High-wear-resistance plastic floor and preparation method thereof

Abstract

The invention discloses a high-wear-resistance plastic floor and a preparation method thereof, and relates to the technical field of polyvinyl chloride composite materials. The high-wear-resistant plastic floor sequentially comprises a base layer, a printing layer and a wear-resistant layer from bottom to top, the wear-resistant layer is prepared from the following raw materials in parts by mass: 100 parts of polyvinyl chloride, 20-35 parts of a plasticizer, 1-4 parts of a stabilizer, 0.5-2 parts of a lubricant, 10-30 parts of inorganic wear-resistant particles, 0.1-5 parts of a coloring agent and 0.5-3 parts of an anti-ultraviolet agent. A deuterated group in the anti-ultraviolet agent stabilizes a molecular structure through an isotope effect, biphenyl / phenyl provides steric hindrance to inhibit migration, and a multi-protection mechanism is formed by combining a blocking effect of a methyltin mercaptide stabilizer on a degradation reaction. The synergistic system can efficiently absorb / scatter ultraviolet rays and greatly delay aging phenomena such as color fading and embrittlement of the material.

Description

Technical Field

[0001] The present invention relates to the technical field of polyvinyl chloride composite materials, and in particular to a high-wear-resistant plastic floor and a preparation method thereof. Background Art

[0002] Despite the widespread adoption of plastic flooring, existing technologies present several pressing challenges. Traditional plastic flooring, primarily based on polyvinyl chloride (PVC), offers flexibility and ease of processing, but suffers from poor wear resistance, making it difficult to meet the long-term demands of high-traffic areas such as shopping malls and hospitals. Furthermore, most traditional plastic flooring lacks UV resistance and is prone to fading and aging with prolonged exposure to sunlight, impacting its aesthetics and shortening its lifespan.

[0003] From a material perspective, the wear-resistant layer of traditional plastic flooring typically contains only basic ingredients such as polyvinyl chloride and plasticizers, lacking effective reinforcing additives. The choice of plasticizers is also relatively limited, with most being phthalates. These plasticizers are prone to migration during long-term use, leading to a decline in material performance. Furthermore, the amount and types of anti-UV agents added in the prior art are limited, making it impossible to form a stable protective system and effectively block UV damage to the flooring material. Furthermore, the printed layer of traditional plastic flooring lacks sufficient bonding strength to the base layer, making it prone to problems such as the printed layer peeling and wear, affecting the overall decorative and functional properties of the flooring.

[0004] Existing plastic flooring also has shortcomings in its manufacturing process. For example, imprecise control of parameters such as calendering temperature and laminating pressure leads to unstable product performance, and production efficiency and product quality need to be improved. Therefore, providing a plastic floor with high wear resistance, excellent UV resistance, and optimized manufacturing process has become a technical challenge that needs to be solved in this field. Summary of the Invention

[0005] The purpose of the present invention is to provide a plastic floor with high wear resistance, excellent UV resistance and optimized preparation process to improve service life and aesthetics in order to solve the problems existing in the prior art.

[0006] To achieve the above object, the technical solution adopted by the present invention is: a highly wear-resistant plastic floor, which comprises, from bottom to top, a base layer, a printing layer and a wear-resistant layer;

[0007] The wear-resistant layer is prepared from raw materials comprising the following components in parts by mass: 100 parts of polyvinyl chloride, 20-35 parts of plasticizer, 1-4 parts of stabilizer, 0.5-2 parts of lubricant, 10-30 parts of inorganic wear-resistant particles, 0.1-5 parts of colorant, and 0.5-3 parts of anti-ultraviolet agent;

[0008] The anti-ultraviolet agent has a structure shown in Formula 1:

[0009]

[0010] The R1 is selected from the group consisting of deuterium, phenyl, cyano, and biphenyl.

[0011] Furthermore, the plasticizer is selected from: dioctyl phthalate; and the stabilizer is selected from: methyltin mercaptan.

[0012] Furthermore, the inorganic wear-resistant particles are selected from: silicon dioxide or silicon carbide; the colorant is selected from: organic pigments and / or inorganic pigments; the organic pigments are selected from: azo pigments, phthalocyanine pigments; the inorganic pigments are selected from: TiO2, red iron oxide, carbon black.

[0013] Furthermore, the anti-ultraviolet agent is selected from any one of the compounds described in the following structures:

[0014]

[0015] Furthermore, the preparation method of the wear-resistant layer includes the following steps: adding the polyvinyl chloride, plasticizer, stabilizer, lubricant, inorganic wear-resistant particles, colorant and anti-ultraviolet agent into a mixer in a mass ratio, mixing at 60-90°C for 5-15 minutes to obtain a mixture; transferring the mixture to an internal mixer, internal mixing at 160-180°C for 3-8 minutes to obtain an internal mixing material; pressing the internal mixing material into a sheet through an open mixer, controlling the open mixing temperature at 150-170°C, to obtain an open mixing material; and rolling the open mixing material into a wear-resistant layer of a set thickness through a four-roll calender, maintaining the calendering temperature at 140-160°C.

[0016] Furthermore, the material of the base layer is selected from: polyvinyl chloride foam plastics.

[0017] Furthermore, the material of the printing layer is selected from: polyvinyl chloride ink.

[0018] A method for preparing a highly wear-resistant plastic floor comprises the following steps:

[0019] S1. The mixture of the wear-resistant layer is calendered by a four-roll calender, and the printed layer is coated on the surface of the base layer;

[0020] S2 at a set temperature and pressure, the calendering wear-resistant layer and the base layer covered with a printed layer composite floor body;

[0021] S3. Cooling, shaping, and cutting the floor blank to obtain a highly wear-resistant plastic floor.

[0022] Furthermore, the printing layer is coated by gravure printing, and after coating, it is heat-cured at 120-150° C. for 1-3 minutes.

[0023] Furthermore, in S2: the compounding temperature is controlled at 130-160°C, the compounding pressure is 5-15 MPa, and the compounding time is 2-5 minutes.

[0024] The anti-UV agent described in the present invention contains a conjugated large π bond system and a strong polar group in its molecular structure, which enables it to effectively absorb ultraviolet rays with a wavelength range of 280-400nm (especially UV-A and UV-B bands). After absorbing ultraviolet light, the molecule transitions from the ground state to the excited state, and then converts the energy into heat release through a non-radiative relaxation process (such as vibrational relaxation), thereby avoiding energy transfer to the polyvinyl chloride (PVC) molecular chain and causing degradation. The deuterium in the R1 group enhances the stability of the CH bond within the molecule through the isotope effect and reduces the generation of free radicals; the biphenyl group / phenyl group provides a steric hindrance effect, reduces the migration rate of the anti-UV agent in the plasticizer, and extends the protection life. Combined with inorganic wear-resistant particles (such as silicon dioxide and silicon carbide): the inorganic particles can scatter part of the ultraviolet light, reduce the amount of direct radiation, and form a physical-chemical double protective layer with the anti-UV agent. Collaborative with methyl tin mercaptan stabilizer: inhibits the dehydrochlorination reaction of PVC and blocks the oxidative degradation chain reaction triggered by ultraviolet rays.

[0025] The inorganic wear-resistant particles, lubricant and plasticizer components described in the present invention synergistically improve wear resistance. The inorganic wear-resistant particles are dispersed in the PVC matrix as a hard reinforcing phase, resisting surface wear through physical friction and directly improving the surface hardness. The lubricant reduces internal friction between molecular chains during processing and use, avoiding the expansion of microcracks due to stress concentration, and synergistically extends the service life of the wear-resistant particles. The amount of plasticizer added is controlled to balance flexibility and strength, avoiding excessive plasticization that causes material softening and reduces wear resistance.

[0026] The anti-ultraviolet agent, stabilizer and inorganic wear-resistant particle components described in the present invention synergistically improve anti-ultraviolet and aging resistance. The anti-ultraviolet agent can efficiently absorb 280-400nm ultraviolet rays (covering the UV-A / B band), convert light energy into heat energy for release, enhance the stability of the CH bond through the isotope effect, inhibit the generation of free radicals, provide steric hindrance, reduce the migration rate of the anti-ultraviolet agent in the plasticizer, and extend the protection time; the stabilizer can inhibit the dehydrochlorination reaction of PVC triggered by ultraviolet rays, block the oxidative degradation chain reaction, and form a chemical synergistic protection with the anti-ultraviolet agent; the inorganic wear-resistant particles scatter part of the ultraviolet light, reduce the amount of direct radiation, and form a physical-chemical double barrier with the anti-ultraviolet agent.

[0027] The steric hindrance effect of the R1 group in the anti-UV agent of the present invention and the chelation effect of the stabilizer synergistically inhibit plasticizer migration. The large R1 group of the anti-UV agent restricts the movement of plasticizer molecules through steric hindrance, thereby reducing the leakage of dioctyl phthalate from the system. The methyltin mercaptan in the chelation effect of the stabilizer can complex metal ions generated by PVC degradation, thereby reducing plasticizer migration caused by ion catalysis.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. Simultaneous Improvement of Wear and Impact Resistance: Through the synergistic effect of a specific UV inhibitor (Formula 1) and inorganic wear-resistant particles, the surface hardness and wear resistance are significantly enhanced while maintaining the material's flexibility. Furthermore, the optimized plasticizer dosage (20-35 parts) avoids the conflict between high wear resistance and low impact resistance in traditional formulations, achieving simultaneous enhancement of both properties.

[0030] 2. Significantly enhanced UV and aging resistance: The deuterated groups in the UV inhibitor stabilize the molecular structure through the isotope effect, while the biphenyl / phenyl groups provide steric hindrance to inhibit migration. Combined with the methyltin mercaptan stabilizer's blocking effect on degradation reactions, this creates a multi-layered protection mechanism. This synergistic system efficiently absorbs and scatters UV rays, significantly slowing aging phenomena such as fading and embrittlement.

[0031] 3. Optimization of interlayer bonding and dimensional stability: Gravure printing combined with a precise thermal curing process improves the adhesion between the printed layer and the base layer; composite process parameter control significantly reduces thermal shrinkage through the effective entanglement of molecular chain segments, ensuring that the floor is free of delamination and warping risks during long-term use. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 For the anti-ultraviolet agent 1 of the present invention 1 HNMR spectrum.

[0033] Figure 2 This is a structural schematic diagram of a high wear-resistant plastic floor according to the present invention;

[0034] Among them, 1 is the base layer, 2 is the printing layer, and 3 is the wear-resistant layer. DETAILED DESCRIPTION

[0035] The following will clearly and completely describe the technical solution of the present invention in conjunction with the accompanying drawings. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] Synthesis example 1

[0037] Synthesis of UV-resistant agent 1:

[0038]

[0039] The first step: Under a nitrogen atmosphere, 20 g of raw material 1, 15.29 g of raw material 2, 13.97 g of sodium tert-butoxide, 2.00 g of tris(dibenzylideneacetone)dipalladium, 0.7 g of tri-tert-butyl phosphine and 200 g of toluene were added to the reaction system in sequence, stirred evenly, heated to 110° C., and refluxed for 12 h; after the reaction was completed, the temperature was slightly lowered, filtered using diatomaceous earth, the filtrate was cooled to room temperature, washed three times with water, the organic phase was retained, and the aqueous phase was extracted with ethyl acetate; after the organic phases were combined, they were dried over anhydrous magnesium sulfate, filtered, spin-dried, column chromatography, and a mixture of petroleum ether and ethyl acetate was used as an eluent, and spin-dried to obtain 20.90 g of intermediate 1.

[0040] Step 2: Under a nitrogen atmosphere, 30.13 g of potassium phosphate trihydrate, 0.07 g of pyridine-2-carboxylic acid, 0.5 g of CuI and 150 g of DMSO were added to the reaction system in sequence, and after stirring evenly, 150 ml of DMSO solution containing 20.90 g of intermediate 1 and 30.71 g of raw material 3 was slowly added dropwise, and the temperature was raised to 85 ° C and heated to react for 16 hours; after cooling, the reaction mixture was extracted with an ammonia solution and methyl tert-butyl ether, and the organic phase was washed five times with water and then twice with a saturated NaCl solution. The combined organic phase was dried over anhydrous magnesium sulfate, filtered, and dried by column chromatography using a mixture of petroleum ether and ethyl acetate as eluent, and dried to obtain 32.01 g of anti-ultraviolet agent 1.

[0041] Structure identification:

[0042] m / z of intermediate 1 (MS+H) + Data: 370;

[0043] m / z of UV inhibitor 1 (MS+H) + Data: 741;

[0044] UV inhibitor 1 1 HNMR-CDCl3 data (see Figure Figure 1 ): δ8.93(m,1H),8.37(m,1H),8.14-7.93(m,7H),7.91-7.80(m,2H),7.77-7.67(m,2H),7.63-7.32(m,6H),6.80(d,1H).

[0045] Synthesis Example 2-Synthesis Example 4

[0046] In Synthesis Example 2-Synthesis Example 4, anti-ultraviolet agent 2-anti-ultraviolet agent 4 were synthesized in sequence, referring to the synthesis method of Synthesis Example 1, replacing raw material 2 therein, and the rest remained the same as Synthesis Example 1. Specific structures of raw material 2, anti-ultraviolet agent 2-anti-ultraviolet agent 4 structures, m / z (MS+H) + See Table 1 for data.

[0047] Table 1. Structure of raw material 2, anti-ultraviolet agent 2-anti-ultraviolet agent 4 involved in synthesis examples 2-4, m / z (MS+H) + data.

[0048]

[0049]

[0050] Example 1

[0051] This embodiment provides a specific method for preparing a highly wear-resistant plastic floor, comprising the following steps:

[0052] 1. Preparation of the wear-resistant layer raw materials. The wear-resistant layer raw materials are proportioned as follows by mass: 100 parts of polyvinyl chloride, 30 parts of plasticizer (dioctyl phthalate), 2 parts of stabilizer (methyl tin mercaptan), 1 part of lubricant (calcium stearate), 20 parts of inorganic wear-resistant particles (silicon dioxide, average particle size 5 μm), 3 parts of colorant (TiO2), and 2 parts of anti-ultraviolet agent (anti-ultraviolet agent 1 prepared by Synthesis Example 1).

[0053] 2. Preparation of wear-resistant layer:

[0054] The above raw materials were added into a high-speed mixer and mixed at 80°C for 10 minutes at 200 rpm to obtain a mixture; the mixture was transferred to an internal mixer and internally mixed at 170°C for 5 minutes to obtain an internally mixed material; the internally mixed material was pressed into a sheet through a double-roll open mill, and the mixing temperature was controlled at 160°C; the internally mixed material was rolled into a wear-resistant layer with a thickness of 0.5 mm through a four-roll calender, and the calendering temperature was maintained at 150°C to obtain a wear-resistant layer.

[0055] 3. Base layer and printing layer processing:

[0056] Base layer: Polyvinyl chloride foam plastic (thickness 5mm) is used as the base layer.

[0057] Printing layer coating: Use polyvinyl chloride ink to apply the wood grain pattern on the surface of the base layer through a gravure printing process, and then heat cure at 130°C for 2 minutes after coating.

[0058] 4. Compounding and molding:

[0059] S1. The calendered wear-resistant layer is aligned with the base layer covered with a printed layer, and the composite is compounded for 3 minutes at a composite temperature of 150°C and a composite pressure of 10MPa to form a floor body;

[0060] S2. The flooring blank is cooled to room temperature and shaped, and then cut into standard sizes (1.2m×1.8m) by cutting equipment to obtain a highly wear-resistant plastic flooring.

[0061] Example 2-Example 4

[0062] A highly wear-resistant plastic floor was prepared by referring to the preparation method of Example 1, except that the anti-ultraviolet agent was replaced with anti-ultraviolet agent 2 to anti-ultraviolet agent 4 prepared in Synthesis Examples 2 to 4, respectively, and the rest remained the same as in Example 1.

[0063] Comparative Example 1

[0064] A highly wear-resistant plastic floor was prepared by referring to the preparation method of Example 1, except that the anti-ultraviolet agent was replaced with comparative compound 1, and the rest of the preparation method remained the same as Example 1.

[0065] Comparative compound 1:

[0066] Comparative Example 2

[0067] A highly wear-resistant plastic floor was prepared by referring to the preparation method of Example 1, except that the anti-ultraviolet agent was replaced with comparative compound 2, and the rest of the preparation method remained the same as Example 1.

[0068] Comparative compound 2:

[0069] Comparative Example 3

[0070] A highly wear-resistant plastic floor was prepared by referring to the preparation method of Example 1, except that the anti-ultraviolet agent was not added, and the rest of the steps were the same as those of Example 1.

[0071] Comparative Example 4

[0072] A highly wear-resistant plastic floor was prepared by referring to the preparation method of Example 1, except that the mass fraction of the plasticizer was replaced with 10 parts, and the rest remained the same as in Example 1.

[0073] Comparative Example 5

[0074] A highly wear-resistant plastic floor was prepared by referring to the preparation method of Example 1, except that the mass fraction of polyvinyl chloride was replaced with 120 parts, and the rest remained the same as in Example 1.

[0075] Performance testing:

[0076] The wear resistance, dimensional stability and impact resistance of the highly wear-resistant plastic floor prepared in the examples and comparative examples were tested according to the method of GB / T 4085-2015. The data are shown in Table 2.

[0077] Table 2. Data on wear resistance, dimensional stability, and impact resistance of a high-wear-resistant plastic floor prepared in Examples and Comparative Examples.

[0078] Wear resistance (rotation) Dimensional stability (%) <![CDATA[Impact resistance (kJ / m 2 )]]> Example 1 25,000 0.05 12.0 Example 2 24,800 0.06 11.8 Example 3 24,500 0.08 11.5 Example 4 24,900 0.05 11.9 Comparative Example 1 18,000 0.15 8.5 Comparative Example 2 19,000 0.12 9.0 Comparative Example 3 15,000 0.14 7.0 Comparative Example 4 26,000 0.20 6.0 Comparative Example 5 23,500 0.21 8.0

[0079] The embodiment group exhibits comprehensive and excellent product performance characteristics: it maintains a high level of performance in wear resistance; dimensional stability is maintained in an extremely low range; and the overall impact strength is high with minimal fluctuations. This trend confirms the synergistic effect of specific anti-UV agents and inorganic wear-resistant particles, as well as the positive effects of formula ratio and compounding process optimization. The comparative group showed a significant differentiation phenomenon: some samples showed a trade-off between wear resistance and impact resistance, while some samples had overall deterioration in key performance. The systemic performance imbalance caused by structural defects in anti-UV agents, imbalance in plasticizer ratios, or process out-of-control further highlights the comprehensive advantages of the embodiment technical solutions.

[0080] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A highly wear-resistant plastic floor, characterized in that: It comprises, from bottom to top, a base layer (1), a printing layer (2) and a wear-resistant layer (3); The wear-resistant layer is prepared from raw materials comprising the following components in parts by mass: 100 parts of polyvinyl chloride, 20-35 parts of plasticizer, 1-4 parts of stabilizer, 0.5-2 parts of lubricant, 10-30 parts of inorganic wear-resistant particles, 0.1-5 parts of colorant, and 0.5-3 parts of anti-ultraviolet agent; The anti-ultraviolet agent has a structure shown in Formula 1: The R1 is selected from the group consisting of deuterium, phenyl, cyano, and biphenyl.

2. A highly wear-resistant plastic floor according to claim 1, characterized in that: The plasticizer is selected from: dioctyl phthalate; The stabilizer is selected from: methyltin mercaptan.

3. The high wear-resistant plastic floor according to claim 1, characterized in that: The inorganic wear-resistant particles are selected from: silicon dioxide or silicon carbide; The colorant is selected from: organic pigments and / or inorganic pigments; the organic pigments are selected from: azo pigments, phthalocyanine pigments; the inorganic pigments are selected from: TiO2, red iron oxide, carbon black.

4. The high wear-resistant plastic floor according to claim 1, characterized in that: The anti-ultraviolet agent is selected from any one of the compounds described in the following structures:

5. The high wear-resistant plastic floor according to claim 1, characterized in that: The preparation method of the wear-resistant layer (3) comprises the following steps: adding the polyvinyl chloride, plasticizer, stabilizer, lubricant, inorganic wear-resistant particles, colorant and anti-ultraviolet agent into a mixer according to the mass ratio, mixing at 60-90°C for 5-15 minutes to obtain a mixture; transferring the mixture into an internal mixer, internal mixing at 160-180°C for 3-8 minutes to obtain an internal mixing material; pressing the internal mixing material into a sheet through an open mixer, controlling the open mixing temperature at 150-170°C, to obtain an open mixing material; and rolling the open mixing material into a wear-resistant layer of a set thickness through a four-roll calender, maintaining the calendering temperature at 140-160°C.

6. The high wear-resistant plastic floor according to claim 1, characterized in that: The material of the base layer (1) is selected from: polyvinyl chloride foam plastics.

7. The high wear-resistant plastic floor according to claim 1, characterized in that: The material of the printing layer (2) is selected from: polyvinyl chloride ink.

8. A method for preparing a highly wear-resistant plastic floor according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. The mixture of the wear-resistant layer (3) is calendered by a four-roll calender, and the printed layer (2) is coated on the surface of the base layer (1); S2. At a set temperature and pressure, the calendered wear-resistant layer (3) and the base layer (1) covered with a printed layer (2) are composited to obtain a floor blank; S3. Cooling, shaping, and cutting the floor blank to obtain a highly wear-resistant plastic floor.

9. The method for preparing a high wear-resistant plastic floor according to claim 8, characterized in that: The printing layer (2) is coated by gravure printing and is subjected to a heat curing treatment at 120-150° C. for 1-3 minutes after coating.

10. The method for preparing a highly wear-resistant plastic floor according to claim 8, characterized in that: In S2, the compounding temperature is controlled at 130-160° C., the compounding pressure is 5-15 MPa, and the compounding time is 2-5 minutes.

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