A spray-type anti-fog functional repair liquid and its preparation method

Abstract

The present application discloses a spray-type anti-fog functional repair liquid and its preparation method. The repair liquid comprises the following raw materials by mass fraction: 2-4% silica sol, 2-4% polysiloxane-acrylic acid compound, 1-2% surfactant, and the balance water; the polysiloxane-acrylic acid compound contains hydroxyl groups on its molecular chain; and the surfactant is polyglycerol laurate. The silica sol, with its tiny particle structure, can tightly fill the damaged gaps in the anti-fog functional layer on the polyethylene film. The polysiloxane segments in the polysiloxane-acrylic acid compound can improve the bonding strength between the repair liquid and the polyethylene film. At the same time, the polyacrylic acid segments can maintain reactivity, increase the crosslinking speed and crosslinking density with the silica sol, and thus increase the film-forming speed of the repair liquid. The hydroxyl groups contained therein cooperate with the polyglycerol laurate to increase the hydrophilicity of the polyethylene film, further improving the anti-fog effect of the polyethylene greenhouse film.

Description

Technical Field

[0001] The present application relates to the field of anti-fog droplets, and in particular to a spray-type anti-fog droplet functional repair liquid and a preparation method thereof. Background Art

[0002] Greenhouses are a key facility in modern agriculture. They change the reliance of traditional planting methods on natural conditions, significantly increasing crop yield and quality per unit area while reducing production costs. Greenhouses are often made from polyethylene film, which has a light weight, high light transmittance, and excellent thermal insulation properties. However, under certain humidity and temperature conditions, the mist and water droplets formed on the surface of polyethylene film can reduce the film's light transmittance, affecting crop growth. Furthermore, the condensed water droplets can cause plant leaf rot, resulting in reduced yields. Therefore, functional films with anti-fog effects have attracted widespread attention.

[0003] Compared to the internal addition method, externally applied anti-fog polyethylene agricultural film is simpler to operate and easier to use. It does not require consideration of the compatibility of the anti-fog agent in polyethylene and has less impact on the anti-aging properties of the polyethylene film. However, externally sprayed anti-fog agents are easily damaged by external friction during use, causing the anti-fog functional coating to peel off, resulting in partial loss of anti-fog effectiveness and affecting the use of the polyethylene film. Therefore, the preparation of a repair solution with anti-fog effectiveness that can repair the anti-fog functional layer of polyethylene film can effectively compensate for these defects during use. Summary of the Invention

[0004] In order to solve the problem that the polyethylene greenhouse film treated with an external spray-type anti-fog agent is damaged during use and the functional coating falls off and loses the anti-fog effect, the present application provides a spray-type anti-fog functional repair liquid and a preparation method thereof.

[0005] In a first aspect, the present application provides a sprayable anti-fog functional repair liquid, comprising the following raw materials by mass fraction:

[0006] Silica sol 2-4%;

[0007] Polysiloxane-acrylic compound 2-4%;

[0008] Surfactant 1-2%;

[0009] Water balance;

[0010] The molecular chain of the polysiloxane-acrylic acid compound contains a hydroxyl group; and the surfactant is polyglycerol laurate monoester.

[0011] Preferably, the solid content of the silica sol is 20-30%, and the particle size is 20-100 nm.

[0012] By adopting this technical solution, the silanol groups on the silica sol particles gradually form siloxane bonds through dehydration condensation, allowing the silica sol to form a continuous film on the surface of the polyethylene film. Furthermore, due to the extremely fine silica sol particles, the formed film layer can tightly fill the gaps in the anti-fog coating on the damaged polyethylene film surface, achieving an excellent repair effect. However, due to the poor bonding strength of silica sol with polyethylene film, a polysiloxane-acrylic acid compound is also added to the repair solution.

[0013] Polysiloxane-acrylic compounds can also form films on polyethylene film surfaces. The hydrophobic siloxane segments within them attract the similarly hydrophobic surface of polyethylene film, improving the bonding strength between the repair fluid and the film and compensating for the poor bonding strength between the silica sol and the film. Furthermore, the hydroxyl groups within the polysiloxane-acrylic compound form strong multiple hydrogen bonds with the silanol groups in the silica sol, accelerating the crosslinking rate and increasing the crosslinking density within the repair fluid. This, in turn, increases the speed at which the repair fluid forms a film on the polyethylene film surface, expediting the repair process.

[0014] Polyglycerol laurate monoester, a surfactant, contains a large number of hydrophilic groups. After film formation, it imparts excellent hydrophilic properties to polyethylene films, allowing water droplets to quickly spread across the film's surface and remain along the inner wall of the polyethylene greenhouse film, preventing them from dripping directly and affecting crop growth, thus achieving the polyethylene film's anti-fog effect. Furthermore, the siloxane segments in the polysiloxane-acrylic compound provide affinity with the polyethylene film, while the polyacrylic acid segments maintain reactivity. The hydroxyl groups contained in the polysiloxane-acrylic acid compound synergize with the polyglycerol laurate monoester to enhance the hydrophilicity of the resulting coating, further improving the polyethylene film's anti-fog performance.

[0015] Preferably, the raw materials of the polysiloxane-acrylic compound include polysiloxane emulsion, acrylic monomer and pentaerythritol in a mass ratio of 1: (1-1.2): (0.1-0.3).

[0016] Preferably, the acrylic monomer is methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:(1.5-2).

[0017] By adopting the above technical solution, polysiloxane emulsion is used as the seed emulsion, polymerized with acrylic monomers, and pentaerythritol is added, and a large number of hydroxyl groups are introduced into the molecular chain of the formed polysiloxane-acrylic compound, thereby increasing the cross-linking speed and cross-linking density with the silica sol, increasing the coating strength and film-forming speed, and being able to increase the hydrophilicity of the coating, further improving the anti-fog effect of the repair liquid on the polyethylene film.

[0018] At the same time, the acrylic monomer is a mixture of methacrylic acid and hydroxyethyl methacrylate, wherein the carboxyl group in methacrylic acid can provide an active site for reaction with pentaerythritol, so that pentaerythritol can be smoothly grafted onto the molecular chain of the polysiloxane-acrylic compound; hydroxyethyl methacrylate can increase the hydroxyl content in the polysiloxane-acrylic compound and improve the reactivity of the polyacrylic acid segment therein.

[0019] Preferably, the polysiloxane-acrylic acid compound is prepared according to the following method:

[0020] Preparation of polysiloxane emulsion: adding emulsifier to water, stirring and mixing, raising the temperature to 70-80°C, adding siloxane monomer, stirring and reacting for 2-3 hours to obtain polysiloxane emulsion;

[0021] Preparation of polysiloxane-acrylic compound: acrylic monomer and cross-linking agent are uniformly mixed to obtain a premixed solution, the obtained polysiloxane emulsion is heated to 80-85°C, 10-20% of the premixed solution is added, and the mixture is stirred for 20-30 minutes, after which the initiator and the remainder of the premixed solution are added, and the mixture is stirred for reaction for 2-3 hours. The temperature is adjusted to 60-80°C, pentaerythritol is added, and the stirring reaction is continued for 1-2 hours. Finally, the polysiloxane-acrylic compound is obtained by filtration.

[0022] Preferably, the siloxane monomer includes one or a combination of octamethylcyclotetrasiloxane, tetramethyltetravinyltetrasiloxane and hexamethyldisiloxane.

[0023] Preferably, the emulsifier includes one or a combination of octylphenol polyoxyethylene ether, dodecylbenzenesulfonic acid, and sodium lauryl sulfate; the added amount of the emulsifier is 2-5% of the mass of the siloxane monomer.

[0024] Preferably, the crosslinking agent includes one or a combination of ethoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and trimethylolpropane triacrylate; and the added amount of the crosslinking agent is 1 to 3% of the mass of the acrylic monomer.

[0025] Preferably, the initiator includes one or a combination of ammonium persulfate, potassium persulfate, benzoyl peroxide, and di-tert-butyl peroxide; the added amount of the initiator is 0.5-2% of the mass of the acrylic monomer.

[0026] By adopting the above technical solution, the siloxane monomer forms a stable polysiloxane emulsion. The acrylic monomer, under the action of an initiator and a crosslinker, undergoes emulsion polymerization to form a polysiloxane-acrylic composite emulsion. Finally, pentaerythritol reacts with the carboxyl groups contained therein to increase the hydroxyl content in the polysiloxane-acrylic compound, thereby increasing the crosslinking speed and crosslinking density with the silica sol, thereby accelerating the film formation speed of the repair liquid coating and improving the mechanical strength of the coating. Furthermore, the large number of hydroxyl groups contained in the monomer can enhance the anti-fog performance of the polyethylene greenhouse film.

[0027] Preferably, the molecular chain of the polyglycerol laurate monoester further contains a carboxyl group.

[0028] By adopting the above technical solution, a cross-linked network structure is formed between the silica sol and the polysiloxane-acrylic compound during the film formation process of the repair liquid, wherein some polar groups contained in the polyglycerol laurate monoester can also form hydrogen bonds with the two, but this binding force is not strong and will reduce the effect of the surfactant on improving the hydrophilicity of the polyethylene film. After the polyglycerol laurate monoester is modified, the carboxyl group contained in its molecular chain can form a chemical bond with the silica sol and the polysiloxane-acrylic compound, thereby improving the binding force between the surfactant and the film-forming component, improving the durability of the anti-fog effect, and avoiding the decline of hydrophilicity, thereby improving the anti-fog effect.

[0029] Preferably, the raw materials of the polyglycerol laurate monoester include polyglycerol, lauric acid and dicarboxylic acid in a mass ratio of 1: (0.2-0.25): (0.05-0.2).

[0030] Preferably, the degree of polymerization of the polyglycerol is 8 to 10; and the dicarboxylic acid includes one or a combination of oxalic acid and adipic acid.

[0031] By adopting the above technical solution, an esterification reaction occurs between polyglycerol and lauric acid to gradually form polyglycerol lauric acid monoester, and dicarboxylic acid is added for modification during the synthesis process. The carboxyl group is introduced through the esterification reaction to improve the affinity with other components, and can also improve the hydrophilic properties of the polyethylene film, increase the surface energy of the film, and enable water to spread on the surface of the polyethylene greenhouse film to form an extremely thin and evenly distributed water film, and then flow down along the inner wall of the greenhouse film, achieving a good anti-fog droplet effect.

[0032] Preferably, the polyglycerol laurate monoester is prepared according to the following method:

[0033] Preparation of polyglycerol: Glycerol was added to a sodium hydroxide aqueous solution and stirred, and the temperature of the mixed solution was adjusted to 240-270° C. under a nitrogen atmosphere, and the mixture was stirred for 4-5 hours to obtain polyglycerol;

[0034] Preparation of polyglycerol lauric acid monoester: lauric acid and sodium hydroxide are added to the obtained polyglycerol, mixed evenly, and then under a nitrogen atmosphere, the temperature is adjusted to 170-180°C and stirred for reaction for 2-3 hours. Then, the temperature is adjusted to 80-90°C, dicarboxylic acid is added, and the stirring reaction is continued for 1-2 hours to obtain polyglycerol lauric acid monoester.

[0035] Preferably, the mass fraction of the sodium hydroxide aqueous solution is 0.6 to 0.8%.

[0036] By adopting the above technical solution, the polyglycerol laurate monoester formed has higher stability than other polyglycerol laurate esters, and the addition of dicarboxylic acid after the formation of polyglycerol laurate monoester can further carry out esterification reaction, introduce carboxyl groups into the polyglycerol laurate, and improve the overall hydrophilicity and binding force.

[0037] Secondly, the present application also provides a method for preparing a spray-type anti-droplet functional repair liquid, which includes the following steps: weighing a surfactant and adding it to water, adjusting the pH value to 3-5, adjusting the temperature to 30-35°C, adding silica sol and polysiloxane-acrylic compound, and stirring and mixing for 30-60 minutes to obtain a spray-type anti-droplet functional repair liquid.

[0038] In summary, this application has the following beneficial effects:

[0039] 1. The spray-type anti-fog functional repair liquid of the present application uses a compound of silica sol and polysiloxane-acrylic compound as the film-forming components of the repair liquid. The silica sol can tightly fill the damaged gaps in the anti-fog functional layer on the polyethylene film due to its tiny particle structure. The polysiloxane segment in the polysiloxane-acrylic compound can improve the bonding force between the repair liquid and the polyethylene film. At the same time, the polyacrylic acid segment can maintain the reaction activity, increase the cross-linking speed and cross-linking density with the silica sol, increase the film-forming speed of the repair liquid, and the hydroxyl groups contained therein can help improve the hydrophilicity of the repair liquid coating for the polyethylene film, further improving the anti-fog effect of the polyethylene greenhouse film.

[0040] 2. The sprayable anti-fog functional repair fluid of this application uses polyglycerol monolaurate as a surfactant, which can significantly increase the hydrophilicity of the resulting repair fluid film, improve the anti-fog performance of the polyethylene film, and compensate for the loss of anti-fog performance caused by damage. Furthermore, polyglycerol monolaurate can be modified to introduce carboxyl groups into the molecular chain, thereby improving the binding force between the surfactant and the film-forming component and enhancing the durability of the anti-fog effect. DETAILED DESCRIPTION

[0041] Preparation Example 1-1, a polysiloxane-acrylic acid compound was prepared according to the following method:

[0042] 0.3 g of octylphenol polyoxyethylene ether (OP-10) was added to 100 ml of water, the mixture was stirred and then the temperature was raised to 80°C, 10 g of siloxane monomer was added, and the mixture was stirred and reacted for 2 hours to obtain a polysiloxane emulsion, wherein the siloxane monomer was a mixture of octamethylcyclotetrasiloxane and hexamethyldisiloxane in a mass ratio of 1:1;

[0043] 11 g of acrylic monomer and 0.25 g of ethoxylated trimethylolpropane triacrylate were uniformly mixed to obtain a premixed solution. Then, 10 g of the obtained polysiloxane emulsion was taken, the temperature was raised to 80° C., 15% of the premixed solution was added, and the mixture was stirred for 20 minutes. After that, 0.1 g of ammonium persulfate and the remainder of the premixed solution were added, and the mixture was stirred for 2 hours. The temperature was adjusted to 70° C., 2 g of pentaerythritol was added, and the mixture was stirred for 1 hour. Finally, the polysiloxane-acrylic compound was obtained by filtration.

[0044] The acrylic monomer is a mixture of methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.8.

[0045] Preparation Example 1-2, a polysiloxane-acrylic compound, differs from Preparation Example 1-1 only in that the amount of acrylic monomer added is 10 g.

[0046] Preparation Example 1-3, a polysiloxane-acrylic compound, differs from Preparation Example 1-1 only in that the amount of acrylic monomer added is 12 g.

[0047] Preparation Example 1-4, a polysiloxane-acrylic acid compound, differs from Preparation Example 1-1 only in that the amount of pentaerythritol added is 1 g.

[0048] Preparation Example 1-5, a polysiloxane-acrylic acid compound, is different from Preparation Example 1-1 only in that the amount of pentaerythritol added is 3 g.

[0049] Preparation Example 1-6, a polysiloxane-acrylic compound, differs from Preparation Example 1-1 only in that the acrylic monomer obtained by mixing equal amounts of methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.5 is replaced by an acrylic monomer obtained by mixing methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.8.

[0050] Preparation Example 1-7, a polysiloxane-acrylic compound, differs from Preparation Example 1-1 only in that the acrylic monomer obtained by mixing equal amounts of methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:2 is replaced by an acrylic monomer obtained by mixing methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.8.

[0051] Preparation Example 1-8, a polysiloxane-acrylic acid compound, is different from Preparation Example 1-1 only in that the amount of acrylic acid monomer added is 8 g.

[0052] Preparation Example 1-9, a polysiloxane-acrylic compound, differs from Preparation Example 1-1 only in that the amount of acrylic monomer added is 15 g.

[0053] Preparation Example 1-10, a polysiloxane-acrylic acid compound, is different from Preparation Example 1-1 only in that the amount of pentaerythritol added is 0.5 g.

[0054] Preparation Example 1-11, a polysiloxane-acrylic acid compound, is different from Preparation Example 1-1 only in that the amount of pentaerythritol added is 5 g.

[0055] Preparation Example 1-12, a polysiloxane-acrylic compound, differs from Preparation Example 1-1 only in that the acrylic monomer obtained by mixing equal amounts of methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.2 is replaced by an acrylic monomer obtained by mixing methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.8.

[0056] Preparation Example 1-13, a polysiloxane-acrylic compound, differs from Preparation Example 1-1 only in that the acrylic monomer obtained by mixing equal amounts of methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:2.5 is replaced by an acrylic monomer obtained by mixing methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.8.

[0057] Preparation Example 1-14, a polysiloxane-acrylic compound, differs from Preparation Example 1-1 only in that an equal amount of methacrylic acid is replaced by an acrylic monomer obtained by mixing methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.8.

[0058] Preparation Example 1-15, a polysiloxane-acrylic acid compound, was prepared according to the following method:

[0059] 0.3 g of octylphenol polyoxyethylene ether (OP-10) was added to 100 ml of water, the mixture was stirred and then the temperature was raised to 80°C, 10 g of siloxane monomer was added, and the mixture was stirred and reacted for 2 hours to obtain a polysiloxane emulsion, wherein the siloxane monomer was a mixture of octamethylcyclotetrasiloxane and hexamethyldisiloxane in a mass ratio of 1:1;

[0060] 11 g of acrylic monomer and 0.25 g of ethoxylated trimethylolpropane triacrylate were mixed evenly to obtain a premixed solution. Then, 10 g of the obtained polysiloxane emulsion was taken and the temperature was raised to 80° C., 15% of the premixed solution was added, and the mixture was stirred for 20 minutes. After that, 0.1 g of ammonium persulfate and the remainder of the premixed solution were added, and the mixture was stirred for 3 hours. Finally, the polysiloxane-acrylic compound was obtained by filtration.

[0061] Preparation Example 1-16, a polysiloxane-acrylic compound, differs from Preparation Example 1-15 only in that an equal amount of methacrylic acid is replaced by an acrylic monomer obtained by mixing methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1:1.8.

[0062] Preparation Example 2-1, a polyglycerol laurate monoester, was prepared according to the following method:

[0063] 10 g of glycerol was added to 150 ml of a 0.6% sodium hydroxide aqueous solution and stirred. The temperature of the mixed solution was adjusted to 250°C under a nitrogen atmosphere and stirred for 5 h to obtain polyglycerol.

[0064] 10 g of the obtained polyglycerol was taken, and 2.2 g of lauric acid and 0.2 g of sodium hydroxide were added and mixed evenly. Then, the temperature was adjusted to 180° C. under a nitrogen atmosphere and stirred for reaction for 2 h to obtain polyglycerol laurate monoester.

[0065] Preparation Example 2-2, a polyglycerol laurate monoester, was prepared according to the following method:

[0066] 10 g of glycerol was added to 150 ml of a 0.6% sodium hydroxide aqueous solution and stirred. The temperature of the mixed solution was adjusted to 250°C under a nitrogen atmosphere and stirred for 5 h to obtain polyglycerol.

[0067] Take 10g of the obtained polyglycerol, and add 2.2g of lauric acid and 0.2g of sodium hydroxide, mix well, adjust the temperature to 180°C under a nitrogen atmosphere, and stir the reaction for 2h, then adjust the temperature to 85°C, add 1g of oxalic acid, and continue stirring the reaction for 1.5h to obtain polyglycerol lauric acid monoester.

[0068] Preparation Example 2-3, a polyglycerol laurate monoester, differs from Preparation Example 2-2 only in that the amount of lauric acid added is 2 g.

[0069] Preparation Example 2-4, a polyglycerol laurate monoester, differs from Preparation Example 2-2 only in that the amount of lauric acid added is 2.5 g.

[0070] Preparation Example 2-5, a polyglycerol laurate monoester, differs from Preparation Example 2-2 only in that the amount of oxalic acid added is 0.5 g.

[0071] Preparation Example 2-6, a polyglycerol laurate monoester, is different from Preparation Example 2-2 only in that the amount of oxalic acid added is 2 g.

[0072] Preparation Example 2-7, a polyglycerol laurate monoester, differs from Preparation Example 2-2 only in that the amount of oxalic acid added is 0.2 g.

[0073] Preparation Example 2-8, a polyglycerol laurate monoester, is different from Preparation Example 2-2 only in that the amount of oxalic acid added is 3 g. Example

[0074] Example 1, a spray-type anti-fog repair liquid, is prepared according to the following method:

[0075] Weigh 15 g of the polyglycerol laurate monoester prepared in Preparation Example 2-1 and add it to water, adjust the pH value to 4, adjust the temperature to 35°C, add 30 g of silica sol and 30 g of the polysiloxane-acrylic compound prepared in Preparation Example 1-1, and stir and mix for 40 minutes to obtain a spray-type anti-fog functional repair liquid with a mass of 1000 g.

[0076] Examples 2 to 7 are spray-type anti-fog repair liquids, which differ from Example 1 only in that the ratio of the added raw materials is adjusted, as shown in Table 1:

[0077] Table 1 Ingredients of Example 1 to Example 7

[0078] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Silica Sol 30 20 40 30 30 30 30 Polysiloxane-acrylic compound 30 30 30 20 40 30 30 Polyglyceryl Laurate 15 15 15 15 15 10 20 water 925 935 915 935 915 930 920

[0079] The polysiloxane-acrylic acid compound used was the polysiloxane-acrylic acid compound prepared in Preparation Example 1-1; and the polyglycerol lauric acid monoester used was the polyglycerol lauric acid monoester prepared in Preparation Example 2-1.

[0080] Example 8 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-2.

[0081] Example 9 is a spray-type anti-fog repair liquid, which differs from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-3.

[0082] Example 10 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-4.

[0083] Example 11 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-5.

[0084] Example 12 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-6.

[0085] Example 13, a spray-type anti-fog repair liquid, is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-7.

[0086] Example 14 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-8.

[0087] Example 15 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-9.

[0088] Example 16 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-10.

[0089] Example 17, a spray-type anti-fog repair liquid, is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-11.

[0090] Example 18 is a spray-type anti-fog repair liquid, which differs from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-12.

[0091] Example 19 is a spray-type anti-fog repair liquid, which differs from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-13.

[0092] Example 20 is a spray-type anti-fog repair liquid, which differs from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-14.

[0093] Example 21 is a spray-type anti-fog repair liquid, which differs from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-15.

[0094] Example 22, a spray-type anti-fog repair liquid, is different from Example 1 only in that the polyglycerol laurate monoester prepared in Preparation Example 2-1 is replaced by an equal amount of polyglycerol laurate monoester prepared in Preparation Example 2-2.

[0095] Example 23, a spray-type anti-fog repair liquid, is different from Example 22 only in that an equal amount of polyglycerol laurate monoester prepared in Preparation Example 2-3 is used to replace the polyglycerol laurate monoester prepared in Preparation Example 2-1.

[0096] Example 24 is a spray-type anti-fog repair liquid, which differs from Example 22 only in that the polyglycerol laurate monoester prepared in Preparation Example 2-1 is replaced by an equal amount of polyglycerol laurate monoester prepared in Preparation Example 2-4.

[0097] Example 25 is a spray-type anti-fog repair liquid, which differs from Example 22 only in that the polyglycerol laurate monoester prepared in Preparation Example 2-1 is replaced by an equal amount of polyglycerol laurate monoester prepared in Preparation Example 2-5.

[0098] Example 26 is a sprayable anti-fog repair liquid, which differs from Example 22 only in that the polyglycerol laurate monoester prepared in Preparation Example 2-1 is replaced by an equal amount of polyglycerol laurate monoester prepared in Preparation Example 2-6.

[0099] Example 27, a spray-type anti-fog repair liquid, is different from Example 22 only in that the polyglycerol laurate monoester prepared in Preparation Example 2-1 is replaced by an equal amount of polyglycerol laurate monoester prepared in Preparation Example 2-7.

[0100] Example 28 is a sprayable anti-fog repair liquid, which differs from Example 22 only in that the polyglycerol laurate monoester prepared in Preparation Example 2-1 is replaced by an equal amount of polyglycerol laurate monoester prepared in Preparation Example 2-8.

[0101] Comparative Example 1 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-1 added is 10 g.

[0102] Comparative Example 2 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-1 added is 50 g.

[0103] Comparative Example 3 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is not added.

[0104] Comparative Example 4 is a spray-type anti-fog repair liquid, which differs from Example 1 only in that the polysiloxane-acrylic compound prepared in Preparation Example 1-1 is replaced by an equal amount of the polysiloxane-acrylic compound prepared in Preparation Example 1-16.

[0105] Comparative Example 5 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the amount of polyglycerol laurate prepared in Preparation Example 2-1 added is 5 g.

[0106] Comparative Example 6 is a spray-type anti-fog repair liquid, which is different from Example 1 only in that the addition amount of the polyglycerol laurate monoester prepared in Preparation Example 2-1 is 25.

[0107] 1. Film forming speed test: According to the "cotton ball method" in GB / T 1728-2020 "Determination of drying time of paint film and putty film", the surface time of the spray-type anti-fog repair liquid obtained in the embodiment and the comparative example on the PE film was tested. The PE film is 50*50cm in size. 2 of film.

[0108] The test results are shown in Table 2.

[0109] 2. Performance testing:

[0110] Sample preparation: The spray-type anti-fog repair liquid obtained in the examples and comparative examples was evenly sprayed on a 50*50cm 2 The surface of the PE film was dried at room temperature for 48 h to obtain the corresponding sample.

[0111] (1) Anti-fog performance test: The anti-fog performance of the sample is tested according to the water bath hot fog method in GB / T 31726-2015 "Test method for anti-fog performance of plastic films". The test results are graded according to the clarity of the eye chart seen through the sample as described in the standard, with grade 1 being the best anti-fog performance and grade 5 being the worst anti-fog performance.

[0112] (2) Water contact angle performance test: At room temperature, add 4±0.5μL of water droplets on the sample and test it using a contact angle tester.

[0113] The test results are shown in Table 3.

[0114] Table 2 Test results of film-forming speed of spray-type anti-fog repair liquid

[0115]

[0116] Table 3 Performance test results of spray-type anti-fog repair fluid

[0117]

[0118] According to Tables 2 and 3, combined with Example 1 and Examples 2-7, it can be seen that the tack-free time, anti-fog performance level, and contact angle of Examples 2-7 are not significantly different from those of Example 1, indicating that the film-forming speed, anti-fog performance, and hydrophilicity exhibited on the PE film of Examples 2-7 are not significantly different from those of Example 1. This may be because the only difference between Examples 2-7 and Example 1 is that the ratio of the raw materials added during the preparation of the repair solution varies within the required range, indicating that varying the raw material ratio of the repair solution within the required range has no significant effect on the performance of the resulting repair solution.

[0119] Combining Example 1 with Examples 8 to 13, it can be seen that the tack-free time, anti-fog performance level, and contact angle of Examples 8 to 13 are not significantly different from those of Example 1, indicating that the film-forming speed, anti-fog droplet performance, and hydrophilicity exhibited on the PE film of Examples 8 to 13 are not significantly different from those of Example 1. This may be because the only difference between Examples 8 to 13 and Example 1 is that the ratio of the added raw materials used in the polysiloxane-acrylic compound in the repair solution was varied within the required range during the preparation process, indicating that varying the raw material ratio of the polysiloxane-acrylic compound within the required range has no significant effect on the performance of the resulting repair solution.

[0120] Comparing Examples 1, 14, and 15, it can be seen that the tack-free time of Examples 14 and 15 increased, and the contact angle of Example 14 improved compared to Example 1, indicating that the film-forming speed and hydrophilicity exhibited on the PE film of Examples 14 and 15 decreased compared to Example 1. This may be due to the fact that the amount of acrylic acid monomer added to the polysiloxane-acrylic compound used in Examples 14 and 15 was varied outside the specified range during the preparation process. In Example 14, the amount of acrylic acid monomer added was reduced, resulting in a decrease in the content of polyacrylic acid segments in the resulting polysiloxane-acrylic compound, and a consequent decrease in reactivity. This reduced crosslinking with silica sol led to a decrease in film-forming speed. Furthermore, the reduction in reactive groups reduced the amount of pentaerythritol introduced, reducing the improvement in hydrophilicity. In Example 15, the amount of acrylic acid monomer added was increased, resulting in a large amount of self-polymerization between the acrylic acid monomers, which in turn reduced the number of reactive groups on the molecular chain.

[0121] Combining Example 1 and Examples 16 to 21, it can be seen that the surface drying time and contact angle of Examples 16 to 21 are increased compared with Example 1, and the anti-fog performance level of Examples 20 and 21 is increased, indicating that the film forming speed of Examples 16 to 21 and the hydrophilicity exhibited on the PE film are decreased compared with Example 1, and the anti-fog droplet performance of Examples 20 and 21 is decreased. The reason for this may be that, compared to Example 1, Examples 16 to 21 made adjustments to the raw material ratios used in the preparation of the polysiloxane-acrylic compound. Specifically, Examples 16, 17, and 21 adjusted the amount of pentaerythritol added. Example 16 reduced the amount of pentaerythritol added, resulting in a decrease in the hydroxyl content in the resulting polysiloxane-acrylic compound. This, in turn, decreased the crosslinking speed and crosslinking density with the silica sol, and reduced the synergistic effect with the surfactant on improving hydrophilicity. This, in turn, resulted in a decrease in the film-forming speed and hydrophilicity of the resulting repair solution. Example 21 omitted pentaerythritol, resulting in a more significant decrease in the amount added. The decrease in hydrophilicity also decreased anti-fog performance. Examples 18, 19, and 20 adjusted the ratio of the hydroxyethyl methacrylate monomer added thereto. Example 18 reduced the amount of hydroxyethyl methacrylate added, resulting in a decrease in the hydroxyl content. Example 20 omitted hydroxyethyl methacrylate, resulting in a more significant decrease in reaction activity.

[0122] Combining Examples 1, 22, and 23 to 26, it can be seen that the contact angle of Example 22 is lower than that of Example 1, indicating that the hydrophilicity of Example 22 is improved compared to Example 1. There is no significant difference in the performance of Examples 23 to 26 compared to Example 22. The reason for this may be that the only difference between Example 22 and Example 1 is that the polyglycerol laurate monoester used has been modified, and its molecular chain contains carboxyl groups, which can compensate for the problem of reduced hydrophilic group content caused by the combination of hydrophilic groups and film-forming components in the repair fluid system, and can also improve the bonding strength with the film. The only difference between Examples 23 to 26 and Example 22 is that the amount of raw materials added during the preparation of polyglycerol laurate monoester was adjusted within a range, indicating that adjusting the raw material ratio within a range has no significant effect on the performance of the resulting repair fluid.

[0123] Combining Examples 22, 27, and 28, it can be seen that the contact angle of Example 27 is increased compared to that of Example 22, indicating a decrease in hydrophilicity. This may be because the only difference between Example 27 and Example 22 is the reduced content of added dicarboxylic acid, which results in a decrease in the number of polar groups and, in turn, a decrease in the hydrophilicity exhibited.

[0124] Combining Example 1 and Comparative Examples 1 to 3, it can be seen that the surface drying time, anti-fog performance level, and contact angle of Comparative Examples 1 to 3 are increased compared to Example 1, indicating that the film formation speed, anti-fog droplet performance, and hydrophilicity exhibited on the PE film of Comparative Examples 1 to 3 are significantly reduced compared to Example 1. The reason for this may be that the only difference between Comparative Examples 1 to 3 and Example 1 is that the amount of polysiloxane-acrylic compound added in Comparative Examples 1 to 3 is adjusted during the preparation of the repair fluid. Specifically, Comparative Example 1 reduces the amount of polysiloxane-acrylic compound added, which reduces the crosslinking density with the silica sol, reduces the film formation speed, and also causes a decrease in the hydrophilic group content in the system, thereby resulting in a significant decrease in anti-fog performance and hydrophilicity. Comparative Example 3 does not add polysiloxane-acrylic compound, which makes it difficult to accelerate the film formation speed of the silica sol, and the binding force between the silica sol and the polyethylene film is reduced. The content of hydrophilic groups is also reduced, resulting in a significant decrease in anti-fog droplet performance.

[0125] Comparing Example 1 and Comparative Example 4, it can be seen that the tack-free time, anti-fog performance level, and contact angle of Comparative Example 4 are improved compared to those of Example 1, indicating that the film-forming speed, anti-fog performance, and hydrophilicity exhibited on the PE film of Comparative Example 4 are significantly reduced compared to those of Example 1. This may be due to the lack of hydroxyl groups in the polysiloxane-acrylic compound in Comparative Example 4, which reduces the cross-linking reaction with the silica sol and the film-forming speed. The reduced polar group content also leads to a decrease in anti-fog performance and hydrophilicity.

[0126] Combining Example 1, Comparative Examples 5, and 6, it can be seen that the tack-free time, anti-fog performance level, and contact angle of Comparative Examples 5 and 6 are increased compared to Example 1, indicating that the film-forming speed, anti-fog performance, and hydrophilicity exhibited on the PE film of Comparative Examples 5 and 6 are significantly reduced compared to Example 1. This may be because the difference between Comparative Examples 5 and 6 compared to Example 1 is that the amount of surfactant added is adjusted outside the required range. Specifically, the reduction in the amount of surfactant added in Comparative Example 5 significantly reduced the improvement in the anti-fog performance of the repair fluid, significantly reduced the polar groups, and significantly reduced the hydrophilicity exhibited. In Comparative Example 6, the increase in the amount of surfactant added reduced the bonding strength with the PE film, and the anti-fog performance was not improved.

[0127] 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 non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A spray-type anti-fog functional repair liquid, characterized in that: Including the following raw materials by mass fraction: Silica sol 2-4%; Polysiloxane-acrylic compound 2-4%; Surfactant 1-2%; Water balance; The molecular chain of the polysiloxane-acrylic acid compound contains a hydroxyl group; the surfactant is polyglyceryl laurate monoester; The raw materials of the polysiloxane-acrylic compound include polysiloxane emulsion, acrylic monomer and pentaerythritol in a mass ratio of 1: (1-1.2): (0.1-0.3); The acrylic monomers are methacrylic acid and hydroxyethyl methacrylate in a mass ratio of 1: (1.5-2); The molecular chain of the polyglycerol laurate monoester also contains a carboxyl group; The polysiloxane-acrylic acid compound is prepared according to the following method: Preparation of polysiloxane emulsion: adding emulsifier to water, stirring and mixing, raising the temperature to 70-80°C, adding siloxane monomer, stirring and reacting for 2-3 hours to obtain polysiloxane emulsion; Preparation of a polysiloxane-acrylic compound: An acrylic monomer and a crosslinking agent are uniformly mixed to obtain a premixed solution, the obtained polysiloxane emulsion is heated to 80-85°C, 10-20% of the premixed solution is added, and the mixture is stirred for 20-30 minutes. An initiator and the remainder of the premixed solution are then added, and the mixture is stirred for 2-3 hours. The temperature is adjusted to 60-80°C, pentaerythritol is added, and the mixture is stirred for 1-2 hours. Finally, the mixture is filtered to obtain the polysiloxane-acrylic compound. The siloxane monomer includes one or a combination of octamethylcyclotetrasiloxane, tetramethyltetravinyltetrasiloxane and hexamethyldisiloxane.

2. The spray-type anti-fog functional repair liquid according to claim 1, characterized in that: The raw materials of the polyglycerol lauric acid monoester include polyglycerol, lauric acid and dicarboxylic acid in a mass ratio of 1: (0.2-0.25): (0.05-0.2).

3. The spray-type anti-fog functional repair liquid according to claim 2, characterized in that: The polymerization degree of the polyglycerol is 8 to 10; the dicarboxylic acid comprises one or a combination of oxalic acid and adipic acid.

4. The spray-type anti-fog functional repair liquid according to claim 2, characterized in that: The polyglycerol laurate monoester is prepared according to the following method: Preparation of polyglycerol: Glycerol was added to a sodium hydroxide aqueous solution and stirred, and the temperature of the mixed solution was adjusted to 240-270° C. under a nitrogen atmosphere, and the mixture was stirred for 4-5 hours to obtain polyglycerol; Preparation of polyglycerol lauric acid monoester: lauric acid and sodium hydroxide are added to the obtained polyglycerol, mixed evenly, and then under a nitrogen atmosphere, the temperature is adjusted to 170-180°C and stirred for reaction for 2-3 hours. Then, the temperature is adjusted to 80-90°C, dicarboxylic acid is added, and the stirring reaction is continued for 1-2 hours to obtain polyglycerol lauric acid monoester.

5. A method for preparing a spray-type anti-fog functional repair liquid according to any one of claims 1 to 4, characterized in that: The preparation comprises the following steps: weighing a surfactant and adding it to water, adjusting the pH value to 3-5, adjusting the temperature to 30-35°C, adding silica sol and polysiloxane-acrylic acid compound, and stirring and mixing for 30-60 minutes to obtain a sprayable anti-fog functional repair liquid.

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