Bio-based plasticizer and shell powder modified bacteriostatic and antiviral PVC self-adhesive tape for automobile wire harness

Abstract

The invention discloses a bio-based plasticizer and shell powder modified bacteriostatic and antiviral PVC (polyvinyl chloride) self-adhesive tape for an automobile wire harness. The bio-based antibacterial and antiviral PVC plastic comprises 100 parts of PVC resin powder, 50-70 parts of a bio-based polyester plasticizer, 2-3.5 parts of a stabilizer, 2.5-5 parts of a bio-based auxiliary stabilizer, 5 parts of a bio-based liquid rubber tackifier, 1.5-3.5 parts of a bio-based resin tackifier, 5-10 parts of an antibacterial modifier, 0.5-1 part of a PVC antibacterial and antiviral agent, 10-25 parts of a filler and 2-4 parts of other auxiliary agents. The bio-based plasticizer is composed of at least one of poly (tetraethylene glycol adipate), dioctyl succinate and castor oil-based diethyl phosphate; the bio-based auxiliary stabilizer is epoxidized soybean oil, and the bio-based liquid rubber tackifier is liquid polybutadiene; the bio-based tackifying resin is zinc resinate; the product provided by the invention has good mechanical properties, high temperature resistance and durability, and can realize adhesive-free self-adhesion; solvents are not used and volatile organic compounds are not released in the production and use processes, so that the product has antibacterial and antiviral functions and conforms to environmental protection laws and regulations.

Description

Technical Field

[0001] The present invention relates to the technical field of PVC electrical adhesive tapes, in particular to a bio-based plasticizer and a bacteriostatic and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder and a preparation process. Background Art

[0002] The base material of traditional PVC tapes is made with petroleum-based phthalate derivatives such as DOP as plasticizers and then coated with solvent-based pressure-sensitive adhesives.

[0003] Phthalate derivative plasticizers such as DOP are low-molecular-weight plasticizers, which are volatile and have poor high-temperature stability; they are also prone to migrating to the material surface or being extracted by solvents such as oil and soapy water, with poor durability, and may also interfere with the endocrine system, leading to physiological toxicity problems after contact with the human body.

[0004] Organic solvents such as toluene also pose environmental pollution and safety problems.

[0005] DOP, DINP, and toluene solvents are petroleum-based products, non-renewable, and face the problem of the gradual depletion of petroleum resources.

[0006] In addition, traditional PVC tapes are also prone to adsorbing dust and are likely to produce mildew after long-term use. Summary of the Invention

[0007] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a bacteriostatic and antiviral PVC self-adhesive tape for automotive wire harnesses modified with a bio-based plasticizer and shell powder to solve the problems raised in the above technical background.

[0008] To achieve the above purpose, the present invention is realized through the following technical solutions:

[0009] A formula and production process of a bacteriostatic and antiviral PVC self-adhesive tape for automotive wire harnesses modified with a bio-based polyester plasticizer and shell powder, which can replace part of the traditional formula and process to produce PVC electrical tapes.

[0010] In the first aspect, the main raw materials of the formula of a bacteriostatic and antiviral PVC self-adhesive tape for automotive wire harnesses modified with a bio-based polyester plasticizer provided by the present invention are PVC resin powder, bio-based plasticizer, stabilizer, bio-based auxiliary stabilizer, bio-based liquid rubber tackifier, bio-based resin tackifier, antibacterial modifier, PVC bacteriostatic and antiviral agent, filler, and other auxiliaries.

[0011] Preferably, the specific formulation components of a bio-based polyester plasticizer and a shell powder-modified antibacterial and antiviral PVC self-adhesive tape for automotive wire harnesses are mainly as follows: 100 parts of PVC resin powder, 50 - 70 parts of bio-based polyester plasticizer, 2 - 3.5 parts of stabilizer, 2.5 - 5 parts of bio-based auxiliary stabilizer, 5 parts of bio-based liquid rubber tackifier, 1.5 - 3.5 parts of bio-based resin tackifier, 5 - 10 parts of antibacterial modifier, 0.5 - 1 part of PVC antibacterial and antiviral agent, 10 - 25 parts of filler, and 2 - 4 parts of other additives.

[0012] Preferably, the degree of polymerization of the PVC resin powder is 1000 - 1300; the manufacturer is Tianjin Dagu Chemical Co., Ltd.

[0013] Preferably, the bio-based plasticizer is composed of at least one of poly(adipic acid - tetraethylene glycol ester), dioctyl succinate, and diethyl castor oil phosphate (PPC); dioctyl succinate and diethyl castor oil phosphate (PPC) are provided by DuPont (USA). Poly(adipic acid - tetraethylene glycol ester) is synthesized from adipic acid and tetraethylene glycol monomers through esterification and polycondensation. For the specific preparation method, refer to the literature: Zhou Feng, Synthesis and Application of Poly(Adipic Acid - Tetraethylene Glycol Ester) (Master's Thesis of Wuhan Textile University), Engineering and Technology I, Issue 09, 2013.

[0014] Preferably, the stabilizer is one of an environmentally friendly liquid composite calcium - zinc stabilizer (Ca - Zn stabilizer) and an environmentally friendly liquid composite barium - zinc stabilizer (Ba - Zn stabilizer); the manufacturer of the stabilizer is Shandong Yueyang New Materials and Energy Technology.

[0015] Preferably, the bio-based auxiliary stabilizer is epoxy soybean oil, model: high purity ESO, industrial grade, and the manufacturer is Guangzhou Yuanda New Materials Co., Ltd.

[0016] Preferably, the bio-based liquid rubber tackifier is liquid polybutadiene, model: Polyvest130; imported from the United States.

[0017] Preferably, the bio-based tackifying resin is zinc resinate, model: RESIN, imported from the United States.

[0018] Preferably, the antibacterial modifier is shell powder, with a specification of 1250 mesh, and the supplier is Tianjin Hongyan.

[0019] Preferably, the PVC antibacterial and antiviral agent is a cationic polymer system, model: SR - AVP - 803; the supplier is SR Corporation of Japan.

[0020] Preferably, the filler is light calcium carbonate, with a specification of 1250 mesh, and the supplier is Yulang New Materials Co., Ltd.

[0021] Preferably, the other auxiliary agent is a color chip, and the supplier is Shandong Jincaiyang New Material Technology.

[0022] Preferably, the ratio of the bio-based liquid rubber tackifier to the bio-based tackifying resin is 5:(1.5 - 3.5); more preferably, the ratio of the bio-based liquid rubber tackifier to the bio-based tackifying resin is 2:1.

[0023] The present invention uses renewable bio-based polyester plasticizers such as poly(adipic acid-tetraethylene glycol ester), dioctyl succinate, diethyl phosphate of castor oil-based (PPC), etc. to replace traditional petroleum-based phthalate derivatives such as DOP. It has good compatibility with polymer materials such as PVC, is not easily migrated to the material surface or extracted by solvents such as oil and soapy water, and can extend the service life of products; the bio-based polyester plasticizer has a large molecular weight, low volatility, stable performance at high temperatures, excellent cold resistance, and can still maintain the flexibility of materials in low-temperature environments; in cooperation with the bio-based auxiliary stabilizer epoxy soybean oil, it can further improve the high-temperature resistance and durability of products; it solves the problem that the petroleum-based phthalate plasticizer DOP is easily migrated and causes physiological toxicity problems after contact with the human body, and meets environmental protection standards.

[0024] The present invention conducts blending modification by adding bio-based liquid rubber such as liquid polybutadiene, bio-based resin acid zinc and other auxiliary agents to improve the polarity and wettability of the polymer film, enhance the self-adhesion, do not require coating adhesives, can achieve self-adhesion without glue, reduce the coating process, improve the process efficiency, shorten the production cycle, and save site, labor, equipment and energy consumption.

[0025] The product of the present invention does not use petroleum-based solvents such as toluene, reduces the consumption of petroleum resources, realizes the development of solvent-free technology, does not release volatile organic compounds (VOCs) during production and use, avoids the risks of fire, explosion, air pollution and photochemical reactions, and meets global environmental protection regulations (such as EU RoHS, China GB 18581 standard).

[0026] In addition, the present invention is modified by adding shell powder and PVC antibacterial and antiviral agents. The modified product can adsorb and decompose harmful substances in the air, achieving various functions such as purifying the air, inhibiting bacteria and viruses, overcoming the disadvantages of traditional products being easy to adsorb dust and mildew, and the product has antibacterial and antiviral functions, solving the problem of tape turning moldy and blackening.

[0027] In the second aspect, the present invention also provides a preparation process for an antibacterial and antiviral PVC self-adhesive tape for automotive wire harnesses modified with bio-based polyester plasticizer and shell powder, comprising the following steps:

[0028] Step 1, Raw Material Pretreatment and Batching: Pretreat and batch the raw materials according to the PVC self-adhesive tape formula described above. The PVC resin powder needs to pass through a 30-mesh sieve to remove impurities, and the liquid additives (such as plasticizers) need to be filtered.

[0029] Step 2, High-Speed Mixing: Add raw materials such as PVC resin powder, bio-based polyester plasticizer, Ba-Zn stabilizer, bio-based auxiliary stabilizer, liquid polybutadiene, zinc resinate, shell powder, PVC antibacterial and antiviral agent, and light calcium carbonate to a high-speed mixer. The mixing time is 200 seconds - 240 seconds, and the temperature is controlled at 80°C - 120°C to allow the resin powder to fully absorb the plasticizer and mix evenly with the added additives to form a dry blend, a mixture with high apparent density, good fluidity, and dry and loose properties.

[0030] Step 3, Plasticization and Extrusion: Discharge the mixture into a planetary twin-screw extruder, then add color chips, and control the temperature at 140°C - 150°C for uniform mixing and plasticization.

[0031] Step 4, Rolling Machine: Discharge the material to a rolling machine for supplementary mixing, and control the temperature of the rolling machine at 140°C - 160°C.

[0032] Step 5, Calendering: Feed the material to a calender, calender it into a film, then emboss, cool, and wind it into a semi-finished PVC film. Control the temperature of the calender at 160°C - 175°C; control the thickness of the PVC film at 0.10 mm ± 0.005 mm.

[0033] Step 6, Rewind the PVC film into small shafts of a specified length and cut it into products of the required specifications.

[0034] Step 7, Inspection, Packaging and Storage.

[0035] Compared with the prior art, the beneficial effects of the present invention are:

[0036] 1. The renewable bio-based plasticizer used in the product of the present invention has good compatibility with high-molecular materials such as PVC and has good plasticization effects.

[0037] 2. The renewable bio-based polyester plasticizer used in the product of the present invention has a large molecular weight, low volatility, is not easily migrated to the material surface or extracted by solvents such as oil and soapy water, and can extend the service life of the product; the cooperation of various bio-based polyester plasticizers and the synergy with the bio-based auxiliary stabilizer epoxy soybean oil can further increase the thermal degradation temperature (Td) and migration resistance of PVC, reduce the precipitation of plasticizers, and improve the heat resistance, mechanical properties, and stability of the plastic.

[0038] 3. The renewable bio-based plasticizer used in the product of the present invention has good biodegradability and is harmless to the environment and human body; it solves the problems of easy migration, volatilization, poor heat resistance and durability, and physiological toxicity of DOP and DINP plasticizers, and meets the environmental protection standards.

[0039] 4. The product of the present invention is modified by bio-based liquid rubber and zinc resin acid, which improves the polarity and wettability of the polymer film, enables self-adhesion without glue, does not require coating adhesives, effectively reduces the consumption of petroleum resources, and meets the national environmental protection and carbon reduction requirements; it solves the problems of high VOC content and safety and environmental protection problems existing in traditional PVC wire harness tapes.

[0040] 5. The product of the present invention is modified by blending shell powder and a special anti-virus agent for PVC. The modified product can adsorb and decompose harmful substances in the air, achieving multiple functions such as purifying the air, inhibiting bacteria and viruses, and overcoming the disadvantages of traditional products being easy to adsorb dust and prone to mildew.

[0041] 6. The products of this project meet the requirements of EU RoHS and REACH regulations. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is a product diagram of the PVC self-adhesive tape obtained in Example 1 of the present invention; Figure 2 It is a product diagram of the PVC self-adhesive tape obtained in Example 2 of the present invention; Figure 3 It is a product diagram of the PVC self-adhesive tape obtained in Example 3 of the present invention; Figure 4 It is a product diagram of the PVC self-adhesive tape obtained in Example 4 of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0043] The following specific examples illustrate the implementation manners of the present invention. Those skilled in the art can easily understand the other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation manners. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, without conflict, the following examples and the features in the examples can be combined with each other.

[0044] The present invention provides a bio-based polyester plasticizer and a formulation and process for an antibacterial and antiviral PVC self-adhesive tape for automotive wiring harnesses modified with shell powder. The main raw materials of the product of the present invention include PVC resin powder, bio-based plasticizer, stabilizer, bio-based auxiliary stabilizer, bio-based liquid rubber tackifier, bio-based resin tackifier, antibacterial modifier, PVC antibacterial and antiviral agent, filler and other auxiliaries. Among them, the bio-based polyester plasticizer is composed of one to three of poly(adipic acid-tetraethylene glycol ester), dioctyl succinate, and diethyl ricinoleate phosphate (PPC); the stabilizer is one of an environmentally friendly liquid composite calcium-zinc stabilizer and an environmentally friendly liquid composite barium-zinc stabilizer; the bio-based auxiliary stabilizer is epoxidized soybean oil, the bio-based liquid rubber tackifier is liquid polybutadiene; the bio-based tackifying resin is zinc resinate; the antibacterial modifier is shell powder; the PVC antiviral agent is a cationic polymer system; the filler is light calcium carbonate; the other auxiliaries are color chips. The specific formulation composition is mainly: 100 parts of PVC resin powder, 50 parts - 70 parts of bio-based polyester plasticizer, 2 parts - 3.5 parts of stabilizer, 2.5 parts - 5 parts of bio-based auxiliary stabilizer, 5 parts of bio-based liquid rubber tackifier, 1.5 parts - 3.5 parts of bio-based resin tackifier, 5 parts - 10 parts of antibacterial modifier, 0.5 parts - 1 part of PVC antibacterial and antiviral agent, 10 parts - 25 parts of filler and 2 parts - 4 parts of other auxiliaries.

[0045] Preferably, the bio-based polyester plasticizer has good compatibility with high-molecular materials such as PVC and high plasticization efficiency; it has a large molecular weight, low volatility, is not easily migrated to the material surface or extracted by solvents such as oil and soapy water, and can extend the service life of the product; further preferably, one to three of poly(adipic acid-tetraethylene glycol ester), dioctyl succinate, and diethyl ricinoleate phosphate (PPC) are used in combination; it can increase the thermal degradation temperature (Td) and migration resistance of PVC, reduce the precipitation of plasticizer, improve the heat resistance of the plastic, and enhance the low-temperature flexibility; further preferably, in cooperation with the bio-based auxiliary stabilizer epoxidized soybean oil, the high-temperature resistance and durability of the product are further improved.

[0046] Further preferably, the present invention conducts blend modification by adding bio-based liquid rubber such as liquid polybutadiene, bio-based zinc resinate and other auxiliaries, improves the polarity and wettability of the polymer film, improves the self-adhesion, can achieve self-adhesion without glue without coating adhesives, reduces the coating process, improves the process efficiency, shortens the production cycle, and saves site, labor, equipment and energy consumption; the product of the present invention does not use petroleum solvents such as toluene, reduces the consumption of petroleum resources, realizes the development of solvent-free technology, does not release volatile organic compounds (VOC) during production and use, avoids the risks of fire, explosion, air pollution and photochemical reactions, and complies with global environmental protection regulations (such as EU RoHS, China GB 18581 standard).

[0047] Further preferably, the present invention is modified by adding shell powder and PVC antibacterial and antiviral agents. The modified product can adsorb and decompose harmful substances in the air, thereby achieving multiple functions such as air purification, antibacterial and antiviral. The disadvantages of traditional products that they are easy to adsorb dust and mold, the product has antibacterial and antiviral functions, and solves the problem of the tape becoming old, moldy and black.

[0048] The present invention also provides a process for preparing an antibacterial and antiviral PVC self-adhesive tape for automobile wiring harness modified with a bio-based polyester plasticizer and shell powder, comprising the following steps:

[0049] Step 1, raw material pretreatment and ingredients: pretreatment and ingredients are carried out according to the above-mentioned PVC self-adhesive tape formula raw materials, PVC resin needs to be sieved through a 30-mesh sieve to remove impurities, and liquid additives (such as plasticizers) need to be filtered.

[0050] Step 2, high-speed mixing: Add raw materials such as PVC resin powder, bio-based polyester plasticizer, Ba-Zn stabilizer, bio-based auxiliary stabilizer, liquid polybutadiene, zinc resinate, shell powder, PVC antibacterial and antiviral agent, and light calcium carbonate into a high-speed mixer. The mixing time is 200 seconds to 240 seconds, and the temperature is controlled at 80°C to 120°C. Allow the resin powder to fully absorb the plasticizer and mix evenly with the added additives to form a dry mix with high apparent density, good fluidity, and dry looseness.

[0051] Step 3, plasticizing and extruding: discharge the mixed material into a planetary twin-screw extruder, add color flakes, control the temperature at 140-150°C, and mix and plasticize evenly.

[0052] Step 4, rolling mill: discharge the material to the rolling mill, supplement the mixing, and control the temperature of the rolling mill at 140℃-160℃;

[0053] Step 5, calendering: feeding the material to the tape machine, calendering into film, and then embossing, cooling, and winding into a semi-finished PVC film. The temperature of the calender is controlled at 160℃-175℃; the thickness of the PVC film is controlled at 0.10mm±0.005mm.

[0054] Step 6: Rewind the PVC film into a small shaft of specified length and cut it into products of required specifications.

[0055] Step 7: Inspection, packaging and storage.

[0056] The technical solution of the present invention will be further described below in conjunction with embodiments and comparative examples.

[0057] Embodiment 1:

[0058] 1. Formula

[0059] 100 parts of PVC resin powder, 70 parts of poly(adipic acid-tetraethylene glycol ester), 2.5 parts of Ba-Zn stabilizer, 5 parts of liquid polybutadiene, 2.5 parts of zinc resinate, 8 parts of shell powder, 0.8 part of PVC antibacterial and antiviral agent, 20 parts of light calcium carbonate, 3.5 parts of epoxidized soybean oil, 2.5 parts of color chips.

[0060] II. Manufacturing process

[0061] 1. Pretreatment of raw materials: The PVC resin needs to pass through a 30-mesh sieve to remove impurities, and the liquid additives (such as plasticizers) need to be filtered.

[0062] 2. High-speed mixing: Add raw materials such as PVC resin powder, bio-plasticizer (poly(adipic acid-tetraethylene glycol ester)), Ba-Zn stabilizer, bio-based auxiliary stabilizer (epoxidized soybean oil), liquid polybutadiene, zinc resinate, shell powder, PVC antibacterial and antiviral agent, and light calcium carbonate into a high-speed mixer. The mixing time is 220 seconds ± 20 seconds, and the temperature is controlled at 100°C ± 20°C to allow the resin powder to fully absorb the plasticizer and mix evenly with the added additives to form a dry blend, a mixture with high apparent density, good fluidity, and dry and loose properties.

[0063] 3. Plasticization and extrusion: Discharge the mixture into a planetary twin-screw extruder, and then add color chips. The temperature is controlled at 145°C ± 5°C, and the mixing and plasticization are made uniform.

[0064] 4. Rolling mill: Discharge the material to the rolling mill for supplementary mixing. The temperature of the rolling mill is controlled at 150°C ± 10°C.

[0065] 5. Calendering: Feed the material to the calender, calender it into a film, then emboss, cool, and wind it into a semi-finished PVC film. The temperature of the calender is controlled at 160°C ± 15°C; the thickness of the PVC film is controlled at 0.10 mm ± 0.005 mm.

[0066] 6. Rewind the PVC film into small shafts of specified length and cut it into products of required specifications.

[0067] 7. Inspection, packaging and warehousing. The product diagram of this embodiment is as Figure 1 shown.

[0068] Example 2:

[0069] I. Formula

[0070] 100 parts of PVC resin powder, 60 parts of poly(adipic acid-tetraethylene glycol ester), 10 parts of diethyl phosphate ricinoleate, 2.5 parts of Ba-Zn stabilizer, 5 parts of liquid polybutadiene, 2.5 parts of zinc resinate, 8 parts of shell powder, 0.8 part of PVC antibacterial and antiviral agent, 20 parts of light calcium carbonate, 3.5 parts of epoxidized soybean oil, 2.5 parts of color chips.

[0071] II. Manufacturing Process

[0072] 1. Raw material pretreatment: The PVC resin needs to pass through a 30-mesh sieve to remove impurities, and liquid additives (such as plasticizers) need to be filtered.

[0073] 2. High-speed mixing: Add raw materials such as PVC resin powder, bio-based plasticizer (poly(adipic acid-tetraethylene glycol ester), diethyl phosphate ricinoleate), Ba-Zn stabilizer, bio-based auxiliary stabilizer (epoxidized soybean oil), liquid polybutadiene, zinc resinate, shell powder, PVC antibacterial and antiviral agent, and light calcium carbonate into a high-speed mixer. The mixing time is 220 seconds ± 20 seconds, and the temperature is controlled at 100°C ± 20°C to allow the resin powder to fully absorb the plasticizer and mix evenly with the added additives to form a dry blend, a mixture with high apparent density, good fluidity, and dry and loose properties.

[0074] 3. Plasticization and extrusion: Discharge the mixture into a planetary twin-screw extruder, and then add color chips. The temperature is controlled at 145°C ± 5°C, and the mixing and plasticization are made uniform.

[0075] 4. Rolling mill: Discharge the material to the rolling mill for supplementary mixing. The temperature of the rolling mill is controlled at 150°C ± 10°C.

[0076] 5. Calendering: Feed the material to a calender, calender it into a film, then emboss, cool, and wind it into a semi-finished PVC film. The temperature of the calender is controlled at 160°C ± 10°C; the thickness of the PVC film is controlled at 0.10 mm ± 0.005 mm.

[0077] 6. Rewind the PVC film into small shafts of a specified length and cut it into products of the required specifications.

[0078] 7. Inspection, packaging, and warehousing. The product diagram of this embodiment is as Figure 2 shown.

[0079] Example 3:

[0080] I. Formula: 100 parts of PVC resin powder, 60 parts of poly(adipic acid-tetraethylene glycol ester), 10 parts of dioctyl succinate, 2.5 parts of Ba-Zn stabilizer, 5 parts of liquid polybutadiene, 2.5 parts of zinc resinate, 8 parts of shell powder, 0.8 part of PVC antibacterial and antiviral agent, 20 parts of light calcium carbonate, 3.5 parts of epoxidized soybean oil, 2.5 parts of color chips.

[0081] II. Manufacturing Process

[0082] 1. Raw material pretreatment: The PVC resin needs to pass through a 30-mesh sieve to remove impurities, and liquid additives (such as plasticizers) need to be filtered.

[0083] 2. High-speed mixing: Add raw materials such as PVC resin powder, bio-plasticizer (poly(ethylene glycol adipate), dioctyl succinate), Ba-Zn stabilizer, bio-based auxiliary stabilizer (epoxidized soybean oil), liquid polybutadiene, zinc resinate, shell powder, PVC antibacterial and antiviral agent, light calcium carbonate, etc. into a high-speed mixer. The mixing time is 220 seconds ± 20 seconds, and the temperature is controlled at 100°C ± 20°C, allowing the resin powder to fully absorb the plasticizer and be evenly mixed with the added additives to form a dry blend, a mixture with high apparent density, good fluidity, and dry and loose properties.

[0084] 3. Plasticization and extrusion: Discharge the mixture into a planetary twin-screw extruder, and then add color chips. The temperature is controlled at 145°C ± 5°C, and the mixing and plasticization are uniform.

[0085] 4. Rolling mill: Discharge the material to the rolling mill for supplementary mixing. The temperature of the rolling mill is controlled at 150°C ± 10°C.

[0086] 5. Calendering: Feed the material to the calender, calender it into a film, then emboss, cool, and wind it into a semi-finished PVC film. The temperature of the calender is controlled at 160°C ± 10°C; the thickness of the PVC film is controlled at 0.10mm ± 0.005mm.

[0087] 6. Rewind the PVC film into small shafts of specified length and cut it into products of required specifications.

[0088] 7. Inspection, packaging and warehousing. The product diagram of this embodiment is as Figure 3 shown.

[0089] Example 4:

[0090] I. Formula

[0091] 100 parts of PVC resin powder, 60 parts of poly(ethylene glycol adipate), 5 parts of diethyl phosphate based on castor oil, 5 parts of dioctyl succinate, 2.5 parts of Ba-Zn stabilizer, 5 parts of liquid polybutadiene, 2.5 parts of zinc resinate, 8 parts of shell powder, 0.8 part of PVC antibacterial and antiviral agent, 20 parts of light calcium carbonate, 3.5 parts of epoxidized soybean oil, 2.5 parts of color chips.

[0092] II. Manufacturing process

[0093] 1. Raw material pretreatment: The PVC resin needs to pass through a 30-mesh sieve to remove impurities, and liquid additives (such as plasticizers) need to be filtered.

[0094] 2. High-speed mixing: Add raw materials such as PVC resin powder, bio-plasticizer (poly(ethylene glycol adipate), diethyl phosphate of castor oil-based, dioctyl succinate), Ba-Zn stabilizer, bio-based auxiliary stabilizer (epoxidized soybean oil), liquid polybutadiene, zinc resinate, shell powder, PVC antibacterial and antiviral agent, light calcium carbonate, etc. into a high-speed mixer. The mixing time is 220 seconds ± 20 seconds, and the temperature is controlled at 100°C ± 20°C to allow the resin powder to fully absorb the plasticizer and mix evenly with the added additives, forming a dry blend, a mixture with high apparent density, good fluidity, and dry and loose properties.

[0095] 3. Plasticization and extrusion: Discharge the mixture into a planetary twin-screw extruder, add color chips, and control the temperature at 145°C ± 5°C for uniform mixing and plasticization.

[0096] 4. Rolling mill: Discharge the material to the rolling mill for supplementary mixing, and control the temperature of the rolling mill at 150°C ± 10°C.

[0097] 5. Calendering: Feed the material to the calender, calender it into a film, then emboss, cool, and wind it into a semi-finished PVC film. Control the temperature of the calender at 160°C ± 10°C; control the thickness of the PVC film at 0.10mm ± 0.005mm.

[0098] 6. Rewind the PVC film into small shafts of specified length and cut it into products of required specifications.

[0099] 7. Inspection, packaging, and warehousing. The product diagram of this embodiment is as Figure 4 shown.

[0100] The ingredients of the adhesives obtained in Examples 1-4 are shown in Table 1, and those of Comparative Examples 1-3 are shown in Table 2.

[0101] Table 1 Ingredient Table

[0102] Raw material name Example 1 Example 2 Example 3 Example 4 PVC resin powder 100 100 100 100 Poly(ethylene glycol adipate) 70 60 60 60 Diethyl ricinoleyl phosphate － 10 － 5 Dioctyl succinate － － 10 5 Ba-Zn stabilizer 2.5 2.5 2.5 2.5 Epoxidized soybean oil 3.5 3.5 3.5 3.5 Liquid polybutadiene 5 5 5 5 Zinc resinate 2.5 2.5 2.5 2.5 Shell powder 8 8 8 8 PVC antibacterial and antiviral agent 0.8 0.8 0.8 0.8 Light calcium carbonate 20 20 20 20 Color chip 2.5 2.5 2.5 2.5

[0103] Based on Example 4, different plasticizers are set in the ingredient table, or epoxidized soybean oil is not added. Except for the different ingredients, other conditions are the same as those in Example 4. The specific ingredient table is shown in Table 2.

[0104] Table 2 Ingredient Table

[0105] Raw material name Example 4 Comparative example 1 Comparative example 2 Comparative example 3 PVC resin powder 100 100 100 100 Poly(ethylene glycol adipate) 60 - 60 - Diethyl ricinoleyl phosphate 5 35 5 - Dioctyl succinate 5 35 5 - Dioctyl phthalate (DOP) - - - 70 Ba-Zn stabilizer 2.5 2.5 2.5 2.5 Epoxidized soybean oil 3.5 3.5 - 3.5 Liquid polybutadiene 5 5 5 5 Zinc resinate 2.5 2.5 2.5 2.5 Shell powder 8 8 8 8 PVC antibacterial and antiviral agent 0.8 0.8 0.8 0.8 Light calcium carbonate 20 20 20 20 Color chip 2.5 2.5 2.5 2.5

[0106] Based on Example 4, different ratios of liquid polybutadiene and zinc resinate are set in the ingredient table. Except for the different ratios, other conditions are the same as those in Example 4. The specific ingredient table is shown in Table 3.

[0107] Table 3 Ingredient Table

[0108] Raw material name Example 4 Example 5 Example 6 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 PVC resin powder 100 100 100 100 100 100 100 Poly(ethylene glycol adipate) 60 60 60 60 60 60 60 Diethyl ricinoleyl phosphate 5 5 5 5 5 5 5 Dioctyl succinate 5 5 5 5 5 5 5 Ba-Zn stabilizer 2.5 2.5 2.5 2.5 2.5 2.5 2.5 Epoxidized soybean oil 3.5 3.5 3.5 3.5 3.5 3.5 3.5 Liquid polybutadiene 5 5 5 5 5 - 5 Zinc resinate 2.5 1.5 3.5 1 4 2.5 - Shell powder 8 8 8 8 8 8 8 PVC antibacterial and antiviral agent 0.8 0.8 0.8 0.8 0.8 0.8 0.8 Light calcium carbonate 20 20 20 20 20 20 20 Color chip 2.5 2.5 2.5 2.5 2.5 2.5 2.5

[0109] The tapes produced from the adhesives prepared in Examples 1-6 and Comparative Examples 1-7 were tested, and the specific data are shown in Tables 4 and 5.

[0110] Inspection methods for tensile strength and elongation at break: Conducted in accordance with GB / T20631.2—2006.

[0111] Inspection method for peel strength (self-adhesion) of the substrate: Conducted in accordance with GB / T20631.2—2006.

[0112] Inspection method for aging performance (high temperature resistance, durability): Conducted in accordance with Appendix A 2.4 of T / CPCIF 0061-2020.

[0113] Table 4 Tape Physical Property Detection 1

[0114] Inspection item Example 1 Example 2 Example 3 Example 4 Comparative example 1 Comparative example 2 Comparative example 3 Tape thickness (mm) 0.103 0.106 0.104 0.106 0.106 0.104 0.104 Tensile strength (N / cm) 30.8 31.1 31.5 34.2 30.4 29 26 Elongation at break (%) 248 253 251 260 234 202 178 Self-adhesion: Peel strength to substrate (N / cm) 2.51 2.57 2.59 2.67 2.47 2.39 2.43 Durability: Aging characteristics (130°C × 240 h) Pass Pass Pass Pass Pass Pass Failed to embrittle Tensile strength after aging (130°C × 240 h, N / cm) 25.9 26.3 26.7 27.9 21.2 18.8 Embrittlement Elongation at break after aging (130°C × 240 h, %) 186 193 197 208 140 138 Embrittlement

[0115] Table 5 Tape Physical Property Detection 2

[0116] Inspection item Example 4 Example 5 Example 6 Comparative example 4 Comparative example 5 Comparative example 6 Comparative example 7 Tape thickness (mm) 0.106 0.106 0.104 0.102 0.103 0.104 0.106 Tensile strength (N / cm) 34.2 30.4 29 33.2 27 35 34.5 Elongation at break (%) 260 234 202 257 170 178 272 Self-adhesion: Peel strength to substrate (N / cm) 2.67 2.47 2.39 1.42 1.02 0.91 1.03 Durability: Aging characteristics (130°C × 240 h) Pass Pass Pass Pass Failed Pass Pass

[0117] As can be seen from Tables 4 and 5, the tapes obtained in Examples 1-4 have good performance. Comparing Example 4 with Example 1, the tensile strength and elongation of the PVC tape in Example 4 are more than 7% greater than those in Example 1. At the same time, when compounded with three plasticizers, namely castor oil-based diethyl phosphate and dioctyl succinate, a mutual synergistic effect occurs among the materials, and the plasticization effect of the PVC film is better; the strength performance can still be maintained above 80% after aging (130°C × 240 h). This shows that poly(adipic acid-tetraethylene glycol ester) as a plasticizer has good physical properties such as tensile strength, elongation, and durability, and the performance is better when multiple plasticizers are compounded.

[0118] As can be seen from Table 4, when comparing Example 4 with Comparative Examples 1-2, the tensile strength and elongation of the tape in Example 4 are 18% and 28.7% greater than those in Comparative Example 2 respectively. For the tape obtained in Example 4: the aging characteristics (130°C × 240 h) meet the requirements, and the strength performance can still be maintained above 80% after aging (130°C × 240 h), which proves that the synergistic effect of poly(adipic acid-tetraethylene glycol ester) and epoxidized soybean oil improves the high temperature resistance and durability of the PVC self-adhesive tape. Comparing Example 4 with Comparative Example 3, the tensile strength and elongation of the PVC tape in Example 4 are also increased by 31.5% and 46% respectively compared with those in Comparative Example 3. The durability of Comparative Example 3 does not meet the requirements, and after aging (130°C × 240 h), the material becomes brittle, indicating that poly(adipic acid-tetraethylene glycol ester) as a plasticizer has significantly better durability than the conventional plasticizer DOP.

[0119] As can be seen from Table 5, the self-adhesive properties of the tapes obtained in Examples 4-6 are good, which proves that when the ratio range of polybutadiene to zinc resinate is 5:(1.5~3.5), preferably 5:2.5, the self-adhesiveness is better; compared with Comparative Examples 4-5, it can be seen from Example 4 that the peel strength of the tape obtained in Example 4 from the substrate is significantly better than that of Comparative Examples 4-5, indicating that outside the ratio range of polybutadiene to zinc resinate of 5:(1.5~3.5), the self-adhesiveness is poor; this is because when the amount of zinc resinate is too small, the wettability is poor, resulting in poor self-adhesiveness; when the amount of zinc resinate is too large, the glass transition temperature of the self-adhesive tape increases, it is easy to be brittle, and the self-adhesiveness will also become poor.

[0120] Compared with Comparative Examples 6-7, it can be seen from Example 4 that the peel strength of the tape obtained in Example 4 from the substrate is significantly better than that of Comparative Examples 6-7, indicating that removing either polybutadiene or zinc resinate results in no self-adhesiveness, which proves that blending and modifying liquid polybutadiene, bio-based zinc resinate and other additives can improve the polarity and wettability of the polymer film, enhance the self-adhesiveness, and can achieve self-adhesion without coating adhesives.

[0121] By reasonably selecting a variety of bio-based plasticizers, adjusting the ratio between them and bio-based liquid tackifiers and bio-based resins, and giving full play to the synergistic cooperation between the components, the present invention realizes a better balance of the physical properties and self-adhesiveness (peel strength from the backing) of the PVC self-adhesive tape, meets the product performance requirements. At the same time, using bio-based renewable raw materials, it is formed in one processing step without using petroleum-based plasticizers and solvents, meeting the requirements of low-carbon environmental protection.

[0122] The above-described embodiments merely represent the specific embodiments of the present invention, and their descriptions are relatively specific and detailed, but should not be construed as limiting the scope of the patent of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention.

Claims

1. A bio-based polyester plasticizer and an antibacterial and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder, characterized in that, It contains the following components by weight parts: 100 parts of PVC resin powder, 50 - 70 parts of bio - based polyester plasticizer, 2 - 3.5 parts of stabilizer, 2.5 - 5 parts of bio - based auxiliary stabilizer, 5 parts of bio - based liquid rubber tackifier, 1.5 - 3.5 parts of bio - based resin tackifier, 5 - 10 parts of antibacterial modifier, 0.5 - 1 part of PVC antibacterial and antiviral agent, 10 - 25 parts of filler, and 2 - 4 parts of other additives; wherein, the antibacterial modifier is shell powder.

2. The bio-based polyester plasticizer and the antibacterial and antiviral PVC self-adhesive tape for automotive wire harness modified with shell powder according to claim 1, characterized in that, It contains the following components by weight parts: 100 parts of PVC resin powder, 70 parts of bio - based polyester plasticizer, 2.5 parts of stabilizer, 3.5 parts of bio - based auxiliary stabilizer, 5 parts of bio - based liquid rubber tackifier, 1.5 - 3.5 parts of bio - based resin tackifier, 8 parts of antibacterial modifier, 0.8 part of PVC antibacterial and antiviral agent, 20 parts of filler, and 2.5 parts of other additives.

3. A bio-based polyester plasticizer and an antibacterial and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder according to claim 1, characterized in that, The bio - based plasticizer contains poly(adipic acid - tetraethylene glycol ester).

4. A bio-based polyester plasticizer and an antibacterial and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder according to claim 3, characterized in that, The bio - based plasticizer also contains at least one of dioctyl succinate and diethyl castor oil - based phosphate.

5. A bio-based polyester plasticizer and an antibacterial and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder according to claim 1, wherein, The stabilizer is one of an environment - friendly liquid composite calcium - zinc stabilizer and an environment - friendly liquid composite barium - zinc stabilizer.

6. A bio-based polyester plasticizer and an antibacterial and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder according to claim 1, wherein, The bio - based auxiliary stabilizer is epoxy soybean oil.

7. A bio-based polyester plasticizer and a bacteriostatic and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder according to claim 1, characterized in that, The bio - based liquid rubber tackifier is liquid polybutadiene.

8. A bio-based polyester plasticizer and an antibacterial and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder according to claim 1, characterized in that The bio - based resin tackifier is zinc resinate.

9. The bio-based polyester plasticizer and the antibacterial and antiviral PVC self-adhesive tape for automotive wire harness modified with shell powder according to claim 1, characterized in that, The PVC antibacterial and antiviral agent is a cationic polymer system, model number SR - AVP - 803; the filler is light calcium carbonate.

10. The preparation process of a bio-based polyester plasticizer and a bacteriostatic and antiviral PVC self-adhesive tape for automotive wire harnesses modified with shell powder according to any one of claims 1-9, characterized in that, It includes the following steps: Step 1, raw material pretreatment and batching: Pretreat and batch the raw materials of the PVC self - adhesive tape according to any one of claims 1 - 9. Among them, the PVC resin powder needs to pass through a 30 - mesh sieve to remove impurities, and the bio - based polyester plasticizer needs to be filtered. Step 2, high - speed mixing: Add the PVC resin powder, bio - based polyester plasticizer, stabilizer, bio - based auxiliary stabilizer, bio - based liquid rubber tackifier, bio - based resin tackifier, antibacterial modifier, PVC antibacterial and antiviral agent, and filler into a high - speed mixer. The mixing time is 200 - 240 seconds, and the temperature is controlled at 80℃ - 120℃, allowing the resin powder to fully absorb the plasticizer and mix evenly with the added additives to form a dry blend, a mixture with high apparent density, good fluidity, and dry and loose properties. Step 3, plasticization and extrusion: Discharge the mixture into a planetary twin - screw extruder, and then add other additive color chips. The temperature is controlled at 140℃ - 150℃, and the mixing and plasticization are made uniform. Step 4, rolling mill: Discharge the material to the rolling mill for supplementary mixing. The temperature of the rolling mill is controlled at 140℃ - 160℃. Step 5, calendering: Feed the material to the calender, calender it into a film, then emboss, cool, and wind it into a semi - finished PVC film. The temperature of the calender is controlled at 160℃ - 175℃; the thickness of the PVC film is controlled at 0.10mm ± 0.005mm. Step 6, Rewind the PVC film into small shafts of a specified length and cut it into products of the required specifications. Step 7, inspection, packaging and warehousing.

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