JP2018141119A - Polyurethane resin aqueous dispersion body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin aqueous dispersion having excellent adhesion and breaking elongation of a dry film. SOLUTION: The polyurethane resin aqueous dispersion containing water and a polyurethane resin (U), wherein the polyurethane resin (U) is a polyol (a) containing a polyester polyol and / or a polyether polyol, a polyisocyanate. (B) A terminal isocyanate group-containing polyurethane prepolymer (P) containing a hydrophilic group and an active hydrogen atom-containing compound (c) and an isocyanate group blocking agent (d) as essential constituent monomers, and a chain extender. A polyurethane resin aqueous dispersion which is a reaction product with (e) and has a content of carbonate bonds in the polyurethane resin (U) of less than 8% by weight based on the weight of the polyurethane resin (U). [Selection diagram] None

Description

  The present invention relates to an aqueous polyurethane resin dispersion.

Since the polyurethane resin aqueous dispersion has excellent flexibility, adhesion, chemical resistance, mechanical strength and impact resistance, the coating obtained by drying has been conventionally used in paints, adhesives, textile processing agents, It has been used for paper processing agents and inks. For example, an aqueous polyurethane resin dispersion containing diisocyanate, polycarbonate diol, and acidic group-containing diol as essential components is disclosed (for example, see Patent Document 1).
However, the aqueous polyurethane resin dispersion described in Patent Document 1 is an aqueous dispersion of a polycarbonate urethane resin having a relatively high glass transition point, and is used for paints, adhesives, fiber processing agents, paper treatment agents, inks, and the like. In this case, the chemical resistance and the water resistance are improved, but there is a problem that the adhesion and breaking elongation of the dry film are inferior.

Japanese Patent Laying-Open No. 2015-7239

  The subject of this invention is providing the polyurethane resin aqueous dispersion which is excellent in the adhesiveness and breaking elongation of a dry film.

  As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention is a polyurethane resin aqueous dispersion containing water and a polyurethane resin (U), wherein the polyurethane resin (U) is a polyol (a) containing a polyester polyol and / or a polyether polyol, End isocyanate group-containing polyurethane prepolymer (P) having an isocyanate (b), a compound (c) containing a hydrophilic group and an active hydrogen atom, and an isocyanate group blocking agent (d) as essential constituent monomers and chain extension A polyurethane resin aqueous dispersion which is a reaction product with the agent (e) and has a carbonate bond content in the polyurethane resin (U) of less than 8% by weight based on the weight of the polyurethane resin (U).

  The dry film obtained from the aqueous polyurethane resin dispersion of the present invention is excellent in adhesion and breaking elongation.

<Polyurethane resin (U)>
The polyurethane resin (U) in the present invention comprises a polyol (a) containing a polyester polyol and / or a polyether polyol, a polyisocyanate (b), a compound (c) containing a hydrophilic group and an active hydrogen atom, and an isocyanate group. It is a reaction product of a terminal isocyanate group-containing polyurethane prepolymer (P) having a blocking agent (d) as an essential constituent monomer and a chain extender (e).

  Polyol (a) containing a polyester polyol and / or a polyether polyol has a number average molecular weight (hereinafter abbreviated as Mn) of 300 or more polyether polyol (a11), polyester polyol (a12) and chemical formula amount or Mn is less than 300. Of the low molecular weight polyol (a2). Polyol (a) may be used individually by 1 type, or may use 2 or more types together.

In addition, Mn of the polyol in this invention can be measured on condition of the following, for example by gel permeation chromatography.
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (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
Detector: Refractive index detector Reference material: Standard polyethylene glycol

  Examples of the polyether polyol (a11) having Mn of 300 or more include aliphatic polyether polyols and aromatic ring-containing polyether polyols.

  Examples of the aliphatic polyether polyol include C2-C20 aliphatic polyhydric alcohol and C2-C20 aliphatic polyhydric alcohol alkylene oxide (hereinafter abbreviated as AO) adducts. Can be mentioned.

  Examples of the aliphatic polyhydric alcohol having 2 to 20 carbon atoms include linear or branched aliphatic dihydric alcohols having 2 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1, 5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, etc. 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,6- Xanthdiol, 3-methyl-1,6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7-heptanediol, 4-methyl-1,7-heptanediol, 2-methyl -1,8-octanediol, branched alcohols such as 3-methyl-1,8-octanediol and 4-methyloctanediol]; alicyclic dihydric alcohols having 6 to 20 carbon atoms [1,4-cyclohexanediol 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5-bis (hydroxymethyl) -1,4-dioxane, 2, 7-norbornanediol, tetrahydrofuran dimethanol, 1,4-bis (hydroxyethoxy) cyclohexane, , 4-bis (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane, etc.]; trivalent alcohols having 3 to 20 carbon atoms [aliphatic triols (such as glycerin and trimethylolpropane)]; carbon 4 to 8 hydric alcohols of 5 to 20 [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.); saccharides (sucrose, glucose, mannose, fructose, methylglucoside and derivatives thereof) ]; Etc. are mentioned.

  Examples of AO having 2 to 12 carbon atoms include ethylene oxide (hereinafter abbreviated as EO), 1,2- or 1,3-propylene oxide (hereinafter abbreviated as PO), 1,2-, 2,3- or 1,3. -Butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran, α-olefin oxide, styrene oxide, epihalohydrin (such as epichlorohydrin) and the like.

  Specific examples of the aliphatic polyether polyol include polyoxyalkylene polyol [polyethylene glycol (hereinafter abbreviated as PEG), etc.], polyoxypropylene polyol [polypropylene glycol, etc.], polyoxyethylene / propylene polyol, and polytetramethylene ether glycol. Etc.

  Commercial products of aliphatic polyether polyols include PTMG1000 [poly (oxytetramethylene) glycol with Mn = 1,000, manufactured by Mitsubishi Chemical Corporation], PTMG2000 [poly (oxytetramethylene) glycol with Mn = 2,000. , Manufactured by Mitsubishi Chemical Corporation], PTMG3000 [poly (oxytetramethylene) glycol with Mn = 3,000, manufactured by Mitsubishi Chemical Corporation], PTGL2000 [modified poly (oxytetramethylene) glycol with Mn = 2,000, Manufactured by Hodogaya Chemical Co., Ltd.], PTGL3000 [modified poly (oxytetramethylene) glycol with Mn = 3,000, manufactured by Hodogaya Chemical Co., Ltd.], and Sanniks Diol GP-3000 [Mn = 3,000. Poly (oxypropylene) triol, manufactured by Sanyo Chemical Industries, Ltd.] It is.

  As an aromatic ring-containing polyether polyol, an AO adduct of an araliphatic dihydric alcohol having 8 to 20 carbon atoms [m- or p-xylylene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene, etc.] And AO adducts of bisphenol compounds (bisphenol A, bisphenol B, bisphenol S and bisphenol F), and the like.

  Specific examples of the aromatic ring-containing polyether polyol include, for example, bisphenol A EO adduct (bisphenol A EO 2 mol adduct, bisphenol A EO 4 mol adduct, bisphenol A EO 6 mol adduct, bisphenol A EO 8 mol adduct Bisphenol A EO 10 mol adduct and bisphenol A EO 20 mol adduct, etc.) and bisphenol A PO adduct (PO2 mol adduct of bisphenol A, PO3 mol adduct of bisphenol A and PO5 mol adduct of bisphenol A) And the like, and EO or PO adducts of resorcin, and the like.

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

  Examples of the polyester polyol (a12) having an Mn of 300 or more include condensed polyester polyols, polylactone polyols, polycarbonate polyols, and castor oil-based polyols.

Examples of the condensed polyester polyol include a polyester polyol of a low molecular polyol (a2) having a chemical formula amount described below or Mn of less than 300 and a polyvalent carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.
Among the low molecular polyols having a chemical formula amount or Mn of less than 300 used for the condensation type polyester polyol, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, EO or PO low molar adducts of bisphenol A and mixtures thereof.

  Examples of polycarboxylic acids having 2 to 10 carbon atoms or ester-forming derivatives thereof used in condensed polyester polyols 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), and the like Anhydrides (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), acid halides (adipic acid dichloride, etc.), low molecular weight alkyl esters (dimethyl succinate, dimethyl phthalate, etc.) ) And mixtures thereof.

  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.

  As a commercially available product of condensed polyester polyol, Sanester 2610 [polyethylene adipate diol with Mn = 1,000, manufactured by Sanyo Chemical Industries, Ltd.], Sanester 4620 [polytetramethylene adipate diol with Mn = 2,000], Sanester 2620 [polyethylene adipate diol with Mn = 2,000, manufactured by Sanyo Chemical Industries, Ltd.], Kuraray polyol P-2010 [poly-3-methyl-1,5-pentane adipate diol with Mn = 2,000], Kuraray polyol P-3010 [poly-3-methyl-1,5-pentane adipate diol with Mn = 3,000] and Kuraray polyol P-6010 [poly-3-methyl-1,5-pentane with Mn = 6,000 Adipate diol] and the like.

The polylactone polyol is a polyadduct of lactone to the low molecular weight polyhydric alcohol, and 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.

  As the polycarbonate polyol, the aliphatic polyhydric alcohol having 2 to 20 carbon atoms and a low-molecular carbonate compound (for example, an alkylene carbonate having an alkyl group having 1 to 6 carbon atoms and an alkylene group having 2 to 6 carbon atoms). And a polycarbonate polyol produced by condensation with a dealcoholization reaction with a diaryl carbonate having an aryl group having 6 to 9 carbon atoms. Two or more aliphatic polyhydric alcohols and alkylene carbonates having 2 to 20 carbon atoms 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 Kuraray polyol C-3090 [poly (3-methyl- with Mn = 3,000). 5-pentanediol / hexamethylene) carbonate diol] and T4672 [poly (tetramethylene / hexamethylene) carbonate diol of Mn = 2,000, manufactured by Asahi Kasei Chemicals Corporation].

  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.

  Among the polyester polyols (a12), preferred are condensed polyester polyols and polylactone polyols.

  Examples of the low molecular polyol (a2) having a chemical formula amount or Mn of less than 300 include an AO addition product of the aliphatic polyhydric alcohol having 2 to 20 carbon atoms and an AO addition of the araliphatic dihydric alcohol having 8 to 20 carbon atoms. Or an AO adduct of the bisphenol compound having a chemical formula amount or Mn of less than 300 and the aliphatic polyhydric alcohol having 2 to 20 carbon atoms.

  Among these, from the viewpoint of water resistance and heat yellowing resistance, preferred are divalent and trivalent aliphatic alcohols, which can form a crosslinked structure in the polyurethane resin particles, and are urethane films. It is also preferable in that the effect of improving water resistance and chemical resistance can be obtained. As the aliphatic dihydric alcohol, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol and 1,6-hexanediol are particularly preferable, and as the aliphatic trihydric alcohol, trimethylolpropane is particularly preferable.

  Among the polyols (a), the polyester polyol (a12) and / or the polyether polyol (a11) are used as essential components, and the content of carbonate bonds in the polyurethane resin (U) is determined by the weight of the polyurethane resin (U). By setting it as less than 8 weight% on the basis of, the elongation at break and adhesion of the polyurethane resin (U) can be improved. The carbonate bond content can be adjusted to a desired range by appropriately adjusting the carbonate bond content of the starting polycarbonate polyol and the amount of the polycarbonate polyol used. The content of carbonate bonds based on the weight of the polyurethane resin (U) in the polyurethane resin (U) is more preferably 5% by weight or less, particularly preferably 2% by weight or less, and most preferably 0% by weight.

  As the polyisocyanate (b), which is an essential component of the polyurethane resin (U), those conventionally used for the production of polyurethane resins can be used. The polyisocyanate (b) is an aromatic polyisocyanate (b1) having 2 to 3 or more isocyanate groups and having 6 to 20 carbon atoms (excluding carbon in the isocyanate group, the same shall apply hereinafter), and 2 to 2 carbon atoms. 18 aliphatic polyisocyanate (b2), alicyclic polyisocyanate (b3) having 4 to 15 carbon atoms, araliphatic polyisocyanate (b4) having 8 to 15 carbon atoms and derivatives of (b1) to (b4) ( For example, isocyanurate product). Polyisocyanate (b) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the aromatic polyisocyanate having 6 to 20 carbon atoms (b1) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 4,4′- or 2,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m- or p-isocyanatophenylsulfonyl isocyanate, crude MDI, etc. It is done.

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

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

  Examples of the araliphatic polyisocyanate (b4) having 8 to 15 carbon atoms include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI). It is done.

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

  Examples of the compound (c) containing a hydrophilic group and an active hydrogen atom include a compound (c1) containing an anionic group and an active hydrogen atom, and a compound (c2) containing a cationic group and an active hydrogen atom. A compound (c) may be used individually by 1 type, or may use 2 or more types together.

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

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

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

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

  Examples of the compound (c2) containing a cationic group and an active hydrogen atom include a compound having a tertiary amino group as a cationic group and a hydroxyl group as an active hydrogen atom, and a tertiary amino group containing 1 to 20 carbon atoms. Diols [N-alkyl dialkanolamines (eg N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamines (eg N, N-dimethylethanolamine) ) And the like], and a salt obtained by neutralizing with a neutralizing agent.

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

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

The amount of (c) used is such that the content of the hydrophilic group in (U) is preferably 0.32 to 3.2% by weight, more preferably 0.40 to 2 based on the weight of (U). 0.0% by weight, particularly preferably 0.48 to 1.2% by weight, and most preferably 0.56 to 0.8% by weight.
If the hydrophilic group content is 0.32% by weight or more, the dispersion stability of the polyurethane resin aqueous dispersion is good, and if the hydrophilic group content is 3.2% by weight or less, the polyurethane resin aqueous dispersion The storage stability of blocked isocyanate groups in the body is good, and good adhesion to the substrate after long-term storage of the aqueous polyurethane resin dispersion can be maintained. When the content of the hydrophilic group is 3.2% by weight or less, the storage stability of the blocked isocyanate group is improved because the water swelling rate of (U) is reduced and the blocked isocyanate group is reduced. It is estimated that the reaction between the group and water can be suppressed.

The content of the hydrophilic group in the present invention means the weight percent of the unneutralized cationic group or anionic group, and does not include the weight of the counter ion. For example, the content of the hydrophilic group in (c1) is such that in the case of 2,2-dimethylolpropionic acid triethylamine salt, the weight percentage of the carboxyl group (—COOH) is 3- (2,3-dihydroxypropoxy). In the case of triethylamine salt of -1-propanesulfonic acid, it means the weight percent of the sulfo group (—SO ³ H). Moreover, content of the hydrophilic group in (c2) means weight% of only the nitrogen atom in a tertiary amino group.

  Examples of the blocking agent (d) for the isocyanate group include lactams having 2 to 6 carbon atoms (ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.), oximes having 1 to 15 carbon atoms [acetoxime, methyl ethyl ketoxime (MEK). Oxime), methyl isobutyl ketoxime (MIBK oxime), cyclohexanone oxime, etc.], secondary amines having 2 to 15 carbon atoms [aliphatic amines (dimethylamine, diisopyramine, di-n-propylamine, diisobutylamine, etc.), carbon C 4-20 alicyclic amines (such as methylhexylamine and dicyclohexylamine), aromatic amines (such as aniline and diphenylamine)], C6-20 phenols and alkylphenols [phenol, cresol, ethylphenol, n-propyl Enol, isopropylphenol, n-butylphenol, octylphenol, nonylphenol, xylenol, diisopropylphenol, di-t-butylphenol, etc.], a 5-membered ring compound having an imino group and a nitrogen-carbon double bond as a ring structural unit [imidazole, 2-methylimidazole, pyrazole, 3-methylpyrazole, 3,5-dimethylpyrazole and 1,2,4-triazole, etc.], imine [ethyleneimine and polyethyleneimine etc.], active methylene-containing compound [dimethyl malonate, malonic acid Diethyl, diisopropyl malonate, acetylacetone, methyl acetoacetate, ethyl acetoacetate and the like], blocking agents described in Patent Publication Nos. 2002-309217 and 2008-239890, and Mixtures of two or more of these and the like. Among these, preferred are an oxime having 1 to 15 carbon atoms, a secondary amine having 2 to 15 carbon atoms, a 5-membered ring compound having an imino group and a nitrogen-carbon double bond as a ring structural unit, and activity. Methylene-containing compounds, more preferably methyl ethyl ketoxime, diisopropylamine, 3,5-dimethylpyrazole and diethyl malonate. The isocyanate group blocking agent (d) may be used alone or in combination of two or more.

  In the case where a dry film of the aqueous polyurethane resin dispersion of the present invention is formed on a substrate, and the substrate has a functional group such as a hydroxyl group reactive with isocyanate, the viewpoint of improving the adhesion of the film The content of the isocyanate group sealed with the blocking agent (d) of the isocyanate group is preferably 0.01 to 1.0 mmol / g, more preferably 0.00 based on the weight of the polyurethane resin (U). It is 02 to 0.8 mmol / g, particularly preferably 0.03 to 0.6 mmol / g, and most preferably 0.04 to 0.4 mmol / g. The content of isocyanate groups not sealed with the blocking agent (d) of the terminal isocyanate group-containing polyurethane prepolymer (P) is preferably based on the weight of (P) from the viewpoint of adhesion and storage stability. Is 0.01 to 1.2 mmol / g, more preferably 0.05 to 1.1 mmol / g, particularly preferably 0.1 to 1.0 mmol / g, most preferably 0.2 to 0.9 mmol / g. is there.

  In order to decrease the dissociation temperature of the blocking agent of the terminal isocyanate group-containing polyurethane prepolymer (P) and accelerate the low temperature curing, the blocked isocyanate dissociation catalyst (f) may be used. Examples of the dissociation catalyst (f) include a metal catalyst (f1) and an amine catalyst (f2). The dissociation catalyst (f) may be used alone or in combination of two or more.

  Examples of the metal catalyst (f1) include an organometallic compound (f11) having a bond between the metal (M) and carbon, a metal complex (f12) having a coordinate bond with the metal (M), and a carboxyl of the metal (M). The 1 type (s) or 2 or more types chosen from the group which consists of an acid salt (f13) are mentioned.

  Examples of the organometallic compound (f11) include dibutyltin dilaurate, dibutyltin di-2-ethylhexanate, dioctyltin dilaurate, dibutyltin diacetate, dimethyltin dimaleate, dibutyltin dioxide, dioctyltin oxide and the like, titanium Examples thereof include organic titanium such as tetra-n-butyl acid, tetraisopropyl titanate, organic bismuth, organic lead, and organic nickel.

  The metal complex (f12) is an acetylacetonate salt of metal (M), for example, tin acetylacetonate, bismuth acetylacetonate, titanium acetylacetonate, lead acetylacetonate, zirconium acetylacetonate, iron acetylacetonate. Examples include narate, aluminum acetylacetonate, zinc acetylacetonate, manganese acetylacetonate and cobalt acetylacetonate.

  Examples of the carboxylate metal salt (f13) include tin carboxylate (such as tin octylate, tin acetate, tin laurate and tin oleate), bismuth carboxylate (such as bismuth octylate and bismuth naphthenate), lead carboxylate Series (lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.), nickel carboxylate (nickel octylate, nickel naphthenate, etc.) and titanium carboxylate (titanium terephthalate, etc.) Can be mentioned.

  Among the metal catalysts (f1), the metal (M) is preferably one or more metals (M1) selected from the group consisting of Sn, Bi, Ti, Pb, Zr, Fe, Al, Zn and Mn. ), An organometallic compound (f111), a metal complex (f121) having a coordination bond with the metal (M1), and a carboxylate (f131) of the metal (M), more preferably dibutyltin dilaurate. Tin octylate, bismuth octylate, bismuth naphthenate, tin acetylacetonate, bismuth acetylacetonate and titanium acetylacetonate.

  Examples of the amine catalyst (f2) include a primary to tertiary amine (f21) and a quaternary ammonium salt (f22).

  As primary to tertiary amines (f21), bis (dimethylaminoethyl) ether, pentamethyldiethylenetriamine, pentamethyldipropylenetriamine, N-methyl- (dimethylaminopropyl) aminoethanolamine, dimorpholinodiethyl ether, dimethylaminoethanol , Dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, dimethylethanolamine, tetramethylethylenediamine, tetramethylpropylenediamine, tetramethylhexamethylenediamine, dimethylcyclohexylamine, methyldicyclohexylamine, triethylenediamine, tris (3-dimethylaminopropyl) Amines, tris (3-dimethylaminopropyl) hexahydro-s-triazine, tris (dimethyl) Minomethyl) phenol, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, methylmorpholine, ethylmorpholine, dimethylaminoethylmorpholine, 1,8-diazabicyclo [5.4.0] -undecene -7,1,8-diazabicyclo [5.4.0] -undecene-7 weak acid salt (phenol salt, 2-ethylhexanoate, formate, etc.), 1,5-diazabicyclo [4.3.0] -Nonene-5, 1,5-diazabicyclo [4.3.0] -nonene-5 weak acid salts (phenol salt, 2-ethylhexanoate, formate, etc.), 1,2-dimethyltetrahydropyrimidine, 2- Weak salts of dimethyltetrahydropyrimidine (phenol salt, 2-ethylhexanoate, formate, etc.) and tetramethyl Guanidine and the like.

  Examples of the quaternary ammonium salt (f22) include the following quaternary ammonium weak acid salts (phenol salt, 2-ethylhexanoate, formate, and the like). As quaternary ammonium, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, Undecyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, heptadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium, octadecyltrimethylammonium, triethylmethylammoni , Tetraethylammonium, tetrapropylammonium, tetrabutylammonium, 1-methyl-1-azania-4-azabicyclo [2.2.2] octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmol Folinium, 1-methylpiperidinium, (2-hydroxypropyl) trimethylammonium, (2-hydroxypropyl) triethylammonium, (2-hydroxypropyl) tripropylammonium, (2-hydroxypropyl) tributylammonium, hydroxyethyltrimethyl Examples include ammonium and 2- (2-hydroxyethoxy) ethyltrimethylammonium.

  Among the amine catalysts (f2), preferred are amine catalysts containing a strong base having an acid dissociation constant (pKa) of 11 or more, and more preferred are 1,8-diazabicyclo [5.4.0]. -Undecene-7, 1,8-diazabicyclo [5.4.0] -undecene-7 weak acid salt (phenol salt, 2-ethylhexanoate, formate, etc.), 1,5-diazabicyclo [4.3. 0] -nonene-5,1,5-diazabicyclo [4.3.0] -nonene-5 weak acid salt (phenol salt, 2-ethylhexanoate, formate, etc.), tetramethylammonium weak acid salt (phenol Salt, 2-ethylhexanoate and formate, etc.), methyltriethylammonium weak acid salt (phenolic salt, 2-ethylhexanoate and formate etc.), tetraethylammonium weak acid salt (phenol) Le salt, 2-ethyl hexanoate and formic acid salts, etc.) and (2-hydroxypropyl) weak acid salt of trimethylammonium (phenol salt, 2-ethyl hexanoate, and salts of formic acid, etc.).

Examples of the chain extender (e) include water, diamines having 2 to 10 carbon atoms (such as ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, toluene diamine, and piperazine), and polyalkylene polyamines having 2 to 10 carbon atoms ( Diethylenetriamine, triethylenetetramine and tetraethylenepentamine), hydrazine or derivatives thereof (dibasic acid dihydrazide such as adipic acid dihydrazide) and amino alcohols having 2 to 10 carbon atoms (ethanolamine, diethanolamine, 2-amino-2- Methyl propanol, triethanolamine, etc.).
Among these, ethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine are preferable from the viewpoints of water resistance, chemical resistance, adhesion, and elongation at break of the film. A chain extender (e) may be used individually by 1 type, or may use 2 or more types together.

  The amount ratio of the polyol (a), the polyisocyanate (b), the compound (c) containing a hydrophilic group and an active hydrogen atom, the blocking agent (d) for the isocyanate group and the chain extender (e) is polyurethane resin aqueous From the viewpoint of storage stability of the dispersion (U), mechanical strength of the film, elongation at break, adhesion, chemical resistance and water resistance, (a) 30 to 90% by weight, (b) 8 to 40% by weight, (C) 1 to 10% by weight, (d) 1 to 10% by weight, and (e) 0.1 to 5% by weight are preferable.

  In the polyurethane resin (U) in the present invention, a reaction terminator can be used if necessary. As the reaction terminator, monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.) and monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, monobutylamine, dioxygen) Mono- or dialkylamines such as butylamine and monooctylamine; mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine). A reaction terminator may be used individually by 1 type, or may use 2 or more types together.

  The polyurethane resin (U) in the present invention can contain additives such as antioxidants, anti-coloring agents, weathering stabilizers, plasticizers, and mold release agents as necessary. The amount of these additives used is 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).

  The urethane group content in the polyurethane resin (U) in the present invention is preferably 0.5 to 2.0 mmol / g, more preferably 0.7 from the viewpoints of mechanical properties, elongation at break and adhesion of the resulting film. It is -1.8 mmol / g, Most preferably, it is 0.9-1.6 mmol / g.

Polyurethane by appropriately adjusting polyol (a), polyisocyanate (b), compound (c) containing hydrophilic group and active hydrogen atom, isocyanate group blocking agent (d) and chain extender (e) The urethane group content of the resin (U) can be within a desired range.
The urethane group content is calculated from the N atom content quantified by a nitrogen analyzer, the ratio of urethane groups and urea groups quantified by ¹ H-NMR, and allohanate group and burette group contents.

  The urea group content in the polyurethane resin (U) is 1.0 mmol / g or less based on the weight of (U) from the viewpoints of film-forming properties and water resistance, elongation at break and adhesion of the resulting film. Is more preferably 0.9 mmol / g or less, particularly preferably 0.8 mmol / g or less, and most preferably 0.7 mmol / g or less.

In order to bring the urea group content in the polyurethane resin (U) into a desired range, the amino group content, water content and isocyanate group content in the raw material of (U) may be appropriately adjusted.
The urea group content is calculated from the N atom content quantified by a nitrogen analyzer, the ratio of urethane group and urea group quantified by ¹ H-NMR, and the allohanate group and burette group contents.

  Mn of the polyurethane resin (U) in the present invention is preferably 3,000 or more, and more preferably from 4,000 to 500, from the viewpoint of mechanical properties, chemical resistance, impact resistance, and the like of the resulting film. 000, particularly preferably 5,000 to 300,000, most preferably 6,000 to 100,000. When Mn is 3,000 or more, the mechanical properties and chemical resistance of the coating are good.

  By appropriately adjusting the amount of the polyol (a), the polyisocyanate (b), the compound (c) containing a hydrophilic group and an active hydrogen atom, the isocyanate group blocking agent (d) and the chain extender (e). Further, the Mn of the polyurethane resin (U) can be set within a desired range.

For example, it can be measured under the following conditions by Mn gel permeation chromatography of the polyurethane resin (U) in the present invention.
Apparatus: “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: “Guardcolumn α” + “TSKgel α-M” [both manufactured by Tosoh Corporation]
Sample solution: 0.125% by weight dimethylformamide solution Injection amount: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene

The polyurethane resin (U) in the present invention preferably has a crosslinked structure in the molecule, and the swelling ratio of ethanol (U) at 25 ° C. (hereinafter referred to as ethanol swelling ratio) is the crosslinking of (U). It is a measure of quantity. The ethanol swelling ratio of (U) is preferably from 0.1 to 300%, more preferably from the weight of (U), from the viewpoints of film-forming properties and mechanical properties, chemical resistance and water resistance of the resulting film. It is 1 to 280% by weight, particularly preferably 5 to 250%. When the swelling ratio with respect to ethanol at 25 ° C. is 0.1% or more, the adhesion and breaking elongation of the resulting film are good, and when it is 300% or less, chemical resistance and water resistance are good.
The ethanol swelling ratio of the polyurethane resin (U) is calculated from the weight change before and after the urethane film is immersed in ethanol.

In order to make the ethanol swelling ratio in the polyurethane resin (U) within a desired range, the content of the trifunctional or higher constituent monomer of (U) may be appropriately adjusted. For example, specifically, the contents of the following [1] to [4] may be appropriately adjusted.
[1] Among the chain extenders (e), polyalkylene polyamines having 2 to 10 carbon atoms (such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine).
[2] A trihydric or higher aliphatic alcohol (trimethylolpropane, pentaerythritol, etc.) in the low molecular polyol (a2) having a chemical formula amount or less than Mn300.
[3] Polyisocyanate (b) having 3 or more isocyanate groups (such as nurate compound of hexamethylene diisocyanate).
[4] C2-C30 polyepoxy compound (1,6-hexanediol diglycidyl ether, trimethylolpropane polyglycidyl ether, etc.).

The glass transition point of the polyurethane resin (U) is preferably −90 to −30 ° C., more preferably −85 to −35 ° C., from the viewpoint of the adhesion and breaking elongation of the resulting film.
The glass transition point in the present invention is measured by “Rheogel E-4000” [manufactured by UBM Co., Ltd.].

  The volume average particle diameter (Dv) of the polyurethane resin (U) is 0.01 to 1 μm, preferably 0.02 to 0.7 μm, more preferably 0 from the viewpoint of dispersion stability of the polyurethane resin aqueous dispersion. 0.03 to 0.4 μm. When (Dv) is 0.01 μm or more, the handling property is good, and when it is 1 μm or less, the dispersion stability is good.

The volume average particle diameter (Dv) of (U) can be controlled by the hydrophilic group in (U), the amount of dispersant, and the type and operating conditions of the disperser used in the dispersion step. Therefore, in order to bring the volume average particle diameter (Dv) of (U) into a desired range, in the dispersion step, an apparatus selected from a rotary disperser, an ultrasonic disperser and a kneader described later is used. If necessary, the content of the hydrophilic group introduced into (U) and the amount of the dispersant (h) to be added may be adjusted as necessary.
The volume average particle diameter (Dv) is measured with a light scattering particle size distribution measuring apparatus.

<Polyurethane resin aqueous dispersion and production method thereof>
The aqueous polyurethane resin dispersion of the present invention is an aqueous polyurethane resin dispersion containing water and a polyurethane resin (U), and the polyurethane resin (U) is a polyester polyol (a12) and / or a polyether polyol (a11). A terminal isocyanate group containing a polyol (a) containing polyisocyanate (b), a compound (c) containing a hydrophilic group and an active hydrogen atom, and an isocyanate group blocking agent (d) as essential constituent monomers The polyurethane prepolymer (P) is preferably produced by dispersing (P) and the chain extender (e) after being dispersed in water.
In addition, (U) preferably has a crosslinked structure in the molecule, and by using a trifunctional or higher functional polyol (a), polyisocyanate (b) and / or chain extender (e). , (U) can introduce a crosslinked structure.
From the viewpoint of the dispersibility of (P) and the stability of the aqueous dispersion, the aqueous polyurethane resin dispersion in the present invention can be dispersed in water in the presence of a dispersant (h) as necessary.

  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 [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, etc.] and amine salt types [diethylaminoethyl stearate. Amide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

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

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

  The dispersant (h) is used before the urethanization reaction of the terminal isocyanate group-containing polyurethane prepolymer (P), during the urethanization reaction, after the urethanization reaction, before the water dispersion step of (P), during the water dispersion step or after water dispersion. However, from the viewpoint of the dispersibility of (P) and the stability of the aqueous dispersion, it is preferably added before or during the water dispersion step.

  The content of (h) is preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, particularly preferably 0.1 to 5% by weight, based on the weight of the polyurethane resin (U). .

  The aqueous polyurethane resin dispersion in the present invention contains organic solvents [ketone solvents (for example, acetone and methyl ethyl ketone), ester solvents (for example, ethyl acetate), ether solvents (for example, tetrahydrofuran), amide solvents (for example, N, N-dimethyl). Formamide and N-methylpyrrolidone), alcohol solvents (for example, isopropyl alcohol), aromatic hydrocarbon solvents (for example, toluene), and the like. An organic solvent may be used individually by 1 type, or may use 2 or more types together.

  The terminal isocyanate group-containing polyurethane prepolymer (P) in the present invention comprises a polyol (a), a polyisocyanate (b), a compound (c) containing a hydrophilic group and an active hydrogen atom, and an isocyanate group blocking agent (d). Can be obtained by reacting by heating in a heatable facility. For example, the raw material of (P) is charged in a container and uniformly stirred, and then heated without stirring in a heating dryer or heating furnace, a simple pressure reactor (autoclave), flask, uniaxial or biaxial kneading And a method of reacting by heating with stirring or kneading in a machine, a plast mill or a universal kneader. Among them, the method of heating and reacting while stirring or kneading increases the homogeneity of the obtained (P), and the mechanical properties, durability, chemical resistance, wear resistance, etc. of the obtained film are higher. This is preferable because it tends to be excellent.

  As a method of adding and reacting the isocyanate group blocking agent (d) at an arbitrary stage of producing the terminal isocyanate group-containing polyurethane prepolymer (P), (1) the total amount of (d) together with the polyol (a) in advance. Method of adding, (2) Method of adding the whole amount of (d) at the beginning of the polyurethane prepolymer formation reaction, (3) Adding part of (d) at the beginning of the polyurethane prepolymer reaction or during the reaction, and blocking at the end of the reaction Examples include a method of adding the remainder of the agent (d) and (4) a method of adding the entire amount of the blocking agent (d) after producing the polyurethane prepolymer. Among these, the method (4) is preferable from the viewpoint of the reproducibility of the reaction.

  The reaction temperature for producing the terminal isocyanate group-containing polyurethane prepolymer (P) is preferably 60 to 120 ° C, more preferably 60 to 110 ° C, from the viewpoint of suppressing the formation of the allophanate group and burette group of (P). And most preferably 60 to 100 ° C. The time for producing (P) can be appropriately selected depending on the equipment to be used, but is generally preferably 1 minute to 100 hours, more preferably 3 minutes to 30 hours, particularly preferably. 5 minutes to 20 hours. If it is this range, (P) which can fully exhibit the effect of the present invention will be obtained.

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

  As an apparatus for dispersing the terminal isocyanate group-containing polyurethane prepolymer (P) in water, any apparatus (A) having a dispersion ability can be used. From the viewpoint of temperature adjustment and dispersion ability, rotary dispersion mixing is possible. It is preferable to use an apparatus (A1), an ultrasonic disperser (A2) or a kneader (A3), and among them, (A1) having particularly excellent dispersibility is more preferable.

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

  Examples of the rotary dispersion mixing device (A1) include a mixing device having general stirring blades such as Max blend and a helical blade, TK homomixer [manufactured by Primics Co., Ltd.], Claremix [manufactured by M Technique Co., Ltd.] , Fillmix [Primics Co., Ltd.], Ultra Turrax [IKA Co., Ltd.], Ebara Milder [Ebara Seisakusho Co., Ltd.], Cavitron (Eurotech Co., Ltd.) and Biomixer [Nippon Seiki Co., Ltd.] The product etc. are illustrated.

  From the viewpoint of dispersion capability, the number of rotations when the terminal isocyanate group-containing polyurethane prepolymer (P) is dispersed using the rotary dispersion mixing device (A1) is preferably 10 to 30000 rpm, more preferably 20 to 20000 rpm, Especially preferably, it is 30-10000 rpm.

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

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

  From the viewpoint of dispersion capability, the frequency at which the terminal isocyanate group-containing polyurethane prepolymer (P) is dispersed using the ultrasonic dispersion device (A2) is preferably 1 to 100 kHz, more preferably 3 to 60 kHz. Particularly preferably, it is 10 to 30 kHz.

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

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

  The number of rotations when the terminal isocyanate group-containing polyurethane prepolymer (P) is dispersed using the kneader (A3) is preferably from 1 to 1000 rpm, more preferably from 3 to 500 rpm, particularly preferably from the viewpoint of dispersion ability. 10-200 rpm.

  The weight ratio of the terminal isocyanate group-containing polyurethane prepolymer (P) and water supplied to the dispersing apparatus (A) is appropriately selected depending on the resin component content of the target aqueous dispersion, but preferably (P) / Water = 10/2 to 10/100, more preferably 10/5 to 10/50.

  In addition, the time for treating (P) and water in the dispersion apparatus (A) is preferably 10 seconds to 10 hours, more preferably 1 minute to more preferably from the viewpoint of preventing decomposition or deterioration of the dispersion (P). 3 hours, most preferably 10-60 minutes.

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

  The device for reacting the chain extender (e) after dispersing the terminal isocyanate group-containing polyurethane prepolymer (P) is not particularly limited, but the reaction may be carried out while mixing with the dispersion device (A) and a static mixer. preferable.

  The solid content concentration (content of components other than volatile components) of the polyurethane resin aqueous dispersion obtained by the production method of the present invention is preferably 20 to 65% by weight from the viewpoint of easy handling of the aqueous dispersion. Preferably it is 25 to 55% by weight. The solid concentration was about 1 g of 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.

The viscosity of the aqueous polyurethane resin dispersion obtained by the production method of the present invention is preferably 10 to 100,000 mPa · s, more preferably 10 to 5,000 mPa · s. The viscosity can be measured at a constant temperature of 25 ° C. using a BL type viscometer.
The pH of the aqueous polyurethane resin dispersion obtained by the production method of the present invention is preferably 2 to 12, more preferably 4 to 10. The pH can be measured at 25 ° C. with pH Meter M-12 [manufactured by Horiba, Ltd.].

  The aqueous polyurethane resin dispersion of the present invention comprises an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a binder composition for pigment printing, a binder composition for nonwoven fabrics, a sizing agent composition for reinforcing fibers, Antibacterial agent binder composition and artificial leather / synthetic leather raw material composition, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition, antifouling coating composition, etc.), aqueous paper treatment composition, It can be used for water-based ink compositions and the like.

  When used in these applications, other resins, crosslinking agents and additives (catalysts, pigments, pigment dispersants, viscosity modifiers, antifoaming agents, leveling agents, antiseptics, deterioration inhibitors, stabilizers, if necessary. 1 type or 2 types or more can be added.

  Examples of other resins include water-dispersible or water-soluble polyurethane resins other than the polyurethane resin (U) in the present invention, polyacrylic resins, and polyester resins. Other resins are capable of reacting with isocyanate groups from the viewpoint of reacting with the isocyanate groups formed by dissociation of the blocking agent (d) of the isocyanate group (U) during drying, and forming a tough film. It is preferable that the active hydrogen group is contained.

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.

Viscosity modifiers include thickeners such as inorganic viscosity modifiers (such as sodium silicate and bentonite), cellulose-based 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, hindered amine, hydrazine, phosphorus, benzophenone or benzotriazole degradation inhibitors and stabilizers. .
Examples of the antifreezing agent include ethylene glycol and propylene glycol.
The content of the viscosity modifier, antifoaming agent, antiseptic, deterioration preventing agent, stabilizer and antifreezing agent is preferably 5% by weight or less, respectively, based on the weight of each composition in the application used, Preferably it is 3 weight% or less.

  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>
A simple pressure reactor equipped with a stirrer and a heating device is used in the types and amounts of polyol (a), polyisocyanate (b), compound (c) containing a hydrophilic group and an active hydrogen atom, and organic as shown in Table 1. Polyurethane prepolymer prepared by adding a solvent and stirring at 85 ° C. for 12 hours to carry out a urethanization reaction, and then adding the type and amount of isocyanate group blocking agent (d) shown in Table 1 and reacting at 85 ° C. for 3 hours. An organic solvent solution of (P-1) was produced.
According to the formulation shown in Table 2, 7.6 parts of triethylamine as a neutralizing agent and 174.3 parts of acetone as an organic solvent were added to 400 parts of the organic solvent solution of the obtained polyurethane prepolymer (P-1), and uniform. Then, 573.5 parts of ion exchange water was added with stirring at 200 rpm to disperse (P-1). To the obtained dispersion was added 23.3 parts of a 10% by weight diethylenetriamine aqueous solution as a chain extender, and the organic solvent was distilled off at 65 ° C. for 8 hours under reduced pressure, to obtain an aqueous polyurethane resin dispersion (Q-1). Got.

<Examples 2-8 and Comparative Examples 1-4>
Using each raw material shown in Table 1, polyurethane prepolymers (P-2) to (P-8) and comparative polyurethane prepolymers (P′-1) to (P′−) in the same manner as in Example 1. 4) The organic solvent solution of 4) was produced, and the polyurethane resin aqueous dispersions (Q-2) to (Q-8) and the polyurethane resin for comparison were prepared in the same manner as in Example 1 using the raw materials shown in Table 2. Aqueous dispersions (Q′-1) to (Q′-4) were obtained.
In Example 3, after preparing an organic solvent solution of the polyurethane prepolymer, 1,8-diazabicyclo [5,4,0] -undecene-7 as a dissociation catalyst for the isocyanate group blocking agent (d) was used. A solution prepared by homogenizing 0.04 part was used as an organic solvent solution of polyurethane prepolymer (P-3).

In addition, the composition of the raw materials represented by trade names in Table 1 is as follows.
PTMG2000: Poly (oxytetramethylene) glycol with Mn = 2,000 [Mitsubishi Chemical Corporation]
PTMG3000: Poly (oxytetramethylene) glycol with Mn = 3,000 [Mitsubishi Chemical Corporation]
PTGL2000: Modified poly (oxytetramethylene) glycol with Mn = 2,000 [made by Hodogaya Chemical Co., Ltd.]
Kuraray polyol P-2010: Poly-3-methyl-1,5-pentaneadipate diol with Mn = 2,000 [manufactured by Kuraray Co., Ltd.]
Kuraray polyol P-6010: poly-3-methyl-1,5-pentaneadipate diol with Mn = 6,000 [manufactured by Kuraray Co., Ltd.]
Nipponran 980R: Polyhexamethylene carbonate diol with Mn = 2,000 [manufactured by Nippon Polyurethane Industry Co., Ltd.]

  Polyurethane resin aqueous dispersions (Q-1) to (Q-8) obtained in Examples 1 to 8 and Comparative Examples 1 to 4 and comparative polyurethane resin aqueous dispersions (Q′-1) to (Q ′) Table 3 shows various physical property values and evaluation results of -4). In addition, the measuring method and evaluation method of various physical property values in the present invention are as follows.

[Measurement methods for various physical properties]
<Urethane group content and urea group content>
The urethane group content and urea group content of the polyurethane resin are the N atom content determined by a nitrogen analyzer [ANTEK7000 (manufactured by Antec)], the ratio of urethane group and urea group determined by ¹ H-NMR, and the later-described allophanate. Calculated from group and burette group content. ^{The 1} H-NMR measurement is carried out by the method described in “Structural study of polyurethane resin by NMR: Takeda Laboratory Report 34 (2), 224-323 (1975)”. That is, when ¹ H-NMR was measured and aliphatic isocyanate was used, the urea group was calculated from the ratio of the integral amount of hydrogen derived from a urea group near a chemical shift of 6 ppm and the integral amount of hydrogen derived from a urethane group near a chemical shift of 7 ppm. And the urethane group content is calculated from the weight ratio, the N atom content, the allophanate group and the burette group content. When aromatic isocyanate is used, the weight ratio of urea group and urethane group is calculated from the ratio of the integral amount of hydrogen derived from urea groups near the chemical shift of 8 ppm and the integral amount of hydrogen derived from urethane groups near the chemical shift of 9 ppm, The urea group content is calculated from the weight ratio and the N atom content.

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

<Ethanol swelling rate>
The ethanol swelling ratio of the polyurethane resin (U) was measured by the method described below.
Pour a polyurethane resin aqueous dispersion in an amount of 200 μm into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, and after drying at room temperature for 12 hours, The film obtained by heating and drying for 3 hours was cut into 2 cm × 8 cm to prepare test pieces, and the weight (W0) was measured with an electronic balance capable of weighing up to 4 digits after the decimal point. The test piece was immersed in ethanol, taken out after being immersed for 24 hours at 25 ° C., and the weight (W1) was measured after lightly wiping off the ethanol adhering to the surface. The ethanol swelling ratio was calculated by the following formula using the obtained numerical values.
Ethanol swelling rate (%) = 100 × [(W1) − (W0)] / (W0)
W0: Weight of urethane film before ethanol immersion W1: Weight of urethane film after ethanol immersion

<Method for measuring glass transition point of polyurethane resin>
The glass transition point was measured by “Rheogel E-4000” [manufactured by UBM Co., Ltd.].

[Evaluation method]
<Elongation at break of polyurethane resin>
Pour a polyurethane resin aqueous dispersion in an amount of 200 μm into a polypropylene mold measuring 10 cm long × 20 cm wide × 1 cm deep, dried at room temperature for 12 hours, and then at 105 ° C. with a circulating dryer. 4. The film according to JIS K7311 using a film obtained by heating and drying for 3 hours. Measurement was performed based on a tensile test, and the elongation at break was calculated by the following formula using the obtained numerical values.
Elongation at break (%) = 100 × [(E1) − (E0)] / (E0)
E0: Length of film before tension E1: Length of film at break

<Adhesiveness of polyurethane resin to electrodeposited surface>
A polyurethane resin aqueous dispersion was applied to a commercially available cationic electrodeposition coating test piece with a thickness of 20 μm and dried at 140 ° C. for 15 minutes to prepare a coating film. The coating surface was cut at 6 mm in length and width at 1 mm intervals, and then a peel test was performed with cello tape (registered trademark) to examine the number of 1 mm square coating films remaining. The indication shows the number of residuals in the numerator and the number of 1 mm square coating films before the peel test in the denominator. This test was carried out with a polyurethane resin aqueous dispersion immediately after production and a polyurethane resin aqueous dispersion after storage at 40 ° C. for 3 months. The smaller the difference in test results immediately after production and after storage for 3 months at 40 ° C., the better the storage stability of the blocked isocyanate groups.
<Adhesiveness of polyurethane resin to OPP film>
A polyurethane resin aqueous dispersion was applied to a commercially available OPP film with a thickness of 20 μm and dried at 140 ° C. for 15 minutes to prepare a coating film. Using this coating film, a peeling test was performed with cello tape (registered trademark), and the area of the peeled portion was evaluated according to the following evaluation criteria. This test was carried out with a polyurethane resin aqueous dispersion immediately after production and a polyurethane resin aqueous dispersion after storage at 40 ° C. for 3 months. The smaller the difference in test results immediately after production and after storage for 3 months at 40 ° C., the better the storage stability of the blocked isocyanate groups.
A: The peeled area is 0%.
A: The peeled area is 1 to 10%.
(Triangle | delta): A peeling area is 11 to 50%.
X: Peeling area is 51 to 100%.

<Chemical resistance of aqueous polyurethane resin dispersion>
Pour a polyurethane resin aqueous dispersion in an amount of 200 μm into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, and after drying at room temperature for 12 hours, use a circulating dryer at 140 ° C. The film obtained by heating and drying for 1 hour was cut into 2 cm × 8 cm to prepare test pieces, and the weight (W0) was measured with an electronic balance capable of weighing up to 4 digits after the decimal point. The test piece was immersed in dimethylformamide, immersed for 1 hour at 25 ° C., taken out, and dimethylformamide adhering to the surface was gently wiped, and the weight (W1) was measured. Using the obtained numerical values, the swelling ratio was calculated by the following formula and evaluated according to the following evaluation criteria.
Swelling ratio (%) = 100 × [(W1) − (W0)] / (W0)
W0: Weight of urethane film before immersion in dimethylformamide W1: Weight of urethane film after immersion in dimethylformamide O: Swelling ratio is 0 to 100%.
X: The swelling rate is 101% or more.

<Water resistance of aqueous polyurethane resin dispersion>
Pour a polyurethane resin aqueous dispersion in an amount of 200 μm into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, and after drying at room temperature for 12 hours, use a circulating dryer at 140 ° C. The film obtained by heating and drying for 1 hour was cut into 2 cm × 8 cm to prepare test pieces, and the weight (W0) was measured with an electronic balance capable of weighing up to 4 digits after the decimal point. The test piece was immersed in water, taken out after being immersed at 50 ° C. for 24 hours, and the weight (W1) was measured after lightly wiping off the water adhering to the surface. Using the obtained numerical values, the swelling ratio was calculated by the following formula and evaluated according to the following evaluation criteria.
Swelling ratio (%) = 100 × [(W1) − (W0)] / (W0)
W0: Weight of urethane film before water immersion W1: Weight of urethane film after water immersion ○: Swell ratio is 0 to 50%.
X: The swelling rate is 51% or more.

  The aqueous polyurethane resin dispersion of the present invention comprises an aqueous coating composition, an aqueous adhesive composition, an aqueous fiber processing agent composition (a binder composition for pigment printing, a binder composition for nonwoven fabrics, a sizing agent composition for reinforcing fibers, Antibacterial agent binder composition and artificial leather / synthetic leather raw material composition, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition, antifouling coating composition, etc.), aqueous paper treatment composition, It can be suitably used for an aqueous ink composition and the like.

Claims (7)

  A polyurethane resin aqueous dispersion containing water and a polyurethane resin (U), wherein the polyurethane resin (U) is a polyol (a) containing a polyester polyol and / or a polyether polyol, a polyisocyanate (b), A terminal isocyanate group-containing polyurethane prepolymer (P) having a hydrophilic group and an active hydrogen atom-containing compound (c) and an isocyanate group blocking agent (d) as essential constituent monomers and a chain extender (e); And an aqueous polyurethane resin dispersion in which the content of carbonate bonds in the polyurethane resin (U) is less than 8% by weight based on the weight of the polyurethane resin (U).   The polyurethane resin aqueous dispersion according to claim 1, wherein the swelling ratio of the polyurethane resin (U) by ethanol at 25 ° C is 0.1 to 300% based on the weight of the (U).   The aqueous polyurethane resin dispersion according to claim 1 or 2, wherein the content of hydrophilic groups in the polyurethane resin (U) is 0.32 to 3.2% by weight.   The polyurethane resin aqueous solution according to any one of claims 1 to 3, wherein the polyurethane group content in the polyurethane resin (U) is 0.5 to 2.0 mmol / g based on the weight of the polyurethane resin (U). Dispersion.   The aqueous polyurethane resin dispersion according to any one of claims 1 to 4, wherein a content of urea groups in the polyurethane resin (U) is 1.0 mmol / g or less based on the weight of the polyurethane resin (U).   The blocking agent (d) has an oxime having 1 to 15 carbon atoms, a secondary amine having 2 to 15 carbon atoms, an active methylene compound, and an imino group and a nitrogen-carbon double bond as a structural unit of the ring. The aqueous polyurethane resin dispersion according to any one of claims 1 to 5, which is at least one blocking agent selected from the group consisting of membered compounds.   The polyurethane resin aqueous dispersion according to any one of claims 1 to 6, wherein the polyurethane resin (U) has a glass transition point of -90 to -30 ° C.