A waterborne organofluorosilicon polyurethane coating material that is degradable, dyeable, waterproof and oil-proof, and a preparation method thereof

Abstract

The present invention belongs to the field of paper surface treatment, and specifically relates to a waterborne organofluorosilicone polyurethane coating material that is degradable, dyeable, waterproof and oil-proof, and a preparation method thereof. It is obtained by mixing and reacting a terminal epoxy waterborne polyurethane emulsion and a polyamine-based epoxy curing agent, coating it on paper, and drying. The terminal epoxy waterborne organofluorosilicone polyurethane emulsion is synthesized from diisocyanate, biodegradable polyester polyol as raw materials, hydroxyl silicone oil with fluorine-containing groups as a modifier, N,N-dihydroxyethyl azo dye, 1,4-dihydroxybutane-2-sulfonic acid sodium as a hydrophilic monomer, 1,4-butanediol as a chain extender, and glycidol as a capping agent. The degradable, dyeable, waterproof and oil-proof waterborne organofluorosilicone polyurethane coating material provided by the present invention has the characteristics of high waterproof and oil-proof performance, adjustable color tone, enhanced paper strength, and biodegradability.

Description

Technical Field

[0001] The present invention belongs to the field of paper surface treatment, and particularly relates to a waterborne organofluorosilicon polyurethane coating material with degradability, dyeability, water and oil resistance, and a preparation method thereof. Background Art

[0002] More than 340 million tons of plastic waste are generated globally every year, of which about 46% comes from the packaging industry. Plastic packaging materials are largely non-recyclable, and the extensive use of plastic packaging materials brings irreversible pollution problems to the natural environment. With the promotion of plastic bans in various countries and China, it is urgent to adopt green alternatives to replace plastic packaging.

[0003] Paper packaging materials have the advantages of low cost, renewable, simple production process, biodegradability, etc., and are widely used in various industries. However, paper is porous and hydrophilic, and is insufficient in terms of grease resistance, moisture resistance and mechanical properties, which limits the application of paper packaging. Currently, methods such as PE / PP film laminating and paper-plastic composite are often used to reduce the pore structure on the paper surface to improve the oil and water resistance of the paper. However, the degradability of the film-laminated paper is extremely low, and there are film-laminated plastics such as PE, which increases the cost and difficulty of paper recycling, bringing great pressure to both the natural environment and the recycling industry. In addition, the current dyeing of paper is usually achieved by directly mixing or dyeing small molecule dyes or pigments, and there are problems such as color fading and oil intolerance, which bring great inconvenience during the use of paper. Developing biodegradable water-resistant, oil-resistant and other multifunctional packaging by coating functional coatings on the paper surface is considered a simple and commercially viable effective way.

[0004] Using biomass materials, such as chitosan, starch, cellulose, etc. combined with polylactic acid, etc. can achieve the water and oil resistance effect of paper. For example, using white cardboard as the base material, waterproof and oil-resistant paper is prepared by coating methyl chitosan solution and polylactic acid solution, endowing the cardboard with waterproof and oil-resistant properties. However, the PLA solution is a dichloromethane solution and cannot be truly environmentally friendly (Packaging and Food Machinery, 2021, 3: 8-14). Literature reports that a copolymer of 2-methylene-1,3-dioxane and vinyl acetate with a degradable backbone is prepared by free radical emulsion polymerization, mainly studying its polymerization behavior, and claiming that it is expected to be used for the coating of paper products [ACS Macro Lett. 2021, 10: 591-597]. However, the polymerizable and degradable monomers are very expensive, undoubtedly increasing the use cost.

[0005] Therefore, there is an urgent need in the market for a coating material with the functions of degradation, dyeing, water and oil resistance. Summary of the Invention

[0006] In view of the problems in the prior art, the present invention provides a water-based organofluorosilicone polyurethane coating material that is degradable, dyeable, waterproof and oil-proof, solving the defects of existing coating materials. A water-based polyurethane coating material with biodegradability, waterproofness, oil-proofness and dyeability is prepared from a degradable polyester polyol, an organofluorosilicone polyol, N,N-dihydroxyethyl azo dye, a polyisocyanate, etc. The material is coated on the surface of paper to achieve the purposes of waterproofing, oil-proofing, dyeability, recyclability, etc. of the paper, replacing the current PP / PE coated paper and promoting the green and sustainable development of packaging materials.

[0007] To achieve the above technical purposes, the technical solution of the present invention is as follows:

[0008] A water-based organofluorosilicone polyurethane coating material that is degradable, dyeable, waterproof and oil-proof, using diisocyanate and degradable polyester polyol as raw materials, hydroxyl silicone oil with a fluorine-containing group as a modifier, N,N-dihydroxyethyl azo dye, 1,4-dihydroxybutane-2-sulfonic acid sodium as a hydrophilic monomer, 1,4-butanediol as a chain extender, and glycidol as a capping agent to synthesize a terminal epoxy water-based organofluorosilicone polyurethane emulsion. Then, the terminal epoxy water-based organofluorosilicone polyurethane emulsion is crosslinked and cured with an amine curing agent on the surface of the paper to form a degradable, waterproof, oil-proof and dyeable coating material.

[0009] The diisocyanate is selected from one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, and dicyclohexylmethane diisocyanate.

[0010] The degradable polyester polyol is selected from one or more of polycaprolactone diol, polycaprolactone triol, and polylactic acid diol, and the molecular weight of the degradable polyester polyol is 500 - 3000 daltons.

[0011] The structure of the hydroxyl silicone oil with a fluorine-containing group is as follows:

[0012]

[0013] Among them, the fluorine-containing component accounts for 5 - 60 mol%, the hydroxyl component accounts for 2 mol%, and the molecular weight of the hydroxyl silicone oil is 600 - 4000 daltons. Further, the preparation process of the hydroxyl silicone oil containing a fluorine-containing group is as follows: In a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, hydrogen-containing polysiloxane, allyl alcohol, fluorinated acrylate, and alkyl acrylate are added in sequence, stirred evenly at a certain temperature, a certain amount of catalyst chloroplatinic acid is added, the temperature is raised to the reaction temperature, and after reacting for a certain time, the low-boiling substances are removed by rotary evaporation to obtain hydroxyl polysiloxane with a fluorine-containing group.

[0014] The N,N-dihydroxyethyl azo dye uses the primary colors of red, yellow and blue dyes, and the specific structure is as follows:

[0015]

[0016] Based on the color matching principle of the three primary colors of red, yellow and blue, various colors are made by using red dye, yellow dye and blue dye.

[0017] The amine curing agent adopts a commercially available water-based polyamine curing agent.

[0018] The preparation steps of the terminal epoxy water-based organic fluorine silicone polyurethane emulsion include: adding vacuum-dehydrated N, N-dihydroxyethyl azo dye, diisocyanate, and dibutyltin laurate in a four-necked flask equipped with a stirrer and a thermometer, stirring thoroughly, and reacting at 40°C for 2 hours; then adding dehydrated polycaprolactone polyol and polylactic acid diol, and fluorinated hydroxy polysiloxane, reacting at 70-80°C for 2-3 hours; adding 1,4-dihydroxybutane-2-sulfonic acid sodium and 1,4-butanediol for chain extension, and continuing to react at 60°C for 3-4 hours; after the isocyanate group reaches a certain level, adding glycidol for end-capping, and sealing the remaining isocyanate groups. Cooling to below 40°C, adding deionized water for emulsification, and obtaining the terminal epoxy water-based organic fluorine silicone polyurethane emulsion.

[0019] The preparation method of the coating material comprises: uniformly mixing the epoxy-terminated water-based organic fluorine silicone polyurethane emulsion and the amine curing agent of the water-based epoxy resin in proportion, and then 2 The material is evenly coated on the surface of the paper and then dried to obtain highly tough, biodegradable, dyeable, waterproof and oil-proof paper.

[0020] It can be seen from the above description that the present invention has the following advantages:

[0021] 1. The present invention solves the defects of existing coating materials. A water-based polyurethane coating material with biodegradability, waterproof and oil-proof properties, and dyeability is prepared from degradable polyester polyols, organic fluorosilicone polyols, N,N-dihydroxyethylazo dyes, polyisocyanates, etc., and the material is coated on the surface of paper to achieve the purposes of making the paper waterproof and oil-proof, dyeable, and recyclable, thereby replacing the current PP / PE coated paper and promoting the green and sustainable development of packaging materials.

[0022] 2. The coating material of the present invention has the characteristics of strong practicality. The low surface energy fluorine-containing side chains and long-chain alkyl side chains form a multi-level connection structure, so that the coating has good hydrophobic and oleophobic properties; polycaprolactone polyol and polylactic acid polyol improve the mechanical strength and biodegradability of the coating; covalently embedded trichromatic dyes reduce dye fading, and the emulsion can be arbitrarily formulated to form various colors; the cross-linking of the terminal epoxy group and the polyamine curing agent promotes the bonding force with the paper and enhances the mechanical properties of the paper, that is, the coating material not only has excellent waterproof and oil-proof properties, but also has good dyeability and high strength. Brief Description of the Drawings

[0023] Figure 1 is the water resistance test chart of the product of this invention patent;

[0024] Figure 2 is the oil resistance test chart of the product of this invention patent;

[0025] Figure 3 is the mechanical property test chart of the product of this invention patent;

[0026] Figure 4 is the dyeing property test chart of the product of this invention patent; Detailed Description of the Invention

[0027] Combined with Figures 1 to 4 , the specific embodiments of the present invention are described in detail, but no limitation is made to the claims of the present invention.

[0028] Example 1

[0029] 1. Preparation of hydroxy silicone oil containing fluorine group:

[0030] 80 ml of toluene, 40 g of methyl hydrogen silicone oil, 48 g of perfluorooctyl ethyl methacrylate (the molar content of carbon-carbon double bond is 30% of the content of silicon-hydrogen bond), and 80 methyl lauryl acrylate are successively added into a four-necked flask under nitrogen protection. The temperature is controlled at 110 - 120 °C, and a solution of chloroplatinic acid / isopropanol is added dropwise with stirring. The mass fraction of chloroplatinic acid is 0.02% of the sum of the masses of methyl hydrogen silicone oil, fluorinated acrylate, and acrylate. After the addition is completed, the reaction is carried out for 3 h. Subsequently, 1.6 g of allyl alcohol (the molar content of hydroxyl group is 2% of the initial content of silicon-hydrogen bond) is added, and the reaction is carried out at 90 °C for 3 h. The solvent and unreacted substances are removed under reduced pressure.

[0031] 2. Preparation of epoxy-terminated aqueous organofluorosilicone polyurethane emulsion:

[0032] 0.4 g of red dye is added to a four-necked flask equipped with a stirrer and a thermometer for degassing and water treatment, and then 10.5 g of isophorone diisocyanate and 0.012 g of dibutyltin dilaurate are added, and the reaction is carried out at 40 °C for 2 h; subsequently, 20 g of polycaprolactone diol (2000 Dalton), 20 g of polylactic acid diol (2000 Dalton), and 2 g of fluorine-containing hydroxy polysiloxane treated by dehydration are added, and the pre-polymerization reaction is carried out at 70 °C for 3 hours. Then 0.2 g of 1,4-butanediol and 0.4 g of 1,4-dihydroxybutane-2-sulfonic acid sodium are added, and the reaction is carried out at 60 °C for 3 hours. After the isocyanate group no longer decreases, 1 g of glycidol is added for end-capping to block the remaining isocyanate groups. The temperature is lowered to below 40 °C, and deionized water is added for emulsification to obtain an epoxy-terminated aqueous organofluorosilicone polyurethane emulsion.

[0033] 3. Preparation of Coating Material

[0034] According to the ratio of epoxy to amino group of 1:1, an appropriate amount of terminal epoxy waterborne organofluorosilicone polyurethane emulsion and waterborne polyamine curing agent 593 were taken and mixed. Then, 5 times the volume of water was added and stirred well for dilution. The base paper was coated with a resin amount of 5 g per square meter and dried at 85 °C for 10 min to obtain a paper with a finally biodegradable, waterproof, oil-proof, flexible, and dyeable polyurethane coating. The performance of the coated paper was tested: it did not fade after being boiled in oil at 180 °C and did not fade after being boiled in water at 100 °C. The water contact angle was greater than 100°, the grease resistance was greater than grade 11, and it degraded by more than 90% within one year.

[0035] Example 2

[0036] 1. Preparation of hydroxy silicone oil containing fluorine group:

[0037] 80 ml of toluene, 40 g of methylhydrogen silicone oil, 36 g of perfluorooctyl ethyl methacrylate (the molar content of carbon-carbon double bond is 20% of the content of silicon-hydrogen bond), and 96 g of lauryl methacrylate were successively added into a four-necked flask under nitrogen protection. The temperature was controlled at 110 - 120 °C, and the solution of chloroplatinic acid / isopropanol was added dropwise with stirring. The mass fraction of chloroplatinic acid was 0.02% of the sum of the masses of methylhydrogen silicone oil, fluorinated acrylate, and acrylate. After the addition was completed, the reaction was carried out for 4 h. Subsequently, 1.6 g of allyl alcohol (the molar content of hydroxyl group was 2% of the initial silicon-hydrogen bond content) was added, and the reaction was carried out at 90 °C for 4 h. The solvent and unreacted substances were removed under reduced pressure.

[0038] 2. Preparation of terminal epoxy waterborne organofluorosilicone polyurethane emulsion:

[0039] 0.4 g of yellow dye was added to a four-necked flask equipped with a stirrer and a thermometer for degassing and water removal treatment. Then, 9.5 g of diphenylmethane diisocyanate and 0.012 g of dibutyltin dilaurate were added, and the reaction was carried out at 40 °C for 2 h. Subsequently, 30 g of polycaprolactone diol (3000 Da) and 10 g of polylactic acid diol (2000 Da) and 2 g of fluorine-containing hydroxy polysiloxane that had been dehydrated were added, and the pre-polymerization reaction was carried out at 70 °C for 3 hours. Then, 0.2 g of 1,4-butanediol and 0.4 g of 1,4-dihydroxybutane-2-sulfonic acid sodium were added, and the reaction was carried out at 60 °C for 3 hours. After the isocyanate group no longer decreased, 1 g of glycidol was added for capping to block the remaining isocyanate groups. The temperature was lowered to below 40 °C, and deionized water was added for emulsification to obtain the terminal epoxy waterborne organofluorosilicone polyurethane emulsion.

[0040] 3. Preparation of Coating Material

[0041] According to the ratio of epoxy to amino group of 1:1.5, appropriate amounts of terminal epoxy waterborne organofluorosilicone polyurethane emulsion and waterborne polyamine curing agent 593 were taken and mixed, and then 5 times the volume of water was added and stirred well for dilution. The base paper was coated with a resin amount of 8 g per square meter and dried at 85 °C for 10 min to obtain the final paper with a polyurethane-based coating that is biodegradable, waterproof, oil-proof, flexible, and dyeable. The performance of the coated paper was tested: it did not fade after being boiled in oil at 180 °C, did not fade after being boiled in water at 100 °C, the water contact angle was greater than 100°, the oil and grease resistance was greater than grade 11, and it degraded by more than 90% within one year.

[0042] Example 3

[0043] 1. Preparation of hydroxy silicone oil containing fluorine group:

[0044] 80 ml of toluene, 45 g of methylhydrogen silicone oil, 24 g of perfluorooctyl ethyl methacrylate (the molar content of carbon-carbon double bond is 10% of the content of silicon-hydrogen bond), and 120 g of heptadecyl methacrylate were successively added into a four-necked flask under nitrogen protection. The temperature was controlled at 110 - 120 °C, and the solution of chloroplatinic acid / isopropanol was added dropwise with stirring, where the mass fraction of chloroplatinic acid was 0.01% of the sum of the masses of methylhydrogen silicone oil, fluorinated acrylate, and acrylate. After the addition was completed, the reaction was carried out for 4 h. Subsequently, 1.6 g of allyl alcohol (the molar content of hydroxyl group was 2% of the initial content of silicon-hydrogen bond) was added, and the reaction was carried out at 90 °C for 4 h. The solvent and unreacted substances were removed under reduced pressure.

[0045] 2. Preparation of terminal epoxy waterborne organofluorosilicone polyurethane emulsion:

[0046] 0.4 g of blue dye was added to a four-necked flask equipped with a stirrer and a thermometer for degassing and water treatment, and then 9.0 g of toluene diisocyanate and 0.012 g of dibutyltin dilaurate were added, and the reaction was carried out at 40 °C for 2 h; subsequently, 20 g of polycaprolactone diol (2000 Dalton), 5 g of polycaprolactone triol, 15 g of polylactic acid diol (2000 Dalton), and 2 g of fluorine-containing hydroxy polysiloxane that had been dehydrated were added, and the prepolymerization reaction was carried out at 70 °C for 3 hours. Then 0.2 g of 1,4-butanediol and 0.4 g of 1,4-dihydroxybutane-2-sulfonic acid sodium were added, and the reaction was carried out at 60 °C for 3 hours. After the isocyanate group no longer decreased, 1 g of glycidol was added for end-capping to seal the remaining isocyanate groups. The temperature was lowered to below 40 °C, and deionized water was added for emulsification to obtain the terminal epoxy waterborne organofluorosilicone polyurethane emulsion.

[0047] 3. Preparation of coating material

[0048] According to the ratio of epoxy to amino group of 1:1 - 1.5, an appropriate amount of terminal epoxy waterborne organofluorosilicone polyurethane emulsion and waterborne polyamine curing agent 593 were taken and mixed, then 5 times the volume of water was added and stirred well for dilution. The base paper was coated with a resin amount of 8 g per square meter and dried at 85 °C for 10 min to obtain the final paper with a biodegradable, waterproof, oil-proof, flexible and dyeable polyurethane coating. The properties of the coated paper were tested: no color fading after boiling in oil at 180 °C, no color fading after boiling in water at 100 °C, water contact angle greater than 100°, oil resistance greater than grade 11, and more than 90% degradation within one year.

[0049] Performance testing

[0050] Taking the products of Examples 1 - 3 as test examples, Control Example 1: A new type of environmentally friendly waterproof and oil-proof paper and its preparation method (Patent No.: CN201911087659.4). Control Group 2: Ordinary paper.

[0051] Waterproof detection:

[0052] The water contact angles of the products of Examples 1 - 3 and the papers of the control group were respectively tested to judge the hydrophilic and hydrophobic situations by looking at the size of the contact angles; the dissolution of the coating was observed by boiling in water at 100 °C to check its stability in water.

[0053] Group Boiling in water at 100°C Water contact angle test Example 1 The coating does not dissolve 101° Example 2 The coating does not dissolve 105° Example 3 The coating does not dissolve 103° Control group 1 The coating has dissolution 95° Control group 2 / /

[0054] Test results: The products of Examples 1 - 3 were all insoluble in the 100 °C aqueous solution and all had good water solubility resistance; and in the contact angle test, it was also found that the contact angles of Examples 1 - 3 were all greater than those of the control group; and through the water resistance standard (QJ 990.9 - 1986 Coating inspection method Coating water resistance inspection method), it was detected that the products of Examples 1 - 3 all had excellent water resistance. That is, the paper coatings prepared in the examples of the present invention have good water resistance performance

[0055] Oil-proof detection

[0056] The oil contact angles of the products of Examples 1 - 3 and the papers of the control group were respectively tested to judge the oil-repellent situation by looking at the size of the contact angles; the dissolution of the coating was observed by boiling in oil at 180 °C to check its stability in oil.

[0057] Group Boiling in oil at 180°C Oil contact angle test Example 1 The coating does not dissolve 102° Example 2 The coating does not dissolve 105° Example 3 The coating does not dissolve 104° Control group 1 The coating has dissolution 93° Control group 2 / /

[0058] Test results: The products of Examples 1-3 were insoluble in an oil bath at 180°C and all had good oil solubility resistance; also, in the oil contact angle test, it was found that the contact angles of Examples 1-3 were all greater than those of the control group; moreover, through the oil resistance standard (QJ 990.1-1986 Coating inspection method - Coating oil resistance inspection method), it was detected that Examples 1-3 all had excellent oil resistance, that is, the paper coatings prepared in the examples of the present invention had good oil resistance performance.

[0059] Mechanical property testing

[0060] The products of Examples 1-3 and the paper of the control group were respectively subjected to mechanical tensile testing, and the maximum force they withstood before fracture was recorded, and then the mechanical properties of these coatings were judged.

[0061] Group The maximum force (N) that the paper can withstand before breaking Example 1 31N Example 2 25N Example 3 36N Control group 1 21N Control group 2 4.5N

[0062] Test results: The tensile resistance of the papers with coatings of Examples 1-3 was much greater than that of Control Groups 1 and 2. It was proved that the coatings prepared in the present invention could significantly improve the mechanical properties of the paper and endow the paper with obvious toughness.

[0063] Degradability testing

[0064] The products of Examples 1-3 and the paper of the control group were respectively subjected to degradability testing, and the tests were carried out according to the test standard (GB / T 39951-2021 Evaluation method for the degradability of disposable paper products), and the following results were finally obtained:

[0065] Group Degradation degree: Biodegradation rate Example 1 90％ Example 2 90％ Example 3 90％ Control group 1 50％ Control group 2 90％

[0066] Test results: The degradation degrees of the papers with coatings of Examples 1-3 were equivalent to that of the blank control group 2 and were both greater than that of the control group 1, which proved that the coatings prepared in the examples of the present invention had good degradability.

[0067] Coating dyeing testing

[0068] The products of Examples 1-3 and the paper of the control group were respectively boiled in water at 100°C and in edible oil at 180°C, and the color fading situation of the paper in them was observed. By whether it faded or how much it faded, the color fastness of the dye was judged, and the following results were finally obtained:

[0069] Group Boiling in water at 100°C Boiling in oil at 180°C Example 1 Does not fade Does not fade Example 2 Does not fade Does not fade Example 3 Does not fade Does not fade Control group 1 / / Control group 2 / /

[0070] Test results: The papers with coatings of Examples 1-3 did not fade whether in oil at 100°C or in water at 180°C, and the coloring was firm.

[0071] In summary, the present invention has the following advantages:

[0072] The degradable and stainable waterborne organofluorosilicone polyurethane waterproof and oil-proof coating material provided by the present invention has excellent properties. After the paper is treated with this coating material, the paper has the excellent characteristics of waterproof, oil-proof, increased mechanical properties of the paper, non-fading, degradable and recyclable, and can completely replace PP / PE coated paper, and is environmentally friendly.

[0073] It can be understood that the above specific description of the present invention is only for explaining the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those of ordinary skill in the art should understand that the present invention can still be modified or equivalently replaced to achieve the same technical effect; as long as it meets the use requirements, it is within the protection scope of the present invention.

Claims

1. A degradable, dyeable, waterproof and oil-proof water-based organic fluorine-silicon polyurethane coating material. Features: The coating material is formed by crosslinking of an epoxy-terminated waterborne organofluorosilicone polyurethane emulsion and an amine curing agent, and the preparation method of the coating material includes: uniformly mixing the epoxy-terminated waterborne organofluorosilicone polyurethane emulsion and the amine curing agent of the waterborne epoxy resin in proportion, and then uniformly coating in an amount of 2-15 g / m 2 on the surface of the paper, and then through drying treatment, a waterproof and oil-proof paper with high toughness, degradability and dyeability can be obtained; The preparation steps of the epoxy-terminated water-based organic fluorine silicone polyurethane emulsion include: adding vacuum-dehydrated N,N-dihydroxyethyl azo dye, diisocyanate, and dibutyltin laurate in sequence into a four-necked flask equipped with a stirrer and a thermometer, stirring thoroughly, and reacting at 40° C. for 2 hours; then adding dehydrated polycaprolactone polyol and polylactic acid diol, and fluorine-containing hydroxy polysiloxane, and reacting at 70-80° C. for 2-3 hours; adding 1,4-dihydroxybutane-2-sulfonic acid sodium and 1,4-butanediol for chain extension, and continuing to react at 60° C. for 3-4 hours; after the isocyanate group reaches a certain level, adding glycidol for end-capping, and sealing the remaining isocyanate groups; cooling to below 40° C., adding deionized water for emulsification, and obtaining the epoxy-terminated water-based organic fluorine silicone polyurethane emulsion; The amine curing agent is a commercially available water-based polyamine curing agent; the epoxy-terminated water-based organic fluorine silicone polyurethane emulsion is synthesized using diisocyanate and degradable polyester polyol as raw materials, hydroxy silicone oil with fluorine-containing groups as a modifier, N,N-dihydroxyethyl azo dye and 1,4-dihydroxybutane-2-sodium sulfonate as hydrophilic monomers, 1,4-butanediol as a chain extender, and glycidol as a capping agent; The structure of the hydroxy silicone oil having a fluorine-containing group is: Among them, the fluorine-containing component accounts for 5-60 mol%, the hydroxyl component accounts for 2 mol%, and the molecular weight of the hydroxy silicone oil is 600-4000 Daltons. The preparation process of the hydroxy silicone oil containing a fluorine-containing group is as follows: in a four-necked flask equipped with a stirrer, a thermometer and a reflux condenser, hydrogen-containing polysiloxane and allyl alcohol, fluorine-containing acrylate, alkyl acrylate are added in sequence, stirred evenly at a certain temperature, a certain amount of catalyst chloroplatinic acid is added, the temperature is raised to the reaction temperature, after a certain reaction time, low boiling points are removed by rotary evaporation to obtain a fluorine-containing hydroxy polysiloxane.

2. The water-based organic fluorine-silicone polyurethane coating material according to claim 1, Features: The diisocyanate is one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate.

3. The water-based organic fluorine-silicone polyurethane coating material according to claim 1, Features: The degradable polyester polyol is one or more of polycaprolactone diol, polycaprolactone triol and polylactic acid diol, and the molecular weight of the degradable polyester polyol can be 500-3000 Daltons.

4. The water-based organic fluorine-silicone polyurethane coating material according to claim 1, Features: The N,N-dihydroxyethylazo dye uses red, yellow and blue primary dyes, and the specific structure is as follows: 。

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