A high wear-resistant plastic flooring and its preparation method

Abstract

This invention discloses a high-wear-resistant plastic flooring and its preparation method, relating to the field of polyvinyl chloride composite materials technology. The high-wear-resistant plastic flooring comprises, from bottom to top, a base layer, a printed layer, and a wear-resistant layer. The wear-resistant layer is prepared from raw materials containing the following components in parts by weight: 100 parts polyvinyl chloride, 20-35 parts plasticizer, 1-4 parts stabilizer, 0.5-2 parts lubricant, 10-30 parts inorganic wear-resistant particles, 0.1-5 parts colorant, and 0.5-3 parts UV stabilizer. The deuterated groups in the UV stabilizer stabilize the molecular structure through isotope effects, while the biphenyl / phenyl groups provide steric hindrance to inhibit migration. Combined with the thiol methyltin stabilizer's blocking effect on degradation reactions, a multiple protection mechanism is formed. This synergistic system can efficiently absorb / scatter ultraviolet light, significantly delaying aging phenomena such as fading and embrittlement of the material.

Description

Technical Field

[0001] This invention relates to the field of polyvinyl chloride composite materials technology, specifically to a high wear-resistant plastic flooring and its preparation method. Background Technology

[0002] With the widespread application of vinyl flooring, existing technologies present several pressing issues. Traditional vinyl flooring primarily uses polyvinyl chloride (PVC) as its base material. While it possesses a degree of flexibility and ease of processing, its wear resistance is poor, making it unsuitable for long-term use in high-traffic areas such as shopping malls and hospitals. Furthermore, most traditional vinyl flooring lacks sufficient UV resistance, and prolonged exposure to sunlight can easily lead to fading and aging, affecting its appearance and shortening its lifespan.

[0003] From a material composition perspective, the wear layer of traditional PVC flooring typically contains only basic components such as polyvinyl chloride (PVC) and plasticizers, lacking effective reinforcing additives. The choice of plasticizers is also relatively limited, mostly phthalates. These plasticizers are prone to migration during long-term use, leading to a decline in material performance. Furthermore, the amount and types of UV stabilizers in current technology are limited, failing to form a stable protective system and effectively blocking UV rays from damaging the flooring material. Simultaneously, the bonding strength between the printed layer and the base layer of traditional PVC flooring is insufficient, easily leading to problems such as printed layer peeling and wear, affecting the overall decorative and functional properties of the flooring.

[0004] Existing PVC flooring manufacturing processes also have shortcomings, such as insufficient precision in controlling parameters like calendering temperature and compounding pressure, leading to unstable product performance and requiring improvements in production efficiency and product quality. Therefore, providing a PVC flooring with high wear resistance, excellent UV resistance, and an optimized manufacturing process has become a pressing technical challenge in this field. Summary of the Invention

[0005] The purpose of this invention is to address the problems existing in the prior art by providing a plastic flooring with high wear resistance, excellent UV resistance, and optimized manufacturing process, thereby improving service life and aesthetics.

[0006] To achieve the above objectives, the technical solution adopted by the present invention is: a high wear-resistant plastic flooring, comprising, 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 containing the following components in parts by weight: 100 parts polyvinyl chloride, 20-35 parts plasticizer, 1-4 parts stabilizer, 0.5-2 parts lubricant, 10-30 parts inorganic wear-resistant particles, 0.1-5 parts colorant, and 0.5-3 parts UV protectant.

[0008] The UV-resistant agent has the structure shown in Formula 1:

[0009]

[0010] R1 is selected from: deuterium, phenyl, cyano, biphenyl.

[0011] Furthermore, the plasticizer is selected from dioctyl phthalate; the stabilizer is selected from methyl tin 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 pigment is selected from: azo pigments and phthalocyanine pigments; the inorganic pigment is selected from: TiO2, iron oxide red, and carbon black.

[0013] Furthermore, the UV stabilizer is selected from any one of the compounds described below:

[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 UV stabilizer into a mixer according to the mass ratio, and mixing at 60-90℃ for 5-15 minutes to obtain a mixture; transferring the mixture to an internal mixer and internally mixing at 160-180℃ for 3-8 minutes to obtain an internally mixed material; pressing the internally mixed material into sheets using an open mill, with the open mill temperature controlled at 150-170℃ to obtain an open mill material; and calendering the open mill material into a wear-resistant layer of a set thickness using a four-roll calender, with the calendering temperature maintained at 140-160℃.

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

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

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

[0019] S1. The mixture of the wear-resistant layer is calendered using a four-roll calender, while the printing layer is coated onto the surface of the base layer.

[0020] S2. Under set temperature and pressure, the wear-resistant layer formed by calendering is combined with the base layer covered with the printed layer to obtain the floor blank;

[0021] S3. The floor blank is cooled, shaped, and cut to obtain a high wear-resistant plastic floor.

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

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

[0024] The UV-resistant agent described in this invention contains a conjugated large π-bond system and strongly polar groups in its molecular structure, enabling it to effectively absorb ultraviolet light in the wavelength range of 280-400 nm (especially the UV-A and UV-B bands). After absorbing ultraviolet light, the molecule transitions from the ground state to an excited state, and then releases energy as heat through a non-radiative relaxation process (such as vibrational relaxation), preventing energy transfer to the polyvinyl chloride (PVC) molecular chain and thus avoiding degradation. The deuterium in the R1 group enhances the stability of the intramolecular CH bonds through isotope effects, reducing the generation of free radicals; the biphenyl / phenyl group provides steric hindrance, reducing the migration rate of the UV-resistant agent in the plasticizer and extending the protective life. Combined with inorganic wear-resistant particles (such as silica and silicon carbide): the inorganic particles can scatter part of the ultraviolet light, reducing the direct exposure and forming a physical-chemical dual protective layer with the UV-resistant agent. Synergistically with thiol methyltin stabilizers: it inhibits the dehydrochlorination reaction of PVC and blocks the chain reaction of oxidative degradation initiated by ultraviolet light.

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

[0026] The UV stabilizer, stabilizer, and inorganic wear-resistant particle components of this invention synergistically enhance UV resistance and aging resistance. The UV stabilizer can efficiently absorb 280-400nm ultraviolet light (covering the UV-A / B bands), converting light energy into heat energy. It enhances CH bond stability through isotope effects, inhibits free radical generation, provides steric hindrance, reduces the migration rate of the UV stabilizer in plasticizers, and prolongs the protective effect. The stabilizer can inhibit the UV-induced dehydrochlorination reaction of PVC, block the oxidative degradation chain reaction, and form a chemical synergistic protection with the UV stabilizer. The inorganic wear-resistant particles scatter part of the ultraviolet light, reducing the direct exposure, and form a physical-chemical dual barrier with the UV stabilizer.

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

[0028] Compared with the prior art, the beneficial effects of the present invention are:

[0029] 1. Simultaneous improvement in wear resistance and impact resistance: Through the synergistic effect of a specific UV stabilizer (Formula 1 structure) and inorganic wear-resistant particles, surface hardness and wear resistance are significantly enhanced while maintaining material flexibility. Meanwhile, optimized plasticizer dosage (20-35 parts) avoids the contradiction between high wear resistance and low impact resistance in traditional formulations, achieving simultaneous enhancement of both properties.

[0030] 2. Significantly enhanced UV resistance and aging resistance: The deuterated groups in the UV stabilizer stabilize the molecular structure through isotope effects, while the biphenyl / phenyl groups provide steric hindrance to inhibit migration. Combined with the thiol methyltin stabilizer's blocking effect on degradation reactions, a multi-layered protection mechanism is formed. This synergistic system can efficiently absorb / scatter ultraviolet light, significantly delaying aging phenomena such as fading and embrittlement of materials.

[0031] 3. Optimized interlayer bonding and dimensional stability: Gravure printing combined with precise thermosetting process improves the adhesion between the printed layer and the base layer; composite process parameter control significantly reduces the heat shrinkage rate through effective entanglement of molecular chain segments, ensuring that the flooring has no risk of delamination or warping during long-term use. Attached Figure Description

[0032] Figure 1 The UV protectant 1 described in this invention 1 HNMR image.

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

[0034] 1 is the base layer, 2 is the printing layer, and 3 is the wear-resistant layer. Detailed Implementation

[0035] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Obviously, the described embodiments are merely some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] Synthesis example 1

[0037] Synthesis of UV stabilizer 1:

[0038]

[0039] Step 1: 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(dibenzylacetone)dipalladium, 0.7 g of tri-tert-butylphosphine, and 200 g of toluene were added sequentially to the reaction system. The mixture was stirred until homogeneous, heated to 110 °C, and refluxed for 12 h. After the reaction was completed, the temperature was slightly lowered, and the mixture was filtered using diatomaceous earth. The filtrate was cooled to room temperature and washed three times with water, retaining the organic phase. The aqueous phase was then extracted with ethyl acetate. The organic phases were combined, dried with anhydrous magnesium sulfate, filtered, evaporated to dryness, and subjected to column chromatography using a mixture of petroleum ether and ethyl acetate as eluent. The solution was evaporated to dryness 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 sequentially to the reaction system. 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. The temperature was raised to 85 °C and the reaction was heated for 16 h. After cooling, the reaction mixture was extracted with ammonia solution and methyl tert-butyl ether. The organic phase was washed five times with water and then twice with saturated NaCl solution. The combined organic phase was dried with anhydrous magnesium sulfate, filtered, evaporated to dryness, and subjected to column chromatography. Petroleum ether and ethyl acetate were used as eluents, and the mixture was evaporated to dryness to obtain 32.01 g of UV stabilizer 1.

[0041] Structural assessment:

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

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

[0044] UV protectant 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 Examples 2-4, UV stabilizer 2 and UV stabilizer 4 were synthesized sequentially, following the same synthesis method as in Synthesis Example 1, except that raw material 2 was replaced; the rest remained the same as in Synthesis Example 1. Specific structures of raw material 2, UV stabilizer 2-UV stabilizer 4, and m / z (MS+H) are detailed below. + The data is shown in Table 1.

[0047] Table 1. Structures of raw material 2, UV stabilizer 2-UV stabilizer 4, and m / z (MS+H) involved in Synthesis Examples 2-4 + data.

[0048]

[0049]

[0050] Example 1

[0051] This embodiment provides a specific method for preparing high wear-resistant plastic flooring, including the following steps:

[0052] 1. Preparation of wear-resistant layer raw materials: The wear-resistant layer raw materials are prepared in the following proportions by weight: 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 (silica, average particle size 5 μm), 3 parts of colorant (TiO2), and 2 parts of UV stabilizer (UV stabilizer 1 prepared using synthesis example 1).

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

[0054] The above raw materials are added to a high-speed mixer and mixed at 200 rpm and 80°C for 10 minutes to obtain a mixture. The mixture is then transferred to an internal mixer and internally mixed at 170°C for 5 minutes to obtain an internally mixed material. The internally mixed material is then pressed into sheets using a two-roll open mill, with the open mill temperature controlled at 160°C. The open mill material is then calendered into a wear-resistant layer with a thickness of 0.5 mm using a four-roll calender, with the calendering temperature maintained at 150°C to obtain the wear-resistant layer.

[0055] 3. Treatment of the base layer and printing layer:

[0056] Substrate layer: Polyvinyl chloride foam (5mm thick) is used as the substrate layer.

[0057] Printing layer coating: Using polyvinyl chloride ink, the wood grain pattern is coated onto the surface of the base layer through gravure printing. After coating, it is heat-cured at 130°C for 2 minutes.

[0058] 4. Composite and molding:

[0059] S1. Align the calendered wear-resistant layer with the base layer covered with the printed layer, and laminate for 3 minutes at a lamination temperature of 150℃ and a lamination pressure of 10MPa to form a floor blank;

[0060] S2. Cool the flooring blank to room temperature to set, and cut it into standard size (1.2m×1.8m) using a cutting device to obtain a high wear-resistant plastic flooring.

[0061] Examples 2-4

[0062] The preparation of a high wear-resistant plastic flooring is carried out by referring to the preparation method of Example 1, except that the UV-resistant agent is replaced in sequence with UV-resistant agent 2-UV-resistant agent 4 prepared in Synthesis Examples 2-4, and the rest is the same as in Example 1.

[0063] Comparative Example 1

[0064] The preparation of a high wear-resistant plastic flooring is carried out by referring to the preparation method of Example 1, except that the UV inhibitor is replaced with comparative compound 1, and the rest is the same as in Example 1.

[0065] Comparative compound 1:

[0066] Comparative Example 2

[0067] The preparation of a high wear-resistant plastic flooring is carried out by referring to the preparation method of Example 1, except that the UV stabilizer is replaced with comparative compound 2, and the rest is the same as in Example 1.

[0068] Comparative compound 2:

[0069] Comparative Example 3

[0070] The preparation of a high wear-resistant plastic flooring is the same as in Example 1, except that the UV stabilizer is not added.

[0071] Comparative Example 4

[0072] The preparation of a high wear-resistant plastic flooring is carried out by referring to the preparation method of Example 1, except that the mass fraction of the plasticizer is replaced with 10 parts, and the rest remains the same as in Example 1.

[0073] Comparative Example 5

[0074] The preparation of a high wear-resistant plastic flooring is carried out by referring to the preparation method of Example 1, except that the mass fraction of polyvinyl chloride is replaced with 120 parts, and the rest remains the same as in Example 1.

[0075] Performance testing:

[0076] The abrasion resistance, dimensional stability, and impact resistance of the high abrasion-resistant plastic flooring 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 the abrasion resistance, dimensional stability, and impact resistance of a high abrasion-resistant plastic flooring prepared in the examples and comparative examples.

[0078] Abrasion resistance (excerpt) 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 example group exhibited comprehensive and superior product performance characteristics: consistently high levels of abrasion resistance; extremely low dimensional stability; and consistently high impact strength with minimal fluctuations. This trend confirms the synergistic effect of specific UV stabilizers and inorganic abrasion-resistant particles, as well as the positive effects of optimized formulation ratios and composite processes. The comparative group, however, showed significant divergence: some samples exhibited a trade-off between abrasion resistance and impact resistance, while others showed comprehensive deterioration in key performance characteristics. Systemic performance imbalances caused by UV stabilizer structural defects, plasticizer ratio imbalances, or process malfunctions further highlight the comprehensive advantages of the example group's technical solutions.

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

Claims

1. A high wear resistant plastic floor, characterized in that, The base layer (1), the printing layer (2) and the wear-resistant layer (3) are sequentially arranged from bottom to top. The wear-resistant layer is prepared from raw materials comprising the following components 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 ultraviolet-resistant agent. The ultraviolet-resistant agent has the structure shown in Formula 1. Formula 1; The R1 is selected from deuterium, phenyl, cyano, and biphenyl. The stabilizer is selected from thiol methyl tin.

2. The high wear-resistant plastic floor as claimed in claim 1, wherein, The inorganic wear-resistant particles are selected from silicon dioxide or silicon carbide. The plasticizer is selected from dioctyl phthalate. The colorant is selected from organic pigments and / or inorganic pigments; the organic pigments are selected from azo pigments and phthalocyanine pigments; and the inorganic pigments are selected from TiO2, red iron oxide, and carbon black.

3. The high wear-resistant plastic floor as claimed in claim 1, wherein, The preparation method of the wear-resistant layer (3) comprises the following steps: the polyvinyl chloride, plasticizer, stabilizer, lubricant, inorganic wear-resistant particles, colorant, and ultraviolet-resistant agent are added into a mixer in a mass ratio, mixed at 60-90°C for 5-15 minutes to obtain a mixture; the mixture is transferred into an internal mixer, and internally mixed at 160-180°C for 3-8 minutes to obtain an internal mixture; the internal mixture is pressed into a sheet by an open mill, and the open mill temperature is controlled at 150-170°C to obtain an open mixture; and the open mixture is calendered into a wear-resistant layer with a set thickness by a four-roll calender, and the calendering temperature is maintained at 140-160°C.

4. The high wear-resistant plastic floor as claimed in claim 1, wherein, The material of the base layer (1) is selected from polyvinyl chloride foam plastics.

5. The high wear-resistant plastic floor as claimed in claim 1, wherein, The material of the printing layer (2) is selected from polyvinyl chloride ink.

6. The method for preparing the high wear-resistant plastic floor according to any one of claims 1-5, characterized in that, The method comprises the following steps: S1. The mixture of the wear-resistant layer (3) is calendered by a four-roll calender, and the printing layer (2) is coated on the surface of the base layer (1); S2. The calendered wear-resistant layer (3) is combined with the base layer (1) coated with the printing layer (2) at a set temperature and pressure to obtain a floor blank; S3. The floor blank is cooled, shaped, cut, and a high-wear plastic floor is obtained.

7. The method for preparing the high wear-resistant plastic floor according to claim 6, characterized in that, The coating method of the printing layer (2) is gravure printing, and the coating is heat-cured at 120-150°C for 1-3 minutes.

8. The method for preparing a high wear-resistant plastic flooring according to claim 6, characterized in that, In S2, the composite temperature is controlled at 130-160°C, the composite pressure is 5-15 MPa, and the composite time is 2-5 minutes.

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