JP2019006936A - Polyurethane resin aqueous dispersion - Google Patents

Abstract

To provide a polyurethane resin aqueous dispersion, providing a dried coating exhibiting flexibility, mechanical physical properties (breaking strength and braking elongation), water resistance and chemical resistance, and especially useful as an ink binder for inkjet printing.SOLUTION: There is provided a polyurethane resin aqueous dispersion (Q) containing a polyurethane resin (U) manufactured by reacting an active hydrogen component (A) containing a polymer polyol component (a1), a compound having a hydrophilic group and an active hydrogen group (a2) and a chain extender (a3), with an organic polyisocyanate component (B), and an aqueous medium, and satisfying all of following (1) to (4): (1) (a1) contains 70 wt.% or more of polycarbonate diol having a hexamethylene group and a specific molecular weight; (2) 60 mol% or more of (B) is hexamethylene diisocyanate; (3) urethane group concentration of (U) is 1.0 to 2.4 mmol/g; and (4) urea group concentration of (U) is 0.20 to 0.70 mmol/g.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous polyurethane resin dispersion and an ink jet ink using the same.

  Inkjet recording methods using pigment inks are widely used in industrial printing applications, taking advantage of cost-saving advantages of selecting the substrate and shape to be ejected. In recent years, studies have been made to develop an ink jet recording method using pigment inks for textile printing. The inkjet textile printing method using pigment ink does not require post-treatment such as a washing step after printing, which is necessary for conventional dye inks, and has an advantage of excellent productivity.

  In the textile printing method using pigment ink, the color material does not penetrate into the inside of the fiber as in the dye ink, and the color material is retained on the fiber in a form that adheres to the fiber, so that the pigment is fixed to the fiber. Therefore, a binder component is essential. As such a binder material, an aqueous polyurethane resin dispersion is widely used because of its excellent fixability and excellent image fastness of the resulting printed fabric.

  For example, Patent Document 1 describes a pigment ink using a polycarbonate urethane resin as a binder as an ink exhibiting excellent friction fastness. Since the polycarbonate urethane resin has a high dry film durability, when used as an ink binder, a printed fabric having excellent friction fastness and washing fastness can be obtained. However, on the other hand, the polycarbonate urethane resin is generally inferior in the flexibility of the film, so that there is a problem that the resulting printed fabric has a hard and stiff texture and the texture of the fiber is impaired.

Japanese Patent Laying-Open No. 2015-193742

  The present invention has been made in view of the above problems, and the resulting dried film exhibits excellent flexibility, mechanical properties (breaking strength and breaking elongation), water resistance and chemical resistance, and particularly ink jet printing. It is an object of the present invention to provide an aqueous polyurethane resin dispersion in which a printed fabric exhibits excellent texture and fastness (friction fastness and washing fastness) when used as an ink binder.

As a result of intensive studies to achieve the above object, the present inventors have reached the present invention. That is, the present invention provides a polymer polyol component (a1), a compound (a2) having a hydrophilic group and an active hydrogen group, an active hydrogen component (A) containing a chain extender (a3), and an organic polyisocyanate component (B). A polyurethane resin aqueous dispersion (Q) containing a polyurethane resin (U) and an aqueous medium obtained by reacting and satisfying all of the following (1) to (4) and the polyurethane resin aqueous dispersion (Q) Ink-jet ink (L).
(1) The polymer polyol component (a1) contains a polycarbonate diol (a11) having a hexamethylene group and a number average molecular weight of 1000 to 5000 based on the weight of the (a1) in an amount of 70% by weight or more;
(2) 60 mol% or more of the organic polyisocyanate component (B) is hexamethylene diisocyanate;
(3) The urethane group concentration of the polyurethane resin (U) is 1.0 to 2.4 mmol / g based on the weight of (U);
(4) The urea group concentration of the polyurethane resin (U) is 0.20 to 0.70 mmol / g based on the weight of (U).

  The dry film obtained from the aqueous polyurethane resin dispersion (Q) of the present invention exhibits excellent flexibility, mechanical properties (breaking strength and breaking elongation), water resistance and chemical resistance, and particularly as an ink binder for inkjet printing. When used, the printed fabric is useful as it exhibits excellent texture and fastness (friction fastness and wash fastness).

  The aqueous polyurethane resin dispersion (Q) of the present invention comprises an active hydrogen component (A) containing a polymer polyol component (a1), a compound (a2) having a hydrophilic group and an active hydrogen group, and a chain extender (a3). And a polyurethane resin (U) obtained by reacting the organic polyisocyanate component (B) with an aqueous medium.

  The polymer polyol component (a1) in the present invention contains, as an essential component, a polycarbonate diol (a11) having a hexamethylene group having a number average molecular weight (hereinafter abbreviated as Mn) of 1000 to 5000. When (a1) contains (a11), a polyurethane resin excellent in mechanical properties, water resistance and chemical resistance of the dried film can be obtained.

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

  As (a11), 1,6-hexanediol, 1,6-hexanediol and one or two or more (preferably 1-3) of a polyhydric alcohol having 2 to 20 carbon atoms and a low molecular carbonate compound ( For example, the alkyl group is condensed from a dialkyl carbonate having 1 to 6 carbon atoms, an alkylene carbonate having an alkylene group having 2 to 6 carbon atoms and a diaryl carbonate having an aryl group having 6 to 9 carbon atoms while carrying out a dealcoholization reaction. The polycarbonate polyol etc. manufactured by this are mentioned. (A11) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the polyhydric alcohol having 2 to 20 carbon atoms include linear diols having 2 to 12 carbon atoms or branched aliphatic diols having 3 to 12 carbon atoms [ethylene glycol, 1,3-propylene glycol, 1,4- Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-dodecanediol, diethylene glycol, triethylene glycol And linear alcohols such as tetraethylene glycol; 1,2-propylene glycol, 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2 , 2-diethyl-1,3-propanediol, 2-methyl-1,5-pentanediol, 3-methyl 1,5-pentanediol, 2-methyl-1,6-hexanediol, 3-methyl-1,6-hexanediol, 2-methyl-1,7-heptanediol, 3-methyl-1,7- A branched alcohol such as heptanediol, 4-methyl-1,7-heptanediol, 2-methyl-1,8-octanediol, 3-methyl-1,8-octanediol and 4-methyloctanediol]; 6-20 alicyclic diols [1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,3-cyclopentanediol, 1,4-cycloheptanediol, 2,5 -Bis (hydroxymethyl) -1,4-dioxane, 2,7-norbornanediol, tetrahydrofuran dimethanol, 1, -Bis (hydroxyethoxy) cyclohexane, 1,4-bis (hydroxymethyl) cyclohexane, 2,2-bis (4-hydroxycyclohexyl) propane and the like]; aromatic ring-containing diol having 8 to 20 carbon atoms [m- or p- Xylylene glycol, bis (hydroxyethyl) benzene, bis (hydroxyethoxy) benzene and the like]; triol having 3 to 20 carbon atoms [aliphatic triol (such as glycerin and trimethylolpropane)]; 4 to 5 having 5 to 20 carbon atoms Octahydric alcohols [aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.); saccharides (sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof)] and the like.

  Among the polyhydric alcohols having 2 to 20 carbon atoms, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1 are preferable from the viewpoints of flexibility and mechanical properties of the polyurethane resin (U). , 5-pentanediol, 1,9-nonanediol and 2-methyl-1,8-octanediol, more preferably 1,4-butanediol and 1,5-pentanediol.

  As a commercial product of (a11), Duranol T6002 [polycarbonate diol of Mn = 2000 using 1,6-hexanediol, manufactured by Asahi Kasei Chemicals Co., Ltd.], ETERNACOLL UH-300 [1,6-hexanediol was used. Polycarbonate diol with Mn = 3000, manufactured by Ube Industries, Ltd.], ETERNACOLL UM-90 (1/3) [1,4-cyclohexanedimethanol / 1,6-hexanediol = 1/3 (molar ratio) was used. Mn = 900 polycarbonate diol, manufactured by Ube Industries, Ltd.], Duranol G4672 [1,4-butanediol / 1,6-hexanediol = 70/30 (molar ratio) Mn = 2000 polycarbonate diol, Asahi Kasei Chemicals Co., Ltd.], DURANOL T56 52 [1,5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio) polycarbonate diol with Mn = 2000, manufactured by Asahi Kasei Chemicals Corporation], Kuraray polyol C-2090 [3-methyl Polycarbonate diol with Mn = 2000 using 1,5-pentanediol / 1,6-hexanediol = 90/10 (molar ratio), manufactured by Kuraray Co., Ltd.], Kuraray polyol C-2050 [3-methyl-1 , 5-pentanediol / 1,6-hexanediol = 50/50 (molar ratio), Mn = 2000 polycarbonate diol, manufactured by Kuraray Co., Ltd.].

  The content of (a11) in (a1) is 70% by weight or more based on the weight of (a1), from the viewpoints of flexibility, mechanical properties, water resistance and chemical resistance of the polyurethane resin (U). Is 80% by weight or more, more preferably 90% by weight or more.

  The content of hexamethylene groups in (a11) is based on the total number of moles of hydrocarbon groups constituting (a11) from the viewpoints of flexibility, mechanical properties, water resistance and chemical resistance of the polyurethane resin (U). Is preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more.

(A1) in the present invention may contain a polymer polyol (a12) other than (a11).
Examples of the polymer polyol (a12) other than (a11) include a polyester polyol (a121) having an Mn of 500 or more and a polyether polyol (a122) having an Mn of 500 or more.
(A12) may be used alone or in combination of two or more.

  Examples of the polyester polyol (a121) include condensed polyester polyols, polylactone polyols, polycarbonate diols other than (a11), and castor oil-based polyols.

  The condensation type polyester polyol is a polyester polyol obtained by dehydration condensation of the polyhydric alcohol having 2 to 20 carbon atoms and the polyvalent carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof.

  Examples of the polyvalent carboxylic acid having 2 to 10 carbon atoms or an ester-forming derivative thereof include aliphatic dicarboxylic acids (such as succinic acid, adipic acid, azelaic acid, sebacic acid, fumaric acid and maleic acid), and alicyclic dicarboxylic acids ( Dimer acids, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.), trivalent or higher polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.), and their anhydrides (succinic anhydride, Maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.), their acid halides (such as adipic acid dichloride), their low molecular weight alkyl esters (such as dimethyl succinate and dimethyl phthalate), and mixtures thereof. . Of these, preferred are aliphatic dicarboxylic acids and ester-forming derivatives thereof.

  Specific examples of the condensed polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyhexamethylene terephthalate 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 aze Rate diol, polybutylene sebacate diol and poly Oh pliers Rutere terephthalate diol.

  Commercially available products of condensed polyester polyol include San Ester 2610 [polyethylene adipate diol with Mn = 1000, manufactured by Sanyo Chemical Industries, Ltd.], San Ester 4620 [Polytetramethylene adipate diol with Mn = 2000], San Ester 2620 [ Polyethylene adipate diol with Mn = 2000, manufactured by Sanyo Chemical Industries, Ltd.], Kuraray polyol P-2010 [poly-3-methyl-1,5-pentane adipate diol with Mn = 2000], Kuraray polyol P-3010 [Mn = 3000 poly-3-methyl-1,5-pentane adipate diol] and Kuraray polyol P-6010 [Mn = 6000 poly-3-methyl-1,5-pentane adipate diol].

The polylactone polyol is a polyaddition product of a lactone to the polyhydric alcohol having 2 to 20 carbon atoms. As the lactone, a lactone having 4 to 12 carbon atoms (for example, γ-butyrolactone, γ-valerolactone, and ε-caprolactone). ) And the like.
Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

  As polycarbonate diols other than (a11), one or two or more of the polyhydric alcohols having 2 to 20 carbon atoms other than 1,6-hexanediol and the low molecular carbonate compound are subjected to a dealcoholization reaction. Examples include polycarbonate polyols produced by condensation.

  As a commercially available polycarbonate diol other than (a11), Mn = 2000 using Kuraray polyol C-2015N [2-methyl-1,8-octanediol / 1,9-nonanediol = 85/15 (molar ratio). Polycarbonate diol, manufactured by Kuraray Co., Ltd.], Kuraray polyol C-2065N [2-methyl-1,8-octanediol / 1,9-nonanediol = 65/15 (molar ratio) Mn = 2000 polycarbonate Diol, manufactured by Kuraray Co., Ltd.], ETERNACOLL UC-100 [polycarbonate diol of Mn = 1000 using 1,4-cyclohexanedimethanol, manufactured by Ube Industries, Ltd.], and the like.

  The castor oil-based polyol includes castor oil and modified castor oil modified with polyol or alkylene oxide (hereinafter abbreviated as 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 castor oil ethylene oxide (hereinafter abbreviated as EO) (addition mole number: 4 to 30 mol). .

  Examples of the polyether polyol (a122) include aliphatic polyether polyols and aromatic ring-containing polyether polyols.

  Examples of the aliphatic polyether polyol include polyoxyalkylene polyol [polyethylene glycol and the like], polyoxypropylene polyol [polypropylene glycol and the like], and polyoxyethylene / propylene polyol and polytetramethylene ether glycol.

  Commercially available products of aliphatic polyether polyols include PTMG1000 [poly (oxytetramethylene) glycol with Mn = 1000, manufactured by Mitsubishi Chemical Corporation], PTMG2000 [poly (oxytetramethylene) glycol with Mn = 2000, Mitsubishi Chemical ( Ltd.], PTMG3000 [poly (oxytetramethylene) glycol with Mn = 3000, manufactured by Mitsubishi Chemical Corporation], PTGL2000 [modified poly (oxytetramethylene) glycol with Mn = 2000, manufactured by Hodogaya Chemical Co., Ltd. ], PTGL3000 [modified poly (oxytetramethylene) glycol with Mn = 3000, manufactured by Hodogaya Chemical Co., Ltd.], SANNICS PP-2000 [polypropylene glycol with Mn = 2000, manufactured by Sanyo Chemical Industries, Ltd.] and Sun Nicksdiol GP-3000 Mn = 3000 polypropylene ether triol, Sanyo Chemical Industries, Ltd.], and the like.

  Examples of aromatic polyether polyols include EO addition products of bisphenol A [EO 2 mol addition product of bisphenol A, EO 4 mol addition product of bisphenol A, EO 6 mol addition product of bisphenol A, EO 8 mol addition product of bisphenol A, and bisphenol A. EO 10 mol adduct and bisphenol A EO 20 mol adduct etc.] and bisphenol A propylene oxide (hereinafter abbreviated as PO) adduct [PO2 mol adduct of bisphenol A, PO3 mol adduct of bisphenol A and bisphenol A PO5 mol adducts, etc.] and other polyols having a bisphenol skeleton, resorcin EO or PO adducts, and the like.

  Mn of (a12) is preferably 500 to 6000, more preferably 1000 to 4000 from the viewpoints of flexibility, mechanical properties, water resistance and chemical resistance of the polyurethane resin (U).

Examples of the compound (a2) having a hydrophilic group and an active hydrogen atom include a compound (a21) having an anionic group and an active hydrogen atom, and a compound (a22) having a cationic group and an active hydrogen atom.
As (a21), for example, a compound having 2 to 10 carbon atoms having a carboxyl group as an anionic group and a hydroxyl group as an active hydrogen atom [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)], having a sulfonic acid group as an anionic group A compound having 2 to 16 carbon atoms having a hydroxyl group as an active hydrogen atom [3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid and sulfoisophthalic acid di (ethylene glycol) ester, etc.], an anionic group A compound having 2 to 10 carbon atoms and having a sulfamic acid group and a hydroxyl group as an active hydrogen atom N, N-bis (2-hydroxyethyl) salts obtained by neutralizing with a neutralizing agent such as sulfamic acid] and the like as well as their compounds. (A2) may be used alone or in combination of two or more.

Examples of the neutralizing agent used in the salt of (a21) 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. The neutralizing agent used for the salt of (a21) may be used individually by 1 type, or may use 2 or more types together.

  As the neutralizing agent used for the salt of (a21), a compound having a high vapor pressure at 25 ° C. is preferable from the viewpoint of the drying property of the aqueous polyurethane resin dispersion to be formed and the water resistance of the resulting film. From such a viewpoint, the neutralizing agent used in the salt of (a21) is preferably ammonia, monomethylamine, monoethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine or dimethylethylamine.

  Among (a21), 2,2-dimethylolpropionic acid and 2,2-dithioic acid are preferred from the viewpoints of mechanical properties, water resistance, chemical resistance and dispersion stability of the polyurethane resin aqueous dispersion. Methylol butanoic acid and salts thereof are more preferred, and neutralized salts of 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid with ammonia or amine compounds having 1 to 20 carbon atoms.

  Examples of the compound (a22) having a cationic group and an active hydrogen atom include a compound having a tertiary amino group as a cationic group and a hydroxyl group as an active hydrogen atom, and a tertiary amino group-containing diol having 1 to 20 carbon atoms. [N-alkyl dialkanolamines (eg N-methyldiethanolamine, N-propyldiethanolamine, N-butyldiethanolamine and N-methyldipropanolamine) and N, N-dialkylmonoalkanolamines (eg N, N-dimethylethanolamine) Etc.] and the like are neutralized with a neutralizing agent.

  Examples of the neutralizing agent used in (a22) include monocarboxylic acids having 1 to 10 carbon atoms (for example, formic acid, acetic acid, propanoic acid, etc.), carbonic acid, dimethyl carbonate, dimethyl sulfate, methyl chloride, and benzyl chloride. .

  The neutralizing agent used in (a21) and (a22) is added before the urethanization reaction, during the urethanization reaction, after the urethanization reaction, before the water dispersion step, during the water dispersion step, or after the water dispersion. However, from the viewpoint of the stability of the urethane resin and the stability of the aqueous dispersion, it is preferably added before or during the water dispersion step. Further, the neutralizing agent volatilized at the time of solvent removal may be added after the solvent removal, and the type of neutralizing agent to be added can be freely selected from those described above.

  The amount of (a2) used is such that the content of the hydrophilic group in (U) is preferably 0.14 to 0.45 mmol / g, more preferably 0.16 to 0, based on the weight of (U). .40 mmol / g, particularly preferably 0.18 to 0.35 mmol / g.

  Examples of the chain extender (a3) include water, the above polyhydric alcohol having 2 to 20 carbon atoms, and an aliphatic polyamine having 2 to 36 carbon atoms [alkylene diamine such as ethylene diamine and hexamethylene diamine; diethylene triamine, dipropylene triamine, dihexylene. Poly (n = 2-6) alkylene (2-6 carbon atoms) poly (n = 3-7) amine etc. such as triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine], C6-C20 alicyclic polyamine (1,3- or 1,4-diaminocyclohexane, 4,4′- or 2,4′-dicyclohexylmethanediamine, isophoronediamine, etc.), C6-C20 aroma Group polyamines (1,3- or 1,4-phenylenediamine, 2,4- or 2 6-tolylenediamine, 4,4′- or 2,4′-methylenebisaniline, etc.), C3-C20 heterocyclic polyamines (2,4-diamino-1,3,5-triazine, piperazine and the like) N-aminoethylpiperazine etc.), hydrazine or derivatives thereof (dibasic acid dihydrazide such as adipic acid dihydrazide etc.) and amino alcohols having 2 to 20 carbon atoms (eg ethanolamine, diethanolamine, 2-amino-2-methylpropanol and Triethanolamine) and the like. (A3) may be used alone or in combination of two or more.

  Among (a3), from the viewpoints of flexibility and mechanical properties of the polyurethane resin (U), water or water and an aliphatic diol having 3 to 12 carbon atoms having the above-mentioned branch are preferable, and water is more preferable. Or water and neopentyl glycol.

The polyurethane resin (U) in this invention can use a reaction terminator (a4) as needed.
As the reaction terminator (a4), monoalcohols having 1 to 20 carbon atoms (methanol, ethanol, butanol, octanol, decanol, dodecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, etc.), monoamines having 1 to 20 carbon atoms (Mono- or dialkylamines such as monomethylamine, monoethylamine, monobutylamine, dibutylamine and monooctylamine, and mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine). As the reaction terminator (a4), one type may be used alone, or two or more types may be used in combination.

  As an organic polyisocyanate component (B) in this invention, C3-C22 aromatic polyisocyanate (b1) which has 2-3 or more isocyanate groups, C4-C22 aliphatic polyisocyanate ( Examples thereof include b2), alicyclic polyisocyanates having 8 to 18 carbon atoms (b3), araliphatic polyisocyanates having 10 to 18 carbon atoms (b4), and modified products of these polyisocyanates (b5). An organic polyisocyanate component (B) may be used individually by 1 type, or may use 2 or more types together.

  Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter referred to as tolylene diisocyanate as TDI). Abbreviation), crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenyl Methane triisocyanate and m- or p-isocyanatophenylsulfonyl Cyanate and the like.

  Examples of the aliphatic polyisocyanate (b2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2 , 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate is mentioned.

  Examples of the alicyclic polyisocyanate having 8 to 18 carbon atoms (b3) include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4′-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, Mention may be made of methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

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

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

  The polyurethane resin (U) in the present invention essentially contains HDI as the organic polyisocyanate component (B), and the content thereof is 60 mol% or more based on the total number of moles of the organic polyisocyanate component (B). By containing 60 mol% or more of HDI with respect to the total number of moles of the organic polyisocyanate (B), a polyurethane resin having excellent dry film flexibility can be obtained.

  From the viewpoint of the flexibility of the polyurethane resin (U), the proportion of HDI in (B) is preferably 60 mol% or more, more preferably 70 mol% or more, particularly preferably relative to the total number of moles of (B). Is 80 mol% or more.

  From the viewpoint of flexibility of the polyurethane resin (U), the organic polyisocyanate component other than HDI used in (B) is preferably the alicyclic polyisocyanate (b3) having 8 to 18 carbon atoms, and IPDI is preferred.

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

  The urethane group concentration of the polyurethane resin (U) in the present invention is preferably 1.0 to 2 on the basis of the weight of (U) from the viewpoints of the flexibility, mechanical properties, water resistance and chemical resistance of (U). 0.4 mmol / g, more preferably 1.2 to 2.0 mmol / g, particularly preferably 1.3 to 1.8 mmol / g.

  The urea group concentration of the polyurethane resin (U) in the present invention is preferably 0.20 to 0, based on the weight of (U), from the viewpoint of the flexibility, mechanical properties, water resistance and chemical resistance of (U). .70 mmol / g, more preferably 0.22 to 0.65 mmol / g, and particularly preferably 0.25 to 0.60 mmol / g.

  Mn of the polyurethane resin (U) in the present invention is preferably 10,000 or more, more preferably 50,000 or more, particularly preferably 100,000 or more, from the viewpoint of mechanical properties, water resistance, and chemical resistance of (U). .

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

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

[1] an active hydrogen component (A) containing a polymer polyol component (a1), a compound (a2) having a hydrophilic group and an active hydrogen group, a chain extender (a3) and, if necessary, a reaction terminator (a4); A polyurethane resin (U) is produced by reacting the organic polyisocyanate component (B) in one or more steps in the presence or absence of the organic solvent (S), and if necessary, hydrophilic groups introduced by (a2) A method in which the organic solvent (S) is distilled off if necessary after the portion is made a salt with a neutralizing agent and dispersed in an aqueous medium.

[2] A polymer polyol component (a1), a compound (a2) having a hydrophilic group and an active hydrogen group, an active hydrogen component (A) containing a chain extender (a3), and an organic polyisocyanate component (B). In the presence or absence of the organic solvent (S), a urethane prepolymer having an isocyanate group at one end or in multiple stages is produced, and then, if necessary, the hydrophilic group portion introduced by (a2) in the prepolymer After neutralization, the salt is dispersed in an aqueous medium and reacted with the chain extender (a3) and, if necessary, the reaction terminator (a4) until the isocyanate group substantially disappears, and then the organic solvent (S) is distilled if necessary. How to leave.

  The reaction temperature for producing the polyurethane resin (U) in [1] and the reaction temperature for producing the urethane prepolymer in [2] are preferably 60 to 120 ° C., more preferably from the viewpoint of suppressing side reactions. It is 60-110 degreeC, Most preferably, it is 60-100 degreeC. The production time can be appropriately selected depending on the equipment to be used, but is generally preferably 1 minute to 100 hours, more preferably 3 minutes to 30 hours, and particularly preferably 5 minutes to 20 hours.

As the organic solvent (S), a solvent substantially non-reactive with an isocyanate group is selected. For example, ketone solvents (for example, acetone and methyl ethyl ketone), ester solvents [for example, ethyl acetate and dibasic acid ester (DBE)], Examples include ether solvents (for example, tetrahydrofuran), amide solvents (for example, N, N-dimethylformamide and N-methylpyrrolidone), and aromatic hydrocarbon solvents (for example, toluene). These organic solvents (S) may be used alone or in combination of two or more.
The aqueous medium in the present invention means water or a mixture of water and the organic solvent (S).

The organic solvent (S) is preferably an organic solvent having a boiling point of less than 100 ° C., and examples thereof include acetone, methyl ethyl ketone, ethyl acetate, and tetrahydrofuran.
By using an organic solvent having a boiling point of less than 100 ° C., it becomes easy to completely remove only the organic solvent from the aqueous medium, and it remains in the aqueous dispersion and it is easy to suppress the generation of the organic solvent during drying. . Moreover, it becomes difficult for the organic solvent to remain in the film, and it becomes easy to suppress changes in mechanical properties of the film over time.

  The content of the organic solvent (S) in the aqueous polyurethane resin dispersion (Q) is 1% by weight or less based on the weight of (Q) from the viewpoint of odor, stability over time, environmental load, and safety. Preferably, it is 0.8 wt% or less, more preferably 0.5 wt% or less.

  In the urethanization reaction in the methods [1] and [2] described above, a known urethanization catalyst can be used as necessary in order to accelerate the reaction. The addition amount of the urethanization catalyst is preferably 0.001 to 3% by weight, more preferably 0.005 to 2% by weight, particularly preferably 0.01 to 1% by weight, based on the weight of the polyurethane resin (U). is there.

  Examples of the urethanization catalyst include metal catalysts (such as tin-based (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate and dibutyltin maleate), lead-based ( Lead oleate, lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc., cobalt (cobalt naphthenate, etc.), bismuth {bismuth tris (2-ethylhexanoate, etc.) and mercury (phenylmercury) Propionate, etc.)], amine catalysts [triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkenes {1,8-diazabicyclo [5.4.0] -7-undecene}, etc .; dialkyl Aminoalkylamines {Dime Ruaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine and dipropylaminopropylamine etc.] or heterocyclic aminoalkylamines [2- (1-aziridinyl) ethylamine and 4- ( 1-piperidinyl) -2-hexylamine etc.] carbonates or organic acid salts (formate etc.) etc .; N-methylmorpholine, N-ethylmorpholine, triethylamine, diethylethanolamine, dimethylethanolamine etc.], and these The mixture of 2 or more types is mentioned.

  The apparatus for dispersing the polyurethane resin (U) of [1] or its organic solvent solution, the urethane prepolymer of [2] or its organic solvent solution in water is not particularly limited, but a rotary dispersion mixing apparatus, ultrasonic wave It is preferable to use a type disperser or a kneader, and among them, a rotary type disperser / mixer having particularly excellent dispersibility is more preferable.

  Examples of the rotary dispersion mixing device 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 MTechnic Co., Ltd.], fill mix [Primics Co., Ltd.], Ultra Turrax [IKA Co., Ltd.], Ebara Milder [Ebara Seisakusho Co., Ltd.], Cavitron (Eurotech Co., Ltd.), Biomixer [Nihon Seiki Co., Ltd.], etc. Is exemplified.

  The polyurethane resin (U) can be dispersed in an aqueous medium using a dispersant (H), but from the viewpoint of water resistance of the resulting dried film, the amount used is preferably as small as possible. It is particularly preferred not to do so.

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

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

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

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

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

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

  The dispersant (H) may be added at any time after the urethanization reaction of the polyurethane resin (U), before the water dispersion step of (U), during the water dispersion step or after water dispersion. From the viewpoint of the dispersibility of the aqueous dispersion and the stability of the aqueous dispersion, it is preferably added before or during the water dispersion step.

  When (H) is used, its content is preferably based on the weight of the polyurethane resin (U) from the viewpoint of the water resistance of the dry film, the dispersibility of the polyurethane resin (U) and the stability of the aqueous dispersion. It is 0.01-7 weight%, More preferably, it is 0.01-5 weight%, Most preferably, it is 0.1-3 weight%.

  The aqueous polyurethane resin dispersion (Q) in the present invention can contain a blocked polyisocyanate (C). The blocked polyisocyanate (C) is particularly useful when the polyurethane resin (U) is fixed to an adherend having a hydroxyl group such as paper or cotton cloth, and after being subjected to a heating step, both the adherend and the polyurethane resin are used. By reacting, the adhesion of the polyurethane resin to the adherend can be improved. For example, when the polyurethane resin aqueous dispersion (Q) is used as an ink binder for ink jet printing, the washing fastness and friction fastness of the printing cloth can be improved by containing (C) in (Q). Can do.

  The blocked polyisocyanate (C) is obtained by reacting the polyisocyanate compound (c1) with the isocyanate blocking agent (c2).

As the polyisocyanate compound (c1) used in (C), a prepolymer having an isocyanate group obtained by a reaction of the organic polyisocyanate component (B) and the active hydrogen component (A) with the organic polyisocyanate component (B). Examples thereof include polymers.
(C1) may be used alone or in combination of two or more.

  The number average functional group number of the isocyanate group of the polyisocyanate compound (c1) is preferably 2.0 or more, more preferably 2.1 or more, particularly preferably from the viewpoint of adhesion of the polyurethane resin (U) to the adherend. Is 2.4 or more.

  The isocyanate group content of the polyisocyanate compound (c1) is preferably 2 to 30% by weight, more preferably 2.5 to 28% by weight, particularly preferably 3 to 25% by weight, from the viewpoint of adhesion of the polyurethane resin (U). %.

  Examples of the isocyanate blocking agent (c2) include lactams having 2 to 6 carbon atoms (for example, ε-caprolactam, δ-valerolactam, γ-butyrolactam, etc.), oximes having 1 to 15 carbon atoms [for example, acetoxime, methyl ethyl ketoxime (MEK). Oxime), methyl isobutyl ketoxime (MIBK oxime), cyclohexanone oxime, etc.], secondary amines having 2 to 15 carbon atoms [for example, aliphatic amines (dimethylamine, diisopyramine, di-n-propylamine, diisobutylamine, etc.), C4-C15 alicyclic amines (such as methylhexylamine and dicyclohexylamine), aromatic amines (such as aniline and diphenylamine)], C6-C20 phenols and alkylphenols [for example, phenol, cresol, ethylphenol , N-propylphenol, isopropylphenol, n-butylphenol, octylphenol, nonylphenol, xylenol, diisopropylphenol and di-t-butylphenol], 5 having an imino group and a nitrogen-carbon double bond as a structural unit of the ring Member ring compounds [for example, imidazole, 2-methylimidazole, pyrazole, 3-methylpyrazole and 3,5-dimethylpyrazole, 1,2,4-triazole, etc.], imines [for example, ethyleneimine and polyethyleneimine, etc.], containing active methylene Compounds [eg, dimethyl malonate, diethyl malonate, diisopropyl malonate, acetylacetone, methyl acetoacetate, ethyl acetoacetate, etc.], Patent Publication No. 2002-309217 and Patent Publication No. 2008-239 Blocking agents described in JP-90 and mixtures of two or more thereof. Among these, preferred are an oxime having 1 to 15 carbon atoms, a secondary amine having 2 to 15 carbon atoms, a 5-membered ring compound having an imino group and a nitrogen-carbon double bond as a ring structural unit, and active methylene. Preferred compounds are methyl ethyl ketoxime, diisopropylamine, 3,5-dimethylpyrazole and diethyl malonate.

  The reaction temperature of the polyisocyanate compound (c1) and the blocking agent (c2) is preferably 20 to 120 ° C, more preferably 40 to 110 ° C, from the viewpoint of suppressing side reactions. The reaction time is preferably 0.5 to 5 hours, more preferably 0.5 to 4 hours from the viewpoint of side reaction suppression.

  As the polyisocyanate compound (c1), when the active hydrogen component (A) and the organic polyisocyanate component (B) are reacted to produce a prepolymer having an isocyanate group, the urethanization catalyst is used to accelerate the urethanization reaction. Can be used.

  The amount of the reaction catalyst used is preferably 1% by weight or less, more preferably 0.001 to 0.1% by weight, based on the weight of the resulting blocked polyisocyanate (C).

The block polyisocyanate (C) of the present invention can be used by diluting with an organic solvent if necessary. As an organic solvent, the thing similar to what was illustrated by the said organic solvent (S), for example is mentioned, A preferable thing is also the same.
Block polyisocyanate (C) may be used individually by 1 type, or may use 2 or more types together.

  From the viewpoints of adhesion of the polyurethane resin (U) to the adherend, dispersion stability and storage stability of the aqueous polyurethane resin dispersion (Q), the amount of the blocked polyisocyanate (C) used is polyurethane resin (U ), Preferably 3 to 50% by weight, more preferably 4 to 40% by weight, particularly preferably 5 to 30% by weight.

  In order to reduce the dissociation temperature of the blocking agent of the blocked polyisocyanate compound (C) and increase the reaction rate, a blocked isocyanate dissociation catalyst may be used.

Examples of the dissociation catalyst include metal catalysts such as dibutyltin dilaurate, tin octylate, bismuth octylate, bismuth naphthenate, tin acetylacetonate, bismuth acetylacetonate and titanium acetylacetonate; 1,8-diazabicyclo [5.4 .0] -undecene-7, 1,8-diazabicyclo [5.4.0] -undecene-7 weak acid salts (phenol salts, 2-ethylhexanoate, formate, etc.), 1,5-diazabicyclo [4 .3.0] -Nonene-5, 1,5-diazabicyclo [4.3.0] -nonene-5 weak acid salt (phenol salt, 2-ethylhexanoate, formate, etc.), tetramethylammonium weak acid Salt (phenol salt, 2-ethylhexanoate, formate, etc.), methyltriethylammonium weak acid salt (phenol salt, 2- Tilhexanoate and formate, etc.), tetraethylammonium weak acid salt (phenol salt, 2-ethylhexanoate, formate, etc.), (2-hydroxypropyl) trimethylammonium weak acid salt (phenol salt, 2-ethylhexanoic acid) And amine catalysts such as salts and formate salts).
A dissociation catalyst may be used individually by 1 type, or may use 2 or more types together.

  In the blocked polyisocyanate (C), the blocking agent is dissociated by heating, and the isocyanate group generated by the dissociation reacts with the adherend and / or the polyurethane resin (U). The temperature required for deblocking is preferably 60 to 200 ° C., and the heating time is preferably 1 minute to 5 hours.

  As a method for producing a polyurethane resin aqueous dispersion (Q) containing a blocked polyisocyanate (C), (C) is dispersed in an aqueous medium separately from (U) by the dispersant (H), and dispersed. A method of blending with the polyurethane resin (U) after the process, or (U) and (C) are mixed before dispersing the (U) in the aqueous medium, and the dispersion process is carried out in the aqueous medium as described above. Methods and the like.

  Among these methods, from the viewpoint of dispersion stability and storage stability of the aqueous polyurethane resin dispersion (Q), it is preferable to mix (U) and (C) before dispersing (U) in an aqueous medium. In this method, a dispersion is obtained through the dispersion step in the aqueous medium.

  The aqueous polyurethane resin dispersion (Q) in the present invention can contain dimethyl silicone (D). When the aqueous polyurethane resin dispersion (Q) is used for ink jet printing, the texture and friction fastness of the printing cloth are improved by the fact that (Q) contains dimethyl silicone (D).

  Examples of dimethyl silicone (D) include oil-type dimethyl silicone (d1) and emulsion-type dimethyl silicone (d2) in which (d1) is dispersed in an aqueous medium using a dispersant. (D) may be used individually by 1 type, or may use 2 or more types together.

  Commercial products of oil-type dimethyl silicone oil (d1) include SH200 series [Toray Dow Corning Co., Ltd.], KF-96 series [Shin-Etsu Chemical Co., Ltd.] and TSF451 series [Momentive Performance Materials Manufactured by Japan GK Co., Ltd.].

  Commercially available products of emulsion type dimethyl silicone (d2) include SM8706EX, FSXE-2098, IE-7045, SM7036EX, IE7046T and SM8701EX [manufactured by Toray Dow Corning Co., Ltd.], POLON MF-7, POLON MF-17, POLON MF-32 and POLON MF-33 [manufactured by Shin-Etsu Chemical Co., Ltd.], TSM630, TSM631, TSM6344 and TSM6343 [manufactured by Momentive Performance Materials Japan GK], and the like.

Of the dimethyl silicone (D), (d2) is preferred from the viewpoint of dispersion stability of the aqueous polyurethane resin dispersion (Q).
Dimethyl silicone (D) may be used alone or in combination of two or more.

  The amount of dimethyl silicone (D) used is the weight of the polyurethane resin (U) from the viewpoint of the texture of the printed fabric, the friction fastness and the wash fastness when the aqueous polyurethane resin dispersion (Q) is used for ink jet printing. Is preferably 1 to 15% by weight, more preferably 2 to 12% by weight, and particularly preferably 3 to 10% by weight.

  As a method for producing an aqueous polyurethane resin dispersion (Q) containing dimethyl silicone oil (D), when (D) is an oil-type dimethyl silicone oil (d1), the polyurethane resin (U) is dispersed in an aqueous medium. (U) and (d1) may be mixed before the dispersion step in the aqueous medium described above. If (D) is an emulsion-type dimethyl silicone oil (d2), after (U) the dispersion step ( What is necessary is just to mix | blend d2).

  The volume average particle diameter (Dv) of the polyurethane resin (U) in the polyurethane aqueous dispersion (Q) is preferably 0.01 to 0.3 μm, more preferably 0, from the viewpoint of dispersion stability of the polyurethane resin aqueous dispersion. 0.01 to 0.2 μm. When (Dv) is 0.01 μm or more, the viscosity is appropriate and the handling property is good, and when it is 0.3 μm or less, the ejection stability of ink when using the ink jet ink (Q) is good.

The volume average particle diameter (Dv) of (U) can be controlled by the hydrophilic group, the neutralizing agent, the amount of the dispersing agent in (U), the type of dispersing machine used in the dispersing step, and the dispersing conditions.
The volume average particle diameter (Dv) can be measured with a light scattering particle size distribution analyzer [LA950 V2 “manufactured by Horiba, Ltd.”].

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

  The viscosity of (Q) is preferably 5000 mPa · s or less, more preferably 1000 mPa · s or less, from the viewpoint of handling properties. The viscosity can be measured at a constant temperature of 25 ° C. using a BL type viscometer.

  The pH of (Q) is preferably 2 to 12 and more preferably 4 to 10 from the viewpoint of dispersion stability. The pH can be measured at 25 ° C. with pH Meter M-12 [manufactured by Horiba, Ltd.].

  The inkjet ink (L) of the present invention contains the aqueous polyurethane resin dispersion (Q) of the present invention. Ink-jet inks containing (Q) are particularly suitable as inks for ink-jet printing because printing fabrics using them exhibit excellent texture and fastness (friction fastness and washing fastness).

  The ink-jet ink (L) of the present invention can contain, in addition to (Q), a coloring material as an essential component and a humectant, a penetrating agent, water and other additives as optional components.

Examples of the color material include dyes and pigments.
Although it does not specifically limit as dye, According to the medium to be used, reactive dye, vat dye, naphthol dye, sulfur dye, direct dye, acid dye, metal complex type dye, disperse dye, cationic dye, etc. are mentioned.

  Examples of the pigment include inorganic pigments (for example, white pigments, black pigments, gray pigments, red pigments, brown pigments, yellow pigments, green pigments, blue pigments, purple pigments and metallic pigments) 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 lakes, Pigments from vat dyes and phthalocyanine pigments).

  Of these coloring materials, pigments are preferred for the ink-jet ink (L) of the present invention. The content of the color material is preferably 50% by weight or less, more preferably 30% by weight or less, based on the weight of the inkjet ink (L). A color material may be used individually by 1 type, or may use 2 or more types together.

  A moisturizing agent plays a role in preventing ink from being dried and preventing clogging of the nozzle by being blended in the ink. The boiling point of the humectant is preferably 150 ° C. or higher.

  The humectant is not particularly limited, and for example, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, pentamethylene glycol, trimethylene glycol, 2-butene-1,4-diol, 2-ethyl-1,3- Hexanediol, 2-methyl-2,4-pentanediol, tripropylene glycol, polyethylene glycol with Mn of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, glycerin, mesoerythritol, pentaerythritol, 2- Examples include pyrrolidone, N-methyl-2-pyrrolidone, and N-ethyl-2-pyrrolidone. A moisturizer may be used individually by 1 type, or may use 2 or more types together.

  The penetrant is an organic solvent or a surfactant, and plays a role of promoting the penetration of the ink into the permeable medium.

  The organic solvent that can be used as the penetrant is not particularly limited. For example, glycol ethers [ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol mono-t-butyl ether, triethylene glycol monobutyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene Recall monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, propylene glycol monobutyl ether and dipropylene glycol monobutyl ether] and fats having 4 to 8 carbon atoms Diols [1,2-alkyldiols such as 1,2-pentanediol and 1,2-hexanediol, and 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Straight chain alcohols such as hexanediol, 1,7-heptanediol and 1,8-octanediol].

  The surfactant that can be used as the penetrating agent is not particularly limited. For example, acetylene glycol surfactant, acetylene alcohol surfactant, polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl Ether surfactants such as ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene oleic acid, polyoxyethylene olein Acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, Ester surfactants such as bitane sesquioleate, polyoxyethylene monooleate and polyoxyethylene stearate, silicone surfactants such as dimethylpolysiloxane, and fluorine-based interfaces such as fluoroalkyl esters and perfluoroalkylcarboxylates Examples include activators. One penetrant may be used alone, or two or more penetrants may be used in combination.

Examples of other additives include preservatives and pH adjusters.
Examples of preservatives include sodium benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, sodium sorbate, sodium dehydroacetate, and 1,2-dibenzthiazolin-3-one.

pH adjusters include potassium dihydrogen phosphate, disodium hydrogen phosphate, sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonia, diethanolamine, triethanolamine, triisopropanolamine, potassium carbonate, sodium carbonate and hydrogen carbonate Sodium etc. are mentioned.
Other additives may be used alone or in combination of two or more.

  The aqueous polyurethane resin dispersion (Q) of the present invention includes, in addition to ink jet inks, aqueous paints, aqueous adhesives, aqueous fiber processing agents (nonwoven fabric binders, reinforcing fiber bundling agents, antibacterial agent binders, and artificial leathers). -Raw materials for synthetic leather, etc.), aqueous coatings, aqueous paper treatment agents, etc.

  When used in these applications, in addition to the above-mentioned pigments, humectants, penetrants, preservatives and pH adjusters, other resins and crosslinking agents, viscosity modifiers, leveling agents, anti-degradation agents, stability agents as necessary 1 type (s) or 2 or more types can be added and an antifreezing agent.

<Production example of blocked polyisocyanate (C)>
<Production Example 1>
In a reaction vessel equipped with a stirrer and a thermometer, isocyanurate of hexamethylene diisocyanate [“Duranate TPA-100” manufactured by Asahi Kasei Co., Ltd.] 45.1 parts, 30 parts of methyl ethyl ketone as a solvent, and 3,5-dimethylpyrazole 24.9 parts were charged, and the blocking reaction was performed at 70 ° C. for 2 hours to obtain a solvent solution of the blocked polyisocyanate (C-1).

<Production Example 2>
In a reaction vessel equipped with a stirrer and a thermometer, 31.2 parts of polyether polyol (“Sanix PP-1000” manufactured by Sanyo Chemical Industries, Ltd .; Mn = 1000), polyether polyol (Sanyo Chemical Industries, Ltd.) “Sanix TP-400” (Mn = 400) manufactured by 12.5 parts, 20.4 parts of tolylene diisocyanate and 30 parts of methyl ethyl ketone as a solvent were prepared and reacted at 80 ° C. for 5 hours in a dry nitrogen atmosphere. After cooling to obtain a polyisocyanate compound, 5.9 parts of methyl ethyl ketone oxime was charged at 40 ° C. and a blocking reaction was performed at 70 ° C. for 2 hours to obtain a solvent solution of the blocked polyisocyanate (C-2). .

<Example 1>
In a simple pressure reactor equipped with a stirrer and a heating device, 204.4 parts of DURANOL G4672 (manufactured by Asahi Kasei Chemicals Co., Ltd.) as (a11), and 26.7 of 2,2-dimethylolpropionic acid as (a2) Parts, 17.9 parts of neopentyl glycol as (a3), 111.0 parts of HDI as the organic polyisocyanate component (B) and 150.0 parts of acetone as the reaction solvent, and stirred at 80 ° C. for 10 hours Urethane reaction was performed to produce an acetone solution of a polyurethane prepolymer. Next, 25.0 parts of a solvent solution of the blocked polyisocyanate (C-1) obtained in Production Example 1 was added to the obtained polyurethane prepolymer, 11.3 parts of triethylamine as a neutralizing agent, and acetone 72. After adding 0 part and homogenizing, the chain extender (a3) and 482.1 parts of water as an aqueous medium are added with stirring at 200 rpm, and the mixture of polyurethane prepolymer and blocked isocyanate (C-1) is added to water. Dispersed. The obtained dispersion was heated to 50 ° C. and stirred for 4 hours to perform an extension reaction with water, and further heated to 60 ° C. under reduced pressure to distill off acetone. Then, after cooling the obtained dispersion to room temperature, SM8.66EX (solid content concentration: 37% by weight, manufactured by Toray Dow Corning Co., Ltd.) as dimethyl silicone (D) was added and homogenized, and water was added. In addition, an aqueous polyurethane resin dispersion (Q-1) was obtained by adjusting the solid content concentration to 30.0% by weight.

<Examples 2 to 8>
Except that the raw materials to be used and the amounts used were those described in Table 1, polyurethane resin aqueous dispersions (Q-2) to (Q-9) were obtained in the same manner as in Example 1.

<Comparative Example 1>
A polyurethane resin aqueous dispersion (Q′-1) was obtained in the same manner as in Example 1 except that the raw materials to be used and the amounts used were as shown in Table 1.

<Comparative Example 2>
A mixture of the polyurethane prepolymer and the blocked isocyanate (C-2) was dispersed in an aqueous medium in the same manner as in Example 1 except that the raw materials used and the amounts used were as described in Table 1. To the obtained dispersion was added 45.8 parts of a 10% by weight aqueous solution of diethylenetriamine as a chain extender (a3), and the mixture was heated to 50 ° C. and stirred for 4 hours to carry out an extension reaction with water and diethylenetriamine. Acetone was distilled off at 60 ° C. under reduced pressure, and after cooling to room temperature, 95.8 parts of POLON MF-32 [solid content concentration 31% by weight, manufactured by Shin-Etsu Chemical Co., Ltd.] as dimethyl silicone (D) was added and uniform. The aqueous polyurethane resin dispersion (Q′-2) was obtained by adding water to adjust the solid content concentration to 30.0% by weight.

<Comparative Examples 3-4>
Except that the raw materials to be used and the amounts used are those described in Table 1, aqueous polyurethane resin dispersions (Q′-3) to (Q′-4) were obtained in the same manner as in Example 1.

The composition of each raw material in Table 1 is as follows.
Duranol G4672: poly (tetramethylene / hexamethylene) carbonate diol (manufactured by Asahi Kasei Chemicals Corporation) with Mn = 2000, content of hexamethylene group = 30 mol%
Duranol T5652: poly (pentamethylene / hexamethylene) carbonate diol (manufactured by Asahi Kasei Chemicals Corporation) with Mn = 2000, content of hexamethylene group = 50 mol%
Duranol T6002: polyhexamethylene carbonate diol (Made by Asahi Kasei Chemicals Co., Ltd.) with Mn = 2000, content of hexamethylene group = 100 mol%
ETERNACOLL UH-300: polyhexamethylene carbonate diol (Made by Ube Industries) with Mn = 3000, content of hexamethylene group = 100 mol%
-Kuraray polyol C-2015N: Mn = 2000 poly (2-methyl-octamethylene / nonamethylene) carbonate diol [manufactured by Kuraray Co., Ltd.]
Kuraray polyol P-6010: poly-3-methyl-pentamethylene adipate with Mn = 6000 [manufactured by Kuraray Co., Ltd.]
-POLON MF-32: Aqueous emulsion of dimethyl sicone (solid content concentration 31% by weight) [manufactured by Shin-Etsu Chemical Co., Ltd.]
SM8706EX: Aqueous emulsion of dimethyl silicone (solid content concentration 37% by weight) [manufactured by Toray Dow Corning Co., Ltd.]

<Examples 10 to 18 and Comparative Examples 5 to 8>
2.7 parts of polyurethane resin aqueous dispersions (Q-1) to (Q-9) or (Q′-1) to (Q′-4) obtained in Examples 1 to 9 or Comparative Examples 1 to 4, 2.5 parts of pigment [carbon black water dispersion (“Aqua-Black162” manufactured by Tokai Carbon Co., Ltd., solid concentration 20% by weight), 1.0 part of glycerin as a moisturizing stabilizing aid, 0.1 part of triethylene glycol Parts, 0.1 part of 1,2-hexanediol as penetrant and 3.6 parts of water are charged in a container, mixed for 10 minutes, and used for ink jet inks (L-1) to (L-9) and for comparison Ink-jet inks (L′-1) to (L′-4) were prepared.

  Various physical property values measured by the following methods for the polyurethane resin aqueous dispersions (Q-1) to (Q-9) and (Q′-1) to (Q′-4) used, and the ink-jet ink obtained ( Tables 2 and 3 show the results of evaluating L-1) to (L-9) and (L′-1) to (L′-4) by the following method.

<Method for evaluating film flexibility and mechanical properties>
Pour 10 parts of an aqueous polyurethane resin dispersion into a polypropylene mold measuring 10 cm in length × 20 cm in width × 1 cm in depth. The amount of film thickness after moisture drying is 200 μm, and after drying at room temperature for 12 hours, a circulating dryer Using a film obtained by heating and drying at 105 ° C. for 3 hours, 100% stress, breaking strength and breaking elongation were measured.
The flexibility of the film can be evaluated by 100% tensile stress of the film obtained above. The smaller the value of 100% tensile stress, the better the flexibility of the film. The mechanical properties of the film can be evaluated by the breaking strength and elongation at break of the film obtained above, and the larger the numerical value, the better the mechanical properties of the film.
In addition, the measurement of breaking strength and breaking elongation is described in JIS K7311. Based on a tensile test.

<Method for evaluating water resistance of polyurethane resin>
Pour 10 parts of an aqueous polyurethane resin dispersion into a polypropylene mold measuring 10 cm in length × 20 cm in width × 1 cm in depth. The amount of film thickness after moisture drying is 200 μm, and after drying at room temperature for 12 hours, a circulating dryer Then, a film obtained by heating and drying at 140 ° C. for 1 hour was cut into 2 cm × 8 cm to prepare a test piece. The obtained test piece was immersed in water, taken out after being immersed at 50 ° C. for 24 hours, and the weight (W ₁ ) was measured after lightly wiping off the water adhering to the surface. Subsequently, the test piece was dried for 1 hour by a circulating air dryer at 130 ° C. and the weight (W ₂ ) was measured. The swelling rate was calculated by the following formula using the obtained numerical value. The smaller the value of the swelling rate, the better the water resistance of the polyurethane resin.
Swelling ratio (%) = {(W ₁ −W ₂ ) / W ₂ } × 100

<Method for evaluating chemical resistance of polyurethane resin>
The test piece prepared in the water resistance evaluation was immersed in a 0.1N sodium hydroxide aqueous solution, immersed for 24 hours at 25 ° C., taken out, and the weight (W ₁ ) was measured after lightly wiping off the water adhering to the surface. Subsequently, the test piece was dried for 1 hour with a circulating dryer at 130 ° C., and the weight (W ₂ ) was measured. Using the obtained numerical values, the swelling ratio was calculated from the following formula. The smaller the value of the swelling rate, the better the chemical resistance of the polyurethane resin.
Swelling ratio (%) = {(W ₁ −W ₂ ) / W ₂ } × 100

<Evaluation method of friction fastness of printing cloth>
The ink jet ink prepared above was applied to a cotton broad cloth so that the coating amount was 1 mg / cm ^2, and dried for 5 minutes with a circulating dryer at 160 ° C. to prepare a printed cloth. Using the obtained printed fabric, a dry test and a wet test were performed in accordance with the method defined in JIS L0849 (Type II), and the contamination of the white cotton fabric for friction was evaluated based on the contaminated gray scale.
<Evaluation method for washing fastness of printed fabric>
Using the printed fabric produced by the above-mentioned evaluation of friction fastness, the contamination of the attached white fabric was evaluated based on the contaminated gray scale in accordance with the method defined in JIS L0844 (A-2).

<Evaluation method of texture of printing cloth>
The cotton broad cloth used in the above-mentioned friction fastness test was dried for 5 minutes with a circulating dryer at 160 ° C. without applying ink to produce a cotton cloth for tactile sensation comparison. The texture of the printed fabric was evaluated by comparing the tactile sensation of the printed fabric produced by the above-mentioned friction fastness test with the cotton fabric for comparing the tactile sensation.
A: There is no change in tactile sensation.
○: The texture is maintained with only slight wrinkles.
X: Hard and stiff.

  The aqueous polyurethane resin dispersion (Q) of the present invention comprises a water-based ink composition (particularly inkjet ink), a water-based coating composition, a water-based adhesive composition, a water-based fiber processing agent composition (a binder composition for pigment printing, a non-woven fabric). Binder composition, sizing agent composition for reinforcing fiber, binder composition for antibacterial agent and raw material composition for artificial leather / synthetic leather, etc.), aqueous coating composition (waterproof coating composition, water repellent coating composition and antifouling) Coating composition, etc.) and aqueous paper treating agent composition.

Claims (9)

An active hydrogen component (A) containing a polymer polyol component (a1), a compound (a2) having a hydrophilic group and an active hydrogen group, and a chain extender (a3) and an organic polyisocyanate component (B) are reacted. A polyurethane resin aqueous dispersion (Q) containing a polyurethane resin (U) and an aqueous medium satisfying all of the following (1) to (4):
(1) The polymer polyol component (a1) contains a polycarbonate diol (a11) having a hexamethylene group and a number average molecular weight of 1000 to 5000 based on the weight of the (a1) in an amount of 70% by weight or more;
(2) 60 mol% or more of the organic polyisocyanate component (B) is hexamethylene diisocyanate;
(3) The urethane group concentration of the polyurethane resin (U) is 1.0 to 2.4 mmol / g based on the weight of (U);
(4) The urea group concentration of the polyurethane resin (U) is 0.20 to 0.70 mmol / g based on the weight of (U).   The polyurethane according to claim 1, wherein the amount of the hydrophilic group of the compound (a2) having the hydrophilic group and the active hydrogen group is 0.14 to 0.45 mmol / g based on the weight of the polyurethane resin (U). Resin aqueous dispersion.   The aqueous polyurethane resin dispersion according to claim 1 or 2, wherein the organic polyisocyanate component (B) further contains isophorone diisocyanate.   The polyurethane resin aqueous dispersion according to any one of claims 1 to 3, wherein the chain extender (a3) is water or an aliphatic diol having 3 to 12 carbon atoms having water and a branch.   The polyurethane resin aqueous dispersion according to any one of claims 1 to 4, wherein a volume average particle diameter (Dv) of the polyurethane resin (U) is 0.01 to 0.3 µm.   The polyurethane resin aqueous dispersion according to any one of claims 1 to 5, comprising 3 to 50% by weight of the blocked polyisocyanate (C) based on the weight of the polyurethane resin (U).   The aqueous polyurethane resin dispersion according to any one of claims 1 to 6, comprising 1 to 15% by weight of dimethyl silicone (D) based on the weight of the polyurethane resin (U).   The aqueous polyurethane resin dispersion according to any one of claims 1 to 7, which is for inkjet ink.   An inkjet ink (L) containing the aqueous polyurethane resin dispersion (Q) according to any one of claims 1 to 8.