manufactured by Nippon Cytec Co., Ltd.
  • the oxazoline compound (c3) is not particularly limited as long as it is a compound having two or more oxazoline groups (oxazoline skeleton) in the molecule, and is, for example, 2,2'-isopropyrinebis (4-phenyl-2-oxazoline) or the like.
  • Examples thereof include copolymers with (meth) acrylic esters, (meth) acrylic acid amidovinyl acetate, styrene, and ⁇ -methylstyrene styrene sulfonate sodium, etc.].
  • Examples of commercially available products of the oxazoline compound (c3) include "Epocross K-2010E”, “Epocross K-2020E” and “Epocross WS-500” manufactured by Nippon Shokubai Co., Ltd.
  • the carbodiimide compound (c4) is not particularly limited as long as it is a compound having two or more carbodiimide groups in the molecule, for example, the aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms and an alicyclic having 8 to 18 carbon atoms.
  • An aliphatic polycarbodiimide [poly (hexamethylene) obtained by polymerizing a formula polyisocyanate (b2), an aromatic aliphatic polyisocyanate (b3) having 10 to 17 carbon atoms or an aromatic polycarbodiimide (b4) having 8 to 22 carbon atoms.
  • Carbodiimide), etc.] alicyclic polycarbodiimide [poly (4,4'-dicyclohexylmethanecarbodiimide), etc.] and aromatic polycarbodiimide [poly (p-phenylene carbodiimide), poly (4,4'-diphenylmethanecarbodiimide) and poly (Diisopropylphenylcarbodiimide), etc.].
  • Commercially available products of the carbodiimide compound (c4) include "carbodilite V-01”, “carbodilite V02”, “carbodilite V-03", “carbodilite V-04", and “carbodilite V-05” manufactured by Nisshinbo Holdings. Examples thereof include “carbodilite V-07", “carbodilite V-09”, “carbodilite E-02", “carbodilite E-03A” and “carbodilite E-04".
  • the aziridine compound (c5) is not particularly limited as long as it is a compound having two or more aziridinyl groups in the molecule, and is, for example, tetramethylolmethanetris ( ⁇ -aziridinyl propionate) and trimethylolpropane tris ( ⁇ -azili). Ridinyl propionate).
  • the epoxy compound (c6) is not particularly limited as long as it is a compound having two or more epoxy groups in the molecule, and is, for example, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and glycerol.
  • examples thereof include polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethyl propane polyglycidyl ether, pentaerythritol polyglycidyl ether and polypropylene glycol diglycidyl ether.
  • the cross-linking agent (C) may be used alone or in combination of two or more.
  • the content of the cross-linking agent (C) in the polyurethane resin aqueous dispersion (Q) is preferably 30% by weight or less, more preferably 0.1 to 25% by weight, based on the solid content weight of the polyurethane resin aqueous dispersion (Q). %.
  • the solid content concentration [weight ratio of components (solid content) other than volatile components] of the polyurethane resin aqueous dispersion (Q) obtained by the production method of the present invention is preferably from the viewpoint of ease of handling of the aqueous dispersion. It is 20 to 65% by weight, more preferably 25 to 55% by weight.
  • For the solid content concentration about 1 g of the aqueous dispersion was thinly spread on a Petri dish, weighed precisely, and then heated at 130 ° C. for 45 minutes using a circulating constant temperature dryer, and then weighed and weighed before heating. It can be obtained by calculating the ratio (percentage) of the residual weight after heating to the weight.
  • the ratio of the total weight of the polyurethane resin (U) contained in the polyurethane resin aqueous dispersion (Q) and the polyurethane resin (U) which is a precursor of the polyurethane resin (U1) is the ratio of the polyurethane resin aqueous dispersion (Q). Based on the weight of the solid content, it is preferably 15 to 100% by weight, more preferably 25 to 100% by weight, particularly preferably 40 to 100% by weight, and 55 to 100% by weight. Is most preferable.
  • the ratio of the total weight of the polyurethane resin (U) contained in the polyurethane resin aqueous dispersion (Q) and the polyurethane resin (U) which is a precursor of the polyurethane resin (U1) is the ratio of the polyurethane resin aqueous dispersion (Q).
  • the weight obtained by subtracting the weight of the cross-linking agent (C) from the weight of the solid content it is preferably 20 to 100% by weight, more preferably 30 to 100% by weight, and 45 to 100% by weight. Is particularly preferable, and 60 to 100% by weight is most preferable.
  • the viscosity of the polyurethane resin aqueous dispersion (Q) obtained by the production method of the present invention is preferably 10 to 100,000 mPa ⁇ s, more preferably 10 to 5,000 mPa ⁇ s.
  • the viscosity is a value measured at a constant temperature of 25 ° C. using a BL type viscometer.
  • the pH of the polyurethane resin aqueous dispersion (Q) obtained by the production method of the present invention is preferably 2 to 12, more preferably 4 to 10.
  • the pH is a value measured at 25 ° C. with pH Meter M-12 [manufactured by HORIBA, Ltd.].
  • the polyurethane resin aqueous dispersion (Q) of the present invention is an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (binder composition for pigment printing, a binder composition for non-woven fabric, a bundling agent for reinforcing fibers).
  • compositions binder compositions for antibacterial agents, raw material compositions for artificial leather / synthetic leather, etc.
  • water-based coating compositions waterproof coating composition, water-repellent coating composition, antifouling coating composition, etc.
  • water-based paper treatment agents Although it can be used in compositions, water-based ink compositions, etc., it is particularly preferably used as a water-based paint composition, a water-based adhesive composition, and a water-based fiber processing agent composition because of its excellent film-forming property and water resistance. can do.
  • additives such as coating resin, cross-linking agent, catalyst, pigment, pigment dispersant, viscosity modifier, defoamer, leveling agent, preservative, deterioration prevention
  • coating resin cross-linking agent
  • catalyst pigment, pigment dispersant, viscosity modifier, defoamer, leveling agent, preservative, deterioration prevention
  • agents stabilizers, antifreeze agents and the like
  • the preparation of the water-based paint using the polyurethane resin aqueous dispersion (Q) of the present invention will be described below.
  • the urethane resin (U) in the polyurethane resin aqueous dispersion (Q) of the present invention other water-dispersible resins or water-soluble paints are used in the water-based paint, if necessary, for the purpose of assisting the formation of a coating film and improving the binder function.
  • a resin may be used in combination.
  • the polyurethane resin aqueous dispersion (Q) used for the aqueous coating material preferably contains the above-mentioned cross-linking agent (C).
  • water-dispersible resins or water-soluble resins used in combination with water-based paints include water-dispersible or water-soluble polyurethane resins, polyacrylic resins, polyester resins, etc. other than the polyurethane resin in the present invention. These other resins can be appropriately selected from those commonly used in each application for each application of the water-based coating material.
  • the solid content of the polyurethane resin aqueous dispersion (Q) of the present invention in the aqueous coating material is preferably 0.1 to 60% by weight, more preferably 1 to 50% by weight, based on the weight of the aqueous coating material.
  • the content of the other resin in the water-based paint is preferably 60% by weight or less, more preferably 50% by weight or less, based on the weight of the water-based paint.
  • the amount of the cross-linking agent (C) added to the water-based paint is preferably 30% by weight or less, more preferably 0.1 to 20% by weight, based on the solid content weight of the water-based paint.
  • the water-based paint can further contain one or more kinds of pigments, pigment dispersants, viscosity modifiers, antifoaming agents, preservatives, deterioration inhibitors, stabilizers, antifreeze agents, water and the like.
  • Pigments include inorganic pigments having a solubility in water of 1 or less (for example, white pigments, black pigments, gray pigments, red pigments, brown pigments, yellow pigments, green pigments, blue pigments, purple pigments and metallic pigments) and organic pigments (for example, purple pigments and metallic pigments).
  • inorganic pigments having a solubility in water of 1 or less
  • organic pigments for example, purple pigments and metallic pigments.
  • the content of the pigment is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the aqueous paint.
  • the pigment dispersant include the above-mentioned dispersant (g), and the content of the pigment dispersant is preferably 20% by weight or less, more preferably 15% by weight or less, based on the weight of the pigment.
  • Viscosity adjusting agents include thickeners such as inorganic viscosity adjusting agents (sodium silicate, bentonite, etc.), cellulose-based viscosity adjusting agents (methyl cellulose having Mn of 20,000 or more, carboxymethyl cellulose, hydroxymethyl cellulose, etc.), and protein-based viscosity. Adjusters (casein, casein soda, ammonium casein, etc.), acrylics (sodium polyacrylate with Mn of 20,000 or more, ammonium polyacrylate, etc.) and vinyl viscosity adjusters (polyvinyl alcohol with Mn of 20,000 or more) Etc.).
  • inorganic viscosity adjusting agents sodium silicate, bentonite, etc.
  • cellulose-based viscosity adjusting agents methyl cellulose having Mn of 20,000 or more, carboxymethyl cellulose, hydroxymethyl cellulose, etc.
  • protein-based viscosity protein-based viscosity. Adjusters (casein, casein soda, ammonium
  • defoaming agent examples include long-chain alcohols (octyl alcohol and the like), sorbitan derivatives (sorbitan monooleate and the like), silicone oils (polymethylsiloxane and polyether-modified silicones and the like) and the like.
  • Examples of the preservative include an organic nitrogen-sulfur compound-based preservative and an organic sulfur halide-based preservative.
  • Examples of the deterioration inhibitor and stabilizer include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based and benzotriazole-based deterioration inhibitor and stabilizer. ..
  • Examples of the antifreeze agent include ethylene glycol and propylene glycol.
  • the contents of the viscosity regulator, antifoaming agent, preservative, deterioration inhibitor, stabilizer and antifreeze agent are preferably 5% by weight or less, more preferably 3% by weight or less, respectively, based on the weight of the water-based paint. be.
  • a solvent may be further added to the water-based paint for the purpose of improving the appearance of the coating film after drying.
  • the solvent to be added include monohydric alcohols having 1 to 20 carbon atoms (methanol, ethanol, propanol, etc.), glycols having 1 to 20 carbon atoms (ethylene glycol, propylene glycol, diethylene glycol, etc.), and 3 having 1 to 20 carbon atoms. Alcohols having a value higher than the value (glycerin, etc.) and cellosolves having 1 to 20 carbon atoms (methyl, ethyl cellosolves, etc.) and the like can be used.
  • the content of the solvent to be added is preferably 20% by weight or less, more preferably 15% by weight or less, based on the weight of the aqueous coating material.
  • the aqueous coating material using the polyurethane resin aqueous dispersion (Q) of the present invention is produced by mixing and stirring the polyurethane resin aqueous dispersion (Q) of the present invention and each of the above-mentioned components. At the time of mixing, all the components may be mixed at the same time, or each component may be added stepwise and mixed.
  • the solid content concentration of the water-based paint is preferably 10 to 70% by weight, more preferably 15 to 60% by weight.
  • the aqueous adhesive using the polyurethane resin aqueous dispersion (Q) of the present invention will be described below.
  • the resin used for the water-based adhesive the polyurethane resin (U) and / or the polyurethane resin (U1) in the polyurethane resin aqueous dispersion (Q) of the present invention may be used as it is, but the SBR latex resin or acrylic resin may be used.
  • a water-dispersible or water-soluble resin other than the typical polyurethane resin can be used in combination.
  • the ratio of the total weight of the polyurethane resin (U) and the polyurethane resin (U1) to the total weight of the resin is preferably 1% by weight or more, more preferably 10% by weight or more.
  • auxiliary materials and additives used in the adhesive for example, a cross-linking agent, a plasticizer, and a tackifier, as long as the cohesiveness of the adhesive containing the polyurethane resin aqueous dispersion (Q) of the present invention is not impaired.
  • Fillers, pigments, thickeners, antioxidants, UV absorbers, surfactants, flame retardants and the like can also be used.
  • the base material (adhesive body) on which the adhesive is used is not particularly limited.
  • a laminate of adherends obtained using an adhesive is also included in the present invention.
  • the fiber processing agent containing the polyurethane resin aqueous dispersion (Q) of the present invention includes, if necessary, known defoaming agents, wetting agents, and various resin aqueous dispersions (polyurethane aqueous dispersions other than the present invention, acrylic aqueous dispersions). Body, SBR latex, etc.) and softeners, etc. can be blended.
  • these blending amounts are preferably 30% by weight or less (more preferably 20% by weight or less) based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1) in terms of solid content.
  • the content is preferably 1% by weight or less (more preferably 0.1 to 0.5% by weight).
  • a pH adjuster can be added.
  • Examples of the pH adjuster include salts of alkaline substances such as strong bases (alkali metals and the like) and weak acids (acids having a pKa of more than 2.0, such as carbonic acid and phosphoric acid) (sodium bicarbonate and the like), or acidic substances (acetic acid and the like). Can be mentioned.
  • the amount of the pH adjuster is preferably 0.01 to 0.3% by weight based on the total weight of the polyurethane resin (U) and the polyurethane resin (U1).
  • the solid content (nonvolatile content) concentration of the aqueous fiber processing agent is not particularly limited, but is preferably 10 to 50% by weight, more preferably 15 to 45% by weight.
  • the viscosity (25 ° C.) is preferably 10 to 100,000 mPa ⁇ s.
  • the part means a weight part.
  • a simple pressurizing reaction device equipped with a stirrer and a heating device is provided with a high molecular weight polyol (A1), a low molecular weight polyol (A2), a compound (A3), and an organic polyisocyanate as the active hydrogen component (A) shown in Table 1.
  • the component (B) and the organic solvent were charged in the weights shown in Table 1 and stirred at 95 ° C. for 15 hours to carry out a urethanization reaction to produce an acetone solution of a polyurethane resin.
  • a polyurethane resin aqueous dispersion (Q-1) containing a polyurethane resin (U1) was obtained by performing a filtration operation in which the content was adjusted to be% by weight and filtered through a SUS mesh having a mesh size of 100 ⁇ m.
  • Example 2 ⁇ Examples 2 to 11>
  • the types and weights of the active hydrogen component (A), the organic polyisocyanate component (B), the organic solvent, the neutralizing agent, and the ion-exchanged water were changed to the contents shown in Table 1, but the same as in Example 1.
  • the same procedure was carried out to obtain polyurethane resin aqueous dispersions (Q-2) to (Q-11) containing a polyurethane resin (U1).
  • a chain extender (A4) as an active hydrogen component (A) was added.
  • a simple pressurizing reaction device equipped with a stirrer and a heating device is provided with a high molecular weight polyol (A1), a low molecular weight polyol (A2), a compound (A3), and an organic polyisocyanate as the active hydrogen component (A) shown in Table 1.
  • the component (B) and the organic solvent were charged in the weights shown in Table 1 and stirred at 95 ° C. for 15 hours to carry out a urethanization reaction, and the urethanization reaction was carried out. %) Was manufactured.
  • the above isocyanate group content was measured in accordance with JIS K7301-1995, 6.3 Isocyanate group content.
  • the reaction terminator (A5) as the active hydrogen component (A) shown in Table 1 was added to the obtained urethane prepolymer acetone solution with stirring at 30 ° C., homogenized at 60 rpm for 60 minutes, and the polyurethane resin acetone solution was added.
  • Manufactured While stirring the acetone solution of the obtained polyurethane resin at 30 ° C., 4.49 parts of triethylamine was added as a neutralizing agent, homogenized at 60 rpm for 30 minutes, kept at 30 ° C., and ionized under stirring at 500 rpm.
  • the emulsification operation was carried out by gradually adding 628.83 parts of exchanged water. Next, after distilling off acetone at 65 ° C.
  • a polyurethane resin aqueous dispersion (Q-12) containing a polyurethane resin (U1) was obtained by performing a filtration operation in which the content was adjusted to be% by weight and filtered through a SUS mesh having a mesh size of 100 ⁇ m.
  • Example 12 ⁇ Examples 13 to 14 and 16> In Example 12, except that the types and weights of the active hydrogen component (A), the organic polyisocyanate component (B), the organic solvent, the neutralizing agent and the ion-exchanged water were changed to the contents shown in Table 1, the same as in Example 12. The same procedure was carried out to obtain polyurethane resin aqueous dispersions (Q-13) to (Q-14) and (Q-16) containing a polyurethane resin (U1).
  • Example 15 the weights of the high molecular weight polyol (A1), the low molecular weight polyol (A2), the compound (A3), the organic polyisocyanate component (B), and the organic solvent as the active hydrogen component (A) are shown in Table 1.
  • the same procedure as in Example 12 was carried out except that the contents were changed to produce an acetone solution of urethane prepolymer (isocyanate group content of the solution: 1.25% by weight).
  • a polyurethane resin aqueous dispersion containing a polyurethane resin (U1) was carried out in the same manner as in Example 12 except that the weights of the active hydrogen component (A5), the neutralizing agent and the ion-exchanged water were changed to the contents shown in Table 1. (Q-15) was obtained.
  • a simple pressurizing reaction device equipped with a stirrer and a heating device is provided with a high molecular weight polyol (A1), a low molecular weight polyol (A2), a compound (A3), and an organic polyisocyanate as the active hydrogen component (A) shown in Table 1.
  • the component (B) and the organic solvent were charged in the weights shown in Table 1 and stirred at 95 ° C. for 15 hours to carry out a urethanization reaction, and the urethanization reaction was carried out. %) Was manufactured.
  • a polyurethane resin aqueous dispersion (Q-17) containing a polyurethane resin (U1) was obtained by performing a filtration operation in which the content was adjusted to be% by weight and filtered through a SUS mesh having a mesh size of 100 ⁇ m.
  • Example 18 In Example 17, except that the types and weights of the active hydrogen component (A), the organic polyisocyanate component (B), the organic solvent, the neutralizing agent, and the ion-exchanged water were changed to the contents shown in Table 1, the same as in Example 17. The same procedure was carried out to obtain a polyurethane resin aqueous dispersion (Q-18) containing a polyurethane resin (U1).
  • Example 19 90 parts by weight of the polyurethane resin aqueous dispersion (Q-12) produced in Example 12 and 10 parts by weight of the polyurethane resin aqueous dispersion (Q'-1) produced in Comparative Example 1 below are mixed to obtain a polyurethane resin.
  • Example 2 the types and weights of the active hydrogen component (A), the organic polyisocyanate component (B), the organic solvent, the neutralizing agent, and the ion-exchanged water were changed to the contents shown in Table 2, except that the contents were changed to those shown in Example 1. The same procedure was carried out to obtain comparative polyurethane resin aqueous dispersions (Q'-2) to (Q'-3) containing a comparative polyurethane resin (U1').
  • Example 2 the emulsification operation was carried out in the same manner as in Example 1 except that triethylamine was not added and the weight of the ion-exchanged water was changed to the weight shown in Table 2. After that, the steps from the distillation operation of acetone to the filtration operation were carried out in the same manner as in Example 1, and the polyurethane resin aqueous dispersion for comparison (Q'-4) containing the polyurethane resin for comparison (U1') was carried out.
  • Q'-4 polyurethane resin aqueous dispersion for comparison
  • U1' the polyurethane resin for comparison
  • the polymer polyols (A1) used in Examples 1 to 19 and Comparative Examples 1 to 4 are as follows.
  • the polyurethane resin aqueous dispersion (Q) or (Q') is poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, dried at 25 ° C. for 12 hours, and then heated at 105 ° C. for 3 hours in a circulation dryer. By drying, a polyurethane resin (U) or (U') for measurement was obtained.
  • the urethane group content and urea group content of the polyurethane resins (U) and (U') are quantified by the N atom content quantified by a nitrogen analyzer [ANTEK7000 (manufactured by Antec)] and 1 H-NMR. It was calculated from the ratio of urethane group to urea group and the content of alohanate group and burette group described later. 1 1 H-NMR measurement was carried out by the method described in "Structural Study of Polyurethane Resin by NMR: Takeda Research Institute Bulletin 34 (2), 224-323 (1975)".
  • the urea group is derived from the ratio of the integrated amount of hydrogen derived from the urea group near the chemical shift of 6 ppm and the integrated amount of hydrogen derived from the urethane group near the chemical shift of 7 ppm.
  • the weight ratio of the urethane group to the urethane group was measured, and the urethane group and urea group contents were calculated from the weight ratio, the N atom content, and the alohanate group and burette group contents.
  • the weight ratio of urea group to urethane group is calculated from the ratio of the integrated amount of hydrogen derived from the urea group near the chemical shift of 8 ppm and the integrated amount of hydrogen derived from the urethane group near the chemical shift of 9 ppm.
  • the urethane group and urea group contents were calculated from the weight ratio, the N atom content, and the alohanate group and burette group contents.
  • the polyurethane resin aqueous dispersion (Q) or (Q') is poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, dried at 25 ° C. for 12 hours, and then heated at 105 ° C. for 3 hours in a circulation dryer. By drying, a polyurethane resin (U) or (U') for measurement was obtained.
  • the polyurethane resin aqueous dispersion (Q) or (Q') is poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, dried at 25 ° C. for 12 hours, and then heated at 105 ° C. for 3 hours in a circulation dryer. By drying, a polyurethane resin (U) or (U') for measurement was obtained.
  • the resin viscosity of the obtained polyurethane resin was measured using a rheometer (“MCR-302” manufactured by AntonioPaar).
  • the polyurethane resin aqueous dispersion (Q) or (Q') is poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, dried at 25 ° C. for 12 hours, and then heated at 105 ° C. for 3 hours in a circulation dryer. By drying, a polyurethane resin (U) or (U') for measurement was obtained.
  • the acid value and hydroxyl value of the polyurethane resins (U) and (U') were measured according to JIS K0070 (1992).
  • Thickening rate (%) (V2-V1) / V1 ⁇ 100 ⁇ : -50% ⁇ thickening rate ⁇ + 50% ⁇ : -100% ⁇ thickening rate ⁇ -50% or + 50% ⁇ thickening rate ⁇ + 100% X: thickening rate ⁇ -100% or + 100% ⁇ thickening rate
  • ⁇ Evaluation method of paint gun cleaning property 70 parts of rutile-type titanium dioxide, 10 parts of "Disperbyk 190" (manufactured by Big Chemie Japan) and 34.3 parts of ion-exchanged water were premixed and then dispersed with a paint shaker for 30 minutes to obtain a pigment-dispersed paste. 205.71 parts of urethane resin aqueous dispersion and 10 parts of "Cymel202" were added to the obtained pigment paste and mixed uniformly to obtain a paint for evaluating paint gun detergency.
  • ⁇ There is no paint residue inside the bell, and there is no paint residue in the discharge hole.
  • ⁇ There is no paint residue on the inside of the bell, and the paint residue on the discharge hole is at a level where there is no problem with painting.
  • ⁇ A little paint remains on the inside of the bell, and a little paint remains on the discharge hole.
  • X A considerable amount of paint remains on the inside of the bell and in the discharge hole.
  • ⁇ Evaluation method of coating film appearance A commercially available cationic electrodeposition coating test piece is coated with the above-mentioned coating gun detergency evaluation paint by air spray coating so that the film thickness is 20 ⁇ m, preheated at 80 ° C. for 5 minutes, and then 30 at 140 ° C. The test piece was heat-cured for 1 minute to obtain a test piece on which a coating film was formed. The quality ( ⁇ or ⁇ ) of the appearance of the coating film on the test piece was visually evaluated.
  • the mixture is applied to a commercially available cationic electrodeposition coating test piece by air spray coating to a thickness of 20 ⁇ m, preheated at 80 ° C. for 5 minutes, and then heat-cured at 140 ° C. for 30 minutes to obtain a coating film. Obtained.
  • the obtained coating film was immersed in warm water at 40 ° C. for 240 hours, pulled up, and the surface moisture was removed with a dry cloth, and then dried at 25 ° C. for 2 hours.
  • the polyurethane resin aqueous dispersion of the present invention is excellent in storage stability and detergency after using a coating gun, and can obtain a film having excellent appearance after coating, water resistance and water resistance, and thus has a coating composition. It can be suitably used for products, adhesive compositions, fiber processing agent compositions and the like.

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

Abstract

La présente invention aborde le problème de la fourniture d'une dispersion aqueuse de résine de polyuréthane qui possède une excellente stabilité au stockage et une excellente aptitude au lavage lorsqu'elle est utilisée dans un pistolet à peinture, et peut fournir un revêtement présentant un aspect après peinture, une adhésivité résistante à l'eau et une adhésivité résistante à l'eau chaude d'excellente qualité.　La solution selon la présente invention porte sur une dispersion aqueuse de résine de polyuréthane (Q) qui contient : un milieu aqueux ; et une résine de polyuréthane (U) comportant un groupe acide et comprenant, en tant que monomère structural essentiel, un composant hydrogène actif (A) et un composant polyisocyanate organique (B), et/ou une résine de polyuréthane (U1) obtenue par neutralisation du groupe acide inclus dans la résine de polyuréthane (U). La résine de polyuréthane (U) comprend un groupe hydroxyle. La valeur acide de la résine de polyuréthane (U) est de 5 à 18 mg de KOH/g. La viscosité de la résine de polyuréthane (U) à 25 °C, mesurée à l'aide d'un rhéomètre à une vitesse de cisaillement de 0,1/s, est de 100 à 1 000 000 Pa·s.
PCT/JP2021/007240 2020-02-28 2021-02-26 Dispersion aqueuse de résine de polyuréthane WO2021172485A1 (fr)

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Cited By (2)

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JP7196349B1 (ja) 2022-04-28 2022-12-26 大日精化工業株式会社 ポリウレタン水分散体、接着剤、合成擬革、及び塗料
JP7198380B1 (ja) 2022-04-28 2022-12-28 大日精化工業株式会社 ポリウレタン水分散体、接着剤、合成擬革、及び塗料

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JP2013060577A (ja) * 2011-08-22 2013-04-04 Basf Japan Ltd 水性ベース塗料組成物及びそれを用いた複層塗膜形成方法
JP2013193058A (ja) * 2012-03-22 2013-09-30 Honda Motor Co Ltd 複層塗膜形成方法
JP2014210225A (ja) * 2013-04-17 2014-11-13 Ｂａｓｆジャパン株式会社 複層塗膜形成方法

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JP2013060577A (ja) * 2011-08-22 2013-04-04 Basf Japan Ltd 水性ベース塗料組成物及びそれを用いた複層塗膜形成方法
JP2013193058A (ja) * 2012-03-22 2013-09-30 Honda Motor Co Ltd 複層塗膜形成方法
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Publication number Priority date Publication date Assignee Title
JP7196349B1 (ja) 2022-04-28 2022-12-26 大日精化工業株式会社 ポリウレタン水分散体、接着剤、合成擬革、及び塗料
JP7198380B1 (ja) 2022-04-28 2022-12-28 大日精化工業株式会社 ポリウレタン水分散体、接着剤、合成擬革、及び塗料
WO2023210300A1 (fr) * 2022-04-28 2023-11-02 大日精化工業株式会社 Dispersion aqueuse de polyuréthanne, adhésif, cuir synthétique, et peinture
WO2023210299A1 (fr) * 2022-04-28 2023-11-02 大日精化工業株式会社 Dispersion aqueuse de polyuréthanne, adhésif, cuir synthétique, et peinture
JP2023163803A (ja) * 2022-04-28 2023-11-10 大日精化工業株式会社 ポリウレタン水分散体、接着剤、合成擬革、及び塗料
JP2023163802A (ja) * 2022-04-28 2023-11-10 大日精化工業株式会社 ポリウレタン水分散体、接着剤、合成擬革、及び塗料

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