Low-temperature-resistant advertising material and preparation method thereof

Abstract

The invention discloses a low-temperature-resistant advertising material and a preparation method thereof, and relates to the technical field of advertising materials, the low-temperature advertising material comprises an aluminum foil layer, a special bonding coating and a bottom layer from top to bottom; the special bonding coating comprises the following raw materials in percentage by mass: 20-40% of waterborne acrylic resin, 5-15% of a modified graphene / polyurethane composite material, 2-6% of a toughening agent, 4-6% of a flatting agent, 1-3% of a defoaming agent, 1-5% of an anti-aging agent and 31-61% of distilled water; the modified graphene / polyurethane composite material is prepared from the following raw materials in parts by weight: 55 to 65 parts of ethylenediamine-terminated waterborne polyurethane, 10 to 14 parts of carbamic acid esterified graphene oxide, 2 to 3 parts of dithiol and 60 to 86 parts of deionized water. The advertising material provided by the invention has relatively strong flame-retardant and low-temperature-resistant characteristics.

Description

Technical Field

[0001] The present application relates to the field of advertising material technology, and in particular to a low-temperature resistant advertising material and a preparation method thereof. Background Art

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

[0003] However, in extremely cold and dry areas, specific climatic conditions place more stringent requirements on the performance of advertising materials. In particular, when the temperature drops to -40℃ or even -50℃, existing advertising materials face severe challenges. Advertising materials are prone to become fragile, with a significant drop in impact resistance, and are prone to cracking or breaking, which seriously affects the display effect of advertising content and the durability of materials, thus limiting the scope of application of advertising materials under 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 effects and physical properties even at extremely low temperatures of -50°C or below. Summary of the invention

[0005] In order to enhance the low temperature resistance of advertising materials, the present application provides a low temperature resistant advertising material and a preparation method thereof.

[0006] The present application provides a low temperature resistant advertising material, which adopts the following technical solution: A low-temperature resistant advertising material and a preparation method thereof. The low-temperature advertising material comprises, from top to bottom, an aluminum foil layer, a special bonding coating layer, and a bottom layer; the special bonding coating layer raw materials comprise, by mass percentage, 20-40% of a water-based 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 water.

[0007] By adopting the above technical scheme, the aluminum foil layer and the bottom material are bonded together by a special bonding coating to obtain an advertising material, wherein the special bonding coating adopts a modified graphene / polyurethane composite material, and the polyurethane has good adhesion and low-temperature resistance. By further modifying the polyurethane material with modified graphene oxide, the low-temperature resistance of the polyurethane material can be significantly enhanced, and the flame retardancy of the material can be effectively improved, thereby effectively enhancing the flame retardancy and low-temperature resistance of the advertising material, being able to withstand temperatures of -50°C and below, and broadening the range of environmental conditions for use.

[0008] Preferably, the special bonding coating raw materials include, by mass percentage: 25-35% water-based acrylic resin, 8-12% modified graphene / polyurethane composite material, 3-5% toughening agent, 4.5-5.5% leveling agent, 1.5-2.5% defoaming agent, 2-4% anti-aging agent, and 39-53% water.

[0009] Preferably, the raw materials of the special bonding coating include, by mass percentage: 30% water-based acrylic resin, 10% modified graphene / polyurethane composite material, 4% toughening agent, 5% leveling agent, 2% defoaming agent, 3% anti-aging agent, and 46% water.

[0010] Preferably, the aluminum foil layer is forged aluminum foil; and the bottom layer is transparent release paper.

[0011] Preferably, the modified graphene / polyurethane composite material is composed of the following raw materials in parts by weight: 55-65 parts of ethylenediamine-terminated waterborne polyurethane, 10-14 parts of carbamate-treated graphene oxide, 2-3 parts of dithiol, and 60-86 parts of deionized water.

[0012] By adopting the above technical scheme, a modified graphene / polyurethane composite material is prepared by reacting ethylenediamine-terminated waterborne polyurethane with carbamate-treated graphene oxide. On the one hand, the waterborne polyurethane terminated with ethylenediamine has good stability, good corrosion resistance, and is easy to modify, while the carbamate-treated graphene oxide has better dispersibility; on the other hand, active groups such as amino groups are introduced into the polyurethane after ethylenediamine termination, and carbamate groups are introduced into the graphene oxide, so that the bonding force between the polyurethane and the graphene oxide is enhanced, which is conducive to obtaining a coating filler with strong dispersibility and low-temperature resistance, thereby effectively enhancing the functional characteristics of the coating.

[0013] Preferably, the ethylenediamine-terminated waterborne polyurethane is composed of the following raw materials in parts by weight: 30-40 parts of polyether diol, 4-5 parts of isophorone diisocyanate, 0.1-0.15 parts of 2,2-dimethylol propionic acid, 0.06-0.12 parts of ethylenediamine, and 60-70 parts of distilled water.

[0014] Preferably, the carbamate-treated graphene oxide is composed of the following raw materials in parts by weight: 0.5-1 parts of graphene oxide, 100-200 parts of deionized water, 1-2 parts of isophorone diisocyanate, and 0.5-1 parts of 2,2-dihydroxymethylpropionic acid.

[0015] Preferably, the toughening agent is W1B POE-g-MAH nylon low temperature modified toughening agent, German Biorich TM A type of nylon toughening agent.

[0016] By adopting the above technical solutions, W1B POE-g-MAH nylon low temperature modified toughening agent, German Biorich TM As a toughening agent, nylon toughening agent can withstand extremely low temperature environment, which can effectively enhance the low temperature tolerance of advertising materials and extend their service life.

[0017] The present application provides a method for preparing a low-temperature resistant advertising material, which adopts the following technical solution: A method for preparing a low-temperature resistant advertising material comprises the following steps: S1. Weigh the raw materials according to the mass ratio, and stir water, water-based acrylic resin, and modified graphene / polyurethane composite materials at 85-95°C for 3-5 hours in a sealed state. After cooling, add toughening agent, leveling agent, defoaming agent, and anti-aging agent, and stir for 30-50 minutes to obtain a special bonding coating; S2. Apply a special adhesive coating on the surface of the aluminum foil layer material, followed by the base material, and after bonding, a low-temperature resistant advertising material is obtained.

[0018] Preferably, the method for preparing the modified graphene / polyurethane composite material comprises the following steps: S0. Preparation of raw materials urethane-modified graphene oxide and ethylenediamine-terminated waterborne polyurethane; S1. Adding carbamate-modified graphene oxide to part of deionized water, adjusting the pH to 6-7, and ultrasonically dispersing for 2-3h to obtain a carbamate-modified graphene oxide dispersion; S2. Add dithiol to the ethylenediamine-terminated waterborne polyurethane and react for 15-25 minutes, increase the stirring speed, add the carbamate-modified graphene oxide dispersion prepared in S1 and the remaining deionized water, and emulsify for 0.5-1.5 hours to obtain a modified graphene / polyurethane composite material.

[0019] In summary, the present application includes at least one of the following beneficial technical effects: By adopting the above technical scheme, the aluminum foil layer and the bottom material are bonded together by a special bonding coating to obtain an advertising material, wherein the special bonding coating adopts a modified graphene / polyurethane composite material, and the polyurethane has good adhesion and low-temperature resistance. By further modifying the polyurethane material with modified graphene oxide, the low-temperature resistance of the polyurethane material can be significantly enhanced, and the flame retardancy of the material can be effectively improved, thereby effectively enhancing the flame retardancy and low-temperature resistance of the advertising material, being able to withstand temperatures of -50°C and below, and broadening the range of environmental conditions for use. DETAILED DESCRIPTION

[0020] The present application is further described in detail below with reference to the embodiments.

[0021] The chemical reagents used in the embodiments and comparative examples provided by the present invention are all commercially available products, and their brands and manufacturers are as follows: Graphene oxide, Shanghai Aladdin Biochemical Technology Co., Ltd.; Polyether diol, Shanghai Aladdin Biochemical Technology Co., Ltd., molecular weight 2000; Water-based acrylic resin, Guangdong Wengjiang Chemical Reagent Co., Ltd., PB93956; W1B POE-g-MAH nylon low temperature modified toughening agent, Pandex (Shanghai) International Trading Co., Ltd.; Biorich, Germany TM Nylon toughening agent, Dongguan Yucheng Plastic Chemical Co., Ltd.; Leveling agent, Guangdong Wengjiang Chemical Reagent Co., Ltd., acrylate leveling agent; Defoamer, Wuhan Hongde Yuexin Pharmaceutical Technology Co., Ltd., mineral oil defoamer; Anti-aging agent, Panhua Chemical (Shanghai) Co., Ltd., KY-405.

[0022] Preparation Example Preparation Example 1 S0. Preparation of raw materials urethanized graphene oxide and ethylenediamine terminated waterborne polyurethane: SO1. Preparation of carbamate-modified graphene oxide: 0.5 g of graphene oxide was added to 100 g of deionized water, and ultrasonic dispersion treatment was performed 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, filtered, and washed twice with dichloromethane to obtain a filter cake, and the filter cake was placed in a drying oven and dried at 60 ° C for 12 h to obtain urethane-esterified graphene oxide; SO2. Preparation of ethylenediamine-terminated waterborne polyurethane: Under N2 environment, 30g of polyether diol was added to a four-necked flask and dehydrated at 120°C for 2h; 4g of isophorone diisocyanate was added and mixed evenly, and stirred and reacted at 75°C for 2h; then 0.1g of 2,2-dimethylolpropionic acid was added, and stirred and reacted 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 speed was adjusted to 3000rpm, and stirred and reacted for 1.5h to obtain an ethylenediamine-terminated waterborne polyurethane; S1. 10 g of the prepared carbamate-modified graphene oxide was added to 40 g of deionized water, the pH was adjusted to 6, and ultrasonic dispersion was performed for 2 h to obtain a carbamate-modified graphene oxide dispersion; S2. Add 2 g of dithiol to 55 g of the prepared ethylenediamine-terminated waterborne polyurethane and react for 15 min, increase the stirring speed to 3000 rpm, then add the carbamate-modified graphene oxide dispersion prepared in S1 and 20 g of deionized water, and react for 0.5 h to obtain a modified graphene / polyurethane composite material.

[0023] Preparation Example 2 S0. Preparation of raw materials urethanized graphene oxide and ethylenediamine terminated waterborne polyurethane: SO1. Preparation of carbamate-modified graphene oxide: 0.75 g of graphene oxide was added to 150 g of deionized water, and ultrasonic dispersion was performed 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 for reaction at 80° C. for 2.5 h; then 0.75 g of 2,2-dihydroxymethylpropionic acid was added, and stirred for reaction at 80° C. for 4.5 h, filtered, and washed twice with dichloromethane to obtain a filter cake, and the filter cake was placed in a drying oven and dried at 65° C. for 13 h to obtain carbamate-modified graphene oxide; SO2. Preparation of ethylenediamine terminated waterborne polyurethane: Under N2 environment, 35g of polyether diol was added to a four-necked flask and dehydrated at 130°C for 3h; 4.5g of isophorone diisocyanate was added and mixed evenly, and stirred and reacted at 80°C for 2.5h; then 0.125g of 2,2-dimethylolpropionic acid was added, and stirred and reacted 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 speed was adjusted to 3500rpm, and stirred and reacted for 2h to obtain an ethylenediamine-terminated waterborne polyurethane; S1. 12 g of the prepared carbamate-modified graphene oxide was added to 50 g of deionized water, the pH was adjusted to 6.5, and ultrasonically dispersed for 2.5 h to obtain a carbamate-modified graphene oxide dispersion; S2. Add 2.5 g of dithiol to 60 g of the prepared ethylenediamine-terminated waterborne polyurethane and react for 20 min, increase the stirring speed to 3500 rpm, then add the carbamate-modified graphene oxide dispersion prepared in S1 and 23 g of deionized water, and react for 1 h to obtain a modified graphene / polyurethane composite material.

[0024] Preparation Example 3 S0. Preparation of raw materials urethanized graphene oxide and ethylenediamine terminated waterborne polyurethane: SO1. Preparation of carbamate-modified graphene oxide: 1 g of graphene oxide was added to 200 g of deionized water, and ultrasonic dispersion treatment was performed for 3 h to obtain a graphene oxide dispersion; then 2 g of isophorone diisocyanate was added to the graphene oxide dispersion, and stirred for reaction at 85° C. for 3 h; then 1 g of 2,2-dihydroxymethylpropionic acid was added, and the mixture was stirred for reaction at 85° C. for 5 h, filtered, and washed twice with dichloromethane to obtain a filter cake, and the filter cake was placed in a drying oven and dried at 70° C. for 14 h to obtain carbamate-modified graphene oxide; SO2. Preparation of ethylenediamine terminated waterborne polyurethane: Under N2 environment, 40g of polyether diol was added to a four-necked flask and dehydrated at 140°C for 4h; 5g of isophorone diisocyanate was added and mixed evenly, and stirred and reacted at 85°C for 3h; then 0.15g of 2,2-dimethylolpropionic acid was added, and stirred and reacted 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 speed was adjusted to 4000rpm, and stirred and reacted for 2.5h to obtain an ethylenediamine-terminated waterborne polyurethane; S1. 14 g of the prepared carbamate-modified graphene oxide was added to 60 g of deionized water, the pH was adjusted to 7, and ultrasonic dispersion was performed for 3 h to obtain a carbamate-modified graphene oxide dispersion; S2. Add 3 g of dithiol to 65 g of the prepared ethylenediamine-terminated waterborne polyurethane and react for 25 min, increase the stirring speed to 4000 rpm, then add the carbamate-modified graphene oxide dispersion prepared in S1 and 26 g of deionized water, and react for 1.5 h to obtain a modified graphene / polyurethane composite material. Example

[0025] Example 1 S1. Weigh 20 g of the raw material water-based acrylic resin, 5 g of the modified graphene / polyurethane composite material prepared in Preparation Example 1, 2 g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4 g of leveling agent, 3 g of defoaming agent, 5 g of anti-aging agent, and 61 g of distilled water according to the mass ratio; seal and stir the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material at 85 ° C for 3 h, cool, add W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent, and stir for 30 min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.15mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.3mm, and then attach a transparent release paper with a thickness of 0.3mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0026] Example 2 S1. Weigh 25g of the raw material water-based acrylic resin, 8g of the 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 defoaming agent, 4g of anti-aging agent, and 53g of distilled water according to the mass ratio; the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material are sealed and stirred at 85°C for 3h, and after cooling, W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent are added, and stirred for 30min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.15mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.3mm, and then attach a transparent release paper with a thickness of 0.3mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0027] Example 3 S1. Weigh 30 g of the raw material water-based acrylic resin, 10 g of the modified graphene / polyurethane composite material prepared in Preparation Example 1, 4 g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 5 g of leveling agent, 2 g of defoaming agent, 3 g of anti-aging agent, and 46 g of distilled water according to the mass ratio; seal and stir the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material at 85 ° C for 3 h, cool, add W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent, and stir for 30 min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.15mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.3mm, and then attach a transparent release paper with a thickness of 0.3mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0028] Example 4 S1. Weigh 35g of the raw material water-based acrylic resin, 12g of the 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 defoaming agent, 2g of anti-aging agent, and 39g of distilled water according to the mass ratio; the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material are sealed and stirred at 85°C for 3h, and after cooling, W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent are added, and stirred for 30min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.15mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.3mm, and then attach a transparent release paper with a thickness of 0.3mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0029] Example 5 S1. Weigh 40g of the raw material water-based acrylic resin, 15g of the 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 defoaming agent, 1g of anti-aging agent, and 31g of distilled water according to the mass ratio; the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material are sealed and stirred at 85°C for 3h, and after cooling, W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent are added, and stirred for 30min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.15mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.3mm, and then attach a transparent release paper with a thickness of 0.3mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0030] Example 6 S1. Weigh 20 g of the raw material water-based acrylic resin, 5 g of the modified graphene / polyurethane composite material prepared in Preparation Example 1, 2 g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4 g of leveling agent, 3 g of defoaming agent, 5 g of anti-aging agent, and 61 g of distilled water according to the mass ratio; the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material are sealed and stirred at 90 ° C for 4 h, and after cooling, W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent are added, and stirred for 40 min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.2mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.35mm, and then attach a transparent release paper with a thickness of 0.35mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0031] Example 7 S1. Weigh 20 g of the raw material water-based acrylic resin, 5 g of the modified graphene / polyurethane composite material prepared in Preparation Example 1, 2 g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4 g of leveling agent, 3 g of defoaming agent, 5 g of anti-aging agent, and 61 g of distilled water according to the mass ratio; seal and stir the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material at 95 ° C for 5 h, cool, add W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent, and stir for 50 min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.25 mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.4 mm, and then attach a transparent release paper with a thickness of 0.4 mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0032] Example 8 The difference between Example 8 and Example 1 is that the modified graphene / polyurethane composite material used in Example 8 comes from Preparation Example 2.

[0033] Example 9 The difference between Example 9 and Example 1 is that the modified graphene / polyurethane composite material used in Example 9 comes from Preparation Example 3.

[0034] Example 10 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.

[0035] Comparative Example 1 S1. Weigh 15 g of the raw material water-based acrylic resin, 2 g of the modified graphene / polyurethane composite material prepared in Preparation Example 1, 1 g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 3 g of leveling agent, 4 g of defoaming agent, 6 g of anti-aging agent, and 69 g of distilled water according to the mass ratio; seal and stir the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material at 85 ° C for 3 h, cool, add W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent, and stir for 30 min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.15mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.3mm, and then attach a transparent release paper with a thickness of 0.3mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0036] Comparative Example 2 S1. Weigh 45g of the raw material water-based 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 defoaming agent, 0.5g of anti-aging agent, and 23g of distilled water according to the mass ratio; the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material are sealed and stirred at 85°C for 3h, and after cooling, W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent are added, and stirred for 30min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.15mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.3mm, and then attach a transparent release paper with a thickness of 0.3mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0037] Comparative Example 3 S1. Weigh 25 g of raw materials of water-based acrylic resin, 2 g of W1B POE-g-MAH nylon low-temperature modified toughening agent, 4 g of leveling agent, 3 g of defoaming agent, 5 g of anti-aging agent, and 61 g of distilled water according to the mass ratio; seal and stir the distilled water, water-based acrylic resin, and modified graphene / polyurethane composite material at 85 ° C for 3 h, cool, add W1B POE-g-MAH nylon low-temperature modified toughening agent, leveling agent, defoaming agent, and anti-aging agent, and stir for 30 min to obtain a special bonding coating; S2. Apply a special adhesive coating on one side of a 0.15mm forged aluminum foil (aluminum foil layer material) with a coating thickness of 0.3mm, and then attach a transparent release paper with a thickness of 0.3mm (bottom layer material). After bonding, a low-temperature resistant advertising material is obtained.

[0038] Performance testing 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. 2. Low temperature resistance test: The low temperature resistant advertising materials obtained in Examples 1-10 and Comparative Examples 1-3 were placed in a -50°C environment and frozen for 1 hour, then taken out and quickly placed in a 50°C environment for 0.5 hour, and this cycle was repeated 50 times; if the material did not lose its light effect, the test result was judged to be "qualified", otherwise it was "unqualified".

[0039] The specific test results are as follows: Table 1 Performance test results It can be seen from the test results in Table 1 that the low-temperature resistant advertising material provided by the present application has a high limiting oxygen index, indicating that the material has good flame retardant properties; and it can be exposed to low temperatures of -50°C without losing its light effect or becoming brittle, indicating that the material has strong low-temperature resistance.

[0040] It can be seen from the test results of Examples 1-5 and Comparative Examples 1-2 that when the percentages of the raw materials are 20-40% of water-based acrylic resin, 5-15% of modified graphene / polyurethane composite material, 2-6% of toughening agent, 4-6% of leveling agent, 1-3% of defoaming agent, 1-5% of anti-aging agent, and 31-61% of distilled water, the obtained advertising materials have strong flame retardancy and low temperature resistance.

[0041] It can be seen from the test results of Examples 1-7 and Comparative Example 3 that the raw material formula and preparation process of the low-temperature resistant advertising material improved in the present 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 materials, the flame retardancy and low-temperature resistance of the advertising material are significantly deteriorated.

[0042] It can be seen from the test results of Examples 1, 8 and 9 that the raw material formula and preparation process of the modified graphene / polyurethane composite material provided in the present application are conducive to obtaining fillers that can improve the flame retardancy and low temperature resistance of advertising materials.

[0043] It can be seen from the test results of Examples 1 and 10 that the toughening agents provided in the present application are conducive to obtaining advertising materials with strong flame retardancy and low temperature resistance.

[0044] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A low temperature resistant advertising material, characterized in that: The low-temperature advertising material comprises an aluminum foil layer, a special adhesive coating layer, and a bottom layer from top to bottom; The special bonding 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% defoaming agent, 1-5% anti-aging agent, and 31-61% water.

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

3. The low temperature resistant advertising material according to claim 2, characterized in that: The raw materials of the special bonding coating include, by mass percentage, 30% water-based acrylic resin, 10% modified graphene / polyurethane composite material, 4% toughening agent, 5% leveling agent, 2% defoaming agent, 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 of ethylenediamine-terminated waterborne polyurethane, 10-14 parts of carbamate-treated graphene oxide, 2-3 parts of dithiol, and 60-86 parts of 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 of polyether diol, 4-5 parts of isophorone diisocyanate, 0.1-0.15 parts of 2,2-dimethylol propionic acid, 0.06-0.12 parts of ethylenediamine, and 60-70 parts of distilled water.

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

7. The low temperature resistant advertising material according to claim 1, characterized in that: The toughening agent is one of W1B POE-g-MAH nylon low temperature modified toughening agent and German Biorich™ nylon toughening agent.

8. A method for preparing a low temperature resistant advertising material according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1. Weigh the raw materials according to the mass ratio, and stir water, water-based acrylic resin, and modified graphene / polyurethane composite materials at 85-95°C for 3-5 hours in a sealed state. After cooling, add toughening agent, leveling agent, defoaming agent, and anti-aging agent, and stir for 30-50 minutes to obtain a special bonding coating; S2. Apply a special adhesive coating on the surface of the aluminum foil layer material, attach the base material, and after bonding, you can get 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 comprises the following steps: S0. Preparation of raw materials urethane graphene oxide and ethylenediamine-terminated waterborne polyurethane; S1. Adding carbamate-modified graphene oxide to part of deionized water, adjusting the pH to 6-7, and ultrasonically dispersing for 2-3 hours to obtain a carbamate-modified graphene oxide dispersion; S2. Add dithiol to the ethylenediamine-terminated waterborne polyurethane and react for 15-25 minutes. Stir at high speed, add the carbamate-modified graphene oxide dispersion prepared in S1 and the remaining deionized water, and emulsify for 0.5-1.5 hours to obtain a modified graphene / polyurethane composite material.

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