High-weather-resistance polyurea-PVC (polyvinyl chloride) composite coiled material as well as preparation method and application thereof

Abstract

The invention discloses a high-weather-resistance polyurea-PVC (polyvinyl chloride) composite coiled material as well as a preparation method and application thereof. The coiled material is formed by compounding a PVC (polyvinyl chloride) base layer, a reaction type priming coat and a polyurea surface layer. The reaction type bottom coating is composed of a bottom coating agent containing isocyanate groups and PVC compatible resin, and the problem of interface bonding between polyurea and PVC is effectively solved. Modified nano silicon dioxide and rubber particles can be added into the polyurea surface layer, so that the wear resistance, the impact resistance and the weather resistance are synergistically improved. The invention further provides a preparation method for carrying out online thermal compounding by utilizing the waste heat of the PVC base layer, and the preparation method is energy-saving and efficient. The composite coiled material disclosed by the invention has excellent weather resistance, excellent physical properties and long service life, can still keep good dimensional stability and mechanical properties at high temperature, and is particularly suitable for outdoor sports fields.

Description

TECHNICAL FIELD

[0001] The application relates to a high-weather-resistance polyurea-PVC composite coiled material and a preparation method and application thereof. BACKGROUND

[0002] Polyvinyl chloride (PVC) coiled material is widely used in the field of ground material due to low cost, good processing performance and excellent physical and mechanical properties. However, the traditional PVC coiled material is prone to problems such as plasticizer migration, surface powdering, discoloration, brittleness and cracking when exposed to harsh outdoor environments such as ultraviolet light, ozone, heat and humidity and temperature difference changes for a long time, which seriously affects the service life. Therefore, developing a composite coiled material structure capable of improving the strength of PVC and having long service life and excellent comprehensive performance and a matching preparation process is a technical problem to be solved in the field. SUMMARY

[0003] The application aims to provide a polyurea-PVC composite coiled material with high weather resistance, long service life and excellent physical properties and application thereof in outdoor sports floors.

[0004] The application adopts the following technical scheme: A high-weather-resistance polyurea-PVC composite coiled material comprises a PVC base layer, a reactive primer layer arranged on the surface of the PVC base layer and a polyurea surface layer arranged on the primer layer.

[0005] Further, the reactive primer layer is formed by coating a primer, and the primer comprises a primer A component and a primer B component in a mass ratio of 1:5-5:1; the primer A component is a polyisocyanate or isocyanate prepolymer; and the primer B component is a solution or emulsion of a vinyl chloride-acetic acid vinyl copolymer resin.

[0006] Further, the polyurea surface layer is formed by the reaction of a polyurea A component and a polyurea B component; the polyurea A component is a polyisocyanate or isocyanate prepolymer; and the polyurea B component comprises 60-80 parts by weight of an amino-terminated polyether, 10-20 parts by weight of DETDA, 2-5 parts by weight of modified nano-SiO2, 3-8 parts by weight of polyurethane rubber particles, 2-5 parts by weight of UV-P weather-resistant agent and 1-2 parts by weight of titanium white.

[0007] Further, the polyurea B component further comprises 10-15 parts by weight of conductive carbon black, 0.5-1 part by weight of a wet dispersing agent and 0.1-0.5 part by weight of a defoaming agent.

[0008] Further, the PVC base layer comprises 100 parts by weight of a polyvinyl chloride resin, 30-50 parts by weight of calcium carbonate, 20-30 parts by weight of DOTP plasticizer and 2-5 parts by weight of calcium-zinc stabilizer.

[0009] Further, the surface of the PVC base layer in contact with the reactive primer layer has a micron-level concave-convex structure with a depth of 50-200 μm.

[0010] A preparation method of the high-weather-resistance polyurea-PVC composite roll material, comprising the following steps: (1) PVC base layer preparation: after high-speed mixing of PVC resin, calcium carbonate, DOTP plasticizer and calcium-zinc stabilizer, plasticizing at 155-160 DEG C through a single-screw extruder, and then rolling through a three-roll calender into a base layer roll material with a thickness of 1.5 mm and a temperature of 120-130 DEG C; (2) surface structuring treatment: hot embossing the surface of the high-temperature base layer roll material using a steel roller with irregular concave-convex patterns preheated to 135-145 DEG C, to form a micro concave-convex structure with a depth of about 50-200 μm; (3) coating primer: immediately after hot embossing, uniformly coating the PVC surface after embossing with a reactive primer, with a coating amount of about 5-15 g / m 2 ; (4) spraying polyurea: when the temperature of the PVC base layer drops to about 80-100 DEG C, spraying polyurea A component and polyurea B component at a volume ratio of 1:1, with a wet film thickness of 0.5-1.0 mm; (5) cooling and winding: after cooling through a cooling water roller to room temperature, winding to obtain the final composite roll material.

[0011] The high-weather-resistance polyurea-PVC composite roll material is applied to the preparation of sports floors.

[0012] The polyurea-PVC composite roll material has excellent anti-aging performance and long service life, and can significantly reduce the resistivity after adding conductive carbon black, so that the anti-static effect can be achieved.

[0013] The polyurea-PVC composite roll material has excellent anti-aging performance and long service life, and can significantly reduce the resistivity after adding conductive carbon black, so that the anti-static effect can be achieved.

[0014] The polyurea-PVC composite roll material has excellent anti-aging performance and long service life, and can significantly reduce the resistivity after adding conductive carbon black, so that the anti-static effect can be achieved. DETAILED DESCRIPTION

[0015] The following provides multiple embodiments to fully illustrate the present application, rather than limiting the scope of the present application.

[0016] Example 1 (1) PVC base layer preparation: 100 kg of PVC resin (SG-5), 40 kg of calcium carbonate (1250 mesh), 25 kg of DOTP plasticizer, and 3 kg of calcium-zinc stabilizer were mixed at high speed, plasticized at 160°C by a single screw extruder, and then rolled by a three-roll calender to form a roll with a thickness of 1.5 mm and a temperature of 125°C.

[0017] (2) Surface structuring treatment: a steel roller with irregular concave-convex patterns preheated to 140°C was used to hot emboss the surface of the high-temperature PVC base layer to form a micro concave-convex structure with a depth of about 100 μm.

[0018] (3) Coating of primer: the reactive primer was uniformly coated on the embossed PVC surface immediately after hot embossing by a micro-gravure coater, with a coating amount of about 10 g / m 2 . The reactive primer included: primer A component: isocyanate (MDI) prepolymer with an isocyanate group (NCO) content of 20%; primer B component: chloroethylene-vinyl acetate copolymer xylene solution with a vinyl acetate (VAC) content of 13%, solid content 30%; mixed in a mass ratio of primer A component to primer B component of 1:2.

[0019] (4) Spraying of polyurea: when the temperature of the PVC base layer dropped to about 95°C, two-component high-temperature high-pressure spraying equipment was used to spray polyurea A component and polyurea B component at a volume ratio of 1:1, with a wet film thickness of 0.8 mm. The polyurea was surface-dried within 60 s using the residual heat of the base layer. Polyurea A component was MDI prepolymer with an NCO content of 18%; polyurea B component was amino-terminated polyether (Mn=2000) 70 kg, DETDA 15 kg, modified nano-SiO2 3 kg, polyurethane rubber particles (particle size 80 μm) 5 kg, UV-P weathering agent 3 kg, and titanium dioxide 1.5 kg.

[0020] (5) Cooling and winding: after cooling by a cooling water roller to room temperature, the final composite roll was obtained.

[0021] Example 2 (1) PVC base layer preparation: same as Example 1.

[0022] (2) Surface structuring treatment: same as Example 1.

[0023] (3) Coating of primer: same as Example 1.

[0024] (4) Spray polyurea: same as Example 1, except that the polyurea B component is amino-terminated polyether (Mn = 2000) 65 kg, DETDA 15 kg, conductive carbon black (particle size 25 nm) 12 kg, modified nano-SiO2 3 kg, polyurethane rubber particles (particle size 80 μm) 5 kg, UV-P weathering agent 3 kg, titanium white 1.5 kg, wetting dispersant (BYK-190) 0.8 kg, and defoaming agent (BYK-066N) 0.2 kg.

[0025] (5) Cooling and winding: same as Example 1.

[0026] Comparative Example 1 (1) PVC base layer preparation: PVC resin (SG-5) 100 kg, calcium carbonate (1250 mesh) 40 kg, DOTP plasticizer 25 kg, calcium-zinc stabilizer 3 kg were mixed at high speed, then plasticized by a single screw extruder at 160°C, and then calendered by a three-roll calender to a thickness of 1.5 mm, cooled at room temperature, and wound for use.

[0027] (2) Spray polyurea: the roll material prepared in step (1) was treated by corona, and then sprayed with polyurea A component and polyurea B component at a volume ratio of 1:1 using a two-component high-temperature high-pressure spraying equipment, with a wet film thickness of 0.8 mm. The polyurea was surface dried within 60 s using the residual heat of the base layer. The polyurea A component was MDI prepolymer with an NCO content of 18%; the polyurea B component was amino-terminated polyether (Mn = 2000) 70 kg, DETDA 15 kg, modified nano-SiO2 3 kg, polyurethane rubber particles (particle size 80 μm) 5 kg, UV-P weathering agent 3 kg, and titanium white 1.5 kg.

[0028] (3) Cooling and winding: after cooling by a cooling water roller to room temperature, the final composite roll material was wound.

[0029] Comparative Example 2 (1) PVC base layer preparation: PVC resin (SG-5) 100 kg, calcium carbonate (1250 mesh) 40 kg, DOTP plasticizer 25 kg, calcium-zinc stabilizer 3 kg were mixed at high speed, then plasticized by a single screw extruder at 160°C, and then calendered by a three-roll calender to a thickness of 1.5 mm, cooled at room temperature, and wound for use.

[0030] (2) Surface texturing treatment: a steel roller preheated to 140°C with irregular concave-convex patterns was used to hot emboss the surface of the PVC base layer to form a micro concave-convex structure with a depth of about 100 μm.

[0031] (3) Coating primer: same as Example 1.

[0032] (4) Spray polyurea: same as Example 1.

[0033] (5) Cooling and winding: same as Example 1.

[0034] Example 1 The properties of the composite rolls obtained in Examples 1-2 and Comparative Examples 1-2 were tested, and the results are shown in Table 1.

[0035] Table 1. Results of property testing of composite rolls .

[0036] The results show that both Examples 1-2 exhibit excellent and durable adhesion, far superior to Comparative Example 1 (without primer and without structure), proving the outstanding effect of the reactive primer and the microstructure. The performance of Example 1 (on-line thermal compounding) is slightly better than that of Example 3 (off-line), proving the process advantage of compounding using the residual heat of the base layer. In terms of functionality, the surface resistivity of Example 2 is significantly reduced to the order of 10 6 Ω, reaching the standard of antistatic materials. In terms of aging resistance, the adhesion retention rate of the surface polyurea layer of all examples is very high (>90%) after severe UV aging, reflecting its weather resistance.

[0037] Example 2 The composite rolls prepared in Examples 1 and 2 were tested for their performance when applied to sports flooring. The test environment was a temperature of (23±2) °C and a humidity of (50±5) %. The results are shown in Table 2.

[0038] Table 2. Performance testing of composite flooring as sports flooring .

[0039] Table 2 shows that the composite rolls of Examples 1 and 2 perform well in key sports performance indicators such as impact absorption, vertical deformation, and ball rebound rate, with very similar results, both of which can meet the requirements of professional competitive sports flooring. This indicates that the basic formula of the present application can provide stable and excellent sports experience. The composite roll of Example 1 has a relative advantage in wear resistance and is more suitable for outdoor sports venues and public indoor venues with high foot traffic. Example 2 is more suitable for places with high equipment density, sensitivity to static electricity, or high cleanliness requirements due to its antistatic performance.

[0040] The results of the dimensional stability test show that the dimensional change rate of the samples of Example 1 and Example 2 at 60°C is much better than the standard requirement, indicating that the floor will not expand or shrink significantly even when the surface temperature rises due to direct sunlight in summer, avoiding problems such as drumming and edge lifting caused by excessive dimensional change, and having good installation stability. After accelerated aging at 85°C, the key sports performance (ball rebound rate) is almost not attenuated, proving that the mechanical properties can still remain stable for a long time at high temperatures. Under high-temperature and wet conditions at 40°C, the slip resistance value (SRV) has a slight decrease, but is still much higher than the safety threshold (≥ 35). This indicates that the floor can still provide sufficient and effective slip resistance protection in hot and humid summer or indoor high-temperature and high-humidity environments, and the safety is not affected.

Claims

1. A high weather-resistant polyurea-PVC composite roll material, characterized in that, It includes a PVC base layer, a reactive primer layer disposed on the surface of the PVC base layer, and a polyurea top layer disposed on the primer layer.

2. The high weather-resistant polyurea-PVC composite roll material according to claim 1, characterized in that, The reactive primer layer is formed by coating with a primer, which comprises primer component A and primer component B in a mass ratio of 1:5 to 5:1; primer component A is a polyisocyanate or isocyanate prepolymer; primer component B is a solution or emulsion of vinyl chloride-vinyl acetate copolymer resin.

3. The high weather-resistant polyurea-PVC composite roll material according to claim 1, characterized in that, The polyurea surface layer is formed by the reaction of polyurea component A and polyurea component B; the polyurea component A is a polyisocyanate or isocyanate prepolymer; the polyurea component B includes 60-80 parts by weight of amino-terminated polyether, 10-20 parts by weight of DETDA, 2-5 parts by weight of modified nano-SiO2, 3-8 parts by weight of polyurethane rubber particles, 2-5 parts by weight of UV-P weathering agent and 1-2 parts by weight of titanium dioxide.

4. The high weather-resistant polyurea-PVC composite roll material according to claim 3, characterized in that, The polyurea B component further includes 10-15 parts by weight of conductive carbon black, 0.5-1 parts by weight of wetting and dispersing agent, and 0.1-0.5 parts by weight of defoamer.

5. The high weather-resistant polyurea-PVC composite roll material according to claim 1, characterized in that, The PVC base layer comprises 100 parts by weight of polyvinyl chloride resin, 30-50 parts by weight of calcium carbonate, 20-30 parts by weight of DOTP plasticizer, and 2-5 parts by weight of calcium-zinc stabilizer.

6. The high weather-resistant polyurea-PVC composite roll according to claim 1, characterized in that, The surface of the PVC base layer in contact with the reactive primer layer has a micron-level uneven structure with a depth of 50μm to 200μm.

7. A method for preparing a high weather-resistant polyurea-PVC composite roll as described in any one of claims 1 to 6, characterized in that, It includes the following steps: (1) Preparation of PVC base layer: PVC resin, calcium carbonate, DOTP plasticizer and calcium zinc stabilizer are mixed at high speed, plasticized at 155~160℃ by a single screw extruder, and then calendered by a three-roll calender into a base layer roll with a thickness of 1.5mm and a temperature of 120~130℃. (2) Surface structuring treatment: Using a steel roller with irregular concave and convex patterns preheated to 135~145℃, hot embossing is performed on the surface of the high-temperature base layer roll material to form a micro-concave and convex structure with a depth of about 50~200μm. (3) Applying primer: Immediately after hot embossing, apply a reactive primer evenly to the embossed PVC surface, with a coating amount of approximately 5~15g / m². 2 ; (4) Spraying polyurea: When the temperature of the PVC substrate drops to about 80~100℃, spray polyurea component A and polyurea component B at a volume ratio of 1:1, with a wet film thickness of 0.5~1.0mm; (5) Cooling and winding: After being cooled to room temperature by cooling water rollers, the material is wound up to obtain the final composite roll.

8. The application of the high weather-resistant polyurea-PVC composite roll material as described in claim 1 in the preparation of sports flooring.