Low-temperature-resistant antiskid adhesive material as well as preparation method and application thereof

Abstract

The invention relates to a low-temperature-resistant anti-skid adhesive material and a preparation method and application thereof, the anti-skid adhesive material comprises a modified HDPE base material layer and an acrylate pressure-sensitive adhesive layer coated on the base material layer, the base material layer comprises HDPE resin, POE elastomer, methyl vinyl silicone rubber, a compatilizer and a peroxide cross-linking agent; the adhesive layer comprises a soft monomer, a hard monomer, a macromonomer containing a polybutadiene chain segment, a functional monomer, a cold-resistant plasticizer, an initiator and a cross-linking agent. The anti-skid adhesive material provided by the invention can still keep high adhesion at a low temperature of-40 DEG C, and has good base material performance and excellent anti-skid performance.

Description

Technical Field

[0001] This invention belongs to the field of adhesive materials (C09J), specifically relating to a low-temperature resistant anti-slip adhesive material, its preparation method, and its application. Background Technology

[0002] Thermoplastic polyolefin waterproofing materials are sheet-like waterproofing materials made from thermoplastic polyolefin polymers as the base material, which can be heat-melted / heat-processed and are widely used in the field of building waterproofing. Pressure-sensitive anti-slip tape is a functional tape with a granular or special textured surface used to increase friction and prevent slippage. However, in cold regions, during winter outdoor operations or in cold chain logistics scenarios, ordinary pressure-sensitive anti-slip tapes face severe performance challenges. Existing tapes generally suffer from the following problems in environments below -20℃: the chain segment movement of the tape substrate is hindered at low temperatures, the material becomes brittle, and it is prone to cracking when bent; the pressure-sensitive adhesive, due to its high glass transition temperature, loses its viscoelasticity at low temperatures, failing to wet the surface of the adhered object, leading to adhesion failure and tape detachment.

[0003] To address these issues, existing technologies attempt to lower the glass transition temperature of adhesives by adding plasticizers. However, excessive plasticizers can lead to a decrease in the cohesive strength of the adhesive layer at room temperature, resulting in insufficient tack. Some studies have also attempted to improve low-temperature performance by introducing rubber components to modify pressure-sensitive adhesives, but poor compatibility and the tendency for phase separation can affect bonding reliability. Regarding substrate modification, for thermoplastic polyolefins like HDPE, while simply adding elastomers such as POE can improve low-temperature toughness, the compatibility between elastomers and HDPE is limited, and the interfacial bonding problem between polar adhesives and non-polar substrates remains unresolved.

[0004] Therefore, it is of great significance to develop an adhesive tape that can maintain excellent adhesion, substrate flexibility, and anti-slip properties in ultra-low temperature environments of -40℃ and below. Summary of the Invention

[0005] The purpose of this invention is to provide a low-temperature resistant anti-slip adhesive material, its preparation method, and its application in order to solve the above-mentioned problems. This tape can maintain high adhesion at a low temperature of -40℃, and the thermoplastic polyolefin substrate is flexible and has excellent anti-slip properties.

[0006] The objective of this invention is achieved through the following technical solution:

[0007] A low-temperature resistant, anti-slip adhesive material includes a modified HDPE substrate layer and an acrylic pressure-sensitive adhesive layer coated on the substrate layer, wherein:

[0008] The modified HDPE substrate layer is made of a blend containing the following components: 70-90 parts by weight of HDPE resin, 5-15 parts by weight of POE elastomer, 1-5 parts by weight of methyl vinyl silicone rubber, 2-8 parts by weight of compatibilizer, and 1-3 parts by weight of peroxide crosslinking agent.

[0009] The acrylate pressure-sensitive adhesive layer is obtained by polymerization reaction of raw materials containing the following components: 60-80 parts by weight of soft monomer, 5-20 parts by weight of macromolecular monomer containing polybutadiene segments, 5-15 parts by weight of hard monomer, 1-5 parts by weight of functional monomer, 3-8 parts by weight of cold-resistant plasticizer, 0.1-0.5 parts by weight of initiator, and 0.2-1.0 parts by weight of crosslinking agent.

[0010] Furthermore, the HDPE resin has a melt index of 0.5-10.5 g / 10 min and a density of 0.95-0.97 g / cm³. 3 Tensile yield strength ≥20MPa, elongation at break ≥280%;

[0011] The compatibilizer is selected from maleic anhydride-grafted polyethylene;

[0012] The peroxide crosslinking agent is selected from dicumyl peroxide and bis-tert-butyl peroxide.

[0013] Furthermore, the modified HDPE substrate layer is prepared by the following method: premixing each component in a high-speed mixer in proportion, melting and granulating it in a specific temperature range using a twin-screw extruder, pressing the granules into shape using a flat vulcanizing machine, controlling the thickness, and winding them up for later use.

[0014] Furthermore, the macromonomer containing polybutadiene segments is a maleic ester derivative of hydrogenated hydroxyl-terminated polybutadiene with a number average molecular weight of 2000-5000, which is prepared by introducing polymerizable double bonds at the ends of the hydroxyl-terminated polybutadiene chain.

[0015] Furthermore, the soft monomer is selected from one or two of isooctyl acrylate and butyl acrylate;

[0016] The hard monomer is selected from one or more of methyl methacrylate, acrylonitrile, and styrene.

[0017] The functional monomer is selected from one or two of acrylic acid and hydroxyethyl methacrylate;

[0018] The cold-resistant plasticizer is dioctyl adipate or dioctyl sebacate.

[0019] The crosslinking agent is aluminum acetylacetonate or isocyanate;

[0020] The initiator is azobisisobutyronitrile.

[0021] Furthermore, the adhesive is prepared by the following method:

[0022] (1) Synthesis of acrylate prepolymer: Soft monomer, hard monomer, functional monomer, macromonomer containing polybutadiene segments and some initiator are added to a reaction vessel, solvent is added, and the reaction is carried out at 70-85℃ for 3-6 hours to obtain acrylate prepolymer;

[0023] (2) Cool the prepared acrylate prepolymer to below 40°C, add cold-resistant plasticizer, remaining initiator and crosslinking agent, stir evenly to obtain adhesive.

[0024] A method for preparing a low-temperature resistant anti-slip adhesive material includes the following steps:

[0025] (1) Apply adhesive to the release film, then laminate it with the substrate, then shape it, and then roll it up to obtain a semi-finished roll material;

[0026] (2) Unwind the semi-finished product with the substrate side facing up, apply adhesive to the surface, and then pass it through the first drying tunnel to allow the pressure-sensitive adhesive to dry.

[0027] (3) On the pre-cured pressure-sensitive adhesive layer, the pre-made abrasion-resistant sand layer is hot-pressed and then enters the second drying tunnel, and the composite is reinforced by pressure rollers;

[0028] (4) After cooling, rewind and the final product is obtained after the performance stabilizes;

[0029] The thickness of the substrate layer is 0.1~0.5mm, and the thickness of the adhesive layer is 0.1~0.6mm.

[0030] Application of a low-temperature resistant anti-slip adhesive material, wherein the anti-slip adhesive material is used as an anti-slip tape.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] This invention improves low-temperature flexibility by introducing POE elastomer and methyl vinyl silicone rubber into a thermoplastic polyolefin (HDPE) substrate and using peroxide for crosslinking. POE imparts basic low-temperature ductility to the thermoplastic polyolefin substrate, while methyl vinyl silicone rubber, due to its lower glass transition temperature, effectively terminates craze propagation and inhibits low-temperature brittle fracture. Simultaneously, the three-dimensional network formed by peroxide crosslinking limits excessive shrinkage of the HDPE molecular chains at low temperatures, allowing the substrate to maintain good performance even at -40°C. Furthermore, the anhydride groups in maleic anhydride-grafted polyethylene can bond with the functional monomers in the acrylate pressure-sensitive adhesive, helping to solve the interfacial bonding problem between the adhesive and the thermoplastic polyolefin substrate, improving the adhesion of the adhesive layer to the substrate and abrasion-resistant components, and ensuring no separation under ultra-low temperatures of -40°C and stress.

[0033] This invention introduces a macromolecular monomer containing polybutadiene segments into an acrylic pressure-sensitive adhesive. Its main chain structure is similar to that of thermoplastic polyolefin (HDPE) substrates, acting as a "bridge" between the adhesive and the substrate and adherends, reducing interfacial tension and enhancing wetting and spreading capabilities at low temperatures. Simultaneously, through the action of soft monomers and cold-resistant plasticizers, the adhesive maintains a low glass transition temperature, preserving chain mobility even at -40°C, providing good initial tack. A moderate crosslinking network ensures the cohesive strength of the adhesive layer, preventing cohesive failure at low temperatures. Attached Figure Description

[0034] Figure 1 Photos showing the anti-slip performance of the samples;

[0035] Figure 2 These are photos of the samples during the low-temperature test.

[0036] Figure 3 This is a photo of the sample after the low-temperature test.

[0037] Figure 4 This is a photograph of the sample during a low-temperature salting test. Detailed Implementation

[0038] To address the problems of material brittleness, easy cracking when bent, loss of adhesion at low temperatures, and material detachment in anti-slip tapes operating below -40℃, this invention provides a low-temperature resistant anti-slip adhesive material, comprising a modified HDPE substrate layer and an acrylic pressure-sensitive adhesive layer coated on the substrate layer, wherein:

[0039] The modified HDPE substrate layer is made of a blend containing the following components: 70-90 parts by weight of HDPE resin, 5-15 parts by weight of POE elastomer, 1-5 parts by weight of methyl vinyl silicone rubber, 2-8 parts by weight of compatibilizer, and 1-3 parts by weight of peroxide crosslinking agent.

[0040] The acrylate pressure-sensitive adhesive layer is obtained by polymerization reaction of raw materials containing the following components: 60-80 parts by weight of soft monomer, 5-20 parts by weight of macromolecular monomer containing polybutadiene segments, 5-15 parts by weight of hard monomer, 1-5 parts by weight of functional monomer, 3-8 parts by weight of cold-resistant plasticizer, 0.1-0.5 parts by weight of initiator, and 0.2-1.0 parts by weight of crosslinking agent.

[0041] This invention improves the low-temperature toughness of HDPE substrates by modifying them, enabling them to maintain excellent performance at -40°C. The addition of a compatibilizer forms hydrogen bonds or chemical bonds with the acrylic pressure-sensitive adhesive, avoiding interfacial bonding problems between polar adhesives and non-polar substrates and improving the adhesion between the adhesive layer and the substrate. Furthermore, the invention introduces macromonomers containing polybutadiene segments into the acrylic pressure-sensitive adhesive, acting as a "bridge" between the adhesive, substrate, and adherends, reducing interfacial tension and enhancing wetting and spreading capabilities at low temperatures.

[0042] In a preferred embodiment of the present invention, the modified HDPE substrate layer is made of a blend comprising the following components: 75-85 parts by weight of HDPE resin, 8-12 parts by weight of POE elastomer, 2-4 parts by weight of methyl vinyl silicone rubber, 3-5 parts by weight of compatibilizer, and 2-3 parts by weight of peroxide crosslinking agent. For example, in a specific preferred embodiment, the modified HDPE substrate layer is made of a blend comprising the following components: 76.5 parts by weight of HDPE resin, 11 parts by weight of POE elastomer, 3 parts by weight of methyl vinyl silicone rubber, 4 parts by weight of compatibilizer, and 2.5 parts by weight of peroxide crosslinking agent.

[0043] In a preferred embodiment of the present invention, the HDPE resin has a melt flow index of 0.5-10.5 g / 10 min (weight 21.6 kg) and a density of 0.95-0.97 g / cm³. 3 Tensile yield strength ≥20MPa, elongation at break ≥280% (e.g., Daqing Petrochemical's HDPE 2200J).

[0044] As a preferred embodiment of the present invention, the POE elastomer can be commercially available Dow ENGAGE 8150 or ExxonMobil Exact 9061. POE, as a toughening modifier, helps to improve the flexibility and impact resistance of the substrate, giving the substrate better flexibility and bending ability.

[0045] In a preferred embodiment of the present invention, the compatibilizer is selected from maleic anhydride-grafted polyethylene (PE-g-MAH), for example, in a specific embodiment, commercially available ExxonMobil PE 1040 can be used.

[0046] In a preferred embodiment of the present invention, the peroxide crosslinking agent is selected from dicumyl peroxide and bis-tert-butyl peroxide.

[0047] In a preferred embodiment of the present invention, the modified HDPE substrate layer further includes pigments.

[0048] As a preferred embodiment of the present invention, the modified HDPE substrate layer is prepared by the following method: premixing each component in a high-speed mixer in proportion, melting and granulating it in a specific temperature range by a twin-screw extruder, pressing the granules into shape by a flat vulcanizing machine (or using casting film), precisely controlling the thickness (e.g., 0.1-1 mm), and winding it up for later use.

[0049] In a preferred embodiment of the present invention, the surface of the modified HDPE substrate layer has a micro-uneven structure, which is obtained by hot pressing (embossing roller imprinting), and the micro-uneven structure provides anti-slip properties.

[0050] In a preferred embodiment of the present invention, the acrylate pressure-sensitive adhesive layer is obtained by polymerization of raw materials containing the following components: 65-75 parts by weight of soft monomer, 10-15 parts by weight of macromonomer containing polybutadiene segments, 8-12 parts by weight of hard monomer, 3-5 parts by weight of functional monomer, 4-6 parts by weight of cold-resistant plasticizer, 0.2-0.4 parts by weight of initiator, and 0.3-0.8 parts by weight of crosslinking agent. For example, in a specific preferred embodiment, the acrylate pressure-sensitive adhesive layer is obtained by polymerization of raw materials containing the following components: 70 parts by weight of soft monomer, 12 parts by weight of macromonomer containing polybutadiene segments, 10 parts by weight of hard monomer, 4 parts by weight of functional monomer, 5 parts by weight of cold-resistant plasticizer, 0.3 parts by weight of initiator, and 0.5 parts by weight of crosslinking agent.

[0051] In a preferred embodiment of the present invention, the macromonomer containing polybutadiene segments is a maleic ester derivative of hydrogenated hydroxyl-terminated polybutadiene with a number average molecular weight of 2000-5000, which is prepared by introducing polymerizable double bonds into the ends of hydroxyl-terminated polybutadiene (HTPB).

[0052] In a specific embodiment, the preparation method is as follows: (1) Add HTPB, solvent cyclohexane, and copper chromite catalyst to a reaction vessel, replace the air with nitrogen, then add hydrogen to a pressure of 6 MPa, raise the temperature to 150°C, stir and react for 6 hours, after the reaction is completed and cooled, filter to remove the catalyst, remove cyclohexane by vacuum distillation, and obtain the hydrogenated product HHTPB. (2) Dissolve the above HHTPB in toluene, add maleic anhydride and p-toluenesulfonic acid, raise the temperature to 80°C, stir and react for 6 hours, remove the solvent and unreacted maleic anhydride, and obtain HHTPB-MAH macromonomer with polymerizable double bonds at the end.

[0053] In a preferred embodiment of the present invention, the soft monomer is selected from one or two of isooctyl acrylate and butyl acrylate; the hard monomer is selected from one or more of methyl methacrylate, acrylonitrile, and styrene; and the functional monomer is selected from one or two of acrylic acid and hydroxyethyl methacrylate.

[0054] In a preferred embodiment of the present invention, the cold-resistant plasticizer is dioctyl adipate or dioctyl sebacate.

[0055] In a preferred embodiment of the present invention, the crosslinking agent is aluminum acetylacetonate or isocyanate.

[0056] As a preferred embodiment of the present invention, the adhesive is prepared by the following method: (1) Synthesis of acrylate prepolymer: soft monomer, hard monomer, functional monomer, macromonomer containing polybutadiene segments and part of the initiator are added to a reaction vessel, solvent is added, and the reaction is carried out at 70-85°C for 3-6 hours to obtain acrylate prepolymer; (2) the obtained acrylate prepolymer is cooled to below 40°C, cold-resistant plasticizer, the remaining initiator and crosslinking agent are added, and the mixture is stirred evenly to obtain the adhesive with a solid content of 30-55%. Preferably, the acrylate prepolymer can be synthesized by seed polymerization process.

[0057] As a preferred embodiment of the present invention, the low-temperature resistant anti-slip adhesive material is prepared by the following method:

[0058] (1) Apply adhesive to the release film, then laminate it with the substrate, then shape it, and then roll it up to obtain a semi-finished roll material;

[0059] (2) Unwind the semi-finished product with the substrate side facing up, apply adhesive to the surface, and then pass it through the first drying tunnel to allow the pressure-sensitive adhesive to dry.

[0060] (3) On the pre-cured pressure-sensitive adhesive layer, the pre-made abrasion-resistant sand layer is hot-pressed and then enters the second drying tunnel, and the composite is reinforced by pressure rollers;

[0061] (4) After cooling, rewind and the final product is obtained after the performance stabilizes;

[0062] The thickness of the substrate layer is 0.1~0.5mm, and the thickness of the adhesive layer is 0.1~0.6mm.

[0063] The wear-resistant sand-like surface layer is specifically prepared by the following method: polyester resin, quartz sand, nano alumina and solvent are added to a disperser and dispersed evenly to obtain a coating mixture; the coating mixture is coated on a light release force PET film, dried, cooled and then rolled up to obtain a prefabricated wear-resistant sand-like surface layer.

[0064] The present invention will be further described in detail below with reference to specific embodiments, but the scope of protection of the present invention is not limited thereto. All raw materials used in the following embodiments are commercially available products. Experimental methods not specifically described in the embodiments were conducted under conventional conditions. All references to "parts" refer to parts by weight.

[0065] [Preparation of modified HDPE substrate samples]

[0066] Prepare the modified HDPE substrate according to the following steps:

[0067] (1) Prepare the raw materials according to the formula shown in Table 1: HDPE resin (Daqing Petrochemical HDPE 2200J), POE elastomer (Dow ENGAGE 8150), methyl vinyl silicone rubber (CAS No.: 68037-87-6), compatibilizer ExxonMobil Exxelor PE1040, peroxide crosslinking agent dicumyl peroxide (CAS No.: 80-43-3) and a small amount of black masterbatch.

[0068] (2) Add each component to the high-speed mixer according to the proportion, and stir for 5-10 minutes until the material is evenly mixed;

[0069] (3) The mixed material is put into a twin-screw extruder for melt blending. The extrusion temperature is 180-210℃. The film is extruded and cast through a T-die. The film thickness is controlled at about 0.15mm. Before the film material is completely cooled, a micro-uneven structure with a depth of about 20μm is formed on the surface by embossing roller. Then, corona treatment is performed, and the film is wound up for use.

[0070] Table 1. Components of Modified HDPE Substrate Formulation (parts by weight)

[0071]

[0072] Note: “—” in the table indicates that it has not been added.

[0073] Low-temperature flexibility test was performed on the samples X1 to X8: the substrate was cut into 100mm×20mm samples, placed in a -40℃ low-temperature box for 4 hours, and immediately folded along a 10mm diameter rod after being taken out. Each sample was tested 5 times and the cracking of the substrate was observed. The test results are detailed in Table 2.

[0074] Table 2 Low-Temperature Flexibility Test Results of Substrates

[0075] sample Low temperature cracking Sample X1 No cracking Sample X2 Micro cracks Sample X3 No cracking Sample X4 No cracking Sample X5 Micro cracks Sample X6 Numerous cracks Sample X7 Minor cracks Sample X8 Minor cracks Ordinary HDPE substrate Severe cracking

[0076] Table 2 shows that samples X1, X3, and X4 did not crack during the -40℃ low-temperature folding test, exhibiting excellent low-temperature flexibility. Samples X2 and X5 showed minor cracks, indicating slightly poorer performance. Samples X6 (without POE), X7 (without methyl vinyl silicone rubber), and X8 (without peroxide crosslinking agent) showed cracks. This indicates that POE elastomer, methyl vinyl silicone rubber, and peroxide crosslinking agent are important components that impart excellent low-temperature resistance to the substrate, and their synergistic effect achieves the desired result.

[0077] [Preparation of acrylic pressure-sensitive adhesive samples]

[0078] Preparation of macromonomers containing polybutadiene segments

[0079] The following steps were taken to prepare a macromonomer containing polybutadiene segments: 100 parts of hydroxyl-terminated polybutadiene (HTPB, CAS No.: 69102-90-5), 500 parts of cyclohexane solvent, and 1 part of copper chromite catalyst were added to a reaction vessel. Nitrogen gas was used to replace the air, and then hydrogen gas was introduced to a pressure of 6 MPa. The temperature was raised to 150°C, and the reaction was stirred for 6 hours. After the reaction was completed and cooled, the catalyst was removed by filtration, and cyclohexane was removed by vacuum distillation to obtain the hydrogenated product HHTPB. HHTPB was dissolved in 200 parts toluene, and 15 parts maleic anhydride (CAS No.: 108-31-6) and 1 part p-toluenesulfonic acid (CAS No.: 104-15-4) were added. The mixture was heated to 80°C and stirred for 6 hours. The solvent was removed by vacuum distillation, and unreacted maleic anhydride was removed by washing to obtain HHTPB-MAH macromonomers with polymerizable double bonds at the ends. The molecular weight was tested according to GB / T 27843-2011, and the number average molecular weight was 3500.

[0080] Acrylic pressure-sensitive adhesive sample Y1

[0081] Prepare the following steps: Mix the soft monomers (35 parts isooctyl acrylate and 35 parts butyl acrylate), the hard monomers (10 parts methyl methacrylate), the functional monomers (4 parts acrylic acid), 12 parts of macromonomers containing polybutadiene segments, and 0.2 parts azobisisobutyronitrile (AIBN) evenly to obtain a monomer mixture for later use; add 100 parts of ethyl acetate solvent to a reaction vessel, add 8 parts of the monomer mixture to the reaction vessel, and gradually heat to 75°C under stirring conditions. Observe the reaction system and start timing from the appearance of foam, reacting for 10 minutes; add the remaining monomer mixture dropwise over 4 hours, and then keep warm for 2 hours to obtain the acrylate prepolymer; cool the obtained acrylate prepolymer to 30°C, add 5 parts of the cold-resistant plasticizer dioctyl sebacate, 0.1 parts of AIBN, and 0.5 parts of the crosslinking agent aluminum acetylacetonate, and stir evenly to obtain the adhesive.

[0082] Acrylic pressure-sensitive adhesive sample Y2

[0083] Prepare the following steps: Mix the soft monomers (30 parts isooctyl acrylate and 35 parts butyl acrylate), hard monomers (4 parts acrylonitrile and 4 parts styrene), functional monomers (3 parts acrylic acid), 10 parts of macromonomers containing polybutadiene segments, and 0.2 parts azobisisobutyronitrile (AIBN) evenly to obtain a monomer mixture for later use; add 100 parts of ethyl acetate solvent to a reaction vessel, add 8 parts of the monomer mixture to the reaction vessel, and gradually heat to 75°C under stirring conditions. Observe the reaction system and start timing from the appearance of foam, reacting for 10 minutes; add the remaining monomer mixture dropwise over 4 hours, and then keep warm for 2 hours to obtain the acrylate prepolymer; cool the obtained acrylate prepolymer to 30°C, add 4 parts of the cold-resistant plasticizer dioctyl adipate, 0.1 parts of AIBN, and 0.3 parts of the crosslinking agent aluminum acetylacetonate, and stir evenly to obtain the adhesive.

[0084] Acrylic pressure-sensitive adhesive sample Y3

[0085] Prepare the following steps: Mix the soft monomers (40 parts isooctyl acrylate and 35 parts butyl acrylate), the hard monomers (12 parts styrene), the functional monomers (4 parts hydroxyethyl methacrylate and 1 part acrylic acid), 15 parts of the macromonomer containing polybutadiene segments, and 0.2 parts of azobisisobutyronitrile (AIBN) evenly to obtain a monomer mixture for later use; add 100 parts of ethyl acetate solvent to a reaction vessel, add 8 parts of the monomer mixture to the reaction vessel, and gradually heat to 75°C under stirring conditions. Observe the reaction system and start timing from the appearance of foam, reacting for 10 minutes; add the remaining monomer mixture dropwise over 3 hours, and then keep warm for 2 hours to obtain the acrylate prepolymer; cool the obtained acrylate prepolymer to 30°C, add 6 parts of the cold-resistant plasticizer dioctyl sebacate, 0.1 parts of AIBN, and 0.8 parts of the crosslinking agent isocyanate, and stir evenly to obtain the adhesive.

[0086] Acrylic pressure-sensitive adhesive sample Y4

[0087] Prepare the following steps: Mix the soft monomer (60 parts butyl acrylate), hard monomer (5 parts methyl methacrylate), functional monomer (1 part hydroxyethyl methacrylate), 5 parts macromonomer containing polybutadiene segments, and 0.1 parts azobisisobutyronitrile (AIBN) evenly to obtain a monomer mixture for later use; add 80 parts ethyl acetate solvent to a reaction vessel, add 6 parts of the monomer mixture to the reaction vessel, and gradually heat to 75°C under stirring conditions. Observe the reaction system and start timing from the appearance of foam, reacting for 10 minutes; add the remaining monomer mixture dropwise over 3 hours, and then keep warm for 2 hours to obtain the acrylate prepolymer; cool the obtained acrylate prepolymer to 30°C, add 3 parts dioctyl adipate plasticizer, 0.1 parts azobisisobutyronitrile (AIBN), and 0.2 parts isocyanate crosslinking agent, and stir evenly to obtain the adhesive.

[0088] Acrylic pressure-sensitive adhesive sample Y5

[0089] Prepare the following steps: Mix the soft monomer (80 parts isooctyl acrylate), hard monomer (15 parts methyl methacrylate), functional monomer (5 parts hydroxyethyl methacrylate), 20 parts of macromonomer containing polybutadiene segments, and 0.3 parts of azobisisobutyronitrile (AIBN) evenly to obtain a monomer mixture for later use; add 120 parts of ethyl acetate solvent to a reaction vessel, add 10 parts of the monomer mixture to the reaction vessel, and gradually heat to 75°C under stirring conditions. Observe the reaction system and start timing from the appearance of foam, reacting for 10 minutes; add the remaining monomer mixture dropwise over 5 hours, and then keep warm for 2 hours to obtain the acrylate prepolymer; cool the obtained acrylate prepolymer to 30°C, add 8 parts of cold-resistant plasticizer dioctyl sebacate, 0.1 parts of AIBN, and 1 part of crosslinking agent aluminum acetylacetonate, and stir evenly to obtain the adhesive.

[0090] Acrylic pressure-sensitive adhesive sample Y6

[0091] Compared with sample Y1, the raw materials do not contain macromonomers containing polybutadiene segments, but are otherwise identical to sample Y1. Specifically, the preparation is as follows: Soft monomers (35 parts isooctyl acrylate, 35 parts butyl acrylate), hard monomers (10 parts methyl methacrylate), functional monomers (4 parts acrylic acid), and 0.2 parts azobisisobutyronitrile are mixed evenly to obtain a monomer mixture for later use; 100 parts of ethyl acetate solvent are added to a reaction vessel, and 8 parts of the monomer mixture are added to the reaction vessel. Under stirring conditions, the mixture is gradually heated to 75°C. The reaction system is observed, and the reaction time is started from the appearance of foam, and the reaction is allowed to proceed for 10 minutes; the remaining monomer mixture is added dropwise over 4 hours, and the mixture is kept at this temperature for another 2 hours to obtain the acrylate prepolymer; the obtained acrylate prepolymer is cooled to 30°C, and 5 parts of the cold-resistant plasticizer dioctyl sebacate, 0.1 parts of azobisisobutyronitrile, and 0.5 parts of the crosslinking agent aluminum acetylacetonate are added and stirred evenly to obtain the adhesive.

[0092] Acrylic pressure-sensitive adhesive sample Y7

[0093] Compared with sample Y1, no cold-resistant plasticizer was added to the raw materials, and all other aspects were the same as sample Y1. The preparation was carried out according to the following steps: Soft monomers (35 parts isooctyl acrylate, 35 parts butyl acrylate), hard monomers (10 parts methyl methacrylate), functional monomers (4 parts acrylic acid), 12 parts macromonomers containing polybutadiene segments, and 0.2 parts azobisisobutyronitrile were mixed evenly to obtain a monomer mixture for later use; 100 parts of ethyl acetate solvent were added to a reaction vessel, and 8 parts of the monomer mixture were added to the reaction vessel. Under stirring conditions, the mixture was gradually heated to 75°C. The reaction system was observed, and the reaction time was started from the appearance of foam, and the reaction lasted for 10 minutes; the remaining monomer mixture was added dropwise over 4 hours, and the mixture was kept at this temperature for another 2 hours to obtain the acrylate prepolymer; the obtained acrylate prepolymer was cooled to 30°C, and 0.1 parts azobisisobutyronitrile and 0.5 parts aluminum acetylacetonate crosslinking agent were added and stirred evenly to obtain the adhesive.

[0094] Acrylic pressure-sensitive adhesive sample Y8

[0095] Compared with sample Y1, the raw materials do not contain the crosslinking agent aluminum acetylacetonate, and are otherwise identical to sample Y1. Specifically, the preparation is as follows: Soft monomers (35 parts isooctyl acrylate, 35 parts butyl acrylate), hard monomers (10 parts methyl methacrylate), functional monomers (4 parts acrylic acid), 12 parts macromonomers containing polybutadiene segments, and 0.2 parts azobisisobutyronitrile are mixed evenly to obtain a monomer mixture for later use; 100 parts of ethyl acetate solvent are added to a reaction vessel, and 8 parts of the monomer mixture are added to the reaction vessel. Under stirring conditions, the mixture is gradually heated to 75°C. The reaction system is observed, and the reaction time is started from the appearance of foam, and the reaction is carried out for 10 minutes; the remaining monomer mixture is added dropwise over 4 hours, and then kept at the temperature for another 2 hours to obtain the acrylate prepolymer; the obtained acrylate prepolymer is cooled to 30°C, and 5 parts of the cold-resistant plasticizer dioctyl sebacate and 0.1 parts azobisisobutyronitrile are added and stirred evenly to obtain the adhesive.

[0096] [Preparation of anti-slip adhesive material samples]

[0097] Preparation of wear-resistant sandblasted surface layer

[0098] Prepare the abrasion-resistant sandblasted surface layer according to the following steps:

[0099] (1) Prepare the raw materials according to the following parts by weight: 50 parts polyester resin (60 mesh particle size, Bosch Vitel 1901NSB-P), 25 parts quartz sand (60 mesh particle size), 3 parts nano alumina and 55 parts solvent methyl ethyl ketone.

[0100] (2) Put all raw materials into a high-speed disperser, disperse at 1200 rpm for 20 minutes, reduce to 400 rpm, stir for 15 minutes until uniform, and obtain a coating mixture;

[0101] (3) Using a slit coating head, apply the above coating mixture onto a light release force PET film and enter a multi-stage drying tunnel: 80℃ (3min) → 120℃ (4min) → 150℃ (2min). After cooling, roll it up to obtain a wear-resistant sand film with a thickness of about 0.3mm, which is ready for use.

[0102] To further prepare adhesive tape samples, according to the raw material composition in Table 3, follow these steps:

[0103] (1) Apply a first layer of adhesive (approximately 0.2 mm thick) to the release film using a slot coating method, and then press it together with the substrate layer (0.15 mm) under a composite roller (temperature 60-80℃, pressure 2-4 bar). Subsequently, cool it to below 40℃ using a cooling roller group (temperature 10-20℃) to set its shape, and then rewind it to obtain a semi-finished roll material.

[0104] (2) Unwind the semi-finished product with the substrate side facing up, apply a second layer of adhesive (about 0.2 mm thick) to its upper surface, and then pass it through the first drying tunnel (60℃ zone 2 min → 80℃ zone 3 min) to allow the pressure-sensitive adhesive to dry to the surface and generate sufficient cohesion.

[0105] (3) On the pre-cured pressure-sensitive adhesive layer, the pre-made abrasion-resistant sand layer is hot-pressed onto the pre-cured pressure-sensitive adhesive layer through a hot composite roller (roller temperature 100±10℃, pressure 0.3MPa). Then it enters the second drying tunnel (80℃ zone 2min→100℃ zone 2min), and at the exit, it is reinforced by a pressure roller (0.3MPa).

[0106] (4) After cooling by the cooling roller (temperature is 20-25℃), the temporary release film of the abrasion-resistant sand layer is removed, and then the product is rolled up. The product is placed in a constant temperature and humidity environment. After the performance is stable, the final product is obtained.

[0107] Table 3 Composition of Anti-slip Adhesive Materials

[0108]

[0109] [Performance Testing of Anti-slip Adhesive Material Samples]

[0110] 1. Slip resistance test: A shoe slope test was conducted according to Annex B of the slip resistance test standard DIN EN 16165:2023-02. See the test photo for sample E1. Figure 1 ;

[0111] 2. Low-temperature test: In accordance with IEC60068-2-1:2007 "Environmental testing for electric and electronic products - Part 2: Test methods - Test A: Cold", place the sample in a climatic chamber at -40°C for 288 h, and observe whether the sample shows chalking, degumming, or separation of adhered materials. If the tape shows no chalking, degumming, or separation of adhered materials, it is considered qualified. For the photos of the low-temperature test of sample E1, see Figure 2 , Figure 3 ;

[0112] 3. Low-temperature adhesive surface test: Cut the sample into a 5 cm × 10 cm long adhesive strip, attach it to the surface of a glass plate, place it in a thermo-hygrostat set at -40°C for 72 h, and observe whether the adhesive surface warps or is easily torn; if the adhesive surface shows no warping or easy tearing after ≥ 72 h, it is considered qualified;

[0113] 4. Sand surface soaking test: Cut the sample into a 5 cm × 10 cm long adhesive strip, attach it to the surface of a glass plate, let it soak statically, completely cover the sample under the water surface, and observe whether the sand surface of the anti-slip adhesive material separates or has bubbles. If there is no separation or bubbles on the sand surface after ≥ 168 h, it is considered qualified;

[0114] 5. Low-temperature salinization test: Cut the sample into a 5 cm × 10 cm long adhesive strip, attach it to the surface of a glass plate, place ice cubes on the tape surface, and use industrial salt to melt the ice. Observe whether the adhesive surface warps or is easily torn; if the adhesive surface shows no warping or easy tearing after ≥ 168 h, it is considered qualified. For the photos of the low-temperature salinization test of sample E1, see Figure 4 .

[0115] The test results are shown in Table 4.

[0116] Table 4 Test results of sample performance

[0117]

[0118] As can be seen from Table 4, samples E1 - E5 using the preferred formula and components of the present invention performed excellently in various tests; while the comparative samples E6 - E10 lacking key components (such as macromolecular monomers, cold-resistant plasticizers, cross-linking agents) showed varying degrees of failure.

[0119] Select samples E1 to E5 for further more stringent chemical solvent resistance tests.

[0120] The specific testing method is as follows: Prepare the following chemical solvents: ① Sodium hypochlorite ② Hydraulic oil ③ Ethylene glycol ④ Sodium hydroxide ⑤ Mineral oil ⑥ Diesel fuel ⑦ Hydrogen peroxide ⑧ Isopropanol ⑨ Industrial brine ⑩ Pure water. Prepare glass plates and a storage box. Cut the test sample into strips of 5cm × 20cm. Attach the sample to the glass plate, flatten the material with a pressure roller to ensure no air bubbles, and let it stand for 24 hours. Then, place the glass plates with the attached samples into the storage box, label them with the solvent names, and pour in the corresponding solvents. After the solvent level is above the sample level, let it stand for a set time (168 hours) and observe whether the sample shows any peeling. The test results are detailed in Table 5.

[0121] Table 5 Results of chemical solvent resistance test on samples

[0122]

[0123] As shown in Table 5, samples E1 to E5 have good resistance to chemical solvents. Among them, sample E1 showed no edge peeling after being immersed in all 10 chemical solvents for 168 hours, demonstrating the best resistance to chemical solvents. Samples E2 and E3 only showed slight peeling in sodium hypochlorite. Samples E4 and E5 showed slight peeling in sodium hypochlorite, sodium hydroxide, and hydrogen peroxide.

[0124] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A low-temperature resistant anti-slip adhesive material, characterized in that, It includes a modified HDPE substrate layer and an acrylic pressure-sensitive adhesive layer coated on the substrate layer, wherein: The modified HDPE substrate layer is made of a blend containing the following components: 70-90 parts by weight of HDPE resin, 5-15 parts by weight of POE elastomer, 1-5 parts by weight of methyl vinyl silicone rubber, 2-8 parts by weight of compatibilizer, and 1-3 parts by weight of peroxide crosslinking agent. The acrylate pressure-sensitive adhesive layer is obtained by polymerization reaction of raw materials containing the following components: 60-80 parts by weight of soft monomer, 5-20 parts by weight of macromolecular monomer containing polybutadiene segments, 5-15 parts by weight of hard monomer, 1-5 parts by weight of functional monomer, 3-8 parts by weight of cold-resistant plasticizer, 0.1-0.5 parts by weight of initiator, and 0.2-1.0 parts by weight of crosslinking agent.

2. The low-temperature resistant anti-slip adhesive material according to claim 1, characterized in that, The HDPE resin has a melt flow index of 0.5-10.5 g / 10 min and a density of 0.95-0.97 g / cm³. 3 ; The compatibilizer is selected from maleic anhydride-grafted polyethylene; The peroxide crosslinking agent is selected from dicumyl peroxide and bis-tert-butyl peroxide.

3. The low-temperature resistant anti-slip adhesive material according to claim 1, characterized in that, The modified HDPE substrate layer is prepared by the following method: the components are premixed in a high-speed mixer in proportion, melt-blended and granulated by a twin-screw extruder, the granules are pressed into shape by a flat vulcanizing machine, the thickness is controlled, and the granules are wound up for later use.

4. The low-temperature resistant anti-slip adhesive material according to claim 1, characterized in that, The macromonomer containing polybutadiene segments is a maleic ester derivative of hydrogenated hydroxyl-terminated polybutadiene with a number average molecular weight of 2000-5000, which is prepared by introducing polymerizable double bonds at the ends of the hydroxyl-terminated polybutadiene chain.

5. The low-temperature resistant anti-slip adhesive material according to claim 1, characterized in that, The soft monomer is selected from one or two of isooctyl acrylate and butyl acrylate; The hard monomer is selected from one or more of methyl methacrylate, acrylonitrile, and styrene.

6. The low-temperature resistant anti-slip adhesive material according to claim 1, characterized in that, The functional monomer is selected from one or two of acrylic acid and hydroxyethyl methacrylate; The cold-resistant plasticizer is dioctyl adipate or dioctyl sebacate.

7. The low-temperature resistant anti-slip adhesive material according to claim 1, characterized in that, The crosslinking agent is aluminum acetylacetonate or isocyanate; The initiator is azobisisobutyronitrile.

8. The low-temperature resistant anti-slip adhesive material according to claim 1, characterized in that, The adhesive is prepared by the following method: (1) Synthesis of acrylate prepolymer: Soft monomer, hard monomer, functional monomer, macromonomer containing polybutadiene segments and some initiator are added to a reaction vessel, solvent is added, and the reaction is carried out at 70-85℃ for 3-6 hours to obtain acrylate prepolymer; (2) Cool the prepared acrylate prepolymer to below 40°C, add cold-resistant plasticizer, remaining initiator and crosslinking agent, stir evenly to obtain adhesive.

9. A method for preparing a low-temperature resistant anti-slip adhesive material as described in any one of claims 1-8, characterized in that, Includes the following steps: (1) Apply adhesive to the release film, then laminate it with the substrate, then shape it, and then roll it up to obtain a semi-finished roll material; (2) Unwind the semi-finished product with the substrate side facing up, apply adhesive to the surface, and then pass it through the first drying tunnel to allow the pressure-sensitive adhesive to dry. (3) On the pre-cured pressure-sensitive adhesive layer, the pre-made abrasion-resistant sand layer is hot-pressed and then enters the second drying tunnel, and the composite is reinforced by pressure rollers; (4) After cooling, rewind and the final product is obtained after the performance stabilizes; The thickness of the substrate layer is 0.1~0.5mm, and the thickness of the adhesive layer is 0.1~0.6mm.

10. The application of the low-temperature resistant anti-slip adhesive material as described in claim 1, characterized in that, The anti-slip adhesive material is used as an anti-slip tape.

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