Antibacterial and damp-proof QPC floor based on nanometer materials and production process of antibacterial and damp-proof QPC floor

Abstract

The invention belongs to the technical field of stone-plastic floors, and particularly relates to an antibacterial damp-proof QPC floor based on a nano material and a production process of the antibacterial damp-proof QPC floor. The antibacterial and moisture-proof QPC floor comprises the mute layer, the base material layer, the pattern layer and the wear-resistant layer which are sequentially arranged from bottom to top, and has excellent antibacterial performance and moisture-proof performance.

Description

Technical Field

[0001] The present invention belongs to the technical field of stone plastic flooring, and in particular relates to an antibacterial and moisture-proof QPC flooring based on nanomaterials and a production process thereof. Background Art

[0002] Traditional stone plastic flooring, also known as SPC flooring, is a composite baseboard mainly composed of polyvinyl chloride resin, high-filler calcium powder and various additives. SPC flooring uses calcium powder as the main raw material, and is plasticized and extruded into sheets, four-roll calendered and hot-applied with a color film decorative layer and a wear-resistant layer. It does not contain heavy metals, formaldehyde and other harmful substances. It is environmentally friendly, inexpensive, waterproof, moisture-proof, anti-slip, insect-proof, flame retardant, no cracking, no deformation, no pollution, 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, a quartz polyvinylchloride (SPC) flooring with a rigid core, incorporates a high-hardness quartz component (SiO2) into the surface layer, significantly improving the surface's wear resistance and hardness. QPC flooring can achieve the highest commercial wear resistance standard, AC5. It combines all the advantages of SPC with increased durability, improved scratch resistance, improved overall clarity, improved resistance to dents and gouges, and superior flame and stain resistance. Furthermore, QPC flooring offers a variety of aesthetic options, with different colors and realistic textures to suit any interior style, combining functionality with aesthetics.

[0004] Existing household flooring, especially laminate flooring, is highly susceptible to bacterial growth and mold, negatively impacting people's lives and health. While laminate flooring with antimicrobial properties is now available on the market, it primarily relies on the addition of antimicrobial agents. However, this approach often offers limited and persistent antimicrobial effectiveness. With extended use, the antimicrobial properties gradually diminish, failing to meet consumer antimicrobial performance requirements. Furthermore, QPC flooring's moisture resistance and hydrophobicity are core strengths, directly impacting its durability, dimensional stability, hygienic safety, and applicability. However, existing QPC flooring no longer meets public expectations for antimicrobial and moisture resistance, necessitating research into its antimicrobial and moisture-resistant properties. Summary of the Invention

[0005] In response to the shortcomings of the existing technology, the present invention aims to provide an antibacterial and moisture-proof QPC flooring based on nanomaterials and its production process to solve the problems of poor antibacterial effect and moisture-proof performance of QPC flooring. To achieve the above objectives, the present invention adopts the following technical solutions: An antibacterial and moisture-proof QPC floor based on nanomaterials, comprising a silent layer, a base material layer, a pattern layer, and a wear-resistant layer arranged in sequence from bottom to top; The substrate layer comprises the following components in parts by weight: 50~80 parts of polyvinyl chloride resin 80-120 parts 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 Modified nano-SiO2 20~30 parts 5~10 parts of plasticizer 1~5 parts calcium zinc stabilizer The preparation method of the modified polyvinyl chloride resin is as follows: polyvinyl chloride resin, antibacterial modifier C The modified polyvinyl chloride is obtained by reacting in the presence of an initiator; The preparation method of modified nano-SiO2 is as follows: nano-SiO2, moisture-proof modifier B The modified nano-SiO2 is obtained by reacting under acidic conditions.

[0006] In some embodiments, the plasticizer is selected from one or more of tributyl citrate, trioctyl citrate, acetyl tributyl citrate, and acetyl trioctyl citrate.

[0007] In some embodiments, the initiator is selected from one or more of azobisisoheptanenitrile, dibenzoyl peroxide, and peroxydicarbonate.

[0008] 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, and the mass ratio of calcium stearate to zinc stearate is (1-5):1.

[0009] In some embodiments, the sound-proof layer is made of a polystyrene foam board and has a thickness of 1 to 5 mm.

[0010] In some embodiments, the pattern layer consists of a polyvinyl chloride layer and a pattern located on the surface of the polyvinyl chloride layer, and has a thickness of 0.1-1.0 mm.

[0011] The present invention also provides a production process for the antibacterial and moisture-proof QPC floor, comprising the following steps: Step 1: Add polyvinyl chloride resin, calcium carbonate, calcium zinc stabilizer, and polyethylene wax by weight into a high-speed mixer for hot mixing; after cooling, add the above mixture into a twin-screw extruder for heating and extrusion, and then enter the sheet die for extrusion molding. The formed sheet is passed through a four-roll calender to adjust the thickness to obtain a substrate layer; Step 2: adding modified polyvinyl chloride, modified nano-SiO2, plasticizer, and calcium zinc stabilizer to a high-speed mixer for hot mixing according to weight; after cooling, adding the above mixture to a twin-screw extruder for heating and extrusion, and then entering a sheet die for extrusion molding, and the formed sheet is passed through a four-roll calender to adjust the thickness to obtain a wear-resistant layer; Step 3: From bottom to top, the sound-proof layer, the base material layer obtained in step 1, the pattern layer and the wear-resistant layer obtained in step 2 are pressed into shape, and then trimmed to obtain the antibacterial and moisture-proof QPC floor.

[0012] In some embodiments, the hot mixing temperature of step 1 is 120-150° C. and the hot mixing time is 1-5 hours; the hot mixing temperature of step 2 is 120-150° C. and the hot mixing time is 1-5 hours.

[0013] In some embodiments, the temperatures of zones 1 to 5 of the twin-screw extruder in step 1 are 180°C, 190°C, 195°C, 200°C, and 210°C, respectively; the temperatures of zones 1 to 5 of the twin-screw extruder in step 2 are 185°C, 190°C, 195°C, 200°C, and 205°C, respectively.

[0014] In some embodiments, the thickness of the substrate layer is 5 to 10 mm; the thickness of the wear-resistant layer is 1 to 3 mm. Compared with the prior art, the present invention has the following beneficial effects: 1) The polyvinyl chloride modified with the antibacterial modifier C of the present invention can greatly improve the antibacterial performance of the QPC floor surface, and the antibacterial rates against Escherichia coli and Staphylococcus aureus are both above 99.5%. This is mainly because the antibacterial modifier C The cyclic quaternary ammonium salt structure it contains has excellent inhibitory activity against Escherichia coli and Staphylococcus aureus, and its effect is better than that of the non-cyclic quaternary ammonium salt antibacterial modifier D; 2) Nano-SiO2 modified by moisture-proof modifier A of the present invention can greatly improve the hydrophobicity of the QPC floor surface, and its water contact angle can be as high as 163°, which is mainly superior to moisture-proof modifier A. The introduction of triphenyl can significantly reduce the free energy of the floor surface, making it super-hydrophobic. It is difficult for water droplets to spread and wet the surface, showing a "lotus effect", thereby significantly reducing the QPC floor's affinity and absorption capacity for water and improving the floor's moisture-proof performance. DETAILED DESCRIPTION

[0015] The following non-limiting examples are provided to enable those skilled in the art to more fully understand the present invention, but are not intended to limit the present invention in any way. The following are merely illustrative of the scope of the present invention, and those skilled in the art may make various changes and modifications to the present invention based on the disclosed content, which should also fall within the scope of the present invention.

[0016] When the embodiments provide numerical ranges, it should be understood that, unless otherwise specified herein, both endpoints of each numerical range and any numerical value between the two endpoints can be selected. Unless otherwise defined, all technical and scientific terms used in the present invention have the same meanings as those generally understood by those of ordinary skill in the art to which the present invention belongs. The present invention will be further described below in the form of specific embodiments. The various chemical reagents used in the embodiments of the present invention are all obtained through conventional commercial channels unless otherwise specified.

[0017] The modifier structure used in the present invention is as follows: The structural formula of moisture-proof modifier A is: ; The structural formula of moisture-proof modifier B is: ; Moisture-proof modifier A and moisture-proof modifier B are compounds known in the prior art, as described in 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, 5022-5032) were prepared by the method disclosed in

[0018] The structural formula of antimicrobial modifier C is: ; The structural formula of antimicrobial modifier D is: ; Antibacterial modifier C and antibacterial modifier D are compounds known in the prior art and can be prepared according to the method disclosed in Reference 2 (CN119948087A, paragraphs 139-141 of the specification).

[0019] Preparation Example 1 Preparation of Nano-SiO2 Modified by Moisture-Proof Modifier A Nano-SiO2 (produced by Shanghai Changbei Nanomaterial 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. Add 5.0 g of dapoxetine to the above nano-SiO2 ethanol solution, adjust the pH of the system to approximately 2-3 with 1 M hydrochloric acid solution, heat to 70°C, and stir for 3 hours. After the reaction, centrifuge, wash the solid three times with anhydrous ethanol, dry in vacuo at 100°C for 12 hours, and grind to obtain modified nano-SiO2.

[0020] Preparation Example 2 Preparation of Nano-SiO2 Modified by Moisture-Proof Modifier B Nano-SiO2 (produced by Shanghai Changbei Nanomaterial Technology Co., Ltd., with an average particle size of 100nm) (20.0g) was dissolved in anhydrous ethanol (100mL) and ultrasonically dispersed for 1h to obtain nano-SiO2 ethanol solution. Add 5.0 g of dapoxetine to the above nano-SiO2 ethanol solution, adjust the pH of the system to approximately 2-3 with 1 M hydrochloric acid solution, heat to 70°C, and stir for 3 hours. After the reaction, centrifuge, wash the solid three times with anhydrous ethanol, dry in vacuo at 100°C for 12 hours, and grind to obtain modified nano-SiO2.

[0021] Preparation Example 3 Preparation of polyvinyl chloride modified with antibacterial modifier C Polyvinyl chloride resin (PVC-SG8, produced by Xinjiang Tianye Group Co., Ltd.) (100.0 g) and toluene (200 mL) were added to the reactor, and then the antibacterial modifier C was added. (10.0 g) and initiator dibenzoyl peroxide (1.0 g) were mixed evenly, then heated to 80 ° C and stirred for reaction for 6 h. After the reaction was completed, the reaction liquid was distilled under reduced pressure and vacuum dried to obtain modified polyvinyl chloride.

[0022] Preparation Example 4 Preparation of polyvinyl chloride modified with antibacterial modifier C Polyvinyl chloride resin (PVC-SG8, produced by Xinjiang Tianye Group Co., Ltd.) (100.0 g) and toluene (200 mL) were added to the reactor, and then the antibacterial modifier D was added. (10.0 g) and initiator dibenzoyl peroxide (1.0 g) were mixed evenly, then heated to 80 ° C and stirred for reaction for 6 h. After the reaction was completed, the reaction liquid was distilled under reduced pressure and vacuum dried to obtain modified polyvinyl chloride.

[0023] Example 1 A production process for an antibacterial and moisture-proof QPC floor based on nanomaterials, wherein the QPC floor comprises a sound-proof layer, a base material layer, a pattern layer, and a wear-resistant layer arranged in sequence from bottom to top, comprising the following steps: Step 1: by weight, 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 are added to a high-speed mixer for hot mixing at a temperature of 140°C and a hot mixing time of 1.5 hours; after cooling to 40°C, the mixture is added to a twin-screw extruder for heating and extrusion, and then enters a sheet die for extrusion molding, and the molded sheet is passed through a four-roll calender and then the thickness is fixed to obtain a substrate layer with a thickness of 6 mm; wherein the calcium zinc stabilizer is a mixture of calcium stearate and zinc stearate, and the mass ratio of calcium stearate to zinc stearate is 2:1; the temperatures of zones 1 to 5 of the twin-screw extruder are 180°C, 190°C, 195°C, 200°C, and 210°C, respectively; Step 2: By weight, 100 parts of polyvinyl chloride modified with the antibacterial modifier C obtained in Preparation Example 3, 20 parts of nano-SiO2 modified with the moisture-proof modifier A obtained in Preparation Example 1, 5 parts of tributyl citrate, and 2 parts of calcium zinc stabilizer are added to a high-speed mixer for hot mixing at a temperature of 150°C for 2.0 hours; after cooling to 50°C, the mixture is added to a twin-screw extruder for heated extrusion, and then enters a sheet die for extrusion molding. The formed sheet is passed through a four-roll calender and then the thickness is fixed to obtain a wear-resistant layer with a thickness of 1.5 mm; wherein the calcium zinc stabilizer is a mixture of calcium stearate and zinc stearate, and the mass ratio of calcium stearate to zinc stearate is 2:1; the temperatures of zones 1 to 5 of the twin-screw extruder are 185°C, 190°C, 195°C, 200°C, and 205°C, respectively; Step 3: Pressing the silent layer, the base material 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 finishing them to obtain the antibacterial and moisture-proof QPC floor; wherein the silent layer is prepared from a polystyrene foam board and has a thickness of 2 mm; the pattern layer is composed of a polyvinyl chloride layer and a pattern located on the surface of the polyvinyl chloride layer, and has a thickness of 0.2 mm.

[0024] Example 2 A production process for an antibacterial and moisture-proof QPC floor based on nanomaterials, wherein the QPC floor comprises a sound-proof layer, a base material layer, a pattern layer, and a wear-resistant layer arranged in sequence from bottom to top, comprising the following steps: 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 a temperature of 140°C and a hot mixing time of 1.5 hours; after cooling to 40°C, the above mixture is added to a twin-screw extruder for heating and extrusion, and then enters a sheet die for extrusion molding, and the molded sheet is passed through a four-roll calender and then the thickness is fixed to obtain a substrate layer with a thickness of 6 mm; wherein the calcium zinc stabilizer is a mixture of calcium stearate and zinc stearate, and the mass ratio of calcium stearate to zinc stearate is 3:1; the temperatures of zones 1 to 5 of the twin-screw extruder are 180°C, 190°C, 195°C, 200°C, and 210°C, respectively; Step 2: By weight, 90 parts of polyvinyl chloride modified with the antibacterial modifier C obtained in Preparation Example 3, 30 parts of nano-SiO2 modified with the moisture-proof modifier A obtained in Preparation Example 1, 10 parts of tributyl citrate, and 2 parts of calcium zinc stabilizer are added to a high-speed mixer for hot mixing at a temperature of 150°C for 2.0 hours; after cooling to 50°C, the mixture is added to a twin-screw extruder for heated extrusion, and then enters a sheet die for extrusion molding. The formed sheet is passed through a four-roll calender and then the thickness is fixed to obtain a wear-resistant layer with a thickness of 1.5 mm; wherein the calcium zinc stabilizer is a mixture of calcium stearate and zinc stearate, and the mass ratio of calcium stearate to zinc stearate is 3:1; the temperatures of zones 1 to 5 of the twin-screw extruder are 185°C, 190°C, 195°C, 200°C, and 205°C, respectively; Step 3: Pressing the silent layer, the base material 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 finishing them to obtain the antibacterial and moisture-proof QPC floor; wherein the silent layer is prepared from a polystyrene foam board and has a thickness of 2 mm; the pattern layer is composed of a polyvinyl chloride layer and a pattern located on the surface of the polyvinyl chloride layer, and has a thickness of 0.2 mm.

[0025] Comparative Example 1 On the basis of Example 1, the polyvinyl chloride modified with the antibacterial modifier C in step 2 was replaced with unmodified polyvinyl chloride resin, and the other operating steps and conditions were the same as those in Example 1.

[0026] Comparative Example 2 On the basis of Example 1, the polyvinyl chloride modified with the antibacterial modifier C in step 2 was replaced with polyvinyl chloride modified with the antibacterial modifier D, and the other operating steps and conditions were the same as those in Example 1.

[0027] Comparative Example 3 On the basis of Example 1, the nano-SiO2 modified with the moisture-proof modifier A in step 2 is replaced with unmodified nano-SiO2, and the other operating steps and conditions are the same as those in Example 1.

[0028] Comparative Example 4 On the basis of Example 1, the nano-SiO2 modified by moisture-proof modifier A in step 2 is replaced by nano-SiO2 modified by moisture-proof modifier B, and the other operating steps and conditions are the same as in Example 1.

[0029] Performance Testing The antibacterial properties and surface hydrophobic properties of the QPC floors prepared in Examples 1-2 and Comparative Examples 1-4 were tested using the following test methods: 1) Antibacterial performance: The test was conducted in accordance with QB / T2591-2003 “Test method for antibacterial performance and antibacterial effect of antibacterial plastics”. The test bacteria were Escherichia coli ATCC25922 and Staphylococcus aureus ATCC6538.

[0030] 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.). The results are shown in Table 1.

[0031] It can be seen from Example 1 and Comparative Examples 1 and 2 that the polyvinyl chloride modified with antibacterial modifier C can greatly improve the antibacterial performance of the QPC floor surface, and the antibacterial rates against Escherichia coli and Staphylococcus aureus are both above 99.5%. This is mainly because the antibacterial modifier C The cyclic quaternary ammonium salt structure it contains has excellent inhibitory activity against Escherichia coli and Staphylococcus aureus, and its effect is better than that of the non-cyclic quaternary ammonium salt antibacterial modifier D; It can be seen from Example 1 and Comparative Examples 3 and 4 that the nano-SiO2 modified by moisture-proof modifier A can greatly improve the hydrophobicity of the QPC floor surface, and the water contact angle can reach 163°, which is mainly superior to moisture-proof modifier A. The introduction of triphenyl can significantly reduce the free energy of the floor surface, making it super-hydrophobic. It is difficult for water droplets to spread and wet the surface, showing a "lotus effect", thereby significantly reducing the QPC floor's affinity and absorption capacity for water and improving the floor's moisture-proof performance.

[0032] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. An antibacterial and moisture-proof QPC floor based on nanomaterials, characterized in that: The antibacterial and moisture-proof QPC floor comprises a silent layer, a base material layer, a pattern layer and a wear-resistant layer arranged in sequence from bottom to top; The substrate layer comprises the following components in parts by weight: 50~80 parts of polyvinyl chloride resin 80-120 parts 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 Modified nano-SiO2 20~30 parts 5~10 parts of plasticizer 1~5 parts calcium zinc stabilizer The preparation method of the modified polyvinyl chloride resin is as follows: polyvinyl chloride resin, antibacterial modifier C The modified polyvinyl chloride is obtained by reacting in the presence of an initiator; The preparation method of modified nano-SiO2 is as follows: nano-SiO2, moisture-proof modifier B The modified nano-SiO2 is obtained by reacting under acidic conditions.

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

3. The antibacterial and moisture-proof QPC floor according to claim 1, characterized in that: The initiator is selected from one or more of azobisisoheptanenitrile, dibenzoyl peroxide, and peroxydicarbonate.

4. The antibacterial and moisture-proof QPC floor according to claim 1, characterized in that: The calcium zinc stabilizer for the substrate layer and the wear-resistant layer is prepared by mixing calcium stearate and zinc stearate, and the mass ratio of calcium stearate to zinc stearate is (1-5):

1.

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

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

7. A production process for the antibacterial and moisture-proof QPC floor 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 into a high-speed mixer and heat mix; After cooling, the mixed material is added to a twin-screw extruder for heating and extrusion, and then enters a sheet die for extrusion molding. The formed sheet is passed through a four-roll calender to adjust the thickness to obtain a substrate layer; Step 2: adding modified polyvinyl chloride, modified nano-SiO2, plasticizer, and calcium zinc stabilizer to a high-speed mixer for hot mixing according to weight; after cooling, adding the above mixture to a twin-screw extruder for heating and extrusion, and then entering a sheet die for extrusion molding, and the formed sheet is passed through a four-roll calender to adjust the thickness to obtain a wear-resistant layer; Step 3: From bottom to top, the sound-proof layer, the base material layer obtained in step 1, the pattern layer and the wear-resistant layer obtained in step 2 are pressed into shape, and then trimmed to obtain the antibacterial and moisture-proof QPC floor.

8. The production process according to claim 7, characterized in that: The hot mixing temperature of step 1 is 120-150° C. and the hot mixing time is 1-5 hours; the hot mixing temperature of step 2 is 120-150° C. and the hot mixing time is 1-5 hours.

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

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

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