CN118995018A - Composition, preparation method and application thereof - Google Patents

Abstract

The present invention relates to compositions, the preparation and use of the compositions, in particular in the field of coatings, adhesives or inks, and articles prepared, coated, bonded, sealed or printed using the compositions. The composition comprises (a) a polyurethane polyurea polymer; (b) a chelating agent; and (c) water. The composition of the invention has excellent low-temperature performance, good hydrolysis resistance and hydrolysis resistance after heat storage, can realize low viscosity and is easy for industrial production.

Description

Composition, preparation method and application thereof

Technical Field

The present invention relates to compositions, the preparation and use of the compositions, in particular in the field of coatings, adhesives or inks, and articles prepared, coated, bonded, sealed or printed using the compositions.

Background

The aqueous polyurethane polyurea dispersion can be widely applied to the fields of coating, adhesive, sealant and printing ink. Compared with the traditional solvent polyurethane, the polyurethane has the advantages of environmental protection, non-inflammability, explosive property, safe storage, high solid content and the like. However, aqueous polyurethane polyurea dispersions, as defined with respect to solvent-borne polyurethanes, contain excess water which, when stored under ambient conditions, can hydrolyze hydrolyzable groups, while metal ions present in the system (e.g., metal ions introduced in the catalyst for polyurethane or precursor synthesis) can also promote hydrolysis of hydrolyzable groups on the aqueous polyurethane polyurea dispersion, which can lead to reduced application properties, in particular in the field of coating products, can affect adhesion, dirt resistance, scratch resistance, impact resistance, elongation at break, water wash resistance, etc. of the coating, in the field of sealant and adhesive products, can affect the application properties, heat resistance, hydrolysis resistance, etc. of the sealant and adhesive.

The patent DE 19954500, DE 4410557 or EP 792908 et al propose to introduce carboxylate salts in polyurethane polyurea dispersions, which are obtained by adding dimethylolpropionic acid to the polyurethane polyurea, and then compounding with carbodiimide to improve the adhesion properties. The reactivity of the reactive carboxyl group with carbodiimide is low.

CN 108250390B describes that by adding a non-sterically hindered difunctional silane and introducing a polyethoxy segment with a terminal as hydrophilic agent, a self-crosslinkable aqueous polyurethane dispersion is obtained.

CN 109081897A describes that by adding non-sterically hindered difunctional, monofunctional or difunctional silanes, the introduction of polyethoxy segments with terminal ends as hydrophilic agents, self-crosslinkable aqueous polyurethane dispersions are obtained.

CN 113136160A describes that by adding a water-soluble chelating agent, it complexes with the metal ions in the system to form stable compounds that no longer promote polyurethane hydrolysis; by introducing non-steric type bifunctional silane (KH 792), the water resistance and heat resistance of the aqueous polyurethane are increased; meanwhile, a small amount of monofunctional polyether with a hydrophilic end group is added to replace a part of hydrophilic groups of sulfonate, so that the content of sulfonate is reduced, and the aqueous polyurethane adhesive with excellent stability is prepared.

EP 3026071 A1 describes a process for preparing aqueous polyurethane dispersions which are obtained from a mixture comprising at least one readily crystallizable polyester polyol and at least one polyether polyol, wherein the polyether polyol is a polyalkylene glycol homo-or copolymer containing ethylene oxide units.

WO 201635162 A1 describes a method for producing aqueous peptide-functionalized polyurethane dispersions (PUDs) useful as adhesives, in particular for metal surfaces, which are produced by reacting maleimide-terminated polyurethane prepolymers with one or more peptides. The amino acid side chain in the peptide and the maleimide group are subjected to coupling reaction, and the adsorption quality of the peptide on the surface of the substrate is improved by utilizing the adsorption characteristic of the peptide. The reaction mixture contains at least a polyether polyol, which may be a polyalkylene glycol homo-or copolymer, and a polyester polyol, which may be a crystalline/semi-crystalline polyol.

US 10640702 BB describes a method of making and using coated particles as proppants in hydraulic fracturing to optimize capital and equipment costs and improve production efficiency. The coated particles consist of substrate particles having a particle size of not more than 3 mesh and a coating comprising a crystalline or semi-crystalline polyester/polyurethane having a decrystallization temperature of at least 35 ℃ and modified with an aminosilane. The crystalline or semi-crystalline polyester/polyurethane may contain monofunctional or difunctional polyether polyols polymerized from ethylene oxide or copolymerized with ethylene oxide and propylene oxide.

WO 2018/158278 A1 describes an aqueous polyurethane polyurea dispersion comprising a soluble chelating agent salt.

Disclosure of Invention

It is an object of the present invention to provide a composition, the preparation and use of a composition, in particular in the field of paints, adhesives or inks, and articles prepared, coated, bonded, sealed or printed using the composition.

The composition according to the invention comprises:

(a) A polyurethane polyurea polymer, the polyurethane polyurea polymer resulting from the reaction of a system comprising:

(a1) A polyisocyanate;

(a2) A polymer conforming to the structure of formula I:

Wherein n is 10-75, R ¹ is alkyl containing 1-10 carbon atoms, and R2 is a structure containing at least two isocyanate-reactive groups;

(a3) A polyol different from component a 2), said polyol having a hydroxyl functionality of from 1.5 to 4;

(a4) A silane compound comprising an isocyanate reactive group and at least two methoxy and/or ethoxy groups attached to a silicon atom;

(a5) A hydrophilic compound other than (a 2) containing 2 to 3 isocyanate-reactive groups; and

(A6) Optionally a compound containing 1 to 3 amino groups and/or hydroxyl groups;

The amount of the polymer conforming to the structure of formula I is 0.7 wt% to 9 wt%, and the amount of the silane compound is 0.14 wt% to 0.6 wt% relative to the total weight of the polyurethane polyurea polymer;

(b) At least one water-soluble chelating agent selected from ethylenediamine tetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate, gluconate, and/or a mixture of at least two thereof; and

(C) And (3) water.

According to one aspect of the present invention, there is provided a process for the preparation of a composition according to the present invention comprising the steps of: mixing the polyurethane polyurea polymer (a) or the components for preparing the polyurethane polyurea polymer, the chelating agent (b) and the water (c) in any way.

According to another aspect of the present invention there is provided a coating, adhesive or ink comprising the composition provided according to the present invention.

According to a further aspect of the present invention there is provided the use of a composition according to the present invention for the preparation of a coated, bonded or printed product.

According to yet another aspect of the present invention, there is provided an article comprising a substrate prepared, coated, bonded, sealed or printed with the composition provided according to the present invention.

The methoxy and/or ethoxy silanes in the polyurethane polyurea in the composition of the invention can be hydrolyzed and subsequently condensed, thereby providing the composition with good hydrolysis resistance; the side group soft segment generated by the polymer conforming to the structure of the formula I of the polyurethane polyurea is more prone to be separated from the polyurethane hard segment, so that the polyurethane soft segment is softer and has strong mobility, thereby preventing the tight arrangement of molecules, reducing the mutual entanglement probability of macromolecular groups of the polyurethane polyurea, ensuring that the polyurethane polyurea is not easy to form a polymer cluster structure, and ensuring that the composition has good low-temperature stability; the chelating agent salt in the composition of the invention can reduce the acting force of electric double layers among particles, thereby well reducing the viscosity of the composition.

Therefore, the composition of the invention has excellent low-temperature performance, good hydrolysis resistance and hydrolysis resistance after heat storage, can realize low viscosity and is easy for industrial production.

Detailed Description

The present invention provides a composition comprising:

(a) A polyurethane polyurea polymer, the polyurethane polyurea polymer resulting from the reaction of a system comprising:

(a1) A polyisocyanate;

(a2) A polymer conforming to the structure of formula I:

Wherein n is 10-75, R ¹ is alkyl containing 1-10 carbon atoms, and R2 is a structure containing at least two isocyanate-reactive groups;

(a3) A polyol different from component a 2), said polyol having a hydroxyl functionality of from 1.5 to 4;

(a4) A silane compound comprising an isocyanate reactive group and at least two methoxy and/or ethoxy groups attached to a silicon atom;

(a5) A hydrophilic compound other than (a 2) containing 2 to 3 isocyanate-reactive groups; and

(A6) Optionally a compound containing 1 to 3 amino groups and/or hydroxyl groups;

The amount of the polymer conforming to the structure of formula I is 0.7 wt% to 9 wt%, and the amount of the silane compound is 0.14 wt% to 0.6 wt% relative to the total weight of the polyurethane polyurea polymer;

(b) At least one water-soluble chelating agent selected from ethylenediamine tetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate, gluconate, and/or a mixture of at least two thereof; and

(C) And (3) water.

The invention also provides the preparation and application of the composition, especially in the fields of paint, adhesives or printing ink, and the product obtained by coating, bonding, sealing or printing by using the composition.

The term "solidification" as used herein refers to the process of a liquid substance in a solid state from a liquid state to ambient conditions.

The term "coating" as used herein refers to a substance that can be applied to the surface of an article using different application processes to form a solid, continuous coating that adheres well, has a certain strength.

The term "adhesive" as used herein refers to a chemical substance that is capable of being applied to the surface of an article by a different application process, forming a coating on the surface of the article itself or one article with another, and bonding the article itself or one article with another article surface, and also serves as a synonym for adhesives and/or sealants and/or binders.

The term "polyurethane polyurea" as used herein refers to polyurethane and/or polyurethane urea and/or polyurea.

The term "aqueous polyurethane polyurea dispersion" as used herein refers to an aqueous polyurethane dispersion and/or an aqueous polyurethane urea dispersion and/or an aqueous polyurea dispersion.

The content of polyurethane polyurea in the aqueous polyurethane polyurea dispersion described herein is equivalent to the solid component content of the aqueous polyurethane polyurea dispersion.

The term "solid component" as used herein refers to a solid or an active component.

The term "isocyanate-reactive compound" as used herein refers to a component containing groups reactive towards isocyanate groups, i.e. a component containing Zerevitinov-active hydrogen, the definition of Zerevitinov-active hydrogen being given in Rompp' S CHEMICAL Dictionary (Rommp Chemie Lexikon), 10th ed., georg THIEME VERLAG Stuttgart,1996. Generally, zerevitinov-active hydrogen-containing groups are understood in the art to mean hydroxyl (OH), amino (NH _x) and thiol (SH).

The term "isocyanate-reactive group" as used herein refers to a group which is reactive towards isocyanate groups, i.e.a group containing Zerevitinov-active hydrogen, zerevitinov-active hydrogen being defined by reference Rompp' S CHEMICAL Dictionary (Rommp Chemie Lexikon), 10th ed., georg THIEME VERLAG Stuttgart,1996. Generally, zerevitinov-active hydrogen-containing groups are understood in the art to mean hydroxyl (OH), amino (NH _x) and thiol (SH).

Component a) polyurethane polyurea polymers

Component a 1) polyisocyanates

The polyisocyanate preferably has an isocyanate functionality of not less than 2, more preferably 2-4, most preferably 2.

The component a 1) polyisocyanates preferably have at least two isocyanate groups, more preferably one or more of the following: aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, araliphatic polyisocyanates, and their derivatives having iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, ureide and/or carbodiimide groups.

The component a 1) polyisocyanates are further preferably isocyanates which correspond to the following general formula: y (NCO) ₂, wherein Y is selected from: a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 15 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms.

The component a 1) polyisocyanates are also preferably one or more of the following: tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1, 4-cyclohexanediisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, 2' -and 2,4' -diphenylmethane diisocyanate, tetramethylxylyl diisocyanate and p-xylyl diisocyanate.

The polyisocyanates of component a 1) are preferably selected from the group consisting of: hexamethylene diisocyanate, isophorone diisocyanate, a mixture of hexamethylene diisocyanate and isophorone diisocyanate, or a mixture of hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.

The component a 1) polyisocyanates are most preferably: a mixture of hexamethylene diisocyanate and isophorone diisocyanate, or a mixture of hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.

The amount of component a 1) is preferably from 5% to 40% by weight, most preferably from 8% to 20% by weight, relative to the total weight of the polyurethane polyurea polymer.

Component a 2) polymers of the formula I

N of formula I is 10-75, which may or may not be an integer, preferably 10-40, more preferably 10-30.

The at least two isocyanate-reactive groups of R2 are preferably selected from at least two amino groups, at least two hydroxyl groups or at least one amino group and at least one hydroxyl group.

The polymer conforming to the structure of formula I is preferably one or more of the following: a polymer conforming to the structure of formula II and a polymer conforming to the structure of formula III,

Wherein a in formula II is 10-75, a may be an integer or not, b is 0-50, and b may be an integer or not; in formula III, x is 10-75, x may be an integer or not, y is 1-50, and y may be an integer or not.

The number average molecular weight of the polymer of component a 2) which corresponds to the structure of formula I is preferably 500g/mol to 4000g/mol, most preferably 600g/mol to 1500g/mol, the number average molecular weight being measured according to gel chromatography using tetrahydrofuran as the mobile phase and calculating the molecular weight based on polystyrene as standard, the component having a molecular weight of 200 or more being selected for calculation and measured by means of a differential refractive detector.

The functionality of the polymers of component a 2) which correspond to the structure of formula I is preferably 2.

The amount of the polymer of component a 2) which corresponds to the structure of formula I is preferably from 0.7% to 9% by weight, most preferably from 0.7% to 4% by weight, relative to the total weight of the aqueous polyurethane polyurea polymer.

Component a 3) a polyol different from component a 2)

The polyols of component a 3) which are different from component a 2) are preferably one or more of the following: diols having a number average molecular weight of 62 to 15000 and polyols having a number average molecular weight of 62 to 15000, more preferably one or more of the following: diols having a number average molecular weight of 62 to 5000 and triols having a number average molecular weight of 92 to 5000, most preferably one or more of the following: a polyester polyol having 1.5 to 3 hydroxyl groups and a number average molecular weight of 500 to 2500, a polycarbonate polyol having 1.5 to 3 hydroxyl groups and a number average molecular weight of 400 to 2500, a polyether polyol having 1.5 to 3 hydroxyl groups and a number average molecular weight of 200 to 2500, a polylactone polyol having 1.5 to 3 hydroxyl groups and a small molecular alcohol, the number average molecular weight being measured by gel chromatography, using tetrahydrofuran as a mobile phase, and calculating a molecular weight based on polystyrene as a standard, selecting a component having a molecular weight of 200 or more for calculation, and measuring with a differential refractive detector.

The polyether polyol having a number average molecular weight of 200 to 2500 and having 1.5 to 3 hydroxyl groups is preferably polytetrahydrofuran polyol having a number average molecular weight of 200 to 2500 and having 1.5 to 3 hydroxyl groups.

The melting enthalpy of the polyols of component a 3) which is different from component a 2) is preferably not less than 15J/g, more preferably from 25J/g to 100J/g, most preferably from 40J/g to 80J/g, as obtained by the first temperature increase profile of DSC from 20℃to 100℃according to DIN65467, in an amount of from 10 to 20mg and a heating rate of 20K/min.

The amount of component a 3) is preferably from 5% to 94% by weight, most preferably from 70% to 90% by weight, relative to the total weight of the composition.

Component a 4) silane Compounds

The component a 4) is a silane compound comprising one isocyanate reactive group and at least two methoxy and/or ethoxy groups attached to a silicon atom; the isocyanate reactive groups are preferably primary or secondary amino groups.

The component a 4) silane compound is preferably one or more of the following: bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, 3-aminopropyl (diethoxy) methylsilane and 3-aminopropyl methyldimethoxysilane; more preferably one or more of the following: bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, 3-aminopropyl (diethoxy) methylsilane and 3-aminopropyl methyldimethoxysilane.

In addition, the corresponding aspartate (formula IV) which can be synthesized from the above-described amino-functional silane and an ester of an unsaturated dicarboxylic acid such as maleic acid can be used.

Wherein X is the same or different and is methoxy, ethoxy, methyl or ethyl, provided that at least two groups are methoxy and/or ethoxy; wherein Q is alkyl, preferably n-propyl, and Z is alkoxy, preferably methoxy or ethoxy.

Further preferred compounds are diethyl N- (3-triethoxysilylpropyl) aspartate, diethyl N- (3-trimethoxysilylpropyl) aspartyl and propyl N- (3-dimethoxymethylsilylpropyl) aspartate.

The component a 4) is most preferably one or more of the following: (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane and 3-aminopropyl methyldimethoxysilane.

The amount of the silane compound of component a 4) is preferably from 0.14 wt% to 0.6 wt%, most preferably from 0.18 wt% to 0.4 wt%, relative to the total weight of the composition.

Component a 5) hydrophilic compounds containing 2 to 3 isocyanate-reactive groups

The hydrophilic group of the hydrophilic compound preferably comprises one or more of the following: ionic groups, potentially ionic groups, and nonionic groups.

The hydrophilic compounds of component a 5) containing 2 to 3 isocyanate-reactive groups are preferably one or more of the following: n- (2-aminoethyl) -2-aminoethane sulfonate, dimethylol propionate and (N- (2-aminoethyl) -2-aminoethane carboxylate.

The amount of component a 5) is preferably from 0.2% to 50% by weight, most preferably from 1% to 5% by weight, relative to the total weight of the composition.

Component a 6) Compounds containing 1 to 3 amino groups and/or hydroxyl groups

The compounds of component a 6) containing 1 to 3 amino groups and/or hydroxyl groups may contain 1 to 3 amino groups or contain 1 to 3 hydroxyl groups or contain a combination of amino and hydroxyl groups.

The compounds of component a 6) containing 1 to 3 amino groups and/or hydroxyl groups preferably contain at least one amino group; further preferred are one or more of the following: aliphatic monoamines, cycloaliphatic monoamines, aliphatic primary and/or secondary diamines, hydrazides, aliphatic primary and/or secondary triamines, aliphatic primary and/or secondary amino alcohols, cycloaliphatic primary and/or secondary diamines, cycloaliphatic primary and/or secondary triamines, cycloaliphatic primary and/or secondary amino alcohols; most preferably one or more of the following: isophorone diamine, N- (2-hydroxyethyl) ethylene diamine, and diethanolamine.

The amount of component a 6) is preferably not more than 10% by weight, most preferably from 0.5% to 3% by weight, relative to the total weight of the composition.

Component b) chelating agent

The chelating agent of component b) is preferably one or more of the following: ethylenediamine tetraacetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate and gluconate.

The amount of component b) is preferably from 0.05 wt% to 0.5 wt%, most preferably from 0.1 wt% to 0.2 wt%, relative to the total weight of the composition.

Preferably, the chelating agent b) is characterized in that the aqueous solution having a concentration of 4.3X10 ^-7 mol/g has a pH in the range of 3-11, preferably in the range of 4-10, most preferably in the range of 5-8 at a temperature of 23 ℃.

Process for the preparation of a composition

Preferably, the polyurethane polyurea polymer (a) and water (c) form an aqueous polyurethane polyurea dispersion, and the chelating agent (b) is then introduced to obtain the composition.

The chelating agent may be added as a solid or as an aqueous solution. Preferably in the form of an aqueous solution of the chelating agent, which will further facilitate the dispersion of the chelating agent.

The water-soluble salt of the chelating agent may be added directly or may be formed in the composition in an acid-base neutralized form. The acid-base neutralization may be complete or incomplete, preferably complete neutralization.

The chelating agent can be added during the chain extension process or the neutralization process of preparing the polyurethane polyurea polymer, can be added after the chain extension process, can be added during or after the dispersion of the polyurethane polymer in water, and can be added during or after the distillation of the polyurethane polymer.

The acid may be a free acid capable of undergoing a neutralization reaction with a base to form a water-soluble salt of the chelating agent. The free acid is preferably one or more of the following: aminocarboxylic acids, hydroxycarboxylic acids, inorganic polyphosphoric acids, hydroxyaminocarboxylic acids, organic polyphosphonic acids and polycarboxylic acids.

The aminocarboxylic acid is preferably one or more of the following: ethylenediamine tetraacetic acid and aminotriacetic acid.

The hydroxycarboxylic acid is preferably one or more of the following: tartaric acid, citric acid and gluconic acid.

The inorganic polyphosphoric acid is preferably one or more of the following: tripolyphosphoric acid, hexametaphosphate, and pyrophosphoric acid.

The hydroxyamino carboxylic acid is preferably one or more of the following: hydroxyethyl ethylenediamine triacetic acid and dihydroxyethyl glycine.

The water in the composition may be introduced prior to the formation of the polyurethane polyurea polymer, during the formation of the polyurethane polyurea polymer, or after the formation of the polyurethane polyurea polymer. The water is preferably introduced after the polyurethane polyurea polymer is formed.

The water and polyurethane polyurea polymer are mixed to form an aqueous polyurethane polyurea dispersion.

The amount of organic solvent in the aqueous polyurethane polyurea dispersion is preferably less than 1% by weight relative to the total weight of the aqueous polyurethane polyurea dispersion.

The aqueous polyurethane polyurea dispersion preferably has a solids content of 15% to 70% by weight, more preferably 30% to 60% by weight, most preferably 45% to 55% by weight, relative to the total weight of the aqueous polyurethane polyurea dispersion, using a HS153 moisture meter from Mettler Toledo company according to DIN-EN ISO 3251:2019 is performed at a heating temperature of 120 ℃ and the test endpoint is determined when the sample weight loss is less than 1mg/140 seconds.

The pH of the aqueous polyurethane polyurea dispersion is preferably from 4 to 11, most preferably from 5 to 10, the pH being measured at 23℃according to the PB-10pH meter from Sartorius Corp.

The aqueous polyurethane polyurea dispersions preferably have an average particle diameter of from 20nm to 750nm, more preferably from 50nm to 450nm, most preferably from 100nm to 250nm, as determined by laser correlation (laser particle sizer) according to the ZEN 1600 tester from Malvern, UK, according to ISO 13321:1996 test method 1 drop (about 0.05 g) of sample was added to 50ml of ultrapure water, and the diluted sample was tested at 23.0.+ -. 0.1 ℃; materials: polystyrene latex (RI: 1.590; absorptivity: 0.010), dispersant: water (temperature: 23.0 ℃ C.; viscosity: 0.9308cP; RI: 0.330), equilibration time: 60 seconds, using disposable cuvette DTS0012, positioning method: automatic attenuation selection, finding the best position: the analytical model is: universal (normal resolution), measurement angle: 173 ° backscatter (NIBS default), run times: 3 times, run duration: 10 seconds, number of measurements: 10 times.

The aqueous polyurethane polyurea dispersion preferably has a viscosity of 300 mPas-6000 mPas, according to DV-II+Pro. Rotational viscometer available from Brookfield, according to ISO 2555:2018 measured at 23 ℃, rotor type: s 62-64, rotating speed: 30RPM, test temperature: 23 ℃.

The aqueous polyurethane polyurea dispersions can be prepared using methods commonly used in the art, such as emulsion dispersion, prepolymer mixing, acetone, melt emulsification, ketimine solid phase dispersion, and related derivatization methods. A summary of the above methods can be found in Methoden der Organischen Chemie (Houben-Weyl,. Sup.4th edition, volume E20/part 2 page 1682, georg THIEME VERLAG, stuttgart, 1987). Among them, the melt emulsification method and the acetone method are preferable, and the acetone method is most preferable.

Preferably, the preparation method of the aqueous polyurethane polyurea dispersion comprises the following steps: i. reacting some or all of component a 1) a polyisocyanate, component a 2) a polymer conforming to the structure of formula I, and component a 3) a polyol different from component a 2) to obtain a prepolymer;

ii reacting said prepolymer, component a 4) a silane compound, component a 5) a hydrophilic compound containing 2-3 isocyanate reactive groups and optionally component a 6) a compound containing 1-3 amino and/or hydroxyl groups to obtain said polyurethane polyurea;

introducing component c) before, during or after step ii) into the aqueous dispersion; in a preferred embodiment, component c) water is slowly added while stirring and the reaction is allowed to proceed at 20 to 60 ℃, preferably 40 to 60 ℃, most preferably 40 to 55 ℃, for 10-30 minutes; and

Adding a chelating agent of component b) to obtain the aqueous polyurethane polyurea dispersion.

Said step i is preferably carried out by adding components a 2), a 3) to the reactor and heating to 30-80 ℃, preferably 50-70 ℃ with stirring. After the water content of the mixture of step i is less than 0.5%, preferably less than 0.2% (by weight of the reactor) component a 1) is added with stirring and the exothermic reaction is allowed to proceed at 50-140 ℃, preferably 60-110 ℃, most preferably 80-90 ℃ until the theoretical calculated reaction end point is reached.

Said step ii) preferably consists in dissolving component a 5) and optionally component a 6) in water and component a 4) in acetone, adding separately to the prepolymer while stirring, and allowing the exothermic reaction to proceed at 20-60 ℃, preferably 40-60 ℃, most preferably 40-55 ℃, for 30 minutes to obtain the polyurethane polyurea.

Said step iv is preferably carried out by slowly adding component b) while stirring at 20-40 ℃, preferably 20-30 ℃.

The preparation process may further comprise a step v. introducing a water-miscible but inert to isocyanate groups during or after step i, and removing the organic solvent from the aqueous polyurethane polyurea dispersion.

The organic solvent is preferably a solvent miscible with water but inert to isocyanate groups, further preferably one or more of the following: acetone, butanone, propylene glycol dimethyl ether, other ethers and esters that do not contain hydroxyl functionality; most preferably one or more of the following: acetone and butanone.

The organic solvent preferably does not contain an N-methyl or N-ethyl pyrrolidone compound.

The organic solvent is preferably removed partially or completely by distillation, preferably at a temperature of from 10 ℃ to 100 ℃ and for a time of from 1 hour to 12 hours.

The distillation temperature is most preferably from 25℃to 60 ℃.

The distillation time is most preferably 2 hours to 7 hours.

The rectification pressure is preferably from 500mbar to 50mbar, most preferably from 200mbar to 60mbar.

In order to accelerate the reaction rate of step i, catalysts customary in prepolymer preparation can be used, for example triethylamine, 1, 4-diazabicyclo- [2, 2] -octane, sebacic acid or bismuth neodecanoate, tin dioctanoate, tin (II) chloride or dibutyltin dilaurate, most preferably tin (II) chloride and bismuth neodecanoate.

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. To this end, spectroscopic measurements, such as infrared or near-infrared spectra, and refractive index measurements or chemical analyses, such as titration, may be performed simultaneously on the extracted sample.

The prepolymer may be in a solid state or a liquid state at ordinary temperature.

The polyisocyanates of component a 1) and the polymers of component a 2) conforming to the structure of formula I can be added in one portion or in multiple portions, and can be the same or different components as previously added.

The organic solvent present in the polyurethane polymer may be removed by distillation. The organic solvent may be removed during the formation of the polyurethane polymer or after the formation of the polyurethane polymer.

Coatings, adhesives or inks

The coating, adhesive or ink preferably further comprises an additive. The additive is preferably one or more of the following: emulsifiers, light stabilizers, antioxidants, bactericides, fillers, antisettling agents, defoamers, wetting agents, flow regulators, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, pigments, dyes, matting agents and adhesion promoters. The additives may be added during and/or after the production of the polyurethane polyurea dispersion.

The additive selection and use metering are in principle known to the person skilled in the art and are readily determinable.

The aqueous polyurethane polyurea dispersions of the invention can also be mixed with and used with other aqueous or solvent-containing oligomers or polymers, for example aqueous or solvent-containing polyesters, polyurethanes, polyurethane-polyacrylates, polyethers, polyester-polyacrylates, alkyd resins, addition polymers, polyamide/imides or polyepoxides. The compatibility of such mixtures must be tested in each case using simple preliminary tests.

The aqueous polyurethane polyurea dispersions of the invention can also be mixed together and used together with other compounds containing functional groups, such as carboxyl groups, hydroxyl groups and/or blocked isocyanate groups.

The coatings, binders or inks according to the invention are processed according to methods known to the person skilled in the art.

Coated, bonded or printed products

The substrate is preferably one or more of the following: wood, metal, glass, fiber, textile, imitation leather, paper, plastic, rubber, foam, ceramic, and various polymer coatings, most preferably one or more of the following: textiles, plastics, ceramics, metals, dermis, artificial leather and various polymer coatings.

The coating may be a coating of the coating, binder or ink onto the entire surface of the substrate or onto only 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.

Drawings

The invention is described and explained in more detail below with reference to the attached drawing figures, wherein:

fig. 1 is a schematic diagram of spline bonding.

FIG. 2 is a schematic illustration of a spline hydrolysis resistance test.

FIG. 3 is a schematic of dry film cracking and non-cracking for a low temperature film forming test.

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. To the extent that the definitions of terms in this specification are inconsistent with the ordinary understanding of those skilled in the art to which this invention pertains, the definitions described herein control.

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 in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties to be obtained.

As used herein, "and/or" means one or all of the elements mentioned.

The use of "including" and "comprising" herein encompasses both the situation in which only the elements are mentioned and the situation in which other elements not mentioned are present in addition to the elements mentioned.

As used in this specification, the terms "a," "an," "the," and "the" are intended to include "at least one" or "one or more," unless otherwise specified. For example, "a component" refers to one or more components, and thus more than one component may be considered and possibly employed or used in the practice of the embodiments.

All percentages in the present invention are by weight unless otherwise indicated.

Analytical measurements according to the invention were carried out at 23.+ -. 2 ℃ unless otherwise indicated.

Method for testing the solids content (solids content) of dispersions of aqueous polyurethane polyureas: the HS153 moisture meter from Mettler Toledo was used in accordance with DIN-EN ISO 3251:2019 is performed at a heating temperature of 120 ℃ and the test endpoint is determined when the sample weight loss is less than 1mg/140 seconds. The average particle diameter of the aqueous polyurethane polyurea dispersion is measured by the following method: the ZEN 1600 tester according to Malvern company in uk was measured by laser correlation (laser particle sizer), according to ISO 13321:1996 test method 1 drop (about 0.05 g) of sample was added to 50ml of ultrapure water, and the diluted sample was tested at 23.0.+ -. 0.1 ℃; materials: polystyrene latex (RI: 1.590; absorptivity: 0.010), dispersant: water (temperature: 23.0 ℃ C.; viscosity: 0.9308cP; RI: 0.330), equilibration time: 60 seconds, using disposable cuvette DTS0012, positioning method: automatic attenuation selection, finding the best position: the analytical model is: universal (normal resolution), measurement angle: 173 ° backscatter (NIBS default), run times: 3 times, run duration: 10 seconds, number of measurements: 10 times.

The method for testing the pH value of the aqueous polyurethane polyurea dispersion comprises the following steps: according to DIN ISO 976:2016-12 was measured at 23℃using a PB-10pH meter from Sartorius, germany.

Method for measuring pH of chelating agent aqueous solution: according to DIN ISO 976:2016-12 was measured at 23℃using a PB-10pH meter from Sartorius, germany, at a concentration of 4.3X10 ^-7 mol/g.

The viscosity test method of the aqueous polyurethane polyurea dispersion comprises the following steps: using a DV-ii+pro. Rotational viscometer from Brookfield, according to ISO 2555:2018 measured at 23 ℃, rotor type: s 62-64, rotating speed: 30RPM, test temperature: 23 ℃.

Isocyanate group (NCO) content according to DIN-EN ISO 11909:2007 by volume.

Raw materials and reagents

Polyester I: semi-crystalline, difunctional polyester polyols based on adipic acid and 1, 4-butanediol, number average molecular weights Mn 2250g/mol, hydroxyl numbers 50mg KOH/g, glass transition temperatures of-61℃and melting temperatures of 49℃and melting enthalpies 80J/g.

Polyester II: semi-crystalline, difunctional polyester polyols based on adipic acid, 1, 6-hexanediol and neopentyl glycol (molar ratio of 1, 6-hexanediol to neopentyl glycol of 3:2), have a number average molecular weight Mn of 1700g/mol, a hydroxyl number of 66mg KOH/g, a glass transition temperature of-63 ℃, a melting temperature of 26℃and a melting enthalpy of 55J/g.

Polyether I: ymer N120,120, a difunctional polyether containing pendant methoxy polyethylene oxide chains, having a number average molecular weight of 1000g/mol, obtainable from Perstorp Chemitec AB (SE).

Polyether II: ymer N180,180, a difunctional polyether containing pendant methoxy polyethylene oxide chains, having a number average molecular weight of 600g/mol, obtainable from Perstorp Chemitec AB (SE).

Polyether III: MPEG 750, monofunctional polyethoxy ether, number average molecular weight 750g/mol, available from Shanghai Dong chemical Co., ltd.

Isocyanate I: H, hexamethylene diisocyanate, available from Kogyo Co., ltd.

Isocyanate II: isophorone diisocyanate is available from Cork, inc., germany.

Silane I: PC1200, N- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, is commercially available from sisbo silicone.

Silane II: PC1210, N-beta- (aminoethyl) -gamma-aminopropyl triethoxysilane, is available from Siebold silicone.

Silane III: PC1130, 3-aminopropyl methyl dimethoxy silane, commercially available from sisbo silicone.

Silane IV: PC1100, (3-aminopropyl) triethoxysilane, commercially available from sisbo silicone.

Silane V: PC1110, (3-aminopropyl) trimethoxysilane, commercially available from sisbo silicone.

Lucramul 1820 and liquid: emulsifiers, fatty alcohol poly (ethylene glycol/propylene glycol) ethers, supplied as 15% -20% aqueous solutions, are commercially available from Levaco GmbH, germany.

Tetra sodium ethylene diamine tetraacetate: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc. (ph= 10.4,4.3 ×10 ^-7 mol/g aqueous solution)

Sodium citrate: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc. (ph= 8.0,4.3 ×10 ^{- 7} mol/g aqueous solution)

Tetrasodium pyrophosphate: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc. (ph=9.9, 4.3x ^-7 mol/g aqueous solution)

Disodium pyrophosphate: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc. (ph= 5.3,4.3 ×10 ^-7 mol/g aqueous solution) sodium salt of N- (2-aminoethyl) -2-aminoethanesulfonic acid: VESTAMIN A95A concentration of 49% in water, commercially available from Yingzhang, germany.

Diethanolamine: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc.

Hydroxyethyl ethylenediamine: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc.

Isophorone diamine: analytical grade specifications are available from national pharmaceutical systems and chemical reagents, inc.

Borchigel Gel L75N: thickeners, clear liquids, 25% strength, are available from Borchers.

DESMODUR 2802: aliphatic polycarbodiimide, beige liquid, solids content 40%, limited, scientific, germany.

Preparation of the composition

The weight of the raw materials in the following examples is the weight comprising water if they are aqueous emulsions or aqueous solutions.

Composition 1

548.4G of polyester I and 5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 56.65g of isocyanate I and 7.51g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.5g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.14g isophoronediamine, a solution of 2.0g hydroxyethyl ethylenediamine dissolved in 50g water and a solution of 2.17g silane IV dissolved in 21.7g acetone were added separately to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for 3.5 hours, after which a 5% aqueous solution of 40g Lucramul 1820 liquid and 12.5g sodium citrate was added, respectively, to obtain a composition having a solid content of 50.6% by weight and an average particle diameter of 162nm in the dispersed phase, a pH value of 6.7 and a viscosity of 318 mPas.

Composition 2

548.4G of polyester I and 5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 56.65g of isocyanate I and 7.51g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.5g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.14g isophoronediamine, a solution of 2.0g hydroxyethyl ethylenediamine dissolved in 50g water and a solution of 1.60g silane III dissolved in 16.0g acetone were added separately to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for 3.5 hours, after which 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium ethylenediamine tetraacetate were added, respectively, to obtain a composition having a solid content of 50.3% by weight and an average particle diameter of 162nm in the dispersed phase, a pH value of 6.7 and a viscosity of 416 mPa.s.

Composition 3

534.4G of polyester I and 12.5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 56.38g of isocyanate I and 7.9g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. A solution of 11.6g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.9g of hydroxyethylethylene diamine in 50g of water and 1.25g of silane V in 12.5g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. After acetone was separated by distillation for 5 hours and the acetone content was less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a composition having a solid content of 50% by weight and an average particle diameter of 163nm in the dispersed phase, a pH value of 6.7 and a viscosity of 1218 mPa.s.

Composition 4

503.4G of polyester I and 25g of polyether I are dehydrated at 110℃for 1 hour at 80mbar, 2.3g of 1, 4-butanediol are added and, while stirring, cooled. 60.62g of isocyanate I and 8.04g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.7% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 12.0g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.03g diethanolamine, a solution of 3.28g hydroxyethylethylenediamine in 50g water and a solution of 1.75g silane V in 17.5g acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. After acetone was separated by distillation for 7 hours and the acetone content was less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a composition having a solid content of 49% by weight and an average particle diameter of 164nm in the dispersed phase, a pH value of 6.6 and a viscosity of 5432 mPas.

Composition 5

542.8G of polyester I and 4.5g of polyether II were dehydrated at 110℃for 1 hour at 80mbar, 2.3g of 1, 4-butanediol were added and cooled while stirring. 59.56g of isocyanate I and 3.78g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. A solution of 11.5g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 2.3g of hydroxyethylethylene diamine in 50g of water and a solution of 1.25g of silane V in 12.5g of acetone were added to the acetone solution in which the prepolymer was dissolved, respectively, while stirring vigorously. The mixture was stirred for 30min and then dispersed by adding 570g of water. After acetone was separated by distillation for 3.5 hours and the acetone content was less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a composition having a solid content of 50.2% by weight and an average particle diameter of 174nm in the dispersed phase, a pH value of 6.7 and a viscosity of 375 mPa.s.

Composition 6

The main composition is the same as composition 5, but disodium pyrophosphate is added in the last step instead of tetrasodium pyrophosphate. A composition was obtained having a solids content of 50.0% by weight and an average particle diameter of 158nm in the dispersed phase, a pH of 6.4 and a viscosity of 520 mPa-s.

Comparative composition 1

548.4G of polyester I and 5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 56.65g of isocyanate I and 7.51g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. A solution of 11.5g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 2.7g of hydroxyethylethylene diamine in 50g of water and 2.17g of silane IV in 21.7g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for 3.5 hours, and after having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid was added to obtain a comparative composition having a solids content of 50.1% by weight and an average particle size of 162nm in the dispersed phase, a pH of 6.8 and a viscosity of 1152 mPas.

Comparative composition 2

548.4G of polyester I and 5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 56.65g of isocyanate I and 7.51g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.5g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, a solution of 2.7g of hydroxyethylethylenediamine in 50g of water and a solution of 1.60g of silane III in 16.0g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for 3.5 hours, and after having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid was added to obtain a comparative composition having a solids content of 49.7% by weight and an average particle size of 162nm in the dispersed phase, a pH of 6.7 and a viscosity of 1280 mPas.

Comparative composition 3

534.4G of polyester I and 12.5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 56.38g of isocyanate I and 7.9g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. A solution of 11.6g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.9g of hydroxyethylethylene diamine in 50g of water and 1.25g of silane V in 12.5g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for 5 hours, and after having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid was added to obtain a comparative composition having a solid content of 50% by weight and an average particle diameter of 163nm in the dispersed phase, a pH of 6.6 and a viscosity of 2800 mPas.

Comparative composition 4

503.4G of polyester I and 25g of polyether I are dehydrated at 110℃for 1 hour at 80mbar, 2.3g of 1, 4-butanediol are added and, while stirring, cooled. 60.62g of isocyanate I and 8.04g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.7% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 12.0g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, a solution of 3.75g of hydroxyethylethylene diamine in 50g of water and a solution of 1.75g of silane V in 17.5g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. Acetone was separated by distillation for 7 hours, and after having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid was added to obtain a comparative composition having a solids content of 49% by weight and an average particle diameter of 164nm in the dispersed phase, a pH of 6.8 and a viscosity of 10400 mPas.

Comparative composition 5

506.3G of polyester I are dehydrated at 110℃for 1 hour at 80mbar, 2.3g of 1, 4-butanediol are added and cooled while stirring. 58.87g of isocyanate I and 3.27g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.7% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 12.6g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, a solution of 3.41g of hydroxyethylethylene diamine in 50g of water and a solution of 1.17g of silane V in 11.7g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. After acetone was separated by distillation for 3.5 hours and the acetone content was less than 1.0% by weight, 33.3g Lucramul 1820 liquid and 11.6g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solids content of 50.3% by weight and an average particle diameter of 179nm in the dispersed phase, a pH of 6.7 and a viscosity of 312 mPa.s.

Comparative composition 6

543.4G of polyester I and 1.9g of polyether I were dehydrated at 110℃and 80mbar for 1 hour and then cooled. 61.5g of isocyanate I and 5.11g of isocyanate II were added at 60℃and stirred at 80-90℃until an isocyanate content of 1.8% was reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 12.0g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 7.08g isophoronediamine, a solution of 2.0g hydroxyethyl ethylenediamine dissolved in 78.92g water and a solution of 1.86g silane V dissolved in 18.6g acetone were added separately to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 542g of water. After acetone was separated by distillation for 3 hours and the acetone content was less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solid content of 52.5% by weight and an average particle diameter of 224nm in the dispersed phase, a pH of 6.6 and a viscosity of 85 mPa.s.

Comparative composition 7

547.2G of polyester I and 3.9g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 0.8g of 1, 4-butanediol were added and, while stirring, cooled. 59.1g of isocyanate I and 5.94g of isocyanate II were added at 60℃and stirred at 80-90℃until an isocyanate content of 1.67% was reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 12.0g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 2.98g isophorone diamine, 1.0g hydroxyethyl ethylenediamine dissolved in 50g water and 1.70g silane V dissolved in 17.0g acetone were added separately to the prepolymer dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 542g of water. After acetone was separated by distillation for 3 hours and the acetone content was less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solid content of 49.6% by weight and an average particle diameter of 181nm in the dispersed phase, a pH of 6.5 and a viscosity of 85 mPa.s.

Comparative composition 8

462.9G of polyester I and 62.9g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 62.41g of isocyanate I and 13.6g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.9% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 13.7g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 7.44g isophoronediamine, 1.0g hydroxyethylethylenediamine in 50g water and 1.23g silane II in 12.3g acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. Stirring is carried out for 30min, and the mixture is then dispersed by adding 1060g of water. After acetone was separated by distillation for 7 hours and the acetone content was less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solid content of 37.6% by weight and an average particle diameter of 155nm in the dispersed phase, a pH of 7.3 and a viscosity of 8416 mPa.s.

Comparative composition 9

506.8G of polyester I,18.9g of polyester II and 18.7g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 65.17g of isocyanate I and 4.17 g of isocyanate II are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.7% is reached. Then dissolved in 890g of acetone and cooled to 50℃to obtain a reaction solution. A solution of 13.2g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 5.05g isophorone diamine, 1.6g hydroxyethyl ethylenediamine dissolved in 60g water was added to the acetone solution with the prepolymer dissolved therein while stirring vigorously. The mixture was stirred for 30min and then dispersed by adding 550g of water. After acetone was separated by distillation for 4 hours, having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solid content of 50.8% by weight and an average particle diameter of 175nm in the dispersed phase, a pH of 6.7 and a viscosity of 712 mPa.s.

Comparative composition 10

542.8G of polyester I and 7.5g of polyether I were dehydrated at 110℃for 1 hour at 80mbar, 2.3g of 1, 4-butanediol were added and cooled while stirring. 62.35g of isocyanate I are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.9% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, a solution of 2.95g of hydroxyethylethylene diamine in 50g of water and a solution of 0.77g of silane III in 7.7g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. After acetone was separated by distillation for 4 hours, having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solids content of 50.3% by weight and an average particle diameter of 165nm in the dispersed phase, a pH of 7.1 and a viscosity of 640 mPa.s.

Comparative composition 11

421.9G of polyester I,170g of polyester II and 11.36g of polyether I are dehydrated at 110℃for 1 hour at 80mbar and cooled, 71.25g of isocyanate I are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.4% is reached. Then dissolved in 1100g of acetone and cooled to 50℃to obtain a reaction solution. 9.64g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, a solution of 4.2g isophoronediamine 1.0g hydroxyethyl ethylenediamine dissolved in 50g water and a solution of 4.83g silane V dissolved in 48.3g acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 534g of water. After acetone was separated by distillation for 3.5 hours and the acetone content was less than 1.0% by weight, 40g Lucramul 1820 liquid and 13.8g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solids content of 55.6% by weight and an average particle diameter of 235nm in the dispersed phase, a pH value of 7.0 and a viscosity of 190mPa.s.

Comparative composition 12

542.8G of polyester I and 12.6g of polyether III were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 62.35g of isocyanate I are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, a solution of 2.81g of hydroxyethylethylenediamine in 50g of water and a solution of 1.26g of silane V in 12.6g of acetone were added to the acetone solution in which the prepolymer was dissolved, respectively, while stirring vigorously. The mixture was stirred for 30min and then dispersed by adding 570g of water. After acetone was separated by distillation for 6 hours, having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solid content of 50.5% by weight and an average particle diameter of 134nm in the dispersed phase, a pH of 6.7 and a viscosity of 2403 mPas.

Comparative composition 13

542.8G of polyester I and 12.6g of polyether III were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and cooled while stirring. 62.35g of isocyanate I are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, a solution of 2.81g of hydroxyethylethylene diamine in 50g of water and a solution of 1.54g of silane IV in 15.4g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. After acetone was separated by distillation for 5 hours and the acetone content was less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solid content of 50.5% by weight and an average particle diameter of 162nm in the dispersed phase, a pH of 6.9 and a viscosity of 1200 mPa.s.

Comparative composition 14

548.4G of polyester I and 5g of polyether I were dehydrated at 110℃under 80mbar for 1 hour, 2.3g of 1, 4-butanediol were added and, while stirring, cooled. 62.35g of isocyanate I are added at 60℃and stirred at 80-90℃until an isocyanate content of 1.3% is reached. Then dissolved in 930g of acetone and cooled to 50℃to obtain a reaction solution. 11.47g N- (2-aminoethyl) -2-aminoethanesulfonic acid sodium salt, 1.87g of hydroxyethylethylene diamine, 1.26g of diethanolamine in 50g of water and 1.17g of silane I in 11.7g of acetone were added to the prepolymer-dissolved acetone solution with vigorous stirring. The mixture was stirred for 30min and then dispersed by adding 570g of water. After acetone was separated by distillation for 4 hours, having an acetone content of less than 1.0% by weight, 40g Lucramul 1820 liquid and 12.5g of a 5% aqueous solution of tetrasodium pyrophosphate were added, respectively, to obtain a comparative composition having a solid content of 49.7% by weight and an average particle diameter of 152nm in the dispersed phase, a pH of 6.9 and a viscosity of 542 mPa.s.

Method for preparing the adhesive of examples and comparative examples

According to the components shown in Table 1 and Table 2, 1.0g DESMODUR 2802 and 0.7g BorchiL Gel L75N were added to 100g of the composition (the composition was allowed to stand and age at room temperature for 7 days in advance) in this order while stirring at 600rpm, and the mixture was stirred at a high speed at 1200rpm for 10 minutes to 15 minutes to be thoroughly mixed and the viscosity was adjusted to 5000 mPas to 10000 mPas for use.

Hydrolysis resistance test

The base materials 1 (black rubber) and 2 (black rubber) with the length of 120mm and the width of 20mm are mechanically polished, then a rubber treatment agent (the rubber treatment agent obtained by dissolving trichloroisocyanuric acid (B powder) in ethyl acetate) is coated, after drying, the adhesive is brushed on the base materials 1 and 2 by using a brush, and the brushing area is 100mm x 20mm. The adhesive was dried and heat activated by heating substrate 1 and substrate 2 at 60 ℃ for 3 minutes, and then substrate 1 and substrate 2 were attached at a pressure of 4bar for 10 seconds, resulting in a test bar as shown in fig. 1. After storing the test bars at room temperature (22.+ -. 2 ℃ C., 50.+ -. 5% RH) for 72 hours, 1kg weight was loaded on one end of the substrate, as shown in FIG. 2, and the test bars were placed in an oven at 70 ℃ C., 95% humidity for the time required for complete detachment of the test bars. The hydrolysis resistance is qualified when the time required for the complete detachment of the spline is not less than 6 hours, and the hydrolysis resistance is unqualified when the time required for the complete detachment of the spline is less than 6 hours.

Hydrolysis resistance test of the adhesive after two weeks of storage at 40 DEG C

The test method is similar to the hydrolysis resistance test described above, except that the adhesive is aged in an oven at 40 ℃ for two weeks before the hydrolysis resistance test, and then removed for the hydrolysis resistance test.

Low temperature film forming property test

The compositions of examples and comparative examples were allowed to stand at room temperature for curing for 7 days, then a 200 μm wet film was scraped on a PP plate with a film scraper at room temperature (22±2 ℃,50±5%rh), and the PP plate was immediately placed in a low temperature oven at 10 ℃ for at least 8 hours to allow complete drying. And taking out the film to check whether the dry film is cracked, wherein the low-temperature film forming property is qualified if the dry film is not cracked, and the low-temperature film forming property is unqualified if the dry film is cracked.

Table 1 shows the evaluation results of hydrolysis resistance, hydrolysis resistance after heat storage and low-temperature film forming property of the adhesives of examples 1 to 5 and comparative examples 1 to 4 of the present invention. Table 2 shows the evaluation results of hydrolysis resistance and low-temperature film forming property of the adhesives of comparative examples 5 to 14 of the present invention.

TABLE 1 evaluation of the binders of examples 1-5 and comparative examples 1-4

Remarks: the compositions of the examples and comparative examples in Table 1 were each present in an amount of 100 g.

Table 2 evaluation of the binders of comparative examples 5-14

Remarks: the compositions of the comparative examples in Table 2 were all present in an amount of 100 g.

The adhesives comprising the compositions of examples 1-5 of the present application have good hydrolysis resistance, hydrolysis resistance after heat storage, and low temperature film forming properties.

Comparative examples 1-4 and comparative examples 1-4, when the composition does not contain a chelating agent, the adhesive containing the composition is poor in hydrolysis resistance after heat storage.

Comparative examples 1-4 and comparative examples 5-7, when the composition does not include the polymer according to the structure of formula I or includes the polymer according to the structure of formula I in an amount of 0.3 wt% and 0.6 wt%, the adhesive including the composition does not combine hydrolysis resistance and low temperature film forming property.

Comparative examples 1 to 4 and comparative examples 9 to 11, when the composition does not contain a silane compound or contains a silane compound in an amount of 0.12 wt% and 0.7 wt%, the hydrolysis resistance of the adhesive containing the composition is poor.

As can be seen from comparative example 8, when the composition contains the polymer conforming to the structure of formula I in an amount of 10 wt%, the hydrolysis resistance of the adhesive containing the composition is poor.

It can be seen from comparative examples 12-13 that when the composition comprises a monofunctional polyether polyol, the hydrolysis resistance of the adhesive comprising the composition is poor.

Comparing comparative example 14 with examples 2-3, when the composition contains only difunctional silane compounds and no monofunctional silane compounds, the hydrolysis resistance of the adhesive containing the composition is poor.

It will be evident to those skilled in the art that the invention is not limited to the precise details set forth, and that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The described 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 (27)

1. A composition comprising:

(a) A polyurethane polyurea polymer, the polyurethane polyurea polymer resulting from the reaction of a system comprising:

(a1) A polyisocyanate;

(a2) A polymer conforming to the structure of formula I:

Wherein n is 10-75, R ¹ is alkyl containing 1-10 carbon atoms, R ² is a structure containing at least two isocyanate-reactive groups;

(a3) A polyol different from component a 2), said polyol having a hydroxyl functionality of from 1.5 to 4;

(a4) A silane compound comprising an isocyanate reactive group and at least two methoxy and/or ethoxy groups attached to a silicon atom;

(a5) A hydrophilic compound other than (a 2) containing 2 to 3 isocyanate-reactive groups; and

(A6) Optionally a compound containing 1 to 3 amino groups and/or hydroxyl groups;

The amount of the polymer conforming to the structure of formula I is 0.7 wt% to 9 wt%, and the amount of the silane compound is 0.14 wt% to 0.6 wt% relative to the total weight of the polyurethane polyurea polymer;

(b) A water-soluble chelating agent which is one or more selected from the group consisting of edetate, tartrate, citrate, pyrophosphate, tripolyphosphate, hexametaphosphate and gluconate; and

(C) And (3) water.

2. The composition of claim 1 wherein the component a 1) polyisocyanate has at least two isocyanate groups; further preferred are isocyanates conforming to the general formula: y (NCO) ₂, wherein Y is selected from: a divalent aliphatic hydrocarbon group having 4 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 6 to 15 carbon atoms, a divalent aromatic hydrocarbon group having 6 to 15 carbon atoms or a divalent araliphatic hydrocarbon group having 7 to 15 carbon atoms; also preferred are one or more of the following: tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1, 4-cyclohexanediisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, 4' -dicyclohexylpropane diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, 4' -diphenylmethane diisocyanate, 2' -and 2,4' -diphenylmethane diisocyanate, tetramethylxylyl diisocyanate and p-xylyl diisocyanate, most preferably: a mixture of hexamethylene diisocyanate and isophorone diisocyanate, or a mixture of hexamethylene diisocyanate and 4,4' -dicyclohexylmethane diisocyanate.

3. The composition of claim 1 or 2, wherein the at least two isocyanate-reactive groups of R2 are selected from at least two amino groups, at least two hydroxyl groups, or at least one amino group and at least one hydroxyl group.

4. A composition according to any one of claims 1 to 3, wherein the polymer conforming to the structure of formula I is one or more of the following: a polymer conforming to the structure of formula II and a polymer conforming to the structure of formula III,

Wherein a in formula II is 10-75, b is 0-50; in the formula III, x is 10-75, and y is 1-50.

5. The composition according to any one of claims 1 to 4, wherein the polymer of component a 2) which corresponds to the structure of formula I has a number average molecular weight of 500g/mol to 4000g/mol, the number average molecular weight being measured according to gel chromatography using tetrahydrofuran as mobile phase and calculating the molecular weight based on polystyrene as standard, the component having a molecular weight of 200 or higher being selected for calculation and measured by a differential refractive detector.

6. The composition of any one of claims 1 to 5, wherein the polymer of component a 2) conforms to the structure of formula I has a functionality of 2.

7. The composition of any of claims 1-6, wherein the polyol of component a 3) that is different from component a 2) is one or more of the following: diols having a number average molecular weight of 62 to 15000 and polyols having a number average molecular weight of 62 to 15000, more preferably one or more of the following: diols having a number average molecular weight of 62 to 5000 and triols having a number average molecular weight of 92 to 5000, most preferably one or more of the following: a polyester polyol having 1.5 to 3 hydroxyl groups and a number average molecular weight of 500 to 2500, a polycarbonate polyol having 1.5 to 3 hydroxyl groups and a number average molecular weight of 400 to 2500, a polyether polyol having 1.5 to 3 hydroxyl groups and a number average molecular weight of 200 to 2500, a polylactone polyol having 1.5 to 3 hydroxyl groups and a small molecular alcohol, the number average molecular weight being measured by gel chromatography, using tetrahydrofuran as a mobile phase, and calculating a molecular weight based on polystyrene as a standard, selecting a component having a molecular weight of 200 or more for calculation, and measuring with a differential refractive detector.

8. Composition according to any of claims 1 to 7, wherein the polyol of component a 3) which is different from component a 2) has a melting enthalpy of not less than 15J/g, most preferably from 25J/g to 100J/g, obtained by the first temperature increase profile from 20 ℃ to 100 ℃ by DSC according to method a in DIN65467, a loading of 10 to 20 mg and a heating rate of 20K/min.

9. The composition of any one of claims 1 to 8, wherein the silane compound of component a 4) comprises at least one amino group.

10. The composition of any one of claims 1 to 9, wherein the silane compound of component a 4) is one or more of the following: n- β - (aminoethyl) - γ -aminopropyl trimethoxysilane, N- β - (aminoethyl) - γ -aminopropyl triethoxysilane, N- (β -aminoethyl) - γ -aminopropyl methyldimethoxysilane, bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, 3-aminopropyl (diethoxy) methylsilane and 3-aminopropyl methyldimethoxysilane; preferably one or more of the following: n- (β -aminoethyl) - γ -aminopropyl methyldimethoxysilane, bis (3-triethoxysilylpropyl) amine, bis (3-trimethoxysilylpropyl) amine, (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane, 3-aminopropyl (diethoxy) methylsilane and 3-aminopropyl methyldimethoxysilane; most preferably one or more of the following: (3-aminopropyl) trimethoxysilane, (3-aminopropyl) triethoxysilane and 3-aminopropyl methyldimethoxysilane.

11. The composition according to any one of claims 1 to 10, wherein the component a 5) a hydrophilic compound containing 2 to 3 isocyanate-reactive groups is one or more of the following: n- (2-aminoethyl) -2-aminoethane sulfonate, dimethylol propionate and N- (2-aminoethyl) -2-aminoethane carboxylate.

12. Composition according to any one of claims 1 to 11, wherein the chelating agent b) is characterized in that the aqueous solution having a concentration of 4.3 x10 ^-7 mol/g has a pH in the range of 3 to 11, preferably in the range of 4 to 10, most preferably in the range of 5to 8 at a temperature of 23 ℃.

13. The composition according to any one of claims 1 to 12, wherein the compound of component a 6) containing 1 to 3 amino groups and/or hydroxyl groups is one or more of the following: aliphatic and/or cycloaliphatic primary and/or secondary mono-or di-or tri-amines or amino-alcohols, most preferably one or more of the following: isophorone diamine, N- (2-hydroxyethyl) ethylene diamine, and diethanolamine.

14. Composition according to any one of claims 1 to 13, wherein the amount of component a 1) is from 5% to 40% by weight, most preferably from 8% to 20% by weight, relative to the total weight of the polyurethane polyurea.

15. The composition according to any one of claims 1 to 14, wherein the amount of component a 2) is from 0.7% to 4% by weight relative to the total weight of the polyurethane polyurea.

16. Composition according to any one of claims 1 to 15, wherein the amount of component a 3) is from 5% to 94% by weight, most preferably from 70% to 90% by weight, relative to the total weight of the polyurethane polyurea.

17. The composition according to any one of claims 1 to 16, wherein the amount of component a 4) is from 0.18% to 0.4% by weight relative to the total weight of the polyurethane polyurea.

18. Composition according to any one of claims 1 to 17, wherein the amount of component a 5) is from 0.2% to 50% by weight, most preferably from 1% to 5% by weight, relative to the total weight of the polyurethane polyurea.

19. Composition according to any one of claims 1 to 18, wherein the amount of component b) is from 0.05% to 0.5% by weight, most preferably from 0.1% to 0.2% by weight, relative to the total weight of the polyurethane polyurea.

20. Composition according to any one of claims 1 to 19, wherein the amount of the compound of component a 6) containing 1 to 3 amino groups and/or hydroxyl groups does not exceed 10% by weight, most preferably 0.5% to 3% by weight, relative to the total weight of the polyurethane polyurea.

21. A process for the preparation of a composition as claimed in any one of claims 1 to 20 comprising the steps of: mixing the polyurethane polyurea polymer (a) or the components for preparing the polyurethane polyurea polymer, the chelating agent (b) and the water (c) in any way.

22. The method of claim 21 wherein said polyurethane polyurea polymer (a) and water (c) form an aqueous polyurethane polyurea dispersion and said chelating agent (c) is introduced to provide said composition.

23. The method of claim 21 or 22, wherein the chelating agent (c) is added as an aqueous solution.

24. A coating, adhesive or ink comprising the composition according to any one of claims 1-20.

25. The coating, adhesive or ink of claim 24, further comprising an additive that is one or more of the following: emulsifiers, light stabilizers, antioxidants, bactericides, fillers, antisettling agents, defoamers, wetting agents, flow regulators, reactive diluents, plasticizers, neutralizing agents, catalysts, auxiliary solvents, thickeners, pigments, dyes, matting agents and adhesion promoters.

26. Use of a composition according to any one of claims 1 to 20 for the preparation of a coated, bonded or printed product.

27. An article comprising a substrate prepared, coated, bonded, sealed or printed from the composition of any one of claims 1-20.