JP4964916B2 - Polyurethane resin water dispersion - Google Patents

Description

  The present invention relates to an aqueous polyurethane resin dispersion excellent in film forming properties and water resistance and a method for producing the same.

Since the polyurethane resin water dispersion has excellent performance such as mechanical properties, durability, chemical resistance and abrasion resistance of the film obtained by drying, as a highly functional water dispersion, paint, adhesive, It is used in textile processing agents, paper processing agents, inks, etc., and is expected to become increasingly important from the viewpoint of environmental conservation, resource saving and safety. As a method for producing a polyurethane resin aqueous dispersion, there is known a method in which an isocyanate group-terminated urethane prepolymer is dispersed in water and chain extended with diamine or the like (so-called prepolymer mixing method) (see Patent Documents 1 to 3). Yes.
This is a method of obtaining a high molecular weight polyurethane resin by extending a chain with water and / or a polyamine compound in water simultaneously with or after dispersion. Since this chain extension reaction is a heterogeneous reaction, the molecular weight distribution of the polyurethane resin after the chain extension reaction becomes broad, the film forming property of the resulting polyurethane resin aqueous dispersion deteriorates, and the performance of the resulting film (machine) Physical properties, durability, chemical resistance, wear resistance, and the like).
Further, the polyurethane resin after the chain extension reaction has an amino group end, and due to its high hydrophilicity, there is a problem that the water resistance of the resulting film is lowered.

Japanese Patent Laid-Open No. 2004-2732 JP 2004-59676 A JP 2004-307721 A

  An object of the present invention is to provide an aqueous polyurethane resin dispersion having good film forming properties and excellent mechanical properties and water resistance.

As a result of intensive studies, the present inventors have found an aqueous polyurethane resin dispersion that can solve the above-described problems. That is, this invention is a polyurethane resin water dispersion which contains water and a polyurethane resin (U), and satisfy | fills all the following (1)-(6).
(1) The urethane group content in (U) is 0.5 to 5.0 mmol / g based on the weight of (U).
(2) The terminal amino group content in (U) is 0.35 mmol / g or less based on the weight of (U).
(3) The number average molecular weight (Mn) of (U) is 10,000 to 1,000,000.
(4) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of (U) is 1.5 to 3.5.
(5) The melting temperature of (U) is 70 to 280 ° C.
(6) The volume average particle diameter (Dv) of (U) is 0.01 to 1 μm.

The polyurethane resin aqueous dispersion of the present invention has the following characteristics.
(1) Since the film forming property is good, a film having excellent mechanical properties, durability, chemical resistance, abrasion resistance, etc. can be obtained as a result.
(2) A film having very excellent water resistance can be obtained.
(3) An aqueous dispersion of polyurethane resin having a very narrow molecular weight distribution.
(4) Excellent dispersion stability.

  The aqueous dispersion of the polyurethane resin (U) in the present invention can be produced by dispersing the polyurethane resin (U) in water.

The polyurethane resin (U) contains the polyol (a) and the polyisocyanate (b) as essential components, and if necessary, a compound (c) containing a hydrophilic group and an active hydrogen atom, a chain extender (d), and a reaction termination. It is produced by reacting the agent (e).
From the viewpoint of dispersibility of (U) in water, the compound (c) containing a hydrophilic group and an active hydrogen atom is preferably used as a component. Therefore, (U) is preferably a polyurethane resin having a hydrophilic group.

Examples of the polyol (a) include a polymer polyol (a1) having a number average molecular weight (hereinafter abbreviated as Mn) of 300 or more and a low molecular polyol (a2) having a Mn of less than 300.
In the present invention, the Mn of the polyol is measured by gel permeation chromatography (GPC) using polyethylene glycol as a standard. However, Mn of the low molecular polyol is a calculated value from the chemical formula.

  Examples of the polymer polyol (a1) having Mn of 300 or more include polyether polyol (a11) and polyester polyol (a12).

  Examples of the polyether polyol (a11) include aliphatic polyether polyols and aromatic ring-containing polyether polyols.

  Examples of the aliphatic polyether polyol include polyoxyethylene polyol [polyethylene glycol (hereinafter abbreviated as PEG), etc.], polyoxypropylene polyol [polypropylene glycol, etc.], polyoxyethylene / propylene polyol, and polytetramethylene ether glycol. Can be mentioned.

  Commercially available products of aliphatic polyether polyols include PTMG1000 [polytetramethylene ether glycol with Mn = 1,000, manufactured by Mitsubishi Chemical Corporation], PTMG2000 [polytetramethylene ether glycol with Mn = 2,000, Mitsubishi Chemical ( Co., Ltd.], PTMG3000 [polytetramethylene ether glycol with Mn = 3,000, manufactured by Mitsubishi Chemical Co., Ltd.] and Sanniks Diol GP-3000 [polypropylene ether triol with Mn = 3,000, Sanyo Chemical Industries, Ltd. Manufactured] and the like.

  Examples of aromatic polyether polyols include ethylene oxide (hereinafter abbreviated as EO) adducts of bisphenol A [EO 2 mol adduct of bisphenol A, EO 4 mol adduct of bisphenol A, EO 6 mol adduct of bisphenol A, and bisphenol A. EO 8 mol adduct, bisphenol A EO 10 mol adduct and bisphenol A EO 20 mol adduct, etc.] and bisphenol A propylene oxide (hereinafter abbreviated as PO) adduct [bisphenol A PO 2 mol adduct, bisphenol A PO3 molar adducts, PO5 molar adducts of bisphenol A, etc.], and EO or PO adducts of resorcin, and the like.

  Mn in (a11) is usually 300 or more, preferably 300 to 10,000, more preferably 300 to 6,000, from the viewpoint of mechanical properties of the polyurethane resin (U).

  Examples of the polyester polyol (a12) include condensed polyester polyols, polylactone polyols, polycarbonate polyols, and castor oil-based polyols.

The condensed polyester polyol is a polyester polyol of 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 dihydric to octahydric or higher aliphatic polyhydric alcohols less than Mn300 and alkylene oxides of dihydric to octavalent or higher phenols less than Mn300 (EO, PO, 1, 2). -, 1,3-, 2,3- or 1,4-butylene oxide and the like, hereinafter abbreviated as AO) and low molar adducts can be used.
Among the low molecular weight polyhydric alcohols that can be used in the condensed polyester polyol, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, bisphenol A EO or PO low mole Adducts and combinations thereof.

  Examples of the polyvalent carboxylic acid having 2 to 10 carbon atoms or ester-forming derivatives thereof that can be used in the condensed polyester polyol include aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid, maleic acid, etc.) , Alicyclic dicarboxylic acids (such as dimer acid), aromatic dicarboxylic acids (such as terephthalic acid, isophthalic acid and phthalic acid), trivalent or higher polycarboxylic acids (such as trimellitic acid and pyromellitic acid), these Anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), acid halides thereof (adipic acid dichloride, etc.), low molecular weight alkyl esters thereof (dimethyl succinate, dimethyl phthalate, etc.) These combinations are listed.

  Specific examples of the condensed polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, 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 seba Kate diol and polyneopentyl terephthalate diol It is.

  Commercially available condensed polyester polyols include San Ester 2610 [polyethylene adipate diol with Mn = 1,000, manufactured by Sanyo Chemical Industries, Ltd.] and San Ester 2620 [Polyethylene adipate diol with Mn = 2,000, Sanyo Chemical Industries. Etc.].

The polylactone polyol is a polyaddition product of a lactone to the low molecular weight polyhydric alcohol. Examples of the lactone include lactones having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone, and ε-caprolactone). It is done.
Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

  Examples of the polycarbonate polyol include the low molecular weight polyhydric alcohol, a low molecular carbonate compound (for example, an alkyl group having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms, and 6 to 9 carbon atoms). And a polycarbonate polyol produced by condensation with a dealcoholization reaction. Two or more low molecular weight polyhydric alcohols and alkylene carbonates may be used in combination.

  Specific examples of the polycarbonate polyol 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). And a diol obtained by condensing a diol with a dialkyl carbonate while causing a dealcoholization reaction).

  Commercially available polycarbonate polyols include NIPPOLAN 980R [polyhexamethylene carbonate diol with Mn = 2,000, manufactured by Nippon Polyurethane Industry Co., Ltd.] and T4672 [poly (tetramethylene / hexamethylene) carbonate diol with Mn = 2,000. Manufactured by Asahi Kasei Chemicals Co., Ltd.].

  The 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 AO addition. Castor oil-based polyols include castor oil, trimethylolpropane-modified castor oil, pentaerythritol-modified castor oil, and EO (4 to 30 mol) adduct of castor oil.

  Of the polyester polyols (a12), preferred are condensed polyester polyols and polycarbonate polyols.

  Examples of the low molecular polyol (a2) having a Mn of less than 300 include aliphatic dihydric alcohols, aliphatic trihydric alcohols and tetrahydric or higher aliphatic alcohols. Among (a2), from the viewpoint of water resistance and heat-resistant yellowing, a divalent or trivalent aliphatic alcohol is preferable. Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol, and 1,4-butanediol. Neopentyl glycol and 1,6-hexanediol are particularly preferable, and trimethylolpropane is particularly preferable as the aliphatic trihydric alcohol.

  As the polyisocyanate (b), which is an essential component of the polyurethane resin (U), those conventionally used for the production of polyurethane resins can be used. The polyisocyanate (b) is an aromatic polyisocyanate (b1) having 2 to 3 or more isocyanate groups and having 6 to 20 carbon atoms (excluding carbon in the isocyanate group, the same shall apply hereinafter), and 2 to 2 carbon atoms. 18 aliphatic polyisocyanate (b2), alicyclic polyisocyanate (b3) having 4 to 15 carbon atoms, araliphatic polyisocyanate (b4) having 8 to 15 carbon atoms and derivatives of (b1) to (b4) ( For example, isocyanurate product).

  Examples of the aromatic polyisocyanate having 6 to 20 carbon atoms (b1) include 1,3- or 1,4-phenylene diisocyanate, 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, etc. Can be mentioned.

  Examples of the aliphatic polyisocyanate (b2) having 2 to 18 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2 -Isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

  Examples of the alicyclic polyisocyanate (b3) having 4 to 15 carbon atoms include isophorone diisocyanate (IPDI), 4,4-dicyclohexylmethane diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, and methylcyclohexylene diisocyanate (hydrogenated TDI). Bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- or 2,6-norbornane diisocyanate, and the like.

  Examples of the aromatic aliphatic polyisocyanate (b4) having 8 to 15 carbon atoms include m- and / or p-xylylene diisocyanate (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). Etc.

  Of the polyisocyanates (b), (b2) and (b3) are preferable from the viewpoint of mechanical properties and weather resistance of the resulting film, (b3) is more preferable, and IPDI and hydrogenated MDI are particularly preferable. is there.

Examples of the compound (c) containing a hydrophilic group and an active hydrogen atom include a compound (c1) containing an anionic group and an active hydrogen atom, and a compound (c2) containing a cationic group and an active hydrogen atom.
(C1) is, for example, a compound having a carboxyl group as an anionic group and having 2 to 10 carbon atoms [dialkylol alkanoic acid (for example, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid). 2,2-dimethylolheptanoic acid and 2,2-dimethyloloctanoic acid), tartaric acid and amino acids (for example, glycine, alanine and valine)], a sulfonic acid group as an anionic group, and having 2 to 2 carbon atoms. 16 compounds [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and sulfoisophthalic acid di (ethylene glycol) ester and the like], containing a sulfamic acid group as an anionic group, and having 2 to 10 carbon atoms [N, N-bis (2-hydroxylethyl) sulfamic acid, etc.] and the like, and these compounds in a neutralizer Like the salt.

Examples of the neutralizing agent used in the salt of (c1) include ammonia, an amine compound having 1 to 20 carbon atoms, or an alkali metal hydroxide (such as sodium hydroxide, potassium hydroxide, and lithium hydroxide).
Examples of the amine compound having 1 to 20 carbon atoms include primary amines such as monomethylamine, monoethylamine, monobutylamine and monoethanolamine, secondary amines such as dimethylamine, diethylamine, dibutylamine, diethanolamine, diisopropanolamine and methylpropanolamine. Examples include amines and tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, dimethylmonoethanolamine and triethanolamine.

  As the neutralizing agent used in the salt of (c1), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the resulting polyurethane resin aqueous dispersion and the water resistance of the resulting film. From such a viewpoint, the neutralizing agent used in the salt of (c1) is preferably ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine or dimethylethylamine, more preferably ammonia or monoethylamine. Dimethylamine and diethylamine, particularly preferred is ammonia.

  Among the (c1), 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and salts thereof are preferable from the viewpoint of the resin physical properties of the obtained film and the dispersion stability of the polyurethane resin aqueous dispersion. More preferred are neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or an amine compound having 1 to 20 carbon atoms.

  As the compound (c2) containing a cationic group and an active hydrogen atom, for example, a tertiary amino group-containing diol having 1 to 20 carbon atoms [N-alkyl dialkanolamine (for example, N-methyldiethanolamine, N-propyldiethanolamine, N -Butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamine (for example, N, N-dimethylethanolamine) and the like] and the like, and the like.

Examples of the neutralizing agent used in (c2) include monocarboxylic acids having 1 to 10 carbon atoms (for example, formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride and benzyl chloride. .
As the neutralizing agent used in (c2), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the aqueous dispersion of the polyurethane resin to be produced and the water resistance of the resulting film. From such a viewpoint, the neutralizing agent used in (c2) is preferably a monocarboxylic acid having 1 to 10 carbon atoms and carbonic acid, more preferably formic acid and carbonic acid, and particularly preferably carbonic acid.

  The neutralizing agent used in (c1) and (c2) is added before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step, during the water dispersion step, or after the water dispersion. However, from the viewpoint of the stability of the urethane resin and the stability of the aqueous dispersion, it is preferably added before or during the aqueous dispersion process.

The amount of (c) used is such that the content of the hydrophilic group in (U) is usually 0.01 to 5% by weight, preferably 0.1 to 4% by weight, based on the weight of (U). Preferably, it is adjusted to 1 to 3% by weight.
The content of the hydrophilic group in the present invention means the weight percent of the unneutralized cationic group or anionic group, and does not include the weight of the counter ion. For example, the content of the hydrophilic group in (c1) is such that in the case of 2,2-dimethylolpropionic acid triethylamine salt, the weight percentage of the carboxyl group (—COOH) is 3- (2,3-dihydroxypropoxy). In the case of triethylamine salt of -1-propanesulfonic acid, it refers to the weight percent of the sulfo group (—SO ₃ H). Further, the content of the hydrophilic group in (c2) refers to the weight% of only the nitrogen atom in the tertiary amino group.

  Examples of the chain extender (d) include water, diamines having 2 to 10 carbon atoms (for example, ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, toluene diamine and piperazine), and polyalkylene polyamines having 2 to 10 carbon atoms ( For example, diethylenetriamine and triethylenetetramine), hydrazine or derivatives thereof (dibasic acid dihydrazide such as adipic acid dihydrazide) and aminoalcohols having 2 to 10 carbon atoms (such as ethanolamine, diethanolamine, 2-amino-2-methylpropanol and Ethanolamine) and the like.

  Examples of the reaction terminator (e) include monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.), monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, mono Mono- or dialkylamines such as butylamine, dibutylamine and monooctylamine; mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine).

Since the amount of (d) and (e) used affects the Mn, terminal amino group content and urea group content of (U), it is necessary to use them in a range that does not impair the effects of the present invention. Specifically, it is necessary that Mn of (U) has a value described later, and when an amine compound is used, the content of the terminal amino group of (U) should be within a value described later. . Moreover, it is preferable to use the quantity from which the urea group content in (U) becomes a below-mentioned value.
Polyurethane resins may be used alone or in combination of two or more.

  The polyurethane resin (U) in the present invention can contain additives such as antioxidants, anti-coloring agents, weathering stabilizers, plasticizers, and mold release agents as necessary. The amount of these additives used is usually 10% by weight or less, more preferably 3% by weight or less, and particularly preferably 1% by weight or less based on the weight of (U).

  In the polyurethane resin aqueous dispersion in the present invention, it is preferable to disperse (U) in water in the presence of the dispersant (h) from the viewpoint of the dispersibility of (U) and the stability of the aqueous dispersion.

  As the dispersant (h), nonionic surfactant (h1), anionic surfactant (h2), cationic surfactant (h3), amphoteric surfactant (h4) and other emulsifying dispersant (h5) ). (H) may be used alone or in combination of two or more.

  Examples of (h1) include AO addition type nonionic surfactants and polyhydric alcohol type nonionic surfactants. As the AO addition type, EO addition product of aliphatic alcohol having 10 to 20 carbon atoms, EO addition product of phenol, EO addition product of nonylphenol, EO addition product of alkylamine having 8 to 22 carbon atoms, and EO addition of polypropylene glycol. Examples of the polyhydric alcohol type include fatty acid (carbon number 8-24) esters (for example, glycerin monostearate, glycerin) of polyhydric (3 to 8 valence or higher) alcohol (2 to 30 carbon atoms). Monooleate, sorbitan monolaurate, sorbitan monooleate and the like) and alkyl (carbon number 4 to 24) poly (degree of polymerization 1 to 10) glycosides.

  Examples of (h2) include ether carboxylic acids having a hydrocarbon group having 8 to 24 carbon atoms or salts thereof [sodium lauryl ether acetate and (poly) oxyethylene (addition mole number 1 to 100) sodium lauryl ether acetate, etc.]; Sulfate ester or ether sulfate ester having a hydrocarbon group having 8 to 24 carbon atoms and salts thereof [sodium lauryl sulfate, (poly) oxyethylene (addition mole number 1 to 100) sodium lauryl sulfate, (poly) oxyethylene (addition) Mole number 1 to 100) lauryl sulfate triethanolamine and (poly) oxyethylene (addition mole number 1 to 100) coconut oil fatty acid monoethanolamide sodium sulfate, etc.]; sulfonate having a hydrocarbon group having 8 to 24 carbon atoms [Sodium dodecylbenzenesulfonate, etc.]; carbon number 8-2 Sulfosuccinates having 1 or 2 hydrocarbon groups; phosphate esters or ether phosphate esters having 8 to 24 carbon atoms and their salts [sodium lauryl phosphate and (poly) oxyethylene ( Addition mole number 1-100) sodium lauryl ether phosphate, etc.]; fatty acid salt having a hydrocarbon group having 8-24 carbon atoms [sodium laurate, triethanolamine laurate, etc.]; and hydrocarbon having 8-24 carbon atoms Acylated amino acid salts having a group [coconut oil fatty acid methyl taurine sodium, coconut oil fatty acid sarcosine sodium, coconut oil fatty acid sarcosine triethanolamine, N-coconut oil fatty acid acyl-L-glutamic acid triethanolamine, N-coconut oil fatty acid acyl- Sodium L-glutamate and lauroylmethyl β- alanine sodium, etc.] and the like.

  Examples of (h3) include quaternary ammonium salt types [stearyltrimethylammonium chloride, behenyltrimethylammonium chloride, distearyldimethylammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyldimethylammonium, etc.] and amine salt types [diethylaminoethyl stearate. Amide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

  Examples of (h4) include betaine-type amphoteric surfactants [coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, laurylhydroxy Sulfobetaine and lauroylamidoethylhydroxyethylcarboxymethylbetaine hydroxypropyl phosphate sodium etc.] and amino acid type amphoteric surfactants [sodium β-laurylaminopropionate etc.].

  Examples of (h5) include polyvinyl alcohol, starch and derivatives thereof, cellulose derivatives such as carboxymethylcellulose, methylcellulose and hydroxyethylcellulose, and carboxyl group-containing (co) polymers such as sodium polyacrylate and US Pat. No. 5,906,704. And emulsifying dispersants having the urethane group or ester group described above [for example, polycaprolactone polyol and polyether diol linked with polyisocyanate] and the like.

  The dispersant (h) is used before the urethane resin (U) urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step (U), during the water dispersion step, or after water dispersion. Although it may be added, it is preferably added before or during the water dispersion step from the viewpoint of the dispersibility of (U) and the stability of the water dispersion.

The content of (h) is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, and more preferably 1 to 5% by weight based on the weight of the polyurethane resin (U).
When (U) is a polyurethane resin having a hydrophilic group, the total content of (c) and (h) based on the weight of (U) is usually 0.3 to 20% by weight. , Preferably 0.6 to 10% by weight, more preferably 1 to 5% by weight.

  In the present invention, the urethane group content in the polyurethane resin (U) is 0.5 to 5.0 mmol / g based on the weight of (U), and the mechanical properties, durability, and chemical resistance of the resulting film are obtained. From the viewpoints of properties and wear resistance, it is preferably 0.8 to 4.2 mmol / g, more preferably 1.1 to 3.4 mmol / g.

The amount of the polyol (a), the polyisocyanate (b), the compound (c) containing a hydrophilic group and an active hydrogen atom, the chain extender (d), and the reaction terminator (e) is adjusted as necessary. Thus, the urethane group content of the polyurethane resin (U) can be set to a desired range.
In addition, the urethane group content in this invention is measured by the method as described in an Example.

In general, the molecular terminal of the polyurethane resin is a hydroxyl group derived from a hydroxyl group of a raw material, or an amino group derived from a reaction of an isocyanate group with water or an amino group of a raw material. In the step of dispersing the polyurethane resin (U) in water, the terminal amino group is generated by hydrolysis of the urethane group, urea group, allophanate group or burette group. Since this terminal amino group has poor water resistance compared to the terminal hydroxyl group, a polyurethane resin having a high content of terminal amino groups tends to have poor water resistance.
Therefore, in the present invention, the terminal amino group content in the polyurethane resin (U) is 0.35 mmol / g or less based on the weight of (U), and preferably 0.2 mmol / g or less from the viewpoint of water resistance. More preferably, it is 0.15 mmol / g or less, and particularly preferably 0.1 mmol / g or less.

The amount of the polyol (a), the polyisocyanate (b), the compound (c) containing a hydrophilic group and an active hydrogen atom, the chain extender (d), and the reaction terminator (e) is adjusted as necessary. By this, the terminal amino group content of the polyurethane resin (U) can be brought into a desired range.
In addition, the terminal amino group content in this invention is measured by the method as described in an Example.

  In the present invention, the urea group content in the polyurethane resin (U) is preferably 2.0 mmol / g or less based on the weight of (U) from the viewpoint of film forming properties and water resistance of the resulting film. More preferably, it is 0.2 mmol / g or less, particularly preferably 0.1 mmol / g or less, particularly preferably 0.05 mmol / g or less, and most preferably 0.02 mmol / g or less.

In order to bring the urea group content in the polyurethane resin (U) into a desired range, the amino group content, water content and isocyanate group content in the raw material of (U) may be appropriately adjusted.
In addition, the urea group content in this invention is measured by the method as described in an Example.

  In the present invention, the total content of allophanate groups and burette groups in the polyurethane resin (U) is 0.1 mmol based on the weight of (U) from the viewpoint of film forming properties and water resistance of the resulting film. / 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. .

In order to set the total content of allophanate groups and burette groups in the polyurethane resin (U) to a desired range, the content of amino groups in the raw material of (U), the equivalents of isocyanate groups to the equivalents of hydroxyl groups and amino groups The ratio, the urethanization reaction temperature and the like may be adjusted as appropriate. Especially about reaction temperature, the production | generation of an allophanate group and a burette group can be suppressed by setting it as 120 degrees C or less or 180 degrees C or more.
In addition, content of the allophanate group and burette group in this invention is measured by the method as described in an Example.

  In the present invention, the content of terminal isocyanate groups before dispersion of the polyurethane resin (U) in water is usually 0.2 mmol / g or less, preferably 0.15 mmol / g or less, more preferably based on the weight of (U). It is 0.1 mmol / g or less, particularly preferably 0.05 mmol / g or less. If it is this range, since the urea group content and terminal amino group content of (U) after dispersion in water can be targeted, the effects of the present invention can be sufficiently exerted.

  The content of the terminal isocyanate group of (U) before dispersion in water is mainly the ratio of the number of equivalents of isocyanate groups in the raw material of (U) to the total number of equivalents of hydroxyl groups, amino groups and water, and the reaction rate of the urethanization reaction. It is possible to control by.

  In the present invention, Mn of the polyurethane resin (U) is 10,000 to 1,000,000, and preferably 10,000 to 1,000 from the viewpoint of mechanical properties, durability, chemical resistance, wear resistance and the like of the obtained film. 500,000, more preferably 10,000 to 200,000, most preferably 10,000 to 100,000.

  The amount of the polyol (a), the polyisocyanate (b), the compound (c) containing a hydrophilic group and an active hydrogen atom, the chain extender (d), and the reaction terminator (e) is adjusted as necessary. Thereby, Mn of a polyurethane resin (U) can be made into a desired range.

  In the present invention, the weight average molecular weight (hereinafter abbreviated as Mw) of the polyurethane resin (U) and the ratio of Mn (Mw / Mn) is 1.5 to 3.5, preferably from the viewpoint of film forming properties. It is 1.75 to 3.25, more preferably 2.0 to 3.0.

  The Mw / Mn of the polyurethane resin (U) can be set within a predetermined range by appropriately adjusting the conditions (for example, stirring and mixing) relating to the uniformity of the urethanization reaction of (U). In addition, Mw and Mn of (U) in this invention are measured by the method as described in an Example.

  In the present invention, the melting temperature of the polyurethane resin (U) is 70 to 280 ° C., preferably from the viewpoint of the heat resistance, mechanical properties, durability, chemical resistance and wear resistance of the resulting film. 80-200 degreeC, More preferably, it is 90-150 degreeC.

The types and amounts of the polyol (a), the polyisocyanate (b), the compound (c) containing a hydrophilic group and an active hydrogen atom, the chain extender (d) and the reaction terminator (e) are adjusted as necessary. By doing, the melting temperature of a polyurethane resin (U) can be made into a desired range.
In addition, the melting temperature in this invention is measured by the method as described in an Example.

  In the present invention, the volume average particle diameter (Dv) of the polyurethane resin (U) is 0.01 to 1 μm, and from the viewpoint of dispersion stability of the polyurethane resin aqueous dispersion, preferably 0.02 to 0.7 μm, More preferably, it is 0.03-0.4 micrometer.

The volume average particle diameter (Dv) of (U) is determined by the hydrophilic group in (U), the amount of the dispersant, the type of the disperser used in the dispersing step, and the operating conditions. Therefore, in order to bring the volume average particle diameter (Dv) of (U) into a desired range, in the dispersion step, an apparatus selected from a rotary disperser, an ultrasonic disperser and a kneader described later is used. The content of the hydrophilic group in (U) and the content of the dispersant (h) may be appropriately adjusted.
In addition, the volume average particle diameter (Dv) in this invention is measured by the method as described in an Example.

  The polyurethane resin aqueous dispersion in the present invention contains an organic solvent [a ketone solvent (for example, acetone and methyl ethyl ketone), an ester solvent (for example, ethyl acetate), an ether solvent (for example, tetrahydrofuran), an amide solvent (for example, N, N-dimethyl). May contain formamide and N-methylpyrrolidone), alcohol solvents (eg isopropyl alcohol) and aromatic hydrocarbon solvents (eg toluene), etc., but odor, stability over time, environmental load, safety and production From the viewpoint of cost and the like, the content of the organic solvent is preferably 1000 ppm or less, more preferably 500 ppm or less, particularly preferably 100 ppm or less, based on the weight of the aqueous dispersion. Most preferably not.

  In order that the polyurethane resin aqueous dispersion in the present invention does not substantially contain an organic solvent, the raw material of (U) and various additives to be used are those that do not substantially contain an organic solvent. It is preferable not to use an organic solvent in the production step and the dispersion step (U).

  In the present invention, the polyurethane resin (U) comprises a polyol (a), a polyisocyanate (b), a compound (c) containing a hydrophilic group and an active hydrogen atom, if necessary, a chain extender (d), and a reaction termination. It can be obtained by reacting the agent (e) by heating it with heatable equipment. For example, the raw material (U) is charged in a container and uniformly stirred, and then heated without stirring in a heating dryer or heating furnace, a simple pressure reactor (autoclave), Kolben, uniaxial or biaxial kneading. And a method of reacting by heating with stirring or kneading in a machine, a plast mill or a universal kneader. Among them, the method of heating and reacting while stirring or kneading increases the homogeneity of the obtained urethane resin (U), and the mechanical properties, durability, chemical resistance and abrasion resistance of the resulting film, etc. Is preferred because it tends to be more excellent. Among the methods of heating and reacting while stirring or kneading, a uniaxial or biaxial kneader excellent in stirring strength and heating ability is preferable. Examples of the uniaxial or biaxial kneader include a continuous kneader (manufactured by Kurimoto Seiko Co., Ltd.), a uniaxial kneader, a biaxial extruder, and the like.

  100-250 degreeC is preferable, as for the reaction temperature at the time of manufacturing a polyurethane resin (U), More preferably, it is 100-120 degreeC or 180-240 degreeC, Most preferably, it is 190-230 degreeC. The time for producing (U) can be appropriately selected depending on the equipment used, but generally 1 minute to 100 hours is preferable, more preferably 3 minutes to 30 hours, and particularly preferably. 5 minutes to 10 hours. If it is this range, (U) which can fully exhibit the effect of the present invention will be obtained.

  In order to control the urethanization reaction rate, known reaction catalysts (such as tin octylate and bismuth octylate) and reaction retarders (such as phosphoric acid) can be used. The addition amount of these catalysts or reaction retarders is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, and particularly preferably 0.01 to 1% by weight based on the weight of (U). %.

  From the viewpoint of ease of handling in the step of dispersing the polyurethane resin (U) in water, the shape of (U) before dispersion is preferably made into a granular or block shape of 0.2 to 500 mm. Preferably it is 0.5-100 mm, Most preferably, it is 0.7-30 mm, Most preferably, it is 1-10 mm.

As means for adjusting the shape to a granular shape or block shape, for example, means such as cutting, pelletizing, granulating, or pulverizing can be used. This granular or block adjustment can be performed in water or in the absence of water.
For example, a polyurethane resin (U) rolled into a sheet shape is granulated with a square pelletizer, a method in which the polyurethane resin (U) is cut into a block shape by cutting with a scissors or an ultrasonic cutter, and the polyurethane resin (U) taken out in a strand shape is pelletized. And a method of cutting into pellets.

  As a device for dispersing the polyurethane resin (U) in water, any device (A) having a dispersion ability can be used. However, from the viewpoint of temperature adjustment, supply of granular or block resin, and dispersion ability, it can be rotated. It is preferable to use a type dispersion mixing apparatus (A1), an ultrasonic dispersion machine (A2), or a kneading machine (A3), and among them, (A1) is particularly preferable because of particularly excellent dispersion ability.

  The main dispersion principle of the rotary dispersion mixing device (A1) is to apply a shearing force to the processed material from the outside by rotation of the drive unit or the like to make fine particles and disperse them. Moreover, (A1) can be operated under normal pressure, reduced pressure, or increased pressure.

  Examples of the rotary dispersion mixing apparatus (A1) include TK homomixer [manufactured by Primics Co., Ltd.], Claremix [manufactured by Mtechnics Co., Ltd.], Filmix [manufactured by Primics Co., Ltd.], Ultra Turrax [IKA ( Co., Ltd.], Ebara Milder [Ebara Seisakusho Co., Ltd.], Cavitron (Eurotech Co., Ltd.), Biomixer [Nippon Seiki Co., Ltd.] and the like.

  The number of rotations when the polyurethane resin (U) is dispersed using the rotary dispersion mixer (A1) is usually 100 to 30000 rpm, preferably 500 to 20000 rpm, and more preferably 1000 to 10,000 rpm from the viewpoint of dispersion capability. is there.

  The main dispersion principle of the ultrasonic dispersion apparatus (A2) is to apply energy from the outside to the processed material by the vibration of the drive unit to form fine particles and disperse them. Moreover, (A2) can be operated under normal pressure, reduced pressure, or increased pressure.

  As the ultrasonic dispersion device (A2), an ultrasonic dispersion device commercially available from Ikemoto Rika Kogyo Co., Ltd., Cosmo Bio Co., Ltd., and Ginsen Co., Ltd. can be used.

  The frequency at which the polyurethane resin (U) is dispersed using the ultrasonic dispersing device (A2) is usually 1 to 100 kHz, preferably 3 to 60 kHz, particularly preferably 10 to 30 kHz, from the viewpoint of dispersion capability. is there.

  The main dispersion principle of the kneading machine (A3) is that the processed material is kneaded in the rotating part of (A3) to give energy to form fine particles and disperse. Moreover, (A3) can be operated under normal pressure, reduced pressure, or increased pressure.

  As the kneading machine (A3), a twin-screw extruder [PCM-30 manufactured by Ikegai Co., Ltd.], a kneader [KRC kneader manufactured by Kurimoto Steel Co., Ltd.], a universal mixer [Hibismix manufactured by Primix Co., Ltd.] Etc.] and plast mill [laboratory plast mill manufactured by Toyo Seiki Seisakusho Co., Ltd.] and the like.

  The number of rotations when the polyurethane resin (U) is dispersed using the kneader (A3) is usually 1 to 1000 rpm, preferably 3 to 500 rpm, particularly preferably 10 to 200 rpm, from the viewpoint of dispersion ability.

The aqueous polyurethane resin dispersion of the present invention is produced by using the dispersing device (A) to disperse the polyurethane resin (U) in water in the process of dispersing (U) under heating and dispersing it to the desired fine particles. Is done. Therefore, it is preferable that the above physical property values of the polyurethane resin (U) are not changed due to degradation such as hydrolysis in the dispersion step.
In order to suppress the deterioration, it is preferable to disperse (U) in water below its melting temperature. The temperature at which (U) is dispersed in water is more preferably 25 to 180 ° C. and 5 to 100 ° C. lower than the melting temperature of (U), particularly preferably 90 to 150 ° C. And it is 10-120 degreeC temperature lower than the melting temperature of (U).

 In order to disperse (U) below the melting temperature of (U), it is preferable that (U) swells with water during the dispersion treatment. The degree of swelling of (U) can be adjusted by appropriately adjusting the content of (c) and / or (h).

  The weight ratio of (U) and water supplied to the dispersing apparatus (A) is appropriately selected depending on the resin component content of the target aqueous dispersion, but usually (U) / water = 10/2 to 10/100, preferably 10/5 to 10/50.

  Moreover, the time which processes (U) and water with a dispersion apparatus (A) is 10 seconds-10 hours normally from a viewpoint of preventing decomposition | disassembly, deterioration, etc. of (U) which is a dispersion, More preferably, it is 1 minute-3 Time, most preferably 10-60 minutes.

  When dispersing in the dispersing apparatus (A), an additive selected from a pH adjuster, an antifoaming agent, a foam inhibitor, an antioxidant, a coloring inhibitor, a plasticizer, a mold release agent, and the like, if necessary. One or more can be added. Moreover, you may perform solvent removal, concentration, dilution, etc. after dispersion | distribution as needed.

  The solid content concentration (content of components other than volatile components) of the polyurethane resin aqueous dispersion obtained by the production method of the present invention is preferably 20 to 65% by weight from the viewpoint of easy handling of the aqueous dispersion. Preferably it is 25 to 55% by weight. The solid concentration was about 1 g of the aqueous dispersion thinly spread on a Petri dish, weighed accurately, then weighed the weight after heating at 130 ° C for 45 minutes using a circulating constant temperature drier, before heating. It can be obtained by calculating the ratio (percentage) of the remaining weight after heating to the weight.

The viscosity of the polyurethane resin aqueous dispersion 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 can be measured at a constant temperature of 25 ° C. using a BL type viscometer.
The pH of the polyurethane resin aqueous dispersion obtained by the production method of the present invention is preferably 2 to 12, more preferably 4 to 10. The pH can be measured at 25 ° C. with pH Meter M-12 [manufactured by Horiba, Ltd.].

  The polyurethane resin aqueous dispersion of the present invention comprises an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a binder composition for pigment printing, a binder composition for nonwoven fabric, a sizing agent composition for reinforcing fibers, Antibacterial agent binder composition and artificial leather / synthetic leather raw material composition, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition, antifouling coating composition, etc.), aqueous paper treatment composition, It can be used for water-based ink compositions and the like, but because of its excellent film-forming properties and water resistance, it can be suitably used especially as a water-based coating composition, water-based adhesive composition and water-based fiber processing agent composition. it can.

  When used in these applications, other additives such as coating forming auxiliary resins, crosslinking agents, catalysts, pigments, pigment dispersants, viscosity modifiers, antifoaming agents, leveling agents, preservatives, anti-degradation are necessary. One, two or more agents, stabilizers, antifreezing agents and the like can be added.

Hereinafter, preparation of an aqueous paint using the polyurethane resin aqueous dispersion of the present invention will be described.
In addition to the urethane resin (U) in the polyurethane resin aqueous dispersion of the present invention, other water-dispersible resins or water-soluble resins are used in combination with the water-based paint, if necessary, for the purpose of coating film formation and improvement of the binder function. You may do it.

  Examples of other water-dispersible resins or water-soluble resins used in combination with water-based paints include water-dispersible or water-soluble polyurethane resins other than the polyurethane resin in the present invention, polyacrylic resins, and polyester resins. These other resins can be appropriately selected from those commonly used in each application for each application of the water-based paint.

The solid content of the aqueous polyurethane resin dispersion of the present invention in the aqueous coating is usually 0.1 to 60% by weight, preferably 1 to 50% by weight, based on the weight of the aqueous coating.
The content of the other resin in the water-based paint is usually 60% by weight or less, preferably 50% by weight or less based on the weight of the water-based paint.

  The water-based paint may further contain one or more of a crosslinking agent, a pigment, a pigment dispersant, a viscosity modifier, an antifoaming agent, an antiseptic, a deterioration preventing agent, a stabilizer, an antifreezing agent, water, and the like. it can.

Examples of the crosslinking agent include water-soluble or water-dispersible amino resins, water-soluble or water-dispersible polyepoxides, water-soluble or water-dispersible blocked polyisocyanate compounds, and polyethylene urea.
The addition amount of the crosslinking agent is usually 30% by weight or less, preferably 0.1 to 20% by weight, based on the solid content weight of the polyurethane resin aqueous dispersion.

  Examples of the pigment include inorganic pigments having a solubility in water of 1 or less (for example, white pigment, black pigment, gray pigment, red pigment, brown pigment, yellow pigment, green pigment, blue pigment, purple pigment and metallic pigment) and organic pigments ( For example, natural organic pigment synthetic organic pigments, nitroso pigments, nitro pigments, pigment dye-type azo pigments, azo lakes made from water-soluble dyes, azo lakes made from poorly soluble dyes, lakes made from basic dyes, lakes made from acid dyes, xanthan lakes , Anthraquinone lake, pigments from vat dyes and phthalocyanine pigments). The content of the pigment is usually 50% by weight or less, preferably 30% by weight or less, based on the weight of the aqueous paint.

  Examples of the pigment dispersant include the above-described dispersant (h), and the content of the pigment dispersant is usually 20% by weight or less, preferably 15% by weight or less based on the weight of the pigment.

Viscosity modifiers include thickeners such as inorganic viscosity modifiers (such as sodium silicate and bentonite), cellulose viscosity modifiers (such as methylcellulose, carboxymethylcellulose, and hydroxymethylcellulose with Mn of 20,000 or more), proteins System viscosity modifiers (casein, casein soda, casein ammonium, etc.), acrylics (sodium polyacrylate and ammonium polyacrylate with Mn of 20,000 or more) and vinyl viscosity modifiers (Mn of 20,000 or more) Polyvinyl alcohol).
Examples of antifoaming agents include long-chain alcohols (such as octyl alcohol), sorbitan derivatives (such as sorbitan monooleate), and silicone oils (such as polymethylsiloxane and polyether-modified silicone).

Examples of the preservative include organic nitrogen sulfur compound preservatives and organic sulfur halide preservatives.
Deterioration inhibitors and stabilizers (such as UV absorbers and antioxidants) include hindered phenol-based, hindered amine-based, hydrazine-based, phosphorus-based, benzophenone-based and benzotriazole-based deterioration inhibitors and stabilizers. .
Examples of the antifreezing agent include ethylene glycol and propylene glycol.
The contents of the viscosity modifier, antifoaming agent, antiseptic, deterioration preventing agent, stabilizer and antifreezing agent are each usually 5% by weight or less, preferably 3% by weight or less, based on the weight of the aqueous paint.

  A solvent may be further added to the water-based paint for the purpose of improving the appearance of the coating film after drying. Examples of the solvent to be added include monohydric alcohols having 1 to 20 carbon atoms (such as methanol, ethanol and propanol), glycols having 1 to 20 carbon atoms (such as ethylene glycol, propylene glycol and diethylene glycol), and 3 having 1 to 20 carbon atoms. Alcohols having higher valences (such as glycerin) and cellosolves having 1 to 20 carbon atoms (such as methyl and ethyl cellosolve) 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 paint.

The water-based paint using the polyurethane resin aqueous dispersion of the present invention is produced by mixing and stirring the polyurethane resin aqueous dispersion of the present invention and each of the components described above. When 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.

Hereinafter, an aqueous adhesive using the aqueous polyurethane resin dispersion of the present invention will be described.
As the resin used for the water-based adhesive, the urethane resin (U) in the polyurethane resin aqueous dispersion of the present invention may be used alone, but water dispersibility other than urethane resin represented by SBR latex resin and acrylic resin. Or water-soluble resin can be used together. When used in combination, the ratio of the polyurethane resin (U) to the total weight of the resin is preferably 1% by weight or more, more preferably 10% by weight or more.

  Furthermore, auxiliary materials and additives used in ordinary adhesives, such as cross-linking agents, plasticizers, tackifiers, and fillers, as long as they do not impair the cohesiveness of the adhesive containing the aqueous polyurethane resin dispersion of the present invention. It is also possible to use agents, pigments, thickeners, antioxidants, ultraviolet absorbers, surfactants, flame retardants, and the like.

  Hereinafter, the preparation of the aqueous fiber processing agent using the polyurethane resin aqueous dispersion of the present invention will be described. The fiber processing agent containing the polyurethane resin aqueous dispersion of the present invention may include known antifoaming agents, wetting agents, various resin water dispersions (polyurethane water dispersions other than the present invention, acrylic water dispersions, SBR if necessary). Latex etc.) and softeners can be blended. In the case of a resin water dispersion, these blending amounts are preferably 30% by weight or less, particularly preferably 20% by weight or less based on the weight of the polyurethane resin (U) in terms of solid content, and in the case of other additives, respectively. It is preferably 1% by weight or less, particularly preferably 0.1 to 0.5% by weight. Moreover, a pH adjuster can also be added as needed. Examples of pH adjusters include alkaline substances such as salts of strong bases (alkali metals, etc.) and weak acids (acids with pKa exceeding 2.0, such as carbonic acid and phosphoric acid) (sodium bicarbonate, etc.), or acidic substances (acetic acid, etc.). Is mentioned. The amount of the pH adjusting agent is usually 0.01 to 0.3% by weight based on the weight of the polyurethane resin (U).

  The solid content (nonvolatile content) concentration of the aqueous fiber processing agent of the present invention is not particularly limited, but is usually 10 to 50% by weight, preferably 15 to 45% by weight. Moreover, a viscosity (25 degreeC) is 10-100,000 mPa * s normally.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to these. Hereinafter, the part means part by weight.

<Example 1>
After mixing each raw material shown in Table 1, it was charged in a KRC kneader (manufactured by Kurimoto Seiko Co., Ltd.), which is a twin-screw kneader, in a nitrogen atmosphere and kneaded at 220 ° C. for 10 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a press machine heated to 180 ° C., and then cut with a square pelletizer [manufactured by Horai Co., Ltd.] to obtain a polyurethane resin (U1-1). Subsequently, each of the raw materials shown in Table 3 was charged into a pressure-controllable container capable of controlling the temperature, and a polyurethane resin aqueous dispersion was obtained by performing a dispersion treatment under the conditions shown in Table 5 using CLEARMIX [M Technique Co., Ltd.]. (Q-1) was obtained.

<Example 2>
After mixing each raw material shown in Table 1, it was charged in a KRC kneader which is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-2). Subsequently, each of the raw materials shown in Table 3 was charged into a pressure-controllable container capable of controlling the temperature, and the polyurethane resin aqueous dispersion was dispersed by treatment under the conditions shown in Table 5 using a TK homomixer [manufactured by Primics Co., Ltd.]. (Q-2) was obtained.

<Example 3>
Each raw material shown in Table 1 was charged into a simple pressure reactor equipped with a stirrer and a heating device, and stirred at 180 ° C. for 15 minutes to carry out a urethanization reaction. A toluene solution of polyurethane resin (U1-3) was then added. Obtained. Subsequently, each raw material shown in Table 3 is charged into a pressure-controllable container which can be controlled in temperature, and subjected to dispersion treatment under the conditions shown in Table 5 using CLEARMIX, and then toluene is distilled off at 90 ° C. under reduced pressure for 5 hours. To obtain a polyurethane resin aqueous dispersion (Q-3).

<Example 4>
After mixing each raw material shown in Table 1, it was charged into a release-treated container and subjected to a urethanization reaction in a circulating dryer at 210 ° C. for 15 minutes without stirring. After cooling to 25 ° C., the reaction product was taken out and cut with a scissors to obtain a polyurethane resin (U1-4). Subsequently, each of the raw materials shown in Table 3 was charged into a pressure-controllable container capable of controlling the temperature, and polyurethane was dispersed by using an ultrasonic dispersing device [manufactured by Ikemoto Rika Kogyo Co., Ltd.] under the conditions shown in Table 5. A resin water dispersion (Q-4) was obtained.

<Example 5>
After mixing each raw material shown in Table 1, it was charged in a KRC kneader that is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. After forming a strand having a diameter of 2 mm by extrusion, the strand was cooled to 90 ° C. This was introduced into ion-exchanged water at 30 ° C. and then cut with a pelletizer to obtain a polyurethane resin (U1-5). Subsequently, each of the raw materials shown in Table 3 was charged into a pressure-controllable container capable of controlling the temperature, and the polyurethane resin aqueous dispersion (Q-5) was dispersed by treatment under the conditions shown in Table 5 using an ultrasonic dispersing device. Got.

<Example 6>
After mixing each raw material shown in Table 1, it was charged in a KRC kneader that is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. After forming a strand having a diameter of 2 mm by extrusion, the strand was cooled to 90 ° C. This was introduced into ion-exchanged water at 30 ° C. and then cut with a pelletizer to obtain a polyurethane resin (U1-6). Subsequently, each raw material shown in Table 3 was charged into a universal mixer [manufactured by Primics Co., Ltd.] and dispersed under the conditions shown in Table 5 to obtain an aqueous polyurethane resin dispersion (Q-6).

<Example 7>
After mixing each raw material shown in Table 1, it was charged in a KRC kneader which is a biaxial kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 5 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-7). Subsequently, each raw material shown in Table 3 was charged into a pressure-controllable container capable of controlling temperature, and a polyurethane resin aqueous dispersion (Q-7) was obtained by performing a dispersion treatment under the conditions shown in Table 5 using CLEARMIX. .

<Example 8>
After mixing each raw material shown in Table 1, it was charged in a KRC kneader which is a biaxial kneader in a nitrogen atmosphere and kneaded at 250 ° C. for 3 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a pressure press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-8). Subsequently, each raw material shown in Table 3 was charged into a pressure-controllable container capable of controlling temperature, and a polyurethane resin aqueous dispersion (Q-8) was obtained by performing a dispersion treatment under the conditions shown in Table 5 using CLEARMIX. .

<Example 9>
After mixing each raw material shown in Table 1, it was charged in a KRC kneader which is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a pressure press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-9). Subsequently, each raw material shown in Table 4 is charged into a temperature-controllable pressure-resistant container and dispersed under the conditions shown in Table 5 using CLEARMIX, and then THF is distilled off at 50 ° C. under reduced pressure for 5 hours. A polyurethane resin aqueous dispersion (Q-9) was obtained.

<Example 10>
Each raw material shown in Table 1 was mixed and then charged into a release-treated container, and a urethanization reaction was performed for 50 hours without stirring in a circulating dryer at 100 ° C. The reaction product was taken out, rolled with a pressure press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-10). Subsequently, each raw material shown in Table 4 was charged in a pressure-controllable container capable of controlling temperature, and a polyurethane resin aqueous dispersion (Q-10) was obtained by performing a dispersion treatment under the conditions shown in Table 5 using CLEARMIX. .

<Example 11>
After mixing each raw material shown in Table 2, it was charged in a KRC kneader which is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a pressure press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-11). Subsequently, each raw material shown in Table 4 was charged into a temperature-controllable pressure-resistant container, and a polyurethane resin aqueous dispersion (Q-11) was obtained by performing a dispersion treatment under the conditions shown in Table 5 using CLEARMIX. .

<Example 12>
After mixing each raw material shown in Table 2, it was charged in a KRC kneader which is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-12). Subsequently, each raw material shown in Table 4 was charged into a pressure-controllable container capable of temperature control, and a polyurethane resin aqueous dispersion (Q-12) was obtained by performing a dispersion treatment under the conditions shown in Table 5 using CLEARMIX. .

<Example 13>
After mixing each raw material shown in Table 2, it was charged in a KRC kneader which is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-13). Subsequently, each raw material shown in Table 4 was charged in a pressure-controllable container capable of controlling temperature, and a polyurethane resin aqueous dispersion (Q-13) was obtained by performing a dispersion treatment under the conditions shown in Table 5 using CLEARMIX. .

<Example 14>
Each raw material shown in Table 2 was mixed, and then charged into a release-treated container, and urethanization reaction was performed for 20 hours without stirring in a circulating dryer at 150 ° C. The reaction product was taken out, cooled to 25 ° C., and then cut with an ultrasonic cutter to obtain a polyurethane resin (U1-14). Subsequently, each raw material described in Table 4 was charged into a pressure-controllable container capable of controlling temperature, and a polyurethane resin aqueous dispersion (Q-14) was obtained by performing a dispersion treatment under the conditions described in Table 5 using CLEARMIX. .

<Example 15>
After mixing each raw material shown in Table 2, it was charged in a KRC kneader which is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a pressure press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-15). Subsequently, each raw material shown in Table 4 was charged in a pressure-controllable container capable of controlling the temperature, and a polyurethane resin aqueous dispersion (Q-15) was obtained by performing a dispersion treatment under the conditions shown in Table 5 using CLEARMIX. .

<Example 16>
After mixing each raw material shown in Table 2, it was charged in a KRC kneader which is a twin-screw kneader in a nitrogen atmosphere and kneaded at 210 ° C. for 15 minutes to carry out a urethanization reaction. The reaction product was taken out, rolled with a press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U1-16). Subsequently, each raw material shown in Table 4 is charged into a pressure-controllable container capable of temperature control, and after dispersion treatment under the conditions shown in Table 5 using CLEARMIX, toluene is distilled off at 90 ° C. under reduced pressure for 5 hours. A polyurethane resin aqueous dispersion (Q-16) was obtained.

<Comparative Example 1>
Each raw material shown in Table 2 was charged into a simple pressure reactor equipped with a stirrer and a heating device and stirred at 85 ° C. for 10 hours to carry out a urethanization reaction to produce an acetone solution of a urethane prepolymer. The isocyanate content per solid in the acetone solution of the urethane prepolymer was 0.42 mmol / g. The acetone solution of the obtained urethane prepolymer in an amount of 395.56 parts was charged into a simple pressure reactor, and 12.85 parts of triethylamine (neutralizing agent) and 589.59 parts of water were added while stirring at 40 ° C. After stirring at 60 rpm for 3 minutes, 2.50 parts of ethylenediamine as a chain extender was added, and acetone was distilled off at 65 ° C. under reduced pressure for 8 hours to obtain a polyurethane resin aqueous dispersion (Q-17).

<Comparative example 2>
A polyurethane resin aqueous dispersion (Q-18) was obtained in the same manner as in Comparative Example 1 except that the raw materials and the amounts charged were changed to those shown in Table 2. In addition, the isocyanate content per solid content of the acetone solution of the urethane prepolymer was 0.42 mmol / g.

<Comparative Example 3>
Each raw material shown in Table 2 was charged into a simple pressure reactor equipped with a stirrer and a heating device and stirred at 85 ° C. for 10 hours to carry out a urethanization reaction to produce an acetone solution of a urethane prepolymer. The isocyanate content per solid in the acetone solution of the urethane prepolymer was 0.55 mmol / g. 396.60 parts of an acetone solution of the obtained urethane prepolymer was charged into a simple pressure reactor, and 5.34 parts of triethylamine (neutralizing agent) and 598.06 parts of water were added while stirring at 40 ° C. After stirring at 60 rpm for 3 minutes, 3.24 parts of ethylenediamine as a chain extender was added. Subsequently, acetone was distilled off at 65 ° C. under reduced pressure for 8 hours to obtain an aqueous polyurethane resin dispersion (Q-19).

Tables 6 and 7 show various physical property values and evaluation results of the polyurethane resin aqueous dispersions (Q-1) to (Q-19) obtained in Examples 1 to 16 and Comparative Examples 1 to 3. In addition, the measuring method and evaluation method of various physical property values in the present invention are as follows.
<Urethane group content and urea group content>
The urethane group content and urea group content of the polyurethane resin are the N atom content determined by a nitrogen analyzer [ANTEK7000 (manufactured by Antec)], the ratio of urethane group and urea group determined by ¹ H-NMR, and the later-described allophanate. Calculated from group and burette group content. ^{The 1} H-NMR measurement is carried out by the method described in “Structural study of polyurethane resin by NMR: Takeda Laboratory Report 34 (2), 224-323 (1975)”. That is, when ¹ H-NMR is measured and an aliphatic group is used, the urea group is determined from the ratio of the integral amount of hydrogen derived from a urea group near a chemical shift of 6 ppm and the integral amount of hydrogen derived from a urethane group near a chemical shift of 7 ppm. The weight ratio of the urethane groups is measured, and the urethane group and urea group contents are calculated from the weight ratio, the N atom content, the allohanate group, and the burette group content. When aromatic isocyanate is used, the weight ratio of urea group and urethane group is calculated from the ratio of the integral amount of hydrogen derived from urea groups near the chemical shift of 8 ppm and the integral amount of hydrogen derived from urethane groups near the chemical shift of 9 ppm, The urea group content is calculated from the weight ratio and the N atom content.

<Terminal isocyanate group content>
Polyurethane resin is dissolved in 30 ml of a 0.5 mol / l di-n-butylamine toluene solution, 100 ml of isopropyl alcohol is added, and automatic titration is performed with an automatic potentiometric titrator using a 0.5 mol / l hydrochloric acid titration solution. The number of ml is read, and the terminal isocyanate group content (mmol / g) is calculated by the following formula.
Terminal isocyanate group content (mmol / g) = [0.5 × (B−A) × f × 100] / S
A: Number of ml of 0.5 mol / l hydrochloric acid titration solution required for this test.
B: Number of ml of 0.5 mol / l hydrochloric acid titration solution required for the blank test.
f: titer of 0.5 mol / l hydrochloric acid titration solution.
S: Amount of polyurethane resin collected (g)

<Terminal amino group content>
The total amine value and tertiary amine value of the polyurethane resin are obtained by the following method, and the terminal amino group content (mmol / g) is calculated by the following formula.
Terminal amino group content (mmol / g) = (total amine value-tertiary amine value) /56.1
(1) Total amine value After dissolving polyurethane resin in 50 ml of toluene in a 100 ml flask, add 20 ml of acetic anhydride and titrate 0.5 mol / l hydrochloric acid / methyl alcohol using xylene cyanol FF / methyl orange mixed indicator. Titration is carried out with the solution (the end point is the point where the color of the indicator has changed from green to reddish brown), the titration ml number is read, and the total amine value is calculated by the following formula.
Total amine number = a × f / (S × 28.05)
a: Titration ml number of 0.5 mol / l hydrochloric acid / methyl alcohol titration solution.
f: titer of 0.5 mol / l hydrochloric acid / methyl alcohol titration solution.
S: Amount of polyurethane resin collected (g)
(2) Tertiary amine value After dissolving the polyurethane resin in 50 ml of toluene in a 100 ml flask, add 20 ml of acetic anhydride and shake well, and let stand at room temperature for 30 minutes. Titrate with 0.5 mol / l hydrochloric acid / methyl alcohol titration solution using xylene cyanol FF / methyl orange mixed indicator (the end point is the point where the indicator color changed from green to reddish brown) and read the titration ml number The tertiary amine value is calculated by the following formula.
Tertiary amine value = a × f / (S × 28.05)
a: titration ml number of 0.5 mol / l hydrochloric acid / methyl alcohol titration solution f: titer of 0.5 mol / l hydrochloric acid / methyl alcohol titration solution S: amount of polyurethane resin collected (g)

<Contents of allophanate group and burette group>
The total of the contents of allophanate groups and burette groups of the polyurethane resin is calculated by a gas chromatograph [Shimadzu GC-9A {manufactured by Shimadzu Corp.}]. A 50 g DMF solution containing 0.01 wt% di-n-butylamine and 0.01 wt% naphthalene (internal standard) is prepared. The sample is weighed into a test tube with a stopper, 2 g of the above DMF solution is added, and the test tube is heated in a constant temperature water bath at 90 ° C. for 2 hours. After cooling to room temperature, 10 μl of acetic anhydride is added and shaken and stirred for 10 minutes. Further, 50 μl of di-n-propylamine is added, shaken for 10 minutes, and then gas chromatographic measurement is performed. In parallel, blank measurement was performed, the consumption of amine was determined from the difference from the test value, and the total content of allophanate groups and burette groups was measured.
(Gas chromatograph conditions)
Apparatus: Shimadzu GC-9A
Column: 10% PEG-20M on Chromosorb WAW DMLS 60/80 mesh glass column 3 mmφ × 2 m
Column temperature: 160 ° C., sample introduction part temperature: 200 ° C., carrier gas: nitrogen 40 ml / min detector: FID, sample injection amount: 2 μl
(Calculation formula for the total content of allophanate groups and burette groups)
Total content of allophanate group and burette group = {(BA) / B} × 0.00155 / S
A: (Di-n-butylacetamide peak area / naphthalene peak area) of sample
B: blank (peak area of di-n-butylacetamide / peak area of naphthalene)
S: Amount of polyurethane resin collected (g)

<Mw and Mn>
A polyurethane resin or polyurethane water dispersion was added to DMF so that the solid content of the polyurethane resin was 0.0125% by weight, stirred and dissolved at room temperature for 1 hour, and then filtered through a filter having a pore size of 0.3 μm. The urethane resin Mw and Mn contained in the obtained filtrate were measured by GPC using DMF as a solvent and polystyrene as a molecular weight standard.

<Melting temperature>
The melting temperature of the polyurethane resin in the present invention is “melt indexer type I” (manufactured by Tester Sangyo Co., Ltd.) as a melt mass flow rate measuring device in JIS K7210 (plastic-thermoplastic plastic melt mass flow rate test method). The temperature at which the melt mass flow is 10 g / 10 min at a load of 2.16 kg.

<Volume average particle diameter (Dv)>
After diluting the polyurethane resin aqueous dispersion with ion-exchanged water so that the solid content of the polyurethane resin is 0.01% by weight, a light scattering particle size distribution analyzer [ELS-8000 {manufactured by Otsuka Electronics Co., Ltd.}] is used. Measured.

<Dispersion stability of polyurethane resin aqueous dispersion>
The polyurethane resin aqueous dispersion whose temperature was adjusted to 25 ° C. was allowed to stand for 12 hours, and the occurrence of sediment was visually evaluated. The case where no sediment was generated was marked as ◯, and the case where sediment was generated was marked as x.

<Water resistance of dry film>
Pour 10 parts of polyurethane resin aqueous dispersion into a polypropylene mold with a length of 10 cm x width 20 cm x depth 1 cm, and after drying for 12 hours at room temperature, dry in a circulating dryer. A film obtained by heating and drying at 105 ° C. for 3 hours was immersed in ion exchange water at 60 ° C. for 14 days, and then the surface state of the film was visually observed. The case where there was no change was marked with ◯, and the case where whitening occurred was marked with ×. Moreover, the taken-out film was dried and the physical property measurement of the dry film | membrane was performed. ◎ when the rate of change in elongation at break after immersion is 0.95 times or more, ○ when it is 0.9 times or more and less than 0.95 times, and 0.8 times or more and less than 0.9 times Δ, when less than 0.8 times, x. The elongation at break is measured according to JIS K7311. Based on a tensile test.

<Film-forming property of polyurethane resin aqueous dispersion>
Pour 10 parts of polyurethane resin aqueous dispersion into a polypropylene mold measuring 10cm in length x 20cm in width x 1cm in depth to form a film after drying for 48 hours at 25 ° C. Judged whether or not. In the case where a film was formed, it was marked as ◯, and in the case where no film was formed, it was marked as x.

Evaluation Example 1 (Evaluation as water-based paint)
90 parts of ion-exchanged water, 70 parts of thickener [“Biseriser AP-2”, manufactured by Sanyo Chemical Industries Ltd.], 10 parts of pigment dispersant [“Caribbon L-400”, manufactured by Sanyo Chemical Industries Ltd.] Then, 140 parts of titanium oxide [“CR-93”, manufactured by Ishihara Sangyo Co., Ltd.], carbon black [“FW200P”, manufactured by Degussa Co., Ltd.] and 160 parts of calcium carbonate were mixed and dispersed for 30 minutes using a paint conditioner. Here, 20 parts of 1-nonanol, 200 parts of an acrylic water dispersion [“Polytron Z330”, manufactured by Asahi Kasei Co., Ltd.] and 200 parts of the polyurethane resin water dispersion (Q-1) obtained in Example 1 were charged for 10 minutes. Mixed and dispersed. Furthermore, it adjusted so that the viscosity in 25 degreeC might be set to 150 mPa * s using ion-exchange water, and the water-based coating material (W-1) was obtained. The viscosity was measured at a rotational speed of 60 rpm using a rotary viscometer manufactured by TOKIMEC. Table 8 shows the results of evaluating the water resistance of the paint film and the film-forming property of the paint based on the following test methods for the water-based paint (W-1).

Comparative evaluation example 1
A comparative water-based paint (W′-1) was obtained in the same manner as in Evaluation Example 1 except that the polyurethane resin water dispersion (Q-17) was used instead of the polyurethane resin water dispersion (Q-1).
Table 8 shows the results of evaluating the water resistance of the paint film and the film-forming property of the paint based on the following test methods for the water-based paint (W′-1).

<Water resistance evaluation method of coating film>
The obtained water-based paint was spray-coated on a 10 cm × 20 cm steel plate and heated at 120 ° C. for 10 minutes to prepare a coating film having a thickness of 20 μm. The coated steel sheet was immersed in ion exchange water at 80 ° C. for 14 days, and then taken out and the surface was lightly wiped. The surface of the coating film was visually evaluated according to the following evaluation criteria.
○: There is no change in the coating film surface before and after immersion.
X: After immersion, a part of the paint is peeled off.

<Method for evaluating film-forming properties of paint>
The obtained water-based paint was spray-coated on a 10 cm × 20 cm steel plate and heated at 80 ° C. for 3 minutes to prepare a coating film having a thickness of 20 μm. This coated steel sheet was immersed in 25 ° C. ion-exchanged water for 10 minutes, then taken out, gently wiped with a cloth, and visually evaluated according to the following evaluation criteria.
○: Color does not transfer to the cloth.
X: Color transfer is observed on the cloth.

Evaluation Example 2 (Evaluation as water-based adhesive)
6 parts of isocyanurate trimer of 1,6-hexamethylene diisocyanate as a curing agent was mixed with 100 parts of the polyurethane resin aqueous dispersion (Q-4) obtained in Example 4 at 25 ° C. The viscosity was adjusted to 4,000 to 5,000 mPa · s with a thickener (“SN thickener A-803” manufactured by San Nopco) to obtain an aqueous adhesive (X-1). Table 9 shows the results of evaluating the adhesive strength and water resistance of the aqueous adhesive (X′-1) based on the following test methods.

Comparative evaluation example 2
A comparative aqueous adhesive (X′-1) was obtained in the same manner as in Evaluation Example 2, except that the polyurethane resin aqueous dispersion (Q-19) was used instead of the polyurethane resin aqueous dispersion (Q-4). .
Table 9 shows the results of evaluating the adhesive strength and water resistance of the aqueous adhesive (X′-1) based on the following test methods.

<Adhesive strength evaluation method of water-based adhesive>
The water-based adhesive was applied to a flexible urethane slab foam (length 100 mm × width 120 mm × thickness 5 mm, bulk specific gravity 0.05) so that the coating amount was 50 g / m ² . After drying at 80 ° C. for 2 minutes, another soft urethane slab foam (length 100 mm × width 120 mm × thickness 5 mm, bulk specific gravity 0.05) not coated with adhesive is pressure-bonded for 10 seconds under a load of 4 kg, and after pressure bonding The peel strength was measured with an autograph (crosshead speed: 500 mm / min.) Using a test piece immediately cut to a width of 25 mm. When the peel strength was 25 mm, 200 g or more was defined as adhesive strength ◯, and less than 200 g was defined as adhesive strength x. The better the film-forming property, the better the adhesive strength.

<Water-resistant adhesive evaluation method of water-based adhesive>
The peel strength was measured immediately after immersing a test piece prepared in the same manner as the above-described method for evaluating the adhesive strength in boiling water for 1 hour. When the peel strength was 25 mm, 100 g or more was regarded as water-resistant adhesion ○, and less than 100 g was regarded as water-resistant adhesion x.

Evaluation Example 3 (Evaluation as aqueous fiber processing agent)
A pigment printing paste was prepared using an aqueous polyurethane resin dispersion as follows.
For 100 parts of the polyurethane resin aqueous dispersion (Q-2) obtained in Example 2, 8.9 parts of a viscoelasticity modifier [“SN thickener 618” manufactured by San Nopco Co., Ltd.], a silicon-based antifoaming agent [“ SN deformer 777 “San Nopco Co., Ltd.” 0.9 parts, water 35 parts, titanium oxide 44.6 parts, and pigment [“NL Red FR3R-D” manufactured by Yamagata Kogyo Co., Ltd.] 18.9 parts Thus, a pigment printing paste (Y-1) was obtained. With respect to the pigment printing paste (Y-1), Table 10 shows the results of testing the water resistance of the fiber fabric subjected to pigment printing and the film forming property of the pigment printing paste based on the following test method.

Comparative evaluation example 3
A comparative pigment printing paste (Y′-1) was obtained in the same manner as in Evaluation Example 3, except that the polyurethane resin water dispersion (Q-20) was used instead of the polyurethane resin water dispersion (Q-2). . Table 10 shows the results of testing the water resistance of the pigment-printed fiber cloth and the film-forming property of the pigment-printed paste for the pigment-printed paste (Y′-1) based on the following test methods.

<Method for evaluating water resistance of textile fabric printed with pigment>
The pigment printing paste was applied onto a cotton-plated mold using a bar coater so that the film thickness was 2 cm × 10 cm and the film thickness was 0.2 mm. This was dried for 5 minutes with a tenter temperature-controlled at 140 ° C. to obtain a textile fabric printed with pigment. This pigment-printed fiber cloth was immersed in ion-exchanged water at 60 ° C. for 1 day, then taken out, and the surface was lightly wiped with a non-printed fiber cloth, and visually evaluated according to the following evaluation criteria.
○: No color transfer to a textile fabric that has not been printed.
X: Color transfer is observed in the fiber cloth not subjected to the printing process.

<Method for evaluating film forming property of pigment printing paste>
The pigment printing paste was applied onto a cotton-plated mold using a bar coater so that the film thickness was 2 cm × 10 cm and the film thickness was 0.2 mm. This was dried with a 120 ° C. tenter for 3 minutes to obtain a textile fabric printed with pigment. The surface of the textile fabric printed with the pigment was lightly wiped with a textile fabric not subjected to textile printing, and visually evaluated according to the following evaluation criteria.
○: No color transfer to a textile fabric that has not been printed.
X: Color transfer is observed in the fiber cloth not subjected to the printing process.

  The aqueous polyurethane resin dispersion of the present invention can be suitably used for a coating composition, an adhesive composition, a fiber processing agent composition, and the like.

Claims (15)

A polyurethane resin aqueous dispersion containing water and a polyurethane resin (U) and satisfying all of the following (1) to (6).
(1) The urethane group content in (U) is 0.5 to 5.0 mmol / g based on the weight of (U).
(2) The terminal amino group content in (U) is 0.35 mmol / g or less based on the weight of (U).
(3) The number average molecular weight (Mn) of (U) is 10,000 to 1,000,000.
(4) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of (U) is 1.5 to 3.5.
(5) The melting temperature of (U) is 70 to 280 ° C.
(6) The volume average particle diameter (Dv) of (U) is 0.01 to 1 μm.   The polyurethane resin aqueous dispersion according to claim 1, wherein the content of urea groups in the polyurethane resin (U) is 2.0 mmol / g or less based on the weight of (U).   The polyurethane resin aqueous dispersion according to claim 1 or 2, wherein the total content of allophanate groups and burette groups in the polyurethane resin (U) is 0.1 mmol / g or less based on the weight of (U).   The polyurethane resin aqueous dispersion according to any one of claims 1 to 3, wherein the polyurethane resin (U) is a polyurethane resin having a hydrophilic group.   The polyurethane resin aqueous dispersion according to any one of claims 1 to 4, wherein the content of the organic solvent is 1000 ppm or less.   The polyurethane resin aqueous dispersion according to any one of claims 1 to 5, which is used for water-based paints.   The polyurethane resin aqueous dispersion according to any one of claims 1 to 5, which is used for an aqueous adhesive.   The aqueous polyurethane resin dispersion according to any one of claims 1 to 5, which is used for an aqueous fiber processing agent.   The method for producing an aqueous polyurethane resin dispersion according to any one of claims 1 to 8, wherein the polyurethane resin (U) is dispersed in water using a rotary disperser, an ultrasonic disperser or a kneader. .   The method for producing a polyurethane resin aqueous dispersion according to claim 9, wherein the polyurethane resin (U) has a hydrophilic group.   The polyurethane resin (U) is a uniaxial compound of the polyol (a), the polyisocyanate (b), the compound (c) containing a hydrophilic group and an active hydrogen atom, and if necessary, the chain extender (d) and the reaction terminator (e). Or the manufacturing method of the polyurethane resin water dispersion of Claim 10 which is a polyurethane resin obtained by making a urethanation reaction at 100-250 degreeC in a biaxial kneading machine.   The method for producing an aqueous polyurethane resin dispersion according to claim 11, which is carried out in the absence of an organic solvent.   The manufacturing method of the polyurethane resin aqueous dispersion in any one of Claims 9-12 made to disperse | distribute in presence of a dispersing agent (h).   The method for producing a polyurethane resin aqueous dispersion according to any one of claims 9 to 13, wherein the polyurethane resin (U) is dispersed in water at a temperature lower than the melting temperature of (U).   The method for producing an aqueous polyurethane resin dispersion according to any one of claims 9 to 14, wherein the polyurethane resin (U) is dispersed in water in the absence of an organic solvent.