CN115746252A - Aqueous polyurethane urea dispersions - Google Patents
Aqueous polyurethane urea dispersions Download PDFInfo
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- CN115746252A CN115746252A CN202111029317.4A CN202111029317A CN115746252A CN 115746252 A CN115746252 A CN 115746252A CN 202111029317 A CN202111029317 A CN 202111029317A CN 115746252 A CN115746252 A CN 115746252A
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Abstract
The invention relates to aqueous polyurethane urea dispersions containing polyurethane urea, to a method for the production and use thereof, in particular in the field of coatings, adhesives or inks, and to products coated, bonded, sealed or printed using said aqueous polyurethane urea dispersions. The polyurethaneurea of the aqueous polyurethaneurea dispersion comprising polyurethaneurea is obtained by reacting a system comprising: polyisocyanate, polycarbonate polyol with the hydroxyl functionality of 1.9-2.1, polyester polyol with the hydroxyl functionality of 1.9-2.1, an amino-containing compound, carboxylic acid with hydroxyl and a neutralizing agent, wherein the weight ratio of the polycarbonate polyol to the polyester polyol is 6: 1-20: 1. The aqueous polyurethane urea dispersoid has small particle size, narrow particle size distribution, good color rendering property, hydrolysis resistance and rubbing color fastness, and can be used as a binder of ink-jet ink.
Description
Technical Field
The invention relates to aqueous polyurethane urea dispersions, to a method for the production thereof and to the use thereof, in particular in the field of coatings, adhesives or inks, and to products coated, bonded, sealed or printed using the aqueous polyurethane urea dispersions.
Background
Inks for textile or leather printing typically comprise an aqueous resin in order to fix the pigment in the ink to a substrate such as a textile or leather. One of the most significant problems currently encountered with ink jet ink formulations is the search for water-based resins with good adhesion.
First, aqueous resins are often critical to the crockfastness performance of the inks. The aqueous resin generally has a milky appearance due to a large particle diameter and a large polydispersity index, and has a negative influence on achieving good color developability of the ink. Thus, inks on the market with higher colour levels generally contain less aqueous resin binder, thus resulting in lower fastness of the ink. On the contrary, in order to ensure that the ink has good rubbing color fastness, a certain amount of water-based resin needs to be contained in the ink, so that the ink does not meet the color development requirement. In addition, the fine nozzle of the ink jet print head is generally only several micrometers in size, and the particle size of the aqueous resin is large, so that the ink jet print head is easily clogged.
Secondly, inks, especially inkjet inks, require a viscosity of the aqueous resinous binder. If the resin viscosity is high, the viscosity of the ink-jet ink may increase, making it difficult to eject from the ink-jet print head.
Finally, the hydrolysis resistance of the waterborne resin itself can also have a significant impact on the color fastness of the printed article over long term use. Articles printed with aqueous resins having poor hydrolysis resistance may be washed several times and then may be peeled off or discolored.
Accordingly, there is a need in the industry for an aqueous resin suitable for inkjet inks that can achieve a balance between color development, crockfastness, and hydrolysis resistance.
Disclosure of Invention
The object of the present invention is to provide an aqueous polyurethaneurea dispersion, a process for its preparation and its use, especially in the field of coatings, adhesives or inks, and also products coated, bonded, sealed or printed with the aqueous polyurethaneurea dispersion.
The aqueous polyurethaneurea dispersion according to the present invention comprising a polyurethaneurea, said polyurethaneurea being obtained from the reaction of a system comprising:
a. at least one polyisocyanate;
b. at least one polycarbonate polyol having a hydroxyl functionality of from 1.9 to 2.1;
c. a polyester polyol having at least one hydroxyl functionality of 1.9 to 2.1, said polyester polyol being obtained by reacting a mixture comprising a diol and at least one of an aromatic diacid and an aromatic anhydride;
d. at least one amino-containing compound that is one or more of the following: amino group-containing carboxylic acids, amino group-containing carboxylic acid salts, amino group-containing sulfonic acids, and amino group-containing sulfonic acid salts;
e. at least one hydroxyl-containing carboxylic acid;
f. at least one neutralizing agent; and
optionally g.an isocyanate group-reactive compound different from component b) to component e) having a molecular weight of from 32g/mol to 400g/mol;
the weight ratio of the polycarbonate polyol to the polyester polyol is 6: 1-20: 1.
According to one aspect of the present invention, there is provided a process for preparing an aqueous polyurethaneurea dispersion comprising polyurethaneureas provided according to the present invention, comprising the steps of:
i. reacting some or all of component a) at least one polyisocyanate, component b) at least one polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1, component c) at least one polyester polyol having a hydroxyl functionality of 1.9 to 2.1, component e) at least one hydroxyl-containing carboxylic acid and optionally component g) an isocyanate group reactive compound different from components b) to e) to obtain a prepolymer;
reacting the prepolymer, component d) at least one amino group containing compound and optionally component g) an isocyanate group reactive compound different from components b) to e) to obtain the polyurethaneurea;
before or after step ii, adding component f) at least one neutralizing agent; and
introducing water before, during or after step ii to obtain the aqueous polyurethaneurea dispersion.
According to another aspect of the present invention, there is provided a coating, adhesive or ink comprising an aqueous polyurethaneurea dispersion provided according to the present invention comprising a polyurethaneurea.
According to a further aspect of the present invention, there is provided the use of the aqueous polyurethaneurea dispersions comprising polyurethaneureas provided according to the present invention for the preparation of coated, bonded or printed products.
According to a further aspect of the present invention there is provided an article or article comprising a substrate prepared, coated, bonded, sealed or printed from an aqueous polyurethaneurea dispersion comprising a polyurethaneurea provided according to the present invention.
According to still another aspect of the present invention, there is provided a printing method comprising the steps of: the aqueous polyurethane urea dispersions provided according to the invention, which comprise polyurethane ureas, are printed onto the surface of a substrate and subsequently cured.
According to a further aspect of the present invention, there is provided a printed product comprising a substrate and a coating formed by printing onto the substrate an aqueous polyurethaneurea dispersion comprising a polyurethaneurea provided according to the present invention.
The aqueous polyurethane urea dispersions of the invention have a low viscosity and are very suitable for use in inks, especially as binders for inkjet inks. In addition, the aqueous polyurethane urea dispersoid has the characteristics of small particle size (Z-average particle size is less than 75 nm), narrow particle size distribution (PDI is less than 0.3) and semitransparent appearance, a formed wet film presents bright color, and a dry film obtained after the wet film is dried has high wet rubbing color fastness and long jungle test time (more than 2 weeks). The dry film formed by the aqueous polyurethane urea dispersion has good color rendering property, rubbing color fastness and hydrolysis resistance.
Detailed Description
The present invention provides an aqueous polyurethaneurea dispersion comprising a polyurethaneurea obtained from the reaction of a system comprising:
a. at least one polyisocyanate;
b. at least one polycarbonate polyol having a hydroxyl functionality of from 1.9 to 2.1;
c. a polyester polyol having at least one hydroxyl functionality of 1.9 to 2.1, said polyester polyol being obtained by reacting a mixture comprising a diol and at least one of an aromatic diacid and an aromatic anhydride;
d. at least one amino-containing compound that is one or more of the following: amino group-containing carboxylic acids, amino group-containing carboxylic acid salts, amino group-containing sulfonic acids, and amino group-containing sulfonic acid salts;
e. at least one hydroxyl-containing carboxylic acid;
f. at least one neutralizing agent; and
optionally g.an isocyanate group-reactive compound different from components b) to e) having a molecular weight of from 32g/mol to 400g/mol; the weight ratio of the polycarbonate polyol to the polyester polyol is 6: 1-20: 1. The invention also provides a preparation method and application of the aqueous polyurethane urea dispersion, in particular to the application in the fields of coating, adhesive or ink, and a product obtained by coating, bonding, sealing or printing by using the aqueous polyurethane urea dispersion.
The term "curing" as used herein refers to the process of a liquid substance from a liquid state to a cured state.
The term "coating" as used herein refers to a substance that can be applied to the surface of an object by various application processes to form a strong, continuous solid coating.
The term "adhesive" as used herein refers to a chemical substance that can be applied to the surface of an object by different application processes, form a coating on the object itself or on the surface of an object and adhere the object itself or an object to the surface of another object, and is also used as a synonym for adhesive and/or sealant and/or binder.
The term "polyurethaneurea" as used herein refers to polyurethane and/or polyurethane polyureas and/or polythiourethanes.
The term "aqueous polyurethane urea dispersion" as used herein refers to aqueous polyurethane dispersions and/or aqueous polyurethane polyurea dispersions and/or aqueous polythiourethane dispersions.
The content of polyurethaneurea in the aqueous polyurethaneurea dispersion described herein is equivalent to the solid component content of the aqueous polyurethaneurea dispersion.
The term "solid component" as used herein refers to a solid component or an effective component.
The term "isocyanate group-reactive compound" as used herein refers to a component containing groups reactive towards isocyanate groups, i.e. a component containing zerewitinov-active hydrogen groups, which are defined with reference to Rompp's Chemical Dictionary (Rommp Chemie Lexikon), 10th ed., georg Thieme Verlag Stuttgart,1996. In general, zerewitinov-active hydrogen-containing radicals are understood in the art to mean hydroxyl (OH), amino (NH) x ) And a thiol group (SH).
Aqueous polyurethane urea dispersions
The amount of organic solvent in the aqueous polyurethaneurea dispersion is preferably less than 1% by weight, relative to the total weight of the aqueous polyurethaneurea dispersion.
The aqueous polyurethane urea dispersion preferably meets at least one of the following characteristics:
a viscosity of from 10 mPas to 1000 mPas according to ISO 3219:1994 standard was tested using a Bohler viscometer (Brookfield DV-II + Pro);
the solid content is 30-40 wt%, and the content is tested by a Mettler Teredo Halogen Moisture Analyzer (Mettler Teredo Halogen Moisture Analyzer Excellence HS 153);
the Z-average particle size is 30nm-75nm, and the particle size is measured by a Malvern Zetasizer Nano ZS; and
the polydispersity is 0-0.3, measured with a Malvern nanosize particle size potential Analyzer (Malvern Zetasizer Nano ZS).
The content of the polyurethaneurea most preferably ranges from 33% to 40% by weight, relative to the total weight of the aqueous polyurethaneurea dispersion.
The wet crockfastness of the aqueous polyurethane urea dispersions is preferably from 4 to 5.
The aqueous polyurethaneurea dispersion preferably has a jungle test of greater than 2 weeks.
Component a) polyisocyanates
The isocyanate functionality of the polyisocyanate is preferably not less than 2, most preferably from 2 to 4.
The polyisocyanate is preferably one or more of the following: aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and their derivatives with iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and/or carbodiimide groups.
The aliphatic polyisocyanate is preferably one or more of the following: hexamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 2,2-dimethylpentylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, butylene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethyl 1,6-hexamethylene diisocyanate, 1,6, 11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanato-4-isocyanatomethyloctane, bis (isocyanatoethyl) carbonate, bis (isocyanatoethyl) ether, lysine methyl diisocyanate, lysine triisocyanate, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis (isocyanatohexyl) sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanatoethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanato-2-isocyanatomethyl-3-thiapentane, 1,2,3-tris (isocyanatomethylthio) propane, 24 zxft 24-tris (isocyanatoethylthio) propane 49494949, 3,5-dith-1,2,6,7-heptane tetraisocyanate, 2,6-diisocyanatomethyl-3,5-dith-1,7-heptane diisocyanate, 2,5-diisocyanatomethylthiophene, isocyanatoethylthio-2,6-dith-1,8-octane diisocyanate, thiobis (3-isothiocyanatopropane), thiobis (2-isothiocyanatoethane), and dithiobis (2-isothiocyanatoethane); most preferred is hexamethylene diisocyanate.
The cycloaliphatic polyisocyanate is preferably one or more of the following: 2,5-bis (isocyanatomethyl) -bicyclo [2.2.1]Heptane, 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1]Heptane, bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, 2,5-diisocyanato tetrahydrothiophene, 2,5-diisocyanato tetrahydrothiophene, 3,4-diisocyanato tetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanato-1,4-dithiane, 4,5-diisocyanato-1,3-dithianeThiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolane, 4,5-diisocyanatomethyl-2-methyl-1,3-dithiolane, norbornane diisocyanate (NBDI), xylylene Diisocyanate (XDI), hydrogenated xylylene diisocyanate (H 6 XDI), 1,4-cyclohexyl diisocyanate (H) 6 PPDI), m-tetramethylxylylene diisocyanate (m-TMXDI) and cyclohexane diisothiocyanate, most preferably one or more of the following: isophorone diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.
The aromatic polyisocyanate is preferably one or more of the following: <xnotran> 3528 zxft 3528- , 3835 zxft 3835- , 3924 zxft 3924- , 3534 zxft 3534- , , , , , , , , , , 5248 zxft 5248 ' - ( ), 5362 zxft 5362 ' - (2- ), -5725 zxft 5725 ' - , ( ) , ( ) , ( ) , ( ) , α, α, α ', α ' - , ( ) , ( ) , ( ) , ( ) , 3432 zxft 3432- ( ) ,2- -4- , (4- ) , (4- ) , (4- ) , (2- -5- ) , (3- -5- ) , </xnotran> Bis (3-methyl-6-isocyanatophenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, bis (4-methoxy-3-isocyanatophenyl) disulfide, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5-diisothiocyanato-m-xylene, 3579 zxft 79 '-methylenebis (isothiocyanatophenyl ester), 4,4' -methylenebis (2-methylphenylisothiocyanate), 4,4 '-methylenebis (3-methylphenylisothiocyanate), 4,4' -diisothiocyanatobenzophenone, 4,4 '-diisothiocyanato-3,3' -dimethylbenzophenone, bis (4-isothiocyanatophenyl) ether, 1-methyl-6-isocyanatophenyl) disulfide, bis (4-isocyanatophenyl) disulfide, TDI, bis (4-thiobenzophenone), most preferably, one or more of the following compounds: 1,2-diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, diphenylmethane diisocyanate, and 2,4-diisocyanatotoluene.
The other isocyanates may also have isocyanate groups and isothiocyanate groups, such as 1-isocyanato-6-isothiocyanate-hexane, 1-isocyanato-4-isothiocyanate-cyclohexane, 1-isocyanato-4-isothiocyanate-benzene, 4-methyl-3-isocyanato-1-isothiocyanate-benzene, 2-isocyanato-4,6-diisothiocyanate-1,3,5-triazine, 4-isocyanatophenyl-4-isothiocyanate sulfide and 2-isocyanato-2-isothiocyanatoethyl disulfide.
The other isocyanate may also be a halogen substituent of the above polyisocyanates, for example a chlorine substituent, a bromine substituent, an alkyl substituent, an alkoxy substituent, a nitro substituent or a silane substituent such as isocyanatopropyltriethoxysilane or isocyanatopropyltrimethoxysilane.
The polyisocyanate is further preferably one or more of the following: hexamethylene diisocyanate and isophorone diisocyanate, most preferably a combination of hexamethylene diisocyanate and isophorone diisocyanate. The molar ratio of hexamethylene diisocyanate to isophorone diisocyanate is preferably 1: 2 to 2: 1.
The amount of the polyisocyanate of component a) is preferably from 10% to 50% by weight, most preferably from 15% to 30% by weight, relative to the total weight of the polyurethaneurea.
Component b) polycarbonate polyols having a hydroxyl functionality of 1.9 to 2.1
The polycarbonate polyol is preferably one or more of the following: hexanediol polycarbonate, butanediol polycarbonate, neopentyl glycol polycarbonate, 3-methylpentanediol polycarbonate and copolymers of the above polycarbonates.
The number-average molecular weight of the polycarbonate polyols is preferably from 800g/mol to 4000g/mol.
The amount of the polycarbonate polyol is preferably 60 wt% to 80 wt%, most preferably 65 wt% to 75 wt%, relative to the total weight of the polyurethaneurea.
Component c) polyester polyols having a hydroxyl functionality of 1.9 to 2.1
The polyester polyol is preferably one or more of the following: linear polyester diols and lightly branched polyester polyols.
The polyester polyol is further preferably one or more of the following: polyhexamethylene phthalate, polybutylene phthalate, neopentyl glycol phthalate, polydiethylene phthalate, 3-methylpentanediol phthalate, polyhexamethylene isophthalate, polybutyleneisophthalate, neopentyl glycol isophthalate, polydiethylene isophthalate, 3-methylpentanediol isophthalate, polyhexamethylene terephthalate, polybutylene terephthalate, polytetramethyleneneopentyl glycol terephthalate, polydiethylene terephthalate, and 3-methylpentanediol terephthalate; most preferably one or more of the following: polyhexamethylene phthalate, polybutylene phthalate, neopentyl glycol phthalate, diethylene glycol phthalate and 3-methylpentanediol phthalate.
The polyester polyol is preferably prepared by comprising the following components: aliphatic, cycloaliphatic or aromatic di-or polycarboxylic acids, such as terephthalic acid, isophthalic acid, phthalic acid; anhydrides, such as phthalic anhydride, trimellitic anhydride or mixtures thereof; low molecular weight polyols such as ethylene glycol, di-, tri-, tetra-ethylene glycol, 1,2-propylene glycol, di-, tri-, tetra-propylene glycol, 1,3-propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, 2,3-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propylene glycol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1, 10-decanediol, 1, 12-dodecanediol, or mixtures thereof; and optionally higher functional polyols, such as trimethylolpropane, glycerol or pentaerythritol, cycloaliphatic and/or aromatic di-and poly-hydroxy compounds.
The polyester polyol is further preferably obtained by reacting a mixture containing a diol and at least one of an aromatic dibasic acid and an aromatic anhydride. The aromatic dibasic acid is preferably one or more of the following: terephthalic acid, isophthalic acid, phthalic acid, the aromatic anhydride is preferably phthalic anhydride, the diol is preferably one or more of the following: 1,6-hexanediol, 1,4-butanediol, neopentyl glycol, 3-methylpentanediol, diethylene glycol.
The number average molecular weight of the polyester polyol is preferably 800g/mol to 4000g/mol.
The amount of the polyester polyol is preferably from 2% to 12% by weight, relative to the total weight of the polyurethaneurea.
Component d) amino-containing compounds
The amino-containing carboxylate is preferably one or more of the following: 6-aminocaproate, lysine and N- (2-aminoethyl) -beta-alanine monosodium salt.
The amino group-containing sulfonate is preferably one or more of the following: 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt and 3- (cyclohexylamine L-1-propanesulfonic acid sodium salt.
Most preferably, the amino-containing compound is one or more of the following: 6-aminocaproate, lysine, N- (2-aminoethyl) -beta-alanine monosodium salt, 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt, and 3- (cyclohexylamine) -1-propanesulfonic acid sodium salt.
The amount of the amino group containing compound of component d) is preferably from 0.5% to 2% by weight, most preferably from 0.5% to 1.0% by weight, relative to the total weight of the polyurethaneurea.
Component e) hydroxy-containing carboxylic acids
The hydroxyl-containing carboxylic acid is preferably one or more of the following: 2,2 dimethylolpropionic acid and 2,2 dimethylolbutyric acid.
The amount of the hydroxyl-containing carboxylic acid is preferably 1% to 5% by weight, most preferably 2% to 3% by weight, relative to the total weight of the polyurethaneurea.
Component f) a neutralizing agent
The neutralising agent is preferably one or more of: organic tertiary amines and inorganic bases; most preferably one or more of the following: triethylamine, triethanolamine, dimethylethanolamine, methyldiethanolamine, ethyldiisopropylamine, ammonia, sodium hydroxide and potassium hydroxide.
The amount of the neutralizing agent is preferably 65 mole% to 105 mole% relative to the total moles of carboxyl groups of the hydroxyl group containing carboxylic acid of component e).
The hydroxyl-containing carboxylic acid and neutralizing agent may be present in the system directly in the form of a salt of the hydroxyl-containing carboxylic acid.
Component g) isocyanate group-reactive compounds different from components b) to e)
The optional isocyanate group reactive compound of component g) different from component b) to component e) may be one or more of the following: polyols having a hydroxyl functionality of 2-3 and amino compounds having an amino functionality of 2-3.
The polyol having a hydroxyl functionality of 2 to 3 is preferably one or more of the following: diethylene glycol, propylene glycol, butylene glycol, hexylene glycol, pentanediol, trimethylolpropane, and glycerol.
The amino compound having an amino functionality of 2 to 3 is preferably one or more of the following: ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, N- (2-hydroxyethyl) -ethylenediamine, isophoronediamine, hydrazine hydrate and diethylenetriamine.
The amount of component g) is preferably from 0.5% to 2.5% by weight, most preferably from 0.5% to 1% by weight, relative to the total weight of the polyurethaneurea.
System of
The system may further comprise one or more of the following: external emulsifiers, solvents, reactive diluents and stabilizers, in amounts customary for the person skilled in the art.
Process for the preparation of aqueous polyurethane urea dispersions comprising polyurethane urea
Preferably, when step iv precedes step ii, step iii precedes step iv.
The sequence of steps of the method is preferably in the order step i, step iii, step ii and step iv.
The preparation process preferably further comprises a step v.
The organic solvent is preferably a solvent miscible with water but inert to isocyanate groups, and further preferably one or more of the following: acetone, methyl ethyl ketone, propylene glycol dimethyl ether, other ethers and esters not containing hydroxyl functional groups; most preferably one or more of the following: acetone and butanone.
The organic solvent preferably does not contain a pyrrolidone-type compound.
The preparation process also preferably further comprises a step vi. Removing the organic solvent introduced in step v from the aqueous polyurethaneurea dispersion.
The organic solvent may be removed by distillation. The solvent may be removed during or after step iv.
The amount of residual organic solvent in the aqueous polyurethaneurea dispersion is preferably less than 1.0% by weight, relative to the total weight of the aqueous polyurethaneurea dispersion.
To accelerate the reaction rate in step i, the catalysts customary for prepolymer preparation, such as triethylamine, 1,4-diazabicyclo- [2,2,2] -octane, tin dioctoate or dibutyltin dilaurate, most preferably dibutyltin dilaurate, can be used.
The catalyst may be placed in the reactor simultaneously with the components of step i or may be added later.
The degree of conversion of the components of step i can be obtained by testing the NCO content of the components. For this purpose, spectroscopic measurements, for example infrared or near-infrared spectroscopy, and refractive index determinations or chemical analyses, for example titration, can be carried out simultaneously on the extracted sample.
The prepolymer may be in a solid state or a liquid state at ordinary temperature.
The degree of neutralization of the prepolymer may be from 50mol% to 125mol%, preferably from 65mol% to 105mol%.
Coatings, adhesives or inks
The coating, adhesive or ink preferably further comprises an additive. The additive is preferably one or more of the following: co-binders, lubricants, emulsifiers, light stabilizers, antioxidants, fillers, anti-settling agents, defoamers, wetting agents, flow control agents, antistatic agents, film-forming aids, reactive diluents, plasticizers, catalysts, thickeners, pigments, dyes, tackifiers and matting agents.
The additive selection and the dosage used are in principle known to the person skilled in the art and can be readily determined.
The aqueous polyurethaneurea dispersions of the present invention can also be mixed together and used with other aqueous or solvent-containing oligomers or polymers, such as aqueous or solvent-containing polyesters, polyurethanes, polyurethane-polyacrylates, polyethers, polyester-polyacrylates, alkyds, addition polymers, polyamides/imides or polyepoxides. The compatibility of such mixtures must be tested in each case using simple preliminary tests.
The aqueous polyurethane urea dispersions of the invention can also be mixed together and used with other compounds containing functional groups, for example carboxyl, hydroxyl and/or blocked isocyanate groups.
The coatings, binders or inks of the present invention are processed according to methods known to those skilled in the art.
Coating method, bonded product or printed product
The substrate is preferably one or more of the following: wood, metal, glass, fiber, textile, artificial leather, dermis, paper, plastic, rubber, foam, ceramic, and various polymer coatings, most preferably one or more of the following: textiles, plastics, ceramics, metals, genuine leather, artificial leather and various polymer coatings.
The coating may be the application of the coating, adhesive or ink to the entire surface of the substrate or only to one or more portions of the surface of the substrate.
The coating may be brushing, dipping, spraying, rolling, knife coating, flow coating, pouring or printing.
Printing method and printed product
The application may be the application of the coating, binder or ink to the entire surface of the substrate or only to one or more portions of the surface of the substrate.
The application may be knife coating or printing. The printing is preferably printing.
Examples
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term in this specification conflicts with a meaning commonly understood by those skilled in the art to which the invention pertains, the definition set forth herein shall govern.
Unless otherwise indicated, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that can vary depending upon the desired properties to be obtained.
As used herein, "and/or" means one or all of the referenced elements.
As used herein, "comprising" and "comprises" encompass the presence of only the recited elements as well as the presence of other, non-recited elements in addition to the recited elements.
As used in this specification, the terms "a", "an" and "the" are intended to include "at least one" or "one or more" unless otherwise indicated. For example, "a component" refers to one or more components, and thus more than one component may be considered and may be employed or used in the practice of the described embodiments.
All percentages in the present invention are by weight unless otherwise indicated.
The analytical measurements according to the invention were carried out at 23. + -. 2 ℃ unless otherwise stated.
The number average molecular weight of the polymer polyol was determined by gel permeation chromatography using tetrahydrofuran as the mobile phase against polystyrene standards at 40 ℃.
Raw materials and reagents
Desmophen C2202 polycarbonate diol with hydroxyl functionality equal to 2.0, number average molecular weight 2000g/mol, available from Kostewa Germany.
P200H/DS: polyhexamethylene phthalate diol having a hydroxyl functionality of 2.0 and a number average molecular weight of 2000g/mol, available from ColtsingChu Germany.
Desmophen C1200: polycarbonate polycyclocaprolactone diol, polycarbonate: polycyclocaprolactone = 1.2: 1 (mass ratio), hydroxyl functionality equal to 2.0, number average molecular weight 2000g/mol, available from kosmark, germany.
AAS: n- (2-aminoethyl) aminoethanesulfonic acid sodium salt aqueous solution NH 2 -CH 2 CH 2 -NH-CH 2 CH 2 -SO 3 Na, concentration 49%, purchased from Kostewa Germany.
Dimethylolpropionic acid: hydroxyl-containing carboxylic acids, available from Aldrich chemical company.
SP-9111: bright red paste, red viscous liquid, available from shanghai xude fine chemicals ltd.
BYK 349: silicone surfactant, available from BYK bike chemistry.
1,2 propylene glycol: cosolvent available from Shanghai glass instruments Ltd.
Tego 825: antifoam agent, purchased from creative specialty chemicals (shanghai) ltd.
Borchigel L75N: rheology auxiliaries, available from Borchers USA.
Borchigel ALA: rheology auxiliaries, available from Borchers, USA.
Imprafix IO 3025: isocyanate crosslinker, available from kostewa.
Test method
Testing of Z-average particle size and polydispersity index PDI of aqueous polyurethaneurea dispersions
1 drop of the aqueous polyurethane urea dispersion was added to 50 ml of ultrapure water, and diluted with gentle stirring. After dilution, the test was carried out using a Malvern nanosize potentiometric analyzer (Malvern Zetasizer Nano ZS). The test temperature was 23.0. + -. 0.1 ℃. Test material setup: polystyrene latex (refractive index 1.590, absorption 0.010); setting a dispersing agent: water (temperature 23.0 ℃, viscosity 0.9308 centipoises, refractive index 1.330); the equilibration time was 60 seconds. Sample cell type: disposable sample cell DTS0012. The positioning method comprises the following steps: automatic attenuation and automatic optimization positioning optimization. Analysis mode: for general purposes (normal resolution). Test angle 173 ° backscattering (NIBS default). Each sample was tested in 3 runs, 10 runs each, with 10 seconds of each test. The Z-average particle diameter and polydispersity were each taken as the average of all tests. Z-average particle size defines the average particle size measured according to the ISO 13321 standard for the principle of dynamic light scattering. The polydispersity represents the particle size distribution, and the closer the PDI is to 0, the narrower the particle size distribution.
The Z-average particle size of less than 75nm is qualified. The polydispersity PDI (narrow particle size distribution) of less than 0.3 is acceptable.
Viscosity of aqueous polyurethane urea dispersions
According to ISO 3219:1994 standard, viscosity was measured using a Brookfield DV-II + Pro viscometer. 150g of the aqueous polyurethaneurea dispersion were weighed into a glass jar and tested for viscosity at 30rpm using a S62 spindle at room temperature (20-25 ℃).
The viscosity of the aqueous polyurethane urea dispersion was less than 1000 mPas.
Solid content (solid content) of aqueous polyurethane urea dispersions
The test was carried out using a Mettlerlington Halogen Moisture analyser (Mettler Teredo Halogen Moisture analyser HS 153). A glass fiber filter paper was placed on a standard aluminum weighing pan, and 1 gram of the aqueous polyurethaneurea dispersion was dropped onto the glass fiber filter paper using standard drying procedures at 120 ℃ and standard grade 5 (1 mg/140 sec) was stopped. That is, the sample was heated while maintaining at 120 ℃ and continuously weighed, and if the sample lost less than 1 mg in 140 seconds, the test was stopped and the remaining weight percent was recorded as a solid content.
Method for evaluating appearance of aqueous polyurethane urea dispersion
50g of the aqueous polyurethane urea dispersoid is filled in a transparent glass bottle with the diameter of 3 cm and is placed in a black and white check paper card for visual observation, and if the back check can be clearly seen through the glass bottle and the color of the check is not obviously changed, the glass bottle is transparent; if the back check can be clearly seen through the glass bottle but the check color is changed, the check is semitransparent; the back check is opaque if it is not clearly visible through the vial.
The aqueous polyurethane urea dispersion is qualified as translucent or transparent in appearance and unqualified as opaque.
Dry film jungle testing method of aqueous polyurethane urea dispersoid
The first step is as follows: film production
99 wt% of the aqueous polyurethaneurea dispersion or the comparative aqueous polyurethaneurea dispersion was added to a compounding tank, followed by 1 wt% of Borchigel ALA, stirred well, and the viscosity was adjusted to about 5000 cps. Mirror release paper with the size of A4 paper is placed on a glass table top and is flatly fixed on the table top by adhesive tape paper. And (3) putting a 500-micron film scraper right at the upper end of the release paper, pressing two ends of the film scraper with two hands, pulling down to the bottom at a constant speed, and cleaning the film scraper after the process is finished. And taking down the scraped sample, placing the scraped sample on a high-temperature resistant plate, placing the sample in a 50 ℃ oven for drying for 30 minutes, after the sample is dried, placing the sample in a 150 ℃ oven for drying for 3 minutes, taking out the sample, coating talcum powder on the front surface of the film in a fume hood, taking down the film from release paper, coating talcum powder on the back surface of the film, placing the film at room temperature for 24 hours, and finishing the preparation of the film.
The films were cut using a standard cutter into dumbbell-shaped test bars conforming to S2 in standard DIN 53504 on a high-iron tensile machine, the samples being tested according to test standard DIN 53504 for initial 100% modulus, initial tensile elongation at break and initial tensile strength.
The second step is that: jungle aging test
The prepared film was placed in a constant temperature and humidity chamber at 70 ℃ and a relative humidity of 95%, and at least 3 parallel samples were prepared for each example or comparative example. After 7 days, the film is removed and cut using a standard cutter into dumbbell-shaped test specimens which conform to the S2 standard in DIN 53504 and are tested after 24 hours at 23 ℃ in an environment of 55% relative humidity. The 100% modulus, tensile elongation at break and tensile strength after ageing were tested on a high-iron tensile machine according to test standard DIN 53504.
If the 100% modulus, the tensile elongation at break and the tensile strength after aging are reduced by less than or equal to 50% compared with the initial 100% modulus, the tensile elongation at break and the tensile strength, the sample is regarded as passing, the sample is continuously placed into a constant temperature and humidity box with the temperature of 70 ℃ and the relative humidity of 95% for storage, and the sample is continuously taken out after 7 days to test the 100% modulus, the tensile elongation at break and the tensile strength after aging; if the sample morphology has deteriorated significantly (e.g., stickiness, deformation, holes, etc.) or the 100% modulus, tensile elongation at break, and tensile strength data after aging have decreased by more than 50% from the initial 100% modulus, tensile elongation at break, and tensile strength data, the aging test is deemed to have failed, and the time (weeks) at which the sample film is stored in the constant temperature and humidity chamber is recorded as the sample jungle aging test results. And if the 100% modulus, the tensile elongation at break and the tensile strength after aging are reduced by less than or equal to 50% compared with the initial 100% modulus, the tensile elongation at break and the tensile strength, the aged sample is regarded as passing, the aged sample is continuously placed into a constant temperature and constant humidity box with the temperature of 70 ℃ and the relative humidity of 95% for storage, the aged sample is continuously sampled and analyzed after 7 days, and the like.
Longer storage times indicate better hydrolysis resistance of the samples. The jungle test is qualified when the aging time is more than 2 weeks.
Device for testing
High-speed rail tensile machine: model GOTECH/AI-3000, available from high-speed railway instrumentation, inc.
A film scraper: the model ISO-500 μm, purchased from Shanghai modern environmental engineering technology, inc.
Constant temperature and humidity case: GWS EW0440, available from environmental instruments, inc., of five houses, guangzhou.
Film thickness meter: model SM-114, available from Derley, japan.
Wet rubbing color fastness test method
The first step is as follows: a printing paste was prepared by mixing the following components: 82 wt% aqueous polyurethaneurea dispersion or comparative aqueous polyurethaneurea dispersion, 10 wt% SP9111, 3 wt% 1,2-propanediol, 0.5 wt% Tego 825, 0.5 wt% BYK349, 1 wt% Borchigel L75N, and 3 wt% Imprafix IO 3025.
The second step is that: preparation of printed samples and testing
1. And (3) printing the prepared printing slurry by using a 120-mesh nylon screen printing plate, wherein the base material is white water-based polyurethane leather, and scraping by using a scraper for 6-blade coating.
2. The printed sample is placed in an environment with the temperature of 25 ℃ and the relative humidity of 50% for 72 hours and naturally dried.
3. Wet crocking fastness was tested using an crock fastness tester (GT-7034-a, high-speed rail tester) according to AATCC-8-2016 standard test method, staining was rated with gray card according to standard CTA rating, for a total of 1-5 grades. Higher scores represent better wet crockfastness. And the wet rubbing color fastness score is not less than 4, and the product is qualified.
Device for testing
A dispersion machine: model SFJ400, available from shanghai modern environmental engineering technologies, inc.
An electronic balance: model BSA4202S Max 4200g d =0.01g, purchased from sydowris group.
Preparation of aqueous polyurethane urea dispersions
Aqueous polyurethane urea dispersions 1
225.14g Desmophen C2202, 34.111g P200H/DS were dehydrated at 100 ℃ for 1 hour at 100 mbar. After cooling to 70 ℃ 9.03g of dimethylolpropionic acid were added and stirred until homogeneously dispersed. 5.99g were added at 65 ℃
H and 61.01g
I, reaction at 100 ℃ until an isocyanate content of 2.84% is reached. Then dissolved in 596g of acetone and cooled to 40 ℃ to obtain a reaction solution. 6.68g of triethylamine are subsequently added and stirred vigorously for 10 minutes. 5.26 of g N (2-aminoethyl) aminoethanesulfonic acid sodium salt solution and a solution of 2.9g ethylenediamine in 33.32g water were added and stirred vigorously for 10 minutes, and the mixture was dispersed by adding 597g water and acetone was subsequently separated off by distillation to give an aqueous polyurethaneurea dispersion 1 having a solids content of 35.8% by weight.
Aqueous polyurethane urea dispersions 2
246.37g Desmophen C2202, 12.88g P200H/DS were dehydrated at 100 ℃ for 1 hour at 100 mbar. After cooling to 70 ℃ 9.03g of dimethylolpropionic acid were added and stirred until homogeneously dispersed. 5.99g were added at 65 ℃
H and 61.01g
I, reaction at 100 ℃ until an isocyanate content of 2.84% is reached. Then dissolved in 596g of acetone and cooled to 40 ℃ to obtain a reaction solution. 6.68g of triethylamine are subsequently added and stirred vigorously for 10 minutes. 5.26. 5.26g N- (2-aminoethyl) aminoethanesulfonic acid sodium salt solution and a solution of 2.9g ethylenediamine in 33.32g water were added and stirred vigorously for 10 minutes, and 596g water was added to disperse the mixture, followed by distillation to separate out acetone to give an aqueous polyurethaneurea dispersion 2 having a solids content of 36.5% by weight.
Comparative aqueous polyurethane urea dispersions 1
259.26g of Desmophen C2202 were dehydrated at 100 ℃ and 100mbar for 1 hour. After cooling to 70 ℃ 9.03g of dimethylolpropionic acid were added and stirred until homogeneously dispersed. 5.99g were added at 65 ℃
H and 61.01g
I, reaction at 100 ℃ until an isocyanate content of 2.84% is reached. Then dissolved in 596g of acetone and cooled to 40 ℃ to obtain a reaction solution. 6.68g of triethylamine are subsequently added and stirred vigorously for 10 minutes. 5.26 of g N- (2-aminoethyl) taurinoacetamide solution and a solution of 7.06g of n-butylamine in 60.67g of water were added and stirred vigorously for 10 minutes, and the mixture was dispersed by addition of 577g of water and the acetone was subsequently separated off by distillation to give comparative aqueous polyurethaneurea dispersion 1 having a solids content of 36.4% by weight.
Comparative aqueous polyurethane urea Dispersion 2
259.26g of Desmophen C2202 were dehydrated at 100 ℃ for 1 hour and at 100 mbar. After cooling to 70 ℃ 9.03g of dimethylolpropionic acid were added with stirring until homogeneous dispersion. At 65 ℃ 68.93g were added
I, reaction at 100 ℃ until an isocyanate content of 2.83% is reached. Then dissolved in 599g of acetone and cooled to 40 ℃ to obtain a reaction solution. 6.68g of triethylamine are subsequently added and stirred vigorously for 10 minutes. 5.26g N- (2-aminoethyl) aminoethanesulfonic acid sodium salt solution and a solution of 2.9g of ethylenediamine in 33.32g of water were added and stirred vigorously for 10 minutes, and the mixture was dispersed by adding 600g of water and subsequently separating off the acetone by distillation to give comparative aqueous polyurethaneurea dispersion 2 having a solids content of 36.8% by weight.
Comparative aqueous polyurethane urea Dispersion 3
216.05g Desmophen C2202, 43.21g P200H/DS were dehydrated at 100 ℃ for 1 hour at 100 mbar. After cooling to 70 ℃ 9.03g of dimethylolpropionic acid were added and stirred until homogeneously dispersed. 5.99g were added at 65 ℃
H and 61.01g
I, reaction at 100 ℃ until an isocyanate content of 2.84% is reached. Then dissolved in 596g of acetone and cooled to 40 ℃ to obtain a reaction solution. 6.68g of triethylamine are subsequently added and stirred vigorously for 10 minutes. 5.26g of sodium N- (2-aminoethyl) tauride and a solution of 2.9g of ethylenediamine in 33.32g of water are added and stirred vigorously for 10 minutes, and 596g of water are added to disperse the mixture, after which acetone is separated off by distillation to give a comparative aqueous polyurethaneurea dispersion 3 having a solids content of 35.5% by weight.
Comparative aqueous polyurethane urea Dispersion 4
420g of Desmophen C1200 were dehydrated at 100 ℃ for 1 hour at 100 mbar. After cooling to 70 ℃ 20.54g of dimethylolpropionic acid were added and stirred until homogeneously dispersed. 25.74g were added at 65 ℃
W and 108.22g
I, reaction at 100 ℃ until an isocyanate content of 3.24% is reached. Then dissolved in 1021g of acetone and cooled to 40 ℃ to obtain a reaction solution. 15.21g of triethylamine are subsequently added and stirred vigorously for 10 minutes. 13.81g N- (2-aminoethyl) aminoethanesulfonic acid sodium salt solution and a solution of 9.6g ethylenediamine in 103.83g water were added and stirred vigorously for 10 minutes, and 968g water were further added to disperse the mixture, followed by distillation to separate off the acetone, to give comparative aqueous polyurethaneurea dispersion 4 having a solids content of 30.7% by weight.
Comparative aqueous polyurethane urea Dispersion 5
225.14g Desmophen C2202, 34.111g P200H/DS were dehydrated at 100 ℃ for 1 hour at 100 mbar. After cooling to 70 ℃, 9.03g dimethylolpropionic acid was added and stirred until uniformly dispersed. 5.99g were added at 65 ℃
H and 61.01g
I, reaction at 100 ℃ until an isocyanate content of 2.84% is reached. Then dissolved in 596g of acetone and cooled to 40 ℃ to obtain a reaction solution. 6.68g of triethylamine are subsequently added and stirred vigorously for 10 minutes. A solution of 3.72g of ethylenediamine in 24.43g of water was added and stirred vigorously for 10 minutes, and then 605g of water was added to disperse the mixture, followed by distillation to separate out the acetone, to give comparative aqueous polyurethaneurea dispersion 5 having a solids content of 35.2% by weight.
Comparative aqueous polyurethane urea Dispersion 6
225.14g Desmophen C2202, 34.11g P200H/DS were dehydrated at 100 ℃ for 1 hour at 100 mbar. At 654.96g of water was added thereto at a temperature below
H and 50.51g
I, reaction at 100 ℃ until an isocyanate content of 3.40% is reached. Then dissolved in 559 g acetone and cooled to 40 ℃ to obtain a reaction solution. 17.34. 17.34g N- (2-aminoethyl) aminoethanesulfonic acid sodium salt solution and a solution of 2.4g of ethylenediamine in 62.76g of water were then added and stirred vigorously for 10 minutes, and the mixture was dispersed by addition of 533g of water and acetone was subsequently separated off by distillation to give comparative aqueous polyurethaneurea dispersion 6 having a solids content of 34.9% by weight.
Table 1 shows the results of evaluation of the viscosity, Z-average particle diameter, polydispersity index (PDI), wet crockfastness, jungle test and appearance of the aqueous polyurethaneurea dispersions of inventive examples and comparative examples.
TABLE 1 evaluation of aqueous polyurethane urea dispersions
Remarking: * The wet rubbing color fastness test is not carried out because the jungle test result is unqualified;
* Unqualified color fastness test result due to wet friction is not subjected to jungle test;
* Wet crockfastness test and jungle test were not performed due to Z-average particle size failure of the aqueous polyurethaneurea dispersions.
The aqueous polyurethane urea dispersion of the examples of the present patent application has characteristics of small particle size, narrow particle size distribution and translucency, and thus, the aqueous polyurethane urea dispersion of the present invention forms a bright wet film color. The aqueous polyurethane urea dispersion of the present application has high wet rubbing color fastness of the paint film and long dry film jungle test time, and therefore, the dry film formed by the aqueous polyurethane urea dispersion has good rubbing color fastness and hydrolysis resistance. The aqueous polyurethaneurea dispersions of the present application have low viscosity and are particularly suitable as a resin binder component in ink formulations for ink jet printing.
The systems of the aqueous polyurethaneurea dispersions of comparative examples 1 and 2 do not contain aromatic polyester polyol, and the aqueous polyurethaneurea dispersions do not compromise the jungle test time and wet crockfastness. Also, the aqueous polyurethaneurea dispersion of comparative example 1 was opaque in appearance, i.e., the film formed therefrom had poor color rendering and was not bright in color.
The aqueous polyurethane urea dispersion of comparative example 3 has a weight ratio of polycarbonate polyol to aromatic polyester polyol of less than 6: 1, and the aqueous polyurethane urea dispersion has a short jungle test time.
The weight ratio of polycarbonate polyol to aliphatic polyester polyol in the system of the aqueous polyurethaneurea dispersion of comparative example 4 was less than 6: 1, the aqueous polyurethaneurea dispersion was high in viscosity and short in the jungle test time.
The aqueous polyurethane urea dispersion of comparative example 5, which does not contain an amino group-containing compound in the system, has a large Z-average particle diameter, poor wet crockfastness, and an opaque appearance.
The aqueous polyurethane urea dispersion of comparative example 6 does not contain a hydroxyl group-containing carboxylic acid in the system, and the aqueous polyurethane urea dispersion has a large Z-average particle diameter, a large polydispersity index, and an opaque appearance.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing description, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description; and therefore any changes which come within the meaning and range of equivalency of the claims are to be embraced within their scope.
Claims (15)
1. An aqueous polyurethaneurea dispersion comprising a polyurethaneurea obtained from reacting a system comprising:
a. at least one polyisocyanate;
b. at least one polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1;
c. a polyester polyol having at least one hydroxyl functionality of 1.9 to 2.1, said polyester polyol being obtained by reacting a mixture comprising a diol and at least one of an aromatic diacid and an aromatic anhydride;
d. at least one amino-containing compound that is one or more of the following: amino group-containing carboxylic acids, amino group-containing carboxylates, amino group-containing sulfonic acids, and amino group-containing sulfonates;
e. at least one hydroxyl-containing carboxylic acid;
f. at least one neutralizing agent; and
optionally g.an isocyanate group-reactive compound different from component b) to component e) having a molecular weight of from 32g/mol to 400g/mol;
the weight ratio of the polycarbonate polyol to the polyester polyol is 6: 1 to 20: 1.
2. The aqueous polyurethaneurea dispersion of claim 1, wherein the amount of organic solvent in the aqueous polyurethaneurea dispersion is less than 1 weight percent relative to the total weight of the aqueous polyurethaneurea dispersion.
3. The aqueous polyurethaneurea dispersion of claim 1 or claim 2, wherein the aqueous polyurethaneurea dispersion is characterized by at least one of:
viscosity of 10mPa · s to 1000mPa · s, according to ISO 3219:1994 standard using a boehler fly viscometer;
the solid content is 30-40 wt%, and the content is tested by a Mettlerlatoduo halogen moisture analyzer;
the Z-average particle size is 30nm-75nm, and the particle size is tested by a Malvern nano particle size potential analyzer; and
the polydispersity is 0-0.3, and is measured by Malvern nanometer particle size potential analyzer.
4. The aqueous polyurethaneurea dispersion of any of claims 1-3, wherein the polyisocyanate is one or more of: hexamethylene diisocyanate and isophorone diisocyanate.
5. The aqueous polyurethane urea dispersion according to any one of claims 1-4, wherein the polycarbonate polyol is one or more of: hexanediol polycarbonate, butanediol polycarbonate, neopentyl glycol polycarbonate, 3-methylpentanediol polycarbonate and copolymers of the above polycarbonates.
6. The aqueous polyurethaneurea dispersion of any of claims 1-5, wherein the polyester polyol is one or more of: polyhexamethylene phthalate, polybutylene phthalate, neopentyl glycol phthalate, diethylene phthalate, 3-methylpentanediol phthalate, polyhexamethylene isophthalate, polybutylene isophthalate, neopentyl glycol isophthalate, diethylene isophthalate, 3-methylpentanediol isophthalate, polyhexamethylene terephthalate, polybutylene terephthalate, neopentyl glycol terephthalate, diethylene terephthalate and 3-methylpentanediol terephthalate; most preferably one or more of the following: polyhexamethylene phthalate, polybutylene phthalate, neopentyl glycol phthalate, diethylene glycol phthalate and 3-methylpentanediol phthalate.
7. The aqueous polyurethaneurea dispersion of any of claims 1-6, wherein the amino group containing compound is one or more of: 6-aminocaproate, lysine, N- (2-aminoethyl) -beta-alanine monosodium salt, 2- [ (2-aminoethyl) amino ] ethanesulfonic acid sodium salt, and 3- (cyclohexylamine) -1-propanesulfonic acid sodium salt.
8. The aqueous polyurethaneurea dispersion of any of claims 1-7, wherein the hydroxyl-containing carboxylic acid is one or more of: 2,2 dimethylolpropionic acid and 2,2 dimethylolbutyric acid.
9. Process for the preparation of an aqueous polyurethaneurea dispersion comprising a polyurethaneurea according to any of claims 1 to 8, comprising the steps of:
i. reacting some or all of component a) at least one polyisocyanate, component b) at least one polycarbonate polyol having a hydroxyl functionality of 1.9 to 2.1, component c) at least one polyester polyol having a hydroxyl functionality of 1.9 to 2.1, component e) at least one hydroxyl-containing carboxylic acid and optionally component g) an isocyanate group reactive compound different from components b) to e) to obtain a prepolymer;
ii reacting the prepolymer, component d) at least one amino group-containing compound and optionally component g) an isocyanate group-reactive compound different from components b) to e) to obtain the polyurethaneurea;
before or after step ii, adding component f) at least one neutralizing agent; and
introducing water before, during or after step ii to obtain said aqueous polyurethaneurea dispersion.
10. The method of claim 9, further comprising a step v. introducing an organic solvent that is miscible with water but inert to isocyanate groups during or after step i and removing the organic solvent from the aqueous polyurethaneurea dispersion.
11. A coating, adhesive or ink comprising the aqueous polyurethaneurea dispersion comprising a polyurethaneurea according to any one of claims 1-8.
12. Use of the aqueous polyurethaneurea dispersion comprising polyurethaneurea according to any of claims 1 to 8 for the preparation of coated, bonded or printed products.
13. An article or article comprising a substrate prepared, coated, bonded, sealed or printed with the aqueous polyurethaneurea dispersion comprising a polyurethaneurea according to any of claims 1-8.
14. A method of printing comprising the steps of: applying the aqueous polyurethaneurea dispersion comprising polyurethaneurea according to any one of claims 1-8 to a substrate surface followed by curing.
15. A printed product comprising a substrate and a coating formed by applying the aqueous polyurethaneurea dispersion comprising a polyurethaneurea of any one of claims 1-8 to the substrate.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
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| CN202111029317.4A CN115746252A (en) | 2021-09-02 | 2021-09-02 | Aqueous polyurethane urea dispersions |
| KR1020247006093A KR20240047382A (en) | 2021-09-02 | 2022-08-26 | Aqueous polyurethane-urea dispersion |
| PCT/EP2022/073752 WO2023031029A1 (en) | 2021-09-02 | 2022-08-26 | Aqueous polyurethane-urea dispersion |
| CN202280059613.5A CN117897424A (en) | 2021-09-02 | 2022-08-26 | Aqueous polyurethane urea dispersions |
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