CN108192072B - Aqueous polyurethane dispersion and preparation method and application thereof - Google Patents
Aqueous polyurethane dispersion and preparation method and application thereof Download PDFInfo
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- CN108192072B CN108192072B CN201711367117.3A CN201711367117A CN108192072B CN 108192072 B CN108192072 B CN 108192072B CN 201711367117 A CN201711367117 A CN 201711367117A CN 108192072 B CN108192072 B CN 108192072B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- Health & Medical Sciences (AREA)
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- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses an aqueous polyurethane dispersion, a preparation method and application thereof, wherein the aqueous polyurethane dispersion is an aqueous polyurethane (Y) dispersion containing hydrophilic side chains; the polyurethane prepolymer (X) for forming the polyurethane (Y) with the hydrophilic side chain is obtained by reacting raw materials comprising a hydroxyl-containing compound (A), an isocyanate-containing compound (B), a polyoxyethylene group-containing single-side chain end polyol (C) and a carboxylic acid-containing polyol (D). The aqueous polyurethane dispersion can adjust the drying speed of the aqueous ink and maintain excellent mechanical properties thereof. And the water resistance of the water-based ink condensate containing the polyurethane (Y) can be controlled by adjusting the content of the nonionic hydrophilic side chain, so as to meet the requirements of the printing operation of the water-based ink and the water resistance of a final product. In addition, the preparation process of the aqueous polyurethane dispersion does not use an organic solvent, and the aqueous polyurethane dispersion is simple in process, green and environment-friendly.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an aqueous polyurethane dispersion, and a preparation method and application thereof.
Background
The water-based ink is widely applied to textile substrates in the sports goods industry, and the main components of the water-based ink are a connecting material and an auxiliary agent. The waterborne polyurethane has the advantages of wear resistance, good elasticity, designable performance and the like, and is a common water-based ink binder. Aqueous ink adjuvants typically include thickeners, humectants or moisturizing components (e.g., slow drying agents, etc.), defoamers, and the like. In order to meet application requirements, the solid content of the waterborne polyurethane serving as a connecting material is generally over 40%, but the high solid content can cause the rapid drying speed of the waterborne ink, and the problems of screen blockage and unqualified printed products can easily occur in the printing operation process. To solve this problem, the prior art adds a slow-drying agent to reduce the drying speed of the ink, and the slow-drying agent mainly consists of a high-boiling-point organic solvent or a highly hydrophilic polymer. The organic solvent is inevitably toxic, and the mechanical property of the ink cured material coating is also deteriorated; the high molecular substance with strong hydrophilicity has poor compatibility with the water-based ink binder, remains in the coating after drying, and seriously reduces the water resistance of the coating.
The production methods of the aqueous polyurethane dispersion reported in the prior art are generally a prepolymer method and an acetone method. The prepolymer method is to prepare a prepolymer under the condition of a small amount of solvent (N-methylpyrrolidone which is a common high-boiling solvent), disperse the prepolymer in an aqueous solution under rapid stirring while the prepolymer is hot, and then chain extend the prepolymer with diamine or hydrazine to prepare the product. The acetone method is that prepolymer is first prepared with polyol, polyisocyanate, low molecular diol, etc. and through cooling, dissolving in great amount of acetone, chain extending with chain extender, dispersing in water and evaporating to eliminate acetone to obtain the product. The two methods use organic solvents, have the problem of Volatile Organic Compound (VOC) emission, and the solvent residue in the aqueous polyurethane dispersion is difficult to avoid. Therefore, the idea of preparing an aqueous polyurethane dispersion by an organic solvent-free method has been proposed in the prior art.
There are three main methods for preparing the aqueous polyurethane dispersion by an organic solvent-free method at home and abroad. Firstly, the hydrophilicity of the polyurethane chain is increased, and the problem of insufficient water resistance of the product exists. For example, US4108814Helmut Reiff and the like use diols containing sulfonic acid groups to prepare organic solvent-free aqueous polyurethane dispersions, which have high sulfonic acid group content to enhance the hydrophilicity of polyurethane molecular chains and can be directly dispersed in water without using organic solvents. Secondly, the alkene-containing reactive monomer is used as a solvent to prepare a composite emulsion. For example, Rolf Gertzmann in US2004/0034146A1 discloses a solvent-free aqueous polyurethane-acrylate composite with DMPA as a hydrophilic component for use in strippable coatings, which is characterized in that acrylate monomers are used as a solvent to reduce the viscosity of polyurethane, thereby facilitating dispersion in water. Liangde super et al in patent CN106893041A disclose a solvent-free method for preparing aqueous polyurethane, which uses acrylate monomer as solvent to obtain acrylate graft modified emulsion. Thirdly, the dispersion speed is improved, and the shearing action is increased. Hong Liu et al, in patent US7240371B2, describe in detail the preparation technology of polyurethane adhesive films for the field of clothing, including solvent-free aqueous polyurethane dispersions, which is achieved by adding prepolymers into water (containing neutralizing agent and surfactant) under the condition of vigorous stirring (5000rpm), and then adding additives and chain extenders to prepare aqueous polyurethane emulsion. The method has high requirements on dispersing equipment and requires a prepolymer with low viscosity.
Disclosure of Invention
In order to solve the problems, the invention discloses a water-based ink moisturizing component which can prolong the drying time of water-based ink and keep the excellent mechanical properties of a cured product of the water-based ink, and the water-based ink moisturizing component is a water-based polyurethane dispersion and has good compatibility with a water-based ink vehicle.
The research shows that the nonionic long chain can be used as a moisture retention/slow drying component of the water-based ink alone, can effectively improve the problem of screen blockage of printing, but can obviously reduce the mechanical properties of cured ink, such as reduced tensile strength, easy deformation and the like. After the water-based ink prepared by embedding the nonionic long chain serving as the chain segment into the polyurethane straight chain is prepared, the water-based ink has no moisturizing/slow drying effect and even can be dried quickly. And when the nonionic chain is used as a side chain, on one hand, the flexibility of the chain is kept, on the other hand, the polyurethane main chain increases the compatibility of the nonionic chain and an ink binder, the molecular weight is increased, and the plasticizing effect of the nonionic chain on the ink is weakened. Based on such studies, the present invention proposes an aqueous dispersion of polyurethane (Y) having hydrophilic side chains; the introduction of hydrophilic side chain, especially non-ionic hydrophilic side chain, can increase the hydrophilicity of polyurethane chain and reduce the regularity of chain structure, and is favorable for obtaining low-viscosity polyurethane prepolymer which can be directly dispersed in water without solvent. The water resistance of the water-based ink condensate containing the polyurethane (Y) can be controlled by adjusting the content of the hydrophilic side chain, particularly the nonionic hydrophilic side chain, so as to meet the requirements of the printing operation of the water-based ink and the water resistance of a final product.
The invention also discloses a preparation method of the aqueous polyurethane dispersion and aqueous ink containing the aqueous polyurethane dispersion.
Specifically, the present invention provides an aqueous polyurethane dispersion which is an aqueous dispersion of polyurethane (Y) having hydrophilic side chains; the polyurethane prepolymer (X) for forming the polyurethane (Y) with the hydrophilic side chain is obtained by reacting raw materials comprising a hydroxyl-containing compound (A), an isocyanate-containing compound (B), a polyoxyethylene group-containing single-side chain end polyol (C) and a carboxylic acid-containing polyol (D).
According to the invention, the polyurethane (Y) containing hydrophilic side chains has a number average molecular weight (Mn), as determined by gel liquid chromatography, of 10000 to 50000, for example 11000 to 35000; the polyurethane (Y) having hydrophilic side chains has a glass transition temperature (Tg) of 0 ℃ or less, for example-70 ℃ to 0 ℃, further for example-65 ℃ to-10 ℃ as measured by DSC.
According to the invention, the aqueous polyurethane dispersion is obtained by adding a neutralizer (E) into the polyurethane prepolymer (X), then adding water, and finally adding a chain extender (F) for reaction.
According to the invention, the hydroxyl-containing compound (A) is selected from one or two of polypropylene glycol and polytetrahydrofuran glycol.
According to the present invention, the hydroxyl group-containing compound (A) is preferably polypropylene glycol in view of the viscosity of the polyurethane prepolymer. From the viewpoint of mechanical properties of the aqueous polyurethane cured product, polytetrahydrofuran diol is preferred. The hydroxyl group-containing compound (A) preferably has a molecular weight of 600 to 3000 in view of viscosity, mechanical properties and low-temperature properties.
According to the invention, the isocyanate group-containing compound (B) is selected from aliphatic and/or cycloaliphatic diisocyanates. For example, one or more of hexamethylene diisocyanate, isophorone diisocyanate, and 4, 4' -diisocyanate dicyclohexylmethane may be used.
According to the invention, the polyethylene oxide-containing single-sided chain end polyol (C) is selected from nonionic diols formed from trimethylolpropane and polyethylene oxide.
Wherein, the structure of C is shown as the following formula:
wherein n is an integer of 1 to 20, and R is an alkyl group.
Wherein the mass fraction of the polyoxyethylene group-containing single-side chain end polyol (C) to the hydrophilic side chain-containing polyurethane (Y) is 5 to 20%.
According to the present invention, the carboxylic acid-containing polyol (D) is selected from one or two of dimethylolpropionic acid and dimethylolbutyric acid.
According to the invention, the neutralizing agent (E) is a basic component, preferably an organic amine, more preferably triethylamine.
According to the invention, the chain extender (F) is selected from aliphatic polyamines which can be one or more of ethylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, hexamethylenediamine, diethylenetriamine, piperazine, isophoronediamine and the like.
The invention provides a preparation method of the aqueous polyurethane dispersion, which comprises the following steps:
(1) reacting raw materials comprising a hydroxyl-containing compound (A), an isocyanate-containing compound (B), a polyoxyethylene-containing single-side chain end polyol (C) and a carboxylic acid-containing polyol (D) to obtain a polyurethane prepolymer (X), wherein the X has a hydrophilic side chain;
(2) adding a neutralizing agent (E) to form a hydrophilic ionomer;
(3) adding water;
(4) adding a chain extender (F), and reacting to obtain the aqueous polyurethane dispersion.
According to the invention, the reaction temperature in step (1) may be 60 to 100 ℃, for example 85 ℃.
According to the present invention, the reaction time of step (1) may be 1 to 5 hours, preferably 2 to 4 hours.
According to the invention, the molar ratio of A, B, C to D in step (1) can be 1 (1-4): 0.1-0.6): 0.1-0.9, preferably 1 (2-3): 0.2-0.4): 0.3-0.7.
According to the present invention, the reaction temperature of the steps (2), (3) and (4) may be 20 to 90 ℃, preferably 40 to 70 ℃, and further preferably 50 to 60 ℃.
According to the present invention, the reaction time of step (2) may be 1 to 30 minutes, for example 10 minutes.
According to the invention, the molar ratio of E to D may be 0.3 to 2, preferably 0.8 to 1.2.
According to the invention, in step (3), a small amount of water is added for pre-emulsification, and then water is added dropwise for dispersion.
According to the invention, the molar ratio of the water to the A can be 100-700, preferably 200-600;
according to the present invention, the reaction time of step (4) may be 0.5 to 2 hours, for example, 1 hour.
According to the invention, the molar ratio of F to A may be 0.2 to 1.6, preferably 0.6 to 1.2.
The invention provides the application of the aqueous polyurethane dispersion, and the aqueous polyurethane dispersion can be used as a moisture retention component of aqueous ink, in particular to a moisture retention component of aqueous screen printing ink and is used for coating fabrics.
The invention also provides a water-based ink which comprises a vehicle and a moisture retention component, wherein the moisture retention component comprises the water-based polyurethane dispersion.
Preferably, the moisturizing component consists of the aqueous polyurethane dispersion.
Preferably, the moisture retention component accounts for 5-50% of the mass of the water-based ink, and preferably 5-30%.
Terms and definitions
Unless otherwise indicated, the definitions of groups and terms described in the specification and claims of the present application, including definitions thereof as examples, exemplary definitions, preferred definitions, definitions described in tables, definitions of specific compounds in the examples, and the like, may be arbitrarily combined and coupled with each other. Such combinations and definitions of groups and structures of compounds after combination are intended to fall within the scope of the present application.
The term "alkyl" as used herein is intended to include both branched and straight chain saturated aliphatic hydrocarbon groups having from 1 to 20, preferably from 1 to 6, carbon atoms (or the specific number of carbon atoms if such specific number is provided). For example, "C1-6Alkyl "denotes straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, and hexyl.
The invention has the advantages of
The invention provides an aqueous polyurethane dispersion, a preparation method and application thereof, the obtained aqueous polyurethane dispersion can adjust the drying speed of aqueous ink and keep excellent mechanical properties of the aqueous ink, and the prepared polyurethane prepolymer has the characteristic of low viscosity and can be directly dispersed in water without a solvent. And the water resistance of the water-based ink condensate containing the polyurethane (Y) can be controlled by adjusting the content of the hydrophilic side chain, particularly the content of the nonionic hydrophilic side chain, so as to meet the requirements of the printing operation of the water-based ink and the water resistance of a final product. In addition, the preparation process of the aqueous polyurethane dispersion does not use an organic solvent, and the aqueous polyurethane dispersion is simple in process, green and environment-friendly.
Detailed Description
The compounds of the general formula and the preparation and use thereof according to the present invention will be described in further detail with reference to the following examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Example 1
Adding metered polypropylene glycol, dimethylolbutyric acid and single-side end group dihydric alcohol (YMER N120) containing polyethylene oxide into a three-neck flask provided with a stirrer, a thermometer and a nitrogen gas guide tube, heating to 80 ℃, removing water in vacuum at 0.1MPa for 2 hours, cooling, adding diisocyanate, and reacting at 85 ℃ for 2-4 hours to obtain the polyurethane prepolymer. Cooling to 50-60 ℃, adding triethylamine, stirring for 10 minutes, adding a small amount of water for pre-emulsification, dropwise adding water for dispersion, then adding a chain extender ethylenediamine solution (15 wt%) into the dispersion, continuously stirring for reaction for 1 hour, and filtering to obtain the aqueous polyurethane dispersion. The amounts of the materials added in the above process are shown in Table 1.
Examples 2 to 5
The aqueous polyurethane dispersions were prepared by adjusting the proportions of the respective raw material components by the method described in example 1, and the properties of the products were tested, the raw material components and the proportions of the respective components, and the test results are shown in table 1.
Initial drying test: the waterborne polyurethane prepared in the examples is blended with a commercial waterborne ink vehicle, the mass ratio is 10/90, the test method of GBT 13217.5-2008 liquid ink initial drying is referred, the drying length of the commercial waterborne ink vehicle is taken as a comparison standard, and the drying length of the blend is short, so that the waterborne polyurethane provided by the invention is considered to be capable of prolonging the drying time of the waterborne ink, has a moisturizing effect and is marked with O, and otherwise is ●.
Mechanical properties: the waterborne polyurethane prepared in the example is blended with a commercial waterborne ink vehicle, the mass ratio is 10/90, the tensile strength of the commercial waterborne ink vehicle is taken as a comparison standard value, and the tensile strength of the blend is within +/-10% of the standard value by referring to the measurement of the tensile properties of GBT 1040-2006 plastics, so that the mechanical properties of the waterborne ink are considered to be not adversely affected by the addition of the waterborne polyurethane, and are marked with 'O', otherwise, the mechanical properties are '●'.
Gel liquid chromatography: the aqueous polyurethane prepared in the example is dried to prepare a film, the dry film is dissolved by tetrahydrofuran, the concentration is 2-5%, the number average molecular weight is detected by a Waters gel liquid chromatograph (comprising a Waters1515 infusion pump, a Waters2414 differential refraction detector, HR5, HR4 and HR3 tandem chromatographic column), the mobile phase is tetrahydrofuran, the flow rate is 1mL/min, and the test temperature is 40 ℃.
Differential Scanning Calorimeter (DSC) test: the aqueous polyurethane prepared in the examples was dried to prepare a film, and the thermal properties were measured. The measurement conditions were as follows: nitrogen atmosphere, 70 ℃ below zero to 150 ℃, and the heating speed is 10 ℃/min.
TABLE 1
The raw materials are illustrated as follows:
PPG2000, polypropylene glycol, molecular weight 2000;
PPG3000, polypropylene glycol, molecular weight 3000;
DMBA, dimethylolbutanoic acid;
ymer N120, single-sided dihydroxy polyethylene oxide, molecular weight 1000;
IPDI, isophorone diisocyanate;
TEA, triethylamine;
EDA, ethylenediamine;
HMDA, 1, 6-hexanediamine;
H2o, water;
unless otherwise indicated, the data in the table are in parts by mass.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. The water-based screen printing ink is characterized by comprising a connecting material and a moisturizing component, wherein the moisturizing component comprises a water-based polyurethane dispersion, and the moisturizing component accounts for 5-30% of the water-based screen printing ink by mass; the aqueous polyurethane dispersion is an aqueous dispersion of polyurethane (Y) having hydrophilic side chains; the polyurethane prepolymer (X) for forming the polyurethane (Y) with the hydrophilic side chain is obtained by reacting raw materials comprising a hydroxyl-containing compound (A), an isocyanate-containing compound (B), a polyoxyethylene-containing single-side chain end polyol (C) and a carboxylic acid-containing polyol (D);
the aqueous polyurethane dispersion is obtained by adding a neutralizer (E) into the polyurethane prepolymer (X), adding water, and finally adding a chain extender (F) for reaction;
the structure of the polyoxyethylene-containing single-side chain-end polyol (C) is shown as the following formula:
in the formula, n is an integer between 1 and 20, and R is alkyl;
the mass fraction of the polyoxyethylene-containing unilateral chain end polyol (C) relative to the polyurethane (Y) containing hydrophilic side chains is 5-20%;
the number average molecular weight (Mn) of the polyurethane (Y) containing the hydrophilic side chain is 10000-50000 measured by gel liquid chromatography;
the polyurethane (Y) having a hydrophilic side chain has a glass transition temperature (Tg) of 0 ℃ or less as measured by DSC.
2. The aqueous screen printing ink according to claim 1, wherein the polyurethane (Y) having hydrophilic side chains has a number average molecular weight (Mn) of 11000 to 35000 as determined by gel liquid chromatography; the polyurethane (Y) having a hydrophilic side chain has a glass transition temperature (Tg) of-65 ℃ to-10 ℃ as measured by DSC.
3. The aqueous screen printing ink according to claim 1, wherein the hydroxyl group containing compound (a) is selected from one or two of polypropylene glycol and polytetrahydrofuran glycol.
4. The aqueous screen printing ink according to claim 1, wherein the hydroxyl group-containing compound (A) has a molecular weight of 600 to 3000.
5. The aqueous screen printing ink of claim 1 wherein the isocyanate group containing compound (B) is one or more of hexamethylene diisocyanate, isophorone diisocyanate or 4, 4' -diisocyanate dicyclohexylmethane.
6. The aqueous screen printing ink of claim 1 wherein the carboxylic acid containing polyol (D) is selected from one or both of dimethylolpropionic acid and dimethylolbutyric acid.
7. Aqueous screen printing ink according to claim 1, characterised in that the neutralising agent (E) is triethylamine.
8. The aqueous screen printing ink of claim 1 wherein the chain extender (F) is one or more of ethylenediamine, 1, 3-propanediamine, 1, 4-butanediamine, hexamethylenediamine, diethylenetriamine, piperazine, isophoronediamine.
9. An aqueous screen printing ink according to any one of claims 1 to 8, characterised in that the aqueous polyurethane dispersion is prepared by a process comprising the steps of:
(1) reacting raw materials comprising a hydroxyl-containing compound (A), an isocyanate-containing compound (B), a polyoxyethylene-containing single-side chain end polyol (C) and a carboxylic acid-containing polyol (D) to obtain a polyurethane prepolymer (X), wherein the X has a hydrophilic side chain;
(2) adding a neutralizing agent (E) to form a hydrophilic ionomer;
(3) adding water;
(4) adding a chain extender (F), and reacting to obtain the aqueous polyurethane dispersion.
10. The aqueous screen printing ink of claim 9 wherein the reaction temperature of step (1) is 85 ℃.
11. The aqueous screen printing ink of claim 9, wherein the reaction time of step (1) is 1 to 5 hours.
12. The water-based screen printing ink of claim 9, wherein the molar ratio of A, B, C to D in step (1) is 1 (2-3): 0.2-0.4): 0.3-0.7.
13. The water-based screen printing ink according to claim 9, wherein the reaction temperature of the steps (2), (3) and (4) is 20-90 ℃; the reaction time of the step (2) is 1-30 minutes.
14. The aqueous screen printing ink of claim 9, wherein the molar ratio of E to D is 0.8 to 1.2.
15. The aqueous screen printing ink of claim 9 wherein in step (3) a small amount of water is added to pre-emulsify and then dispersed dropwise;
the molar ratio of the water to the (A) is 100-700.
16. The aqueous screen printing ink of claim 9, wherein the reaction time of step (4) is 0.5 to 2 hours.
17. The aqueous screen printing ink of claim 9, wherein the molar ratio of F to a is 0.6 to 1.2.
18. Use of the aqueous screen printing ink of any of claims 1 to 17 for textile coating.
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Effective date of registration: 20230721 Address after: 130213 Group 3, Gengjiawobaotun, Xinglonggou Village, Fulongquan Town, Nong'an County, Changchun City, Jilin Province Patentee after: Lu Zhongmin Address before: Fuzhou City, Fujian province 350002 Yangqiao Road No. 155 Patentee before: FUJIAN INSTITUTE OF RESEARCH ON THE STRUCTURE OF MATTER, CHINESE ACADEMY OF SCIENCES |