JP6557269B2 - Polyurethane resin water dispersion - Google Patents

Description

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

  Polyurethane resin water dispersions are used in paints, adhesives, textile processing agents, paper treatment agents, inks, etc. as highly functional water dispersions because they have excellent film properties obtained by drying. However, from the viewpoint of environmental protection, resource saving, safety, etc., it is thought that the importance will increase more and more. 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.

  However, since the urethane resin is dissolved in the solvent in the solvent-based urethane, the film-forming property is good regardless of the heating temperature, whereas the urethane resin aqueous dispersion has a particle shape, Since the film is formed by fusing, the film forming property is inferior to that of the solvent-based urethane, so that there is a problem that the adhesion of the obtained film to the substrate is lowered.

  In order to improve the affinity between the urethane film and the substrate, an aqueous urethane resin dispersion (see Patent Document 1) having a tertiary amino group in the molecular side chain has been proposed. Therefore, the required level of adhesion is increased, and further improvement in adhesion to the substrate is required.

No. 2012-111360

  The subject of this invention is providing the polyurethane resin aqueous dispersion excellent in adhesiveness.

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 a polyurethane resin (U) having a polymer polyol (a) and an organic polyisocyanate (b) as essential constituent monomers, and water, under the following conditions: The polymer polyol (a) contains 2 to 14 different polymer polyols (ai ) of the polymer polyols (a1) to (a14) satisfying all of (1) to (3), and the polymer polyol (a1) ~ any der molar ratio also 7 mole percent of the polymer polyol (ai) of the relative to the total mole number (a1) ~ (a14) of (a14) is, the polymer polyol (a) Are polyether polyols (excluding polypropylene glycol), polyester polyols (excluding polybutylene adipate diol and polycaprolactone polyols) and / or polyester polyols. A polycarbonate polyol (excluding polyhexamethylene carbonate diol), the organic polyisocyanate (b) is isophorone diisocyanate, alone or 4,4-dicyclohexylmethane diisocyanate alone der Ru polyurethane resin aqueous dispersion and and said polyurethane resin aqueous dispersion It is a water-based paint, water-based adhesive or water-based fiber processing agent containing a body.
(1) The repeating unit is the same.
(2) The difference in the number average molecular weight (Mn) measured by any two gel permeation chromatography of the polymer polyol (ai) is 300 or more.
(3) (a1) to (a14) are the following polymer polyols.
(A1): Polymer polyol with Mn of 500 or more and less than 800 (a2): Polymer polyol with Mn of 800 or more and less than 1100 (a3): Polymer polyol with Mn of 1100 or more and less than 1400 (a4): Mn Is a polymer polyol (a5): Mn is 1700 or more and less than 2000: Polymer polyol (a6): Mn is 2000 or more and less than 2300 Mn is 2400 or more and less than 2600 Polymer polyol (a8): Mn is 2600 or more and less than 2900 Polymer polyol (a9): Mn is 2900 or more and less than 3200 Polymer polyol (a10): Mn is 3200 or more and less than 3500 (A11): Mn is 3500 or more and less than 3800 Child polyol (a12): Mn is high molecular weight polyol is less than 3800 or 4100 (a13): Mn is 4100 or more 4400 less than a is a polymer polyol (a14): a polymer polyol Mn is less than 4400 or 4700

  The aqueous polyurethane resin dispersion of the present invention can provide a film with very good adhesion.

<Polyurethane resin (U)>
The polyurethane resin (U) comprises a high molecular polyol (a) and a polyisocyanate (b) as essential constituent monomers, and if necessary, a low molecular polyol (c), a compound (d) containing a hydrophilic group and an active hydrogen atom. , A resin comprising a chain extender (e) and a reaction terminator (f) as constituent monomers.
Each component will be described below.

The polymer polyol (a) has the same repeating unit from the viewpoint of adhesion of the resulting film to the substrate, and the number average molecular weight (Mn) measured by gel permeation chromatography is represented by the above. The number average molecular weight (Mn) of (a1) to (a14) containing 2 to 14 different polymer polyols (ai) different from (a1) to (a14) is any of (ai) The difference d (ai) between the two Mn is also 300 or more.
d (ai) is preferably 500 or more, and more preferably 900 or more, from the viewpoint of adhesion of the resulting film to the substrate. When d (ai) is less than 300, the adhesion to the substrate is lowered.

The ratio (Mw / Mn) of each weight average molecular weight (Mw) and number average molecular weight (Mw / Mn) of (a1) to (a14) is 1 to 2 from the viewpoint of mechanical properties, durability, wear resistance and the like of the resulting coating. Is preferable, and 1 to 1.2 is more preferable.

2-14 types of different polymer polyols (ai) among the polyols (a1) to (a14), wherein the polymer polyol (a) contains (ai). (Ai) is 2 or more types, and preferably 3 or more types, and most preferably 4 or more types from the viewpoint of adhesion to the substrate. The number average molecular weight (hereinafter abbreviated as Mn) and the weight average molecular weight (hereinafter abbreviated as Mw) of the polymer polyol in the present invention are measured by gel permeation chromatography (GPC) using polystyrene as a standard. is there.

Mw and Mn are measured by the following measuring methods.
<Method for measuring Mw and Mn>
Polymer polyol or polyurethane resin or polyurethane water dispersion is added to DMF so that the solid content is 0.125 wt%, and after stirring and dissolving at room temperature for 1 hour, it is filtered with a filter having a pore size of 0.3 μm. The components Mw and Mn contained in the obtained filtrate are measured by GPC using DMF as a solvent and polystyrene as a molecular weight standard.
<GPC measurement conditions>
The conditions for GPC measurement of the polymer polyol, polyurethane resin, and polyurethane water dispersion in the present invention are as follows.
Apparatus: “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: “Guardcolumn α” + “TSKgel α-M” [both manufactured by Tosoh Corporation]
Sample solution: 0.125 wt% dimethylformamide solution Eluent: dimethylformamide Solution injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) [manufactured by Tosoh Corporation]

From the viewpoint of adhesion, the molar ratio of any of the polymer polyols (ai) of (a1) to (a14) to the total number of moles of the polymer polyols (a1) to (a14) is also 7 mol% or more. It is preferable.
In the case of two types, the molar ratio of each component of the polymer polyol (ai) is preferably 10 to 90:90 to 10, more preferably 30 to 70:70 to 30, more preferably 40 to 40 in the case of two types. The molar ratio is 60: 60-40.
In the case of three types, the molar ratio is preferably 10 to 90:10 to 90:10 to 90, and more preferably 30 to 70:30 to 70:30 to 70.
In the case of four types, the molar ratio is preferably 10 to 90:10 to 90:10 to 90:10 to 90, and more preferably 20 to 80:20 to 80:20 to 80:20 to 80.

  As a specific method for producing the polymer polyols (a1) to (a14), when polytetramethylene ether glycol (PTMG), which is a polyether polyol, is taken as an example, ring opening of tetrahydrofuran (THF) which is a general production method PTMG produced by polymerization, and the polymer polyols (a1) to (a14) used in the present invention refer to polyols having different molecular weight distributions depending on the degree of polymerization (number of segments).

  As a method for detecting the difference in the number average molecular weight of the polymer polyols (a1) to (a14) in the polyurethane resin (U), for example, the obtained polyurethane resin (U) is hydrolyzed and gel permeation chromatography is performed. And a method of calculating from a graph.

  Examples of the polymer polyols (a1) to (a14) include polyether polyols, polyester polyols, and polycarbonate polyols.

  Examples of polyether polyols 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 aliphatic polyether polyols include PTMG1000 [polytetramethylene ether glycol with Mn = 1,000, manufactured by Mitsubishi Chemical Corporation], PTMG1300 [polytetramethylene ether glycol with Mn = 1,300, Mitsubishi Chemical ( Ltd.], PTMG1500 [polytetramethylene ether glycol with Mn = 1,500, manufactured by Mitsubishi Chemical Corporation], PTMG1800 [polytetramethylene ether glycol with Mn = 1,800, manufactured by Mitsubishi Chemical Corporation], PTMG2000 [Polytetramethylene ether glycol with Mn = 2,000, manufactured by Mitsubishi Chemical Corporation], PTMG3000 [Polytetramethylene ether glycol with Mn = 3,000, manufactured by Mitsubishi Chemical Corporation], PTMG4000 [Mn = 4,000 Polytetramethylene Terglycol, manufactured by Mitsubishi Chemical Corporation], PTGL3000 [modified PTMG with Mn = 3,000, manufactured by Hodogaya Chemical Co., Ltd.], and Sanixdiol GP-3000 [polypropylene ether triol with Mn = 3,000, Sanyo Chemical Industries, Ltd.].

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

  Examples of the polyester polyol 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, Kuraray polyol P-1010 [poly (3-methylpentylene adipate) diol of Mn = 1,000, manufactured by Kuraray Co., Ltd.], Kuraray polyol P-2010 [Mn = 2, 000 poly (3-methylpentylene adipate) diol, manufactured by Kuraray Co., Ltd.], Kuraray polyol P-3010 [Mn = 3,000 poly (3-methylpentylene adipate) diol, manufactured by Kuraray Co., Ltd.], Kuraray polyol P-4010 [poly (3-methylpentylene adipate) diol with Mn = 4,000, manufactured by Kuraray Co., Ltd.], Sanester 2610 [polyethylene adipate diol with Mn = 1,000, Sanyo Chemical Industries, Ltd. Manufactured by], Sanester 4620 [polytetramethylene adipate with Mn = 2,000 All], Sanester 2620 [polyethylene adipate diol with Mn = 2,000, manufactured by Sanyo Chemical Industries, Ltd.] and the like.

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-1090 [poly (3-methyl- with Mn = 1,000). 5-pentanediol / hexamethylene) carbonate diol, manufactured by Kuraray Co., Ltd.], Kuraray polyol C-2090 [Mn = 2,000 poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol, Kuraray Co., Ltd. )], Kuraray polyol C-3090 [poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol of Mn = 3,000, manufactured by Kuraray Co., Ltd.], Kuraray polyol C-4090 [Mn = 4 000 poly (3-methyl-5-pentanedi) Lumpur / hexamethylene) carbonate diol, Kuraray Co., Ltd.], and T4672 [Mn = 2,000 Poly (tetramethylene / hexamethylene) carbonate diol include Asahi Kasei Chemicals Co., Ltd.] or 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.

  Among the polymer polyols (a), polyether polyols are preferable from the viewpoint of adhesion of the resulting film, aliphatic polyether polyols are more preferable, and polytetramethylene ether glycol is more preferable. .

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

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

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

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

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

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

Examples of the low molecular polyol (c) include low molecular polyols having a number average molecular weight (hereinafter abbreviated as Mn) of less than 300.
In addition, Mn of a low molecular polyol is a calculated value from a chemical formula.

  Examples of the low molecular polyol (c) having a Mn of less than 300 include aliphatic dihydric alcohols, aliphatic trihydric alcohols and tetrahydric or higher aliphatic alcohols. Among (c), 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.

Examples of the compound (d) containing a hydrophilic group and an active hydrogen atom include a compound (d1) containing an anionic group and an active hydrogen atom, and a compound (d2) containing a cationic group and an active hydrogen atom.
(D1) 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 (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.

  As the neutralizing agent used for the salt of (d1), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the resulting polyurethane resin aqueous dispersion and the water resistance of the resulting film. From this point of view, the neutralizing agent used in the salt of (d1) is preferably ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine or dimethylethylamine, more preferably ammonia or monoethylamine. Dimethylamine and diethylamine, particularly preferred is ammonia.

  Among (d1), 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid and salts thereof are preferable from the viewpoint of the resin physical properties of the obtained film and the dispersion stability of the polyurethane resin aqueous dispersion. More preferred are neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or an amine compound having 1 to 20 carbon atoms.

  As the compound (d2) containing a cationic group and an active hydrogen atom, for example, a tertiary amino group-containing diol having 1 to 20 carbon atoms [N-alkyl dialkanolamine (for example, N-methyldiethanolamine, N-propyldiethanolamine, N -Butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamine (for example, N, N-dimethylethanolamine) and the like] and the like, and the like.

Examples of the neutralizing agent used in (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. .
As the neutralizing agent used in (d2), 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 (d2) 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 (d1) and (d2) is added before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step, during the water dispersion step, or after the water dispersion. However, from the viewpoint of the stability of the urethane resin and the stability of the aqueous dispersion, it is preferably added before or during the aqueous dispersion process.

The amount of (d) used is such that the content of the hydrophilic group in (U) is preferably 0.01 to 5% by weight, more preferably 0.1 to 4% by weight, based on the weight of (U). More preferably, the content is adjusted to 0.5 to 3% by weight.
The content of the hydrophilic group in the present invention means the weight percent of the unneutralized cationic group or anionic group, and does not include the weight of the counter ion. For example, the content of the hydrophilic group in (d1) is such that, in the case of 2,2-dimethylolpropionic acid triethylamine salt, the weight percentage of the carboxyl group (—COOH) is 3- (2,3-dihydroxypropoxy). In the case of triethylamine salt of -1-propanesulfonic acid, it refers to the weight percent of the sulfo group (—SO 3 H). Further, the content of the hydrophilic group in (d2) refers to the weight% of only the nitrogen atom in the tertiary amino group.

  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).

  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).

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

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

  From the viewpoint of mechanical properties and chemical resistance, the ratio of the urethane group content to the urea group content in the polyurethane resin (U) is based on the weight of the (U) urethane group content / urea group content = 1/1 to 15/1. The ratio is preferably 3/2 to 3/1.

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 determined by a nitrogen analyzer, the ratio of urethane group and urea group determined by 1H-NMR, and the allohanate group and burette group content.

  In the present invention, the total content of allophanate groups and burette groups in the polyurethane resin (U) is 0.1 mmol based on the weight of (U) from the viewpoint of film forming properties and water resistance of the resulting film. / G or less, more preferably 0.03 mmol / g or less, particularly preferably 0.01 mmol / g or less, particularly preferably 0.003 mmol / g or less, and most preferably 0.001 mmol / g or less. .

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

High molecular polyol (a), polyisocyanate (b), and low molecular polyol (c) used if necessary, compound (d) containing a hydrophilic group and an active hydrogen atom, chain extender (e) and reaction terminator ( By appropriately adjusting the amount of f), the urethane group content of the polyurethane resin (U) can be set within a desired range.
Here, the hydrophilic group refers to an anionic hydrophilic group such as a carboxyl group, a sulfo group, —NHSO ₃ H, and an anionic group thereof, a cationic hydrophilic group such as a quaternary amino group, and a polyoxyethylene group. It refers to a nonionic hydrophilic group.
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 1H-NMR, and the allohanate group and burette group contents.

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

Polyol (a), polyisocyanate (b) and optionally used low molecular diol (c), compound (d) containing a hydrophilic group and an active hydrogen atom, chain extender (e) and reaction terminator (f) The terminal amino group content of the polyurethane resin (U) can be adjusted to a desired range by appropriately adjusting the amount of.
The terminal amino group content can be determined from the total amine value and the tertiary amine value.

  The Mn of the polyurethane resin (U) is preferably 10,000 or more, more preferably 10,000 to 1,000,000 from the viewpoints of mechanical properties, durability, chemical resistance, and abrasion resistance of the resulting film. More preferably, it is 10,000 to 500,000, and most preferably 10,000 to 300,000.

High molecular polyol (a), polyisocyanate (b) and optionally used low molecular diol (c), compound (d) containing a hydrophilic group and an active hydrogen atom, chain extender (e) and reaction terminator ( By appropriately adjusting the amount of f), the Mn of the polyurethane resin (U) can be set within a desired range.
Mn can be measured by gel permeation chromatography (GPC).
In the GPC measurement, when the solubility of the polyurethane resin (U) in the solvent used for the measurement is less than 90%, the GPC measurement accuracy is lowered. In that case, since it is difficult to accurately measure the molecular weight, the molecular weight of the polyurethane resin was infinite.

<Polyurethane resin aqueous dispersion, production method thereof>
The aqueous dispersion of the polyurethane resin (U) in the present invention can be produced by dispersing the polyurethane resin (U) in water.
The polyurethane resin (U) contains the polyol (a) and the polyisocyanate (b) as essential components, and if necessary, a low-molecular diol (c), a compound (d) containing a hydrophilic group and an active hydrogen atom, chain extension. It is produced by reacting the agent (e) and the reaction terminator (f). Moreover, (U) has a crosslinked structure in the molecule, and in order to introduce the crosslinked structure into (U), polyol (a), polyisocyanate (b) and / or chain extender (e) By using a polyfunctional monomer having three or more functional groups, it is possible to introduce a crosslinked structure in (U).
Further, from the viewpoint of dispersibility of (U) in water, it is preferable to use a compound (d) containing a hydrophilic group and an active hydrogen atom as a component. Therefore, (U) is preferably a polyurethane resin having a hydrophilic group.
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 salt 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 preferably 0.01 to 20% by weight, more preferably 0.01 to 10% by weight, still more preferably 0.1 to 5% by weight, based on the weight of the polyurethane resin (U). is there.
When (U) is a polyurethane resin having a hydrophilic group, the total content of (d) and (g) based on the weight of (U) is preferably 0.01 to 20 wt. %, More preferably 0.1 to 15% by weight, still 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 the present invention, the polyurethane resin (U) comprises a polyol (a), a polyisocyanate (b), a low molecular diol (c) to be used if necessary, a compound (d) containing a hydrophilic group and an active hydrogen atom, chain extension. It can be obtained by reacting the agent (e) and the reaction terminator (f) by heating them with heatable equipment. For example, the raw material (U) is charged in a container and uniformly stirred, and then heated without stirring in a heating dryer or heating furnace, a simple pressure reactor (autoclave), Kolben, uniaxial or biaxial kneading. And a method of reacting by heating with stirring or kneading in a machine, a plast mill or a universal kneader. Among them, the method of heating and reacting while stirring or kneading increases the homogeneity of the obtained urethane resin (U), and the mechanical properties, durability, chemical resistance and abrasion resistance of the resulting film, etc. Is preferred because it tends to be more excellent.

  The reaction temperature for producing the polyurethane resin (U) is preferably 60 to 120 or 180 to 250 ° C., more preferably 60 to 110, from the viewpoint of the contents of allophanate groups and burette groups of the polyurethane resin (U). It is 60 degreeC or 180-240 degreeC, Most preferably, it is 60-100 degreeC or 180-230 degreeC. The time for producing (U) can be appropriately selected depending on the equipment used, but is preferably 1 minute to 100 hours, more preferably 3 minutes to 30 hours, and particularly preferably 5 minutes to 20 hours. If it is this range, (U) which can fully exhibit the effect of the present invention will be obtained.

In order to control the urethanization reaction rate, known reaction catalysts (such as tin octylate and bismuth octylate) and reaction retarders (such as phosphoric acid) can be used. The addition amount of these catalysts or reaction retarders is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, and particularly preferably 0.01 to 1% by weight based on the weight of (U). %.
From the viewpoint of ease of handling in the step of dispersing the polyurethane resin (U) in water, the shape of (U) before dispersion can be made into a granular or block shape of 0.2 to 500 mm. The size is preferably 0.5 to 100 mm, more preferably 0.7 to 30 mm, and most preferably 1 to 10 mm.

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

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

  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.

  The number of rotations when the polyurethane resin (U) is dispersed using the rotary dispersion mixer (A1) is preferably 10 to 30000 rpm, more preferably 20 to 20000 rpm, and even more preferably 30 to 30 from the viewpoint of dispersion capability. 10,000 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.

  The frequency when the polyurethane resin (U) is dispersed using the ultrasonic dispersion device (A2) is preferably 1 to 100 kHz, more preferably 3 to 60 kHz, and particularly preferably 10 to 10 from the viewpoint of dispersion capability. 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 polyurethane resin (U) is dispersed using the kneader (A3) is preferably 1 to 1000 rpm, more preferably 3 to 500 rpm, and particularly preferably 10 to 200 rpm, from the viewpoint of dispersion capability. .

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

  The time for treating (U) and water with the dispersion apparatus (A) is preferably 10 seconds to 10 hours, more preferably 1 minute to prevent decomposition or deterioration of (U) as a dispersion. 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 solid content concentration (content of components other than volatile components) of the polyurethane resin aqueous dispersion obtained by the production method of the present invention is preferably 20 to 65% by weight from the viewpoint of easy handling of the aqueous dispersion. Preferably it is 25 to 55% by weight. The solid concentration was about 1 g of the aqueous dispersion thinly spread on a Petri dish, weighed accurately, then weighed the weight after heating at 130 ° C for 45 minutes using a circulating constant temperature drier, before heating. It can be obtained by calculating the ratio (percentage) of the remaining weight after heating to the weight.

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

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

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

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

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

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

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

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

Examples of the pigment include inorganic pigments having a solubility in water of 1 or less (for example, white pigment, black pigment, gray pigment, red pigment, brown pigment, yellow pigment, green pigment, blue pigment, purple pigment and metallic pigment) and organic pigments ( For example, natural organic pigment synthetic organic pigments, nitroso pigments, nitro pigments, pigment dye-type azo pigments, azo lakes made from water-soluble dyes, azo lakes made from poorly soluble dyes, lakes made from basic dyes, lakes made from acid dyes, xanthan lakes , Anthraquinone lake, pigments from vat dyes and phthalocyanine pigments). The content of the pigment is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the aqueous paint.
Examples of the pigment dispersant include the above-described dispersant (g), and the content of the pigment dispersant is preferably 20% by weight or less, more preferably 15% by weight or less based on the weight of the pigment.

Viscosity 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 preferably 5% by weight or less, more preferably 3% by weight or less, based on the weight of the aqueous paint. is there.

  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 for the adhesive within a range not inhibiting the cohesiveness of the adhesive containing the aqueous polyurethane resin dispersion of the present invention, such as a crosslinking agent, a plasticizer, a tackifier, a filler, It is also possible to use pigments, thickeners, antioxidants, ultraviolet absorbers, surfactants and flame retardants.

  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 adjuster is preferably 0.01 to 0.3% by weight based on the weight of the polyurethane resin (U).

  The solid content (nonvolatile content) concentration of the aqueous fiber processing agent of the present invention is not particularly limited, but is preferably 10 to 50% by weight, and more preferably 15 to 45% by weight. The viscosity (25 ° C.) is preferably 10 to 100,000 mPa · s.

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

<Example 1>
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. Each raw material shown in Table 3 was charged into a simple pressure reactor equipped with a stirrer and a heating reactor as follows. After putting 500.00 parts of acetone solution of the obtained urethane prepolymer and stirring at 40 ° C., 155.89 parts of acetone and 10.77 parts of triethylamine (neutralizing agent) were added and homogenized at 60 rpm for 30 minutes. The mixture was emulsified by gradually adding 403.87 parts of water while stirring at 500 rpm while maintaining the temperature at 60 ° C., and then 8.92 parts of diethylenetriamine as a chain extender was added, and the mixture was taken at 65 ° C. under reduced pressure for 12 hours. Then, acetone was distilled off to obtain an aqueous polyurethane resin dispersion (Q-1).

<Examples 2 to 19>
Except that the polyol component (a) described in Tables 1 to 4 was changed, the reaction was performed in the same manner as in Example 1 to produce acetone solutions (P-2) to (P-19) of urethane prepolymer, and polyurethane Resin water dispersions (Q-2) to (Q-19) were obtained.

<Comparative Examples 1-10>
Except having changed the polyol component (a) described in Tables 2 and 4, the reaction was performed in the same manner as in Example 1 to produce acetone solutions (P′-1) to (P′-10) of urethane prepolymer. The polyurethane resin aqueous dispersions (Q′-1) to (Q′-10) were obtained.

The polymer polyols (a1) to (a14) used in Examples 1 to 19 and Comparative Examples 1 to 10 are as follows.
PTMG1000: [Polytetramethylene ether glycol of Mn = 1,002, Mw / Mn = 1.1, manufactured by Mitsubishi Chemical Corporation]
PTMG1300: [Polytetramethylene ether glycol with Mn = 1,303, Mw / Mn = 1.1, manufactured by Mitsubishi Chemical Corporation]
PTMG1500: [Polytetramethylene ether glycol with Mn = 1,488, Mw / Mn = 1.1, manufactured by Mitsubishi Chemical Corporation]
PTMG1500: [Polytetramethylene ether glycol with Mn = 1,516, Mw / Mn = 1.1, manufactured by Mitsubishi Chemical Corporation]
PTMG1800: [Polytetramethylene ether glycol of Mn = 1,810, Mw / Mn = 1.1, manufactured by Mitsubishi Chemical Corporation]
PTMG2000: [polytetramethylene ether glycol of Mn = 2,004, Mw / Mn = 1.1, manufactured by Mitsubishi Chemical Corporation]
PTMG3000: [polytetramethylene ether glycol with Mn = 2,993, Mw / Mn = 1.1, manufactured by Mitsubishi Chemical Corporation],
PTMG4000: [Polytetramethylene ether glycol with Mn = 3,994, Mw / Mn = 1.1, manufactured by Mitsubishi Chemical Corporation]
Kuraray polyol P-2010 [Mn = 1,997, poly (3-methylpentylene adipate) diol having Mw / Mn = 1.1, manufactured by Kuraray Co., Ltd.]
Kuraray polyol P-3010 [poly (3-methylpentylene adipate) diol with Mn = 3,009 Mw / Mn = 1.1, manufactured by Kuraray Co., Ltd.]
Kuraray polyol C-2090 [Mn = 2,000, Mw / Mn = 1.1 poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol, manufactured by Kuraray Co., Ltd.]
Kuraray polyol C-3090 [poly (3-methyl-5-pentanediol / hexamethylene) carbonate diol with Mn = 3,001, Mw / Mn = 1.1, manufactured by Kuraray Co., Ltd.]

<Method for measuring Mw and Mn>
The polymer polyol is added to DMF so that the solid content is 0.125 wt%, stirred and dissolved at room temperature for 1 hour, filtered through a filter having a pore size of 0.3 μm, and contained in the obtained filtrate. The components Mw and Mn were measured by GPC using DMF as a solvent and polystyrene as a molecular weight standard.
<GPC measurement conditions>
Apparatus: “HLC-8220GPC” [manufactured by Tosoh Corporation]
Column: “Guardcolumn α” + “TSKgel α-M” [both manufactured by Tosoh Corporation]
Sample solution: 0.125 wt% dimethylformamide solution Eluent: dimethylformamide Solution injection volume: 100 μl
Flow rate: 1 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference material: Standard polystyrene (TSK standard POLYSTYRENE) [manufactured by Tosoh Corporation]

  Various physical property values of polyurethane resin aqueous dispersions (Q-1) to (Q-19) and (Q′-1) to (Q′-10) obtained in Examples 1 to 19 and Comparative Examples 1 to 10 and The evaluation results are shown in Tables 3 and 4. In addition, the measuring method and evaluation method of various physical property values in the present invention are as follows.

<Urethane group content and urea group content>
The urethane group content and urea group content of the polyurethane resin are the N atom content determined by a nitrogen analyzer [ANTEK7000 (manufactured by Antec)], the ratio of urethane group and urea group determined by 1H-NMR, and the allophanate group described later. And calculated from the burette group content. About 1H-NMR measurement, it carries out by the method as described in "Structural study of the polyurethane resin by NMR: Takeda Laboratory report 34 (2), 224-323 (1975)." That is, when 1H-NMR is measured and aliphatic is used, urea group and urethane are calculated from the ratio of the integral amount of hydrogen derived from urea group near chemical shift 6 ppm and the integral amount of hydrogen derived from urethane group near chemical shift 7 ppm. The weight ratio of the groups is measured, and the urethane group and urea group contents are calculated from the weight ratio, the N atom content and the allohanate group and burette group contents. 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.

<Evaluation of adhesion of polyurethane resin aqueous dispersion>
A polyurethane resin aqueous dispersion was applied to a hot dip galvanized steel sheet so that the film thickness after drying was 50 μm, dried in an atmosphere of 25 ° C. and 50% RH for 7 days, and then a temperature of 5 ° C. ( Cured under conditions of ± 2 ° C and relative humidity of 10% (± 10%), and a cellar cellophane tape (registered trademark) at a temperature of 5 ° C (± 2 ° C) and a relative humidity of 10% (± 10%) ) A peel test was conducted to evaluate the adhesion to the steel sheet. Conditions other than temperature and humidity were evaluated in accordance with JIS K5600-5-6, using cellophane tape (registered trademark) (manufactured by Nichiban Co., Ltd.). The case where 100 cells were not peeled was rated as ◎, the case where 90 to 99 cells were not peeled off was marked as ◯, and the case where there were less than 90 cells were not marked as ×.

In Production Example 18, regarding the polymer polyol (a), PTMG1300 (Mn = 1,303) and PTMG1500 (Mn = 1,516) have a Mn difference of 213 and less than 300, but PTMG1500 (Mn = 1,516) ) And PTMG3000 (Mn = 2,993), or a combination of PTMG1300 (Mn = 1,303) and PTMG3000 (Mn = 2,993) satisfies the conditions of the present invention, so that a film having excellent adhesion can be obtained. There is an effect.
On the other hand, the polymer polyol (a) of Comparative Production Examples 1 to 8 is a single component, and the polymer polyol (a) of Comparative Production Example 9 contains only a combination having a Mn difference of 213 and less than 300, so Does not play. Moreover, since the high molecular polyol (a) of Comparative Production Example 10 contains only combinations having different repeating units, the effect of the present application is not achieved.

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 (6)

A polyurethane resin aqueous dispersion containing a polyurethane resin (U) having a polymer polyol (a) and an organic polyisocyanate (b) as essential constituent monomers and water, wherein the following conditions (1) to (3) The polymer polyol (a) contains 2 to 14 different polymer polyols (ai ) out of the polymer polyols (a1) to (a14) satisfying all of the formulas (a1) to (a14). any of der molar ratio also 7 mole percent of the polymer polyol (ai) of the relative to the total mole number (a1) ~ (a14) of a14) is, the polymer polyol (a) is a polyether polyol (polypropylene Glycols), polyester polyols (excluding polybutylene adipate diol and polycaprolactone polyols) and / or polycarbonate polyols. Triol is (except polyhexamethylene carbonate diol), the organic polyisocyanate (b) is isophorone diisocyanate, alone or 4,4-dicyclohexylmethane diisocyanate alone der Ru polyurethane resin water dispersion.
(1) The repeating unit is the same.
(2) The difference in the number average molecular weight (Mn) measured by any two gel permeation chromatography of the polymer polyol (ai) is 300 or more.
(3) (a1) to (a14) are the following polymer polyols.
(A1): Polymer polyol with Mn of 500 or more and less than 800 (a2): Polymer polyol with Mn of 800 or more and less than 1100 (a3): Polymer polyol with Mn of 1100 or more and less than 1400 (a4): Mn Is a polymer polyol (a5): Mn is 1700 or more and less than 2000: Polymer polyol (a6): Mn is 2000 or more and less than 2300 Mn is 2400 or more and less than 2600 Polymer polyol (a8): Mn is 2600 or more and less than 2900 Polymer polyol (a9): Mn is 2900 or more and less than 3200 Polymer polyol (a10): Mn is 3200 or more and less than 3500 (A11): Mn is 3500 or more and less than 3800 Child polyol (a12): Mn is high molecular weight polyol is less than 3800 or 4100 (a13): Mn is 4100 or more 4400 less than a is a polymer polyol (a14): a polymer polyol Mn is less than 4400 or 4700   The ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mw / Mn), wherein each Mw / Mn of the polymer polyols (a1) to (a14) is 1-2. The polyurethane resin aqueous dispersion as described. The polyurethane resin aqueous dispersion according to claim 1 or 2 , wherein the ratio of the urethane group content and the urea group content in the polyurethane resin (U) is within a range of 1/1 to 15/1. The water-based coating material containing the polyurethane resin water dispersion of any one of Claims 1-3 . An aqueous adhesive containing the polyurethane resin aqueous dispersion according to any one of claims 1 to 3 . The aqueous fiber processing agent containing the polyurethane resin aqueous dispersion of any one of Claims 1-3 .