A long-lasting bacteriostatic polyvinyl chloride film composition and a method for preparing the same

Abstract

The application discloses a long-acting bacteriostatic polyvinyl chloride film composition and a preparation method thereof, and belongs to the technical field of long-acting bacteriostatic materials and preparation methods thereof, and comprises polyvinyl chloride resin, quaternary ammonium salt, hyperbranched polymer, modified epoxy soybean oil, surface active stabilizer, plasticizer, filler, toughening agent and lubricant; the polyvinyl chloride film material of the application has high antibacterial activity and stable and durable antibacterial performance due to the addition of the quaternary ammonium salt and the hyperbranched polymer; and the modified epoxy soybean oil in the formula system of the composition serves as a dispersant, so that the material has good dispersibility, and also serves as an environment-friendly plasticizer of the matrix composite material, thereby improving the plasticity of the composite material and being green, healthy and environment-friendly.

Description

Technical Field

[0001] This invention relates to the technical field of long-acting antibacterial materials and their preparation methods, and particularly to a long-acting antibacterial polyvinyl chloride film composition and its preparation method. Background Technology

[0002] Polyvinyl chloride (PVC) is a polymer formed by the polymerization of vinyl chloride monomer (VCM) through a free radical polymerization mechanism under the action of initiators such as peroxides and azo compounds, or under the influence of light and heat. Vinyl chloride homopolymers and vinyl chloride copolymers are collectively referred to as vinyl chloride resins.

[0003] Polyvinyl chloride (PVC) film is made from PVC resin and other modifiers through calendering or blow molding. It is typically 0.08-0.2 mm thick; films thicker than 0.25 mm are called PVC sheets. Plasticizers, stabilizers, lubricants, and other functional processing aids are added to PVC resin, which is then calendered into a film. This type of film has good heat retention and light transmission, is flexible and easy to shape, making it suitable as an outer covering material for greenhouses, sheds, and small to medium-sized sheds.

[0004] Chinese patent CN202010518685.4 discloses an antibacterial polyvinyl chloride (PVC) film and its preparation method. This patented antibacterial PVC film uses silver ions as the effective antibacterial component, exhibiting effective and long-lasting inhibition against *Escherichia coli*, *Staphylococcus aureus*, and *Klebsiella pneumoniae*. The silver ion content in the raw material of the antibacterial PVC film provided by this invention is lower than that of commonly available silver-containing PVC films, yet it achieves stronger and more durable antibacterial properties. However, the silver ion antibacterial agent in this technology suffers from problems such as easy discoloration, manufacturing difficulties, and complex processes in its use in materials.

[0005] The problems with polyvinyl chloride (PVC) films using silver ions as antibacterial agents in the prior art are as follows: (1) The free silver ions in the PVC film are easily reduced to elemental silver under sunlight or after being heated to a certain temperature, resulting in gray or brown color, which affects the color of the product; (2) Generally, silver ions need to be supported by a carrier. Due to the role of the carrier, the silver-loaded antibacterial agent will seriously affect the light transmittance of the product, especially film-type plastic products; (3) Due to the high cost of silver raw materials, the cost of silver-based antibacterial agents has remained high; (4) PVC films prepared using silver ions as antibacterial agents have poor antifungal and antimold effects. Summary of the Invention

[0006] To address the above problems, this invention provides a long-lasting antibacterial polyvinyl chloride film composition and its preparation method. The contents of this invention are as follows:

[0007] The first objective of this invention is to provide a long-lasting antibacterial polyvinyl chloride film composition, the technical point of which is that, by weight, it comprises 100 parts by weight of polyvinyl chloride resin, 0.5-0.9 parts by weight of quaternary ammonium salt, 1.0-3.0 parts by weight of hyperbranched polymer, 2.0-3.0 parts by weight of modified epoxidized soybean oil, 1.5-3.0 parts by weight of surfactant stabilizer, 10-30 parts by weight of plasticizer, 10-20 parts by weight of filler, 2-6 parts by weight of toughening agent, and 0.1-0.2 parts by weight of lubricant.

[0008] In some embodiments of the present invention, the hyperbranched polymer in the above-mentioned long-lasting antibacterial polyvinyl chloride film composition is at least one of hyperbranched polyamide-amine, hyperbranched polyethyleneimine, hyperbranched polyester, and hyperbranched polyurethane.

[0009] In some embodiments of the present invention, the modified epoxidized soybean oil in the above-mentioned long-acting antibacterial polyvinyl chloride film composition is modified with acrylic acid, wherein the acrylic acid grafting rate of the modified epoxidized soybean oil is 20-80%, and the epoxy value of the modified epoxidized soybean oil is 0.5-3.0%.

[0010] In some embodiments of the present invention, the surface active stabilizer in the above-mentioned long-acting antibacterial polyvinyl chloride film composition is at least one of alkylphenol polyoxyethylene ether series surface active stabilizers, fatty alcohol polyoxyethylene ether series surface active stabilizers, and fatty acid polyoxyethylene ether series surface active stabilizers.

[0011] In some embodiments of the present invention, the plasticizer in the above-mentioned long-lasting antibacterial polyvinyl chloride film composition is at least one of polyol ester plasticizer, polyester plasticizer, citrate ester plasticizer and phthalate ester plasticizer.

[0012] In some embodiments of the present invention, the filler in the above-mentioned long-lasting antibacterial polyvinyl chloride film composition is at least one selected from starch, cellulose, wood flour, straw powder, calcium carbonate, mica, talc, halloysite, wollastonite, silica and carbon black.

[0013] In some embodiments of the present invention, the toughening agent in the above-mentioned long-lasting antibacterial polyvinyl chloride film composition is at least one selected from methyl methacrylate-butadiene-styrene terpolymer, styrene-butadiene thermoplastic elastomer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, and polyamide resin.

[0014] In some embodiments of the present invention, the lubricant in the above-mentioned long-lasting antibacterial polyvinyl chloride film composition is at least one of polyethylene glycol lubricants, fluoropolymer lubricants, organosilicon lubricants, fatty alcohol lubricants, fatty acid lubricants, fatty acid ester lubricants, stearamide lubricants, fatty acid metal soap lubricants, alkane and oxidized alkane lubricants, and micro / nanoparticle lubricants.

[0015] The second objective of this invention is to provide a method for preparing a long-lasting antibacterial polyvinyl chloride film, the technical point of which is that it includes the following steps:

[0016] Step 1, Grinding: The modified epoxidized soybean oil, surfactant stabilizer, plasticizer, filler and lubricant are ground into a slurry using a three-roll mill, which is beneficial for material dispersion;

[0017] Step 2: High-speed mixing and feeding: While adding polyvinyl chloride resin during the high-speed, low-speed mixing stage, add quaternary ammonium salt and hyperbranched polymer; when the high-speed mixing starts at high speed, the toughening agent is automatically metered and fed, and after mixing, it is added to the ground slurry for grinding.

[0018] Process parameters: High-speed stage: speed 600-1000 rpm, time 300-500s;

[0019] Low-speed stage: speed 300-500 rpm, time 120-300 s; material temperature controlled at 110-130℃ at the end of high-speed stirring;

[0020] Step 3, film making: The materials prepared in step 2 are fed into the mixing and plasticizing machine. The plasticizing and degassing of the open mill is fed into the filter to remove impurities. The material is then fed into the calender. The PVC film sheet produced by calendering is drawn away by the traction roller, expanded and widened, cooled and shaped, and then wound up to obtain a long-lasting antibacterial polyvinyl chloride film.

[0021] In some embodiments of the present invention, the grinding in steps one and two of the above-mentioned method for preparing long-lasting antibacterial polyvinyl chloride film is performed no less than three times.

[0022] Compared with the prior art, the long-lasting antibacterial polyvinyl chloride film composition and its preparation method of the present invention have the following beneficial effects:

[0023] 1. A long-lasting antibacterial polyvinyl chloride (PVC) film composition of the present invention comprises polyvinyl chloride resin, quaternary ammonium salt, hyperbranched polymer, modified epoxidized soybean oil, surfactant stabilizer, plasticizer, filler, toughening agent and lubricant. The PVC film material of the present invention contains quaternary ammonium salt and hyperbranched polymer, which have high antibacterial activity and long-lasting and stable antibacterial performance.

[0024] 2. The modified epoxidized soybean oil in the long-lasting antibacterial polyvinyl chloride film composition of the present invention is modified with acrylic acid. The modified epoxidized soybean oil has an acrylic acid grafting rate of 20-80% and an epoxy value of 0.5-3.0%. The modified epoxidized soybean oil of the present invention acts as a dispersant in the formulation system of the composition, which not only gives the material good dispersibility, but also acts as an environmentally friendly plasticizer for the matrix composite material, which improves the plasticity of the composite material and is green, healthy and environmentally friendly. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the technical solutions of this invention will be clearly and completely described below in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0026] Example 1

[0027] A long-lasting antibacterial polyvinyl chloride film composition comprises the following components:

[0028] 100kg of polyvinyl chloride resin: In this example, polyvinyl chloride S-1000 from a company in Ningbo was selected;

[0029] 0.9 kg of quaternary ammonium salt: In this example, quaternary ammonium salt-73 from a company in Wuhan was selected;

[0030] 3.0 kg of hyperbranched polymer: hyperbranched polyethyleneimine;

[0031] 3.0 kg of modified epoxidized soybean oil: The modified epoxidized soybean oil is modified with acrylic acid, wherein the acrylic acid grafting rate of the modified epoxidized soybean oil is 80%, and the epoxy value of the modified epoxidized soybean oil is 0.5%.

[0032] 3.0 kg of surfactant stabilizer: fatty alcohol polyoxyethylene ether series surfactant stabilizers;

[0033] 30kg of plasticizer: polyester plasticizer;

[0034] 20kg of filler: cellulose;

[0035] 6 kg of toughening agent: styrene-butadiene thermoplastic elastomer;

[0036] 0.2kg of lubricant: fluoropolymer lubricant.

[0037] According to the above formula, the preparation method of a long-lasting antibacterial polyvinyl chloride film of this embodiment includes the following steps:

[0038] Step 1, Grinding: The modified epoxidized soybean oil, surfactant stabilizer, plasticizer, filler and lubricant are ground at least three times using a three-roll mill to make a slurry, which is beneficial for material dispersion;

[0039] Step 2: High-speed mixing and feeding: While adding polyvinyl chloride resin during the high-speed low-speed mixing stage, add quaternary ammonium salt and hyperbranched polymer; when the high-speed mixing starts at high speed, the toughening agent is automatically metered and fed. After mixing, add the ground slurry and grind it at least three times.

[0040] Process parameters: High-speed stage: speed 1000 rpm, time 300 s;

[0041] Low-speed stage: speed 500 rpm, time 120 s; material temperature controlled at 130℃ at the end of high-speed stirring;

[0042] Step 3, film making: The materials prepared in step 2 are fed into the mixing and plasticizing machine. The plasticizing and degassing of the open mill is fed into the filter to remove impurities. The material is then fed into the calender. The PVC film sheet produced by calendering is drawn away by the traction roller, expanded and widened, cooled and shaped, and then wound up to obtain a long-lasting antibacterial polyvinyl chloride film.

[0043] Example 2

[0044] A long-lasting antibacterial polyvinyl chloride film composition comprises the following components:

[0045] 100kg of polyvinyl chloride resin: In this example, polyvinyl chloride SG-8 from a company in Qingdao was selected;

[0046] 0.5 kg of quaternary ammonium salt: In this example, quaternary ammonium salt-7 from a company in Shandong Province was selected;

[0047] 1.0 kg of hyperbranched polymer: hyperbranched polyamide-amine;

[0048] 2.0 kg of modified epoxidized soybean oil: The modified epoxidized soybean oil is modified with acrylic acid, wherein the acrylic acid grafting rate of the modified epoxidized soybean oil is 20%, and the epoxy value of the modified epoxidized soybean oil is 0.5%.

[0049] 1.5 kg of surfactant stabilizer: alkylphenol polyoxyethylene ether series surfactant stabilizers;

[0050] 10kg of plasticizer: polyol ester plasticizer;

[0051] 10kg of filler: starch;

[0052] 2kg of toughening agent: methyl methacrylate-butadiene-styrene terpolymer;

[0053] 0.1kg of lubricant: polyethylene glycol-based lubricant.

[0054] According to the above formula, the preparation method of a long-lasting antibacterial polyvinyl chloride film of this embodiment includes the following steps:

[0055] Step 1, Grinding: The modified epoxidized soybean oil, surfactant stabilizer, plasticizer, filler and lubricant are ground at least three times using a three-roll mill to make a slurry, which is beneficial for material dispersion;

[0056] Step 2: High-speed mixing and feeding: While adding polyvinyl chloride resin during the high-speed low-speed mixing stage, add quaternary ammonium salt and hyperbranched polymer; when the high-speed mixing starts at high speed, the toughening agent is automatically metered and fed. After mixing, add the ground slurry and grind it at least three times.

[0057] Process parameters: High-speed stage: speed 600 rpm, time 500 s;

[0058] Low-speed stage: speed 300 rpm, time 300 s; material temperature controlled at 110℃ at the end of high-speed stirring;

[0059] Step 3, film making: The materials prepared in step 2 are fed into the mixing and plasticizing machine. The plasticizing and degassing of the open mill is fed into the filter to remove impurities. The material is then fed into the calender. The PVC film sheet produced by calendering is drawn away by the traction roller, expanded and widened, cooled and shaped, and then wound up to obtain a long-lasting antibacterial polyvinyl chloride film.

[0060] Example 3

[0061] A long-lasting antibacterial polyvinyl chloride film composition comprises the following components:

[0062] 100kg of polyvinyl chloride resin: In this example, polyvinyl chloride A2165 from a company in Dongguan was selected;

[0063] 0.7 kg of quaternary ammonium salt: In this example, quaternary ammonium salt-10 from a company in Guangdong was selected;

[0064] 2.0 kg of hyperbranched polymers: hyperbranched polyester and hyperbranched polyurethane;

[0065] 2.5 kg of modified epoxidized soybean oil: The modified epoxidized soybean oil is modified with acrylic acid, wherein the acrylic acid grafting rate of the modified epoxidized soybean oil is 50%, and the epoxy value of the modified epoxidized soybean oil is 1.75%.

[0066] 2.25 kg of surfactant stabilizer: fatty acid polyoxyethylene ether series surfactant stabilizers;

[0067] 20kg of plasticizer: citrate ester plasticizer;

[0068] 15kg of filler: wood flour;

[0069] 4 kg of toughening agent: acrylonitrile-butadiene-styrene copolymer;

[0070] 0.15kg of lubricant: silicone-based lubricant.

[0071] According to the above formula, the preparation method of a long-lasting antibacterial polyvinyl chloride film of this embodiment includes the following steps:

[0072] Step 1, Grinding: The modified epoxidized soybean oil, surfactant stabilizer, plasticizer, filler and lubricant are ground at least three times using a three-roll mill to make a slurry, which is beneficial for material dispersion;

[0073] Step 2: High-speed mixing and feeding: While adding polyvinyl chloride resin during the high-speed low-speed mixing stage, add quaternary ammonium salt and hyperbranched polymer; when the high-speed mixing starts at high speed, the toughening agent is automatically metered and fed. After mixing, add the ground slurry and grind it at least three times.

[0074] Process parameters: High-speed stage: speed 800 rpm, time 400 s;

[0075] Low-speed stage: speed 400 rpm, time 210 s; material temperature controlled at 120℃ at the end of high-speed stirring;

[0076] Step 3, film making: The materials prepared in step 2 are fed into the mixing and plasticizing machine. The plasticizing and degassing of the open mill is fed into the filter to remove impurities. The material is then fed into the calender. The PVC film sheet produced by calendering is drawn away by the traction roller, expanded and widened, cooled and shaped, and then wound up to obtain a long-lasting antibacterial polyvinyl chloride film.

[0077] Test case

[0078] The long-lasting antibacterial polyvinyl chloride (PVC) films prepared in Examples 1-3, Comparative Example 1 (without the addition of "hyperbranched polymer," otherwise the same as Example 1), Comparative Example 2 (the amount of "quaternary ammonium salt" added was 0.3 kg, otherwise the same as Example 1), and Comparative Example 3 (the "modified epoxidized soybean oil" in Example 1 was replaced with "epoxidized soybean oil," otherwise the same as Example 1) were subjected to antibacterial experiments. The antibacterial test standard was QB / T2591-2003A, "Test Methods and Antibacterial Effects of Antibacterial Plastics." The bacteria used for testing were: Staphylococcus aureus ATCC6538, Escherichia coli ATCC25922, Aspergillus niger ATCC6257, and Trichoderma oxytetracycline AS3.3935. The test results are shown in Table 1.

[0079] Table 1

[0080]

[0081]

[0082] The above description is merely an embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention should be included within the scope of the claims of the present invention.

Claims

1. A long-lasting antibacterial polyvinyl chloride film composition, characterized in that, The product comprises, by weight, 100 parts polyvinyl chloride resin, 0.5-0.9 parts quaternary ammonium salt, 1.0-3.0 parts hyperbranched polymer, 2.0-3.0 parts modified epoxidized soybean oil, 1.5-3.0 parts surfactant stabilizer, 10-30 parts plasticizer, 10-20 parts filler, 2-6 parts toughening agent, and 0.1-0.2 parts lubricant; the modified epoxidized soybean oil is modified with acrylic acid, the acrylic acid grafting rate of the modified epoxidized soybean oil is 20-80%, and the epoxy value of the modified epoxidized soybean oil is 0.5-3.0%; the hyperbranched polymer is at least one of hyperbranched polyethyleneimine and hyperbranched polyamide-amine.

2. The long-lasting antibacterial polyvinyl chloride film composition according to claim 1, characterized in that, The surfactant is at least one of the following: alkylphenol polyoxyethylene ether series surfactants, fatty alcohol polyoxyethylene ether series surfactants, and fatty acid polyoxyethylene ether series surfactants.

3. The long-lasting antibacterial polyvinyl chloride film composition according to claim 1, characterized in that, The plasticizer is at least one of polyol ester plasticizers, polyester plasticizers, citrate ester plasticizers, and phthalate ester plasticizers.

4. The long-lasting antibacterial polyvinyl chloride film composition according to claim 1, characterized in that, The filler is at least one of starch, cellulose, wood flour, straw powder, calcium carbonate, mica, talc, halloysite, wollastonite, silicon dioxide, and carbon black.

5. The long-lasting antibacterial polyvinyl chloride film composition according to claim 1, characterized in that, The toughening agent is at least one of the following: methyl methacrylate-butadiene-styrene terpolymer, styrene-butadiene thermoplastic elastomer, acrylonitrile-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, and polyamide resin.

6. The long-lasting antibacterial polyvinyl chloride film composition according to claim 1, characterized in that, The lubricant is at least one of the following: polyethylene glycol lubricant, fluoropolymer lubricant, organosilicon lubricant, fatty alcohol lubricant, fatty acid lubricant, fatty acid ester lubricant, stearamide lubricant, fatty acid metal soap lubricant, alkane and oxidized alkane lubricant, and micro / nanoparticle lubricant.

7. A method for preparing a long-lasting antibacterial polyvinyl chloride film, characterized in that, Includes the following steps: Step 1, Grinding: Grind 2.0-3.0 parts by weight of modified epoxidized soybean oil, 1.5-3.0 parts by weight of surfactant stabilizer, 10-30 parts by weight of plasticizer, 10-20 parts by weight of filler and 0.1-0.2 parts by weight of lubricant into a slurry using a three-roll mill. This facilitates material dispersion. The modified epoxidized soybean oil is modified with acrylic acid, and the acrylic acid grafting rate of the modified epoxidized soybean oil is 20-80%. Step 2: High-speed mixing and feeding: During the high-speed, low-speed mixing stage, 100 parts by weight of polyvinyl chloride resin are added, along with 0.5-0.9 parts by weight of quaternary ammonium salt and 1.0-3.0 parts by weight of hyperbranched polymer. When the high-speed mixing reaches high speed, 2-6 parts by weight of toughening agent are automatically metered and fed in. After mixing, the mixture is added to the ground slurry for further grinding. The epoxy value of the modified epoxidized soybean oil is 0.5-3.0%. The hyperbranched polymer is at least one of hyperbranched polyethyleneimine and hyperbranched polyamide-amine. Process parameters: High-speed stage: speed 600-1000 r / min, time 300-500 s; Low-speed stage: speed 300-500 r / min, time 120-300 s; material temperature controlled at 110-130℃ at the end of high-speed stirring; Step 3, film making: The materials prepared in step 2 are fed into the mixing and plasticizing machine. The plasticizing and degassing of the open mill is fed into the filter to remove impurities. The material is then fed into the calender. The PVC film sheet produced by calendering is drawn away by the traction roller, expanded and widened, cooled and shaped, and then wound up to obtain a long-lasting antibacterial polyvinyl chloride film.

8. The method for preparing a long-lasting antibacterial polyvinyl chloride film according to claim 7, characterized in that, The grinding in steps one and two shall be performed no less than three times.

Images