Wear-resistant environment-friendly PET base material adhesive tape and preparation method thereof

Abstract

The invention discloses a wear-resistant environment-friendly PET base material adhesive tape and a preparation method thereof, and belongs to the technical field of adhesive tapes, raw materials comprise a PET adhesive tape film and an EB curing modified adhesive, the surface of the modified PET adhesive tape film subjected to corona treatment is coated with the EB curing modified adhesive, then electron beam radiation curing is carried out, the absorbed dose of electron beams is 38-42 kGy, and the EB curing modified adhesive is prepared. And then cooling, rolling and curing to obtain the wear-resistant environment-friendly PET base material adhesive tape. The modified PET adhesive tape film is prepared from the following raw materials: PET resin and modified polyolefin elastomer master batch; the EB curing modified adhesive is prepared from the following raw materials: butyl acrylate, 2-ethylhexyl acrylate, tripropylene glycol diacrylate, acrylate resin, urethane acrylate and starch modified core-shell microsphere powder. According to the mode, a modification process is added in the preparation process of the PET adhesive tape film and the adhesive, and finally the environment-friendly PET base material adhesive tape with excellent comprehensive performance is prepared.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesive tape, in particular to a wear-resistant and environment-friendly PET substrate adhesive tape and a preparation method thereof. BACKGROUND

[0002] PET adhesive tapes are widely used in the fields of insulation coating of electronic and electrical products, fixing of precision parts, surface protection and assembly of automotive interiors, etc. due to their excellent mechanical strength, dimensional stability, electrical insulation and chemical resistance.

[0003] With the continuous expansion of application scenarios and the increasingly stringent environmental regulations, the market has higher requirements for PET adhesive tapes. On the one hand, in the environment of frequent friction, assembly or long-term use, the adhesive tape needs to have excellent wear resistance to maintain its appearance integrity and functionality. On the other hand, especially in closed or near-person environments such as automotive interiors, home appliances and interior decoration, the adhesive tape must meet the environmental requirements of low volatile organic compound (VOC) emissions to avoid releasing harmful substances such as benzene and formaldehyde, which endanger human health.

[0004] The prior art has made many improvements to PET adhesive tapes. For example, Chinese patent CN120209722A discloses a modified PET composite adhesive tape and a preparation method thereof, which comprises the following steps: step one: mixing PET resin, modifier and dispersant, then melt blending and extruding to obtain modified masterbatch, and then melt extruding the modified masterbatch into a thick sheet, stretching, shaping and surface treatment to obtain a modified PET film; step two: uniformly coating the modified adhesive onto the surface of the modified PET film, drying and curing to obtain a modified PET composite adhesive tape. The composite adhesive tape prepared by this method has excellent mechanical properties, ultraviolet resistance and bonding properties.

[0005] However, the above-mentioned modified PET composite adhesive tape and the PET adhesive tapes in the prior art still have the following shortcomings in actual application: 1. The above-mentioned modified PET composite adhesive tape uses a large amount of organic solvents and chemicals such as chloromethyl methyl ether in the process, which poses a risk to production safety, and uses a thermal curing method, which has high energy consumption and VOC emission risk; 2. The PET adhesive tapes in the prior art still need to be further improved in wear resistance while maintaining ultraviolet resistance and bonding properties.

[0006] Therefore, the present application provides a wear-resistant and environment-friendly PET substrate adhesive tape and a preparation method thereof to solve the above-mentioned problems. SUMMARY

[0007] In view of the above-mentioned shortcomings of the prior art, the present application provides a wear-resistant and environment-friendly PET substrate adhesive tape and a preparation method thereof.

[0008] To achieve the above objectives, the present invention provides the following technical solution: A wear-resistant and environmentally friendly PET-based tape, the raw materials include PET tape film and EB curing modified adhesive. The surface of the modified PET tape film after corona treatment is coated with EB curing modified adhesive, and then cured by electron beam radiation. The absorbed dose of the electron beam is 38-42kGy. After cooling, winding and curing, the wear-resistant and environmentally friendly PET-based tape is obtained. The raw materials for the modified PET tape film include PET resin and modified polyolefin elastomer masterbatch. The raw materials of the EB-cured modified adhesive include butyl acrylate, isooctyl acrylate, tripropylene glycol diacrylate, acrylate resin, polyurethane acrylate, and starch-modified core-shell microsphere powder. The modified polyolefin elastomer masterbatch is prepared by: adding sodium periodate solution dropwise to sodium alginate solution to react and obtain sodium dialdehyde alkanoate; adding an organic solution of long-chain fatty amine to the organic solution of sodium dialdehyde alkanoate to obtain hydrophobically modified sodium dialdehyde alkanoate; and blending and pelletizing the hydrophobically modified sodium dialdehyde alkanoate with polyolefin elastomer in an extruder to obtain the modified polyolefin elastomer masterbatch. The method for preparing the starch-modified core-shell microsphere powder is as follows: Corn starch solution is modified with alkenyl succinic anhydride, dried and redispersed to obtain modified starch solution, methyl methacrylate, butyl acrylate, acrylic acid and crosslinking agent are mixed to obtain a mixture, the mixture and hydrogen peroxide aqueous solution are simultaneously added dropwise to the modified starch solution to react, and after the reaction is completed, the starch-modified core-shell microsphere powder is obtained by spray drying.

[0009] To better achieve the objectives of this invention, this invention also provides a method for preparing a wear-resistant and environmentally friendly PET substrate tape, specifically including the following steps: I. Preparation of modified PET tape film Sodium periodate solution was added dropwise to sodium alginate solution under stirring conditions. After the reaction was completed, ethylene glycol was added and stirred to obtain a reaction solution. The reaction solution was poured into anhydrous ethanol, allowed to stand, filtered and the precipitate was obtained. After washing and drying, sodium alginate dialdehyde was obtained. Sodium dialdehyde alginate was dispersed in an organic solvent and ultrasonically dispersed to obtain solution C. Long-chain fatty amines were dissolved in the organic solvent and then slowly added dropwise to solution C. After the addition was completed, the mixture was refluxed, and then precipitated, filtered, washed and dried to obtain hydrophobically modified sodium dialdehyde alginate. Hydrophobically modified sodium dialdehyde alkanoate, polyolefin elastomer and antioxidant are added to a twin-screw extruder for blending and pelletizing to obtain modified polyolefin elastomer masterbatch; The PET resin and the modified polyolefin elastomer master batch are added into a double screw extruder for blending, and the modified PET mixed master batch is obtained by pelletizing, and the modified PET adhesive tape film is obtained by melting, extruding into a thick sheet, stretching, shaping and surface treatment of the modified PET mixed master batch; II. Preparation of EB-cured modified adhesive The corn starch solution is modified by using alkenyl succinic anhydride, filtered after adjusting pH, washed with ethanol-water solution after filtration, and the modified starch powder is obtained after low-temperature vacuum drying. The modified starch solution is obtained by redispersion after drying, a mixed solution is obtained by mixing methyl methacrylate, butyl acrylate, acrylic acid and a crosslinking agent, the mixed solution and an aqueous hydrogen peroxide solution are synchronously added into the modified starch solution for reaction, and the starch modified core-shell microsphere powder is obtained by spray drying after the reaction is completed. The butyl acrylate, isooctyl acrylate and tripropylene glycol diacrylate crosslinking agent are added into a reaction bottle and uniformly mixed, then the acrylate resin and the polyurethane acrylate are added and stirred, the starch modified core-shell microsphere powder is added and continuously stirred, and the EB-cured modified adhesive is obtained after defoaming. III. Preparation of wear-resistant and environmentally friendly PET substrate adhesive tape The modified PET adhesive tape film is coated with the EB-cured modified adhesive, and then subjected to electron beam radiation curing, the absorption dose of the electron beam is 38-42 kGy, and then the wear-resistant and environmentally friendly PET substrate adhesive tape is obtained after cooling, winding and aging.

[0010] Further, the preparation process of the dialdehyde sodium alginate is as follows: 95-100 parts of sodium alginate is slowly added into 1500-2000 parts of deionized water cooled by ice bath, dispersed under mechanical stirring at 300-500 rpm, and a uniform viscous solution is obtained, which is solution A; 60-120 parts of sodium periodate is dissolved in 400-500 parts of deionized water to obtain solution B; Under the conditions of continuous stirring at 200-400 rpm and light shielding, solution B is added dropwise into solution A, the pH of the reaction system is adjusted to 3.0-4.0 with 10wt% citric acid, and after the pH adjustment is completed, the reaction is carried out at 25-40℃ for 10-14 hours in the dark, after the reaction is completed, 15-30 parts of ethylene glycol is added and stirred at a speed of 200-300 rpm for 1-2 hours to obtain a reaction solution; The reaction solution is poured into 3-5 times the volume of anhydrous ethanol, and the precipitate is obtained by standing and filtering, and the precipitate is washed with an ethanol aqueous solution, and the dialdehyde sodium alginate is obtained after drying the washed precipitate.

[0011] Further, the preparation process of the hydrophobically modified dialdehyde sodium alginate is as follows: Disperse 90-110 parts of sodium dialdehyde alginate in 800-1000 parts of organic solvent, and obtain solution C after ultrasonic-assisted dispersion; Dissolve 30-80 parts of long-chain fatty amine in 160-200 parts of organic solvent, and then slowly add it dropwise to solution C; After the addition is complete, the temperature is raised to 60-70℃ and refluxed for 12-16 hours. Then, precipitation, filtration, washing and drying are performed to obtain hydrophobically modified sodium dialdehyde alginate.

[0012] Furthermore, the preparation process of the modified polyolefin elastomer masterbatch is detailed as follows: 85-120 parts of hydrophobically modified sodium dialdehyde alkanoate, 950-1100 parts of polyolefin elastomer and 2-5 parts of antioxidant are premixed in a high-speed mixer for 5-10 minutes, and then blended using a twin-screw extruder at a processing temperature of 130-150℃ and a screw speed of 200-300 rpm. The extruded strip is then water-cooled and pelletized to obtain modified polyolefin elastomer masterbatch.

[0013] Furthermore, the specific preparation process of the modified PET tape film is as follows: 900-1000 parts of PET resin and 80-120 parts of modified polyolefin elastomer masterbatch are blended in a twin-screw extruder. The extruded strip is water-cooled and pelletized to obtain modified PET blended masterbatch. The modified PET blended masterbatch is melted, extruded into thick sheets, stretched, shaped and surface-treated to obtain modified PET tape film.

[0014] Furthermore, the specific preparation process of modified starch powder is as follows: Disperse 90-100 parts of corn starch in 120-150 parts of sodium carbonate buffer solution with pH 8.0-9.0, add 3-8 parts of alkenyl succinic anhydride while stirring at 600-800 rpm, and after the addition is complete, heat to 35-40℃ and continue to react for 4-6 hours. After the reaction was completed, the pH was adjusted to 6.5 with dilute hydrochloric acid and then filtered. After filtration, the powder was washed several times with an ethanol-water solution and then dried under low temperature and vacuum to obtain modified starch powder.

[0015] Furthermore, the specific preparation process of starch-modified core-shell microsphere powder is as follows: Mix 8-12 parts of modified starch powder with 85-95 parts of deionized water to obtain a modified starch aqueous dispersion. Add the modified starch aqueous dispersion to a reactor, under nitrogen protection, and heat to 40-45℃ with stirring at 300-400 rpm. Add 0.05-0.15 parts of ferrous sulfate solution as an initiator to obtain mixture D. Mix 60-70 parts of methyl methacrylate, 25-35 parts of butyl acrylate, 1-3 parts of acrylic acid and 0.5-2.0 parts of tripropylene glycol diacrylate crosslinking agent to obtain mixture E; Mixture E and hydrogen peroxide aqueous solution were simultaneously and slowly added dropwise to mixture D. After all the addition was completed, the reaction was maintained at 45-50℃ and stirred continuously for 0.8-1.2 hours. After the reaction was completed, starch-modified core-shell microsphere powder was obtained by spray drying.

[0016] Furthermore, the specific preparation process of EB-cured modified adhesive is as follows: Add 30-40 parts of butyl acrylate, 20-30 parts of isooctyl acrylate, and 10-20 parts of tripropylene glycol diacrylate crosslinking agent to a reaction flask and mix evenly. Then add 25-35 parts of acrylate resin and 100-120 parts of polyurethane acrylate and stir at 400-500 rpm for 20-30 minutes. Add 5-15 parts of starch-modified core-shell microsphere powder and continue stirring for 15-25 minutes. After homogenization and degassing, the EB-cured modified adhesive is obtained.

[0017] To better achieve the objectives of this invention, this invention also provides a wear-resistant and environmentally friendly PET substrate tape prepared by the above-described preparation method.

[0018] Compared with the prior art, the beneficial effects of this invention are as follows: 1. Modification processes are added to both the preparation of PET tape film and adhesive, resulting in the final preparation of PET substrate tape with excellent wear resistance, tensile properties, UV resistance, high temperature resistance and peel strength, and low VOC value. 2. The modification sequence in the preparation of modified PET tape film and the pre-modification of starch by alkenyl succinic anhydride in the preparation of EB-cured modified adhesive have a synergistic effect on the wear resistance, high temperature resistance and peel strength of the prepared wear-resistant and environmentally friendly PET substrate tape. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0020] Example 1: A method for preparing a wear-resistant and environmentally friendly PET substrate tape, specifically including the following steps: I. Preparation of modified PET tape film (1) Preparation of sodium dialdehyde alkanoate: 95 parts of sodium alginate were slowly added to 2000 parts of deionized water cooled in an ice bath (0°C) and dispersed under mechanical stirring at 500 rpm until a homogeneous viscous solution was formed, thus obtaining solution A. Dissolve 60 parts of sodium periodate in 500 parts of deionized water to obtain solution B; Under continuous stirring at 200 rpm and in the dark, solution B was added dropwise to solution A (dropping rate of 2 mL / min). The pH of the reaction system was adjusted to 4.0 with 10 wt% citric acid. After pH adjustment, the reaction was carried out at 25°C in the dark for 14 hours. After the reaction was completed, 15 parts of ethylene glycol were added and stirred at 300 rpm for 2 hours to obtain the reaction solution, in order to consume the remaining sodium periodate. Pour the reaction solution into anhydrous ethanol at a volume of 3 times that of the reaction solution, let it stand, filter and obtain the precipitate. Wash it with an ethanol aqueous solution (80% by volume) until no white precipitate is detected in the washing solution when tested with silver nitrate solution, which means that the washing is complete. After drying the washed precipitate, sodium dialdehyde alginate is obtained.

[0021] (2) Preparation of hydrophobically modified sodium dialdehyde alginate: 90 parts of sodium dialdehyde alginate were dispersed in 1000 parts of organic solvent (the organic solvent was a mixture of ethanol and isopropanol in a volume ratio of 1:1), and the dispersion was ultrasonically assisted (ultrasonically assisted for 30 minutes at 200W and 40kHz) to obtain solution C. Dissolve 30 parts of long-chain fatty amine (octadecylamine) in 200 parts of organic solvent, and then slowly add it dropwise to solution C; After the addition is complete, the temperature is raised to 60°C and refluxed for 16 hours. Then, precipitation, filtration, washing and drying are performed to obtain hydrophobically modified sodium dialdehyde alginate.

[0022] (3) Preparation of modified polyolefin elastomer masterbatch: 85 parts of hydrophobically modified sodium dialdehyde alkanoate, 1100 parts of polyolefin elastomer and 2 parts of antioxidant were premixed in a high-speed mixer for 10 minutes, and then blended using a twin-screw extruder at a processing temperature of 130°C and a screw speed of 300 rpm. The extruded strip was then water-cooled and pelletized to obtain modified polyolefin elastomer masterbatch.

[0023] (4) Preparation of modified PET tape film: 900 parts of PET resin and 120 parts of modified polyolefin elastomer masterbatch were blended in a twin-screw extruder. The extruded strip was water-cooled and pelletized to obtain modified PET blended masterbatch. After melting, extruding into thick sheets, stretching, shaping and surface treatment, modified PET tape film was obtained.

[0024] II. Preparation of EB-cured modified adhesives 90 parts of corn starch were dispersed in 150 parts of sodium carbonate buffer solution with pH 8.0. 3 parts of alkenyl succinic anhydride were added while stirring at 800 rpm. After the addition was completed, the temperature was raised to 40°C and the reaction was continued for 4 hours.

[0025] After the reaction was completed, the pH was adjusted to 6.5 with dilute hydrochloric acid and then filtered. After filtration, the powder was washed several times with an ethanol-water solution and then dried under low temperature and vacuum to obtain modified starch powder.

[0026] Eight parts of modified starch powder were mixed with 95 parts of deionized water to obtain a modified starch aqueous dispersion. The modified starch aqueous dispersion was added to a reactor under nitrogen protection and heated to 45°C with stirring at 300 rpm. 0.05 parts of ferrous sulfate solution were added as an initiator to obtain mixture D. Mix 60 parts of methyl methacrylate, 35 parts of butyl acrylate, 1 part of acrylic acid and 2 parts of tripropylene glycol diacrylate crosslinking agent to obtain mixture E; Mixture E and hydrogen peroxide aqueous solution were simultaneously and slowly added dropwise to mixture D. After all the addition was completed, the reaction was maintained at 45°C and stirred continuously for 1.2 hours. After the reaction was completed, starch-modified core-shell microsphere powder was obtained by spray drying.

[0027] Weigh the following raw materials according to the following parts by weight: 30 parts butyl acrylate, 30 parts isooctyl acrylate, 20 parts tripropylene glycol diacrylate, 35 parts acrylate resin, 100 parts polyurethane acrylate and 15 parts starch-modified core-shell microsphere powder.

[0028] Butyl acrylate, isooctyl acrylate, and tripropylene glycol diacrylate crosslinking agent were added to a reaction flask and mixed evenly. Then, acrylate resin and polyurethane acrylate were added and stirred at 400 rpm for 30 min. Starch-modified core-shell microsphere powder was added and stirred for another 15 min. After homogenization and degassing, EB-cured modified adhesive was obtained.

[0029] III. Preparation of Wear-Resistant and Environmentally Friendly PET Substrate Tape The surface of the modified PET tape film after corona treatment is coated with EB curing modified adhesive, and then cured by electron beam (EB) radiation with an absorbed dose of 38 kGy. After cooling, winding and curing, wear-resistant and environmentally friendly PET substrate tape is obtained.

[0030] IV. VOC Value Environmental Testing VOCs are volatile organic compounds, including benzene, toluene, ethylbenzene, xylene, styrene, formaldehyde, acetaldehyde, acrolein, acetone, and other organic compounds. In this embodiment, the wear-resistant and environmentally friendly PET substrate tape was used as the test sample to test the benzene and formaldehyde content in the VOCs. The testing procedure followed the national standard "Guidelines for Evaluating Air Quality in Passenger Cars," which specifies that the benzene content in the vehicle interior should be ≤0.11 mg / m³. 3 Formaldehyde content ≤ 0.10 mg / m³ 3 Then it meets the standard.

[0031] The benzene content of the wear-resistant and environmentally friendly PET substrate tape prepared in this embodiment was tested and found to be 0 mg / m³. 3 The formaldehyde content is 0 mg / m³ 3 Therefore, the above-mentioned wear-resistant and environmentally friendly PET substrate tape meets the national standards in terms of low VOC environmental protection requirements.

[0032] Example 2: A method for preparing a wear-resistant and environmentally friendly PET substrate tape, specifically including the following steps: I. Preparation of modified PET tape film (1) Preparation of sodium dialdehyde alkanoate: 100 parts of sodium alginate were slowly added to 1500 parts of deionized water cooled in an ice bath (5°C) and dispersed under mechanical stirring at 300 rpm until a homogeneous viscous solution was formed, thus obtaining solution A. Dissolve 120 parts of sodium periodate in 400 parts of deionized water to obtain solution B; Under continuous stirring at 400 rpm and in the dark, solution B was added dropwise to solution A (dropping rate of 5 mL / min). The pH of the reaction system was adjusted to 3.0 with 10 wt% citric acid. After pH adjustment, the reaction was carried out at 40°C in the dark for 10 hours. After the reaction was completed, 30 parts of ethylene glycol were added and stirred at 200 rpm for 2 hours to obtain the reaction solution, in order to consume the remaining sodium periodate. Pour the reaction solution into anhydrous ethanol at a volume of 5 times that of the reaction solution, let it stand, filter and obtain the precipitate. Wash it with an ethanol aqueous solution (80% by volume) until no white precipitate is detected in the washing solution when tested with silver nitrate solution, which means the washing is complete. Dry the washed precipitate to obtain sodium dialdehyde alginate.

[0033] (2) Preparation of hydrophobically modified sodium dialdehyde alginate: 110 parts of sodium dialdehyde alginate were dispersed in 800 parts of organic solvent (the organic solvent was a mixture of ethanol and isopropanol in a volume ratio of 1:1), and the dispersion was ultrasonically assisted (ultrasonically assisted for 30 minutes at 200W and 40kHz) to obtain solution C. Dissolve 80 parts of long-chain fatty amine (octadecylamine) in 160 parts of organic solvent, and then slowly add it dropwise to solution C; After the addition is complete, the temperature is raised to 70°C and refluxed for 12 hours. Then, precipitation, filtration, washing and drying are performed to obtain hydrophobically modified sodium dialdehyde alginate.

[0034] (3) Preparation of modified polyolefin elastomer masterbatch: 120 parts of hydrophobically modified sodium dialdehyde alkanoate, 950 parts of polyolefin elastomer and 5 parts of antioxidant were premixed in a high-speed mixer for 5 minutes, and then blended using a twin-screw extruder at a processing temperature of 150°C and a screw speed of 200 rpm. The extruded strip was then water-cooled and pelletized to obtain modified polyolefin elastomer masterbatch.

[0035] (4) Preparation of modified PET tape film: 1000 parts of PET resin and 80 parts of modified polyolefin elastomer masterbatch were blended in a twin-screw extruder. The extruded strip was water-cooled and pelletized to obtain modified PET blended masterbatch. After the modified PET blended masterbatch was melted, extruded into thick sheets, stretched, shaped and surface treated, modified PET tape film was obtained.

[0036] II. Preparation of EB-cured modified adhesives 100 parts of corn starch were dispersed in 120 parts of sodium carbonate buffer solution with pH 9.0. 8 parts of alkenyl succinic anhydride were added while stirring at 600 rpm. After the addition was completed, the temperature was raised to 35°C and the reaction was continued for 6 hours.

[0037] After the reaction was completed, the pH was adjusted to 6.5 with dilute hydrochloric acid and then filtered. After filtration, the powder was washed several times with an ethanol-water solution and then dried under low temperature and vacuum to obtain modified starch powder.

[0038] 12 parts of modified starch powder were mixed with 85 parts of deionized water to obtain a modified starch aqueous dispersion. The modified starch aqueous dispersion was added to a reactor under nitrogen protection and heated to 40°C with stirring at 400 rpm. 0.15 parts of ferrous sulfate solution were added as an initiator to obtain mixture D. Mix 70 parts of methyl methacrylate, 25 parts of butyl acrylate, 3 parts of acrylic acid and 0.5 parts of tripropylene glycol diacrylate crosslinking agent to obtain mixture E; Mixture E and hydrogen peroxide aqueous solution were simultaneously and slowly added dropwise to mixture D. After all the addition was completed, the reaction was maintained at 50°C and stirred continuously for 0.8 hours. After the reaction was completed, starch-modified core-shell microsphere powder was obtained by spray drying.

[0039] Weigh the following raw materials according to the following weight proportions: 40 parts butyl acrylate, 20 parts isooctyl acrylate, 20 parts tripropylene glycol diacrylate, 25 parts acrylate resin, 120 parts polyurethane acrylate, and 5 parts starch-modified core-shell microsphere powder.

[0040] Butyl acrylate, isooctyl acrylate, and tripropylene glycol diacrylate crosslinking agent were added to a reaction flask and mixed evenly. Then, acrylate resin and polyurethane acrylate were added and stirred at 500 rpm for 20 min. Starch-modified core-shell microsphere powder was added and stirred for another 25 min. After homogenization and degassing, EB-cured modified adhesive was obtained.

[0041] III. Preparation of Wear-Resistant and Environmentally Friendly PET Substrate Tape The surface of the modified PET tape film after corona treatment is coated with EB curing modified adhesive, and then cured by electron beam (EB) radiation with an absorbed dose of 42 kGy. After cooling, winding and curing, the wear-resistant and environmentally friendly PET substrate tape is obtained.

[0042] IV. VOC Value Environmental Testing The testing procedures were based on the national standard "Guidelines for Evaluating Air Quality in Passenger Cars". The benzene content of the wear-resistant and environmentally friendly PET substrate tape prepared in this embodiment was found to be 0 mg / m³. 3 The formaldehyde content is 0 mg / m³ 3 Therefore, the above-mentioned wear-resistant and environmentally friendly PET substrate tape meets the national standards in terms of low VOC environmental protection requirements.

[0043] Example 3: A method for preparing a wear-resistant and environmentally friendly PET substrate tape, specifically including the following steps: I. Preparation of modified PET tape film (1) Preparation of sodium dialdehyde alkanoate: 98 parts of sodium alginate were slowly added to 1750 parts of deionized water cooled in an ice bath (1°C) and dispersed under mechanical stirring at 450 rpm until a homogeneous viscous solution was formed, thus obtaining solution A. Dissolve 100 parts of sodium periodate in 480 parts of deionized water to obtain solution B; Under continuous stirring at 300 rpm and in the dark, solution B was added dropwise to solution A (dropping rate of 3.5 mL / min). The pH of the reaction system was adjusted to 3.5 with 10 wt% citric acid. After pH adjustment, the reaction was carried out at 32°C in the dark for 12 hours. After the reaction was completed, 25 parts of ethylene glycol were added and stirred at 250 rpm for 1.5 hours to obtain the reaction solution, in order to consume the remaining sodium periodate. Pour the reaction solution into anhydrous ethanol at a volume of 4 times that of the reaction solution, let it stand, filter and obtain the precipitate. Wash it with an ethanol aqueous solution (80% by volume) until no white precipitate is detected in the washing solution when tested with silver nitrate solution, which means the washing is complete. Dry the washed precipitate to obtain sodium dialdehyde alginate.

[0044] (2) Preparation of hydrophobically modified sodium dialdehyde alginate: 100 parts of sodium dialdehyde alginate were dispersed in 900 parts of organic solvent (the organic solvent was a mixture of ethanol and isopropanol in a volume ratio of 1:1), and the dispersion was ultrasonically assisted (ultrasonically assisted for 30 minutes at 200W and 40kHz) to obtain solution C. Dissolve 50 parts of long-chain fatty amine (octadecylamine) in 170 parts of organic solvent, and then slowly add it dropwise to solution C; After the addition is complete, the temperature is raised to 65°C and refluxed for 14 hours. Then, precipitation, filtration, washing and drying are performed to obtain hydrophobically modified sodium dialdehyde alginate.

[0045] (3) Preparation of modified polyolefin elastomer masterbatch: 105 parts of hydrophobically modified sodium dialdehyde alkanoate, 1000 parts of polyolefin elastomer and 3 parts of antioxidant were premixed in a high-speed mixer for 8 minutes, and then blended using a twin-screw extruder at a processing temperature of 140°C and a screw speed of 250 rpm. The extruded strip was then water-cooled and pelletized to obtain modified polyolefin elastomer masterbatch.

[0046] (4) Preparation of modified PET tape film: 950 parts of PET resin and 100 parts of modified polyolefin elastomer masterbatch were blended in a twin-screw extruder. The extruded strip was water-cooled and pelletized to obtain modified PET blended masterbatch. The modified PET blended masterbatch was melted, extruded into thick sheets, stretched, shaped and surface-treated to obtain modified PET tape film.

[0047] II. Preparation of EB-cured modified adhesives 95 parts of corn starch were dispersed in 130 parts of sodium carbonate buffer solution with pH 8.5. 5 parts of alkenyl succinic anhydride were added while stirring at 700 rpm. After the addition was completed, the temperature was raised to 38°C and the reaction was continued for 5 hours.

[0048] After the reaction was completed, the pH was adjusted to 6.5 with dilute hydrochloric acid and then filtered. After filtration, the powder was washed several times with an ethanol-water solution and then dried under low temperature and vacuum to obtain modified starch powder.

[0049] 10 parts of modified starch powder were mixed with 90 parts of deionized water to obtain a modified starch aqueous dispersion. The modified starch aqueous dispersion was added to a reactor, and under nitrogen protection, the temperature was raised to 42°C with stirring at 350 rpm. 0.1 parts of ferrous sulfate solution was added as an initiator to obtain mixture D. Mix 65 parts of methyl methacrylate, 30 parts of butyl acrylate, 2 parts of acrylic acid and 1.2 parts of tripropylene glycol diacrylate crosslinking agent to obtain mixture E; Mixture E and hydrogen peroxide aqueous solution were simultaneously and slowly added dropwise to mixture D. After all the addition was completed, the reaction was maintained at 47°C and stirred continuously for 1 hour. After the reaction was completed, starch-modified core-shell microsphere powder was obtained by spray drying.

[0050] Weigh the following raw materials according to the following weight proportions: 35 parts butyl acrylate, 25 parts isooctyl acrylate, 15 parts tripropylene glycol diacrylate, 30 parts acrylate resin, 110 parts polyurethane acrylate, and 10 parts starch-modified core-shell microsphere powder.

[0051] Butyl acrylate, isooctyl acrylate, and tripropylene glycol diacrylate crosslinking agent were added to a reaction flask and mixed evenly. Then, acrylate resin and polyurethane acrylate were added and stirred at 450 rpm for 25 min. Starch-modified core-shell microsphere powder was added and stirred for another 20 min. After homogenization and degassing, EB-cured modified adhesive was obtained.

[0052] III. Preparation of Wear-Resistant and Environmentally Friendly PET Substrate Tape The surface of the modified PET tape film after corona treatment is coated with EB curing modified adhesive, and then cured by electron beam (EB) radiation with an absorbed dose of 40 kGy. After cooling, winding and curing, wear-resistant and environmentally friendly PET substrate tape is obtained.

[0053] IV. VOC Value Environmental Testing The testing procedures were based on the national standard "Guidelines for Evaluating Air Quality in Passenger Cars". The benzene content of the wear-resistant and environmentally friendly PET substrate tape prepared in this embodiment was found to be 0 mg / m³. 3 The formaldehyde content is 0 mg / m³ 3 Therefore, the above-mentioned wear-resistant and environmentally friendly PET substrate tape meets the national standards in terms of low VOC environmental protection requirements.

[0054] Comparative Example 1: Unlike Example 3, in the preparation of the modified PET tape film, the polyolefin elastomer was first blended with PET resin, and then the blended composite resin material was modified with hydrophobically modified sodium dialdehyde phosphate. The specific steps are as follows: 950 parts of PET resin and 100 parts of polyolefin elastomer masterbatch were blended in a twin-screw extruder. The extruded strip was water-cooled and pelletized to obtain PET composite resin masterbatch. 105 parts of hydrophobically modified sodium dialdehyde alkanoate, 1000 parts of PET composite resin masterbatch and 3 parts of antioxidant were premixed in a high-speed mixer for 8 minutes, and then blended in a twin-screw extruder at a processing temperature of 140°C and a screw speed of 250 rpm. The extruded strip was water-cooled and pelletized to obtain modified PET mixed masterbatch. The modified PET mixed masterbatch was melted, extruded into thick sheets, stretched, shaped and surface-treated to obtain modified PET tape film.

[0055] The remaining steps are the same as in Example 3.

[0056] Comparative Example 2: Unlike Example 3, in the preparation of the EB-cured modified adhesive, alkenyl succinic anhydride was not used to modify the corn starch. The specific steps are as follows: 10 parts corn starch and 90 parts deionized water were mixed to obtain a starch aqueous dispersion. The starch aqueous dispersion was added to a reactor, and under nitrogen protection, the temperature was raised to 42°C with stirring at 350 rpm. 0.1 parts ferrous sulfate solution was added as an initiator to obtain mixture D. Mix 65 parts of methyl methacrylate, 30 parts of butyl acrylate, 2 parts of acrylic acid and 1.2 parts of tripropylene glycol diacrylate crosslinking agent to obtain mixture E; Mixture E and hydrogen peroxide aqueous solution were simultaneously and slowly added dropwise to mixture D. After all the addition was completed, the reaction was maintained at 47°C and stirred continuously for 1 hour. After the reaction was completed, starch-modified core-shell microsphere powder was obtained by spray drying.

[0057] The remaining steps are the same as in Example 3.

[0058] Comparative Example 3: Unlike Example 3, in the process of preparing the modified PET tape film, the polyolefin elastomer was first blended with PET resin, and then the blended composite resin material was modified with hydrophobically modified sodium dialdehyde alkanoate; at the same time, in the process of preparing the EB curing modified adhesive, alkenyl succinic anhydride was not used to modify the corn starch.

[0059] The remaining steps are the same as in Example 3.

[0060] Experimental Example: The following performance tests were conducted on the abrasion-resistant and environmentally friendly PET substrate tapes prepared in Examples 1-3 and Comparative Examples 1-3: Abrasion resistance (number of abrasion cycles): ISO 6722-1 2011; Tensile properties (tensile strength, N / cm) 2 GB / T 1040.12025; UV resistance (tack retention rate / %): GB / T 16422.22022; Peel strength (N / cm): GB / T 2792-2014; High temperature resistance (temperature resistance / °C): GB / T 32368-2015.

[0061] Table 1. Performance test results of abrasion-resistant and environmentally friendly PET substrate tapes prepared in Examples 1-3 and Comparative Examples 1-3 Item Wear resistance Tensile strength Adhesion retention rate Peeling strength Temperature resistance Example 1 33153 91.0 90.3 48.4 109 Example 2 33798 90.6 90.9 47.8 105 Example 3 34512 91.8 90.8 48.9 108 Comparative Example 1 31650 85.2 88.5 46.2 98 Comparative Example 2 33240 90.1 84.7 43.5 106 Comparative Example 3 29870 80.5 80.2 39.8 95 As can be seen from Examples 1-3, the preparation method described above can stably produce PET substrate tapes with excellent abrasion resistance, tensile properties, UV resistance, high temperature resistance, and peel strength. The performance indicators of the three examples are all at a high and similar level, which proves that the preparation process has good reproducibility and stability.

[0062] As shown in Example 3 and Comparative Example 1, if the preparation order of the modified PET tape film is changed (blending first and then modification), the abrasion resistance of the prepared abrasion-resistant and environmentally friendly PET substrate tape decreases by 2862 cycles, and the tensile strength decreases by 6.6 N / cm. 2 The adhesive retention rate decreased by 2.3%, the peel strength decreased by 2.7 N / cm, and the temperature resistance decreased by 10℃. In other words, the wear resistance, tensile properties, UV resistance, high temperature resistance, and peel strength of the wear-resistant and environmentally friendly PET substrate tape all decreased.

[0063] As can be seen from Example 3 and Comparative Example 2, if the alkenyl succinic anhydride modification of starch is removed, the adhesive retention rate of the prepared wear-resistant and environmentally friendly PET substrate tape will decrease significantly by 6.1%, the peel strength will decrease significantly by 5.4 N / cm, and the wear resistance and tensile strength will also decrease slightly. That is, the overall performance of the wear-resistant and environmentally friendly PET substrate tape has decreased, especially the impact on the adhesive-related properties.

[0064] As can be seen from Example 3 and Comparative Example 3, the modification sequence in the preparation of modified PET tape film and the pre-modification of starch by alkenyl succinic anhydride in the preparation of EB-cured modified adhesive have a synergistic effect on the wear resistance, high temperature resistance and peel strength of the prepared wear-resistant and environmentally friendly PET substrate tape.

[0065] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.

Claims

1. A wear-resistant and environmentally friendly PET substrate tape, characterized in that, The raw materials include PET tape film and EB curing modified adhesive. The surface of the modified PET tape film after corona treatment is coated with EB curing modified adhesive, and then cured by electron beam radiation. The absorbed dose of the electron beam is 38-42kGy. After cooling, winding and curing, wear-resistant and environmentally friendly PET substrate tape is obtained. The raw materials for the modified PET tape film include PET resin and modified polyolefin elastomer masterbatch. The raw materials of the EB-cured modified adhesive include butyl acrylate, isooctyl acrylate, tripropylene glycol diacrylate, acrylate resin, polyurethane acrylate, and starch-modified core-shell microsphere powder. The modified polyolefin elastomer masterbatch is prepared by: adding sodium periodate solution dropwise to sodium alginate solution to react and obtain sodium dialdehyde alkanoate; adding an organic solution of long-chain fatty amine to the organic solution of sodium dialdehyde alkanoate to obtain hydrophobically modified sodium dialdehyde alkanoate; and blending and pelletizing the hydrophobically modified sodium dialdehyde alkanoate with polyolefin elastomer in an extruder to obtain the modified polyolefin elastomer masterbatch. The method for preparing the starch-modified core-shell microsphere powder is as follows: Corn starch solution is modified with alkenyl succinic anhydride, dried and redispersed to obtain modified starch solution, methyl methacrylate, butyl acrylate, acrylic acid and crosslinking agent are mixed to obtain a mixture, the mixture and hydrogen peroxide aqueous solution are simultaneously added dropwise to the modified starch solution to react, and after the reaction is completed, the starch-modified core-shell microsphere powder is obtained by spray drying.

2. A method for preparing a wear-resistant and environmentally friendly PET substrate tape according to claim 1, characterized in that, Specifically, the following steps are included: I. Preparation of modified PET tape film Sodium periodate solution was added dropwise to sodium alginate solution under stirring conditions. After the reaction was completed, ethylene glycol was added and stirred to obtain a reaction solution. The reaction solution was poured into anhydrous ethanol, allowed to stand, filtered and the precipitate was obtained. After washing and drying, sodium alginate dialdehyde was obtained. Sodium dialdehyde alginate was dispersed in an organic solvent and ultrasonically dispersed to obtain solution C. Long-chain fatty amines were dissolved in the organic solvent and then slowly added dropwise to solution C. After the addition was completed, the mixture was refluxed, and then precipitated, filtered, washed and dried to obtain hydrophobically modified sodium dialdehyde alginate. Hydrophobically modified sodium dialdehyde alkanoate, polyolefin elastomer and antioxidant are added to a twin-screw extruder for blending and pelletizing to obtain modified polyolefin elastomer masterbatch; PET resin and modified polyolefin elastomer masterbatch are added to a twin-screw extruder for blending, and then pelletized to obtain modified PET blend masterbatch. After the modified PET blend masterbatch is melted, extruded into thick sheets, stretched, shaped and surface treated, modified PET tape film is obtained. II. Preparation of EB-cured modified adhesives Corn starch solution was modified using alkenyl succinic anhydride, the pH was adjusted and then filtered, washed with ethanol-water solution, and dried under low temperature vacuum to obtain modified starch powder. After drying, the modified starch solution is redispersed. Methyl methacrylate, butyl acrylate, acrylic acid and crosslinking agent are mixed to obtain a mixture. The mixture and hydrogen peroxide aqueous solution are simultaneously added dropwise to the modified starch solution to react. After the reaction is completed, the starch-modified core-shell microsphere powder is obtained by spray drying. Butyl acrylate, isooctyl acrylate, and tripropylene glycol diacrylate crosslinking agent are added to a reaction flask and mixed evenly. Then, acrylate resin and polyurethane acrylate are added and stirred. Starch-modified core-shell microsphere powder is added and stirred again. After degassing, EB-cured modified adhesive is obtained. III. Preparation of Wear-Resistant and Environmentally Friendly PET Substrate Tape The surface of the modified PET tape film is coated with EB-cured modified adhesive, and then cured by electron beam radiation with an absorbed dose of 38-42 kGy. After cooling, winding and curing, a wear-resistant and environmentally friendly PET substrate tape is obtained.

3. The method for preparing the wear-resistant and environmentally friendly PET substrate tape according to claim 2, characterized in that, The specific preparation process of sodium dialdehyde alginate is as follows: Slowly add 95-100 parts of sodium alginate to 1500-2000 parts of deionized water cooled in an ice bath, and disperse under mechanical stirring at 300-500 rpm until a homogeneous viscous solution is formed, to obtain solution A. Dissolve 60-120 parts of sodium periodate in 400-500 parts of deionized water to obtain solution B; Under continuous stirring at 200-400 rpm and in the dark, solution B is added dropwise to solution A. The pH of the reaction system is adjusted to 3.0-4.0 with 10 wt% citric acid. After pH adjustment, the reaction is carried out at 25-40℃ in the dark for 10-14 hours. After the reaction is completed, 15-30 parts of ethylene glycol are added and stirred at 200-300 rpm for 1-2 hours to obtain the reaction solution. Pour the reaction solution into anhydrous ethanol at a volume of 3-5 times the reaction solution, let it stand, filter to obtain a precipitate, wash it with an ethanol-water solution, and dry the washed precipitate to obtain sodium dialdehyde alkanoate.

4. The method for preparing the wear-resistant and environmentally friendly PET substrate tape according to claim 2, characterized in that, The specific preparation process of hydrophobically modified sodium dialdehyde alginate is as follows: Disperse 90-110 parts of sodium dialdehyde alginate in 800-1000 parts of organic solvent, and obtain solution C after ultrasonic-assisted dispersion; Dissolve 30-80 parts of long-chain fatty amine in 160-200 parts of organic solvent, and then slowly add it dropwise to solution C; After the addition is complete, the temperature is raised to 60-70℃ and refluxed for 12-16 hours. Then, precipitation, filtration, washing and drying are performed to obtain hydrophobically modified sodium dialdehyde alginate.

5. The method for preparing the wear-resistant and environmentally friendly PET substrate tape according to claim 2, characterized in that, The specific preparation process of modified polyolefin elastomer masterbatch is as follows: 85-120 parts of hydrophobically modified sodium dialdehyde alkanoate, 950-1100 parts of polyolefin elastomer and 2-5 parts of antioxidant are premixed in a high-speed mixer for 5-10 minutes, and then blended using a twin-screw extruder at a processing temperature of 130-150℃ and a screw speed of 200-300 rpm. The extruded strip is then water-cooled and pelletized to obtain modified polyolefin elastomer masterbatch.

6. The method for preparing the wear-resistant and environmentally friendly PET substrate tape according to claim 2, characterized in that, The specific preparation process of modified PET tape film is as follows: 900-1000 parts of PET resin and 80-120 parts of modified polyolefin elastomer masterbatch are blended in a twin-screw extruder. The extruded strip is water-cooled and pelletized to obtain modified PET blended masterbatch. The modified PET blended masterbatch is melted, extruded into thick sheets, stretched, shaped and surface-treated to obtain modified PET tape film.

7. The method for preparing the wear-resistant and environmentally friendly PET substrate tape according to claim 2, characterized in that, The specific preparation process of modified starch powder is as follows: Disperse 90-100 parts of corn starch in 120-150 parts of sodium carbonate buffer solution with pH 8.0-9.0, add 3-8 parts of alkenyl succinic anhydride while stirring at 600-800 rpm, and after the addition is complete, heat to 35-40℃ and continue to react for 4-6 hours. After the reaction was completed, the pH was adjusted to 6.5 with dilute hydrochloric acid and then filtered. After filtration, the powder was washed several times with an ethanol-water solution and then dried under low temperature and vacuum to obtain modified starch powder.

8. The method for preparing the wear-resistant and environmentally friendly PET substrate tape according to claim 2, characterized in that, The specific preparation process of starch-modified core-shell microsphere powder is as follows: Mix 8-12 parts of modified starch powder with 85-95 parts of deionized water to obtain a modified starch aqueous dispersion. Add the modified starch aqueous dispersion to a reactor, under nitrogen protection, and heat to 40-45℃ with stirring at 300-400 rpm. Add 0.05-0.15 parts of ferrous sulfate solution as an initiator to obtain mixture D. Mix 60-70 parts of methyl methacrylate, 25-35 parts of butyl acrylate, 1-3 parts of acrylic acid and 0.5-2.0 parts of tripropylene glycol diacrylate crosslinking agent to obtain mixture E; Mixture E and hydrogen peroxide aqueous solution were simultaneously and slowly added dropwise to mixture D. After all the addition was completed, the reaction was maintained at 45-50℃ and stirred continuously for 0.8-1.2 hours. After the reaction was completed, starch-modified core-shell microsphere powder was obtained by spray drying.

9. The method for preparing the wear-resistant and environmentally friendly PET substrate tape according to claim 2, characterized in that, The specific preparation process of EB-cured modified adhesive is as follows: Add 30-40 parts of butyl acrylate, 20-30 parts of isooctyl acrylate, and 10-20 parts of tripropylene glycol diacrylate crosslinking agent to a reaction flask and mix evenly. Then add 25-35 parts of acrylate resin and 100-120 parts of polyurethane acrylate and stir at 400-500 rpm for 20-30 minutes. Add 5-15 parts of starch-modified core-shell microsphere powder and continue stirring for 15-25 minutes. After homogenization and degassing, the EB-cured modified adhesive is obtained.

10. A wear-resistant and environmentally friendly PET substrate tape prepared by the preparation method according to any one of claims 2-9.