Water-slip resistant polyurethane surface material and its preparation method

Abstract

The application discloses a kind of water anti-skid polyurethane surface layer material and preparation method thereof, the polyurethane surface layer material includes A component, B component and auxiliary material;The raw materials for preparing A component include: isocyanate, first polyether polyol, first plasticizer and modified hollow glass microsphere;B component includes: amine chain extender, second polyether polyol, inorganic salt whisker, second plasticizer, thixotropic agent, short fiber, hollow microsphere, catalyst, defoaming agent, ultraviolet absorber, light stabilizer, other fillers and optional pigment;Auxiliary material includes: quartz sand, glue powder and optional ethyl acetate.The application solves the problem that the anti-skid value of surface layer material decreases after water, the anti-skid value decreases after wear, and achieves the effect of weather-resistant, durable, wear-resistant, anti-skid.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coatings, more particularly, relates to a water-resistant anti-slip polyurethane surface layer material and a preparation method thereof. BACKGROUND

[0002] Common polyurethane plastic tracks have full plastic type, hybrid type and breathable type, and the construction levels thereof are base coat, middle elastic layer and anti-slip surface layer. The anti-slip surface layer mainly has self-textured, sprayed particles, scattered particles and pat particles, which mainly rely on the three-dimensional concave-convex properties of the self-textured surface layer, the three-dimensional concave-convex properties of the particles to provide anti-slip effect.

[0003] The self-textured surface layer is a two-component polyurethane material, wherein the A component is an NCO-terminated polyurethane prepolymer, and the B component is a thixotropic material composed of polyether, amine chain extender, thixotropic agent, filler and additive. In construction, the AB components are mixed, a certain amount of EPDM rubber powder, quartz sand and solvent are added, and the mixture is stirred uniformly to form a high thixotropy material. The material is sprayed by a special spraying equipment, and a surface layer material with protruding particles is formed on the middle layer of the polyurethane track after two spraying. The uneven particles and textures provide anti-slip performance.

[0004] The three types of particle surface layers, i.e. sprayed particles, scattered particles and pat particles, have different construction processes, but the final anti-slip performance is provided by the uneven particles on the surface.

[0005] Due to the smooth surface of the polyurethane material, it is not easy to absorb water. When water is encountered, a layer of water film is formed on the surface of the material, thereby reducing the friction coefficient of the material surface. Even if the quartz sand and other fillers can provide certain anti-slip and wear resistance, the anti-slip performance of the surface layer material will still be significantly reduced after encountering water, which will cause the athletes to easily slip and fall, and will bring potential safety hazards to the athletes. In addition, with the use of the site, the protruding parts on the surface of the material will be worn out or even flattened. In addition, the material will age, powder and harden after being exposed to sunlight, and the anti-slip value of the material will show a trend of becoming lower and lower.

[0006] In the current standard GB 36246-2018, only the anti-slip value of the sports site during acceptance is specified, and the anti-slip value during the use of the material and after aging is not specified. The current standard or specification also does not give specific indicators that can be quantified for the site service life or the site performance attenuation to what standard the site needs to be replaced. Therefore, from the perspective of prolonging the service life of the site or improving the safety protection of the athletes, the problem of reduced anti-slip performance of the site after wear and tear and after encountering water is an urgent problem to be solved in the industry. SUMMARY

[0007] The present application aims to provide a water-resistant anti-slip polyurethane coating material and a preparation method thereof.

[0008] To achieve the above-mentioned purpose, one aspect of the present application provides a water-resistant anti-slip polyurethane coating material, which comprises a component A, a component B and an auxiliary material.

[0009] The raw materials for preparing the component A include isocyanate, first polyether polyol, first plasticizer and modified hollow glass microspheres.

[0010] The component B includes amine chain extender, second polyether polyol, inorganic salt whisker, second plasticizer, thixotropic agent, short fiber, hollow microsphere, catalyst, defoaming agent, ultraviolet absorber, light stabilizer, other filler and optional pigment.

[0011] The auxiliary material includes quartz sand, glue powder and optional ethyl acetate.

[0012] In the present application, the short fibers exposed on the surface will swell after water, which improves the roughness of the material surface, and the friction coefficient of the swollen fibers increases, so that the water-resistant anti-slip property of the coating is improved under the double effects; the irregularly distributed short fibers will continuously expose to the surface of the material with the abrasion of the material, so that the long-term anti-slip property of the coating can be ensured.

[0013] The inorganic salt whisker is added in the component B in an appropriate amount, which will swell after water absorption, so as to improve the roughness of the material surface and increase the friction coefficient of the material surface, and the inorganic salt whisker and the short fibers synergistically act (the water absorption process of the fiber is relatively long, which needs more than half an hour, while the inorganic salt whisker can realize water absorption and swelling within a few minutes), so as to improve the water-resistant anti-slip value of the material.

[0014] According to the present application, preferably, the raw materials for preparing the component A include isocyanate 10-45 parts, first polyether polyol 15-60 parts, first plasticizer 5-40 parts and modified hollow glass microspheres 0.1-5 parts in terms of mass fraction.

[0015] The component B includes amine chain extender 0.5-10 parts, second polyether polyol 5-25 parts, inorganic salt whisker 0.5-5 parts, second plasticizer 3-25 parts, thixotropic agent 1-10 parts, short fiber 0.5-5 parts, hollow microsphere 0.1-5 parts, catalyst 0.1-1 part, defoaming agent 0.1-2 parts, ultraviolet absorber 0.1-1 part, light stabilizer 0.1-1 part, other filler 15-45 parts and pigment 0-3 parts in terms of mass fraction.

[0016] The amount of the quartz sand is 10-30wt%, the amount of the powder is 5-15wt%, and the amount of the ethyl acetate is 0-3wt%, based on the total weight of the component A and the component B.

[0017] According to the application, preferably, the modified hollow glass microspheres are tetraisocyanate-silane modified hollow glass microspheres.

[0018] Preferably, the tetraisocyanate-silane modified hollow glass microspheres are prepared by a preparation method comprising the following steps: reacting dry hollow glass microspheres and tetraisocyanate-silane to obtain the tetraisocyanate-silane modified hollow glass microspheres.

[0019] Preferably, the dry hollow glass microspheres have a drying temperature of 100-120℃, and a moisture content of less than 0.2wt%, based on the total weight of the dry hollow glass microspheres.

[0020] The mass ratio of the hollow glass microspheres to the tetraisocyanate-silane is 1:(0.1-0.5), the reaction temperature is 70-85℃, and the reaction time is 3-5h.

[0021] In the application, the pre-modified hollow glass microspheres are added in the component A, the hollow glass microspheres are reacted with the tetraisocyanate-silane, the hydroxyl groups on the surface are grafted with NCO, which reinforces the polyurethane material and improves the mechanical properties of the material. The irregularly distributed short fibers on the surface and inside of the material after construction improve the anti-skid performance.

[0022] According to the application, preferably, the short fibers are at least one of polyether type spandex short fibers, nylon short fibers and PET short fibers, and preferably are polyether type spandex short fibers.

[0023] The length of the short fibers is 0.1-3cm, and preferably is 0.1-1cm; the thickness is 10-280D / str, and preferably is 40-280D / str.

[0024] In the application, the polyether type spandex short fibers are added in the component B, which improves the thixotropy of the material, reduces the amount of the chemical thixotropic agent, and the short fibers are irregularly distributed on the surface and inside of the material after construction, thereby improving the anti-skid value of the material.

[0025] Specifically, the polyurethane fiber is a short name of polyurethane fiber, also known as polyurethane elastic fiber, and is called spandex in China. According to the raw material, it is divided into two types of polyester spandex and polyether spandex, and the water absorption rate is generally between 0.3-1.2%, and the spandex will swell after water absorption. The main material of polyether spandex is polyether polyol and isocyanate, and the material surface has a large number of -OH groups, which can react with NCO in component A. At the same time, since the spandex itself is a polyurethane fiber, the compatibility with the polyurethane surface material is better than that of EPDM powder or particles with polyurethane surface material, and the spandex fiber can also reinforce the surface layer.

[0026] A certain proportion of spandex short fibers in component B can improve the thixotropy of the material and reduce the amount of chemical thixotropic agent, while not affecting the construction. The existing spraying equipment can be used, and part of the short fibers will be exposed on the surface of the material after spraying, forming a rough surface, thereby improving the anti-slip value of the material. Because the spandex has good flexibility, even if the exposed fibers come into contact with the human body, the athlete will not be injured or scratched, so the use of spandex short fibers will not cause damage or harm to the athlete. The spandex fiber has a certain water absorption and swelling property, and after encountering water, the exposed fibers will swell after water absorption, which can effectively improve the roughness of the material surface, and the friction coefficient of the fiber itself will also increase after swelling, thereby improving the wet-slip resistance of the surface layer. After a period of use in the sports field, the fibers distributed in the surface layer will gradually emerge to the surface of the material along with the wear of the surface layer, so the anti-slip value of the surface layer will not be significantly reduced due to the wear of the surface layer.

[0027] The spandex fiber has high strength and good wear resistance, and its service life is much higher than that of the surface layer, and it also plays a role in wear resistance and reinforcement in the surface layer.

[0028] In addition to spandex fiber, other polyester fibers such as nylon short fibers and PET short fibers can also be selected. Among them, spandex has the best effect. In order to enable the fiber to better contact with water and swell after water absorption, the length of the fiber should be controlled within a suitable range, and the preferred fiber length is 0.1-1cm, and the thickness is 40-280D / roots.

[0029] According to the present application, preferably, the inorganic salt whisker includes at least one of calcium carbonate whisker, calcium sulfate whisker and silicon carbide whisker.

[0030] Whisker refers to a fiber which is naturally formed or grown in a single crystal form under artificial control conditions (main form), has a very small diameter (micron order), does not contain defects (grain boundaries, dislocations, cavities, etc.) commonly existing in materials, has a highly ordered atomic arrangement, and thus has a strength close to the theoretical value of a complete crystal, and has a mechanical strength equal to the force between adjacent atoms. Common inorganic salt whiskers such as calcium carbonate whiskers and calcium sulfate whiskers, while improving the mechanical properties of materials, due to their water absorption and water-swellable properties, can make the material surface roughness greater, improve the friction coefficient of the material after encountering water, and thus improve the anti-skid performance of the material in the case of encountering water.

[0031] The inorganic salt whisker capable of water absorption and swelling in a short time and the short fiber needing a certain time for water absorption synergistically improve the water anti-skid value of the material; the whisker and the short fiber are irregularly embedded on the surface and inside of the material, and can bring a lasting anti-skid effect to the material.

[0032] According to the present application, preferably, the first polyether polyol and the second polyether polyol are each independently at least one of an EO-capped polyether diol, a PO-capped polyether diol, an EO-capped polyether triol, a PO-capped polyether triol, an EO-capped polyether tetrol and a PO-capped polyether tetrol.

[0033] The other filler is at least one of heavy calcium carbonate, light calcium carbonate, talcum powder and barium sulfate.

[0034] In the present application, the first polyether polyol and the second polyether polyol are each independently preferably at least one of polyether 2000, polyether 330N and polyether 3050, and further preferably polyether 2000 and polyether 3050.

[0035] According to the present application, preferably, the isocyanate comprises an aliphatic isocyanate and optionally a non-aliphatic isocyanate; further preferably, the content of the aliphatic isocyanate is 80-100wt%, and the content of the non-aliphatic isocyanate is 0-20wt%, based on the total weight of the isocyanate.

[0036] The aliphatic isocyanate is at least one of isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4'-diisocyanate (HMDI), methylcyclohexane diisocyanate (HTDI) and trimethylhexamethylene diisocyanate (TMDI), and is preferably hexamethylene diisocyanate (HDI) and / or 4'-diisocyanate (HMDI); the non-aliphatic isocyanate is phenylene diisocyanate (XDI) and / or diphenylmethane diisocyanate (MDI).

[0037] In the present application, the A component uses an aliphatic isocyanate to improve weather resistance.

[0038] According to the present application, preferably, the amine chain extender is at least one of primary amino diamine, secondary amino diamine, primary amino triamine and secondary amino triamine; preferably primary amino diamine;

[0039] The thixotropic agent is polyamide wax and optional other thixotropic agent, the other thixotropic agent is bentonite and / or fumed silica;

[0040] The hollow microspheres are at least one of hollow glass microspheres, hollow plastic microspheres and hollow ceramic microspheres;

[0041] The first plasticizer and the second plasticizer are each independently an environmentally friendly plasticizer, preferably, the first plasticizer and the second plasticizer each independently include at least one of long-chain carbon chlorinated paraffin, chlorinated palm oil methyl ester, terephthalate and citric acid ester plasticizer;

[0042] The ultraviolet absorber is at least one of salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine ultraviolet absorber;

[0043] The light stabilizer is a hindered amine light stabilizer;

[0044] The defoaming agent includes silicone defoaming agent and / or non-silicone defoaming agent;

[0045] The catalyst is a mixture of organic zinc catalyst and organic bismuth catalyst, the mass ratio of the organic zinc catalyst and the organic bismuth catalyst is 1:(1-6);

[0046] The pigment is at least one of carbon black, iron oxide red, phthalocyanine green, phthalocyanine blue, chromium oxide green and fast lightfast scarlet;

[0047] The diameter of the quartz sand is 150-200 mesh;

[0048] The rubber powder is ethylene propylene diene rubber powder (EPDM rubber powder).

[0049] In the present application, the amine chain extender is preferably at least one of Wanhua's E300, E100, 1104, 6200, and the TDMA series amine chain extender of Youyun.

[0050] According to the present application, preferably, the mass ratio of the A and B components is 1:(1-3).

[0051] Another aspect of the present application provides a preparation method of the above-mentioned polyurethane coating material, the preparation method comprising:

[0052] Preparation of the A component: the first polyether polyol and the first plasticizer are added to a reactor, stirred, heated to 100-120 DEG C, and vacuumed to remove water, then cooled to 60-70 DEG C, and the formula amount of 90-95 wt% isocyanate is added, heated to 80-85 DEG C, and reacted for 1-2 hours to measure NCO, and after the NCO is completely reacted, the remaining isocyanate is added to the reactor, reacted for 1-2 hours, and after the NCO reaches the theoretical value, the modified hollow glass microspheres after water removal are added to the reactor and stirred for 0.5-1 hour to obtain the A component;

[0053] Preparation of the B component: the second plasticizer, the second polyether polyol, the amine chain extender, the inorganic salt whisker, the short fiber, the hollow microsphere, the other filler, and the optional pigment are added to a reactor, heated to 100-120 DEG C, vacuumed to remove water, then cooled to 55-75 DEG C, and the thixotropic agent is added, stirred and dispersed, and after the thixotropic performance is qualified, the defoaming agent, the catalyst, the ultraviolet absorber, and the light stabilizer are added below 50 DEG C, stirred, and vacuumed to remove bubbles to obtain the B component;

[0054] The quartz sand, the rubber powder, and the optional ethyl acetate are respectively weighed according to the measurement;

[0055] Preferably, in the A component, the vacuum is opened to remove water, and after the water content is not more than 0.3 wt%, the temperature is cooled to 60-70 DEG C;

[0056] Preferably, in the B component, the vacuum is removed to remove water until the water content is not more than 0.3 wt%, and then the temperature is cooled to 55-75 DEG C.

[0057] In the present application, the water content not more than 0.3 wt% is based on the total weight of the material to be removed.

[0058] In the present application, in the process of synthesizing the A component, the isocyanate is added in steps through the NCO differential method, the molecular weight of the polyurethane prepolymer is controlled in a relatively narrow range, and the mechanical properties of the material are improved without increasing the amount of the polyurethane prepolymer.

[0059] The isocyanate of the A component is added in two batches, the first batch is 90-95 wt% of the formula amount, and after the complete reaction of NCO is tracked by infrared spectrogram, the remaining isocyanate is added at one time, and after the NCO approaches the theoretical value, the temperature is cooled and packaged.

[0060] In the present application, NCO refers to the NCO group; the "theoretical value" in "after the NCO reaches the theoretical value" refers to the value of unreacted NCO calculated according to the formula amount of isocyanate and the first polyether polyol.

[0061] The technical scheme of the present application has the following beneficial effects:

[0062] (1) The present application improves the roughness of the material surface and the friction coefficient of the material by adding short fibers and inorganic whisker materials in the formula, both of which swell after encountering water, thereby significantly improving the anti-skid value of the material after encountering water. At the same time, because the fibers are randomly distributed inside and on the surface of the material, with the abrasion of the material, part of the fibers will always be exposed on the surface of the material, thereby ensuring that the anti-skid value of the material will not be greatly reduced due to material abrasion, and even will be improved.

[0063] (2) The present application improves the anti-skid performance by adding modified hollow glass microspheres, which not only play a reinforcing role, but also are irregularly distributed inside and on the surface of the material after construction.

[0064] (3) The water-resistant anti-skid polyurethane surface layer material of the present application improves the weather resistance of the material by using aliphatic isocyanate.

[0065] (4) The present application solves the problems of reduced anti-skid value after the surface layer material encounters water and reduced anti-skid value after abrasion, achieving the effects of weather resistance, durability, abrasion resistance, and long-term anti-skid.

[0066] Other features and advantages of the present application will be described in detail in the following specific embodiments. DETAILED DESCRIPTION

[0067] The preferred embodiments of the present application will be described in more detail below. Although the preferred embodiments of the present application are described below, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments described herein. On the contrary, these embodiments are provided to make the present application more thorough and complete, and to fully convey the scope of the present application to those skilled in the art.

[0068] The present application will be further illustrated by the following examples:

[0069] In the following examples and comparative examples:

[0070] The preparation method of the modified hollow glass microspheres used is as follows: (1) dry the hollow glass microspheres at 100-120℃ to make the moisture content of the dried hollow glass microspheres less than 0.2wt% (based on the total weight of the dried hollow glass microspheres); (2) add a certain amount of dried hollow glass microspheres to a reactor, then add 0.3 times the mass of tetraisocyanate-based silane, heat to 80℃, react for 3h, then cool down to obtain modified hollow glass microspheres.

[0071] The polyether-based spandex short fibers are Millennium Spandex of Huafeng Chemical Co., Ltd.; the PET short fibers are PET Fiber of Changzhou Tianyi Engineering Fiber Co., Ltd.

[0072] The calcium carbonate whisker is purchased from Hebei Sena Nano Technology Co., Ltd., and the brand is TS-1016; the calcium sulfate whisker is 1250-mesh calcium sulfate whisker from Hebei Sena Nano Technology Co., Ltd.;

[0073] The polyether polyol DL2000 belongs to a PO-terminated polyether diol, which is purchased from Shanghai Dongda Chemical Co., Ltd.; the polyether polyol 3050 belongs to a PO-terminated polyether triol, which is purchased from Shanghai Dongda Chemical Co., Ltd.; the polyether polyol 6200 belongs to an EO-terminated polyether diol, which is purchased from Shanghai Dongda Chemical Co., Ltd.;

[0074] The amine chain extender TDMA belongs to a primary amino diamine, which is purchased from Guangzhou Yourun Synthetic Material Co., Ltd.; the amine chain extender TDMA-2 belongs to a primary amino diamine, which is purchased from Guangzhou Yourun Synthetic Material Co., Ltd.; the amine chain extender 1104 belongs to a primary amino diamine, which is purchased from Wanhua Chemical Group Co., Ltd.;

[0075] The thixotropic agent MT belongs to a polyamide, specifically CRAYVALLAC MT from Arkema; the thixotropic agent SF belongs to a polyamide, specifically CRAYVALLAC SF from Arkema;

[0076] The long-chain carbon chlorinated paraffin is purchased from Luxi Chemical Group Co., Ltd. Chlorinated Paraffin Branch, and the brand is 52# chlorinated paraffin;

[0077] The ultraviolet absorber is BASF Tinuvin 326;

[0078] The light stabilizer is a hindered amine light stabilizer, specifically BASF Tinuvin 770;

[0079] The defoaming agent is an organic silicon defoaming agent, which is purchased from Guangzhou Yourun Synthetic Material Co., Ltd., and the brand is YRXP-07B;

[0080] The catalyst is a mixture of an organic zinc catalyst and an organic bismuth catalyst, and the mass ratio of the organic zinc catalyst to the organic bismuth catalyst is 1:4; the organic zinc catalyst is purchased from Guangzhou Yourun Synthetic Material Co., Ltd., and the brand is ZCAT-X16; the organic bismuth catalyst is purchased from Guangzhou Yourun Synthetic Material Co., Ltd., and the brand is BCAT-20AP;

[0081] The quartz sand used is 150-200-mesh quartz sand;

[0082] The rubber powder used is EPDM rubber powder, which is purchased from Zhejiang Lven Sports Industry Co., Ltd., and the brand is red rubber powder;

[0083] In the preparation of the B component, the thixotropy is detected according to the butterfly method to determine whether it is qualified.

[0084] The unit of the amount of the components A and B in the following examples and comparative examples is equal to parts; each amount of the components A and B is mass parts.

[0085] Example 1

[0086] The present example provides a water-resistant anti-slip polyurethane surface material, which specifically comprises the following:

[0087] Raw materials for preparing the component A:

[0088]

[0089] The component B:

[0090]

[0091]

[0092] In the component B, the length of the polyether-based spandex staple fiber used is 3 mm, and the fineness is 120 D / strand.

[0093] Auxiliary materials: the mixing mass ratio of the components A and B is 1:1, and the amount of the quartz sand is 30 wt%, the amount of the rubber powder is 10 wt%, and the amount of the ethyl acetate is 1 wt% based on the total weight of the components A and B.

[0094] The preparation method is as follows:

[0095] Preparation of the component A: the first polyether polyol and the first plasticizer are added to a reaction kettle, stirred, and heated to 110°C, and vacuum water removal is started. After the water content is less than or equal to 0.3 wt%, the temperature is lowered to 70°C, and the isocyanate is added in batches. The first batch is 93 wt% of the formula amount. After the temperature is raised to 83°C and reacted for 1.5 hours, the NCO is measured by infrared. After the NCO is fully reacted, the remaining isocyanate is added to the reaction kettle. After 1.5 hours of reaction, the NCO reaches the theoretical value. The modified hollow glass microspheres are added to the reaction kettle and continue to stir for 1 hour. Then, the temperature is lowered for packaging.

[0096] Preparation of the component B: the second plasticizer, the second polyether polyol, the amine chain extender, the inorganic salt whisker, the other filler, the pigment, the staple fiber, the hollow microsphere are added to a reaction kettle, heated to 110°C, vacuum water removal is started until the water content is less than or equal to 0.3 wt%, then the temperature is lowered to 60°C, the thixotropic agent is added, then high-speed dispersion is performed, the linear speed of the stirring paddle edge is 10 m / s, the dispersion time is 30 min, the thixotropic performance is checked, and after passing, the temperature is lowered to below 50°C, the defoaming agent, the catalyst, the ultraviolet absorber, and the light stabilizer are added, stirred and vacuum degassed, and then the temperature is lowered for packaging.

[0097] The quartz sand, the rubber powder, and the optional ethyl acetate are weighed according to the metering.

[0098] In use: first mix A, B components according to mass ratio 1:1 uniformly, then add quartz sand, glue powder and optional ethyl acetate according to the above dosage ratio, stir uniformly to obtain the mixture, and then spray the mixture through a spraying device for construction.

[0099] Example 2

[0100] Raw materials for preparing A component:

[0101]

[0102] B component:

[0103]

[0104] The polyether type spandex short fiber used in the B component has a length of 6 mm and a fineness of 80 D / strand.

[0105] Auxiliary materials: the mixing mass ratio of A component and B component is 1:2, the amount of quartz sand is 20 wt%, the amount of glue powder is 8 wt%, and the amount of ethyl acetate is 0 wt% based on the total weight of the A component and the B component.

[0106] The preparation method of this example is the same as that of Example 1.

[0107] In use: first mix A, B components according to mass ratio 1:2 uniformly, then add quartz sand, glue powder and optional ethyl acetate according to the above dosage ratio, stir uniformly to obtain the mixture, and then spray the mixture through a spraying device for construction.

[0108] Example 3

[0109] Raw materials for preparing A component:

[0110]

[0111] B component:

[0112]

[0113]

[0114] The polyether type spandex short fiber used in the B component has a length of 12 mm and a fineness of 280 D / strand.

[0115] Auxiliary materials: the mixing mass ratio of A component and B component is 1:3, the amount of quartz sand is 30 wt%, the amount of glue powder is 15 wt%, and the amount of ethyl acetate is 3 wt% based on the total weight of the A component and the B component.

[0116] The preparation method of this example is the same as that of Example 1.

[0117] Use: first mix A, B components according to mass ratio 1:3, then add quartz sand, glue powder and optional ethyl acetate according to the above dosage ratio, stir evenly to obtain the mixture, and then spray the mixture through a spraying device for construction.

[0118] Comparative Example 1

[0119] The embodiment provides a conventional self-textured surface layer material without adding fibers and whiskers, and specifically comprises the following:

[0120] Raw materials for preparing the A component:

[0121]

[0122]

[0123] The B component:

[0124]

[0125] Auxiliary materials: the mixing mass ratio of the A component and the B component is 1:1, the amount of the quartz sand is 30wt%, the amount of the glue powder is 10wt%, and the amount of the ethyl acetate is 1wt% based on the total weight of the A component and the B component.

[0126] The preparation method is as follows:

[0127] Preparation of the A component: polyether polyol DL2000, polyether polyol 3050 and chloropalm oil methyl ester are added to a reaction kettle, stirring is performed, and the temperature is raised to 110 DEG C; vacuum is opened to remove water; after the water content is less than or equal to 0.3wt%, the temperature is lowered to 70 DEG C; isocyanate is added in batches; 93wt% of the first batch is added; the temperature is raised to 83 DEG C; reaction is performed for 1.5 hours; NCO is measured by infrared; after the NCO is fully reacted, the remaining isocyanate is added to the reaction kettle; reaction is performed for 1.5 hours; after NCO reaches the theoretical value, the modified hollow glass microspheres are added to the reaction kettle; stirring is continuously performed for 1 hour; and then the temperature is lowered for packaging.

[0128] Preparation of the B component: chloropalm oil methyl ester, long-chain chlorinated paraffin, polyether polyol 3050, amine chain extender, heavy calcium carbonate, iron oxide red and hollow microspheres are added to a reaction kettle; the temperature is raised to 110 DEG C; vacuum is opened to remove water until the water content is less than or equal to 0.3wt%; then the temperature is lowered to 60 DEG C; thixotropic agent MT and thixotropic agent SF are added; high-speed dispersion is performed; the linear speed of the edge of the stirring paddle is 10m / s; the dispersion time is 30min; the thixotropic performance is checked; after passing, the temperature is lowered to below 50 DEG C; defoaming agent, catalyst, ultraviolet absorber and light stabilizer are added; stirring and vacuum defoaming are performed; and then the temperature is lowered for packaging.

[0129] The quartz sand, the glue powder and the optional ethyl acetate are respectively weighed according to the metering.

[0130] In use: first, the components A and B are mixed uniformly according to the mass ratio of 1:1, then the quartz sand, the glue powder and the optional ethyl acetate are added according to the above-mentioned dosage ratio, and the mixture is obtained after stirring uniformly. The mixture is sprayed by a spraying equipment.

[0131] Comparative Example 2

[0132] The difference between this comparative example and Example 1 is that 5 parts of modified hollow glass microspheres in component A are replaced by 5 parts of hollow glass microspheres; the others are the same as Example 1.

[0133] Comparative Example 3

[0134] The difference between this comparative example and Example 3 is that the length of the PET short fiber used in component B is 4 mm; the others are the same as Example 3.

[0135] Test Example

[0136] The components A and B are mixed uniformly according to the above-mentioned ratio, then the auxiliary materials in the above-mentioned dosage ratio are added and stirred, and then a 3mm-thick self-textured surface layer is sprayed. According to the method for testing wet slip value in GB 36246-2018, the slip resistance value of the sprayed material is tested. A 2000-mesh sandpaper is used to simulate the wear of the surface layer material by the shoe sole, and the self-textured part of the surface layer material is polished off 1mm. Then, the slip resistance value of the polished surface layer material is tested according to the above-mentioned slip resistance value test method. The weather resistance test method is to use a xenon lamp to age for 500h, and then test the slip resistance value of the xenon lamp aged surface layer material according to the above-mentioned slip resistance value test method. The wear resistance value is tested according to the test method in GB / T 30314-2021, in which a 750g rubber wheel is used to polish for 2000 revolutions. The specific test results are shown in Table 1.

[0137] Table 1

[0138]

[0139] The above has described various embodiments of the present application, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A water slip resistant polyurethane finish material, characterized by, The polyurethane coating material comprises an A component, a B component and an auxiliary material; Raw materials for preparing the A component include, in mass parts, isocyanate 10-45 parts, first polyether polyol 15-60 parts, first plasticizer 5-40 parts and modified hollow glass microspheres 0.1-5 parts; The B component comprises, in mass parts, amine chain extender 0.5-10 parts, second polyether polyol 5-25 parts, inorganic salt whisker 0.5-5 parts, second plasticizer 3-25 parts, thixotropic agent 1-10 parts, short fiber 0.5-5 parts, hollow microspheres 0.1-5 parts, catalyst 0.1-1 parts, defoaming agent 0.1-2 parts, ultraviolet absorber 0.1-1 parts, light stabilizer 0.1-1 parts, other fillers 15-45 parts and pigment 0-3 parts; The auxiliary material comprises quartz sand, glue powder and optional ethyl acetate; the amount of the quartz sand is 10-30 wt%, the amount of the glue powder is 5-15 wt% and the amount of the ethyl acetate is 0-3 wt% based on the total weight of the A component and the B component; The modified hollow glass microspheres are tetraisocyanate-silane modified hollow glass microspheres. The short fiber is at least one of polyether type spandex short fiber, nylon short fiber and PET short fiber, the length of the short fiber is 0.1-1 cm and the fineness is 10-280 D / strand.

2. The polyurethane surfacing material of claim 1, wherein, The tetraisocyanate-silane modified hollow glass microspheres are prepared by a preparation method comprising the following steps: reacting dry hollow glass microspheres and tetraisocyanate-silane to obtain the tetraisocyanate-silane modified hollow glass microspheres.

3. The polyurethane surfacing material of claim 2, wherein, The dry hollow glass microspheres have a drying temperature of 100-120℃ and a moisture content of less than 0.2 wt% based on the total weight of the dry hollow glass microspheres; The mass ratio of the hollow glass microspheres to the tetraisocyanate-silane is 1:(0.1-0.5); the reaction is carried out at a temperature of 70-85℃ for 3-5 h.

4. The polyurethane surfacing material of claim 1, wherein, The short fiber is polyether type spandex short fiber. The fineness of the short fiber is 40-280 D / strand.

5. The polyurethane surfacing material of claim 1, wherein, The inorganic salt whisker comprises at least one of calcium carbonate whisker, calcium sulfate whisker and silicon carbide whisker.

6. The polyurethane surfacing material of claim 1, wherein, The first and second polyether polyols are each independently at least one of EO-capped polyether diol, PO-capped polyether diol, EO-capped polyether triol, PO-capped polyether triol, EO-capped polyether tetrol and PO-capped polyether tetrol. The other fillers are at least one of heavy calcium carbonate, light calcium carbonate, talcum powder and barium sulfate.

7. The polyurethane surfacing material of claim 1, wherein, The isocyanate comprises aliphatic isocyanate and optional non-aliphatic isocyanate; The aliphatic isocyanate is at least one of isophorone diisocyanate, hexamethylene diisocyanate, methylcyclohexane diisocyanate and trimethylhexamethylene diisocyanate; the non-aliphatic isocyanate is phenylene diisocyanate and / or diphenylmethane diisocyanate.

8. The polyurethane surfacing material of claim 7, wherein, The content of the aliphatic isocyanate is 80-100 wt% and the content of the non-aliphatic isocyanate is 0-20 wt% based on the total weight of the isocyanate.

9. The polyurethane surfacing material of claim 7, wherein, The aliphatic isocyanate is hexamethylene diisocyanate.

10. The polyurethane surfacing material of claim 1, wherein, The amine chain extender is at least one of primary diamine, secondary diamine, primary triamine and secondary triamine; The thixotropic agent is polyamide wax and optionally other thixotropic agents, the other thixotropic agents being bentonite and / or fumed silica; The hollow microspheres are at least one of hollow glass microspheres, hollow plastic microspheres and hollow ceramic microspheres; The first plasticizer and the second plasticizer are each independently an environmentally friendly plasticizer; The ultraviolet absorber is at least one of salicylate, benzophenone, benzotriazole, substituted acrylonitrile and triazine ultraviolet absorbers; The light stabilizer is a hindered amine light stabilizer; The defoaming agent comprises an organosilicon defoaming agent and / or a non-silicon defoaming agent; The catalyst is a mixture of an organic zinc catalyst and an organic bismuth catalyst, the mass ratio of the organic zinc catalyst to the organic bismuth catalyst being 1: (1-6); The pigment is at least one of carbon black, red iron oxide, phthalocyanine green, phthalocyanine blue, chromium oxide green and fast scarlet; The diameter of the quartz sand is 150-200 mesh; The rubber powder is ethylene-propylene-diene rubber powder.

11. The polyurethane surfacing material of claim 10, wherein, The amine chain extender is primary diamine; The first plasticizer and the second plasticizer each independently comprise at least one of long-chain carbon chlorinated paraffin, chlorinated palm oil methyl ester, terephthalate and citrate plasticizers.

12. The polyurethane surfacing material of claim 1, wherein, The mass ratio of the A component to the B component is 1: (1-3).

13. Process for the production of polyurethane coating materials according to any of claims 1 to 12, characterized in that The preparation method comprises: Preparation of the A component: the first polyether polyol and the first plasticizer are added to a reactor, stirred, heated to 100-120℃ and vacuumed to remove water, then cooled to 60-70℃, 90-95 wt% of the isocyanate is added in the formula amount, heated to 80-85℃, reacted for 1-2 hours to measure NCO, after the NCO is fully reacted, the remaining isocyanate is added to the reactor, reacted for 1-2 hours, NCO is measured to reach the theoretical value, the modified hollow glass microspheres after water removal are added to the reactor for continuous stirring for 0.5-1 hour to obtain the A component; Preparation of the B component: the second plasticizer, the second polyether polyol, the amine chain extender, the inorganic salt whisker, the short fiber, the hollow microspheres, the other fillers and the optional pigment are added to a reactor, heated to 100-120℃, vacuumed to remove water, then cooled to 55-75℃, the thixotropic agent is added, stirred and dispersed, after the thixotropic performance is qualified, cooled to below 50℃, the defoaming agent, the catalyst, the ultraviolet absorber and the light stabilizer are added, stirred and vacuumed to remove bubbles to obtain the B component; The quartz sand, the rubber powder and the optional ethyl acetate are respectively weighed according to the metering.

14. The production method according to claim 13, wherein, In the A component, vacuum is opened to remove water, and after the water content is not more than 0.3 wt%, the temperature is reduced to 60-70℃; In the B component, vacuum is applied to remove water until the water content is not more than 0.3 wt%, and then the temperature is reduced to 55-75℃.

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