Low-temperature-resistant advertising material and preparation method therefor

Abstract

The present application relates to the technical field of advertising materials and discloses a low-temperature-resistant advertising material and a preparation method therefor. The low-temperature-resistant advertising material comprises, from top to bottom, an aluminum foil layer, a special bonding coating layer, and a bottom layer. Raw materials for the special bonding coating layer include, by mass percentage, 20-40% of an aqueous acrylic resin, 5-15% of a modified graphene / polyurethane composite material, 2-6% of a toughening agent, 4-6% of a leveling agent, 1-3% of a defoaming agent, 1-5% of an anti-aging agent, and 31-61% of distilled water. Raw materials for the modified graphene / polyurethane composite material include 55-65 parts of an ethylenediamine-terminated aqueous polyurethane, 10-14 parts of carbamylated graphene oxide, 2-3 parts of dithiol, and 60-86 parts of deionized water. The advertising material provided by the present application has strong flame retardant and low temperature resistant properties.

Description

A low-temperature resistant advertising material and its preparation method Technical Field

[0001] This application relates to the field of advertising materials technology, and in particular to a low-temperature resistant advertising material and its preparation method. Background Technology

[0002] With the booming development of the modern advertising industry, the exploration and application of advertising materials within this field are becoming increasingly diverse, aiming to meet the personalized and functional needs of different scenarios. PVC (polyvinyl chloride) materials are widely used due to their excellent processing flexibility and relatively low cost. PVC materials are easy to mold, come in a variety of colors, are lightweight and durable, and these characteristics make them play an important role in many fields such as outdoor billboards, light boxes, and display racks.

[0003] However, in extremely cold and dry regions, specific climatic conditions place even more stringent demands on the performance of advertising materials. Especially when temperatures plummet to -40°C or even -50°C, existing advertising materials face severe challenges. They become extremely fragile, their impact resistance decreases significantly, and they are prone to cracking or breaking, seriously affecting the display effect of advertising content and the durability of the materials, thus limiting their application in these extreme climatic conditions.

[0004] Therefore, there is an urgent need to provide an advertising material that is resistant to low temperatures, and can maintain good light efficacy and physical properties even at extreme low temperatures of -50℃ and below. Summary of the Invention

[0005] To enhance the low-temperature resistance of advertising materials, this application provides a low-temperature resistant advertising material and its preparation method.

[0006] This application provides a low-temperature resistant advertising material, which adopts the following technical solution:

[0007] A low-temperature resistant advertising material and its preparation method are disclosed. The low-temperature advertising material comprises, from top to bottom, an aluminum foil layer, a special adhesive coating, and a bottom layer. The special adhesive coating raw materials include, by mass percentage: 20-40% water-based acrylic resin, 5-15% modified graphene / polyurethane composite material, 2-6% toughening agent, 4-6% leveling agent, 1-3% defoamer, 1-5% anti-aging agent, and 31-61% water.

[0008] By adopting the above technical solution, an advertising material is obtained by bonding the aluminum foil layer and the underlying material together with a special adhesive coating. The special adhesive coating uses a modified graphene / polyurethane composite material. Polyurethane has good adhesion and low temperature resistance. By using modified graphene oxide to further modify the polyurethane material, the low temperature resistance of the polyurethane material can be significantly enhanced, and the flame retardancy of the material can be effectively improved. Thus, the flame retardancy and low temperature resistance of the advertising material are effectively enhanced, and it can withstand temperatures of -50℃ and below, thus broadening the range of application environments.

[0009] Preferably, the special adhesive coating raw materials comprise, by weight percentage: 25-35% waterborne acrylic resin, 8-12% modified graphene / polyurethane composite material, 3-5% toughening agent, 4.5-5.5% leveling agent, 1.5-2.5% defoamer, 2-4% anti-aging agent, and 39-53% water.

[0010] Preferably, the special adhesive coating raw materials comprise, by weight percentage: 30% water-based acrylic resin, 10% modified graphene / polyurethane composite material, 4% toughening agent, 5% leveling agent, 2% defoamer, 3% anti-aging agent, and 46% water.

[0011] Preferably, the aluminum foil layer is forged aluminum foil; the bottom layer is transparent release paper.

[0012] Preferably, the modified graphene / polyurethane composite material is composed of the following raw materials in parts by weight: 55-65 parts ethylenediamine-terminated waterborne polyurethane, 10-14 parts urethane-esterified graphene oxide, 2-3 parts dithiol, and 60-86 parts deionized water.

[0013] By adopting the above technical solution, modified graphene / polyurethane composite materials are prepared by reacting ethylenediamine-terminated waterborne polyurethane with urethane-coated graphene oxide. On the one hand, the ethylenediamine-terminated waterborne polyurethane has good stability, good corrosion resistance, and is easy to modify, while the urethane-coated graphene oxide has better dispersibility. On the other hand, the ethylenediamine-terminated polyurethane introduces active groups such as amino groups, and the graphene oxide introduces urethane groups, which enhances the bonding force between polyurethane and graphene oxide. This is beneficial for obtaining coating fillers with strong dispersibility and low-temperature resistance, thereby effectively enhancing the functional properties of the coating.

[0014] Preferably, the ethylenediamine-terminated waterborne polyurethane is composed of the following raw materials in parts by weight: 30-40 parts polyether diol, 4-5 parts isophorone diisocyanate, 0.1-0.15 parts 2,2-dimethylolpropionic acid, 0.06-0.12 parts ethylenediamine, and 60-70 parts distilled water.

[0015] Preferably, the urethane-esterified graphene oxide is composed of the following raw materials in parts by weight: 0.5-1 parts graphene oxide, 100-200 parts deionized water, 1-2 parts isophorone diisocyanate, and 0.5-1 parts 2,2-dimethylolpropionic acid.

[0016] Preferably, the toughening agent is W1B POE-g-MAH nylon low-temperature modified toughening agent or Biorich (Germany). TM One type of toughening agent for nylon.

[0017] By adopting the above technical solutions, W1B POE-g-MAH nylon low-temperature modified toughening agent and German Biorich... TM Nylon toughening agents, as toughening agents, can withstand extremely low temperature environments, effectively enhancing the low-temperature resistance of advertising materials and extending their service life.

[0018] This application provides a method for preparing a low-temperature resistant advertising material, which adopts the following technical solution:

[0019] A method for preparing a low-temperature resistant advertising material includes the following steps:

[0020] S1. Weigh the raw materials according to the mass ratio, add water, water-based acrylic resin, and modified graphene / polyurethane composite material, and stir in a sealed container at 85-95℃ for 3-5 hours. After cooling, add toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30-50 minutes to obtain a special adhesive coating.

[0021] S2. Apply a special adhesive coating to the surface of the aluminum foil material, then attach the base material, and after bonding, you will get a low-temperature resistant advertising material.

[0022] Preferably, the preparation method of the modified graphene / polyurethane composite material includes the following steps:

[0023] S0. Preparation of raw materials: urethane-esterified graphene oxide and ethylenediamine-terminated waterborne polyurethane;

[0024] S1. Add urethane-esterified graphene oxide to a portion of deionized water, adjust the pH to 6-7, and ultrasonically disperse for 2-3 hours to obtain a urethane-esterified graphene oxide dispersion.

[0025] S2. Add dithiol to ethylenediamine-terminated waterborne polyurethane and react for 15-25 min. Increase the stirring speed, add the urethane-esterified graphene oxide dispersion prepared in S1 and the remaining deionized water, and emulsify for 0.5-1.5 h to obtain the modified graphene / polyurethane composite material.

[0026] In summary, this application includes at least one of the following beneficial technical effects:

[0027] By adopting the above technical solution, an advertising material is obtained by bonding the aluminum foil layer and the underlying material together with a special adhesive coating. The special adhesive coating uses a modified graphene / polyurethane composite material. Polyurethane has good adhesion and low temperature resistance. By using modified graphene oxide to further modify the polyurethane material, the low temperature resistance of the polyurethane material can be significantly enhanced, and the flame retardancy of the material can be effectively improved. Thus, the flame retardancy and low temperature resistance of the advertising material are effectively enhanced, and it can withstand temperatures of -50℃ and below, thus broadening the range of application environments. Detailed Implementation

[0028] The present application will be further described in detail below with reference to the embodiments.

[0029] The chemical reagents used in the embodiments and comparative examples provided in this invention are all commercially available products, and their brands and manufacturers are as follows:

[0030] Graphene oxide, Shanghai Aladdin Biochemical Technology Co., Ltd.;

[0031] Polyether diol, Shanghai Aladdin Biochemical Technology Co., Ltd., molecular weight 2000;

[0032] Water-based acrylic resin, Guangdong Wengjiang Chemical Reagent Co., Ltd., PB93956;

[0033] W1B POE-g-MAH Nylon Low-Temperature Modifier, Pande (Shanghai) International Trading Co., Ltd.;

[0034] Biorich, Germany TM Nylon toughening agent, Dongguan Yucheng Plastics Co., Ltd.;

[0035] Leveling agent, Guangdong Wengjiang Chemical Reagent Co., Ltd., acrylate leveling agent;

[0036] Defoamer, Wuhan Hongde Yuexin Pharmaceutical Technology Co., Ltd., mineral oil defoamer;

[0037] Anti-aging agent, Panhua Chemical (Shanghai) Co., Ltd., KY-405.

[0038] Preparation Example

[0039] Preparation Example 1

[0040] S0. Preparation of raw materials: urethane-esterified graphene oxide and ethylenediamine-terminated waterborne polyurethane:

[0041] S01. Preparation of urethane-esterified graphene oxide:

[0042] 0.5 g of graphene oxide was added to 100 g of deionized water and ultrasonically dispersed for 2 h to obtain a graphene oxide dispersion. Then, 1 g of isophorone diisocyanate was added to the graphene oxide dispersion and stirred at 75 °C for 2 h. Then, 0.5 g of 2,2-dimethylolpropionic acid was added and stirred at 75 °C for 4 h. After filtration, the mixture was washed twice with dichloromethane to obtain a filter cake. The filter cake was placed in a drying oven and dried at 60 °C for 12 h to obtain urethane-esterified graphene oxide.

[0043] S02. Preparation of ethylenediamine-terminated waterborne polyurethane:

[0044] Under N2 environment, 30g of polyether diol was added to a four-necked flask and dehydrated at 120℃ for 2h; 4g of isophorone diisocyanate was added and mixed evenly, and stirred at 75℃ for 2h; then 0.1g of 2,2-dimethylolpropionic acid was added, and stirred for 4h to obtain a polyurethane prepolymer; a mixture of 0.06g of ethylenediamine and 60g of distilled water was added to the polyurethane prepolymer, the stirring speed was adjusted to 3000rpm, and stirred for 1.5h to obtain ethylenediamine-terminated waterborne polyurethane;

[0045] S1. Add 10g of the prepared urethane-esterified graphene oxide to 40g of deionized water, adjust the pH to 6, and ultrasonically disperse for 2h to obtain a urethane-esterified graphene oxide dispersion.

[0046] S2. Add 2g of dithiol to 55g of ethylenediamine-terminated waterborne polyurethane and react for 15min. Increase the stirring speed to 3000rpm, then add the urethane-esterified graphene oxide dispersion prepared in S1 and 20g of deionized water. After reacting for 0.5h, the modified graphene / polyurethane composite material is obtained.

[0047] Preparation Example 2

[0048] S0. Preparation of raw materials: urethane-esterified graphene oxide and ethylenediamine-terminated waterborne polyurethane:

[0049] S01. Preparation of urethane-esterified graphene oxide:

[0050] 0.75 g of graphene oxide was added to 150 g of deionized water and ultrasonically dispersed for 2.5 h to obtain a graphene oxide dispersion. Then, 1.5 g of isophorone diisocyanate was added to the graphene oxide dispersion and stirred at 80 °C for 2.5 h. Then, 0.75 g of 2,2-dimethylolpropionic acid was added and stirred at 80 °C for 4.5 h. After filtration, the mixture was washed twice with dichloromethane to obtain a filter cake. The filter cake was placed in a drying oven and dried at 65 °C for 13 h to obtain urethane-esterified graphene oxide.

[0051] S02. Preparation of ethylenediamine-terminated waterborne polyurethane:

[0052] Under N2 environment, 35g of polyether diol was added to a four-necked flask and dehydrated at 130℃ for 3h; 4.5g of isophorone diisocyanate was added and mixed evenly, and the mixture was stirred at 80℃ for 2.5h; then 0.125g of 2,2-dimethylolpropionic acid was added, and the mixture was stirred for 4.5h to obtain a polyurethane prepolymer; a mixture of 0.09g of ethylenediamine and 65g of distilled water was added to the polyurethane prepolymer, the stirring speed was adjusted to 3500rpm, and the mixture was stirred for 2h to obtain ethylenediamine-terminated waterborne polyurethane;

[0053] S1. Add 12g of the prepared urethane-esterified graphene oxide to 50g of deionized water, adjust the pH to 6.5, and ultrasonically disperse for 2.5h to obtain a urethane-esterified graphene oxide dispersion.

[0054] S2. Add 2.5g of dithiol to 60g of the prepared ethylenediamine-terminated waterborne polyurethane and react for 20min. Increase the stirring speed to 3500rpm, then add the urethane-esterified graphene oxide dispersion prepared in S1 and 23g of deionized water. After reacting for 1h, the modified graphene / polyurethane composite material is obtained.

[0055] Preparation Example 3

[0056] S0. Preparation of raw materials: urethane-esterified graphene oxide and ethylenediamine-terminated waterborne polyurethane:

[0057] S01. Preparation of urethane-esterified graphene oxide:

[0058] 1g of graphene oxide was added to 200g of deionized water and ultrasonically dispersed for 3h to obtain a graphene oxide dispersion. Then, 2g of isophorone diisocyanate was added to the graphene oxide dispersion and stirred at 85℃ for 3h. Then, 1g of 2,2-dimethylolpropionic acid was added and stirred at 85℃ for 5h. After filtration, the mixture was washed twice with dichloromethane to obtain a filter cake. The filter cake was placed in a drying oven and dried at 70℃ for 14h to obtain urethane-esterified graphene oxide.

[0059] S02. Preparation of ethylenediamine-terminated waterborne polyurethane:

[0060] Under N2 environment, 40g of polyether diol was added to a four-necked flask and dehydrated at 140℃ for 4h; 5g of isophorone diisocyanate was added and mixed evenly, and the mixture was stirred at 85℃ for 3h; then 0.15g of 2,2-dimethylolpropionic acid was added, and the mixture was stirred for 5h to obtain a polyurethane prepolymer; a mixture of 0.12g of ethylenediamine and 70g of distilled water was added to the polyurethane prepolymer, the stirring speed was adjusted to 4000rpm, and the mixture was stirred for 2.5h to obtain ethylenediamine-terminated waterborne polyurethane;

[0061] S1. Add 14g of the prepared urethane-esterified graphene oxide to 60g of deionized water, adjust the pH to 7, and ultrasonically disperse for 3h to obtain a urethane-esterified graphene oxide dispersion.

[0062] S2. Add 3g of dithiol to 65g of the prepared ethylenediamine-terminated waterborne polyurethane and react for 25min. Increase the stirring speed to 4000rpm, then add the urethane-esterified graphene oxide dispersion prepared in S1 and 26g of deionized water. After reacting for 1.5h, the modified graphene / polyurethane composite material is obtained.

[0063] Example

[0064] Example 1

[0065] S1. Weigh out 20g of waterborne acrylic resin, 5g of modified graphene / polyurethane composite material prepared in Preparation Example 1, 2g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4g of leveling agent, 3g of defoamer, 5g of anti-aging agent, and 61g of distilled water according to the mass ratio. Seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 85°C for 3 hours. After cooling, add W1BPOE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30 minutes to obtain a special adhesive coating.

[0066] S2. Apply a special adhesive coating to one side of a 0.15mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.3mm. Then attach a 0.3mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0067] Example 2

[0068] S1. Weigh out 25g of waterborne acrylic resin, 8g of modified graphene / polyurethane composite material prepared in Preparation Example 1, 3g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4.5g of leveling agent, 2.5g of defoamer, 4g of anti-aging agent, and 53g of distilled water according to the mass ratio. Seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 85°C for 3 hours. After cooling, add W1BPOE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30 minutes to obtain a special adhesive coating.

[0069] S2. Apply a special adhesive coating to one side of a 0.15mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.3mm. Then attach a 0.3mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0070] Example 3

[0071] S1. Weigh out 30g of waterborne acrylic resin, 10g of modified graphene / polyurethane composite material prepared in Preparation Example 1, 4g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 5g of leveling agent, 2g of defoamer, 3g of anti-aging agent, and 46g of distilled water according to the mass ratio. Seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 85°C for 3 hours. After cooling, add W1BPOE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30 minutes to obtain a special adhesive coating.

[0072] S2. Apply a special adhesive coating to one side of a 0.15mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.3mm. Then attach a 0.3mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0073] Example 4

[0074] S1. Weigh out 35g of waterborne acrylic resin, 12g of modified graphene / polyurethane composite material prepared in Preparation Example 1, 5g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 5.5g of leveling agent, 1.5g of defoamer, 2g of anti-aging agent, and 39g of distilled water according to the mass ratio. Seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 85°C for 3 hours. After cooling, add W1BPOE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30 minutes to obtain a special adhesive coating.

[0075] S2. Apply a special adhesive coating to one side of a 0.15mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.3mm. Then attach a 0.3mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0076] Example 5

[0077] S1. Weigh out 40g of waterborne acrylic resin, 15g of modified graphene / polyurethane composite material prepared in Preparation Example 1, 6g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 6g of leveling agent, 1g of defoamer, 1g of anti-aging agent, and 31g of distilled water according to the mass ratio. Seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 85°C for 3 hours. After cooling, add W1BPOE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30 minutes to obtain a special adhesive coating.

[0078] S2. Apply a special adhesive coating to one side of a 0.15mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.3mm. Then attach a 0.3mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0079] Example 6

[0080] S1. Weigh out 20g of waterborne acrylic resin, 5g of modified graphene / polyurethane composite material prepared in Preparation Example 1, 2g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4g of leveling agent, 3g of defoamer, 5g of anti-aging agent, and 61g of distilled water according to the mass ratio. Seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 90°C for 4 hours. After cooling, add W1BPOE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 40 minutes to obtain a special adhesive coating.

[0081] S2. Apply a special adhesive coating to one side of a 0.2mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.35mm. Then attach a 0.35mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0082] Example 7

[0083] S1. Weigh out 20g of waterborne acrylic resin, 5g of modified graphene / polyurethane composite material prepared in Preparation Example 1, 2g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4g of leveling agent, 3g of defoamer, 5g of anti-aging agent, and 61g of distilled water according to the mass ratio. Seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 95°C for 5 hours. After cooling, add W1BPOE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 50 minutes to obtain a special adhesive coating.

[0084] S2. Apply a special adhesive coating to one side of a 0.25mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.4mm. Then attach a 0.4mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0085] Example 8

[0086] The difference between Example 8 and Example 1 is that the modified graphene / polyurethane composite material used in Example 8 is derived from Preparation Example 2.

[0087] Example 9

[0088] The difference between Example 9 and Example 1 is that the modified graphene / polyurethane composite material used in Example 9 is derived from Preparation Example 3.

[0089] Example 10

[0090] The difference between Example 10 and Example 1 is that the toughening agent used in Example 10 is Biorich from Germany. TM Nylon toughening agent.

[0091] Comparative Example 1

[0092] S1. Weigh out 15g of waterborne acrylic resin, 2g of modified graphene / polyurethane composite material prepared in Preparation Example 1, 1g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 3g of leveling agent, 4g of defoamer, 6g of anti-aging agent, and 69g of distilled water according to the mass ratio. Seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 85°C for 3 hours. After cooling, add W1BPOE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30 minutes to obtain a special adhesive coating.

[0093] S2. Apply a special adhesive coating to one side of a 0.15mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.3mm. Then attach a 0.3mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0094] Comparative Example 2

[0095] S1. Weigh out the following raw materials according to the mass ratio: 45g of waterborne acrylic resin, 18g of the modified graphene / polyurethane composite material prepared in Preparation Example 1, 6.5g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 6.5g of leveling agent, 0.5g of defoamer, and anti-aging agent.

[0096] 0.5g of agent and 23g of distilled water; the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material are sealed and stirred at 85℃ for 3h. After cooling, W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent are added and stirred for 30min to obtain a special adhesive coating.

[0097] S2. Apply a special adhesive coating to one side of a 0.15mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.3mm. Then attach a 0.3mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0098] Comparative Example 3

[0099] S1. Weigh out 25g of waterborne acrylic resin, 2g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4g of leveling agent, 3g of defoamer, 5g of anti-aging agent, and 61g of distilled water according to the mass ratio; seal and stir the distilled water, waterborne acrylic resin, and modified graphene / polyurethane composite material at 85℃ for 3h. After cooling, add W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30min to obtain a special adhesive coating.

[0100] S2. Apply a special adhesive coating to one side of a 0.15mm thick forged aluminum foil (aluminum foil layer material), with a coating thickness of 0.3mm. Then attach a 0.3mm thick transparent release paper (bottom material). After bonding, a low-temperature resistant advertising material is obtained.

[0101] Performance testing

[0102] 1. The limiting oxygen index of the low-temperature resistant advertising materials obtained in Examples 1-10 and Comparative Examples 1-3 was tested using GB / T 2406.2-2009 "Determination of Combustion Behavior by Oxygen Index Method for Plastics". The results are shown in Table 1.

[0103] 2. Low temperature resistance test: The low temperature resistant advertising materials obtained in Examples 1-10 and Comparative Examples 1-3 were frozen at -50°C for 1 hour, and then quickly placed at 50°C for 0.5 hours. This cycle was repeated 50 times. If the material did not lose its light effect, the test result was deemed "qualified"; otherwise, it was deemed "unqualified".

[0104] The specific test results are as follows:

[0105] Table 1 Performance Test Results

[0106] As can be seen from the test results in Table 1, the low-temperature resistant advertising material provided in this application has a high limiting oxygen index, indicating that the material has good flame retardant properties; and it can remain luminous or brittle at a low temperature of -50℃, indicating that the material has strong low-temperature resistance.

[0107] The test results of Examples 1-5 and Comparative Examples 1-2 show that when the percentages of raw materials are 20-40% waterborne acrylic resin, 5-15% modified graphene / polyurethane composite material, 2-6% toughening agent, 4-6% leveling agent, 1-3% defoamer, 1-5% anti-aging agent, and 31-61% distilled water, the resulting advertising materials all have strong flame retardancy and low-temperature resistance.

[0108] As can be seen from the test results of Examples 1-7 and Comparative Example 3, the improved raw material formulation and preparation process of the low-temperature resistant advertising material in this application are conducive to obtaining advertising materials with strong flame retardancy and low-temperature resistance. However, when the modified graphene / polyurethane composite material is not added to the raw material, the flame retardancy and low-temperature resistance of the advertising material deteriorate significantly.

[0109] As can be seen from the test results of Examples 1, 8, and 9, the modified graphene / polyurethane composite material raw material formulation and preparation process provided in this application are all conducive to obtaining fillers that can improve the flame retardancy and low-temperature resistance of advertising materials.

[0110] As can be seen from the test results of Examples 1 and 10, the toughening agents provided in this application are all beneficial to obtaining advertising materials with strong flame retardancy and low temperature resistance.

[0111] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. A low-temperature resistant advertising material, characterized in that: The low-temperature advertising material comprises, from top to bottom, an aluminum foil layer, a special adhesive coating, and a bottom layer; The special adhesive coating raw materials include, by weight percentage: 20-40% waterborne acrylic resin, 5-15% modified graphene / polyurethane composite material, 2-6% toughening agent, 4-6% leveling agent, 1-3% defoamer, 1-5% anti-aging agent, and 31-61% water.

2. The low-temperature resistant advertising material according to claim 1, characterized in that: The special adhesive coating raw materials include, by weight percentage: 25-35% waterborne acrylic resin, 8-12% modified graphene / polyurethane composite material, 3-5% toughening agent, 4.5-5.5% leveling agent, 1.5-2.5% defoamer, 2-4% anti-aging agent, and 39-53% water.

3. The low-temperature resistant advertising material according to claim 2, characterized in that: The special adhesive coating raw materials comprise, by weight percentage: 30% water-based acrylic resin, 10% modified graphene / polyurethane composite material, 4% toughening agent, 5% leveling agent, 2% defoamer, 3% anti-aging agent, and 46% water.

4. A low-temperature resistant advertising material according to claim 1, 2, or 3, characterized in that: The modified graphene / polyurethane composite material is composed of the following raw materials in parts by weight: 55-65 parts ethylenediamine-terminated waterborne polyurethane, 10-14 parts urethane-esterified graphene oxide, 2-3 parts dithiol, and 60-86 parts deionized water.

5. The low-temperature resistant advertising material according to claim 4, characterized in that: The ethylenediamine-terminated waterborne polyurethane is composed of the following raw materials in parts by weight: 30-40 parts polyether diol, 4-5 parts isophorone diisocyanate, 0.1-0.15 parts 2,2-dimethylolpropionic acid, 0.06-0.12 parts ethylenediamine, and 60-70 parts distilled water.

6. The low-temperature resistant advertising material according to claim 4, characterized in that: The carbamate-esterified graphene oxide is composed of the following raw materials in parts by weight: 0.5-1 parts graphene oxide, 100-200 parts deionized water, 1-2 parts isophorone diisocyanate, and 0.5-1 parts 2,2-dimethylolpropionic acid.

7. The low-temperature resistant advertising material according to claim 1, characterized in that: The toughening agent is W1B POE-g-MAH nylon low-temperature modified toughening agent, Biorich (Germany). TM One type of toughening agent for nylon.

8. A method for preparing a low-temperature resistant advertising material according to any one of claims 1-7, characterized in that: Includes the following steps: S1. Weigh the raw materials according to the mass ratio, add water, water-based acrylic resin, and modified graphene / polyurethane composite material, and stir in a sealed container at 85-95℃ for 3-5 hours. After cooling, add toughening agent, leveling agent, defoamer, and anti-aging agent, and stir for 30-50 minutes to obtain a special adhesive coating. S2. Apply a special adhesive coating to the surface of the aluminum foil material, attach the base material, and bond them together to obtain a low-temperature resistant advertising material.

9. The method for preparing a low-temperature resistant advertising material according to claim 8, characterized in that: The preparation method of the modified graphene / polyurethane composite material includes the following steps: S0. Preparation of raw materials: urethane-esterified graphene oxide and ethylenediamine-terminated waterborne polyurethane; S1. Add urethane-esterified graphene oxide to a portion of deionized water, adjust the pH to 6-7, and ultrasonically disperse for 2-3 hours to obtain a urethane-esterified graphene oxide dispersion. S2. Add dithiol to ethylenediamine-terminated waterborne polyurethane and react for 15-25 min with high-speed stirring. Then add the urethane-esterified graphene oxide dispersion prepared in S1 and the remaining deionized water. After emulsification for 0.5-1.5 h, the modified graphene / polyurethane composite material is obtained.

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