Polyurea coating for sole coating and application thereof

Abstract

The invention relates to the technical field of coatings, and provides a polyurea coating for a sole coating and application of the polyurea coating. The polyurea coating comprises a first component and a second component. The first component comprises an isocyanate prepolymer with the NCO content of 5 to 20 percent; the second component is prepared from 1 to 15 parts of first polyhydric alcohol, 1 to 15 parts of small molecular alcohol, 5 to 15 parts of diacetylethylenediamine and 1 to 10 parts of epoxidized soybean oil modified ceramic powder. The polyurea coating not only has wear resistance and scratch resistance, but also has good wettability and leveling property during spraying, and can form a decorative coating with good construction performance, wettability and strong adhesive force on the surface of a sole.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and particularly to a polyurea coating for sole coatings and its applications. Background Art

[0002] Spray polyurea coatings are a new type of solvent-free, pollution-free, highly safe, and non-toxic green environmental protection coatings developed in the past decade following low (or solvent-free) pollution coatings such as high-solid coatings, waterborne coatings, UV-curable coatings, and powder coatings to meet environmental protection requirements.

[0003] Polyurea coatings are two-component, solvent-free, and fast-curing elastic coatings. Among them, the first component is a semi-prepolymer prepared by reacting a hydroxyl-terminated compound with an isocyanate, and the second component is a mixture composed of an amino chain extender without a catalyst. The first component and the second component are sprayed out of the spray gun of a dedicated spraying device and quickly react and cure to form an elastomeric film. During construction, it is less affected by ambient temperature and humidity, is insensitive to moisture and humidity, has excellent physical properties of the coating, and can be widely used in the anti-corrosion and waterproof fields of oil pipelines, oil refining and chemical industries, power equipment, bridge engineering, ship protection, marine facilities, airport runways, sewage treatment, furniture and home furnishings, clothing and textile industries, etc.

[0004] For example, spraying polyurea coatings on soles (outer soles, mid-soles, etc.) is a common way to improve the wear resistance and scratch resistance of soles. Although the spray polyurea coatings on the market have shown excellent performance as sole coating materials, some problems still emerge during use. For example, the reaction speed is too fast, and the gel time is only a few seconds to more than ten seconds. Special large spraying equipment is required, and it is difficult to construct on small areas or irregular surfaces, and the surface effect is poor. In addition, due to the too fast reaction speed, the polyurea coating has poor wettability to the sole substrate, low adhesion, concentrated reaction heat release, large thermal shrinkage rate, large internal stress, poor color retention and anti-aging performance of the polyurea, poor decorative performance, and is not easy to repair after problems occur. Summary of the Invention

[0005] Based on the above problems, the purpose of the present invention is to provide a polyurea coating for sole coatings and its applications. This polyurea coating not only has wear resistance and scratch resistance, but also has good wettability and leveling property during spraying, and can form a decorative coating with good construction performance, strong wettability and adhesion on the sole surface.

[0006] To achieve the above purpose, on the one hand, the present invention provides a polyurea coating for sole coatings. The polyurea coating includes a first component and a second component. The first component includes an isocyanate prepolymer with an NCO content of 5-20%. By weight fraction, the second component includes 1-15 parts of a first polyol, 1-15 parts of a small molecule alcohol, 5-15 parts of diacetyldiethylenediamine, and 1-10 parts of epoxy soybean oil-modified ceramic powder.

[0007] The technical solution adopted by the present invention has at least the following technical effects.

[0008] (1) The second component includes a first polyol and diacetyldiethylenetriamine. During subsequent construction, when the first component and the second component are mixed and reacted, the first polyol can react with the isocyanate prepolymer to form polyurethane, and diacetyldiethylenetriamine can react with the isocyanate prepolymer to form polyurea, that is, a polyurethane / polyurea composite coating is formed. Polyurea can be used to improve the wear resistance and scratch resistance of the coating. The formation of polyurethane can not only slow down the gel reaction during spraying, but also improve the flexibility of the coating by incorporating polyurethane into polyurea. Therefore, the coating used for the sole has better anti-cracking performance and scratch resistance.

[0009] (2) Diacetyldiethylenetriamine is used as a chain extender for preparing polyurea. Its reaction activity is low, and it will not react too fast with the isocyanate prepolymer, resulting in poor wettability of the polyurea coating on the sole substrate and low adhesion.

[0010] (3) Adding small molecule alcohols can improve the solubility of each substance in the system, reduce the viscosity of the system, and increase the self-leveling property. Therefore, during spraying, it has good wettability on the sole and can form a coating with strong adhesion.

[0011] (4) Using epoxy soybean oil-modified ceramic powder as a filler, it has better flexibility and good dispersion performance in the system. Epoxy soybean oil has the function of active dilution. After modifying the ceramic powder, it can be better fused into small molecule alcohols, and together with small molecule alcohols, it can play the role of wetting and leveling. Good construction performance can be obtained without using wetting agents and leveling agents.

[0012] As a technical solution of the present invention, the isocyanate prepolymer is obtained by reacting a polyisocyanate with a second polyol.

[0013] As a technical solution of the present invention, the polyisocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanate, and hexamethylene diisocyanate.

[0014] As a technical solution of the present invention, the first polyol and the second polyol are each independently a polyether polyol or a polyester polyol.

[0015] As a technical solution of the present invention, the polyether polyol includes one or more of polypropylene glycol, polytetrahydrofuran diol, and tetrahydrofuran oxypropylene copolymer diol.

[0016] As a technical solution of the present invention, the polyester polyol includes one or more of polybutylene adipate diol, polyethylene adipate diol, ethylene-propylene glycol adipate, diethylene glycol adipate, polycaprolactone polyol, and polycarbonate diol.

[0017] As a technical solution of the present invention, the small molecule alcohol includes neopentyl glycol, cyclohexanedimethanol, diethylene glycol, and trimethylolpropane.

[0018] As a technical solution of the present invention, the ceramic powder includes at least one of silicon nitride, aluminum nitride, titanium nitride, silicon carbide, and boron nitride.

[0019] As a technical solution of the present invention, the second component further includes an auxiliary agent, and the auxiliary agent includes at least one of a pigment and a leveling agent.

[0020] On the other hand, the present invention provides that the aforementioned polyurea coating for sole coating is sprayed on the midsole or outsole of a shoe. Detailed Description of the Invention

[0021] The sole (outsole, midsole) generally plays a role in supporting the shoe and should possess properties such as wear resistance, water resistance, oil resistance, heat resistance, pressure resistance, impact resistance, good elasticity, easy to fit the foot shape, not easy to deform after shaping, heat preservation, easy to absorb moisture, etc. It should also have a braking effect when changing feet while walking to prevent slipping and easy to stop. The main materials of the sole include SBS, PVC, PU, EVA, etc. The polyurea coating of the present invention can be used on such sole materials as a coating to improve wear resistance and scratch resistance, and is particularly suitable for PU shoe materials. The polyurea coating of the present invention has better compatibility and stronger adhesion with PU shoe materials.

[0022] The polyurea coating for sole coating of the present invention includes a first component and a second component.

[0023] The first component includes an isocyanate prepolymer with an NCO content of 5-20%. The free NCO content in the isocyanate prepolymer needs to be sufficient to react with the first polyol and diacetyldiamine in the second component, that is, the NCO content needs to satisfy the equivalent reaction with hydroxyl groups and amino groups. The NCO content can be detected by chemical analysis according to the principle of "Determination of Isocyanate Group Content in Polyurethane Prepolymers HG / T2409-92", or by instrumental analysis methods, etc. The NCO content in the isocyanate prepolymer can be, but is not limited to, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%.

[0024] The isocyanate prepolymer is obtained by reacting a polyisocyanate with a second polyol. The polyisocyanate includes at least one of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), polymethylene polyphenyl polyisocyanate (PAPI), and hexamethylene diisocyanate (HDI). The second polyols are each independently a polyether polyol and / or a polyester polyol. The polyether polyols include one or more of polypropylene glycol, polytetrahydrofuran diol, and tetrahydrofuran-oxypropylene copolymer diol. The polyester polyols include one or more of polybutylene adipate diol, polyethylene adipate diol, ethylene glycol-propylene glycol adipate, diethylene glycol adipate, polycaprolactone polyol, and polycarbonate diol. The reaction of the polyisocyanate with the second polyol can be a conventional polyurethane preparation reaction. The NCO content in the polyisocyanate and the hydroxyl content of the second polyol not only need to satisfy the formation of polyurethane, but also need to be blocked with isocyanate to retain sufficient NCO content for reaction with the first polyol and diacetyldiethylamine in the second component. A catalyst needs to be added when the polyisocyanate reacts with the second polyol. The catalyst can be a metal catalyst or ethanolamine. The metal catalyst can be dibutyltin dilaurate or stannous octoate. The ethanolamine can be diethanolamine or triethanolamine.

[0025] The second component includes 1 to 15 parts of the first polyol, 1 to 15 parts of a small molecule alcohol, 5 to 15 parts of diacetyldiethylamine, and 1 to 10 parts of epoxy soybean oil-modified ceramic powder.

[0026] Among them, the first polyols are each independently a polyether polyol or a polyester polyol. The polyether polyols include one or more of polypropylene glycol, polytetrahydrofuran diol, and tetrahydrofuran-oxypropylene copolymer diol. The polyester polyols include one or more of polybutylene adipate diol, polyethylene adipate diol, ethylene glycol-propylene glycol adipate, diethylene glycol adipate, polycaprolactone polyol, and polycarbonate diol. The first polyol can be, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts.

[0027] The small molecule alcohols include neopentyl glycol, cyclohexanedimethanol, diethylene glycol, and trimethylolpropane. The small molecule alcohols can be, but are not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts.

[0028] Diacetyldiethylamine can be obtained by reacting ethylenediamine and glacial acetic acid as raw materials under the catalysis of phosphoric acid. It can be, but is not limited to, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts.

[0029] The ceramic powder modified with epoxy soybean oil can be obtained by mixing epoxy soybean oil and ceramic powder, heating to 90-120 °C, stirring at a speed of 70-100 r / min for 30-60 min, and then extracting with a Soxhlet extractor and drying under vacuum for purification. The mass ratio of epoxy soybean oil to ceramic powder can be 1:2-6, and the mass ratio can be, but is not limited to, 1:2, 1:3, 1:4, 1:5, 1:6. The ceramic powder includes at least one of silicon nitride, aluminum nitride, titanium nitride, silicon carbide, and boron nitride. Preferably, the ceramic powder includes silicon nitride or aluminum nitride. The surface of the silicon nitride powder usually has a tertiary amine structure, the chemical bond of the surface silicon atoms is not saturated, and there are silicon dangling bonds that need to be saturated. This structure has high reactivity. In addition, the surface of the aluminum nitride powder usually contains -OH, -NH2, -NH-. Therefore, silicon nitride and aluminum nitride are easily reacted with epoxy soybean oil and modified. The content of the ceramic powder modified with epoxy soybean oil can be, but is not limited to, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts.

[0030] The second component also includes additives, and the content of the additives can be 0.1-10.0 parts. Preferably, the content of the additives can be, but is not limited to, 0.1 part, 0.5 part, 1.0 part, 2.0 part, 3.0 part, 4.0 part, 5.0 part, 6.0 part, 7.0 part, 8.0 part, 9.0 part, 10.0 part. The additives include at least one of pigments and leveling agents. The pigments can be titanium dioxide, zinc oxide, lithopone, iron oxide red, toluidine red, big red powder, cadmium red, molybdenum chromate orange, chrome yellow, iron oxide yellow, lead chromate green, chromium oxide green, phthalocyanine green, iron blue, or phthalocyanine blue. The leveling agents can be polyurethane leveling agents or silicone leveling agents.

[0031] The preparation method of the polyurea coating of the present invention can include weighing the first polyol, small molecule alcohol, diacetyldiethylamine, and the ceramic powder modified with epoxy soybean oil according to the formula amount, and then dispersing on a high-speed disperser for 20-60 min to obtain the second component. The first component and the second component are separately packaged. When in use, the first component and the second component are sprayed out through a spraying device by a spray gun, and after the first component and the second component come into contact, they are cured into a paint film.

[0032] To better illustrate the purpose, technical solution, and beneficial effects of the present invention, the present invention will be further described below in conjunction with specific embodiments. It should be noted that the methods described in the following embodiments are further explanatory descriptions of the present invention and should not be regarded as limitations on the present invention. The raw materials involved in the embodiments of the present invention can be obtained through commercial channels except as otherwise specified.

[0033] (1) Preparation of isocyanate prepolymer

[0034] Preparation of Isocyanate Prepolymer 1#: Add TDI into a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Use a water bath, start the stirrer, begin heating and raising the temperature, and control the temperature in the flask at 80 ± 2 °C. Drop the formulated amount of polytetrahydrofuran diol into the flask, stir evenly, detect the NCO content in the reactants every hour, stop the reaction until the NCO content is 10% by instrumental analysis, add butyl acetate solvent, continue to stir evenly for 30 min, cool down to 40 °C, and discharge to obtain Isocyanate Prepolymer 1#.

[0035] Preparation of Isocyanate Prepolymer 2#: Add MDI into a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Use a water bath, start the stirrer, begin heating and raising the temperature, and control the temperature in the flask at 80 ± 2 °C. Drop the formulated amount of butanediol adipate diol into the flask, stir evenly, detect the NCO content in the reactants every hour, stop the reaction until the NCO content is 14% by instrumental analysis, add butyl acetate solvent, continue to stir evenly for 30 min, cool down to 40 °C, and discharge to obtain Isocyanate Prepolymer 2#.

[0036] Preparation of Isocyanate Prepolymer 3#: Add IPDI into a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Use a water bath, start the stirrer, begin heating and raising the temperature, and control the temperature in the flask at 80 ± 2 °C. Drop the formulated amount of polypropylene glycol into the flask, stir evenly, detect the NCO content in the reactants every hour, stop the reaction until the NCO content is 15% by instrumental analysis, add butyl acetate solvent, continue to stir evenly for 30 min, cool down to 40 °C, and discharge to obtain Isocyanate Prepolymer 3#.

[0037] Preparation of Isocyanate Prepolymer 4#: Add MDI into a four-necked flask equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser. Use a water bath, start the stirrer, begin heating and raising the temperature, and control the temperature in the flask at 80 ± 2 °C. Drop the formulated amount of polytetrahydrofuran diol and ethylene glycol adipate diol (the mass ratio of the two is 2:1) into the flask, stir evenly, detect the NCO content in the reactants every hour, stop the reaction until the NCO content is 18% by instrumental analysis, add butyl acetate solvent, continue to stir evenly for 30 min, cool down to 40 °C, and discharge to obtain Isocyanate Prepolymer 4#.

[0038] (II) Preparation of Diacetyldiethylenediamine

[0039] Preparation of N,N'-Diacetylethylenediamine 1#: In a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, start stirring and add 50 g of ethylenediamine. Then control the temperature at 75 ± 2 °C and dropwise add a mixture of 120 g of glacial acetic acid and 0.7 g of phosphoric acid. After the addition is complete, heat under reflux for 2 h and control the reaction temperature at 120 ± 2 °C. After the reflux ends, distill out the water generated in the reaction. Then continue refluxing for 1 h. After pouring out the reactant, grind, filter by suction, and wash. Dry under vacuum at 120 °C to constant weight to completely remove the residual acetic acid to obtain N,N'-Diacetylethylenediamine 1#.

[0040] Preparation of N,N'-Diacetylethylenediamine 2#: In a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, start stirring and add 50 g of ethylenediamine. Then control the temperature at 70 ± 2 °C and dropwise add a mixture of 120 g of glacial acetic acid and 0.5 g of phosphoric acid. After the addition is complete, heat under reflux for 2 h and control the reaction temperature at 120 ± 2 °C. After the reflux ends, distill out the water generated in the reaction. Then continue refluxing for 1 h. After pouring out the reactant, grind, filter by suction, and wash. Dry under vacuum at 120 °C to constant weight to completely remove the residual acetic acid to obtain N,N'-Diacetylethylenediamine 2#.

[0041] Preparation of N,N'-Diacetylethylenediamine 3#: In a four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser, start stirring and add 50 g of ethylenediamine. Then control the temperature at 75 ± 2 °C and dropwise add a mixture of 130 g of glacial acetic acid and 1.0 g of phosphoric acid. After the addition is complete, heat under reflux for 3 h and control the reaction temperature at 130 ± 2 °C. After the reflux ends, distill out the water generated in the reaction. Then continue refluxing for 1 h. After pouring out the reactant, grind, filter by suction, and wash. Dry under vacuum at 120 °C to constant weight to completely remove the residual acetic acid to obtain N,N'-Diacetylethylenediamine 3#.

[0042] (III) Preparation of Epoxidized Soybean Oil-Modified Ceramic Powders

[0043] Preparation of Epoxidized Soybean Oil-Modified Ceramic Powder 1#: Mix 20 g of epoxidized soybean oil and 200 g of silicon nitride powder, heat to 100 °C, stir at a speed of 90 r / min for 45 min, and then purify by extraction with a Soxhlet extractor followed by vacuum drying to obtain Epoxidized Soybean Oil-Modified Ceramic Powder 1#.

[0044] Preparation of Epoxidized Soybean Oil-Modified Ceramic Powder 2#: Mix 20 g of epoxidized soybean oil and 200 g of aluminum nitride powder, heat to 100 °C, stir at a speed of 90 r / min for 45 min, and then purify by extraction with a Soxhlet extractor followed by vacuum drying to obtain Epoxidized Soybean Oil-Modified Ceramic Powder 2#.

[0045] Preparation of Epoxy Soybean Oil-Modified Ceramic Powder 3#: After mixing 20 g of epoxy soybean oil and 200 g of silicon carbide powder, heat the mixture to 100 °C, stir it at a speed of 90 r / min for 45 min, and then extract it with a Soxhlet extractor and vacuum dry and purify it to obtain epoxy soybean oil-modified ceramic powder 3#.

[0046] Preparation of Epoxy Soybean Oil-Modified Ceramic Powder 4#: After mixing 15 g of epoxy soybean oil and 200 g of boron nitride powder, heat the mixture to 100 °C, stir it at a speed of 80 r / min for 40 min, and then extract it with a Soxhlet extractor and vacuum dry and purify it to obtain epoxy soybean oil-modified ceramic powder 4#.

[0047] Example 1

[0048] This example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diacetyldiethylenetriamine 1#, and 5 parts of epoxy soybean oil-modified ceramic powder 1#. After mixing the raw materials of the second component, disperse them on a high-speed disperser for 40 min and then package for standby.

[0049] Example 2

[0050] This example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of trimethylolpropane, 7 parts of diacetyldiethylenetriamine 1#, and 5 parts of epoxy soybean oil-modified ceramic powder 1#. After mixing the raw materials of the second component, disperse them on a high-speed disperser for 40 min and then package for standby.

[0051] Example 3

[0052] This example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 6 parts of polytetrahydrofuran diol, 4 parts of neopentyl glycol, 3 parts of trimethylolpropane, 7 parts of diacetyldiethylenetriamine 1#, and 5 parts of epoxy soybean oil-modified ceramic powder 1#. After mixing the raw materials of the second component, disperse them on a high-speed disperser for 40 min and then package for standby.

[0053] Example 4

[0054] This example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diacetyldiethylenetriamine 1#, and 5 parts of epoxy soybean oil-modified ceramic powder 2#. After mixing the raw materials of the second component, disperse them on a high-speed disperser for 40 min and then package for standby.

[0055] Example 5

[0056] This embodiment is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diacetyldiethylenetriamine 1#, and 5 parts of epoxy soybean oil-modified ceramic powder 3#. After the raw materials of the second component are mixed, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0057] Example 6

[0058] This embodiment is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diacetyldiethylenetriamine 1#, and 5 parts of epoxy soybean oil-modified ceramic powder 4#. After the raw materials of the second component are mixed, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0059] Example 7

[0060] This embodiment is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 2#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diacetyldiethylenetriamine 2#, and 5 parts of epoxy soybean oil-modified ceramic powder 1#. After the raw materials of the second component are mixed, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0061] Example 8

[0062] This embodiment is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 3#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diacetyldiethylenetriamine 2#, and 5 parts of epoxy soybean oil-modified ceramic powder 1#. After the raw materials of the second component are mixed, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0063] Example 9

[0064] This embodiment is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 4#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diacetyldiethylenetriamine 3#, and 5 parts of epoxy soybean oil-modified ceramic powder 1#. After the raw materials of the second component are mixed, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0065] Example 10

[0066] This example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 10 parts of polytetrahydrofuran diol, 5 parts of neopentyl glycol, 5 parts of diacetyldiethylenetriamine 1#, and 7 parts of epoxy soybean oil-modified ceramic powder 1#. After mixing the raw materials of the second component, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0067] Example 11

[0068] This example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 10 parts of polytetrahydrofuran diol, 13 parts of neopentyl glycol, 15 parts of diacetyldiethylenetriamine 1#, and 8 parts of epoxy soybean oil-modified ceramic powder 1#. After mixing the raw materials of the second component, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0069] Example 12

[0070] This example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 6 parts of polytetrahydrofuran diol, 10 parts of neopentyl glycol, 7 parts of diacetyldiethylenetriamine 1#, 5 parts of epoxy soybean oil-modified ceramic powder 1#, 2 parts of titanium dioxide, and 1 part of MONENG-1071 silicone leveling agent. After mixing the raw materials of the second component, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0071] Comparative Example 1

[0072] This comparative example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 7 parts of neopentyl glycol, 9 parts of diacetyldiethylenetriamine 1#, and 5 parts of epoxy soybean oil-modified ceramic powder 1#. After mixing the raw materials of the second component, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0073] Comparative Example 2

[0074] This comparative example is a polyurea coating, which includes a first component and a second component. The first component is isocyanate prepolymer 1#. The second component includes 6 parts of polytetrahydrofuran diol, 7 parts of diacetyldiethylenetriamine 1#, and 5 parts of epoxy soybean oil-modified ceramic powder 1#. After mixing the raw materials of the second component, they are dispersed on a high-speed disperser for 40 minutes and then packaged for standby.

[0075] Comparative Example 3

[0076] This comparative example is a polyurea coating, comprising a first component and a second component. The first component is an isocyanate prepolymer 1#. The second component comprises 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diethyltoluenediamine and 5 parts of ceramic powder 1# modified by epoxy soybean oil. The raw materials of the second component are mixed and dispersed on a high-speed disperser for 40 minutes before packaging for use.

[0077] Comparative Example 4

[0078] This comparative example is a polyurea coating, comprising a first component and a second component. The first component is isocyanate prepolymer 1#. The second component comprises 6 parts of polytetrahydrofuran diol, 7 parts of neopentyl glycol, 7 parts of diacetylethylenediamine 1# and 5 parts of silicon nitride powder. The raw materials of the second component are mixed and dispersed on a high-speed disperser for 40 minutes before packaging for standby use.

[0079] The viscosity of the second component was first tested, and the NCO of the first component in Examples 1 to 12 and Comparative Examples 1 to 4, and the sum of the OH and NH contents of the first polyol in the second component were mixed in an equivalent ratio and then tested by making a plate. The plate thickness was 0.5±0.05 mm. The test was carried out in accordance with GB T 23446-2009 Spray Polyurea Waterproof Coating. The test results are shown in Table 1.

[0080] Table 1 Properties of polyurea coatings of Examples 1 to 12 and Comparative Examples 1 to 4

[0081]

[0082]

[0083] From the results in Table 1, it can be seen that the viscosity of the second component of the polyurea coatings of Examples 1 to 12 is relatively low, and its viscosity is ≤6Pa·s, so it has better construction performance. In addition, when the polyurea coatings of Examples 1 to 12 are used to make boards, the gel time is 16 to 26 seconds, the surface drying time is 30 to 40 seconds, and the actual drying time is ≤2.0 hours. The gel and surface drying time are relatively long, so there is enough time for construction, and the boards have better strength, hardness and wear resistance after making. Therefore, the polyurea coating of the present invention is used for the sole coating, and it has good wettability with the sole substrate and strong adhesion, and can produce a decorative coating with strong adhesion, wear resistance and scratch resistance.

[0084] From the comparison of Examples 1 to 3, it can be seen that when the small molecule alcohol includes neopentyl glycol and trimethylolpropane, that is, includes polar and non-polar alcohols, the viscosity of the second component is smaller and the performance after board making is better. This is because the use of a mixture of polar and non-polar alcohols can improve the solubility, reticulation and branching of the isocyanate prepolymer.

[0085] Comparing Examples 1, 4 to 6, it can be seen that when silicon nitride or aluminum nitride is selected as the ceramic powder, the viscosity of the second component is lower, and the gel time and surface drying time are shorter. This is because silicon nitride or aluminum nitride is more easily modified by epoxy soybean oil, and the surface properties of the modified ceramic powder are better.

[0086] In Comparative Example 1, the first polyol was not added, so the formed polyurea coating did not contain polyurethane. Its gel time and surface drying time were very short, and the strength and wear resistance after plate making were not good.

[0087] In Comparative Example 2, the small molecule alcohol was not added, the viscosity of the second component was very high, it was not easy to construct, it was difficult to form a uniform coating after plate making, the actual drying time was long, and the strength and wear resistance after plate making were not good.

[0088] In Comparative Example 3, diethyltoluenediamine was used as the chain extender, its activity was strong, it gelled and surface dried quickly. When used for the sole coating, the wettability to the sole substrate was not good and the adhesion was low.

[0089] In the comparative example, the ceramic powder was not modified by epoxy soybean oil, its dispersibility in the system was not good, which would also lead to a high viscosity of the second component, not conducive to construction, and the performance after plate making was not good.

[0090] Finally, it should be noted that the above examples are only used to illustrate the technical solutions of the present invention rather than to limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, it is not limited to only those listed in the embodiments. Those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A polyurea coating for sole coating, characterized in that, It includes a first component and a second component. The first component includes an isocyanate prepolymer with an NCO content of 5-20%. By weight fraction, the second component includes 1-15 parts of a first polyol, 1-15 parts of a small molecule alcohol, 5-15 parts of diacetyldiethylenediamine, and 1-10 parts of a ceramic powder modified by epoxy soybean oil.

2. The polyurea coating for sole coating according to claim 1, characterized in that, The isocyanate prepolymer is obtained by reacting a polyisocyanate with a second polyol.

3. The polyurea coating for sole coating according to claim 2, characterized in that, The polyisocyanate includes at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, polymethylene polyphenyl polyisocyanate, and hexamethylene diisocyanate.

4. The polyurea coating for sole coating according to claim 2, characterized in that, The first polyol and the second polyol are each independently a polyether polyol or a polyester polyol.

5. The polyurea coating for sole coating according to claim 4, characterized in that, The polyether polyol includes one or more of polypropylene glycol, polytetrahydrofuran diol, and tetrahydrofuran propylene oxide copolymer diol.

6. The polyurea coating for sole coating according to claim 4, characterized in that, The polyester polyol includes one or more of polybutylene adipate diol, polyethylene adipate diol, ethylene glycol 1,2-propylene adipate, diethylene glycol adipate, polycaprolactone polyol, and polycarbonate diol.

7. The polyurea coating for sole coating according to claim 1, characterized in that, The small molecule alcohol includes neopentyl glycol, cyclohexanedimethanol, diethylene glycol, and trimethylolpropane.

8. The polyurea coating for sole coating according to claim 1, characterized in that, The ceramic powder includes at least one of silicon nitride, aluminum nitride, titanium nitride, silicon carbide, and boron nitride.

9. The polyurea coating for sole coating according to claim 1, characterized in that, The second component further includes an additive, and the additive includes at least one of a pigment and a leveling agent.

10. The polyurea coating for sole coating according to any one of claims 1 to 9 is sprayed on the midsole or outsole of the shoe.

Images