A kind of organosilicon modified acrylic resin and tile adhesive

Abstract

The present invention belongs to the technical field of polymer materials and adhesives, and discloses an organosilicon-modified acrylic resin and a tile adhesive. The preparation method of the organosilicon-modified acrylic resin is as follows: a terminal hydroxyl polyether-modified polydimethoxysiloxane and isocyanate ethyl acrylate are stirred and reacted under catalyst conditions at 70-85°C until the NCO group content is less than 0.1%, thereby obtaining an organosilicon-modified acrylic ester macromonomer; the organosilicon-modified acrylic ester macromonomer is emulsified with an acrylic acid monomer and an acrylic ester monomer, and the temperature is raised to 60-80°C for insulation reaction, thereby obtaining an organosilicon-modified acrylic emulsion. The tile adhesive comprises an organosilicon-modified acrylic resin emulsion, an epoxy resin-modified polyurethane emulsion, water, silicate cement, quartz sand and white carbon black. The tile adhesive prepared by using the organosilicon-modified acrylic resin of the present invention has significantly improved water resistance, heat resistance and bonding strength.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and adhesives, and in particular relates to an organosilicon-modified acrylic resin and a tile adhesive. Background Art

[0002] Tile adhesives mainly include cementitious adhesives (a powdery mixture of hydraulic cementitious materials, aggregates, additives, etc.), disperslon adhesives (an organic adhesive composed of water-based polymer emulsions, additives and mineral fillers, etc.) and reaction resin adhesives (a single-component or multi-component mixture of synthetic resins, mineral fillers and additives, an adhesive cured by chemical reaction). Among them, cementitious adhesives have lower costs, but poor adhesion, flexibility and weather resistance; reaction resin adhesives have better adhesion and weather resistance, but slightly poorer stability and higher requirements for construction conditions; disperslon adhesives have been widely used due to their good stability and easy construction.

[0003] Currently, the paste-like emulsion-based adhesives on the market mainly use acrylic acid solution, styrene acrylic emulsion, and polyvinyl acetate emulsion as water-based polymer emulsion components. However, single polymer emulsions generally have the defects of insufficient adhesion, poor water resistance and heat resistance.

[0004] Patent CN 110317026A discloses a tile adhesive, which includes the following components by weight: 45-75 parts of ordinary Portland cement, 80-150 parts of quartz sand, 40-60 parts of epoxy resin modified water-based acrylic latex powder, 10-20 parts of cellulose ether, 5-10 parts of gelatin, and 2-7 parts of powdered sodium silicate. The invention utilizes the mixture of epoxy resin modified water-based acrylic latex powder with ordinary Portland cement and quartz sand to improve the bonding performance of the material and is not prone to hollowing. However, the epoxy resin modified water-based acrylic latex powder is too hydrophilic, resulting in insufficient water resistance of its bonding; at the same time, the heat resistance of epoxy resin modified water-based acrylic needs to be further improved.

[0005] Silicone-modified acrylic resin has the effect of improving water resistance and heat resistance due to the introduction of hydrophobic and high-temperature resistant silicone, but conventional silicone-modified acrylic resin mainly uses short-chain organosilanes for graft copolymerization, and its improvement effect is limited. Summary of the invention

[0006] In view of the shortcomings and deficiencies of the above prior art, the primary purpose of the present invention is to provide a silicone-modified acrylic resin emulsion and a preparation method thereof.

[0007] Another object of the present invention is to provide a tile adhesive prepared from the above-mentioned organosilicon-modified acrylic resin emulsion.

[0008] The purpose of the present invention is achieved through the following technical solutions:

[0009] A method for preparing a silicone-modified acrylic resin emulsion comprises the following preparation steps:

[0010] (1) adding terminal hydroxyl polyether modified polydimethoxysiloxane, isocyanate ethyl acrylate and organotin catalyst into a reaction kettle and stirring and mixing them evenly, heating to 70-85° C. and stirring and reacting until the NCO group content (mass percentage) is less than 0.1%, thereby obtaining an organosilicon modified acrylate macromonomer;

[0011] (2) adding the organosilicon-modified acrylate macromonomer, acrylic acid monomer and acrylate monomer into the emulsifier aqueous solution and stirring to emulsify uniformly, heating to 60-80° C. under nitrogen protection, adding an initiator and maintaining the temperature for reaction, thereby obtaining an organosilicon-modified acrylic emulsion.

[0012] The hydroxy-terminated polyether-modified polydimethoxysiloxane is a conventional raw material in the art, which can be obtained by a conventional hydrogen-terminated silicone oil and an allyl polyether through a hydrosilylation reaction, and its structural formula is shown below:

[0013]

[0014] Where A is -CH2CH2CH2(OCH2CH2) a (OCH2CH(CH3)) b OH-terminated hydroxyl polyether; n is an integer of 1 to 50, a is an integer of 1 to 20, and b is an integer of 0 to 10.

[0015] The organotin catalyst in step (1) is preferably dibutyltin dilaurate.

[0016] The molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane to isocyanate ethyl acrylate added in step (1) is 1:1.5-2.

[0017] The acrylic acid monomer in step (2) is (meth)acrylic acid; the acrylic acid ester monomer is one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate.

[0018] The mass ratio of the organosilicon-modified acrylate macromonomer, acrylic acid monomer and acrylate monomer added in step (2) is 1:1-3:2-4.

[0019] The emulsifier aqueous solution in step (2) is an aqueous solution of sodium allyloxyhydroxypropane sulfonate, allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, alkylphenol polyoxyethylene ether ammonium sulfate, allyloxy nonylphenol polyoxyethylene ether, and alkylphenol polyoxyethylene ether with a mass concentration of 4% to 8%.

[0020] The initiator in step (2) is ammonium persulfate or potassium persulfate, and the amount of the initiator added is 0.2% to 0.8% of the total mass of the polymerization monomers.

[0021] The solid content of the organosilicon-modified acrylic emulsion in step (2) is 30% to 60%.

[0022] An organosilicon-modified acrylic resin emulsion is prepared by the method.

[0023] A tile adhesive, comprising a liquid material and a powder material;

[0024] The liquid material comprises the following components in parts by weight: 50-80 parts of silicone modified acrylic resin emulsion, 20-30 parts of epoxy resin modified polyurethane emulsion, and 0-30 parts of water;

[0025] The powder comprises the following components in parts by weight: 50-80 parts of silicate cement, 20-30 parts of quartz sand, and 2-10 parts of white carbon black.

[0026] The epoxy resin modified polyurethane emulsion is prepared by the following method:

[0027] Add polyether diol, diisocyanate and organotin catalyst into a reaction kettle and stir to mix evenly, heat to 70-85°C and stir to react until the NCO group content is 0.5%-2%, then add hydrophilic chain extender and epoxy resin and continue to stir to react until the NCO group content is less than 0.2%, after the reaction is completed, cool to below 50°C, add triethylamine acetone solution for neutralization, then add deionized water and stir to emulsify, evaporate the organic solvent under reduced pressure to obtain epoxy resin modified polyurethane emulsion.

[0028] Preferably, the polyether glycol is polypropylene glycol (PPG) or polyethylene glycol (PEG) with a molecular weight ranging from 400 to 2000.

[0029] Preferably, the diisocyanate is hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (HMDI), toluene diisocyanate (TDI) or diphenylmethane diisocyanate (MDI).

[0030] Preferably, the molar ratio of the polyether diol and diisocyanate added is 1:1.5-2 (OH / NCO).

[0031] Preferably, the organotin catalyst is dibutyltin dilaurate.

[0032] Preferably, the hydrophilic chain extender is DMPA (2,2-dihydroxymethylpropionic acid) or DMBA (2,2-dihydroxymethylbutyric acid); the amount of the hydrophilic chain extender added is 4% to 10% of the total mass of the polyether diol and the diisocyanate; the amount of the epoxy resin added is 4% to 10% of the total mass of the polyether diol and the diisocyanate; the amount of the triethylamine added is 1% to 5% of the total mass of the polyether diol and the diisocyanate.

[0033] Preferably, the solid content of the epoxy resin modified polyurethane emulsion is 30% to 50%.

[0034] Compared with the prior art, the present invention has the following beneficial effects:

[0035] (1) The organosilicon-modified acrylic resin emulsion of the present invention adopts a specific organosilicon-modified acrylate macromonomer to crosslink and modify the acrylic resin, which can significantly improve its water resistance, heat resistance and adhesion.

[0036] (2) The tile adhesive of the present invention is compounded with epoxy resin modified polyurethane emulsion and silicone modified acrylic resin emulsion. The introduction of polyurethane emulsion can further improve the low temperature resistance of the adhesive, and the epoxy resin modification can further improve the bonding strength. DETAILED DESCRIPTION

[0037] The present invention is further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.

[0038] Example 1

[0039] A method for preparing a silicone-modified acrylic resin emulsion comprises the following preparation steps:

[0040] (1) Add terminal hydroxyl polyether modified polydimethoxysiloxane (the average molecular weight of the polydimethoxysiloxane chain segment is 2000, and the terminal hydroxyl polyether is propyl polyoxyethylene ether with an average molecular weight of 800) and ethyl isocyanate acrylate in a molar ratio of 1:1.8 and a catalytic amount of dibutyltin dilaurate into a reaction kettle and stir to mix evenly. Heat to 80° C. and stir to react for 4 hours. The NCO group content of the product is detected to be 0.09%, thereby obtaining a silicone modified acrylate macromonomer.

[0041] (2) Add the organosilicon-modified acrylate macromonomer, acrylic acid, methyl methacrylate and butyl acrylate in a mass ratio of 1:1.5:1:1.5 to a 5% aqueous solution of an emulsifier (composed of allyloxy nonylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stir to emulsify evenly. Heat to 75°C under nitrogen protection, add 0.4% ammonium persulfate and keep warm for 4 hours to obtain an organosilicon-modified acrylic resin emulsion with a solid content of 48%.

[0042] A tile adhesive, comprising a liquid material and a powder material;

[0043] The liquid material comprises the following components in parts by weight: 60 parts of the above-mentioned organosilicon-modified acrylic resin emulsion, 25 parts of epoxy resin-modified polyurethane emulsion, and 2.7 parts of water.

[0044] The powder comprises the following components in parts by weight: 70 parts of silicate cement, 25 parts of quartz sand, and 5 parts of white carbon black.

[0045] The epoxy resin modified polyurethane emulsion is prepared by the following method:

[0046] PPG-800 and HDI in a molar ratio of 1:1.7 and a catalytic amount of dibutyltin dilaurate are added to a reactor and stirred to mix evenly. The temperature is raised to 80°C and stirred for reaction for 3 hours until the NCO group content is 0.94%. Then, 6% of the total mass of PPG-800 and HDI as a hydrophilic chain extender DMPA (preliminarily dissolved in a small amount of butanone) and 5% of E44 epoxy resin are added and stirred for reaction for 2 hours until the NCO group content is 0.12%. After the reaction is completed, the temperature is lowered to below 50°C, 3% triethylamine acetone solution is added for neutralization, and deionized water is added for stirring and emulsification. The organic solvent is evaporated under reduced pressure to obtain an epoxy resin modified polyurethane emulsion with a solid content of 42%.

[0047] Example 2

[0048] A method for preparing a silicone-modified acrylic resin emulsion comprises the following preparation steps:

[0049] (1) Add terminal hydroxyl polyether modified polydimethoxysiloxane (the average molecular weight of the polydimethoxysiloxane chain segment is 1000, and the terminal hydroxyl polyether is propyl polyoxyethylene polyoxypropylene ether with an average molecular weight of 1000) and ethyl isocyanate acrylate in a molar ratio of 1:1.5 and a catalytic amount of dibutyltin dilaurate into a reaction kettle and stir to mix evenly. Heat to 70° C. and stir to react for 4 hours. The NCO group content of the product is detected to be 0.06%, thereby obtaining a silicone modified acrylate macromonomer.

[0050] (2) Add the organosilicon-modified acrylate macromonomer, acrylic acid, methyl methacrylate and butyl acrylate in a mass ratio of 1:2:1.5:1.5 to a 6% aqueous solution of an emulsifier (composed of sodium allyloxyhydroxypropane sulfonate and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stir to emulsify evenly. Heat to 70°C under nitrogen protection, add 0.4% ammonium persulfate and keep warm for 4 hours to obtain an organosilicon-modified acrylic resin emulsion with a solid content of 54%.

[0051] A tile adhesive, comprising a liquid material and a powder material;

[0052] The liquid material comprises the following components in parts by weight: 80 parts of the above-mentioned organosilicon-modified acrylic resin emulsion, 20 parts of epoxy resin-modified polyurethane emulsion, and 4.4 parts of water.

[0053] The powder comprises the following components in parts by weight: 50 parts of silicate cement, 30 parts of quartz sand, and 10 parts of white carbon black.

[0054] The epoxy resin modified polyurethane emulsion is prepared by the following method:

[0055] PPG-1000 and IPDI in a molar ratio of 1:1.8 and a catalytic amount of dibutyltin dilaurate are added to a reactor and stirred to mix evenly. The temperature is raised to 80°C and stirred for reaction for 3 hours until the NCO content is 1.15%. Then, 7% of the total mass of PPG-1000 and IPDI as a hydrophilic chain extender DMPA (pre-dissolved in a small amount of butanone) and 6% of E51 epoxy resin are added and stirred for reaction for 2 hours until the NCO content is 0.10%. After the reaction is completed, the temperature is lowered to below 50°C, 4% triethylamine acetone solution is added for neutralization, and deionized water is added for stirring and emulsification. The organic solvent is evaporated under reduced pressure to obtain an epoxy resin modified polyurethane emulsion with a solid content of 46%.

[0056] Example 3

[0057] A method for preparing a silicone-modified acrylic resin emulsion comprises the following preparation steps:

[0058] (1) Add terminal hydroxyl polyether modified polydimethoxysiloxane (the average molecular weight of the polydimethoxysiloxane chain segment is 3000, and the terminal hydroxyl polyether is propyl polyoxyethylene ether with an average molecular weight of 1200) and ethyl isocyanate acrylate in a molar ratio of 1:2 and a catalytic amount of dibutyltin dilaurate into a reaction kettle and stir to mix evenly. Heat to 75° C. and stir to react for 4 hours. The NCO group content of the product is detected to be 0.08%, thereby obtaining a silicone modified acrylate macromonomer.

[0059] (2) Add the organosilicon-modified acrylate macromonomer, acrylic acid, methyl methacrylate, and hydroxyethyl methacrylate in a mass ratio of 1:3:1:1 to a 4% aqueous solution of an emulsifier (composed of sodium allyloxyhydroxypropane sulfonate and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stir to emulsify evenly. Heat to 75°C under nitrogen protection, add 0.4% ammonium persulfate and keep warm for 4 hours to obtain an organosilicon-modified acrylic resin emulsion with a solid content of 42%.

[0060] A tile adhesive, comprising a liquid material and a powder material;

[0061] The liquid material comprises the following components in parts by weight: 50 parts of the above-mentioned organosilicon-modified acrylic resin emulsion, 30 parts of epoxy resin-modified polyurethane emulsion, and 10.6 parts of water.

[0062] The powder comprises the following components in parts by weight: 80 parts of silicate cement, 20 parts of quartz sand, and 2 parts of white carbon black.

[0063] The epoxy resin modified polyurethane emulsion is prepared by the following method:

[0064] Add PEG-600 and TDI in a molar ratio of 1:1.6 and a catalytic amount of dibutyltin dilaurate into a reactor and stir to mix evenly. Heat to 80°C and stir to react for 3 hours until the NCO content is 0.91%. Then add 8% of the total mass of PEG-600 and TDI as a hydrophilic chain extender DMPA (pre-dissolved in a small amount of butanone) and 7% of E44 epoxy resin and continue to stir to react for 2 hours until the NCO content is 0.08%. After the reaction is completed, cool to below 50°C, add 5% triethylamine acetone solution for neutralization, add deionized water for stirring and emulsification, and evaporate the organic solvent under reduced pressure to obtain an epoxy resin modified polyurethane emulsion with a solid content of 48%.

[0065] Comparative Example 1

[0066] A tile adhesive, compared with Example 1, uses an equal amount of pure acrylic emulsion to replace the silicone-modified acrylic resin emulsion.

[0067] The pure acrylic emulsion is prepared by the following method:

[0068] Acrylic acid, methyl methacrylate and butyl acrylate were added in a mass ratio of 1.5:1:1.5 to a 5% aqueous emulsifier (composed of allyloxynonylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stirred for uniform emulsification. The temperature was raised to 75°C under nitrogen protection, 0.4% ammonium persulfate was added and the reaction was kept warm for 4 hours to obtain a pure acrylic emulsion with a solid content of 48%.

[0069] Comparative Example 2

[0070] A tile adhesive, compared with Example 1, uses an equal amount of silicone-acrylic emulsion to replace the silicone-modified acrylic resin emulsion. The silicone-acrylic emulsion is prepared by the following method:

[0071] Add vinyl triethoxysilane, acrylic acid, methyl methacrylate and butyl acrylate in a mass ratio of 1:1.5:1:1.5 to a 5% aqueous emulsifier (composed of allyloxy nonylphenol polyoxyethylene ether and nonylphenol polyoxyethylene ether in a mass ratio of 1:1) and stir to emulsify evenly. Heat to 75°C under nitrogen protection, add 0.4% ammonium persulfate and keep warm for 4 hours to obtain a silicone-acrylic emulsion with a solid content of 48%.

[0072] Comparative Example 3

[0073] A tile adhesive, compared with Example 1, uses an equal amount of unmodified polyurethane emulsion to replace the epoxy resin modified polyurethane emulsion. The unmodified polyurethane emulsion is prepared by the following method:

[0074] PPG-800 and HDI in a molar ratio of 1:1.7 and a catalytic amount of dibutyltin dilaurate are added to a reactor and stirred to mix evenly. The temperature is raised to 80°C and stirred for reaction for 3 hours until the NCO content is 0.93%. Then, a hydrophilic chain extender DMPA (preliminarily dissolved in a small amount of butanone) of 6% of the total mass of PPG-800 and HDI is added and stirred for reaction for 2 hours until the NCO content is 0.15%. After the reaction is completed, the temperature is lowered to below 50°C, 3% triethylamine acetone solution is added for neutralization, and deionized water is added for stirring and emulsification. The organic solvent is evaporated under reduced pressure to obtain a polyurethane emulsion with a solid content of 42%.

[0075] The tile adhesives of the above embodiments and comparative examples were subjected to performance tests, wherein the liquid material and the powder material were mixed at a mass ratio of 2:1, and the test standard was JC / T 547-2017. The test results are shown in Table 1 below.

[0076] Table 1

[0077]

[0078] It can be seen from the results of the above Examples 1 to 3 that the organosilicon-modified acrylic resin emulsion of the present invention and the tile adhesive prepared therefrom have high bonding strength, and excellent water resistance and heat resistance. It can be seen from the comparison results of Example 1 with Comparative Examples 1 and 2 that the tile adhesive prepared therefrom by the organosilicon-modified acrylic resin emulsion of the present invention has significantly improved water resistance and high temperature resistance compared to pure acrylic emulsion and silicone acrylic emulsion, and the bonding strength is improved to a certain extent. It can be seen from the comparison results of Example 1 and Comparative Example 3 that the present invention uses epoxy resin-modified polyurethane emulsion and organosilicon-modified acrylic resin emulsion for compounding, which can further improve the bonding strength of the obtained tile adhesive compared to the unmodified polyurethane emulsion.

[0079] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. A method for preparing a silicone-modified acrylic resin emulsion, characterized in that: The method comprises the following preparation steps: (1) Adding terminal hydroxyl polyether modified polydimethoxysiloxane, isocyanate ethyl acrylate and organotin catalyst into a reaction kettle and stirring and mixing them evenly, heating to 70-85° C. and stirring and reacting until the NCO group content is less than 0.1%, thereby obtaining an organosilicon modified acrylate macromonomer; (2) adding the organosilicon-modified acrylate macromonomer, acrylic acid monomer and acrylate monomer into the emulsifier aqueous solution and stirring to emulsify evenly, heating to 60-80°C under nitrogen protection, adding an initiator and keeping the temperature to react, thereby obtaining an organosilicon-modified acrylic emulsion; The structural formula of the hydroxy-terminated polyether-modified polydimethoxysiloxane is as follows: ， Where A is -CH2CH2CH2(OCH2CH2) a (OCH2CH(CH3)) b OH-terminated polyether; n is an integer of 1 to 50, a is an integer of 1 to 20, and b is an integer of 0 to 10; The organic tin catalyst is dibutyltin dilaurate; the molar ratio of the terminal hydroxyl polyether modified polydimethoxysiloxane to isocyanate ethyl acrylate is 1:1.5-2.

2. The method for preparing a silicone-modified acrylic resin emulsion according to claim 1, characterized in that: The acrylic acid monomer in step (2) is (meth)acrylic acid; the acrylic acid ester monomer is one or more of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate; the mass ratio of the silicone-modified acrylic acid ester macromonomer, acrylic acid monomer, and acrylic acid ester monomer added is 1:1~3:2~4.

3. The method for preparing a silicone-modified acrylic resin emulsion according to claim 1, characterized in that: The emulsifier aqueous solution in step (2) is an aqueous solution of sodium allyloxyhydroxypropane sulfonate, allyloxy nonylphenol polyoxyethylene ether ammonium sulfate, alkylphenol polyoxyethylene ether ammonium sulfate, allyloxy nonylphenol polyoxyethylene ether, and alkylphenol polyoxyethylene ether with a mass concentration of 4% to 8%; the initiator is ammonium persulfate or potassium persulfate, and the amount of the initiator added is 0.2% to 0.8% of the total mass of the polymerized monomers; the solid content of the silicone-modified acrylic emulsion is 30% to 60%.

4. A silicone-modified acrylic resin emulsion, characterized in that: It is prepared by the method according to any one of claims 1 to 3.

5. A tile adhesive, characterized in that: Including liquid and powder; The liquid material comprises the following components in parts by weight: 50-80 parts of the organosilicon-modified acrylic resin emulsion according to claim 4, 20-30 parts of epoxy resin-modified polyurethane emulsion, and 0-30 parts of water; The powder comprises the following components in parts by weight: 50-80 parts of silicate cement, 20-30 parts of quartz sand, and 2-10 parts of white carbon black.

6. A tile adhesive according to claim 5, characterized in that: The epoxy resin modified polyurethane emulsion is prepared by the following method: Add polyether diol, diisocyanate and organotin catalyst into a reactor and stir to mix evenly, heat to 70-85°C and stir to react until the NCO group content is 0.5%-2%, then add hydrophilic chain extender and epoxy resin and continue stirring to react until the NCO group content is less than 0.2%, after the reaction is completed, cool to below 50°C, add triethylamine acetone solution for neutralization, then add deionized water and stir to emulsify, evaporate the organic solvent under reduced pressure to obtain epoxy resin modified polyurethane emulsion.

7. A tile adhesive according to claim 6, characterized in that: The polyether diol is polypropylene glycol or polyethylene glycol with a molecular weight range of 400 to 2000; the diisocyanate is hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, toluene diisocyanate or diphenylmethane diisocyanate; the molar ratio of the polyether diol and the diisocyanate is 1:1.5 to 2.

8. A tile adhesive according to claim 6, characterized in that: The organic tin catalyst is dibutyltin dilaurate; the hydrophilic chain extender is DMPA or DMBA; the amount of the hydrophilic chain extender added is 4% to 10% of the total mass of the polyether diol and the diisocyanate; the amount of the epoxy resin added is 4% to 10% of the total mass of the polyether diol and the diisocyanate; the amount of the triethylamine added is 1% to 5% of the total mass of the polyether diol and the diisocyanate; and the solid content of the epoxy resin modified polyurethane emulsion is 30% to 50%.

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