JP2013227528A - Polyurethane-based resin aqueous dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane-based resin aqueous dispersion (UE) that has a good film-forming property and is excellent in mechanical properties and durability such as water resistance, solvent resistance and the like of a dried film thereof.SOLUTION: A polyurethane-based resin aqueous dispersion (UE) includes a polyurethane resin that is obtained by reacting a polyurethane resin (U) having a carboxy group in the molecule with a compound (P) that is reactive with a carboxy group and has an SP value which is different by 3 or less from the SP value of the polyurethane-based resin (U) having a carboxy group, and water.

Description

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

  Since the polyurethane resin aqueous dispersion has excellent performance such as mechanical properties, durability, chemical resistance and abrasion resistance of the film obtained by drying, as a highly functional aqueous 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 (so-called prepolymer mixing method) in which a urethane prepolymer having an isocyanate group at a terminal is dispersed in water and chain-extended with water or polyamine (so-called prepolymer mixing method). Patent Literatures 1 to 3). However, this method has a problem that the resulting polyurethane resin aqueous dispersion has poor film-forming properties and mechanical properties of the dry film are lowered, and the water resistance and solvent resistance of the dry film are not sufficient.

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 durability such as mechanical properties of a dry film and water resistance and solvent resistance.

As a result of intensive studies, the present inventors have reached the present invention. That is, the present invention includes a polyurethane resin having a carboxyl group in the molecule (U _0), having reactivity with a carboxyl group, the difference between the SP value of the polyurethane resin (U ₀₎ having a carboxyl group is 3 or less A polyurethane resin aqueous dispersion (UE) containing a polyurethane resin obtained by reacting a compound (P) having a certain SP value and water; a polyurethane resin (U ₀ ) having a carboxyl group in the molecule The difference between the SP value of the polyurethane resin aqueous dispersion (U ₀ E) containing particles and water and the SP value of the polyurethane resin (U ₀ ) having reactivity with the carboxyl group and having the carboxyl group is 3 or less. to obtain the compound (P) were mixed with a mixed solution having a value, it is absorbed the compound particles of the polyurethane resin (U ₀₎ the (P) having a carboxyl group And degree, followed by heating the mixture, the polyurethane resin having a carboxyl group (U ₀₎ and the compound (P) and a polyurethane resin aqueous dispersion which comprises a step of reacting ( UE) manufacturing method.

The polyurethane resin aqueous dispersion (UE) of the present invention has the following effects.
(1) A dry film having excellent mechanical properties can be obtained.
(2) A dry film having excellent water resistance, solvent resistance and abrasion resistance can be obtained.
(3) Excellent dispersion stability.

The aqueous dispersion (UE) of the polyurethane resin (U) of the present invention includes, for example, an aqueous dispersion of a polyurethane resin (U ₀ ) having a carboxyl group, and a polyurethane resin having reactivity with the carboxyl group and having the carboxyl group. It can be produced by reacting a compound (P) having an SP value having a difference from the SP value of (U ₀ ) of 3 or less.

The polyurethane resin (U ₀ ) having a carboxyl group in the present invention comprises, for example, a polyol (a), a polyisocyanate (b), and a compound (c) containing a carboxyl group and an active hydrogen atom as essential components, and if necessary, a carboxyl group It is produced by reacting a compound (d) containing a hydrophilic group other than a group and an active hydrogen atom, a chain extender (e) and a reaction terminator (f).

  Examples of the polyol (a) include a high molecular polyol (a1) having a number average molecular weight (hereinafter abbreviated as Mn) of 300 or more and a low molecular polyol (a2) having Mn or a chemical formula of less than 300.

The Mn of the polyol in the present invention can be measured, for example, under the following conditions using gel permeation chromatography (hereinafter abbreviated as GPC).
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 each connected one” [all manufactured by Tosoh Corporation]
Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection amount: 10 μl
・ Flow rate: 0.6 ml / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene glycol

  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.], Sanniks PP-2000 [polypropylene ether glycol with Mn = 2,000, manufactured by Sanyo Chemical Industries, Ltd. And Sanniks Diol GP-3000 [polypropylene ether triol with Mn = 3,000, manufactured by Sanyo Chemical Industries, Ltd.].

  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 ₀ ) having a carboxyl group.

  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 (Mn or chemical formula amount less than 300) polyhydric alcohol and a polyhydric carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.
Low molecular weight polyhydric alcohols include Mn or dihydric to octavalent or higher aliphatic polyhydric alcohols having a chemical formula of less than 300 and alkylene oxides of Mn or dihydric to octavalent or higher phenols having a chemical formula of less than 300. A low molar adduct can be used (representing EO, PO, 1,2-, 1,3-, 2,3- or 1,4-butylene oxide, hereinafter abbreviated as AO).
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).

  Examples of commercially available polycarbonate polyols include NIPPOLAN 980R [polyhexamethylene carbonate diol with Mn = 2,000, manufactured by Nippon Polyurethane Industry Co., Ltd.] and Duranol G4672 [poly (tetramethylene / hexamethylene) carbonate with Mn = 2,000. Diol, manufactured by Asahi Kasei Chemicals Co., Ltd.], ETERNACOLL UM-90 [polycarbonate diol produced using 1,4-cyclohexanedimethanol and 1,6-hexanediol in a molar ratio of 1: 1, manufactured by Ube Industries, Ltd. ], ETERNACOLL UH-200 [poly (hexamethylene carbonate) diol of Mn = 2,000, manufactured by Ube Industries, Ltd.], and the like.

  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.

  As the low molecular polyol (a2) having an Mn or a chemical formula amount less than 300, aliphatic dihydric alcohols (ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6- Hexanediol, 1,8-octanediol, 1,4-cyclohexanedimethanol and their EO and / or PO adducts), aliphatic trihydric alcohols (glycerin, trimethylolpropane and their EO and / or PO addition) And tetrahydric or higher aliphatic alcohols (pentaerythritol, sorbitol and their EO and / or PO adducts, etc.).

  Among (a2), preferred from the viewpoints of water resistance and heat-resistant yellowing are divalent or trivalent aliphatic alcohols, and particularly preferred among the aliphatic dihydric alcohols are ethylene glycol, propylene glycol, 1, 4-Butanediol, neopentyl glycol, and 1,6-hexanediol, and trimethylolpropane is particularly preferable among the aliphatic trihydric alcohols.

As the polyisocyanate (b) which is an essential component of the polyurethane resin having a carboxyl group (U ₀ ), those conventionally used in the production of polyurethane resins can be used. For example, 2 to 3 or more isocyanate groups are used. The chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms, the alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms, the aromatic polyisocyanate (b3) having 8 to 26 carbon atoms, and 10 to 10 carbon atoms 18 araliphatic polyisocyanates (b4), modified products of these polyisocyanates (b5), and the like. Polyisocyanate (B) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the chain aliphatic polyisocyanate (b1) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, and 2,2,4- Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl-2,6-di Isocyanato hexanoate.

  Examples of the alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methyl. Examples include cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the aromatic polyisocyanate having 8 to 26 carbon atoms (b3) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), and crude TDI. 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4 '-Diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate and m- or p -Isocyanatophenylsulfonyl isocyanate.

  Examples of the araliphatic polyisocyanate (b4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

  As the modified polyisocyanate (b5) of (b1) to (b4), the modified polyisocyanate (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group) Or modified product containing oxazolidone group, etc .; free isocyanate group content is usually 8 to 33% by weight, preferably 10 to 30% by weight, especially 12 to 29% by weight), such as modified MDI (urethane modified MDI, carbodiimide modified MDI) And modified products of polyisocyanates such as urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI.

  Of the polyisocyanates (b), (b1) and (b2) are preferable from the viewpoint of mechanical properties, solvent resistance, and weather resistance of the resulting film, and HDI and (b2) are more preferable, and particularly preferable. HDI, IPDI and hydrogenated MDI.

As the compound (c) containing a carboxyl group and an active hydrogen atom, which are essential components of the polyurethane resin (U ₀ ) having a carboxyl group, a compound 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 (eg glycine, alanine and valine) etc.] and the like Examples thereof include salts obtained by neutralizing these compounds with a neutralizing agent.

Examples of the neutralizing agent used in the salt of (c) include ammonia, amine compounds having 1 to 20 carbon atoms, and alkali metal hydroxides (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.

  Among these, ammonia and an amine compound having 1 to 20 carbon atoms are preferable from the viewpoint of the drying property of the resulting polyurethane resin aqueous dispersion (UE) and the water resistance of the resulting film, and more preferably 25 ° C. Are compounds having high vapor pressure, i.e. ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine, particularly preferred are ammonia, monoethylamine, dimethylamine, diethylamine and triethylamine, most preferred Is ammonia.

  Among (c), 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are preferable from the viewpoint of the resin physical properties of the resulting film and the dispersion stability of the polyurethane resin aqueous dispersion (UE). And salts thereof, and 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.

The amount of (c), the content of the carboxyl groups of the (U ₀₎ in, based on the weight of the (U _0), preferably 0.01 to 10 wt%, more preferably 0.1 to 5 wt %, Particularly preferably 0.5 to 3% by weight.

  As the compound (d) containing a hydrophilic group other than a carboxyl group and an active hydrogen atom, for example, a compound having a sulfonic acid group as an anionic group and having 2 to 16 carbon atoms [3- (2,3-dihydroxy Propoxy) -1-propanesulfonic acid and sulfoisophthalic acid di (2-hydroxyethyl) ester and the like], a sulfamic acid group as an anionic group, and a compound having 2 to 10 carbon atoms [N, N-bis (2 -Hydroxylethyl) sulfamic acid and the like] and salts obtained by neutralizing these compounds with a neutralizing agent.

  Examples of the neutralizing agent used for the salt of (d) include the same as those exemplified as the neutralizing agent used for the salt of (c), and preferred ones are also the same.

When using (d), the amount used is the content of hydrophilic groups in the (U _0), based on the weight of the (U _0), preferably from 0.01 to 5 wt%, more preferably 0 0.1 to 4% by weight, particularly preferably 0.5 to 3% by weight.

  The neutralizing agent used in (c) and (d) is used before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the dispersion step into the aqueous medium, during the dispersion step into the aqueous medium, or into the aqueous medium. It may be added at any time after the dispersion, but from the viewpoint of the stability of the polyurethane resin (U) and the stability of the aqueous dispersion, it is added before the dispersion process in the aqueous medium or during the dispersion process in the aqueous medium. It is preferable to do.

The content of the hydrophilic group in the present invention means the weight% of the non-neutralized anionic group, and does not include the weight of the counter ion. For example, the content of the hydrophilic group in (c) is the weight percentage of the carboxyl group (—COOH) in the case of the triethylamine salt of 2,2-dimethylolpropionic acid, and the content of the hydrophilic group in (d). Refers to the weight percent of the sulfo group (—SO ₃ H) in the case where (d) is a triethylamine salt of 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid having a sulfo group.

  Examples of the chain extender (e) include water, diamines having 2 to 10 carbon atoms (for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine and piperazine), and poly (n = 2) having 2 to 10 carbon atoms. -6) alkylene (2 to 6 carbon atoms) poly (n = 3 to 7) amines (for example, diethylenetriamine and triethylenetetramine), hydrazine or a derivative thereof (dibasic acid dihydrazide such as adipic acid dihydrazide) and 2 to 2 carbon atoms 10 amino alcohols (for example, ethanolamine, diethanolamine, 2-amino-2-methylpropanol, and triethanolamine). The Mn or low molecular weight polyol (a2) having a chemical formula of less than 300 also functions as a chain extender.

  As the reaction terminator (f), C1-C8 monoalcohols (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.), C1-C10 monoamines (monomethylamine, monoethylamine, mono Mono- or dialkylamines such as butylamine, dibutylamine and monooctylamine; mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine).

The polyurethane resin (U ₀ ) having a carboxyl group may be used alone or in combination of two or more.

The polyurethane resin (U ₀ ) having a carboxyl group in the present invention can contain additives such as an antioxidant, an anti-coloring agent, a weathering stabilizer, a plasticizer, and a release agent, if necessary. 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 weight of (U ₀ ).

The aqueous dispersion (U ₀ E) of the polyurethane resin (U ₀ ) having a carboxyl group in the present invention is obtained by dispersing (U ₀ ) in water in the presence or absence of the dispersant (h). Can do.

  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 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 any of the urethane resin (U ₀ ) before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step of (U ₀ ), during the water dispersion step, or after water dispersion. Although it may be added at a time, it is preferably added before or during the water dispersion step from the viewpoint of the dispersibility of (U ₀ ) and the stability of the aqueous dispersion.

The content of (h) is preferably 0 to 20% by weight, more preferably 0 to 10% by weight, in particular, based on the weight of the polyurethane resin (U ₀ ) having a carboxyl group from the viewpoint of water resistance of the dry film. It is preferably 0 to 5% by weight, and most preferably not used.

When (U ₀ ) is a polyurethane resin having a hydrophilic group, the total amount of the amount of the hydrophilic group and the amount of (h) in (c) and (d) based on the weight of (U ₀ ) is: Preferably it is 0.3 to 20 weight%, More preferably, it is 0.6 to 10 weight%, Most preferably, it is 1 to 5 weight%.

In the present invention, the Mn of the polyurethane resin having a carboxyl group (U ₀ ) is 10,000 to 1,000,000, and from the viewpoints of mechanical properties, durability, chemical resistance, and abrasion resistance of the resulting film, It is preferably 10,000 to 500,000, more preferably 10,000 to 200,000, and most preferably 10,000 to 100,000.

Mn of the polyurethane resin (U ₀ ) having a carboxyl group can be measured, for example, under the following conditions using gel permeation chromatography (hereinafter abbreviated as GPC).
・ Device: “HLC-8120GPC” [manufactured by Tosoh Corporation]
Column: “Guardcolumn H _XL- H” (1), “TSKgel GMH _XL ” (2) [both manufactured by Tosoh Corporation]
Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection amount: 100 μl
・ Flow rate: 1 ml / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polystyrene

Polyol (a), polyisocyanate (b), compound (c) containing carboxyl group and active hydrogen atom, compound (d) containing hydrophilic group and active hydrogen atom if necessary, chain extender (e) And by appropriately adjusting the amount of the reaction terminator (f), the Mn of the polyurethane resin (U ₀ ) having a carboxyl group can be brought into a desired range.

In the present invention, the melting temperature of the polyurethane resin (U ₀ ) having a carboxyl group is 70 to 280 ° C., and the resulting film has heat resistance, mechanical properties, durability, chemical resistance, wear resistance, and the like. From the viewpoint, it is preferably 80 to 200 ° C, more preferably 90 to 150 ° C.

Polyol (a), polyisocyanate (b), compound (c) containing carboxyl group and active hydrogen atom, compound (d) containing hydrophilic group and active hydrogen atom if necessary, chain extender (e) By appropriately adjusting the amount of the reaction terminator (f), the melting temperature of the polyurethane resin (U ₀ ) having a carboxyl group can be brought to a desired range.

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

Examples of the method for producing the aqueous polyurethane resin dispersion (U ₀ E) in the present invention include the following methods [1] and [2].

[1] Polyol (a), polyisocyanate (b), compound (c) containing carboxyl group and active hydrogen atom, compound (d) containing hydrophilic group and active hydrogen atom if necessary, chain extender The polyurethane resin (U ₀ ) having a carboxyl group is formed by reacting (e) and the reaction terminator (f) in the presence or absence of the organic solvent (S) in a single step or multiple steps, and the carboxyl group and the activity An organic solvent which forms a salt by neutralization or quaternization of the hydrophilic group introduced by the compound (c) containing a hydrogen atom and the hydrophilic group used if necessary and the compound (d) containing an active hydrogen atom (S) and / or a method of dispersing in an aqueous medium in the presence or absence of the aforementioned non-reactive active agent (h).

[2] Polyol (a), polyisocyanate (b), compound (c) containing carboxyl group and active hydrogen atom, compound (d) containing hydrophilic group and active hydrogen atom if necessary, chain extender (E) and the reaction terminator (f) are reacted in one or more stages in the presence or absence of the organic solvent (S) to form a urethane prepolymer having an isocyanate group at the end, and then if necessary Neutralization or quaternization of the hydrophilic group portion introduced by the compound (c) containing a carboxyl group and an active hydrogen atom of the prepolymer and the compound (d) containing a hydrophilic group and an active hydrogen atom if necessary In the presence or absence of an organic solvent (S), a non-reactive activator (h), a chain extender (e) and / or a chain terminator (f). How over preparative groups reacted to substantially eliminated [water or (e) by chain extension, and chain stopping by (f) if necessary.

The method [1] for producing the aqueous polyurethane resin dispersion (U ₀ E) will be described below.
The polyurethane resin (U ₀ ) having a carboxyl group in this method includes a polyol (a), a polyisocyanate (b), a compound (c) containing a carboxyl group and an active hydrogen atom, and a hydrophilic group and an active hydrogen used as necessary. It is obtained by reacting an atom-containing compound (d), a chain extender (e) and a reaction terminator (f) in the presence or absence of an organic solvent (S). The reaction temperature is preferably 20 to 250 ° C, more preferably 60 to 250 ° C, particularly preferably 60 to 220 ° C.

  Examples of the organic solvent (S) include ketone solvents [for example, acetone and methyl ethyl ketone, ester solvents (for example, ethyl acetate and γ-butyrolactone), ether solvents (for example, tetrahydrofuran (hereinafter abbreviated as THF)], amide solvents (for example, N , N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and N-methylcaprolactam), alcohol solvents (eg isopropyl alcohol) and aromatic hydrocarbon solvents (eg toluene and xylene), etc. Can be mentioned. An organic solvent (S) may be used individually by 1 type, and may use 2 or more types together.

  In order to promote the reaction in the urethanization reaction, a catalyst used in a normal urethanization reaction may be used as necessary. Examples of the catalyst include amine catalysts such as triethylamine, N-ethylmorpholine, triethylenediamine, and cycloamidines [1,8-diaza-bicyclo [5,4,0] -7-undecene described in US Pat. No. 4,524,104. ("DBU" manufactured by San Apro Co., Ltd.)]; tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and tin octylate; titanium-based catalysts such as tetrabutyl titanate; bismuth-based catalysts such as bismuth trioctylate; .

  The apparatus for performing the urethanization reaction can be used without any problem as long as it can be heated and stirred. However, when the organic solvent (S) is not used, it is preferable to use a uniaxial or biaxial kneader. Examples of the uniaxial or biaxial kneader include a continuous kneader [manufactured by Kurimoto Steel Works] and PCM30 [manufactured by Ikegai Co., Ltd.].

Polyurethane resin (U ₀ ) having a carboxyl group or an organic solvent solution thereof, compound (c) containing a carboxyl group and an active hydrogen atom, and compound (d) containing a hydrophilic group and an active hydrogen atom to be used if necessary The aqueous polyurethane resin dispersion (U) in the present invention is obtained by dispersing the hydrophilic group moiety introduced by the above as a salt by neutralization or quaternization or by dispersing it in an aqueous medium in the presence of the aforementioned non-reactive activator (h). ₀ E) is obtained.

  The aqueous medium in the present invention means water and a mixture of water and the organic solvent (S). The organic solvent (S) used in the aqueous medium is preferably a water-soluble organic solvent from the viewpoint of dispersibility.

When the organic solvent (S) is used, the weight ratio [water / (S)] of water to the organic solvent (S) is preferably 99 from the viewpoint of the dispersibility of the polyurethane resin (U ₀ ) having a carboxyl group. / 1 to 50/50.

Examples of the dispersion mixing device for dispersing the carboxyl group-containing polyurethane resin (U ₀ ) or these organic solvent solutions in an aqueous medium include a rotary dispersion mixing device, a media-type dispersion mixing device, and a high-pressure dispersion mixing device. However, a rotary dispersion mixing apparatus is preferable from the viewpoints of temperature adjustment, supply of solid particles, dispersion ability, and the like.

  Examples of the rotary dispersion mixing apparatus include TK homomixer [manufactured by Primics Co., Ltd.], Claremix [manufactured by Mtechnics Co., Ltd.], Philmix [manufactured by Primix Co., Ltd.], and Ultra Turrax [manufactured by IKA Corporation]. ], Ebara Milder [manufactured by Ebara Manufacturing Co., Ltd.], Cavitron (manufactured by Eurotech) and biomixer [manufactured by Nippon Seiki Co., Ltd.].

As the rotary dispersion mixing apparatus, two or more kinds of apparatuses selected from these rotary dispersion mixing apparatuses may be used in combination.
The rotational speed when using these rotary dispersion mixing devices is usually 100 to 30000 rpm, preferably 500 to 30000 rpm, more preferably from the viewpoint of dispersion stability of the polyurethane resin aqueous dispersion (U ₀ E). 1000 to 30000 rpm, particularly preferably 2000 to 30000 rpm.

The temperature of the dispersion during the dispersion mixing treatment using the rotary dispersion mixing apparatus is such that the polyurethane resin having a carboxyl group (U ₀ ) is used from the viewpoint of preventing decomposition or deterioration of the polyurethane resin having a carboxyl group (U ₀ ). It is preferable that the temperature is lower than the melting temperature, preferably 5 ° C. or more lower than the melting temperature and higher than room temperature, more preferably 10 to 120 ° C. lower than the melting temperature and higher than room temperature.

The weight ratio of the carboxyl group-containing polyurethane resin (U ₀ ) supplied to the rotary dispersion mixing apparatus and the aqueous medium is appropriately selected depending on the resin component content of the target aqueous dispersion. Aqueous medium = 10/2 to 10/100, more preferably 10/5 to 10/50.
The residence time in the rotary dispersion mixing apparatus of the polyurethane resin (U ₀ ) having a carboxyl group and the aqueous medium is preferably 0.1 to 60 minutes, more preferably 10 to 30 minutes.

The method [2] for producing the aqueous polyurethane resin dispersion (U ₀ E) will be described below.
In this method, the urethane prepolymer having an isocyanate group at the end includes a polyol (a), a polyisocyanate (b), a compound (c) containing a carboxyl group and an active hydrogen atom, and a hydrophilic group and an active hydrogen atom used as necessary. An isocyanate for an active hydrogen-containing group (excluding a carboxyl group, a sulfonic acid group and a sulfamic acid group) in the presence or absence of an organic solvent (S) It is formed by the urethanization reaction at a ratio such that the equivalent ratio of the groups is preferably 1.01 to 3, more preferably 1.1 to 2.

The urethane prepolymerization reaction is preferably performed at a reaction temperature of 20 ° C. to 150 ° C., more preferably 60 ° C. to 110 ° C., and the reaction time is preferably 2 to 15 hours. The isocyanate group content in the urethane prepolymer having an isocyanate group at the terminal is preferably 0.1 to 5% by weight.
In order to accelerate the reaction in the urethane prepolymerization reaction, a catalyst used in the above-mentioned urethanization reaction may be used as necessary.

The obtained urethane prepolymer having an isocyanate group at the terminal or an organic solvent solution thereof, if necessary, a compound (c) containing a carboxyl group and an active hydrogen atom of the prepolymer, and a hydrophilic group and an active hydrogen atom to be used if necessary The hydrophilic group part introduced by the compound (d) containing a salt as a salt by neutralization, the organic solvent (S), the aforementioned non-reactive activator (h), the chain extender (e) and / or the chain terminator Disperse in an aqueous medium in the presence or absence of (f) and carry out the reaction [chain extension with water and, if necessary, chain extension with (e) and chain termination with (f)] until substantially no isocyanate groups are present. Thus, the aqueous polyurethane resin dispersion (U ₀ E) in the present invention can be obtained.

  The system of the apparatus for emulsifying and dispersing the urethane prepolymer having an isocyanate group at the terminal or an organic solvent solution thereof in an aqueous medium is not particularly limited. For example, (1) vertical stirring system, (2) rotor-stator system [For example, Ebara Milder (manufactured by Ebara Manufacturing Co., Ltd.), (3) Line mill method [for example, line flow mixer], (4) Static tube mixing type [for example, static mixer], (5) Vibration type [for example, “VIBRO MIXER” (Manufactured by Chilling Industry Co., Ltd.)], (6) Ultrasonic impact type [for example, ultrasonic homogenizer], (7) High pressure impact type [for example, Gaurin homogenizer (Gaurin)], (8) Membrane emulsification type [for example, membrane emulsification module ] And (9) Centrifugal thin film contact type [e.g., "Fillmix" (manufactured by Primemix)] and the like.

When the organic solvent (S) is used in the above methods [1] and [2], it may be distilled off if necessary after the production of the polyurethane resin aqueous dispersion (U ₀ E). From the viewpoint of odor, stability over time, environmental load, safety and production cost, the content of the organic solvent is preferably 10000 ppm or less, more preferably 8000 ppm or less, particularly preferably 8000 ppm or less, based on the weight of the aqueous dispersion. Preferably it is 5000 ppm or less.

  When dispersing in the above methods [1] and [2], if necessary, addition of a pH adjuster, an antifoaming agent, an antifoaming agent, an antioxidant, a coloring inhibitor, a plasticizer, a mold release agent, etc. An agent can be added. Moreover, you may perform 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 (U ₀ E) in 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 an aqueous dispersion thinly stretched on a Petri dish, weighed accurately, then weighed the weight after heating at 130 ° C for 45 minutes using a circulating constant temperature dryer, and before weighing, It can be obtained by calculating the ratio (percentage) of the remaining weight after heating to the weight.

As the compound (P) having reactivity with a carboxyl group and having an SP value that is 3 or less from the SP value of the polyurethane resin (U ₀ ) having a carboxyl group, an epoxy compound, an aziridine compound, a carbodiimide compound, and An oxazoline compound etc. are mentioned.

  When the compound (P) has one functional group having reactivity with a carboxyl group in the molecule, a coating film excellent in water resistance can be formed. In addition, when the compound (P) has two or more functional groups having reactivity with a carboxyl group in the molecule, a crosslinked structure can be introduced into the molecule, and in addition to water resistance, solvent resistance is improved. An excellent coating film can be formed.

The epoxy compound is not particularly limited as long as the SP value difference with the polyurethane resin having a carboxyl group (U ₀ ) is 3 or less and has an epoxy group in the molecule, for example, one having 4 to 40 carbon atoms ( Methyl glycidyl ether, phenyl glycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, polypropylene glycol diglycidyl ether and 3-glycidyl Trimethoxysilane etc.). These may be used alone or in combination of two or more.

From the viewpoint of water resistance and solvent resistance of the dry film of the polyurethane resin aqueous dispersion (UE) and absorbability to the polyurethane resin (U ₀ ), the epoxy compound preferably has 4 to 30 carbon atoms, Preferably it is 4-25.

The aziridine compound is not particularly limited as long as the SP value difference with the polyurethane resin (U ₀ ) having a carboxyl group is 3 or less and has an aziridinyl group in the molecule. For example, an aziridine having 3 to 30 carbon atoms Compounds [1-aziridinemethanol, 1-aziridineethanol, tetramethylolmethane tris (β-aziridinylpropionate), 2,2-bishydroxymethylbutanol-tris {3- (1-aziridinyl) propionate} and trimethylol Propanetris (β-aziridinyl propionate) and the like].

  Among these, a compound having two or more aziridinyl groups in the molecule is preferable from the viewpoint of water resistance and solvent resistance of the dry film of the polyurethane resin aqueous dispersion (UE).

As the carbodiimide compound, any compound having a carbodiimide group in the molecule can be used as long as the difference in SP value from the polyurethane resin having a carboxyl group (U ₀ ) is 3 or less. A chain aliphatic polyisocyanate (b1), an alicyclic polyisocyanate (b2) having 8 to 18 carbon atoms, an aromatic polyisocyanate (b3) having 8 to 26 carbon atoms, or an aromatic aliphatic polyisocyanate having 10 to 18 carbon atoms. Aliphatic polycarbodiimide [poly (hexamethylene carbodiimide) etc.] obtained by polymerizing isocyanate (b4), alicyclic polycarbodiimide [poly (4,4′-dicyclohexylmethanecarbodiimide) etc.] and aromatic polycarbodiimide [poly (P-phenylenecarbodiimide), poly (4,4′-diphenylmethanecarbodi) Bromide) and poly (diisopropylphenylcarbodiimide), etc.] can be used.

  Of these, those having two or more carbodiimide groups in the molecule are preferable from the viewpoint of water resistance and solvent resistance of the dry film of the polyurethane-based resin aqueous dispersion (UE), and more preferable is a degree of polymerization of 3 It is a polymer of the said polyisocyanate of -100.

The oxazoline compound is not particularly limited as long as it is a compound having an SP value difference of 3 or less from the polyurethane resin having a carboxyl group (U ₀ ) and having an oxazoline group in the molecule, for example, an oxazoline group such as 2-ethyloxazoline. A compound having two oxazoline groups such as 2,2′-isopropylidenebis (4-phenyl-2-oxazoline); 2-isopropenyl-2-oxazoline, 2-vinyl-2-oxazoline and (Co) polymer of polymerizable oxazoline compound such as 2-vinyl-4-methyl-2-oxazoline; the polymerizable oxazoline compound and methyl (meth) acrylate, ethyl (meth) acrylate, hydroxy (meth) acrylate (Meth) acrylic esters such as ethyl and polyethylene glycol (meth) acrylate And a copolymer with a copolymerizable monomer that does not react with an oxazoline group such as (meth) acrylic acid vinyl acetate, styrene, and sodium α-methylstyrene styrenesulfonate. These may be used alone or in combination of two or more.

  Among these, a compound having two or more oxazoline groups in the molecule is preferable from the viewpoint of water resistance and solvent resistance of the dry film of the polyurethane resin aqueous dispersion (UE).

  Among these compounds (P), an epoxy compound is preferable from the viewpoint of water resistance of the dry film. A compound (P) may be used individually by 1 type, or may use 2 or more types together.

The difference in SP value between the compound (P) and the polyurethane resin having a carboxyl group (U ₀ ) needs to be 3 or less, preferably 2 or less. When the ratio is larger than 3, compound (P) cannot be absorbed by particles of polyurethane resin (U ₀ ) having a carboxyl group when compound (P) and aqueous polyurethane resin dispersion (U ₀ E) are mixed. .

In order to make the difference in SP value between the compound (P) and the polyurethane resin having a carboxyl group (U ₀ ) 3 or less, for example, the difference in SP value from the compound (P) is 3 or less (U or adjusting the composition of _0), may be selected (U ₀₎ the difference between the SP values of the like becomes 3 or less compound (P).

In the present invention, the SP value of the polyurethane resin (U ₀ ) having a carboxyl group and the compound (P) is determined by the method of Fedors [Polym. Eng. Sci. 14 (2) 152, (1974)]. The hydrophilic group of the compound (c) containing a carboxyl group and an active hydrogen atom used in (U ₀ ) and the hydrophilic group other than the carboxyl group and the compound (d) containing an active hydrogen atom are not neutralized. SP values are calculated for the hydrophilic groups (carboxyl group, sulfo group, etc.).

The amount of the compound (P) used can be appropriately selected depending on the type of the compound to be used, but it is an amount that reacts with 1 to 95 mol% of the carboxyl group of the carboxyl group-containing polyurethane resin (U ₀ ). Is preferable, more preferably 5 to 80 mol%, and particularly preferably 20 to 60 mol%. Even if the carboxyl group of (U ₀ ) is neutralized with a neutralizing agent, the reaction between this carboxyl group and compound (P) proceeds.

In order for the compound (P) to be absorbed in the polyurethane resin (U ₀ ) having a carboxyl group, the compound (P) needs to be water-soluble or liquid at the temperature at which (U ₀ ) is absorbed. is there. The melting point of the compound (P) is preferably 120 ° C. or lower, more preferably 100 ° C. or lower. When the compound (P) is solid at room temperature, the compound (P) is mixed with the polyurethane resin aqueous dispersion (U ₀ E) in advance so that the (U ₀ ) particles can absorb the compound (P). It is preferable to heat the compound (P) to be liquid.

As an apparatus for mixing the compound (P) and the aqueous polyurethane resin dispersion (U ₀ E) and absorbing the compound (P) in the particles, any apparatus having a stirring ability can be used. For example, a vertical stirring type apparatus or a rotor-stator type system exemplified as an apparatus for emulsifying and dispersing the urethane prepolymer having an isocyanate group at the terminal or an organic solvent solution thereof in an aqueous medium. Can be used.

The step of mixing the compound (P) and the aqueous polyurethane resin dispersion (U ₀ E) and causing the polyurethane resin (U ₀ ) having a carboxyl group to absorb the compound (P) is carried out in the presence of the dispersant (h) or It can be performed in the absence.

The temperature and time for mixing the compound (P) and the aqueous polyurethane resin dispersion (U ₀ E) and allowing the polyurethane resin (U ₀ ) having a carboxyl group to absorb the compound (P) depend on the compound (P) and carboxyl used. Depending on the type of polyurethane resin (U ₀ ) having a group, the temperature is preferably 10 to 80 ° C., the time is preferably 5 minutes to 10 hours, more preferably 10 minutes to 3 hours, and particularly preferably 15 minutes to 60 minutes.

The fact that the compound (P) was absorbed by the particles of the polyurethane resin (U ₀ ) having a carboxyl group was sampled at regular intervals after the start of mixing of the compound (P) and the polyurethane resin aqueous dispersion (U ₀ E). The sample collected can be left still for 30 minutes, and confirmed by a method of confirming that it has not been separated visually.

After the compound (P) was absorbed to the particles of the polyurethane resin having a carboxyl group (U _0), as the device of reacting the polyurethane resin (U ₀₎ with the compound (P) having a carboxyl group by heating, Any apparatus capable of stirring and heating can be used. For example, a vertical stirring system exemplified as an apparatus for emulsifying and dispersing the urethane prepolymer having an isocyanate group at its terminal or an organic solvent solution thereof in an aqueous medium. Or a rotor-stator type can be used.

The temperature at which the polyurethane resin (U ₀ ) having a carboxyl group and the compound (P) are reacted is preferably 80 to 140 ° C, more preferably 90 to 120 ° C, and particularly preferably 90 to 110 ° C.

  The reaction time can be appropriately selected depending on the apparatus to be used, the type of the compound (P), etc., but is generally preferably 10 minutes to 100 hours, more preferably 30 minutes to 30 hours, particularly preferably. 60 minutes to 10 hours.

The viscosity of the polyurethane resin aqueous dispersion (UE) 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 aqueous polyurethane resin dispersion (UE) 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 volume average particle diameter (Dv) of the polyurethane resin aqueous dispersion (UE) of the present invention is preferably 0.01 to 1 μm, more preferably 0.02 to 0.7 μm, particularly preferably from the viewpoint of dispersion stability. Is 0.03-0.4 μm.

The volume average particle diameter (Dv) of the polyurethane-based resin aqueous dispersion (UE) is the hydrophilic group in (U ₀ ), the amount of the dispersing agent, the type and operating conditions of the disperser used in the dispersing step, compound (P) The desired range can be obtained by appropriately adjusting the type of the above and the conditions in which the compound (P) is absorbed and reacted in the aqueous polyurethane resin dispersion (U ₀ E).

  The volume average particle diameter (Dv) in the present invention is determined by diluting an aqueous resin dispersion with ion-exchanged water so that the solid content of the resin becomes 0.01% by weight, and then measuring a light scattering particle size distribution analyzer [ELS- 8000 {manufactured by Otsuka Electronics Co., Ltd.}].

The aqueous polyurethane resin dispersion (UE) of the present invention can further contain a crosslinking agent (D) such as a blocked isocyanate compound (D1) and a melamine compound (D2). (D1) is used when the polyurethane resin having a carboxyl group (U ₀ ) has a hydroxyl group or an amino group, and (D2) is a polyurethane resin having a carboxyl group (U ₀ ) having a hydroxyl group, an amino group or a carboxyl group. Used when having

As a method for introducing a hydroxyl group into a polyurethane resin (U ₀ ) having a carboxyl group, a polyol (a), a polyisocyanate (b), a compound (c) containing a carboxyl group and an active hydrogen atom, and a hydrophilic used as necessary. When the compound (d) containing a functional group and an active hydrogen atom, the chain extender (e) and the reaction terminator (f) are reacted, (a), ( c) and a method of reacting so that the equivalents of the hydroxyl groups used in (d), (e) and (f) are excessive, and after obtaining a urethane prepolymer having an isocyanate group at the terminal, Examples thereof include a method of reacting mono- or dialkanolamine as the reaction terminator (f).

As a method for introducing an amino group into the polyurethane resin having a carboxyl group (U ₀ ), after obtaining a urethane prepolymer having an isocyanate group at the terminal, an excess equivalent of the isocyanate of the urethane prepolymer is obtained. Examples include a method of reacting a diamine having 2 to 10 carbon atoms and / or a poly (n = 2 to 6) alkylene (2 to 6 carbon atoms) poly (n = 3 to 7) amine as the chain extender (e). It is done.

  The blocked isocyanate compound (D1) is not particularly limited. For example, the polyisocyanate (b) is converted into a blocking agent (phenol, thiophenol, chlorophenol, cresol, resorcinol, p-sec-butylphenol, p-tert-butylphenol, p- phenols such as sec-amylphenol, p-octylphenol and p-nonylphenol; secondary or tertiary alcohols such as isopropyl alcohol and tert-butyl alcohol; oximes such as acetoxime, methylethylketoxime and cyclohexanone oxime; dimethylamine Secondary amine bonded to primary carbon such as diethylamine, di-n-propylamine, ethylmethylamine, diisopropylamine, di-sec-butylamine, dicyclo Carbon number of secondary amine bonded to secondary carbon such as xylamine, isopropylcyclohexylamine, secondary amine bonded to tertiary carbon such as di-t-butylamine, and other secondary amines such as isopropylethylamine 2 to 15 aliphatic secondary amines; aromatic secondary amines such as diphenylamine and xylidine; phthalic imides; lactams such as ε-caprolactam and δ-valerolactam; malonic acid dialkyl ester, acetylacetone and acetoacetate Active methylene compounds such as alkyl acetates; pyrazole, 3,5-dimethylpyrazole, 3-methylpyrazole, 4-benzyl-3,5-dimethylpyrazole, 4-nitro-3,5-dimethylpyrazole, 4-bromo-3 , 5-dimethylpyrazole and 3-methyl-5-pheny Pyrazole compounds such as pyrazole; those blocks and the like in an acidic sodium sulfite, etc.) and the like.

  As a commercial product of (D1), Duranate series (Duranate 22A-75P, 24A-100, 21S-75E, TPA-100, TKA-100, MFA-75B, MHG-80B, TLA-100 manufactured by Asahi Kasei Corporation. , TSA-100, TSS-100, TSE-100, P301-75E, E402-80B, E405-70B, AE700-100, D101, D201 and A201H, etc.) and Takenate series (Takenate D) manufactured by Mitsui Chemicals, Inc. -103N, D-160N, D-140N, D-110N, D-181N, D-120N, D-165N90CX, D-204, D-170N, PW series, and B series).

  The blocking agent used for (D1) is preferably methyl ethyl ketoxime in oximes and secondary in aliphatic secondary amines having 2 to 15 carbon atoms from the viewpoint of both reactivity and storage stability. Secondary amines bonded to carbon (particularly diisopropylamine), diethyl malonate among active methylene compounds and 3,5-dimethylpyrazole among pyrazole-based compounds.

  The melamine compound (D2) 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. For example, Uban series (manufactured by Mitsui Chemicals, Inc.) Uban 120, 20HS, 2021, 2028, 228, 2860 and 22R, etc.) and Cymel series manufactured by Nippon Cytec Co., Ltd. (Cymel 202, 232, 235, 238, 254, 266, 267, 272, 285, 301, 303) 325, 327, 350, 370, 701, 703, 736, 738, 771, 114, 1156 and 1158, etc.) and Sumitomo Chemical Co., Ltd.'s Sumimar series (Sumimar M-30W, M-50W, M-55) , M-66B and 50B).

The content of the blocked isocyanate compound (D1) is preferably 0.01 to 25% by weight, more preferably, based on the polyurethane resin (U ₀ ) having a carboxyl group, from the viewpoint of film forming properties and water resistance. 0.1 to 20% by weight.

  The polyurethane resin aqueous dispersion (UE) 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, and a bundle for reinforcing fibers. Agent composition, antibacterial 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 Can be used for adhesive compositions and water-based ink compositions, etc., but because of its excellent film-forming properties and water resistance, it is particularly suitable as an aqueous coating composition, aqueous adhesive composition and aqueous fiber processing agent composition. Can be used.

  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.

  When the aqueous polyurethane resin dispersion (UE) of the present invention is used in an aqueous coating material, the polyurethane system in the aqueous polyurethane resin dispersion (UE) of the present invention is optionally used for the purpose of assisting the formation of a coating film or improving the binder function. In addition to the resin (U), other water-dispersible resins or water-soluble resins may be used in combination.

  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 (U) in the present invention, polyacrylic resins, and polyester resins. It is done. 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 (UE) of the present invention in the aqueous coating is preferably 0.1 to 60% by weight, more 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 preferably 60% by weight or less, more 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 preferably 30% by weight or less, more preferably 0.1 to 20% by weight, based on the solid content weight of the polyurethane resin aqueous dispersion (UE).

  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 preferably 50% by weight or less, more 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 preferably 20% by weight or less, more 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 (such as 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 content of the viscosity modifier, antifoaming agent, preservative, deterioration preventing agent, stabilizer and antifreezing agent is preferably 5% by weight or less, more preferably 3% by weight or less, respectively, based on the weight of the aqueous paint. It is.

  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 aqueous paint using the polyurethane resin aqueous dispersion (UE) of the present invention is produced by mixing and stirring the polyurethane resin aqueous dispersion (UE) 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.

  When the aqueous polyurethane resin dispersion (UE) of the present invention is used in an aqueous adhesive, the polyurethane resin (U) in the aqueous polyurethane resin dispersion (UE) of the present invention may be used alone as the resin to be used. Of course, a water-dispersible or water-soluble resin other than the urethane resin typified by SBR latex resin or acrylic resin can be used in combination. When using together, the ratio of the polyurethane-type resin (U) with respect to the resin total weight becomes like this. Preferably it is 1 weight% or more, More preferably, it is 10 weight% or more.

  Furthermore, auxiliary materials and additives used for ordinary adhesives, such as cross-linking agents, plasticizers, and adhesives, as long as the cohesiveness of the adhesive containing the aqueous polyurethane resin dispersion (UE) of the present invention is not impaired. It is also possible to use an imparting agent, a filler, a pigment, a thickener, an antioxidant, an ultraviolet absorber, a surfactant, a flame retardant, and the like.

  When the polyurethane-based resin aqueous dispersion (UE) of the present invention is used as an aqueous fiber processing agent, known antifoaming agents, wetting agents, various resin aqueous dispersions (polyurethane aqueous dispersions other than the present invention, acrylic water based, if necessary) Dispersion, SBR latex, etc.) and softeners can be blended. In the case of an aqueous resin 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 Each 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 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.

  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 (U ₀ -1) having an SP value of 9.9. It was. 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 4 using CLEARMIX [M-Technic Co., Ltd.]. (U ₀ E-1) was obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-1) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-1) was obtained.

In addition, the composition and SP value of the compound (P) described in Table 5 are as follows.
Denacor EX-201: Resorcinol diglycidyl ether (SP value: 10.2) manufactured by Nagase ChemteX Corporation
Denacol EX-211: Neopentyl glycol diglycidyl ether (SP value: 9.1) manufactured by Nagase ChemteX Corporation
Denacol EX-411: Pentaerythritol polyglycidyl ether (SP value: 10.0) manufactured by Nagase ChemteX Corporation
Denacol EX-931: Polypropylene glycol diglycidyl ether (SP value: 8.8) manufactured by Nagase ChemteX Corporation
Denacor EX-141: Phenylglycidyl ether (SP value: 9.6) manufactured by Nagase ChemteX Corporation
Denacol EX-212: 1,6-hexanediol diglycidyl ether (SP value: 9.3) manufactured by Nagase ChemteX Corporation
KBM-403: Shin-Etsu Chemical Co., Ltd. 3-glycidoxypropyltrimethoxysilane (SP value: 8.5)
Chemitite PZ-33: 2,2′-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate] manufactured by Nippon Shokubai Co., Ltd. (SP value: 12.4)

<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 pressure press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U ₀ -2) having an SP value of 10.6. Subsequently, each raw material 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 4 using a TK homomixer [manufactured by Primix Co., Ltd.]. (U ₀ E-2) was obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-2) in the amount shown in Table 5 and reacted under the absorption and conditions shown in Table 6 to obtain a polyurethane resin dispersion ( UE-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 urethanation reaction. A polyurethane resin having an SP value of 10.8 (U A toluene solution of _0-3 ) was obtained. Subsequently, each raw material shown in Table 3 is charged into a temperature-controllable pressure-resistant container, and after dispersion treatment under the conditions shown in Table 4 using CLEARMIX, toluene is distilled off at 90 ° C. under reduced pressure for 5 hours. A polyurethane resin aqueous dispersion (U ₀ E-3) was obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-3) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6 to obtain a polyurethane resin dispersion ( UE-3) was obtained.

<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 (U ₀ -4) having an SP value of 9.8. Subsequently, each raw material 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 4 using a TK homomixer [manufactured by Primix Co., Ltd.]. (U ₀ E-4) was obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-4) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-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 (U ₀ -5) having an SP value of 10.8. Subsequently, each of the raw materials shown in Table 3 was charged in a pressure-controllable container having a temperature controllable and dispersed under the conditions shown in Table 4 using a TK homomixer [manufactured by Primics Co., Ltd.], thereby an aqueous polyurethane resin dispersion ( U ₀ E-5) was obtained. The compound (P) shown in Table 5 is added to the polyurethane resin-based aqueous dispersion (U ₀ E-5) in the amount shown in Table 5, and is absorbed and reacted under the conditions shown in Table 6. (UE-5) was obtained.

<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 (U ₀ -6) having an SP value of 10.0. 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 4 to obtain an aqueous polyurethane resin dispersion (U ₀ E-6). It was. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-6) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-6) was obtained.

<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 pressure press machine heated to 180 ° C., and then cut with a square pelletizer to obtain a polyurethane resin (U ₀ -7) having an SP value of 9.9. Subsequently, each raw material shown in Table 3 was charged into a pressure-controllable container capable of controlling temperature, and the aqueous polyurethane resin dispersion (U ₀ E-7) was dispersed by treatment under the conditions shown in Table 4 using CLEARMIX. Obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-7) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-7) was obtained.

<Example 8>
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 (U ₀ -8) having an SP value of 10.0. Subsequently, each raw material shown in Table 3 is charged into a temperature-controllable pressure-resistant container, and after dispersion treatment under the conditions shown in Table 4 using CLEARMIX, THF is distilled off at 50 ° C. under reduced pressure for 5 hours. A polyurethane resin aqueous dispersion (U ₀ E-8) was obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-8) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-8) was obtained.

<Example 9>
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 (U ₀ -9) having an SP value of 10.8. Subsequently, each raw material shown in Table 3 was charged into a pressure-controllable container capable of controlling the temperature, and the polyurethane resin aqueous dispersion (U ₀ E-9) was dispersed by treatment under the conditions shown in Table 4 using CLEARMIX. Obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-9) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-9) was obtained.

<Example 10>
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 (U ₀ -10) having an SP value of 10.4. Subsequently, each raw material shown in Table 3 was charged in a pressure-controllable container capable of controlling temperature, and a polyurethane resin aqueous dispersion (U ₀ E-10) was dispersed by using a CLEARMIX under the conditions shown in Table 4. Obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-10) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-10) was obtained.

<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 (U ₀ -11) having an SP value of 10.0. Subsequently, each raw material shown in Table 3 was charged into a pressure-controllable container capable of controlling temperature, and the aqueous polyurethane resin dispersion (U ₀ E-11) was dispersed by treatment under the conditions shown in Table 4 using CLEARMIX. Obtained. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-11) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-11) was obtained.

<Example 12>
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. A polyurethane resin (U ₀ with an SP value of 10.0) Acetone solution of -12) was produced. 466.7 parts of an acetone solution of the obtained urethane resin was charged into a simple pressure reactor, and 13.4 parts of dimethylmonoethanolamine (neutralizing agent) and 519.9 parts of water were added while stirring at 40 ° C. Acetone was distilled off at 65 ° C. for 8 hours under reduced pressure to obtain an aqueous polyurethane resin dispersion (U ₀ E-12). The compound (P) shown in Table 5 is added to the polyurethane resin aqueous dispersion (U ₀ E-12) in the amount shown in Table 5, and is absorbed and reacted under the conditions shown in Table 6. UE-12) was obtained.

<Example 13>
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. A polyurethane resin (U ₀ with an SP value of 10.0) An acetone solution of -13) was produced. 469.7 parts of an acetone solution of the obtained urethane resin was charged into a simple pressure reactor, and 10.4 parts of dimethylmonoethanolamine (neutralizing agent) and 519.9 parts of water were added while stirring at 40 ° C. Acetone was distilled off at 65 ° C. under reduced pressure for 8 hours to obtain an aqueous polyurethane resin dispersion (U ₀ E-13). The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-13) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-13) was obtained.

<Example 14>
A simple pressure reactor equipped with a stirrer and a heating device was charged with each raw material shown in Table 2 and stirred at 85 ° C. for 10 hours to carry out a urethanization reaction, and an acetone solution of a urethane prepolymer having an isocyanate group at the terminal Manufactured. The isocyanate content per solid in the acetone solution of the urethane prepolymer having an isocyanate group at the end was 0.37 mmol / g. 535.56 parts of an acetone solution of urethane prepolymer having an isocyanate group at the terminal thus obtained was charged into a simple pressure reactor, and 17.44 parts of triethylamine (neutralizing agent) and 442.51. 01 parts were added. After stirring for 3 minutes at 60 rpm, 0.23 parts of ethylenediamine and 4.26 parts of diethylenetriamine as chain extenders were added, and acetone was distilled off at 65 ° C. for 8 hours under reduced pressure to obtain an aqueous polyurethane resin dispersion (U ₀ E-14) was obtained. The SP value of the polyurethane resin (U ₀ -14) in (U ₀ E-14) was 10.33. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-14) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-14) was obtained.

<Example 15>
A simple pressure reactor equipped with a stirrer and a heating device was charged with each raw material shown in Table 2 and stirred at 85 ° C. for 10 hours to carry out a urethanization reaction, and an acetone solution of a urethane prepolymer having an isocyanate group at the terminal Manufactured. The isocyanate content per solid in the acetone solution of the urethane prepolymer having an isocyanate group at the end was 0.41 mmol / g. 493.09 parts of an acetone solution of urethane prepolymer having an isocyanate group at the terminal thus obtained was charged into a simple pressure reactor, and 11.45 parts of triethylamine (neutralizing agent) and 491.37 parts of water were stirred at 40 ° C. Was added. After stirring for 3 minutes at 60 rpm, 2.03 parts of ethylenediamine and 2.06 parts of monoethanolamine as chain extenders were added, and acetone was distilled off at 65 ° C. for 8 hours under reduced pressure. U ₀ E-15) was obtained. The SP value of the polyurethane resin (U ₀ -15) in (U ₀ E-15) was 10.0. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-15) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-15) was obtained.

<Example 16>
A simple pressure reactor equipped with a stirrer and a heating device was charged with each raw material shown in Table 2 and stirred at 85 ° C. for 10 hours to carry out a urethanization reaction, and an acetone solution of a urethane prepolymer having an isocyanate group at the terminal Manufactured. The isocyanate content per solid in the acetone solution of the urethane prepolymer having an isocyanate group at the end was 0.43 mmol / g. 491.18 parts of an acetone solution of urethane prepolymer having an isocyanate group at the terminal thus obtained was charged into a simple pressure reactor, and while stirring at 40 ° C., 14.76 parts of triethylamine (neutralizing agent) and 489.80 parts of water Was added. After stirring at 60 rpm for 3 minutes, 2.11 parts of chain extender ethylenediamine and 2.15 parts of monoethanolamine were added, and acetone was distilled off at 65 ° C. under reduced pressure for 8 hours to obtain an aqueous polyurethane resin dispersion ( U ₀ E-16) was obtained. The SP value of the polyurethane resin (U ₀ -16) in (U ₀ E-16) was 10.0. The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-16) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-16) was obtained.

<Example 17>
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. A polyurethane resin (U ₀ with an SP value of 10.0) Acetone solution of -17) was produced. 466.7 parts of an acetone solution of the obtained urethane resin was charged into a simple pressure reactor, and 13.4 parts of dimethylmonoethanolamine (neutralizing agent) and 519.9 parts of water were added while stirring at 40 ° C. Acetone was distilled off at 65 ° C. for 8 hours under reduced pressure to obtain an aqueous polyurethane resin dispersion (U ₀ E-17). The compound (P) shown in Table 5 was added to the polyurethane resin aqueous dispersion (U ₀ E-17) in the amount shown in Table 5, and was absorbed and reacted under the conditions shown in Table 6. UE-17) was obtained.

<Comparative Example 1>
A simple pressure reactor equipped with a stirrer and a heating device was charged with each raw material shown in Table 2 and stirred at 85 ° C. for 10 hours to carry out a urethanization reaction, and an acetone solution of a urethane prepolymer having an isocyanate group at the terminal Manufactured. The isocyanate content per solid in the acetone solution of the urethane prepolymer having an isocyanate group at the terminal was 0.42 mmol / g. 393.56 parts of an acetone solution of a urethane prepolymer having an isocyanate group at the terminal thus obtained was charged into a simple pressure reactor, and 12.85 parts of triethylamine (neutralizing agent) and 589.59 parts of water were stirred at 40 ° C. Was added. 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 an aqueous polyurethane resin dispersion (U ₀ E′-1). Obtained. The SP value of the polyurethane resin (U ₀ '-1) in (U ₀ E'-1) was 9.7.

<Comparative example 2>
After mixing each raw material shown in Table 2, the mixture 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 (U ₀ ′ -2) having an SP value of 10.0. 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 4 to obtain an aqueous polyurethane resin dispersion (U ₀ E′-2). Obtained.

Polyurethane resin aqueous dispersions (UE-1) to (UE-17) obtained in Examples 1 to 17 and polyurethane resin aqueous dispersions (U ₀ E′-1) obtained in Comparative Examples 1 to 2 Table 7 shows various physical property values and evaluation results of (U ₀ E′-2). The evaluation method is as follows.

<Water resistance of dry film>
Pour 10 parts of polyurethane-based 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, air circulation dryer The film obtained by heating and drying at 105 ° C. for 3 hours was immersed in ion-exchanged water at 50 ° 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.

<Solvent resistance of dry film>
The polyurethane-based resin aqueous dispersion was spray-coated on a 10 cm × 20 cm steel plate and heated at 80 ° C. for 3 minutes to prepare a 20 μm coating film. The coated steel sheet was immersed in dimethylformamide at 25 ° C. for 1 minute, then taken out and lightly wiped, and the surface of the coating film was visually evaluated according to the following evaluation criteria.
(Double-circle): There is no change of the coating-film surface before and behind immersion.
○: After dipping, the surface of the coating film has slight irregularities.
Δ: There are small irregularities on the surface of the coating film after immersion.
X: After immersion, the coating film surface has irregularities, and the paint is dissolved in dimethylformamide.

<Film-forming property of aqueous polyurethane resin dispersion>
Pour 10 parts of an aqueous polyurethane resin dispersion into a polypropylene mold measuring 10 cm in length × 20 cm in width × 1 cm 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 [“Calibon 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 resin aqueous dispersion [“Polytron Z330”, manufactured by Asahi Kasei Co., Ltd.] and 200 parts of the polyurethane resin aqueous dispersion (UE-1) obtained in Example 1 were charged. Mix and disperse for 10 minutes. 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 aqueous solution was used in the same manner as in Evaluation Example 1 except that the aqueous polyurethane resin dispersion (U ₀ E′-2) obtained in Comparative Example 2 was used instead of the aqueous polyurethane resin dispersion (UE-1). A paint (W′-1) was obtained.
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>
A 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>
A water-based paint was spray-coated on a 10 cm × 20 cm steel plate and heated at 80 ° C. for 3 minutes to produce 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)
To 100 parts of the polyurethane resin aqueous dispersion (UE-4) obtained in Example 4, 6 parts of 1,6-hexamethylene diisocyanate isocyanurate trimer was mixed as a curing agent at 25 ° C. Was adjusted with a thickener ("SN thickener A-803" manufactured by San Nopco) so that the viscosity of the water-based adhesive (X-1) was obtained. 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 solution was used in the same manner as in Evaluation Example 2 except that the polyurethane resin aqueous dispersion (U ₀ E′-2) obtained in Comparative Example 2 was used instead of the polyurethane resin aqueous dispersion (UE-4). An adhesive (X′-1) was obtained.
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)
Using a polyurethane resin aqueous dispersion, a pigment printing paste was prepared as follows.
Viscoelasticity modifier [“SN thickener 618” manufactured by San Nopco Co., Ltd.] 8.9 parts, silicon-based antifoaming agent [100 parts of the polyurethane resin aqueous dispersion (UE-2) obtained in Example 2] "SN deformer 777" manufactured by San Nopco Co., Ltd.] 0.9 parts, 35 parts of water, 44.6 parts of titanium oxide, and pigment ["NL Red FR3R-D" manufactured by Yamagata Kogyo Co., Ltd.] 18.9 parts By mixing, 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 as in Evaluation Example 3, except that the aqueous polyurethane resin dispersion (U ₀ E′-1) obtained in Comparative Example 1 is used instead of the aqueous polyurethane resin dispersion (UE-2). A printing paste (Y′-1) was obtained. 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 3 days, 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 for 3 minutes with a tenter temperature-controlled at 120 ° C. 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 (UE) of the present invention has an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a binder composition for pigment printing) because of its excellent film forming property and water resistance. Non-woven fabric binder composition, reinforcing fiber sizing agent composition, antibacterial binder composition and artificial leather / synthetic leather raw material composition, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition, and the like) Antifouling coating composition, etc.), aqueous paper treatment composition, aqueous ink composition, etc., and particularly suitable as an aqueous coating composition, aqueous adhesive composition, and aqueous fiber processing composition. .

Claims (5)

A polyurethane resin having a carboxyl group in the molecule (U _0), having reactive carboxyl groups, the SP value difference is 3 or less with the SP value of the polyurethane resin (U ₀₎ having a carboxyl group A polyurethane resin aqueous dispersion (UE) comprising a polyurethane resin obtained by reacting with the compound (P) and water. The aqueous polyurethane-based resin dispersion according to claim 1, wherein 1 to 95 mol% of carboxyl groups of the polyurethane resin (U ₀ ) are reacted with the compound (P).   The polyurethane resin aqueous dispersion according to claim 1 or 2, wherein the compound (P) is at least one compound selected from the group consisting of an epoxy compound, an aziridine compound, a carbodiimide compound, and an oxazoline compound. 2. The carboxyl group which is not reacted with the compound (P) among the carboxyl groups of the urethane resin (U ₀ ) is neutralized with ammonia or an amine compound having 1 to 20 carbon atoms. The aqueous polyurethane-based resin dispersion according to any one of -3. A polyurethane resin aqueous dispersion (U ₀ E) containing polyurethane resin (U ₀ ) particles having a carboxyl group in the molecule and water, a polyurethane resin (U ₀ E) having reactivity with a carboxyl group and having the carboxyl group (U ₀ ) is mixed with a compound (P) having an SP value of 3 or less to obtain a mixed liquid, and then the compound (P) is added to the particles of the polyurethane resin (U ₀ ) having a carboxyl group. A polyurethane system comprising: a step of absorbing P), and a step of reacting the compound (P) with the polyurethane resin having a carboxyl group by subsequently heating the mixed solution (U ₀ ) Manufacturing method of resin aqueous dispersion (UE).