CN115572526A - Waterborne polyurethane transfer coating and preparation method thereof - Google Patents
Waterborne polyurethane transfer coating and preparation method thereof Download PDFInfo
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- CN115572526A CN115572526A CN202211154877.7A CN202211154877A CN115572526A CN 115572526 A CN115572526 A CN 115572526A CN 202211154877 A CN202211154877 A CN 202211154877A CN 115572526 A CN115572526 A CN 115572526A
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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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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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
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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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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- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/20—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for coatings strippable as coherent films, e.g. temporary coatings strippable as coherent films
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Abstract
The invention relates to a waterborne polyurethane transfer coating and a preparation method thereof, wherein the coating comprises the following components in percentage by weight: 19.5 to 23 parts of polyester diol, 25 to 32 parts of polyether diol, 38 to 47 parts of diisocyanate, 5.8 to 7.2 parts of chain extender and a proper amount of neutralizer 2 to 4 parts, wherein the polyester diol has a molecular weight of 1000 to 1500 and is synthesized on the basis of diacid and diol, and the diacid is mainly isophthalic acid. The molecular weight of the polyether diol is 1000-1500. The diisocyanate includes TDI and dicyclohexylmethane diisocyanate (H12 MDI). The preparation process comprises the following steps: compared with products generated by the prior art, the coating solves the problems of unclean film uncovering and roller sticking, has excellent high temperature resistance and water resistance, particularly has high temperature resistance performance which can not soften and whiten at the high temperature of 130 ℃ after film forming, and has the characteristic indexes of 30-40% of solid content (%), 200-1000 PH value (1/10) of viscosity (cps/25 ℃) of 7-8, 100% tensile film quantity (MPa) of 50-90, more than or equal to 20-40% of tensile strength (MPa), more than or equal to 50-200% of elongation at break (%), and more than or equal to 130 ℃ of thermal deformation temperature (DEG C).
Description
Technical Field
The invention relates to the technical field of polyurethane coatings, in particular to a waterborne polyurethane transfer coating and a preparation method thereof.
Background
The transfer coating is usually a solvent-based coating, but with the strengthening of the national environmental protection policy and the strengthening of the environmental protection health consciousness of people, the solvent-based coating is gradually replaced by a safer and more environment-friendly waterborne polyurethane coating.
The waterborne polyurethane takes water as a dispersion medium, has the advantages of difficult combustion, no environmental pollution, low toxicity, safety, reliability and the like, is widely concerned at home and abroad in recent years, and is used as an adhesive and a coating.
The main difficulty of the waterborne polyurethane transfer coating is that waterborne polyurethane has large latent heat of volatilization, and is slow in drying speed compared with solvent-based products, so that the problems of unclean film uncovering and roller sticking are easily caused; solvent-type polyurethanes generally have a small molecular weight and are easily peeled off, while aqueous polyurethanes have a relatively large molecular weight and strong intermolecular interactions, which cause deterioration in the peeling properties on the film surface.
The invention aims to overcome the defects of the prior art and provide the waterborne polyurethane transfer coating which is clean in film uncovering and does not stick to a roller by changing the component content of the hard segment and the soft segment.
Disclosure of Invention
The purpose of the invention is realized by the following technical scheme:
the waterborne polyurethane transfer coating is characterized by comprising the following components in percentage by weight:
the polyester diol has a molecular weight of 1000-1500, and is synthesized based on a dibasic acid and a diol, wherein the dibasic acid is mainly isophthalic acid.
The polyether diol comprises a molecular weight of 1000 to 1500.
The diisocyanate includes TDI and dicyclohexylmethane diisocyanate (H) 12 MDI)。
The chain extender comprises a hydrophilic chain extender and a chain extender, and comprises hexanediol, ethylenediamine, ethylene glycol and diethylene glycol.
The neutralizing agent comprises triethylamine.
The solvent comprises N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and acetone.
The waterborne polyurethane transfer coating and the preparation method thereof are characterized by comprising the following steps:
(1) Raw material preparation
Preparing the following components in percentage by weight:
(2) Premixing and heating raw materials
Measuring polyester diol and polyether diol, adding chain extender hexanediol, mixing uniformly, heating to 120-125 ℃, dehydrating in vacuum for 0.5h, and then cooling to 75-95 ℃.
(3) Prepolymerization reaction
Adding diisocyanate into dihydric alcohol, stirring and reacting for 1.5-2h, then adding a chain extender and a small amount of solvent, maintaining the temperature and continuing to react for 1-2h, then cooling to 50 ℃, adding the solvent to dilute the mixture, and reacting for 2-3h at the temperature to synthesize the prepolymer.
(4) Reflux reaction
Adding solvent into the prepolymer, and refluxing at 50-60 deg.C for 2-4 hr.
(5) Neutralization reaction
And (3) reducing the temperature of the prepolymer to 40-50 ℃, transferring the prepolymer into a high-speed dispersion machine, adding a neutralizing agent triethylamine at a medium speed for neutralization reaction, and adjusting to a high speed and stirring for 1h.
(6) Dispersion emulsification and chain extension reaction
And cooling the temperature of the prepolymer to room temperature, adding deionized water at a high speed to disperse the prepolymer in water, and then adding a chain extender to rapidly perform chain extension. And removing the solvent to obtain the waterborne polyurethane transfer coating.
Compared with the prior art, the invention has the following advantages:
(1) The product increases the proportion of hard segments, reduces the molecular weight of the prepolymer, increases the degree of phase separation, makes the coating film become brittle and easy to peel off, and solves the problems of unclean film uncovering and roller sticking.
(2) The product has excellent water resistance, and the film does not turn white, soften or become sticky after being soaked in water for 80 h.
(3) The product has excellent high temperature resistance, and does not soften or whiten at 130 ℃ after film forming.
(4) The characteristic indexes of the product emulsion are as follows:
solid content (%): 30-40%;
viscosity (cps/25 deg.C) of 200-1000;
pH (1/10): 7-8.
(5) The characteristic indexes of the product adhesive film are as follows:
50-90% of 100% stretch film amount (MPa);
the tensile strength (MPa) is more than or equal to 20-40;
elongation at break (%): more than or equal to 50-200;
temperature of thermal denaturation (. Degree. C.): 130 or more.
Drawings
FIG. 1 is a flow chart of the preparation of the waterborne polyurethane transfer coating of the present invention.
Detailed Description
The technical solution of the present invention will be further described with reference to the following embodiments.
The first embodiment is as follows: a preparation method of the waterborne polyurethane transfer coating comprises the following steps:
1. raw material preparation
19.5KG of 1000 molecular weight of polyester diol, 25KG of 1000 molecular weight of polyether diol, 47KG diisocyanate, 6KG hexanediol and 2KG triethylamine.
2. Premixing and heating raw materials
Measuring polyester diol and polyether diol, adding chain extender hexanediol, uniformly mixing, heating to 120 ℃, carrying out vacuum dehydration for 0.5h, and then cooling to 75 ℃.
3. Prepolymerization reaction
Adding diisocyanate into dihydric alcohol, stirring and reacting for 1.5h, then adding a chain extender and a small amount of solvent, maintaining the temperature for continuous reaction for 2h, then cooling to 50 ℃, adding the solvent to dilute the mixture, and reacting for 2h at the temperature to synthesize the prepolymer.
4. Reflux reaction
The prepolymer was added with a solvent and refluxed at 50 ℃ for 2 hours.
5. Neutralization reaction
And (3) reducing the temperature of the prepolymer to 40 ℃, transferring the prepolymer into a high-speed dispersion machine, adding a neutralizing agent triethylamine to perform neutralization reaction at medium speed, and adjusting to high speed and stirring for 1h.
6. Dispersing, emulsifying and chain extending:
and cooling the temperature of the prepolymer to room temperature, adding deionized water at a high speed to disperse the prepolymer in water, and then adding a chain extender to rapidly perform chain extension. And removing the solvent to obtain the waterborne polyurethane transfer coating.
Example two: a preparation method of the waterborne polyurethane transfer coating comprises the following steps:
1. raw material preparation
22KG of 1000 molecular weight of polyester diol, 28KG of 1000 molecular weight of polyether diol, 45KG of diisocyanate, 6KG of hexanediol and 2KG of triethylamine.
2. Premixing and heating raw materials
Measuring polyester diol and polyether diol, adding chain extender hexanediol, uniformly mixing, heating to 125 ℃, carrying out vacuum dehydration for 0.5h, and then cooling to 80 ℃.
3. Prepolymerization reaction
Adding diisocyanate into dihydric alcohol, stirring for reaction for 2h, adding a chain extender and a small amount of solvent, maintaining the temperature for continuous reaction for 1.5h, cooling to 50 ℃, adding the solvent to dilute the mixture, and reacting for 2.5h at the temperature to synthesize the prepolymer.
4. Reflux reaction
The prepolymer was added with a solvent and refluxed at 60 ℃ for 2.5 hours.
5. Neutralization reaction
And (3) reducing the temperature of the prepolymer to 40 ℃, transferring the prepolymer into a high-speed dispersion machine, adding a neutralizing agent triethylamine to perform neutralization reaction at medium speed, and adjusting to high speed and stirring for 1h.
6. Dispersing, emulsifying and chain extending:
and cooling the temperature of the prepolymer to room temperature, adding deionized water at a high speed to disperse the prepolymer in water, and then adding a chain extender to rapidly perform chain extension. And removing the solvent to obtain the waterborne polyurethane transfer coating.
Example three: a preparation method of the waterborne polyurethane transfer coating comprises the following steps:
1. raw material preparation
20KG of 1000 molecular weight of polyester diol, 25KG of 1000 molecular weight of polyether diol, 46KG of diisocyanate, 6KG of hexanediol and 1KG of triethylamine.
2. Premixing and heating raw materials
Measuring polyester diol and polyether diol, adding chain extender hexanediol, uniformly mixing, heating to 125 ℃, carrying out vacuum dehydration for 0.5h, and then cooling to 80 ℃.
3. Prepolymerization reaction
Adding diisocyanate into dihydric alcohol, stirring and reacting for 1.5h, then adding a chain extender and a small amount of solvent, maintaining the temperature for continuous reaction for 2h, then cooling to 50 ℃, adding the solvent to dilute the mixture, and reacting for 2h at the temperature to synthesize the prepolymer.
4. Reflux reaction
The prepolymer was added with a solvent and refluxed at 50 ℃ for 3 hours.
5. Neutralization reaction
And (3) reducing the temperature of the prepolymer to 50 ℃, transferring the prepolymer to a high-speed dispersion machine, adding triethylamine serving as a neutralizing agent at a medium speed for neutralization reaction, and adjusting to stir at a high speed for 1h.
6. Dispersing, emulsifying and chain extending:
and cooling the temperature of the prepolymer to room temperature, adding deionized water at a high speed to disperse the prepolymer in water, and then adding a chain extender to rapidly perform chain extension. And removing the solvent to obtain the waterborne polyurethane transfer coating.
Example four: a preparation method of the waterborne polyurethane transfer coating comprises the following steps:
1. raw material preparation
22KG of 1000 molecular weight of polyester diol, 28KG of 1000 molecular weight of polyether diol, 45KG of diisocyanate, 7KG of hexanediol and 3KG of triethylamine.
2. Premixing and heating raw materials
Measuring polyester diol and polyether diol, adding chain extender hexanediol, uniformly mixing, heating to 120 ℃, dehydrating in vacuum for 0.5h, and then cooling to 80 ℃.
3. Prepolymerization reaction
Adding diisocyanate into dihydric alcohol, stirring for reaction for 2h, adding a chain extender and a small amount of solvent, maintaining the temperature for continuous reaction for 2h, cooling to 50 ℃, adding the solvent to dilute the mixture, and reacting for 2h at the temperature to synthesize the prepolymer.
4. Reflux reaction
The solvent was added to the prepolymer and refluxed at 60 ℃ for 4 hours.
5. Neutralization reaction
And (3) reducing the temperature of the prepolymer to 50 ℃, transferring the prepolymer to a high-speed dispersion machine, adding triethylamine serving as a neutralizing agent at a medium speed for neutralization reaction, and adjusting the temperature to be high-speed and stirring for 1 hour.
6. Dispersing, emulsifying and chain extending:
and cooling the temperature of the prepolymer to room temperature, adding deionized water at a high speed to disperse the prepolymer in water, and then adding a chain extender to rapidly perform chain extension. And removing the solvent to obtain the waterborne polyurethane transfer coating.
In the examples, the raw materials are used in different amounts, and the obtained product has only a little change in flexibility, has no change in water resistance and high temperature resistance, and meets the technical requirements of use regulations.
Through detection, the product emulsion characteristic indexes are as follows:
solid content (%): 30-40%;
viscosity (cps/25 deg.C) of 200-1000;
pH (1/10): 7-8.
The characteristic indexes of the product adhesive film are as follows:
50-90% of 100% stretch film amount (MPa);
the tensile strength (MPa) is more than or equal to 20-40;
elongation at break (%): more than or equal to 50-200;
temperature of thermal denaturation (. Degree. C.): 130 or more.
The product has excellent high temperature resistance, does not become soft and whiten at the high temperature of 130 ℃ after film forming, and breaks through the limitation of the high temperature resistance of the existing product at 100 ℃; the water resistance is good, and the film does not turn white, soften or become sticky after being soaked in water for 80 hours; the product is easy to peel off, the film is cleanly uncovered, and the roller is not stuck.
Claims (3)
1. The waterborne polyurethane transfer coating is characterized by comprising the following components in percentage by weight:
the polyester diol has a molecular weight of 1000-1500, and is synthesized based on a diacid and a diol, wherein the diacid is mainly isophthalic acid.
The molecular weight of the polyether diol is 1000-1500.
The diisocyanate includes TDI and dicyclohexylmethane diisocyanate (H) 12 MDI)。
The chain extender comprises a hydrophilic chain extender and a chain extender, and comprises hexanediol, ethylenediamine, ethylene glycol and diethylene glycol.
The neutralizing agent comprises triethylamine.
The solvent comprises N-methylpyrrolidone (NMP), N-Dimethylformamide (DMF) and acetone.
2. A preparation method of a waterborne polyurethane transfer coating is characterized by comprising the following steps:
(1) Raw material preparation
Preparing the following components in percentage by weight:
(2) Premixing and heating raw materials
Measuring polyester diol and polyether diol, adding chain extender hexanediol, uniformly mixing, heating to 120-125 ℃, dehydrating in vacuum for 0.5h, and then cooling to 75-95 ℃.
(3) Prepolymerization reaction
Adding diisocyanate into dihydric alcohol, stirring and reacting for 1.5-2h, then adding a chain extender and a small amount of solvent, maintaining the temperature and continuing to react for 1-2h, then cooling to 50 ℃, adding the solvent to dilute the mixture, and reacting for 2-3h at the temperature to synthesize the prepolymer.
(4) Reflux reaction
Adding solvent into the prepolymer, and refluxing at 50-60 deg.C for 2-4 hr.
(5) Neutralization reaction
And (3) reducing the temperature of the prepolymer to 40-50 ℃, transferring the prepolymer into a high-speed dispersion machine, adding a neutralizing agent triethylamine to perform neutralization reaction at medium speed, and adjusting to high speed and stirring for 1h.
(6) Dispersion emulsification and chain extension reaction
And cooling the temperature of the prepolymer to room temperature, adding deionized water at a high speed to disperse the prepolymer in water, and then adding a chain extender to rapidly perform chain extension. And removing the solvent to obtain the waterborne polyurethane transfer coating.
3. The waterborne polyurethane transfer coating is characterized in that the product emulsion characteristic indexes are as follows: solid content (%): 30-40%; viscosity (cps/25 deg.C) of 200-1000; pH (1/10): 7-8. The adhesive film characteristic index of the product is as follows: 50-90% of 100% stretch film amount (MPa); the tensile strength (MPa) is more than or equal to 20-40; elongation at break (%): more than or equal to 50-200; temperature of thermal denaturation (. Degree. C.): 130 or more.
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| CN202211154877.7A CN115572526A (en) | 2022-09-21 | 2022-09-21 | Waterborne polyurethane transfer coating and preparation method thereof |
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| CN202211154877.7A CN115572526A (en) | 2022-09-21 | 2022-09-21 | Waterborne polyurethane transfer coating and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328253A (en) * | 2008-07-17 | 2008-12-24 | 安徽大学 | Method for preparing high solid content aqueous polyurethane emulsion by continuous process |
| CN101948659A (en) * | 2010-09-17 | 2011-01-19 | 淄博奥德美高分子材料有限公司 | Aqueous polyurethane resin and preparation method thereof |
| CN103360570A (en) * | 2013-07-31 | 2013-10-23 | 常德市武陵金德镭射科技有限公司 | Waterborne polyurethane, preparation method therefor and waterborne transfer painting |
| CN107033765A (en) * | 2017-05-23 | 2017-08-11 | 山东奥德美高分子材料有限公司 | A kind of fire resistant water-based transfer coatings and preparation method thereof |
-
2022
- 2022-09-21 CN CN202211154877.7A patent/CN115572526A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101328253A (en) * | 2008-07-17 | 2008-12-24 | 安徽大学 | Method for preparing high solid content aqueous polyurethane emulsion by continuous process |
| CN101948659A (en) * | 2010-09-17 | 2011-01-19 | 淄博奥德美高分子材料有限公司 | Aqueous polyurethane resin and preparation method thereof |
| CN103360570A (en) * | 2013-07-31 | 2013-10-23 | 常德市武陵金德镭射科技有限公司 | Waterborne polyurethane, preparation method therefor and waterborne transfer painting |
| CN107033765A (en) * | 2017-05-23 | 2017-08-11 | 山东奥德美高分子材料有限公司 | A kind of fire resistant water-based transfer coatings and preparation method thereof |
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