Antibacterial and moisture-proof qpc floor based on nanomaterials and production process thereof

Abstract

The application belongs to the technical field of stone plastic floor, and particularly relates to an antibacterial and moisture-proof QPC floor based on nanomaterials and a production process thereof. The antibacterial and moisture-proof QPC floor comprises, from bottom to top, a mute layer, a base material layer, a color layer and a wear-resistant layer, and has excellent antibacterial and moisture-proof performances.

Description

Technical Field

[0001] This invention belongs to the field of stone-plastic flooring technology, specifically relating to an antibacterial and moisture-proof QPC flooring based on nanomaterials and its manufacturing process. Background Technology

[0002] Traditional stone-plastic flooring, also known as SPC flooring, is a composite board mainly composed of polyvinyl chloride resin, high-filled calcium powder, and various additives. SPC flooring uses calcium powder as the main raw material, and is produced through plasticized extrusion sheets, four-roll calendering, heat-applied colored film decorative layer, wear-resistant layer, etc. It does not contain heavy metals, formaldehyde, or other harmful substances, and has the advantages of being environmentally friendly, inexpensive, waterproof, moisture-proof, slip-resistant, insect-proof, flame-retardant, crack-resistant, non-deformable, pollution-free, and easy to clean. It is widely used in schools, hotels, guesthouses, KTVs, office buildings, hospitals, apartments, home decoration, and other places.

[0003] QPC flooring, made of quartz polyvinyl chloride, is a rigid-core SPC. It incorporates high-hardness quartz (SiO2) into the surface layer, significantly improving its abrasion resistance and hardness. QPC flooring achieves the highest commercial abrasion resistance standard of AC5. It combines all the advantages of SPC with enhanced durability, scratch resistance, overall transparency, dent and chisel resistance, and excellent fire and stain resistance. Furthermore, QPC flooring offers a diverse range of aesthetic choices; different colors and realistic textures can match various interior styles, combining functionality and beauty.

[0004] Existing residential flooring, especially composite flooring, is highly susceptible to bacterial growth and mold, negatively impacting people's lives and health. While antibacterial composite flooring has emerged in the market, it primarily relies on the addition of antibacterial agents. However, the antibacterial effect of this method is often limited and unsustainable; its antibacterial properties gradually weaken with use, failing to meet consumer demands. Furthermore, the moisture-proof and hydrophobic properties of QPC flooring are among its core advantages, directly determining the product's durability, dimensional stability, hygiene safety, and applicability. However, existing QPC flooring no longer meets public requirements for antibacterial and moisture-proof performance. Therefore, research on the antibacterial and moisture-proof properties of QPC flooring is of significant importance. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention aims to provide an antibacterial and moisture-proof QPC flooring based on nanomaterials and its manufacturing process, thereby solving the problems of poor antibacterial effect and inadequate moisture-proof performance of QPC flooring. To achieve the above objective, this invention adopts the following technical solution:

[0006] An antibacterial and moisture-proof QPC flooring based on nanomaterials, the antibacterial and moisture-proof QPC flooring comprising, from bottom to top, a sound-absorbing layer, a substrate layer, a pattern layer and a wear-resistant layer;

[0007] The substrate layer comprises the following components in parts by weight:

[0008] 50-80 parts of polyvinyl chloride resin

[0009] 80-120 parts of calcium carbonate

[0010] 5-10 parts calcium-zinc stabilizer

[0011] 1-10 parts of polyethylene wax

[0012] The wear-resistant layer comprises the following components in parts by weight:

[0013] 80-100 parts of modified polyvinyl chloride resin

[0014] 20-30 parts of modified nano-SiO2

[0015] 5-10 parts plasticizer

[0016] Calcium and zinc stabilizer 1-5 parts

[0017] The modified polyvinyl chloride resin is prepared by: polyvinyl chloride resin, antibacterial modifier C Modified polyvinyl chloride was obtained by reacting in the presence of an initiator;

[0018] The preparation method of modified nano-SiO2 is as follows: nano-SiO2, moisture-proof modifier B Modified nano-SiO2 was obtained by reacting under acidic conditions.

[0019] In some embodiments, the plasticizer is selected from one or more of tributyl citrate, trioctyl citrate, acetylated tributyl citrate, and acetylated trioctyl citrate.

[0020] In some embodiments, the initiator is selected from one or more of azobisisobutyronitrile, benzoyl peroxide, and dicarbonate peroxide.

[0021] In some embodiments, the calcium-zinc stabilizer of the substrate layer and the wear-resistant layer is a mixture of calcium stearate and zinc stearate, with a mass ratio of calcium stearate to zinc stearate of (1~5):1.

[0022] In some embodiments, the sound-absorbing layer is made of polystyrene foam board with a thickness of 1 to 5 mm.

[0023] In some embodiments, the patterned layer consists of a polyvinyl chloride layer and a pattern on the surface of the polyvinyl chloride layer, with a thickness of 0.1 to 1.0 mm.

[0024] This invention also provides a manufacturing process for the above-mentioned antibacterial and moisture-proof QPC flooring, comprising the following steps:

[0025] Step 1: By weight, add polyvinyl chloride resin, calcium carbonate, calcium zinc stabilizer and polyethylene wax to a high-speed mixer for hot mixing; after cooling, add the above mixture to a twin-screw extruder for heated extrusion, and then enter the sheet die for extrusion molding. The shaped sheet is then calendered to a fixed thickness to obtain the base material layer.

[0026] Step 2: By weight, add modified polyvinyl chloride, modified nano-SiO2, plasticizer, and calcium-zinc stabilizer to a high-speed mixer for hot mixing; after cooling, add the above mixture to a twin-screw extruder for heated extrusion, and then enter the sheet die for extrusion molding. The molded sheet is then processed through a four-roll calender to determine the thickness and obtain a wear-resistant layer.

[0027] Step 3: Press the sound-absorbing layer, the substrate layer obtained in Step 1, the pattern layer and the wear-resistant layer obtained in Step 2 into shape from bottom to top, and then perform finishing treatment to obtain antibacterial and moisture-proof QPC flooring.

[0028] In some implementations, the hot mixing temperature in step 1 is 120~150℃ and the hot mixing time is 1~5h; the hot mixing temperature in step 2 is 120~150℃ and the hot mixing time is 1~5h.

[0029] In some implementations, the temperatures of zones one to five of the twin-screw extruder in step 1 are 180°C, 190°C, 195°C, 200°C, and 210°C, respectively; and the temperatures of zones one to five of the twin-screw extruder in step 2 are 185°C, 190°C, 195°C, 200°C, and 205°C, respectively.

[0030] In some implementations, the thickness of the substrate layer is 5-10 mm; the thickness of the wear-resistant layer is 1-3 mm.

[0031] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0032] 1) The antibacterial modifier C of this invention can significantly improve the antibacterial properties of QPC flooring surfaces, achieving an inhibition rate of over 99.5% against Escherichia coli and Staphylococcus aureus. This is mainly due to the antibacterial modifier C. The cyclic quaternary ammonium salt structure it contains exhibits excellent inhibitory activity against Escherichia coli and Staphylococcus aureus, and its effect is superior to that of the non-cyclic quaternary ammonium salt antibacterial modifier D.

[0033] 2) The nano-SiO2 modified by the moisture-proof modifier A of this invention can greatly improve the hydrophobic properties of the QPC floor surface, with a water contact angle as high as 163°, which is mainly superior to that of moisture-proof modifier A. Triphenyl is introduced, which can significantly reduce the free energy of the floor surface, making it superhydrophobic. Water droplets are difficult to spread and wet the surface, exhibiting a "lotus effect". This significantly reduces the affinity and absorption capacity of QPC flooring for moisture, improving the flooring's moisture resistance. Detailed Implementation

[0034] The following non-limiting embodiments are intended to enable those skilled in the art to gain a more comprehensive understanding of the present invention, but do not limit the invention in any way. The following content is merely an exemplary description of the scope of protection claimed by the present invention, and those skilled in the art can make various changes and modifications to the present invention based on the disclosed content, and such changes should also fall within the scope of protection claimed by the present invention.

[0035] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The invention is further described below by way of specific embodiments. All chemical reagents used in the embodiments of this invention, unless otherwise specified, are obtained through conventional commercial means.

[0036] The modifier used in this invention has the following structure:

[0037] The structural formula of moisture-proof modifier A is: ;

[0038] The structural formula of moisture-proof modifier B is: ;

[0039] Moisture-proof modifier A and moisture-proof modifier B are compounds known in the prior art, referring to reference 1 (“Spacing and Site Isolation of Amine Groups in 3-Aminopropyl-Grafted Silica Materials: The Role of Protecting Groups”, Jason C. Hicks et al., Chem. Mater. 2006, 18, It was prepared by the method disclosed in 5022-5032.

[0040] The structural formula of antibacterial modifier C is: ;

[0041] The structural formula of antibacterial modifier D is: ;

[0042] Antibacterial modifier C and antibacterial modifier D are known compounds in the prior art and can be prepared by referring to the method disclosed in reference 2 (CN119948087A, paragraphs 139-141 of the specification).

[0043] Preparation Example 1: Preparation of Nano-SiO2 Modified by Moisture-proof Modifier A

[0044] Nano-SiO2 (produced by Shanghai Changbei Nanomaterials Technology Co., Ltd., with an average particle size of 100 nm) (20.0 g) was dissolved in anhydrous ethanol (100 mL) and ultrasonically dispersed for 1 h to obtain a nano-SiO2 ethanol solution. Then, moisture-proof modifier A was added. (5.0 g) was added to the above nano-SiO2 ethanol solution, and the pH of the system was adjusted to about 2-3 using 1M hydrochloric acid solution. The temperature was raised to 70℃ and the reaction was stirred for 3 h. After the reaction was completed, the solid was separated by centrifugation, washed three times with anhydrous ethanol, dried under vacuum at 100℃ for 12 h, and ground to obtain modified nano-SiO2.

[0045] Preparation Example 2: Preparation of Nano-SiO2 Modified by Moisture-proof Modifier B

[0046] Nano-SiO2 (produced by Shanghai Changbei Nanomaterials Technology Co., Ltd., with an average particle size of 100 nm) (20.0 g) was dissolved in anhydrous ethanol (100 mL) and ultrasonically dispersed for 1 h to obtain a nano-SiO2 ethanol solution. Then, moisture-proof modifier B was added. (5.0 g) was added to the above nano-SiO2 ethanol solution, and the pH of the system was adjusted to about 2-3 using 1M hydrochloric acid solution. The temperature was raised to 70℃ and the reaction was stirred for 3 h. After the reaction was completed, the solid was separated by centrifugation, washed three times with anhydrous ethanol, dried under vacuum at 100℃ for 12 h, and ground to obtain modified nano-SiO2.

[0047] Preparation Example 3: Preparation of polyvinyl chloride modified with antibacterial modifier C

[0048] 100.0 g of polyvinyl chloride resin (PVC-SG8, produced by Xinjiang Tianye Group Co., Ltd.) and 200 mL of toluene were added to the reactor, followed by the addition of antibacterial modifier C. 10.0g of benzoyl peroxide (1.0g) and the initiator were mixed evenly and then heated to 80℃ and stirred for 6 hours. After the reaction was completed, the reaction solution was distilled under reduced pressure and dried under vacuum to obtain modified polyvinyl chloride.

[0049] Preparation Example 4: Preparation of polyvinyl chloride modified with antibacterial modifier C

[0050] 100.0 g of polyvinyl chloride resin (PVC-SG8, produced by Xinjiang Tianye Group Co., Ltd.) and 200 mL of toluene were added to the reactor, followed by the addition of antibacterial modifier D. 10.0g of benzoyl peroxide (1.0g) and the initiator were mixed evenly and then heated to 80℃ and stirred for 6 hours. After the reaction was completed, the reaction solution was distilled under reduced pressure and dried under vacuum to obtain modified polyvinyl chloride.

[0051] Example 1

[0052] A manufacturing process for antibacterial and moisture-proof QPC flooring based on nanomaterials, wherein the QPC flooring comprises a sound-absorbing layer, a substrate layer, a pattern layer, and a wear-resistant layer arranged sequentially from bottom to top, including the following steps:

[0053] Step 1: By weight, add 50 parts of polyvinyl chloride resin (PVC-SG8, produced by Xinjiang Tianye Group Co., Ltd.), 100 parts of calcium carbonate, 5 parts of calcium-zinc stabilizer, and 1 part of polyethylene wax to a high-speed mixer for hot mixing at 140°C for 1.5 hours. After cooling to 40°C, add the mixture to a twin-screw extruder for heated extrusion, then extrude it through a sheet die. The formed sheet is then calendered to a fixed thickness to obtain a substrate layer with a thickness of 6 mm. The calcium-zinc stabilizer is a mixture of calcium stearate and zinc stearate in a mass ratio of 2:1. The temperatures of zones one to five of the twin-screw extruder are 180°C, 190°C, 195°C, 200°C, and 210°C, respectively.

[0054] Step 2: By weight, 100 parts of polyvinyl chloride modified with antibacterial modifier C obtained in Preparation Example 3, 20 parts of nano-SiO2 modified with moisture-proof modifier A obtained in Preparation Example 1, 5 parts of tributyl citrate, and 2 parts of calcium-zinc stabilizer were added to a high-speed mixer for hot mixing at 150°C for 2.0 hours. After cooling to 50°C, the mixture was added to a twin-screw extruder for heated extrusion, and then extruded into a sheet die. The formed sheet was then calendered to a fixed thickness to obtain a wear-resistant layer with a thickness of 1.5 mm. The calcium-zinc stabilizer was composed of calcium stearate and zinc stearate in a mass ratio of 2:1. The temperatures of zones one to five of the twin-screw extruder were 185°C, 190°C, 195°C, 200°C, and 205°C, respectively.

[0055] Step 3: Press the sound-absorbing layer, the substrate layer obtained in Step 1, the pattern layer, and the wear-resistant layer obtained in Step 2 sequentially from bottom to top, and then perform finishing treatment to obtain antibacterial and moisture-proof QPC flooring; wherein, the sound-absorbing layer is made of polystyrene foam board with a thickness of 2mm; the pattern layer is composed of a polyvinyl chloride layer and a pattern on the surface of the polyvinyl chloride layer with a thickness of 0.2mm.

[0056] Example 2

[0057] A manufacturing process for antibacterial and moisture-proof QPC flooring based on nanomaterials, wherein the QPC flooring comprises a sound-absorbing layer, a substrate layer, a pattern layer, and a wear-resistant layer arranged sequentially from bottom to top, including the following steps:

[0058] Step 1: By weight, 60 parts of polyvinyl chloride resin (PVC-SG8, produced by Xinjiang Tianye Group Co., Ltd.), 90 parts of calcium carbonate, 10 parts of calcium-zinc stabilizer, and 2 parts of polyethylene wax are added to a high-speed mixer for hot mixing at 140°C for 1.5 hours. After cooling to 40°C, the mixture is added to a twin-screw extruder for heated extrusion, and then extruded through a sheet die. The formed sheet is then calendered to a fixed thickness to obtain a substrate layer with a thickness of 6 mm. The calcium-zinc stabilizer is a mixture of calcium stearate and zinc stearate in a mass ratio of 3:1. The temperatures of zones one to five of the twin-screw extruder are 180°C, 190°C, 195°C, 200°C, and 210°C, respectively.

[0059] Step 2: By weight, 90 parts of polyvinyl chloride modified with antibacterial modifier C obtained in Preparation Example 3, 30 parts of nano-SiO2 modified with moisture-proof modifier A obtained in Preparation Example 1, 10 parts of tributyl citrate, and 2 parts of calcium-zinc stabilizer were added to a high-speed mixer for hot mixing at 150°C for 2.0 hours. After cooling to 50°C, the mixture was added to a twin-screw extruder for heated extrusion, and then extruded into a sheet die. The formed sheet was then calendered to a fixed thickness to obtain a wear-resistant layer with a thickness of 1.5 mm. The calcium-zinc stabilizer was composed of calcium stearate and zinc stearate in a mass ratio of 3:1. The temperatures of zones one to five of the twin-screw extruder were 185°C, 190°C, 195°C, 200°C, and 205°C, respectively.

[0060] Step 3: Press the sound-absorbing layer, the substrate layer obtained in Step 1, the pattern layer, and the wear-resistant layer obtained in Step 2 sequentially from bottom to top, and then perform finishing treatment to obtain antibacterial and moisture-proof QPC flooring; wherein, the sound-absorbing layer is made of polystyrene foam board with a thickness of 2mm; the pattern layer is composed of a polyvinyl chloride layer and a pattern on the surface of the polyvinyl chloride layer with a thickness of 0.2mm.

[0061] Comparative Example 1

[0062] Based on Example 1, the polyvinyl chloride modified by antibacterial modifier C in step 2 was replaced with unmodified polyvinyl chloride resin, and other operating steps and conditions were the same as in Example 1.

[0063] Comparative Example 2

[0064] Based on Example 1, the polyvinyl chloride modified with antibacterial modifier C in step 2 is replaced with polyvinyl chloride modified with antibacterial modifier D, and other operating steps and conditions are the same as in Example 1.

[0065] Comparative Example 3

[0066] Based on Example 1, the nano-SiO2 modified by moisture-proof modifier A in step 2 was replaced with unmodified nano-SiO2, and other operating steps and conditions were the same as in Example 1.

[0067] Comparative Example 4

[0068] Based on Example 1, the nano-SiO2 modified by moisture-proof modifier A in step 2 is replaced with nano-SiO2 modified by moisture-proof modifier B, and other operating steps and conditions are the same as in Example 1.

[0069] Performance testing

[0070] The antibacterial properties and surface hydrophobic properties of the QPC flooring prepared in Examples 1-2 and Comparative Examples 1-4 were tested using the following methods:

[0071] 1) Antibacterial properties: The test was conducted in accordance with the method of QB / T2591-2003 "Test method for antibacterial properties and antibacterial effect of antibacterial plastics". The bacteria used for testing were: Escherichia coli ATCC25922 and Staphylococcus aureus ATCC6538.

[0072] 2) The surface water contact angle of the QPC floor was tested using an optical contact angle meter (SZ-CAMC13, Shanghai Xuanzhun Instrument Co., Ltd.), and the results are shown in Table 1.

[0073]

[0074] As shown in Example 1 and Comparative Examples 1 and 2, the antibacterial modifier C-modified polyvinyl chloride can significantly improve the antibacterial properties of QPC flooring surfaces, achieving an inhibition rate of over 99.5% against both Escherichia coli and Staphylococcus aureus. This is mainly due to the antibacterial modifier C. The cyclic quaternary ammonium salt structure it contains exhibits excellent inhibitory activity against Escherichia coli and Staphylococcus aureus, and its effect is superior to that of the non-cyclic quaternary ammonium salt antibacterial modifier D.

[0075] As shown in Example 1 and Comparative Examples 3 and 4, the nano-SiO2 modified by moisture-proof modifier A can significantly improve the hydrophobicity of the QPC floor surface, with a water contact angle reaching 163°. This is mainly due to its superior performance compared to moisture-proof modifier A. Triphenyl is introduced, which can significantly reduce the free energy of the floor surface, making it superhydrophobic. Water droplets are difficult to spread and wet the surface, exhibiting a "lotus effect". This significantly reduces the affinity and absorption capacity of QPC flooring for moisture, improving the flooring's moisture resistance.

[0076] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. An antibacterial and moisture-proof QPC flooring based on nanomaterials, characterized in that, The antibacterial and moisture-proof QPC flooring includes, from bottom to top, a sound-absorbing layer, a substrate layer, a pattern layer, and a wear-resistant layer. The substrate layer comprises the following components in parts by weight: 50-80 parts of polyvinyl chloride resin 80-120 parts of calcium carbonate 5-10 parts calcium-zinc stabilizer 1-10 parts of polyethylene wax The wear-resistant layer comprises the following components in parts by weight: 80-100 parts of modified polyvinyl chloride resin 20-30 parts of modified nano-SiO2 5-10 parts plasticizer Calcium and zinc stabilizer 1-5 parts The modified polyvinyl chloride resin is prepared by: polyvinyl chloride resin, antibacterial modifier C Modified polyvinyl chloride was obtained by reacting in the presence of an initiator; The preparation method of modified nano-SiO2 is as follows: nano-SiO2, moisture-proof modifier A Modified nano-SiO2 was obtained by reacting under acidic conditions.

2. The antibacterial and moisture-proof QPC flooring according to claim 1, characterized in that, The plasticizer is selected from one or more of tributyl citrate, trioctyl citrate, acetylated tributyl citrate, and acetylated trioctyl citrate.

3. The antibacterial and moisture-proof QPC flooring according to claim 1, characterized in that, The initiator is selected from one or more of azobisisobutyronitrile, benzoyl peroxide, and dicarbonate peroxide.

4. The antibacterial and moisture-proof QPC flooring according to claim 1, characterized in that, The calcium-zinc stabilizer of the substrate layer and the wear-resistant layer is composed of calcium stearate and zinc stearate, with a mass ratio of calcium stearate to zinc stearate of (1~5):

1.

5. The antibacterial and moisture-proof QPC flooring according to claim 1, characterized in that, The sound-absorbing layer is made of polystyrene foam board with a thickness of 1~5 mm.

6. The antibacterial and moisture-proof QPC flooring according to claim 1, characterized in that, The patterned layer consists of a polyvinyl chloride layer and a pattern on the surface of the polyvinyl chloride layer, with a thickness of 0.1~1.0 mm.

7. A manufacturing process for antibacterial and moisture-proof QPC flooring according to any one of claims 1 to 6, comprising the following steps: Step 1: Add polyvinyl chloride resin, calcium carbonate, calcium zinc stabilizer, and polyethylene wax to a high-speed mixer for hot mixing according to the weight parts; After cooling, the above mixture is added to a twin-screw extruder for heating and extrusion, and then enters a sheet die for extrusion molding. The shaped sheet is then passed through a four-roll calender for thickness determination to obtain the base material layer. Step 2: By weight, add modified polyvinyl chloride, modified nano-SiO2, plasticizer, and calcium-zinc stabilizer to a high-speed mixer for hot mixing; after cooling, add the above mixture to a twin-screw extruder for heated extrusion, and then enter the sheet die for extrusion molding. The molded sheet is then processed through a four-roll calender to determine the thickness and obtain a wear-resistant layer. Step 3: Press the sound-absorbing layer, the substrate layer obtained in Step 1, the pattern layer and the wear-resistant layer obtained in Step 2 into shape from bottom to top, and then perform finishing treatment to obtain antibacterial and moisture-proof QPC flooring.

8. The production process according to claim 7, characterized in that, The hot mixing temperature in step 1 is 120~150℃ and the hot mixing time is 1~5h; the hot mixing temperature in step 2 is 120~150℃ and the hot mixing time is 1~5h.

9. The production process according to claim 7, characterized in that, In step 1, the temperatures of zones 1 to 5 of the twin-screw extruder are 180℃, 190℃, 195℃, 200℃, and 210℃, respectively; in step 2, the temperatures of zones 1 to 5 of the twin-screw extruder are 185℃, 190℃, 195℃, 200℃, and 205℃, respectively.

10. The production process according to claim 7, characterized in that, The thickness of the substrate layer is 5~10mm; the thickness of the wear-resistant layer is 1~3mm.

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