Antibacterial and water-resistant aluminum-plastic composite hose and preparation method thereof

Abstract

The invention discloses an antibacterial and water-resistant aluminum-plastic composite hose and a preparation method thereof, and belongs to the technical field of aluminum-plastic pipes. The antibacterial and water-resistant aluminum-plastic composite hose provided by the invention comprises the following components: a pipe head and a pipe body, wherein the pipe body is formed by overlapping antibacterial and water-resistant aluminum-plastic composite sheets, and the antibacterial and water-resistant aluminum-plastic composite sheets sequentially comprise an outer PE film, a hyperbranched copolymer, an aluminum foil, an ethylene-methacrylic acid copolymer and an inner PE film; the hyperbranched copolymer and the ethylene-methacrylic acid copolymer are cross-linked and copolymerized by an acrylate cross-linking agent and a mercapto-silicone ether cross-linking agent. The hyperbranched copolymer provided by the invention can meet the requirements of the aluminum-plastic composite hose for peeling strength as an adhesive layer, and the aluminum-plastic composite hose also has good tensile strength, water-proof and oil-resistant effects and antibacterial properties.

Description

Technical Field

[0001] The invention relates to the technical field of aluminum-plastic pipes, in particular to an antibacterial and water-resistant aluminum-plastic composite hose and a preparation method thereof. Background Art

[0002] Hose packaging refers to a soft packaging container used to package paste-like or liquid products with high viscosity. It has the characteristics of light weight, easy to carry, strong and durable, recyclable, easy to squeeze, good processing performance and printing adaptability, etc. At the same time, it is cheap compared to plastic bottle packaging, so it is widely favored by cosmetics and other manufacturers. At present, the composite hose packaging materials used in toothpaste, cosmetics, medicines and other products on the market are mainly aluminum-plastic composite or all-plastic composite structures. Aluminum-plastic composite hose is a packaging container made of aluminum foil and plastic film through co-extrusion composite process, and then processed into a tube by a special tube making machine. Its typical structure is PE / PE+EAA+AL+EAA+PE. Among them, aluminum foil is used as a barrier layer, which has excellent barrier properties such as light barrier, oxygen barrier and water barrier. With the continuous improvement of technology, the thickness of the aluminum foil barrier layer in the aluminum-plastic composite hose has been reduced from the traditional 40μm to 12μm, or even 9μm, which greatly saves resources. However, some studies have found that due to the thinness of the overall sheet, some problems have occurred in the packaging process of toothpaste, such as the penetration of the inner PE film of the composite hose after the composite hose is loaded with toothpaste containing lipid flavors, and after a period of time, the PE film is penetrated, causing the adhesive layer to dissolve, so that the inner PE film is separated from the aluminum foil, resulting in a decrease in barrier performance. Therefore, the inner PE film still needs to be adjusted to improve barrier properties such as water resistance and oil resistance. In addition, the adhesive layer of the aluminum-plastic composite hose generally uses ethylene-acrylic acid copolymer EAA or ethylene-methyl acrylic acid copolymer EMAA. These two substances have excellent adhesion to aluminum foil, but most of the main sales brands are currently monopolized by foreign companies such as DuPont, and the price cost is high. Therefore, it is still necessary to develop a new type of adhesive with good adhesion to both PE and aluminum foil to replace or partially replace the existing brands for aluminum-plastic composite hoses. Finally, in daily life, toothpaste is often stored in a relatively humid environment such as the bathroom, which is easy to breed microorganisms such as bacteria and fungi, affecting human health, so the antibacterial effect of the outer PE film cannot be ignored. Summary of the invention

[0003] In order to overcome the deficiencies of the above-mentioned prior art, the present invention provides an antibacterial and water-resistant aluminum-plastic composite hose and a preparation method thereof, thereby obtaining an antibacterial and water-resistant aluminum-plastic composite hose with an antibacterial outer layer, a water-resistant and oil-resistant inner layer and high sheet peeling strength.

[0004] The technical solution for achieving the purpose of the present invention is as follows:

[0005] An antibacterial and water-resistant aluminum-plastic composite hose comprises a pipe head and a pipe body, wherein the pipe body is formed by overlapping antibacterial and water-resistant aluminum-plastic composite sheets, wherein the antibacterial and water-resistant aluminum-plastic composite sheets sequentially comprise an outer PE film, a hyperbranched copolymer, an aluminum foil, an ethylene-methacrylic acid copolymer and an inner PE film;

[0006] The outer PE film comprises the following components by weight: 70-90 parts of polyethylene, 20-50 parts of calcium carbonate, and 1-10 parts of antibacterial agent;

[0007] The inner PE film comprises the following components by weight: 50-70 parts of polyethylene and 20-30 parts of cycloolefin copolymer;

[0008] The preparation method of the hyperbranched copolymer is as follows:

[0009] S1. 11-mercapto-1-undecanol was added to anhydrous dichloromethane, stirred in an ice bath, imidazole was added, dichlorodiisopropylsilane was added dropwise in a nitrogen atmosphere, and after a precipitate was formed, the temperature was raised to room temperature and the reaction was continued for 10 to 20 hours. The solvent was evaporated under reduced pressure to obtain a white precipitate, which was washed with ether and filtered. The ether solution was collected and dried to obtain a yellow liquid, which was purified by silica gel column chromatography to obtain a mercapto-silyl ether crosslinker;

[0010] S2. The acrylate crosslinking agent and the mercapto-silyl ether crosslinking agent are mixed in ethyl acetate, triethylamine is added as a catalyst, and the mixture is stirred at room temperature for 10 to 20 hours. The solvent is evaporated and removed under ventilation conditions to obtain a hyperbranched copolymer.

[0011] Specifically, the hyperbranched copolymer and the ethylene-methacrylic acid copolymer are used as adhesives in the antibacterial and water-resistant aluminum-plastic composite sheet.

[0012] Specifically, the polyethylene in the outer PE film and the inner PE film may be the same or different polyethylenes.

[0013] Among them, the outer PE film has calcium carbonate filler and antibacterial agent added to polyethylene. The white calcium carbonate can increase the whiteness of PE, cover the grayish white aluminum foil and yellowish adhesive, and increase the surface tension of the PE film, which is beneficial to the subsequent heat sealing and printing of the pipe.

[0014] The inner PE film has cyclic olefin copolymer (COC) added to polyethylene. COC is an ethylene-cyclic olefin copolymer prepared by addition polymerization of ethylene and norbornene monomers under a metallocene catalytic system. It has high water and oxygen barrier properties, excellent transparency, good dimensional stability, rigidity and heat resistance, and meets FDA standards. Blending PE and COC resins into films can effectively improve the water and oil resistance of the inner PE film.

[0015] A copolymer with a sticky hyperbranched cross-linked structure is synthesized by using an acrylate cross-linking agent and a mercapto-silicone ether cross-linking agent, wherein the end group of the copolymer is a mercapto group, which has a strong adhesion to aluminum foil, and the Si-O and alkyl groups in the copolymer chain segments have strong adhesion to PE, so that the hyperbranched copolymer meets the peel strength requirements of the aluminum-plastic composite hose.

[0016] In a specific embodiment, the thickness of the outer PE film is 75-100 μm; the thickness of the hyperbranched copolymer is 20-50 μm; the thickness of the aluminum foil is 9-20 μm; the thickness of the ethylene-methacrylic acid copolymer is 20-50 μm; and the thickness of the inner PE film is 65-85 μm.

[0017] In a specific embodiment, the antibacterial agent is at least one of a silver-based antibacterial agent, a zinc-based antibacterial agent, or a silver-zinc composite antibacterial agent.

[0018] In a specific embodiment, the polyethylene is at least one of low-density polyethylene or linear low-density polyethylene, the melt flow rate of the polyethylene at 190°C and 2.16kg is 1-3g / 10min, and the test standard of the melt flow rate is ISO 1133-2022.

[0019] Preferably, the polyethylene is a combination of low-density polyethylene and linear low-density polyethylene; the mass ratio of the low-density polyethylene to the linear low-density polyethylene is (3-4):1.

[0020] In a specific embodiment, the acrylate crosslinking agent is selected from ethoxylated trimethylolpropane triacrylate or propoxylated trimethylolpropane triacrylate.

[0021] In a specific embodiment, the molar ratio of 11-mercapto-1-undecanol to dichlorodiisopropylsilane is (2.1-2.5):1.

[0022] In a specific embodiment, the molar ratio of the acrylic ester crosslinking agent to the mercapto-silicone ether crosslinking agent is 1:(2.5-3).

[0023] In a specific embodiment, the melt flow rate of the cycloolefin copolymer at 230°C and 2.16kg is 5-15g / 10min. Preferably, the melt flow rate of the cycloolefin copolymer at 230°C and 2.16kg is 5-10g / 10min, and the test standard of the melt flow rate is ISO 1133-2022.

[0024] In a specific embodiment, the outer layer of the antibacterial and water-resistant aluminum-plastic composite sheet also includes a printed PE film for printing a trademark pattern. The thickness of the printed PE film is 20 to 80 μm. The printed PE film may be transparent or white. The transparent printed PE film includes 80 to 90 parts of polyethylene and 5 to 10 parts of antibacterial agent by weight. The components and weight of the white printed PE film are consistent with those of the outer PE film.

[0025] In a specific embodiment, the antibacterial and water-resistant aluminum-plastic composite sheet is produced by a multi-layer co-extrusion process.

[0026] In a specific embodiment, polyethylene, calcium carbonate, and an antibacterial agent are added to a first extruder according to a ratio and melt-extruded to form an outer PE melt. Polyethylene and cycloolefin copolymers are added to a second extruder according to a ratio and melt-extruded to form an inner PE melt. The outer PE melt, hyperbranched copolymer, aluminum foil, ethylene-methyl acrylic acid copolymer, and inner PE melt are put into the extruder corresponding to the five-layer co-extrusion casting machine, and a film is made by a co-extrusion casting process, and then a corona treatment is performed using a corona machine to obtain an antibacterial and water-resistant aluminum-plastic composite sheet.

[0027] The present invention also protects a method for preparing an antibacterial and water-resistant aluminum-plastic composite hose, comprising the following steps: overlapping the antibacterial and water-resistant aluminum-plastic composite sheets into a tube body using a hose reel, induction heating and pressurized cooling the overlapping parts using a high-frequency induction coil, to obtain an aluminum-plastic composite hose.

[0028] Preferably, the overlap size is 2-2.5 mm; the induction heating temperature is 85-95° C., and the compression ratio of the weld after pressurization is 5-20%.

[0029] Beneficial Effects

[0030] The present invention provides an antibacterial and water-resistant aluminum-plastic composite hose and a preparation method thereof, wherein the outer PE film is made of polyethylene by adding calcium carbonate filler and antibacterial agent, achieving the effects of antibacterial, coloring and increasing surface tension, which is beneficial to the subsequent heat sealing and printing of the pipe; the inner PE film is made of polyethylene by adding cycloolefin copolymer, achieving the effects of water and oxygen blocking, water and oil resistance of the inner PE film, and effectively ensuring the activity and safety of the contents of the aluminum-plastic composite hose. A copolymer with a viscous hyperbranched cross-linked structure is synthesized by using an acrylate cross-linking agent and a mercapto-silicon ether cross-linking agent, wherein the end group of the copolymer is a mercapto group, which has a strong adhesion to aluminum foil, and the Si-O and alkyl groups in the copolymer chain segment have strong adhesion to PE, so that the hyperbranched copolymer meets the peel strength requirements of the aluminum-plastic composite hose. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 Schematic diagram of the synthesis route of hyperbranched copolymers;

[0032] Figure 2 is the H NMR spectrum of the mercapto-silyl ether crosslinker;

[0033] Figure 3 This is the infrared spectrum of the hyperbranched copolymer. DETAILED DESCRIPTION

[0034] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0035] In the examples, the experimental methods used are conventional methods unless otherwise specified, and the materials, reagents, etc. used are all commercially available unless otherwise specified.

[0036] The raw materials used in the embodiments and comparative examples are described as follows:

[0037] Polyethylene 1: linear low-density polyethylene, DFDC7050, Sinopec, melt flow rate at 190°C, 2.16 kg is 2 g / 10 min;

[0038] Polyethylene 2: low-density polyethylene, LD 2119.LN Molding, ExxonMobil, melt flow rate at 190 °C, 2.16 kg is 2.1 g / 10 min;

[0039] Calcium carbonate: ultrafine calcium carbonate powder, KL8, Guangxi Hezhou Kelong Powder Co., Ltd.;

[0040] Antimicrobial agents: Zeolite-silver / zinc, Bactekiller BM-102BG, Kanebo;

[0041] Cyclic olefin copolymer 1: 9506F-500, TOPAS, melt flow rate 6 g / 10 min at 230 °C and 2.16 kg;

[0042] Cyclic olefin copolymer 2: 5013-04, TOPAS, melt flow rate 9 g / 10 min at 230 °C and 2.16 kg;

[0043] Cyclic olefin copolymer 3: 8007F-600, TOPAS, melt flow rate 12 g / 10 min at 230 °C and 2.16 kg;

[0044] 11-Mercapto-1-undecanol: 97%, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0045] Diisopropyl dichlorosilane: 97%, Shanghai MacLean Biochemical Technology Co., Ltd.;

[0046] Acrylate crosslinker: ethoxylated trimethylolpropane triacrylate, 99%, Guangzhou Shanghe Chemical Technology Co., Ltd.; propoxylated trimethylolpropane triacrylate, 99%, Guangzhou Shanghe Chemical Technology Co., Ltd.;

[0047] Anhydrous dichloromethane: 99.9%, Shandong Zhengxing New Materials Co., Ltd.;

[0048] Triethylamine: 99%, Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0049] Hyperbranched copolymer 1: Homemade, the preparation method is as follows:

[0050] 1.05 equivalents of 11-mercapto-1-undecanol were added to anhydrous dichloromethane, stirred at 0°C in an ice bath, 1 equivalent of imidazole was added, nitrogen was purged for 10 minutes, and 0.5 equivalents of dichlorodiisopropylsilane were added dropwise in a nitrogen atmosphere, and a white precipitate was immediately generated. The temperature was then raised to room temperature and the reaction was continued for 15 hours. The solvent was removed by evaporation under reduced pressure, and the remaining white precipitate was washed with ether and filtered. The ether solution was collected and dried to obtain a yellow liquid, which was purified by silica gel column chromatography to obtain a mercapto-silyl ether crosslinker. The flowability of the column silica gel chromatography was n-hexane: ethyl acetate = 15:1; wherein the yield of the mercapto-silyl ether crosslinker was 95%, and the nuclear magnetic hydrogen spectrum was as follows Figure 2 As shown, 1H NMR (400 MHz, CDCl3) δ = 1-1.58 (m, 50H), 2.53 (q, -CH2-SH, 4H), 3.67 (t, -O-CH2-, 4H).

[0051] S2. 1 equivalent of ethoxylated trimethylolpropane triacrylate and 2.5 equivalents of mercapto-silyl ether crosslinking agent were mixed in ethyl acetate, 0.1 equivalent of triethylamine was added as a catalyst, and the mixture was stirred and reacted at room temperature for 15 hours. The mixture was placed in a fume hood and the solvent was evaporated under ventilation to obtain a viscous mixture, i.e., a hyperbranched copolymer 1. The number average molecular weight Mn of the hyperbranched copolymer 1 was determined to be 15232 by gel permeation chromatography (GPC).

[0052] The hyperbranched copolymer 1 was subjected to infrared spectroscopy analysis, and the obtained spectrum was as follows: Figure 3 As shown, at 1083cm -1 and 2842-2918cm -1There are strong absorption peaks of silicon-oxygen bond (Si–O) and carbon-hydrogen bond (C–H) at 2553 cm -1 A weak sulfur-hydrogen bond (SH) characteristic peak appears at 719 cm -1 The characteristic absorption peak of carbon-sulfur bond (CS) appeared at , proving the successful synthesis of hyperbranched copolymer.

[0053] Hyperbranched copolymer 2: homemade. The preparation method is similar to that of hyperbranched copolymer 1, except that ethoxylated trimethylolpropane triacrylate is replaced by propoxylated trimethylolpropane triacrylate. The number average molecular weight Mn of hyperbranched copolymer 2 is 16785 as determined by gel permeation chromatography (GPC).

[0054] Aluminum foil: thickness 9 μm, purchased from Xiashun Aluminum Foil Co., Ltd.

[0055] Ethylene-methacrylic acid copolymer: Surlyn EMAA 7940, DuPont;

[0056] Unless otherwise specified, the components and raw materials used in the embodiments and comparative examples of the present invention are all commercially available raw materials, and the components and raw materials used in each parallel experiment are all of the same kind.

[0057] Examples 1 to 5 and Comparative Examples 1 to 3

[0058] As shown in Table 1, polyethylene, calcium carbonate, and antimicrobial agent are added to the first extruder according to the ratio and melt-extruded to form an outer layer of PE melt;

[0059] As shown in Table 1, polyethylene and cycloolefin copolymer are added to the second extruder according to the ratio and melt-extruded to form an inner layer of PE melt;

[0060] The outer layer PE melt, the hyperbranched copolymer 1, the aluminum foil, the ethylene-methacrylic acid copolymer and the inner layer PE melt are put into the extruder corresponding to the five-layer co-extrusion casting machine, and a film is made by a co-extrusion casting process, and then a corona treatment is performed by a corona machine to obtain an antibacterial and water-resistant aluminum-plastic composite sheet, wherein the thickness of the outer layer PE film is 80 μm, the thickness of the hyperbranched copolymer 1 is 20 μm, the thickness of the aluminum foil is 9 μm, the thickness of the ethylene-methacrylic acid copolymer is 20 μm, and the thickness of the inner layer PE film is 80 μm.

[0061] The antibacterial and water-resistant aluminum-plastic composite sheet is overlapped and formed into a pipe body by a hose reel, and the overlap is induction heated and pressurized cooled by a high-frequency induction coil to obtain an aluminum-plastic composite hose, wherein the overlap size is 2.5 mm; the induction heating temperature is 95°C, and the weld compression ratio after pressurization is 5%. The weld compression ratio is calculated as follows: weld compression ratio = (thickness of the overlap before welding - thickness of the joint after welding) / thickness of the overlap before welding × 100%.

[0062] Table 1 Components and ratios of the outer PE film and inner PE film of the antibacterial and water-resistant aluminum-plastic composite sheet

[0063]

[0064] Example 6

[0065] Compared with Example 1, the difference is that hyperbranched copolymer 2 is used instead of hyperbranched copolymer 1;

[0066] Comparative Example 4

[0067] Compared with Example 1, the difference is that ethylene-methacrylic acid copolymer is used instead of hyperbranched copolymer 1 as the adhesive layer;

[0068] The prepared antibacterial and water-resistant aluminum-plastic composite sheet and aluminum-plastic composite hose were subjected to the following performance tests, and the results are shown in Table 2:

[0069] (1) Tensile strength: The tensile properties of the antibacterial and water-resistant aluminum-plastic composite sheet were characterized using a TCD-225 digital tensile tester produced by Chatillon Company in accordance with the test standard GB / T 8804-2003. The tensile test was conducted at an angle of 180° and a tensile speed of 100 mm / min.

[0070] (2) Interlayer peeling strength: Tested according to the method of the national light industry standard "Aluminum-plastic composite hose for toothpaste (QB / T 2901-2012)" (unit: N / 15mm), with the following specific requirements: 1) Instrument used: universal tensile testing machine; 2) Take 3 to 5 material samples with a width of 15mm, a length of about 150mm, and flat edges for testing, and take the average value; 3) Peel off the layered sheet at a speed of 100mm / min, and the force tested by the instrument is the required force. The peeling strength between the aluminum foil and the outer PE film shall not be less than 3N / 15mm, and the peeling strength between the aluminum foil and the inner PE film shall not be less than 5N / 15mm to meet the standard requirements;

[0071] (3) Water barrier performance: The composite sheet was tested for water vapor barrier performance using a 3-33MA moisture permeability tester in accordance with GB / T 1037-1988 standard, and the water permeability of the composite sheet was tested under standard atmospheric pressure for 24 hours. The specific test conditions were as follows: test temperature room temperature: 25°C, test pressure: 1atm, ambient humidity: 90%RH, gas atmosphere: water vapor, test time: 24 hours;

[0072] (4) Oil resistance: The aluminum-plastic composite hose is filled with toothpaste containing lipid flavors, heat-sealed and placed in a constant temperature box at 50°C for 90 days. The aluminum-plastic composite hose is cut open to observe whether the inner PE film has pitting or stratification, and the oil resistance level is recorded. The oil resistance levels are as follows: Level 0 - no pitting and stratification, that is, no pitting is observed under a microscope (magnification 50 times); Level 1 - a small amount of pitting, that is, pitting is visible to the naked eye, but no stratification occurs; Level 2 - the pitting covers an area of ​​not less than 10%, and there is stratification;

[0073] (5) Antibacterial rate: Refer to Appendix A of QB / T2591-2003 to test and calculate the outer PE film of the aluminum-plastic composite hose. The antibacterial rate calculation formula is: R(%)=(BC) / B×100, where: R-antibacterial rate (%), B-average number of recovered bacteria on the blank control sample (cfu / piece), C-average number of recovered bacteria on the outer PE surface of the aluminum-plastic composite hose (cf / piece).

[0074] (6) Surface tension: Use A.Shine dyne pen to test the dyne value of the outer PE film;

[0075] Table 2 Performance test results of antibacterial and water-resistant aluminum-plastic composite hose

[0076]

[0077] From the data of the embodiments and comparative examples, the antibacterial and water-resistant composite hose provided by the present invention has the advantages of antibacterial outer layer, water-resistant and oil-resistant inner layer and high sheet peeling strength, and has good water permeability and oil resistance, which can ensure the activity and safety of the contents, and at the same time, the outer layer has antibacterial and high surface tension effects.

[0078] From the results of Example 1 and Comparative Examples 1, 3 and 4, the peel strength between the outer PE film and the aluminum foil is significantly higher than that between the inner PE film and the aluminum foil due to two aspects: first, the addition of calcium carbonate increases the surface tension of the outer PE film; second, the adhesive property of the hyperbranched polymer is better than that of the ethylene-methacrylic acid copolymer in the prior art.

[0079] It can be seen from Examples 1, 2 and 3 that when the polyethylene of the outer PE film and the inner PE film is a combination of low-density polyethylene and linear low-density polyethylene, the overall performance of the antibacterial and water-resistant composite hose is better.

[0080] It can be seen from Examples 1, 4 and 5 that when the melt flow rate of the cycloolefin copolymer is 5-15g / 10min at 230°C / 2.16kg, the antibacterial and water-resistant composite hose sheet has good water permeability and oil resistance, but its water permeability decreases with the increase of the melt flow rate of the cycloolefin copolymer.

[0081] It can be seen from Example 1 and Example 6 that the acrylate crosslinking agent selected from ethoxylated trimethylolpropane triacrylate or propoxylated trimethylolpropane triacrylate has strong adhesive properties.

[0082] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An antibacterial and water-resistant aluminum-plastic composite hose, characterized in that: It comprises a pipe head and a pipe body, wherein the pipe body is formed by overlapping antibacterial and water-resistant aluminum-plastic composite sheets, and the antibacterial and water-resistant aluminum-plastic composite sheets sequentially comprise an outer PE film, a hyperbranched copolymer, an aluminum foil, an ethylene-methacrylic acid copolymer and an inner PE film; The outer PE film comprises the following components by weight: 70-90 parts of polyethylene, 20-50 parts of calcium carbonate, and 1-10 parts of antibacterial agent; The inner PE film comprises the following components by weight: 50-70 parts of polyethylene and 20-30 parts of cycloolefin copolymer; The preparation method of the hyperbranched copolymer is as follows: S1. 11-mercapto-1-undecanol is added to anhydrous dichloromethane, stirred in an ice bath, imidazole is added, dichlorodiisopropylsilane is added in a nitrogen atmosphere, the temperature is raised to room temperature after a precipitate is generated and the reaction is continued for 10 to 20 hours, the solvent is evaporated under reduced pressure to obtain a white precipitate, which is washed with ether and filtered, the ether solution is collected and dried to obtain a yellow liquid, which is purified by silica gel column chromatography to obtain a mercapto-silyl ether crosslinking agent, wherein the molar ratio of the 11-mercapto-1-undecanol to dichlorodiisopropylsilane is (2.1 to 2.5): 1; S2. An acrylate crosslinking agent and a mercapto-silicone ether crosslinking agent are mixed in ethyl acetate, triethylamine is added as a catalyst, the mixture is stirred at room temperature for 10 to 20 hours, and the solvent is evaporated and removed under ventilation conditions to obtain a hyperbranched copolymer; the molar ratio of the acrylate crosslinking agent to the mercapto-silicone ether crosslinking agent is 1:(2.5 to 3); the acrylate crosslinking agent is selected from ethoxylated trimethylolpropane triacrylate or propoxylated trimethylolpropane triacrylate.

2. The antibacterial and water-resistant aluminum-plastic composite hose according to claim 1, characterized in that: The thickness of the outer PE film is 75-100 μm; the thickness of the hyperbranched copolymer is 20-50 μm; the thickness of the aluminum foil is 9-20 μm; the thickness of the ethylene-methacrylic acid copolymer is 20-50 μm; and the thickness of the inner PE film is 65-85 μm.

3. The antibacterial and water-resistant aluminum-plastic composite hose according to claim 1, characterized in that: The antibacterial agent is at least one of a silver-based antibacterial agent, a zinc-based antibacterial agent or a silver-zinc composite antibacterial agent.

4. The antibacterial and water-resistant aluminum-plastic composite hose according to claim 1, characterized in that: The polyethylene is at least one of low-density polyethylene or linear low-density polyethylene; the polyethylene has a melt flow rate of 1 to 3 g / 10 min at 190° C. and 2.16 kg.

5. The antibacterial and water-resistant aluminum-plastic composite hose according to claim 1, characterized in that: The cycloolefin copolymer has a melt flow rate of 5-15 g / 10 min at 230° C. and 2.16 kg.

6. The antibacterial and water-resistant aluminum-plastic composite hose according to claim 1, characterized in that: The antibacterial and water-resistant aluminum-plastic composite sheet is produced by adopting a multi-layer co-extrusion process.

7. The method for preparing the antibacterial and water-resistant aluminum-plastic composite hose according to any one of claims 1 to 6, characterized in that: The method comprises the following steps: overlapping and forming the antibacterial and water-resistant aluminum-plastic composite sheets into a pipe body by a hose reel; and induction heating and pressurized cooling of the overlapping parts by a high-frequency induction coil to obtain an aluminum-plastic composite hose.

8. The method for preparing the antibacterial and water-resistant aluminum-plastic composite hose according to claim 7, characterized in that: The overlap size is 2~2.5mm; the induction heating temperature is 85~95℃, and the compression ratio of the weld after pressurization is 5~20%.

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