A highly waterproof, moisture-permeable and breathable water-based coating resin and a preparation method thereof

Abstract

The present application relates to the field of textile coating resins, and specifically discloses a highly waterproof, moisture-permeable and breathable water-based coating resin and a preparation method thereof. A highly waterproof, moisture-permeable and breathable water-based coating resin is made of the following raw materials: water-based polyurethane emulsion, water-based acrylic emulsion, thickener, defoamer, leveling agent, and hand-feeling agent; each weight portion of the water-based polyurethane emulsion is made of the following weight portions of raw materials: polyol, diisocyanate, trimethylolpropane, catalyst, hydrophilic agent, salt-forming agent, chain extender, organic solvent, and deionized water; its preparation method is: according to the ratio, the water-based polyurethane emulsion and the water-based acrylic emulsion are mixed, other ingredients are added, stirred and mixed, and the viscosity is increased to the viscosity setting value to obtain the highly waterproof, moisture-permeable and breathable water-based coating resin. The present application has the effect of improving the water pressure resistance, moisture permeability, aging resistance and anti-adhesion of the water-based coating resin.

Description

Technical Field

[0001] The present application relates to the field of textile coating resins, and more specifically, to a highly waterproof, moisture-permeable and breathable water-based coating resin and a preparation method thereof. Background Art

[0002] Textile coating resin is a polymer compound that is evenly coated on the surface of fabric. It forms one or more layers of film on the surface of fabric through bonding, which can not only improve the appearance and style of fabric, but also increase the function of fabric, making the fabric waterproof, water pressure resistant, breathable and breathable, flame retardant and antifouling, as well as light shading and reflection. Among them, waterborne polyurethane resin is a textile coating resin made by dispersing high polymer polyurethane in water. It has good film-forming properties, good waterproof, moisture permeability, good flexibility and environmental protection, so it is used for fabric coating finishing.

[0003] At present, the preparation method of waterborne polyurethane is to react oligomer polyol and diisocyanate at a certain temperature to obtain polyurethane prepolymer; then add a small molecule chain extender to carry out chain extension reaction; then add a hydrophilic chain extender to convert the prepolymer into a hydrophilic prepolymer; then use a salt-forming reagent to carry out neutralization reaction to make the polyurethane prepolymer ionic; add water to disperse and emulsify the ionic polyurethane prepolymer; then add a small molecule chain extender to carry out post-chain extension reaction in water to obtain a waterborne polyurethane dispersion.

[0004] Waterborne polyurethane resin has good film-forming properties, good waterproof, moisture permeability, and flexibility. However, it also has defects such as poor aging resistance and poor anti-adhesion, which also limits the application scope of waterborne polyurethane resin. Summary of the invention

[0005] In order to improve the performance of waterborne polyurethane emulsion and expand the application scope of waterborne coating resin, the present application provides a highly waterproof, moisture-permeable and breathable waterborne coating resin and a preparation method thereof.

[0006] In the first aspect, the present application provides a highly waterproof, moisture-permeable and breathable water-based coating resin, which adopts the following technical solution:

[0007] A highly waterproof, moisture-permeable and breathable water-based coating resin is prepared from the following raw materials in parts by weight: 65-85 parts of water-based polyurethane emulsion, 15-30 parts of water-based acrylic emulsion, 0.5-2 parts of thickener, 0.2-1 parts of defoamer, 0.8-1.5 parts of leveling agent and 0.5-1.5 parts of hand feeling agent; each part by weight of the water-based polyurethane emulsion is prepared from the following raw materials in parts by weight: 250-350 parts of polyol, 35-50 parts of castor oil, 100-150 parts of diisocyanate, 1-5 parts of trimethylolpropane, 0.01-2 parts of catalyst, 12-25 parts of hydrophilic agent, 9-25 parts of salt-forming agent, 3-35 parts of chain extender, 50-300 parts of organic solvent and 600-1000 parts of deionized water.

[0008] By adopting the above technical scheme, the water-based acrylic emulsion is used to modify the water-based polyurethane emulsion, and the acrylate monomer in the water-based acrylic emulsion can swell into the interior of the polyurethane particles to carry out free radical polymerization reaction, so that the viscosity of the water-based polyurethane emulsion changes, and at the same time, the hydrostatic pressure resistance, aging resistance, wear resistance and adhesion resistance of the water-based coating resin are enhanced; the thickener can make the water-based polyurethane emulsion have good viscosity, so that the water-based polyurethane emulsion maintains a uniform and stable state; the defoamer can reduce the surface tension of the water-based polyurethane emulsion and reduce the formation of foam; the leveling agent can effectively promote the flow and leveling ability of the water-based polyurethane emulsion without affecting the interlayer adhesion; the feel agent makes the water-based polyurethane emulsion have good feel and adhesion resistance.

[0009] Preferably, the mass ratio of the aqueous polyurethane emulsion to the aqueous acrylic emulsion is 2.8-4.3:1.

[0010] By adopting the above technical scheme, the amount of water-based acrylic emulsion will affect the particle size of the water-based polyurethane emulsion, and the particle size directly affects the viscosity of the emulsion. As the amount of water-based acrylic emulsion increases, the viscosity of the system decreases; if the amount of water-based acrylic emulsion continues to increase, the water-based polyurethane emulsion will not be sufficient to wrap all the acrylate monomers to form stable latex particles, thereby affecting the dispersion stability of the water-based polyurethane emulsion; adding a certain amount of water-based acrylic emulsion to the water-based acrylic emulsion can give the water-based polyurethane emulsion better aging resistance, wear resistance, anti-adhesion properties and other properties.

[0011] Preferably, the water-based acrylic emulsion is selected from pure acrylic emulsion, styrene acrylic emulsion, or a combination of the two.

[0012] By adopting the above technical scheme, the water-based acrylic emulsion modifies the water-based polyurethane emulsion, so that the coating of the prepared water-based coating resin has excellent softness, elasticity, anti-aging and wear resistance, and has high water pressure resistance, moisture permeability and anti-adhesion.

[0013] Preferably, the polyol is selected from one or more combinations of polyhexane carbonate, polyhexane adipate-1,6-hexanediol, polyoxypropylene glycol, trimethylolpropane, and castor oil.

[0014] By adopting the above technical scheme, polyol is the raw material constituting the soft short part of waterborne polyurethane, which gives the waterborne polyurethane flexibility and low temperature resistance.

[0015] Preferably, the polyol is a combination of castor oil, polyoxypropylene glycol and poly(hexylene carbonate), and the mass ratio of castor oil, polyoxypropylene glycol and poly(hexylene carbonate) is 1:3-5.2:1.6-3.3.

[0016] By adopting the above technical scheme, castor oil has hydroxyl groups in its molecular structure and an average functionality of 2.7. Using castor oil as the soft segment of the water-based polyurethane emulsion can improve the mechanical properties of the water-based coating resin; the long-chain non-polar fatty acid chain in the castor oil molecule makes the coating of the water-based coating resin have a good hydrophobic effect, while giving the coating good flexibility and flex resistance; using specific polyols to prepare the water-based polyurethane emulsion, the water-based polyurethane emulsion has good hydrolysis resistance, low-temperature compliance, high mechanical strength, excellent wear resistance and oil resistance.

[0017] Preferably, the diisocyanate is selected from one or more combinations of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

[0018] Through the above technical solution, the water-based polyurethane emulsion has good hydrolysis resistance and storage stability.

[0019] Preferably, the diisocyanate is isophorone diisocyanate.

[0020] Through the above technical solution, the coating of the water-based coating resin is given better hydrolysis resistance and storage stability.

[0021] Preferably, the hydrophilic agent is selected from dimethylol propionic acid, dimethylol butyric acid, and a hydrophilic agent with a carboxyl group on the side chain, or a combination of the two or more thereof, and each part by weight of the aqueous polyurethane emulsion comprises 8-15 parts of a salt-forming agent.

[0022] By adopting the above technical scheme, a hydrophilic agent is added, a hydrophilic group is introduced into the polyurethane molecular chain, and an aqueous polyurethane emulsion is prepared by a self-emulsification method, which is beneficial to improving the dispersion stability of the aqueous polyurethane emulsion; and since dimethylolpropionic acid and dimethylolbutyric acid have small molecular weights, a better self-emulsification effect can be obtained by using a smaller amount, and the cost is low; a salt-forming agent is added to neutralize the hydrophilic agent, thereby improving the hydrophilicity of the aqueous polyurethane emulsion.

[0023] Preferably, the salt-forming agent is selected from one or a combination of triethylamine, tributylamine, tripropylamine, triethanolamine, sodium hydroxide, ammonia water, and dimethylethanolamine.

[0024] By adopting the above technical solution, the salt-forming agent neutralizes the carboxyl groups in the reaction system, the polyurethane segments are ionized, the polarity is enhanced, hydrogen bonds are more easily formed, and the hydrophilicity of the waterborne polyurethane emulsion is improved.

[0025] Preferably, the salt-forming agent is triethylamine.

[0026] By adopting the above technical solution, the waterborne polyurethane emulsion is given better hydrophilicity.

[0027] Preferably, the chain extender is one or a combination of two of an alcohol chain extender and an amine chain extender; the alcohol chain extender is selected from one or a combination of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,2-propylene glycol, dipropylene glycol, trimethylolpropane, and trimethylolbutane; the amine chain extender is selected from one or a combination of hydrazine hydrate, ethylenediamine, propylenediamine, diethylenetriamine, isophoronediamine, hydroxyethylethylenediamine, diethanolamine, aminopropyltrimethoxysilane, and aminoethylaminopropyltrimethoxysilane.

[0028] By adopting the above technical solution, the chain extender extends the chain of the polyurethane prepolymer, increases the molecular weight of the polymer, and improves the mechanical properties, heat resistance and wear resistance.

[0029] Preferably, the chain extender is one or more combinations of ethylenediamine, hydroxyethylethylenediamine, ethanolamine, diethanolamine, and isophoronediamine.

[0030] By adopting the technical solution, the waterborne polyurethane emulsion is given better aging resistance and anti-adhesion properties.

[0031] Preferably, the chain extender is selected from one or a combination of isophoronediamine and ethylenediamine.

[0032] By adopting the above technical solution, the waterborne polyurethane emulsion is given better aging resistance and anti-adhesion properties.

[0033] Preferably, the organic solvent is acetone.

[0034] By adopting the above technical solution, acetone can dissolve polyurethane and is miscible with water. Adding acetone to the reaction system can dilute the reaction mixture to reduce the viscosity of the system and facilitate stirring of the mixture reaction system.

[0035] Preferably, the defoamer is selected from one or a combination of polysiloxane defoamers, polyether defoamers, and silicone defoamers.

[0036] By adopting the above technical solution, the surface tension of the water-based coating resin can be reduced and the formation of foam can be reduced.

[0037] Preferably, the defoamer is a silicone defoamer.

[0038] By adopting the above technical scheme, the organosilicon defoamer has stable chemical properties, low volatility, non-toxicity, and outstanding defoaming ability, and can reduce the surface tension of the water-based coating resin and reduce the formation of foam.

[0039] Preferably, the leveling agent is a polyether-modified siloxane leveling agent.

[0040] By adopting the above technical solution, the surface tension of the water-based coating resin is reduced, its leveling and uniformity are improved, and the coating formed by the water-based coating resin during the drying and film-forming process is made flat, smooth and uniform.

[0041] Preferably, the thickener is selected from one or a combination of water-based acrylic thickeners, water-based polyurethane associative thickeners, and water-based non-ionic polyurethane thickeners.

[0042] By adopting the above technical solution, the viscosity of the water-based coating resin is increased so as to maintain a stable and uniform state.

[0043] Preferably, the thickener is an aqueous non-ionic polyurethane thickener.

[0044] By adopting the above technical solution, the water-based coating resin can maintain a stable and uniform viscosity state.

[0045] Preferably, the feel agent is selected from one or a combination of water-based oily feel agents, water-based anti-stick feel agents, and water-based silky feel agents.

[0046] By adopting the above technical solution, the coating of the water-based coating resin is given better hand feel and anti-adhesion property.

[0047] Preferably, the feel agent is a water-based silky feel agent.

[0048] By adopting the above technical solution, the coating of the water-based coating resin is given a better feel.

[0049] In a second aspect, the present application provides a method for preparing a highly waterproof, moisture-permeable and breathable water-based coating resin, using the following technical solution:

[0050] A method for preparing a highly waterproof, moisture-permeable and breathable water-based coating resin:

[0051] Step 1: According to the ratio, the polyol and the hydrophilic agent are vacuum dehydrated at 100-110°C, and when the temperature drops to 50-80°C, diisocyanate and catalyst are added to react; when the residual value of NCO (isocyanate group) drops to 2%-5%, an organic solvent is added to reduce the viscosity, and then a salt-forming agent is added, and the reaction is carried out at 55-65°C for 10-40 minutes to form a waterborne polyurethane prepolymer;

[0052] Step 2: High-speed shear emulsification of waterborne polyurethane prepolymer and deionized water, adding a chain extender and stirring for 0.5-2 hours after emulsification, and then removing the organic solvent by vacuum distillation to obtain a waterborne polyurethane emulsion;

[0053] Step 3: Mix the aqueous polyurethane emulsion and the aqueous acrylic emulsion according to the ratio, adjust the pH value to 7-9, add defoaming agent, leveling agent, hand feeling agent and thickener, stir and mix, increase the viscosity to the set value, and obtain the highly waterproof, moisture permeable and breathable aqueous coating resin.

[0054] By adopting the above technical scheme, a water-based coating resin with excellent waterproof, moisture-permeable, air-permeable, aging-resistant and anti-adhesive properties can be prepared; by adjusting the pH value to 7-9, the flocculation phenomenon when the water-based polyurethane emulsion is mixed with the acidic water-based acrylic emulsion can be reduced, making the water-based polyurethane emulsion and the water-based acrylic emulsion more compatible.

[0055] In a specific embodiment, the viscosity setting value is 5000-8000 mPa·s (25°C)

[0056] By adopting the above technical scheme, the viscosity of the water-based coating resin will affect the rheological properties of the water-based coating resin. If the viscosity is too high, the rheological properties of the water-based coating resin will be low and the workability will be poor. If the concentration is too low, the required film thickness cannot be achieved and may cause incompatibility. By adding a thickener to the system and stirring continuously, the viscosity is increased to the set viscosity value through hydrophobic association, so that the coating film of the water-based coating resin can have good physical properties and maintain durability.

[0057] In summary, this application has the following beneficial effects:

[0058] 1. This application adopts adding an appropriate amount of water-based acrylic emulsion to the water-based polyurethane emulsion. The acrylic ester can swell inside the polyurethane particles to carry out free radical polymerization reaction, which affects the particle size of the water-based polyurethane emulsion, and then directly affects the viscosity of the emulsion. At the same time, it can give the water-based coating resin better hydrostatic pressure resistance, aging resistance, wear resistance and anti-adhesion properties;

[0059] 2. In the present application, a combination of castor oil, polyoxypropylene glycol and polycarbonate glycol is preferably used as a specific polyol to participate in the preparation of the waterborne polyurethane emulsion, which gives the waterborne coating resin better hydrolysis resistance, low temperature flexibility, high mechanical strength, excellent wear resistance and oil resistance. DETAILED DESCRIPTION

[0060] The present application is further described in detail below with reference to the embodiments.

[0061] Preparation example of polyol

[0062] Preparation Example 1

[0063] Each weight portion of the polyol is composed of raw materials in the following mass ratio: castor oil: polyoxypropylene glycol: polycarbonate hexane glycol = 1:4:2.5.

[0064] Castor oil, polyoxypropylene glycol and polycarbonate glycol were added into a beaker according to the proportion and mixed evenly to obtain polyol for later use.

[0065] Preparation Example 2

[0066] The only difference between this preparation example and preparation example 1 is that each part by weight of the polyol is composed of raw materials in the following mass ratio: castor oil: polyoxypropylene glycol: polycarbonate hexanediol = 1:3:3.3.

[0067] Preparation Example 3

[0068] The only difference between this preparation example and preparation example 1 is that each part by weight of the polyol is composed of raw materials in the following mass ratio: castor oil: polyoxypropylene glycol: polycarbonate hexanediol = 1:5.2:1.6.

[0069] Preparation Example 4

[0070] The only difference between this preparation example and preparation example 1 is that each weight portion of polyol is composed of raw materials including the following mass ratio: castor oil: polyoxypropylene glycol: polycarbonate hexanediol = 1:2:4.5.

[0071] Preparation Example 5

[0072] The only difference between this preparation example and preparation example 1 is that the polyol is made from raw materials including the following weights: 100 g of polyhexane carbonate, 155 g of polyoxypropylene glycol, and 30 g of castor oil.

[0073] Preparation Example 6

[0074] The only difference between this preparation example and preparation example 1 is that the polyol is made from raw materials including the following weights: 94 g of polyadipate-1,6-hexanediol, 150 g of polyoxypropylene glycol, and 35 g of castor oil.

[0075] Preparation example of waterborne polyurethane emulsion

[0076] Preparation Example 1

[0077] The waterborne polyurethane emulsion is prepared from the following raw materials by weight: 300 g of polyol, 125 g of diisocyanate, 3 g of trimethylolpropane, 0.4 g of catalyst, 17 g of hydrophilic agent, 14 g of salt-forming agent, 12 g of chain extender, 150 g of organic solvent, and 700 g of deionized water.

[0078] The polyol is polyhexanediol-1,6-adipate; the diisocyanate is isophorone diisocyanate; the catalyst is organic bismuth catalyst DY-20; the hydrophilic agent is dimethylolpropionic acid; the salt-forming agent is triethylamine; the chain extender is diethanolamine; and the organic solvent is acetone.

[0079] The preparation method of waterborne polyurethane emulsion is:

[0080] Step 1. Add the above polyol and hydrophilic agent to the reactor in sequence, perform vacuum dehydration at 110 degrees Celsius for 1 hour, cool to 56 degrees Celsius, add diisocyanate and catalyst to react, wait until the residual NCO value drops to 3%, add organic solvent to reduce viscosity, then add salt-forming agent, react at 60 degrees Celsius for 20 minutes to obtain waterborne polyurethane prepolymer;

[0081] Step 2: Press the waterborne polyurethane prepolymer into high-speed stirred deionized water for shear emulsification. After emulsification, add the chain extender and stir for 1 hour. Then, remove the organic solvent by vacuum distillation to obtain a waterborne polyurethane emulsion with a solid content of 35%.

[0082] Preparation Example 2

[0083] The only difference between this preparation example and preparation example 1 is that the aqueous polyurethane emulsion is made of raw materials including the following weights: 250 g of polyol, 100 g of diisocyanate, 1 g of trimethylolpropane, 0.01 g of catalyst, 12 g of hydrophilic agent, 9 g of salt-forming agent, 3 g of chain extender, 50 g of organic solvent, and 600 g of deionized water.

[0084] Preparation Example 3

[0085] The only difference between this preparation example and preparation example 1 is that the aqueous polyurethane emulsion is made of raw materials including the following weights: 350 g of polyol, 150 g of diisocyanate, 5 g of trimethylolpropane, 2 g of catalyst, 35 g of hydrophilic agent, 35 g of salt-forming agent, 25 g of chain extender, 300 g of organic solvent, and 1000 g of deionized water.

[0086] Preparation Example 4

[0087] The only difference between this preparation example and preparation example 1 is that polyhexane carbonate is used as the polyol and ethylene glycol is used as the chain extender.

[0088] Preparation Example 5

[0089] The only difference between this preparation example and preparation example 1 is that this preparation example uses the polyol preparation example 1 to prepare the waterborne polyurethane emulsion.

[0090] Preparation Example 6

[0091] The only difference between this preparation example and preparation example 1 is that this preparation example uses preparation example 2 of polyol to prepare the waterborne polyurethane emulsion.

[0092] Preparation Example 7

[0093] The only difference between this preparation example and preparation example 1 is that this preparation example uses preparation example 3 of polyol to prepare the waterborne polyurethane emulsion.

[0094] Preparation Example 8

[0095] The only difference between this preparation example and preparation example 1 is that this preparation example uses preparation example 4 of polyol to prepare the waterborne polyurethane emulsion.

[0096] Preparation Example 9

[0097] The only difference between this preparation example and preparation example 1 is that the aqueous polyurethane emulsion is made from the following raw materials by weight: 285 g of polyol, 100 g of isophorone diisocyanate, 1 g of trimethylolpropane, 0.3 g of catalyst, 14 g of dimethylolpropionic acid, 10.6 g of triethylamine, 11.8 g of chain extender, 60 g of acetone, and 750 g of deionized water.

[0098] In this preparation example, the polyol is selected from Preparation Example 5 of the polyol, and the chain extender is selected from 5 g of ethylenediamine and 6.8 g of isophoronediamine.

[0099] Preparation Example 10

[0100] The only difference between this preparation example and preparation example 1 is that the aqueous polyurethane emulsion is made from the following raw materials by weight: 279 g of polyol, 105 g of isophorone diisocyanate, 1 g of trimethylolpropane, 0.3 g of catalyst, 15 g of dimethylolpropionic acid, 11.3 g of triethylamine, 10.1 g of chain extender, 65 g of acetone, and 750 g of deionized water.

[0101] In this preparation example, the polyol is selected from Preparation Example 6 of the polyol, and the chain extender is selected from 5.6 g of ethylenediamine and 4.5 g of isophoronediamine.

[0102] Preparation Example 11

[0103] The only difference between this preparation example and preparation example 1 is that toluene diisocyanate is used as the diisocyanate.

[0104] Preparation Example 12

[0105] The only difference between this preparation example and preparation example 1 is that dimethylolbutyric acid is used as the hydrophilic agent.

[0106] Preparation Example 13

[0107] The only difference between this preparation example and preparation example 1 is that the amount of the salt-forming agent is 20 g.

[0108] Preparation Example 14

[0109] The only difference between this preparation example and preparation example 1 is that ammonia water is used as the salt-forming agent.

[0110] Preparation Example 15

[0111] The only difference between this preparation example and preparation example 1 is that equal amounts of ethylenediamine and isophoronediamine are used as chain extenders.

[0112] Example

[0113] Example 1

[0114] The water-based coating resin is made of raw materials including the following weights: 75 g of water-based polyurethane emulsion, 22 g of water-based acrylic emulsion, 1.5 g of thickener, 0.5 g of defoamer, 1.2 g of leveling agent, and 1 g of hand feeling agent.

[0115] This embodiment uses the preparation example 1 of the water-based polyurethane emulsion; the water-based acrylic emulsion uses the pure acrylic emulsion Tekspro7612, the feel agent uses the water-based silky feel agent Silok-9159, the leveling agent uses the polyether modified siloxane leveling agent BYK-306, the thickener uses the water-based non-ionic polyurethane thickener Vesmody U506, and the defoamer uses the silicone defoamer BYK-024.

[0116] Preparation method of water-based coating resin:

[0117] Step 1: Prepare an aqueous polyurethane emulsion according to the method in Preparation Example 1 of the aqueous polyurethane emulsion;

[0118] Step 2 Add triethylamine to the aqueous acrylic emulsion and adjust the pH value to 8;

[0119] Step 3: Add the water-based polyurethane emulsion into a stirring container, and add the water-based acrylic emulsion, the feel agent, the leveling agent, the thickener and the defoaming agent into the container in sequence while stirring, and stir evenly until the viscosity rises to 5000 mPa·s (25°C) to obtain a highly waterproof, moisture-permeable and breathable water-based coating resin.

[0120] Example 2

[0121] The only difference between this embodiment and embodiment 1 is that the water-based coating resin is made of raw materials including the following weights: 65 g water-based polyurethane emulsion, 15 g water-based acrylic emulsion, 0.5 g thickener, 0.2 g defoamer, 0.8 g leveling agent, and 0.5 g feel agent.

[0122] Example 3

[0123] The only difference between this embodiment and embodiment 1 is that the water-based coating resin is made of raw materials including the following weights: 85 g water-based polyurethane emulsion, 30 g water-based acrylic emulsion, 2 g thickener, 1 g defoamer, 1.5 g leveling agent, and 1.5 g feel agent.

[0124] Example 4

[0125] The only difference between this embodiment and embodiment 1 is that the weight of the aqueous acrylic emulsion is 17.4 g.

[0126] Example 5

[0127] The only difference between this embodiment and embodiment 1 is that the weight of the aqueous acrylic emulsion is 26.8 g.

[0128] Example 6

[0129] The only difference between this comparative example and Example 1 is that the weight of the aqueous acrylic emulsion is 15 g.

[0130] Example 7

[0131] The only difference between this comparative example and Example 1 is that the weight of the aqueous acrylic emulsion is 30 g.

[0132] Example 8

[0133] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 2.

[0134] Example 9

[0135] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 3.

[0136] Example 10

[0137] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 4.

[0138] Embodiment 11

[0139] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 5.

[0140] Example 12

[0141] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 6.

[0142] Embodiment 13

[0143] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 7.

[0144] Embodiment 14

[0145] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 8.

[0146] Embodiment 15

[0147] The only difference between this embodiment and embodiment 1 is that the water-based coating resin is made of raw materials including the following weights: 80 g water-based polyurethane emulsion, 20 g water-based acrylic emulsion, 0.5 g thickener, 1 g defoamer, 1 g leveling agent, and 1.5 g feel agent.

[0148] In this embodiment, the aqueous polyurethane emulsion is selected from Preparation Example 9 of the aqueous polyurethane emulsion.

[0149] Example 16

[0150] The only difference between this embodiment and embodiment 1 is that the water-based coating resin is made of raw materials including the following weights: 85 g of water-based polyurethane emulsion, 15 g of water-based acrylic emulsion, 0.5 g of thickener, 1 g of defoamer, 1 g of leveling agent, and 1.5 g of feel agent.

[0151] In this embodiment, the aqueous polyurethane emulsion is selected from Preparation Example 10 of the aqueous polyurethane emulsion.

[0152] Embodiment 17

[0153] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 11.

[0154] Embodiment 18

[0155] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 12.

[0156] Embodiment 19

[0157] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 13.

[0158] Embodiment 20

[0159] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 14.

[0160] Embodiment 21

[0161] The only difference between this embodiment and embodiment 1 is that the aqueous polyurethane emulsion is the aqueous polyurethane emulsion preparation example 15.

[0162] Embodiment 22

[0163] The only difference between this embodiment and embodiment 1 is that the water-based acrylic emulsion is styrene acrylic emulsion.

[0164] Embodiment 23

[0165] The difference between this embodiment and embodiment 1 is that the defoaming agent is polyether defoaming agent BK-L099.

[0166] Embodiment 24

[0167] The only difference between this embodiment and embodiment 1 is that the thickener is water-based acrylic thickener CO-0015.

[0168] Embodiment 25

[0169] The only difference between this embodiment and embodiment 1 is that the water-based anti-sticking feeling agent Silok 359 is used as the feeling agent.

[0170] Embodiment 26

[0171] The only difference between this embodiment and embodiment 1 is that, when preparing the water-based coating resin, no triethylamine is added to adjust the pH value of the water-based acrylic emulsion.

[0172] Embodiment 27

[0173] The only difference between this embodiment and embodiment 1 is that, when preparing the water-based coating resin, the mixture system is stirred to increase the viscosity to 4000 mPa·s (25° C.).

[0174] Embodiment 28

[0175] The only difference between this embodiment and embodiment 1 is that, when preparing the water-based coating resin, the mixture system is stirred to increase the viscosity to 9000 mPa·s (25° C.).

[0176] Comparative Example

[0177] Comparative Example 1

[0178] The difference between this comparative example and Example 15 is that the aqueous polyurethane emulsion is 100 g and no aqueous acrylic emulsion is added.

[0179] Comparative Example 2

[0180] The only difference between this comparative example and Example 16 is that the aqueous polyurethane emulsion is 100 g and no aqueous acrylic emulsion is added.

[0181] Comparative Example 3

[0182] The only difference between this comparative example and Example 1 is that a total of 37.5 g of aqueous acrylic emulsion is added.

[0183] Comparative Example 4

[0184] The only difference between this comparative example and Example 1 is that a total of 10 g of aqueous acrylic emulsion is added.

[0185] Comparative Example 5

[0186] A method for preparing a waterborne polyurethane resin:

[0187] S1, add 50g of polyester polyol with a molecular weight of 500-10000g / mol into the reactor, vacuum dehydrate at 95°C for 1 hour, and cool to 50°C to obtain material A;

[0188] S2, add 15g of isophorone diisocyanate to material A, keep the reaction at 60°C for 2 hours, and cool to 75°C to obtain material B;

[0189] S3, add 1g of dimethylolpropionic acid to material B, then add 1g of 1,4-butanediol and 2g of triethylamine solution dissolved in acetone solution dropwise to the reactor, keep warm for reaction at 45°C for 1 hour, add 0.02g of bismuth catalyst and 0.2g of light stabilizer, keep warm for reaction at 45°C for 1 hour, and obtain material C;

[0190] After the S4 and C materials were cooled to room temperature, 18.5 g of triethylamine was added for neutralization, 1.2 g of ethylenediamine was added, and the mixture was stirred and reacted at a speed of 800 r / min for 1 hour. 24 g of deionized water was added for emulsification and dispersion, wherein the emulsification speed was 1200 r / min and the emulsification time was 30 min. Finally, the mixture was distilled under reduced pressure to obtain a waterborne polyurethane resin.

[0191] Performance testing

[0192] The water-based coating resin was evenly scraped on the base fabric with a thickness of 0.06 mm using a knife, and the water was dried at 130° C. to form a film. The coating performance of the water-based coating resin was tested using the following test method:

[0193] Test 1: Referring to the national standard GB / T 4744-2013, the water pressure resistance of the water-based coating resin in each embodiment and each comparative example was tested.

[0194] Test 2: referring to the standard JIS L1099 A, the moisture permeability of the water-based coating resin in each embodiment and each comparative example was detected.

[0195] Test three, referring to the industry standard FZ / T 01063-2008, the anti-blocking property of the water-based coating resin in each embodiment and each comparative example was tested.

[0196] Test 4, referring to the industry standard QB / T4671-2014, the aging resistance of the water-based coating resin in each embodiment and each comparative example was detected.

[0197] Table 1 Performance test results

[0198]

[0199]

[0200] Referring to Table 1, in combination with Example 1, Example 15, Example 16 and Comparative Examples 1-2 and Comparative Example 4, it can be concluded that when preparing the water-based coating resin, the water-based acrylic emulsion is added to the water-based polyurethane emulsion, and the acrylate monomer in the water-based acrylic emulsion can swell into the polyurethane particles in the water-based polyurethane emulsion to carry out free radical polymerization reaction. The polyurethane particles in the water-based polyurethane emulsion include the acrylic monomer to form stable latex particles, which significantly improves the water pressure resistance, moisture permeability, aging resistance and anti-adhesion properties of the water-based coating resin.

[0201] Combined with Examples 1-3, the performance values ​​of the water-based coating resins in Examples 1, 2 and 3 are all good, indicating that the water-based coating resins prepared with reference to the weight ratio disclosed in the present application can ensure that the water-based coating resins have better water pressure resistance, moisture permeability, aging resistance and anti-adhesion. At the same time, combined with Comparative Examples 3 and 4, the water pressure resistance, moisture permeability and anti-adhesion of the water-based coating resins in Comparative Examples 3 and 4 are slightly worse than those in Examples 1-3. It can be concluded that when the amount of the water-based acrylic emulsion is too low, its modification effect on the water-based coating resin is not obvious, and when the amount of the water-based acrylic emulsion is too high, the polyurethane particles in the water-based polyurethane emulsion are insufficient to include acrylic monomers, so that the water-based coating resin cannot form a stable dispersion emulsion, resulting in a reduction in the various properties of the water-based coating resin.

[0202] In combination with Example 1, Examples 4-7, the various properties of the water-based coating resins of Examples 6 and 7 are slightly worse, indicating that when the mass ratio of the aqueous polyurethane emulsion to the aqueous acrylic emulsion is 2.8-4.3:1, the aqueous acrylic emulsion can work together with the aqueous polyurethane emulsion to form a stable dispersion, giving the aqueous coating resin better water pressure resistance, moisture permeability, aging resistance and anti-adhesion properties.

[0203] Combined with Example 1 and Examples 8-9, it is shown that preparing the waterborne polyurethane emulsion according to the weight ratio disclosed in the present application can ensure that the waterborne coating resin has better water pressure resistance, moisture permeability, aging resistance and anti-adhesion properties.

[0204] In combination with Example 1, Example 10, and Examples 11-13, the water pressure resistance and moisture permeability of the water-based coating resin of Examples 11-13 are better than those of Examples 1 and 10, indicating that the combination of castor oil, polyoxypropylene glycol and polyhexanediol carbonate is selected as a polyol to participate in the preparation of the water-based polyurethane emulsion, which can give the water-based coating resin better water pressure resistance and moisture permeability. In combination with Example 14, the water pressure resistance and moisture permeability of the water-based coating resin of Example 14 are worse than those of Examples 11-13, indicating that the selection of castor oil, polyoxypropylene glycol and polyhexanediol carbonate as polyols according to the weight ratio disclosed in this application can ensure that the water-based coating resin has better water pressure resistance and moisture permeability.

[0205] Combining Example 1 and Example 21, the performance of the water-based coating resin of Example 21 is better than that of Example 1, indicating that the use of isophorone diamine and ethylenediamine as chain extenders can improve the temperature resistance and wear resistance of the water-based coating resin and give the water-based coating resin better performance.

[0206] In combination with Example 1, Example 17 and Example 20, it can be concluded that the use of isophorone diisocyanate as diisocyanate and triethylamine as salt-forming agent can give the water-based coating resin better performance.

[0207] In combination with Example 1 and Example 18, the various properties of the water-based coating resins of Example 1 and Example 18 are all relatively good, indicating that using dimethylolpropionic acid or dimethylolbutanoic acid as a hydrophilic agent and introducing hydrophilic groups into the polyurethane molecular chain can ensure a better self-emulsification effect when preparing the water-based polyurethane emulsion.

[0208] Combining Example 1 and Example 19, the water pressure resistance and moisture permeability of the water-based coating resin of Example 1 are better than those of Example 19, indicating that when the hydrophilic agent is selected from dimethylolpropionic acid or dimethylolbutyric acid, and each weight part of the aqueous polyurethane emulsion includes 8-15 parts of the salt-forming agent, the water-based coating resin can have better water pressure resistance and moisture permeability.

[0209] In combination with Example 1 and Example 22, it can be concluded that adding styrene acrylic emulsion or pure acrylic emulsion to the aqueous polyurethane emulsion can make the aqueous coating resin have excellent softness, elasticity, anti-aging and wear resistance, and have higher water pressure resistance, moisture permeability and anti-adhesion properties.

[0210] Combined with Example 1 and Examples 23-25, it is shown that using an aqueous non-ionic polyurethane thickener, a silicone defoamer, and an aqueous silky feel agent to prepare an aqueous coating resin in accordance with the preferred method disclosed in the present application can give the aqueous coating resin better performance.

[0211] Referring to Example 1 and Example 26, the various properties of the water-based coating resin of Example 26 are inferior to those of Example 1, indicating that when the pH value of the water-based acrylic emulsion is adjusted to 7-9, the water-based acrylic emulsion and the water-based polyurethane emulsion can be better compatible, and the water-based coating resin can have better water pressure resistance, moisture permeability, aging resistance and anti-adhesion properties.

[0212] Referring to Example 1, Example 27 and Example 28, when the viscosity of the water-based coating resin is too low, the coating film thickness is low, so that the various performances of the water-based coating resin of Example 27 are lower than those of Example 1; when the viscosity of the water-based coating resin is too high, the rheology of the water-based coating resin is low and the workability is poor, which in turn affects the water pressure resistance and moisture permeability of the water-based coating resin of Example 28.

[0213] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A highly waterproof, moisture-permeable and breathable water-based coating resin, characterized in that: The invention is prepared from the following raw materials in parts by weight: 65-85 parts of waterborne polyurethane emulsion, 15-30 parts of waterborne acrylic emulsion, 0.5-2 parts of thickener, 0.2-1 parts of defoamer, 0.8-1.5 parts of leveling agent and 0.5-1.5 parts of hand feeling agent; The aqueous polyurethane emulsion is prepared from the following raw materials in parts by weight: 250-350 parts of polyol, 100-150 parts of diisocyanate, 1-5 parts of trimethylolpropane, 0.01-2 parts of catalyst, 12-25 parts of hydrophilic agent, 3-35 parts of chain extender, 50-300 parts of organic solvent, 600-1000 parts of deionized water, and 8-15 parts of salt-forming agent per part by weight; The mass ratio of the aqueous polyurethane emulsion to the aqueous acrylic emulsion is: 2.8-4.3:1; The polyol is a combination of castor oil, polyoxypropylene glycol and polycarbonate glycol, and the mass ratio of castor oil, polyoxypropylene glycol and polycarbonate glycol is 1:3-5.2:1.6-3.3; The water-based acrylic emulsion uses pure acrylic emulsion Tekspro7612; The thickener is a water-based non-ionic polyurethane thickener; The hydrophilic agent is selected from one or a combination of dimethylol propionic acid and dimethylol butyric acid; The chain extender is one or a combination of two of an alcohol chain extender and an amine chain extender; the alcohol chain extender is selected from one or a combination of ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,2-propylene glycol, dipropylene glycol, trimethylolpropane, and trimethylolbutane; the amine chain extender is selected from one or a combination of hydrazine hydrate, ethylenediamine, propylenediamine, diethylenetriamine, isophoronediamine, hydroxyethylethylenediamine, diethanolamine, aminopropyltrimethoxysilane, and aminoethylaminopropyltrimethoxysilane.

2. The highly waterproof, moisture-permeable and breathable water-based coating resin according to claim 1, characterized in that: The salt-forming agent is one or a combination of triethylamine, tributylamine, tripropylamine, triethanolamine, sodium hydroxide, ammonia water, and dimethylethanolamine.

3. The highly waterproof, moisture-permeable and breathable water-based coating resin according to claim 1, characterized in that: The chain extender is selected from one or a combination of isophoronediamine and ethylenediamine.

4. The method for preparing a highly waterproof, moisture-permeable and breathable water-based coating resin according to any one of claims 1 to 3, characterized in that: The following steps are involved: Step 1: According to the ratio, the polyol and the hydrophilic agent are vacuum dehydrated at 100-110° C., and after the temperature is lowered to 50-80° C., diisocyanate and a catalyst are added to react; after the residual NCO value of the isocyanate group is reduced to 2%-5%, an organic solvent is added to reduce the viscosity, and then a salt-forming agent is added, and the reaction is carried out at 55-65° C. for 10-40 minutes to form a waterborne polyurethane prepolymer; Step 2: Mixing the waterborne polyurethane prepolymer and deionized water and emulsifying them by high-speed shearing. After the emulsification is completed, adding a chain extender and stirring for 0.5-2 hours, and then removing the organic solvent by vacuum distillation to obtain a waterborne polyurethane emulsion; Step 3: Mix the aqueous polyurethane emulsion and the aqueous acrylic emulsion according to the ratio, adjust the pH value to 7-9, add defoaming agent, leveling agent, feel agent and thickener, stir and mix well, increase the viscosity of the highly waterproof, moisture permeable and breathable water-based coating resin to the viscosity setting value, and obtain the highly waterproof, moisture permeable and breathable water-based coating resin.

5. The method for preparing the highly waterproof, moisture-permeable and breathable water-based coating resin according to claim 4, characterized in that: The viscosity setting value is 5000-8000 mPa·s at 25°C.

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