CN115353654A - High-weather-resistance water-based polyurethane adhesive film and manufacturing method thereof - Google Patents

High-weather-resistance water-based polyurethane adhesive film and manufacturing method thereof Download PDF

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CN115353654A
CN115353654A CN202210972123.6A CN202210972123A CN115353654A CN 115353654 A CN115353654 A CN 115353654A CN 202210972123 A CN202210972123 A CN 202210972123A CN 115353654 A CN115353654 A CN 115353654A
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parts
mass
adhesive film
aqueous polyurethane
stirring
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林永忠
张全稳
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Chang Tai Chemical Huizhou Co ltd
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Chang Tai Chemical Huizhou Co ltd
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    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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    • C08G18/6611—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 having at least three hydroxy groups
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    • 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
    • C08G18/6614—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 C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6618—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 C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to a strong weather resistance waterborne polyurethane adhesive film, and a preparation method of the strong weather resistance waterborne polyurethane adhesive film, which comprises the following steps: a prepolymer manufacturing step, a chain extension step, an emulsification step and a filler adding step: adding 2-3 parts by mass of filler into the waterborne polyurethane emulsion, and fully and uniformly stirring; thickening: adding 0.8-1.2 parts by mass of a thickening agent into the aqueous polyurethane emulsion; weathering resistance: adding 0.1-0.2 part by mass of antioxidant, 0.2-0.3 part by mass of ultraviolet resistant agent and 0.1-0.2 part by mass of preservative into the aqueous polyurethane emulsion, and fully and uniformly stirring to prepare aqueous polyurethane feed liquid; the adhesive film manufacturing step: adding the aqueous polyurethane feed liquid into a film forming die, and drying a glue film: and drying the aqueous polyurethane feed liquid in the die to obtain the aqueous polyurethane adhesive film with strong weather resistance.

Description

High-weather-resistance water-based polyurethane adhesive film and manufacturing method thereof
Technical Field
The invention relates to the field of polyurethane composite films, in particular to a high-weather-resistance water-based polyurethane adhesive film and a manufacturing method thereof.
Background
Polyurethane, a full name of which is polyurethane, is a high molecular compound. Polyurethanes fall into the two broad categories of polyester and polyether. They can be made into polyurethane plastics, polyurethane fibre, polyurethane rubber and elastomer, etc. Polyurethane plastics are classified into soft polyurethane plastics and hard polyurethane plastics. The soft polyurethane mainly has a thermoplastic linear structure, has better stability, chemical resistance, rebound resilience and mechanical property than a PVC foaming material, and has smaller compression deformability. In addition, the soft polyurethane has good heat insulation, sound insulation, shock resistance and gas resistance. Therefore, the soft polyurethane is used as a packaging, sound insulation and filtering material. The hard polyurethane plastic has the advantages of light weight, excellent sound insulation and heat insulation performance, chemical resistance, good electrical property, easy processing and low water absorption rate. The hard polyurethane plastic is mainly used for building, automobile and aviation industry and heat-insulating structural materials. The polyurethane elastomer has the performance between that of plastic and rubber, is oil-resistant, wear-resistant, low-temperature-resistant, ageing-resistant, high in hardness and elastic, and is mainly used for the shoe making industry and the medical industry. In addition, the polyurethane can also be used for preparing adhesives, coatings, synthetic leather and the like.
However, the aqueous polyurethane is a novel polyurethane system in which water is used as a dispersion medium instead of an organic solvent, and is also referred to as water-dispersed polyurethane, aqueous polyurethane, or water-based polyurethane. The waterborne polyurethane takes water as a solvent, and has the advantages of no pollution, safety, reliability, excellent mechanical property, good compatibility, easy modification and the like. The traditional waterborne polyurethane plastic film for packaging has poor oxidation resistance and weather resistance, and cannot meet the requirement of high weather resistance of the waterborne polyurethane plastic film on the market.
Disclosure of Invention
Therefore, the waterborne polyurethane adhesive film with strong weather resistance is needed to be provided for solving the technical problems that the traditional waterborne polyurethane plastic film for packaging has poor oxidation resistance and weather resistance and cannot meet the high weather resistance requirement of the waterborne polyurethane plastic film on the market.
A preparation method of a high-weather-resistance water-based polyurethane adhesive film comprises the following steps:
a prepolymer preparation step: carrying out dehydration drying treatment on 8-12 parts by mass of polyhydric alcohol; adding 4-6 parts by mass of isocyanate into the dried polyol, heating and stirring, and adding 0.004 part by mass of catalyst in the stirring process; adding 0.08 to 0.12 part by mass of dimethyl ketone after the polyol and the isocyanate are fully reacted, and fully reacting to obtain a prepolymer;
chain extension: adding 4-6 parts by mass of a chain extender into the prepolymer, and fully stirring for reaction to generate a chain extender;
emulsifying; adding 60 to 80 parts by mass of deionized water, 1 to 1.5 parts by mass of a salt forming agent and 1 to 1.5 parts by mass of methyl acrylate into the chain extender, and uniformly mixing and stirring to obtain an aqueous polyurethane emulsion;
a filler adding step: adding 2-3 parts by mass of filler into the waterborne polyurethane emulsion, and fully and uniformly stirring;
thickening: adding 0.8-1.2 parts by mass of a thickening agent into the aqueous polyurethane emulsion;
weather-resistant step: adding 0.1 to 0.2 part by mass of antioxidant, 0.2 to 0.3 part by mass of ultraviolet resistant agent and 0.1 to 0.2 part by mass of preservative into the aqueous polyurethane emulsion, and fully and uniformly stirring to prepare aqueous polyurethane feed liquid;
the adhesive film manufacturing step: adding the aqueous polyurethane feed liquid into a film forming die,
drying the adhesive film: and drying the aqueous polyurethane feed liquid in the mold to obtain the aqueous polyurethane adhesive film with strong weather resistance.
In one embodiment, the polyol comprises the following components in parts by mass: 12 to 18 parts of polyester diol, 14 to 12 parts of polyethylene glycol, 14 to 20 parts of poly neopentyl glycol adipate, 20 to 26 parts of polycarbonate diol and 22 to 28 parts of polyester diol.
In one embodiment, in the chain extension step, the chain extender includes a hydrophilic chain extender and a micromolecular chain extender, and after 2 to 3 parts by mass of the hydrophilic chain extender is added to the prepolymer for sufficient reaction, 2 to 3 parts by mass of the micromolecular chain extender is added.
In one embodiment, the catalyst comprises the following components in parts by mass: 40 to 60 parts of dibutyltin dilaurate and 40 to 60 parts of stannous octoate.
In one embodiment, before the thickening step, the method further comprises: defoaming step: adding 0.4-0.6 part by mass of organic silicon modified defoaming agent into the aqueous polyurethane emulsion, and uniformly mixing and stirring.
In one embodiment, the filler comprises the following components in parts by mass: 20 to 30 parts of calcium carbonate powder, 10 to 20 parts of talcum powder, 20 to 40 parts of kaolin and 20 to 30 parts of vermiculite powder.
In one embodiment, the isocyanate comprises the following components in parts by mass: 20 to 24 parts of lysine diisocyanate, 15 to 20 parts of hexamethylene diisocyanate, 14 to 18 parts of methylcyclohexyl diisocyanate, 16 to 22 parts of dicyclohexylmethane diisocyanate and 18 to 22 parts of cyclohexanedimethylene diisocyanate.
In one embodiment, after the defoaming step, the method further comprises: a coupling step: adding 0.6-0.8 part by mass of polymerization modified organic siloxane into the aqueous polyurethane emulsion, and uniformly mixing and stirring.
In one embodiment, after the coupling step, the method further comprises: a wetting step: adding 0.4-0.6 part by mass of an organosilicon wetting agent into the aqueous polyurethane emulsion, and uniformly mixing and stirring.
In one embodiment, the adhesive film is prepared by the method for preparing the strong weather-resistant water-based polyurethane adhesive film in any one of the above embodiments.
The preparation method of the strong weather-resistant waterborne polyurethane adhesive film is simple and delicate, easy to operate, high in production efficiency, free of pollution, excellent in mechanical property, high in chemical stability, excellent in oxidation resistance, ultraviolet resistance and corrosion resistance and long in service life.
Drawings
FIG. 1 is a flow chart illustrating a method for manufacturing a highly weatherable waterborne polyurethane adhesive film according to one embodiment.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, the present invention provides a method for preparing a high weather resistance aqueous polyurethane film, comprising the following steps:
step 101: a prepolymer preparation step: and (3) dehydrating and drying 8-12 parts by mass of polyol. Adding 4 to 6 parts by mass of isocyanate into the dried polyol, heating and stirring, and adding 0.004 part by mass of catalyst during stirring. And (3) fully reacting the polyol and the isocyanate, adding 0.08-0.12 part by mass of dimethyl ketone, and fully reacting to obtain the prepolymer.
In the embodiment, the polyol comprises the following components in parts by mass: 12 to 18 parts of polyester diol, 14 to 12 parts of polyethylene glycol, 14 to 20 parts of poly neopentyl glycol adipate, 20 to 26 parts of polycarbonate diol and 22 to 28 parts of polyester diol. In one embodiment, the isocyanate comprises the following components in parts by mass: 20 to 24 parts of lysine diisocyanate, 15 to 20 parts of hexamethylene diisocyanate, 14 to 18 parts of methylcyclohexyl diisocyanate, 16 to 22 parts of dicyclohexylmethane diisocyanate and 18 to 22 parts of cyclohexane dimethylene diisocyanate. In one embodiment, the catalyst comprises the following components in parts by mass: 40 to 60 parts of dibutyltin dilaurate and 40 to 60 parts of stannous octoate.
Specifically, 8 to 12 parts by mass of polyol is subjected to dehydration drying treatment in a vacuum drying oven. Adding 4 to 6 parts by mass of isocyanate into the dried polyol, heating to 88 to 92 ℃, and stirring, wherein 0.004 part by mass of catalyst is added in the stirring process. And (3) fully reacting the polyol and the isocyanate, adding 0.08-0.12 part by mass of dimethyl ketone, and fully reacting to obtain the prepolymer.
Step 102: chain extension: and adding 4-6 parts by mass of a chain extender into the prepolymer, and fully stirring for reaction to generate a chain extender.
Specifically, in one embodiment, in the chain extension step, the chain extender includes a hydrophilic chain extender and a micromolecular chain extender, the hydrophilic chain extender is added to the prepolymer in an amount of 2 to 3 parts by mass, and after the prepolymer is heated to 76 to 80 ℃ for sufficient reaction, the micromolecular chain extender is added in an amount of 2 to 3 parts by mass and heated to 42 to 44 ℃ for sufficient reaction. The hydrophilic chain extender comprises the following components in parts by mass: 24 to 28 parts of dimethylolpropionic acid, 26 to 30 parts of dimethylolbutyric acid, 22 to 26 parts of dimethylolpentanoic acid and 24 to 28 parts of dimethyloloctanoic acid. The micromolecule chain extender comprises the following components in parts by mass: ethylene glycol 16 to 24 parts, neopentyl glycol 14 to 23 parts, diethylene glycol 12 to 26 parts, glycerin 15 to 22 parts, and ethylenediamine 16 to 24 parts.
Step 103: and (4) an emulsification step. Adding 60 to 80 parts by mass of deionized water, 1 to 1.5 parts by mass of a salt forming agent and 1 to 1.5 parts by mass of methyl acrylate into the chain extender, and uniformly mixing and stirring to obtain the waterborne polyurethane emulsion.
Wherein the salt forming agent is triethylamine.
Specifically, 60 to 80 parts by mass of deionized water, 1 to 1.5 parts by mass of triethylamine and 1 to 1.5 parts by mass of methyl acrylate are added to the chain extender, and the mixture is uniformly mixed and stirred at a temperature of 42 to 44 ℃ to form the aqueous polyurethane emulsion.
Step 104: a filler adding step: adding 2-3 parts by mass of filler into the waterborne polyurethane emulsion, and fully and uniformly stirring.
In the embodiment, the filler comprises the following components in parts by mass: 20 to 30 parts of calcium carbonate powder, 10 to 20 parts of talcum powder, 20 to 40 parts of kaolin and 20 to 30 parts of vermiculite powder.
Specifically, 2 to 3 parts by mass of filler is added into the aqueous polyurethane emulsion, and the mixture is fully and uniformly stirred. The calcium carbonate powder, the talcum powder, the kaolin and the vermiculite powder have good chemical stability and weather resistance, and the filler consisting of the calcium carbonate powder, the talcum powder, the kaolin and the vermiculite powder increases the surface smoothness and smoothness of the high-weather-resistance waterborne polyurethane adhesive film, reduces the shrinkage rate of the high-weather-resistance waterborne polyurethane adhesive film, and improves the wear resistance and chemical corrosion resistance of the high-weather-resistance waterborne polyurethane adhesive film.
Step 105: thickening: adding 0.8-1.2 parts by mass of a thickening agent into the aqueous polyurethane emulsion.
Wherein the thickener is associative polyurethane thickener.
Specifically, 0.8 to 1.2 parts by mass of associative polyurethane thickener is added into the aqueous polyurethane emulsion to increase the viscosity of the aqueous polyurethane emulsion and ensure that the aqueous polyurethane emulsion has good rheological property.
Step 106: weather-resistant step: adding 0.1 to 0.2 part by mass of antioxidant, 0.2 to 0.3 part by mass of ultraviolet resistant agent and 0.1 to 0.2 part by mass of preservative into the aqueous polyurethane emulsion, and fully and uniformly stirring to prepare aqueous polyurethane feed liquid.
Wherein the antioxidant is pentaerythritol diphosphite stearyl alcohol ester, the ultraviolet resistant agent is benzotriazole, and the preservative is aqueous preservative.
Specifically, 0.1 to 0.2 part by mass of an antioxidant, 0.2 to 0.3 part by mass of an ultraviolet resistant agent and 0.1 to 0.2 part by mass of a preservative are added into the aqueous polyurethane emulsion and are fully and uniformly stirred to prepare the aqueous polyurethane feed liquid, so that the oxidation resistance, the ultraviolet resistance and the corrosion resistance of the strong weather-resistant aqueous polyurethane adhesive film are greatly improved.
Step 107: the adhesive film manufacturing step: adding the aqueous polyurethane feed liquid into a film forming die.
Specifically, the aqueous polyurethane feed liquid is added into a special film forming die so as to be convenient for curing and forming of the aqueous polyurethane feed liquid.
Step 108: drying the adhesive film: and drying the aqueous polyurethane feed liquid in the die to obtain the aqueous polyurethane adhesive film with strong weather resistance.
Specifically, the waterborne polyurethane feed liquid in the mold is dried in a vacuum drying oven to obtain the waterborne polyurethane adhesive film with strong weather resistance.
In order to avoid generating a large amount of bubbles in the manufacturing process, in one embodiment, a defoaming step is further included before the thickening step: adding 0.4-0.6 part by mass of organic silicon modified defoaming agent into the aqueous polyurethane emulsion, and uniformly mixing and stirring. The organic silicon modified defoaming agent has excellent defoaming effect, and can effectively prevent the strong weather-resistant waterborne polyurethane adhesive film from generating a large amount of bubbles in the manufacturing process, thereby increasing the manufacturing efficiency and stability of the strong weather-resistant waterborne polyurethane adhesive film.
In order to uniformly and stably combine the components in the strong weather-resistant waterborne polyurethane adhesive film, in one embodiment, the method further comprises a coupling step after the defoaming step: adding 0.6-0.8 part by mass of polymerization modified organic siloxane into the aqueous polyurethane emulsion, and uniformly mixing and stirring. The polymerization modified organic siloxane can increase the adhesive force and the dispersibility of each component in the strong weather-resistant waterborne polyurethane adhesive film. Improves the compatibility and combination of all components in the high-weather-resistance waterborne polyurethane adhesive film. Thus, all components in the high-weatherability waterborne polyurethane adhesive film are uniformly and stably combined together
In order to make the solid component in the strong weather-resistant waterborne polyurethane adhesive film be well combined with other liquid components, in one embodiment, a wetting step is further included after the coupling step: adding 0.4-0.6 part by mass of an organosilicon wetting agent into the aqueous polyurethane emulsion, and uniformly mixing and stirring. In this way, the solid component in the water-based polyurethane adhesive film with strong weather resistance can be well combined with other liquid components.
In this embodiment, the present invention provides a weatherable waterborne polyurethane adhesive film, which is made by the method of any one of the above embodiments.
The preparation method of the strong weather-resistant waterborne polyurethane adhesive film is simple and delicate, easy to operate, high in production efficiency, free of pollution, excellent in mechanical property, high in chemical stability, excellent in oxidation resistance, ultraviolet resistance and corrosion resistance and long in service life.
The technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (10)

1. The preparation method of the water-based polyurethane adhesive film with strong weather resistance is characterized by comprising the following steps:
a prepolymer preparation step: carrying out dehydration drying treatment on 8-12 parts by mass of polyhydric alcohol; adding 4-6 parts by mass of isocyanate into the dried polyol, heating and stirring, and adding 0.004 part by mass of a catalyst during stirring; adding 0.08 to 0.12 part by mass of dimethyl ketone after the polyol and the isocyanate are fully reacted, and fully reacting to obtain a prepolymer;
chain extension: adding 4-6 parts by mass of a chain extender into the prepolymer, and fully stirring for reaction to generate a chain extender;
emulsifying; adding 60 to 80 parts by mass of deionized water, 1 to 1.5 parts by mass of a salt forming agent and 1 to 1.5 parts by mass of methyl acrylate into the chain extender, and uniformly mixing and stirring to obtain an aqueous polyurethane emulsion;
a step of adding a filler: adding 2-3 parts by mass of filler into the waterborne polyurethane emulsion, and fully and uniformly stirring;
thickening: adding 0.8-1.2 parts by mass of a thickening agent into the aqueous polyurethane emulsion;
weather-resistant step: adding 0.1 to 0.2 part by mass of antioxidant, 0.2 to 0.3 part by mass of ultraviolet resistant agent and 0.1 to 0.2 part by mass of preservative into the aqueous polyurethane emulsion, and fully and uniformly stirring to prepare aqueous polyurethane feed liquid;
the adhesive film manufacturing step: adding the aqueous polyurethane feed liquid into a film forming mould,
drying the adhesive film: and drying the aqueous polyurethane feed liquid in the mold to obtain the aqueous polyurethane adhesive film with strong weather resistance.
2. The method for preparing the strong weather-resistant waterborne polyurethane adhesive film according to claim 1, wherein the polyol comprises the following components in parts by mass: 12 to 18 parts of polyester diol, 14 to 12 parts of polyethylene glycol, 14 to 20 parts of poly neopentyl glycol adipate, 20 to 26 parts of polycarbonate diol and 22 to 28 parts of polyester diol.
3. The method for preparing the waterborne polyurethane adhesive film with strong weather resistance according to claim 1, wherein in the chain extension step, the chain extender comprises a hydrophilic chain extender and a micromolecular chain extender, and after 2 to 3 parts by mass of the hydrophilic chain extender is added to the prepolymer for full reaction, 2 to 3 parts by mass of the micromolecular chain extender is added.
4. The method for preparing the high-weatherability water-based polyurethane adhesive film according to claim 1, wherein the catalyst comprises the following components in parts by mass: 40 to 60 parts of dibutyltin dilaurate and 40 to 60 parts of stannous octoate.
5. The method of claim 1, further comprising, before the thickening step: defoaming step: adding 0.4-0.6 part by mass of organic silicon modified defoaming agent into the aqueous polyurethane emulsion, and uniformly mixing and stirring.
6. The method for preparing the strong weather-resistant waterborne polyurethane adhesive film according to claim 1, wherein the filler comprises the following components in parts by mass: 20 to 30 portions of calcium carbonate powder, 10 to 20 portions of talcum powder, 20 to 40 portions of kaolin and 20 to 30 portions of vermiculite powder.
7. The method for preparing the strong weather-resistant waterborne polyurethane adhesive film according to claim 1, wherein the isocyanate comprises the following components in parts by mass: 20 to 24 parts of lysine diisocyanate, 15 to 20 parts of hexamethylene diisocyanate, 14 to 18 parts of methylcyclohexyl diisocyanate, 16 to 22 parts of dicyclohexylmethane diisocyanate and 18 to 22 parts of cyclohexanedimethylene diisocyanate.
8. The method for preparing a highly weather-resistant aqueous polyurethane adhesive film according to claim 5, further comprising, after the defoaming step: a coupling step: adding 0.6-0.8 part by mass of polymerization modified organic siloxane into the aqueous polyurethane emulsion, and uniformly mixing and stirring.
9. The method of claim 8, further comprising, after the coupling step: a wetting step: adding 0.4-0.6 part by mass of an organosilicon wetting agent into the aqueous polyurethane emulsion, and uniformly mixing and stirring.
10. A highly weather-resistant waterborne polyurethane adhesive film, which is characterized in that the film is prepared by the method for preparing the highly weather-resistant waterborne polyurethane adhesive film of claims 1 to 9.
CN202210972123.6A 2022-08-15 2022-08-15 High-weather-resistance water-based polyurethane adhesive film and manufacturing method thereof Pending CN115353654A (en)

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CN111732850A (en) * 2020-07-15 2020-10-02 沾化神茂皮革助剂有限公司 Formula of waterborne polyurethane ink binder for food flexible packaging and preparation method thereof
CN111944117A (en) * 2020-08-28 2020-11-17 陕西科技大学 Amino silicone oil modified waterborne polyurethane and preparation method thereof
CN113527622A (en) * 2021-07-22 2021-10-22 长泰化学工业(惠州)有限公司 Novel waterproof perspective polyurethane film
WO2022057855A1 (en) * 2020-09-21 2022-03-24 兰州科时西西里健康科技有限公司 Aqueous polyurethane emulsion, preparation method therefor and use thereof

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* Cited by examiner, † Cited by third party
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CN101935449A (en) * 2010-07-28 2011-01-05 丽水市优耐克水性树脂科技有限公司 Method for preparing water-based polyurethane resin and water-based polyurethane resin
CN103739818A (en) * 2013-12-30 2014-04-23 长春工业大学 Waterborne polyurethane-acrylic emulsion as well as preparation method and application thereof
CN107141438A (en) * 2017-06-21 2017-09-08 广东工业大学 A kind of preparation method of the aqueous polyurethane emulsion of enhanced water resistance
CN111732850A (en) * 2020-07-15 2020-10-02 沾化神茂皮革助剂有限公司 Formula of waterborne polyurethane ink binder for food flexible packaging and preparation method thereof
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Application publication date: 20221118