JP2017165884A - Polyurethane resin water dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin water dispersion which has good dispersion stability and excellent water resistance.SOLUTION: There is provided a polyurethane resin water dispersion containing water and a polyurethane resin (U), where (U) is a polyurethane resin obtained by neutralizing or quaternizing (α) or (β) of the polyurethane resin containing diol (a), polyisocyanate (b) and a compound (c) having a group (γ) having an acid group (α) or an amino group (β) and an active hydrogen atom other than (α) and (β), as essential constituent monomers, where the total content of (α), neutralized acid group (α1) and (β), neutralized amino group (β1) and quaternized amino group (β2) is 0.1-0.8 mmol/g with respect to the weight of (U), a neutralization index represented by expression (1) or (2) is 30-90%, and a volume average particle size of the polyurethane resin particles in the polyurethane resin water dispersion is 50-600 nm.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous polyurethane resin dispersion and a method for producing the same.

  Since the polyurethane resin water dispersion has excellent performance such as mechanical properties, durability, chemical resistance and abrasion resistance of the film obtained by drying, as a highly functional water dispersion, paint, adhesive, It is used in textile processing agents, paper processing agents, inks, etc., and is expected to become increasingly important from the viewpoint of environmental conservation, resource saving and safety. Conventionally, solvent-based urethanes dissolved in organic solvents have been used in these applications. However, due to the disadvantages of organic solvent toxicity, fire hazard, environmental pollution, etc., in recent years, solvent-based urethanes have been replaced with polyurethane resin water. The switch to the dispersion is spurring.

Unlike the solvent-based urethane, the polyurethane resin aqueous dispersion enables emulsification and dispersion in water by imparting hydrophilicity to the resin. This polyurethane resin aqueous dispersion may be used alone, but in many cases, it is mixed with other resin emulsions, additives, solvents and the like. At that time, aggregation of urethane resin particles may occur due to pH change or interaction with other components in the mixing process, and the stability and performance of the mixture will be significantly reduced, so the materials to be mixed with the polyurethane resin aqueous dispersion are limited. There is a problem that versatility is low as compared with solvent-based urethane, such as that the polyurethane resin aqueous dispersion itself cannot be used.

For this reason, a nonionic urethane resin aqueous dispersion with improved mixing stability of urethane resin (see Patent Document 1) has been proposed. There was a problem that the adhesiveness decreased due to bleeding out of the active agent.

JP 2005-336405 A

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

As a result of intensive studies, the present inventors have found an aqueous polyurethane resin dispersion that can solve the above-described problems. That is, the present invention is a polyurethane resin aqueous dispersion containing water and a polyurethane resin (U), wherein the polyurethane resin (U) comprises a diol (a), a polyisocyanate (b), and an acid group (α). Or an acid group (c) having an active hydrogen atom that is neither an amino group (β) nor an acid group (α) nor an amino group (β) (c) as an essential constituent monomer. α) or an amino group (β) is a neutralized or quaternized polyurethane resin,
The total content of acid group (α), neutralized acid group (α1), amino group (β), neutralized amino group (β1) and quaternized amino group (β2) is (U) 0.1 to 0.8 mmol / g based on the weight of
And the neutralization rate represented by the following formula (1) is 30 to 90%, or the neutralization and quaternization rate represented by the following formula (2) is 30 to 90%, and the polyurethane A polyurethane resin water dispersion in which the volume average particle diameter of polyurethane resin particles in the resin water dispersion is 50 to 600 nm; an aqueous paint containing the polyurethane resin water dispersion; an aqueous adhesive containing the polyurethane resin water dispersion An aqueous fiber processing agent containing the polyurethane resin aqueous dispersion; a method for producing the polyurethane resin aqueous dispersion.

The polyurethane resin aqueous dispersion of the present invention has the following characteristics.
(1) Good dispersion stability in water.
(2) A film having very excellent water resistance can be obtained.

<Polyurethane resin (U)>

The polyurethane resin (U) contained in the polyurethane resin aqueous dispersion of the present invention satisfies all the following conditions (1) to (3).
(1) (U) was quaternized with (U) acid group (α), neutralized acid group (α1), amino group (β), neutralized amino group (β1) The total content of amino groups (β2) (hereinafter sometimes referred to as content x) is 0.1 to 0.8 mmol / g, preferably 0.12 to 0, based on the weight of (U). .75 mmol / g, more preferably 0.14 to 0.7 mmol / g. When the content x is less than 0.1 mmol / g, there is a concern that the stability of the urethane particles in water is reduced and the particles are aggregated. When the content x exceeds 0.8 mmol / g, the water resistance may be deteriorated.

Here, the polyurethane resin (U) is polyol (a), polyisocyanate (b), and active hydrogen that is neither an acid group (α) or an amino group (β) nor an acid group (α) nor an amino group (β). It is a polyurethane resin comprising the compound (c) having an atom-containing group (γ) as an essential constituent monomer, and the acid group (α) or amino group (β) of (U) is neutralized or quaternized. A part of the compound (d) is neutralized or quaternized.
Examples of the acid group (α) include a carboxyl group, a sulfonic acid group, and a sulfamic acid group.
A tertiary amino group is mentioned as an amino group ((beta)).
Examples of the group (γ) include a hydroxyl group.

The total content of acid groups (α) and neutralized acid groups (α1) is determined by calculating the acid value of the polyurethane resin by the following method and calculating the acid group content (mmol / g) by the following formula. Can do.
Acid group content (mmol / g) = (acid value) /56.1
<Acid value>
A predetermined amount of polyurethane resin is dissolved in 50 ml of dimethylformamide (hereinafter referred to as DMF) in a 100 ml flask, and titrated with a 0.1 mol / l potassium hydroxide / methyl alcohol titration solution using a phenolphthalein indicator ( The end point is the point where the color of the indicator has changed from transparent to slightly red) The number of titration ml is read, and the acid value is calculated by the following formula.
Acid value = 5.61 × a × f / S
a: 0.1 ml / l titration ml of potassium hydroxide / methyl alcohol titration solution
f: Potency of 0.1 mol / l potassium hydroxide / methyl alcohol titration solution.
S: Amount of polyurethane resin collected (g)
The amine value derived from the neutralizing agent (d1) and the content (%) of the polyurethane resin (U) in the emulsion were determined by the following method, and the content of the acid group (α1) neutralized by the following formula was determined. Can be calculated.
Neutralized acid group (α1) content (mmol / g) = (amine value derived from neutralizer (d1)) × 100 / {56.1 × (solid content of urethane emulsion (%))}

(2) The neutralization rate represented by the above formula (1) is 30 to 90%, or the neutralization and quaternization rate represented by the above formula (2) is 30 to 90% (below) The neutralization rate, or the neutralization and quaternization rate may be described as the neutralization rate etc. y) is 30 to 90%, preferably 40 to 85%, more preferably 45 to 80. %. When the neutralization rate or the like is less than 30%, the dispersion stability of the urethane emulsion is deteriorated. When the neutralization rate or the like exceeds 90%, the water resistance of the urethane resin film obtained by drying the urethane emulsion is deteriorated. .

(3) In the present invention, the volume average particle diameter (Dv) of the polyurethane resin particles of the polyurethane resin (U) in the polyurethane resin aqueous dispersion is 50 to 600 nm, and the dispersion stability and blending of the polyurethane resin aqueous dispersion From the viewpoint of stability, the thickness is preferably 60 to 500 nm, more preferably 70 to 400 nm. When (Dv) is less than 50 nm, the blending stability of the polyurethane resin (U) is deteriorated, and when it exceeds 600 nm, the dispersion stability of the urethane emulsion is lowered.

  The polyurethane resin (U) comprises polyol (a), polyisocyanate (b), and active hydrogen atoms that are neither acid groups (α) or amino groups (β) nor acid groups (α) nor amino groups (β). It is obtained by neutralizing or quaternizing a polyurethane resin comprising a compound (c) having a group having an essential constituent monomer with a compound (d) for neutralizing or quaternizing an acid group or amino group. If necessary, it can be obtained by reacting a chain extender (e) and a reaction terminator (f).

  Polyol (a), polyisocyanate (b), compound (c), acid group or amino group neutralization or quaternizing agent (d), and optionally used chain extender (e) and reaction terminator (f) ) Is adjusted appropriately, the content of the neutralized or quaternized hydrophilic group of the polyurethane resin (U) and the content of the neutralized or quaternized hydrophilic group can be within a desired range. .

The volume average particle diameter (Dv) of (U) is determined by the amount of hydrophilic groups in (U), the amount of neutralized or quaternized hydrophilic groups, and the amount of dispersant. Therefore, in order to bring the volume average particle diameter (Dv) of (U) into a desired range, the content of the hydrophilic group introduced into (U), its neutralization rate or quaternization rate, and What is necessary is just to adjust suitably the quantity of the dispersing agent (h) added as needed.
The volume average particle diameter (Dv) is measured with a light scattering particle size distribution measuring apparatus.
Each component will be described below.

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

  Of the polyols described below, only one kind of polyol (a) may be used, or two or more kinds may be used in combination.

  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 of Mn = 3,000, manufactured by Mitsubishi Chemical Co., Ltd.], PTGL3000 [modified PTMG of Mn = 3,000, manufactured by Hodogaya Chemical Co., Ltd.], and Sun Nickxdiol GP-3000 [polypropylene ether triol with Mn = 3,000, manufactured by Sanyo Chemical Industries, Ltd.] and the like.

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

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

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

The condensed polyester polyol is a polyester polyol of a low molecular weight (less than Mn300) polyhydric alcohol and a polyvalent carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.
Low molecular weight polyhydric alcohols include dihydric to octahydric or higher aliphatic polyhydric alcohols less than Mn300 and alkylene oxides of dihydric to octavalent or higher phenols less than Mn300 (EO, PO, 1, 2). -, 1,3-, 2,3- or 1,4-butylene oxide and the like, hereinafter abbreviated as AO) and low molar adducts can be used.
Among the low molecular weight polyhydric alcohols that can be used in the condensed polyester polyol, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexane glycol, bisphenol A EO or PO low mole Adducts and combinations thereof.

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

  Specific examples of the condensed polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene Hexamethylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene seba Kate diol and polyneopentyl terephthalate diol It is.

  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], And Sanester 2620 [polyethylene adipate diol with Mn = 2,000, manufactured by Sanyo Chemical Industries, Ltd.].

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 Kuraray polyol C-3090 [poly (3-methyl- with Mn = 3,000). 5-pentanediol / hexamethylene) carbonate diol], T4672 [poly (tetramethylene / hexamethylene) carbonate diol of Mn = 2,000, manufactured by Asahi Kasei Chemicals Corporation], 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.

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

  An oxyethylene group can be introduce | transduced into a polyurethane resin (U) by using PEG as an essential component among the said polyol (a). The oxyethylene group content introduced into the polyurethane resin (U) is preferably 0.8 mmol / g to 10.0 mmol / g, more preferably 1 from the viewpoint of water resistance and blending stability of the polyurethane resin (U). 0.0 to 9.0 mmol / g, particularly preferably 1.5 to 8.0 mmol / g. When the polyoxyethylene group content is less than 0.8 mmol / g, the blending stability may deteriorate, and 10.0 mmol. If it exceeds g, the water resistance deteriorates.

In the present invention, the polyurethane resin (U) further contains a polyol (k) having three or more hydroxyl groups as an essential constituent monomer, and the weight of the polyol (k) is 0.1 to 0.1% by weight of the polyol (a). It can be 4.0 wt%.
Polyol (k) is preferable because it can form a crosslinked structure in the polyurethane resin particles, and can obtain the effects of improving the water resistance and chemical resistance of the urethane film.

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

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

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

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

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

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

The compound (c) having an acid group (α) and / or an amino group (β) and a group (γ) having an active hydrogen atom which is neither an acid group (α) nor an amino group (β) includes an acid group and a group. And a compound (c1) containing (γ) and a compound (c2) containing an amino group and a group (γ).
(C1) includes, for example, a carboxyl group as an acid group and 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 (for example, glycine, alanine and valine)], containing a sulfonic acid group as an acid group, and having 2 to 16 carbon atoms Compound [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and sulfoisophthalic acid di (ethylene glycol) ester and the like], a compound having a sulfamic acid group as an acid group and having 2 to 10 carbon atoms [ N, N-bis (2-hydroxylethyl) sulfamic acid and the like].

  Among (c1), 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid are preferred from the viewpoint of the resin physical properties of the resulting film and the dispersion stability of the polyurethane resin aqueous dispersion.

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

The compound (d) that neutralizes or quaternizes the compound (c) includes a neutralizer (d1) of the compound (c1) and a neutralization or quaternary of the compound (c2) containing an amino group and an active hydrogen atom. An agent (d2) may be mentioned.

Examples of (d1) 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.

  (D1) is preferably a compound having a high vapor pressure at 25 ° C. from the viewpoint of the drying property of the resulting polyurethane resin aqueous dispersion and the water resistance of the resulting film. From such a viewpoint, as (d1), ammonia or an amine compound having 1 to 20 carbon atoms is preferable, and ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine and dimethylethylamine are particularly preferable.

  Examples of (d2) include C1-C10 monocarboxylic acids (for example, formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, benzyl chloride, and the like.

  (D1) and (d2) may be 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. From the viewpoint of the stability of the resin and the stability of the aqueous dispersion, it is preferably added before or during the aqueous dispersion process.

  The amount of (c) used is such that the content of the hydrophilic group in (U) is usually 0.1 to 0.8 mmol / g, preferably 0.12 to 0.75 mmol / g, based on the weight of (U). g, more preferably 0.15 to 0.7 mmol / g.

  The amount of (d) used is adjusted so that the neutralization rate or quaternization rate represented by the above formula (1) or (2) is 30 to 90%.

Examples of the chain extender (e) include water, diamines having 2 to 10 carbon atoms (for example, ethylene diamine, propylene diamine, hexamethylene diamine, isophorone diamine, toluene diamine and piperazine), and polyalkylene polyamines having 2 to 10 carbon atoms ( For example, diethylenetriamine and triethylenetetramine), hydrazine or a derivative thereof (dibasic acid dihydrazide such as adipic acid dihydrazide), polyepoxy compound having 2 to 30 carbon atoms (for example, 1,6-hexanediol diglycidyl ether, trimethylolpropane poly) Glycidyl ether and the like) and amino alcohols having 2 to 10 carbon atoms (for example, ethanolamine, diethanolamine, 2-amino-2-methylpropanol, and triethanolamine).
In the present invention, by using a compound having three or more functional groups capable of reacting with isocyanate groups in the aqueous dispersion of polyurethane resin particles, a crosslinked structure can be formed in the polyurethane resin particles, and the water resistance of the urethane film is increased. The effect of improving the chemical resistance and chemical resistance can be obtained.
Of these, ethylenediamine and diethylenetriamine are preferred.

  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).

  (E) and (f) may be used alone or in combination of two or more.

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

<Polyurethane resin aqueous dispersion, production method thereof>
The aqueous dispersion of the polyurethane resin (U) in the present invention comprises a polyurethane resin (U) having an acid group (α) or amino group (β) of 0.1 to 0.8 mmol / g, represented by the above formula (1) or ( 2) The neutralized or quaternized polyurethane resin (U1) obtained by neutralization or quaternization so that the neutralization rate or quaternization rate represented by 2) is 30 to 90% is dispersed in water, A polyurethane resin aqueous dispersion in which the volume average particle diameter of particles in the polyurethane resin aqueous dispersion is 50 to 600 nm is obtained.

In the present invention, the aqueous dispersion of the polyurethane resin (U) includes the polyol (a), the polyisocyanate (b), the compound (c), and the compound (d for neutralizing or quaternizing the acid group or amino group). ) As an essential component, and if necessary, it can be obtained by reacting the chain extender (e) and the reaction terminator (f) through the steps described below.
(1) Polyol (a), polyisocyanate (b), and an acid group (α) and / or an amino group (β) and an active hydrogen atom other than the acid group (α) and amino group (β) (c ) As necessary in the presence of an organic solvent to synthesize a prepolymer having an isocyanate group at the molecular end.
(2) A step of adding the compound (d) to the prepolymer obtained in the step (1) to neutralize or quaternize it.
(3) A step of dispersing the compound obtained in the step (2) in water and, if necessary, adding a chain extender (e) and a reaction terminator (f).
(4) A step of distilling off the organic solvent from the aqueous dispersion obtained in the step (3) if necessary.

In addition, (U) may have a crosslinked structure in the molecule. In order to introduce a crosslinked structure into (U), polyol (a), polyisocyanate (b) and / or chain extender (e) It is possible to introduce a crosslinked structure in (U) by using a trifunctional or higher polyfunctional monomer.
In addition, (U) may have a nonionic hydrophilic group from the viewpoint of dispersion stability in water. In order to introduce a nonionic hydrophilic group into (U), the polyol (a) By using at least one compound having an internal polyoxyethylene group, it is possible to introduce a nonionic hydrophilic group into (U).
From the viewpoint of the dispersibility of (U) and the stability of the aqueous dispersion, the polyurethane resin aqueous dispersion in the present invention can be dispersed in water in the presence of a dispersant (g) as necessary.

  As the dispersing agent (g), nonionic surfactant (g1), anionic surfactant (g2), cationic surfactant (g3), amphoteric surfactant (g4) and other emulsifying dispersant (g5) ). (G) may be used alone or in combination of two or more.

  Examples of (g1) 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 (g2) 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 and the like]; 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 (g3) include quaternary ammonium salt type [stearyl trimethyl ammonium chloride, behenyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, ethyl lanolin sulfate fatty acid aminopropylethyl dimethyl ammonium, etc.] and amine salt type [diethylaminoethyl stearate. Amide lactate, dilaurylamine hydrochloride, oleylamine lactate, etc.].

  Examples of (g4) 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 (g5) 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 (g) is used before the urethanization reaction of the urethane resin (U), during the urethanization reaction, after the urethanization reaction, before the water dispersion step of (U), during the water dispersion step, or after water dispersion. Although it may be added, it is preferably added before or during the water dispersion step from the viewpoint of the dispersibility of (U) and the stability of the water dispersion.

The content of (g) is usually 0.01 to 20% by weight, preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, based on the weight of the polyurethane resin (U).
When (U) is a polyurethane resin having a hydrophilic group, the total content of (c) and (g) based on the weight of (U) is usually 0.01 to 20% by weight. The content is preferably 0.1 to 15% by weight, more preferably 0.6 to 10% by weight.

  The polyurethane resin aqueous dispersion in the present invention contains an organic solvent [a ketone solvent (for example, acetone and methyl ethyl ketone), an ester solvent (for example, ethyl acetate), an ether solvent (for example, tetrahydrofuran), an amide solvent (for example, N, N-dimethyl). Formamide and N-methylpyrrolidone), alcohol solvents (for example, isopropyl alcohol), aromatic hydrocarbon solvents (for example, toluene), and the like.

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

  When the polyurethane resin (U) is dispersed in water, it is selected from pH adjusters, antifoaming agents, antifoaming agents, antioxidants, anti-coloring agents, plasticizers, mold release agents, and the like as necessary. One or more additives can be added. Moreover, you may perform solvent removal, concentration, dilution, etc. after dispersion | distribution as needed.

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

The viscosity of the polyurethane resin aqueous dispersion obtained by the production method of the present invention is preferably 1 to 100,000 mPa · s, more preferably 5 to 5,000 mPa · s. The viscosity can be measured at a constant temperature of 25 ° C. using a BL type viscometer.
The pH of the polyurethane resin aqueous dispersion obtained by the production method of the present invention is preferably 2 to 12, more preferably 4 to 10. The pH can be measured at 25 ° C. with pH Meter M-12 [manufactured by Horiba, Ltd.].

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

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

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

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

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

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

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

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

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

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

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

  A solvent may be further added to the water-based paint for the purpose of improving the appearance of the coating film after drying. Examples of the solvent to be added include monohydric alcohols having 1 to 20 carbon atoms (such as methanol, ethanol and propanol), glycols having 1 to 20 carbon atoms (such as ethylene glycol, propylene glycol and diethylene glycol), and 3 having 1 to 20 carbon atoms. Alcohols having higher valences (such as glycerin) and cellosolves having 1 to 20 carbon atoms (such as methyl and ethyl cellosolve) can be used. The content of the solvent to be added is preferably 20% by weight or less, more preferably 15% by weight or less, based on the weight of the aqueous paint.

The water-based paint using the polyurethane resin aqueous dispersion of the present invention is produced by mixing and stirring the polyurethane resin aqueous dispersion of the present invention and each of the components described above. When mixing, all the components may be mixed at the same time, or each component may be added stepwise and mixed.
The solid content concentration of the water-based paint is preferably 10 to 70% by weight, more preferably 15 to 60% by weight.

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

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

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

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

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

<Example 1>
The raw materials listed in Table 1 were 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. An acetone solution of urethane prepolymer (P-1) was prepared. Manufactured. The isocyanate content per solid in the acetone solution of the urethane prepolymer was 0.77 mmol / g. 460.69 parts of an acetone solution of the urethane prepolymer obtained in a simple pressure reactor equipped with a stirrer and a heating reaction apparatus was added, and 2.45 parts of triethylamine (neutralizing agent) was added while stirring at 40 ° C., and 60 rpm For 30 minutes, and after emulsification by gradually adding 346.98 parts of water while maintaining the temperature at 30 ° C. and stirring at 100 rpm, add 4.55 parts of diethylenetriamine which is a chain extender, and reduce the pressure. Acetone was distilled off at 65 ° C. for 12 hours to obtain an aqueous polyurethane resin dispersion (Q-1).

<Examples 2 to 8>
Each raw material of the polyurethane resin aqueous dispersion is the same as the method described in Example 1 except that each raw material described in Table 1 Examples 2 to 8 is used instead of each raw material described in Table 1 Example 1. Polyurethane resin water dispersions (Q-2) to (Q-8) were obtained.

<Example 9>
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 85 ° C. for 10 hours to carry out a urethanization reaction. An acetone solution of urethane prepolymer (P-9) was obtained. Manufactured. The isocyanate content per solid in the acetone solution of the urethane prepolymer was 0.77 mmol / g. Put 460.22 parts of acetone solution of urethane prepolymer obtained in a simple pressure reactor equipped with a stirrer and a heating reactor, and add 2.21 parts of dimethyl sulfate (quaternizing agent) while stirring at 40 ° C. The quaternization reaction was carried out at 40 ° C. for 3 hours. Thereafter, the mixture was emulsified by gradually adding 234.02 parts of water while stirring at 100 rpm while maintaining the temperature at 30 ° C., and then 4.55 parts of diethylenetriamine, which is a chain extender, was added, and the mixture was added at 65 ° C. under reduced pressure at 12 ° C. Acetone was distilled off over time to obtain an aqueous polyurethane resin dispersion (Q-9).

<Examples 10 to 12>
Each raw material of the polyurethane resin aqueous dispersion is the same as the method described in Example 9, except that each raw material described in Table 1 Examples 10 to 12 is used instead of each raw material described in Table 1 Example 9. Thus, polyurethane resin aqueous dispersions (Q-10) to (Q-12) were obtained.

<Example 13>
The raw materials listed in Table 1 were 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. An acetone solution of urethane prepolymer (P-1) was prepared. Manufactured. The isocyanate content per solid content of the acetone solution of the urethane prepolymer was 0.45 mmol / g. 460.25 parts of an acetone solution of urethane prepolymer obtained in a simple pressure reactor equipped with a stirrer and a heating reactor was added, and 1.31 parts of formic acid (neutralizing agent) was added while stirring at 40 ° C., and 60 rpm After stirring for 30 minutes, the mixture was emulsified by gradually adding 346.98 parts of water while maintaining the temperature at 30 ° C. and stirring at 100 rpm, and then acetone was distilled off at 65 ° C. under reduced pressure for 12 hours. As a result, an aqueous polyurethane resin dispersion (Q-13) was obtained.
<Comparative Example 1>
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 85 ° C. for 10 hours to carry out a urethanization reaction. An acetone solution of urethane prepolymer (P′-1) Manufactured. The isocyanate content per solid content of the acetone solution of the urethane prepolymer was 0.87 mmol / g. 458.36 parts of an acetone solution of urethane prepolymer obtained in a simple pressure reactor equipped with a stirrer and a heating reactor was added, and 0.35 part of triethylamine (neutralizing agent) was added while stirring at 40 ° C., and 60 rpm And then emulsifying by gradually adding 340.00 parts of water while stirring at 100 rpm, adding 4.55 parts of diethylenetriamine, which is a chain extender, and reducing the pressure. Acetone was distilled off at 65 ° C. for 12 hours to obtain an aqueous polyurethane resin dispersion (Q′-1).

<Comparative example 2>
In the same manner as in the method described in Comparative Example 1, except that each raw material of the polyurethane resin aqueous dispersion was used instead of the raw materials described in Table 1 Comparative Example 1, the polyurethane resin An aqueous dispersion (Q′-2) was obtained.

<Comparative 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 85 ° C. for 10 hours to carry out a urethanization reaction. An acetone solution of urethane prepolymer (P′-3) Manufactured. The isocyanate content per solid in the acetone solution of the urethane prepolymer was 0.26 mmol / g. Put 492.65 parts of acetone solution of urethane prepolymer obtained in a simple pressure reactor equipped with stirrer and heating reactor, and add 2.21 parts of dimethyl sulfate (quaternizing agent) while stirring at 40 ° C. The quaternization reaction was carried out at 40 ° C. for 3 hours. Thereafter, the mixture was emulsified by gradually adding 497.15 parts of water while stirring at 100 rpm while maintaining the temperature at 30 ° C., and then 1.68 parts of diethylenetriamine, which is a chain extender, was added, and 12 ° C. at 65 ° C. under reduced pressure. Acetone was distilled off over time to obtain an aqueous polyurethane resin dispersion (Q′-3).

<Comparative Example 4>
Each raw material of the polyurethane resin aqueous dispersion is the same as the method described in Comparative Example 3 except that each raw material described in Table 1 Comparative Example 4 is used instead of each raw material described in Table 1 Comparative Example 3. A polyurethane resin aqueous dispersion (Q′-4) was obtained.

  Various physical property values of polyurethane resin aqueous dispersions (Q-1) to (Q-13) and (Q′-1) to (Q′-4) obtained in Examples 1 to 13 and Comparative Examples 1 to 4 The evaluation results are shown in Table 4. In addition, the measuring method and evaluation method of various physical property values in the present invention are as follows.

The hydrophilic group content of each polyurethane resin can be determined by measuring the acid value or amine value of the resin before neutralization or quaternization. When measurement is difficult, it can obtain | require with the following formula from content of the compound (c) containing a hydrophilic group and an active hydrogen atom.
In the case of an anion hydrophilic group content (mmol / g) = (content of (c) (g)) x (number of acid groups in one molecule of (c)) x1000 / {(molecular weight of (c)) x (Weight of polyurethane resin (g))}
In the case of a cation hydrophilic group content (mmol / g) = (content of (c) (g)) × (number of amino groups in one molecule of (c)) × 1000 / {(molecular weight of (c)) x (Weight of polyurethane resin (g))}

<Acid group content>
The acid value of the polyurethane resin is determined by the following method, and the acid group content (mmol / g) is calculated by the following formula.
Acid group content (mmol / g) = (acid value) /56.1
<Acid value>
After dissolving unneutralized or quaternized polyurethane resin in 50 ml of dimethylformamide (hereinafter referred to as DMF) in a 100 ml flask, 0.1 mol / l potassium hydroxide / methyl alcohol titration with phenolphthalein indicator Titration is carried out with the solution (the end point is the point where the color of the indicator has changed from colorless to slightly reddish).
Acid value = 0.561xa × f / S
a: The number of ml of titration of a 0.1 mol / l hydrochloric acid / methyl alcohol titration solution.
f: Potency of 0.1 mol / l hydrochloric acid / methyl alcohol titration solution.
S: Amount of polyurethane resin collected (g)

<Amino group content>
The amine value of the polyurethane resin is determined by the following method, and the amino group content (mmol / g) is calculated by the following formula.
Terminal amino group content (mmol / g) = Amine value / 56.1
(1) Amine number After dissolving unneutralized or unquaternized polyurethane resin in 50 ml of toluene in a 100 ml flask, 0.5 mol / l hydrochloric acid / methyl alcohol using xylene cyanol FF / methyl orange mixed indicator Titrate with the titration solution (the end point is the point where the indicator color changed from green to reddish brown).
Total amine number = a × f / (S × 28.05)
a: Titration ml number of 0.5 mol / l hydrochloric acid / methyl alcohol titration solution.
f: titer of 0.5 mol / l hydrochloric acid / methyl alcohol titration solution.
S: Amount of polyurethane resin collected (g)

<Neutralization rate or quaternization rate>
By calculating the molar ratio of the compound (c) containing a hydrophilic group and an active hydrogen atom and the neutralizing agent or quaternizing agent (d) used as a raw material for the aqueous dispersion of the polyurethane resin (U) The neutralization rate or quaternization rate of the polyurethane resin (U) can be calculated.
Neutralization rate or quaternization rate (%) = (number of moles of (d)) / (number of moles of (c)) × 100
When the polyurethane resin (U) has an acid group and an amine is used as the neutralizing agent (d), the acid value (A) of the polyurethane resin aqueous dispersion obtained by the method described above, polyurethane From the value of the amine value (B) of the resin water dispersion, it can be determined by the following formula.
・ Neutralization rate (%) when polyurethane resin (U) has acid groups and amines are used as neutralizing agent (d)
= (B) / (A) x 100

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

Evaluation method

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

<Water resistance of dry film>
(1) Appearance 10 parts of a polyurethane resin aqueous dispersion was poured into a polypropylene mold having a length of 10 cm, a width of 20 cm, and a depth of 1 cm, and after drying for 12 hours at room temperature, the film thickness after drying was poured into a 200 μm film. A film obtained by heating and drying at 105 ° C. for 3 hours with an air dryer was immersed in ion exchange water at 60 ° C. for 14 days, and then the surface state of the film was visually observed. The case where there was no change was marked with ◎, the case where the whitened portion was less than 50% of the total area was marked with ◯, and the case where the whole was whitened was marked with ×.
(2) Maintenance rate of breaking elongation The film taken out is dried and described in JIS K7311. The measurement was performed based on a tensile test, and the ratio of the breaking elongation after immersion to the breaking elongation before immersion and the maintenance ratio of the elongation at break were determined.

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 water dispersion [“Polytron Z330”, manufactured by Asahi Kasei Co., Ltd.] and 200 parts of the polyurethane resin water dispersion (Q-1) obtained in Example 1 were charged for 10 minutes. Mixed and dispersed. Furthermore, it adjusted so that the viscosity in 25 degreeC might be set to 150 mPa * s using ion-exchange water, and the water-based coating material (W-1) was obtained. The viscosity was measured at a rotational speed of 60 rpm using a rotary viscometer manufactured by TOKIMEC.

Evaluation Examples 2 to 5 (Evaluation as water-based paint)
Instead of the polyurethane resin water dispersion (Q-1), the polyurethane resin water dispersions (Q-2) to (Q-5) are equivalent in solid content to (Q-1) used in Evaluation Example 1. Aqueous paints (W-2) to (W-5) for Evaluation Examples 2 to 5 were obtained in the same manner as in Evaluation Example 1 except that they were added.
Table 4 shows the results of evaluating the water resistance of the coating and the blending stability of the coating based on the following test methods for the water-based coatings (W-1) to (W-5).

Comparative evaluation examples 1-2
Instead of polyurethane resin water dispersion (Q-1), polyurethane resin water dispersions (Q′-1) and (Q′-2) are equivalent in solid content to (Q-1) used in Evaluation Example 1. Comparative water-based paints (W′-1) and (W′-2) were obtained in the same manner as in Evaluation Example 1 except that the addition was performed.
Table 4 shows the results of evaluating the water resistance of the coating and the blending stability of the coating based on the following test methods for the water-based coatings (W′-1) and (W′-2).

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

<Method of evaluating the stability of paint blending>
(1) Presence or absence of gel product generation The temperature of the obtained water-based paint was adjusted to 30 ° C. and allowed to stand for 5 days. The generation of the gel product was visually evaluated using a particle gauge, and the viscosity was B type. It was measured with a viscometer and the change in viscosity before and after standing was evaluated. The case where the gel material was not generated was marked with ◯, and the case where the gel material was generated was marked with x.
(2) Viscosity change The obtained water-based coating material was temperature-controlled at 30 degreeC, left still for 5 days, and the viscosity change before and behind stillness was measured with the B-type viscometer. The viscosity change rate was calculated according to the following formula, and the case where the rate of change was less than 50% was evaluated as “◯”, the case where it was 50 to less than 150% as “Δ”, and the case where it was 150% or more as “X”.
Viscosity change rate (%) = {(viscosity after standing) − (viscosity before standing)} / (viscosity before standing) × 100

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

Evaluation Examples 7 to 8 (Evaluation as aqueous adhesive)
Instead of the polyurethane resin water dispersion (Q-6), the polyurethane resin water dispersions (Q-7) to (Q-8) are equivalent in solid content to (Q-6) used in Evaluation Example 6. Except for using such addition, aqueous adhesives (X-2) to (X-3) for Evaluation Examples 7 to 8 were obtained in the same manner as in Evaluation Example 6.
Table 5 shows the results of evaluating water resistance and adhesive blending stability based on the following test methods for the water-based adhesives (X-1) to (X-3).

Comparative evaluation examples 3 to 4
Instead of the polyurethane resin water dispersion (Q-6), the polyurethane resin water dispersions (Q′-1) and (Q′-2) are equivalent in solid content to (Q-6) used in Evaluation Example 6. Comparative water-based adhesives (X′-1) and (X′-2) were obtained in the same manner as in Evaluation Example 6 except that they were added so as to be.
Table 5 shows the results of evaluating the water resistance and the blending stability of the adhesive based on the following test methods for the aqueous adhesives (X′-1) and (X′-2).

<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.

<Method for evaluating blending stability of water-based adhesive>
(1) Presence or absence of gel product generation The temperature of the obtained aqueous adhesive was adjusted to 30 ° C. and allowed to stand for 5 days. The generation of the gel product was visually evaluated using a grain gauge, and the viscosity was B It was measured with a viscometer and the viscosity change before and after standing was evaluated. The case where the gel material was not generated was marked with ◯, and the case where the gel material was generated was marked with x.
(2) Viscosity change The obtained water-based adhesive was temperature-controlled at 30 ° C. and allowed to stand for 5 days, and the viscosity change before and after standing was measured with a B-type viscometer. The viscosity change rate was calculated according to the following formula, and the case where the rate of change was less than 50% was evaluated as “◯”, the case where it was 50 to less than 150% as “Δ”, and the case where it was 150% or more as “X”.
Viscosity change rate (%) = {(viscosity after standing) − (viscosity before standing)} / (viscosity before standing) × 100

Evaluation Example 9 (Evaluation as aqueous fiber processing agent)
A pigment printing paste was prepared using an aqueous polyurethane resin dispersion as follows.
For 100 parts of the polyurethane resin aqueous dispersion (Q-9) obtained in Example 9, 8.9 parts of a viscoelasticity modifier [“SN thickener 618” manufactured by San Nopco Co., Ltd.], a silicon-based antifoaming agent [“ SN deformer 777 “San Nopco Co., Ltd.” 0.9 parts, water 35 parts, titanium oxide 44.6 parts, and pigment [“NL Red FR3R-D” manufactured by Yamagata Kogyo Co., Ltd.] 18.9 parts Thus, a pigment printing paste (Y-1) was obtained. Table 6 shows the results of testing the water resistance of the pigment-printed fiber cloth and the film-forming property of the pigment-printing paste based on the following test method for the pigment-printing paste (Y-1).

Evaluation Examples 10 to 13 (Evaluation as aqueous fiber processing agent)
Instead of the polyurethane resin water dispersion (Q-9), the polyurethane resin water dispersions (Q-10) to (Q-13) have the same solid content as (Q-9) used in Evaluation Example 9. Except for using such addition, aqueous fiber processing agents (X-2) to (X-5) for Evaluation Examples 10 to 13 were obtained in the same manner as in Evaluation Example 9.
Table 6 shows the results of evaluating the water resistance and the blending stability of the fiber processing agents based on the following test methods for the aqueous fiber processing agents (X-1) to (X-5).

Comparative Evaluation Examples 5-6
Instead of the polyurethane resin water dispersion (Q-9), the polyurethane resin water dispersions (Q′-3) and (Q′-4) are equivalent in solid content to (Q-9) used in Evaluation Example 9. Comparative pigment printing pastes (Y′-1) and (Y′-2) were obtained in the same manner as in Evaluation Example 9 except that the addition was performed in the same manner as in Evaluation Example 9. Table 6 shows the results of testing the water resistance of the pigment-printed fiber cloth and the blending stability of the pigment-printing paste for the pigment-printing pastes (Y′-1) and (Y′-2) based on the following test methods. .

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

<Method of evaluating blending stability of pigment printing paste>
(1) Presence / absence of gel product generation The temperature of the obtained pigment printing paste was adjusted to 30 ° C. and allowed to stand for 5 days. The generation of the gel product was visually evaluated using a grain gauge, and the viscosity was B It was measured with a viscometer and the viscosity change before and after standing was evaluated. The case where the gel material was not generated was marked with ◯, and the case where the gel material was generated was marked with x.
(2) Viscosity change The obtained pigment printing paste was temperature-controlled at 30 ° C. and allowed to stand for 5 days, and the viscosity change before and after standing was measured with a B-type viscometer. The viscosity change rate was calculated according to the following formula, and the case where the rate of change was less than 50% was evaluated as “◯”, the case where it was 50 to less than 150% as “Δ”, and the case where it was 150% or more as “X”.
Viscosity change rate (%) = {(viscosity after standing) − (viscosity before standing)} / (viscosity before standing) × 100

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

Claims (9)

A polyurethane resin aqueous dispersion containing water and a polyurethane resin (U), wherein the polyurethane resin (U) is a diol (a), a polyisocyanate (b), and an acid group (α) or amino group (β). And an acid group (α) or amino group () of a polyurethane resin comprising the compound (c) having an active hydrogen atom group (γ) that is neither an acid group (α) nor an amino group (β) as an essential constituent monomer. β) is a neutralized or quaternized polyurethane resin,
The total content of acid group (α), neutralized acid group (α1), amino group (β), neutralized amino group (β1) and quaternized amino group (β2) is (U) 0.1 to 0.8 mmol / g based on the weight of
And the neutralization rate represented by the following formula (1) is 30 to 90%, or the neutralization and quaternization rate represented by the following formula (2) is 30 to 90%, and the polyurethane A polyurethane resin aqueous dispersion in which the volume average particle diameter of polyurethane resin particles in the resin aqueous dispersion is 50 to 600 nm.
The polyurethane resin aqueous dispersion according to claim 1, wherein the acid group (α) is a carboxyl group.   The polyurethane resin aqueous dispersion according to claim 1 or 2, wherein the polyurethane resin (U) has a polyoxyethylene group. The polyurethane resin (U) is a compound further comprising a chain extender (e) as an essential constituent monomer and the chain extender (e) having a total of two or more primary amino groups and secondary amino groups. The polyurethane resin aqueous dispersion of any one of -3.   The polyurethane resin (U) further comprises a polyol (k) having 3 or more hydroxyl groups as an essential constituent monomer, and the weight of the polyol (k) is 0.1 to 4.0 weight with respect to the weight of the polyol (a). %. The polyurethane resin aqueous dispersion according to any one of claims 1 to 4.   An aqueous paint containing the polyurethane resin aqueous dispersion according to any one of claims 1 to 5.   An aqueous adhesive containing the polyurethane resin aqueous dispersion according to any one of claims 1 to 5.   The aqueous fiber processing agent containing the polyurethane resin aqueous dispersion of any one of Claims 1-5. Whether the polyurethane resin (U0) having an acid group (α) or amino group (β) of 0.1 to 0.8 mmol / g has a neutralization rate of 30 to 90% represented by the following formula (1), Alternatively, the neutralized or quaternized polyurethane resin (U1) obtained by neutralization or quaternization so that the neutralization and quaternization ratio represented by the following formula (2) is 30 to 90% is submerged in water. The polyurethane resin aqueous dispersion is obtained by dispersing to obtain a polyurethane resin aqueous dispersion in which the volume average particle diameter of the polyurethane resin particles in the polyurethane resin aqueous dispersion is 50 to 600 nm. A method for producing a polyurethane resin aqueous dispersion.