A flame retardant and antibacterial polyurethane coating agent and method and application thereof

Abstract

The present invention relates to a flame retardant antibacterial polyurethane coating agent and a method and application thereof. The flame retardant antibacterial polyurethane coating agent comprises an aqueous polyurethane component, a phytic acid guanidine salt phosphorus / nitrogen type flame retardant component (a salt formed by phytic acid and polyhexamethylene biguanide combined by ionic bonds) and a blocked polyisocyanate crosslinking agent component; the method is: the components are mixed and stirred evenly according to a ratio, wherein the preparation process of the phytic acid guanidine salt phosphorus / nitrogen type flame retardant is: after phytic acid and polyhexamethylene biguanide are mixed and dissolved in a solvent, the pH of the solution is adjusted to 8-9, and continuous stirring is performed until precipitation is generated, and the precipitation is the phytic acid guanidine salt phosphorus / nitrogen type flame retardant; the application is: the flame retardant antibacterial polyurethane coating agent is coated on a single side surface of a polyester fabric, and then pre-baked and baked to obtain a flame retardant antibacterial polyester coating canopy material. The method of the present invention is simple, the flame retardant antibacterial polyurethane coating agent has good flame retardant properties, and the flame retardant antibacterial polyester coating canopy material still has a flame retardant effect after being washed 45 times.

Description

Technical Field

[0001] The invention belongs to the technical field of functional finishing of textiles, and in particular relates to a flame retardant and antibacterial polyurethane coating agent and a method and application thereof. Background Art

[0002] Polyester fabric has good wrinkle resistance, shape retention, high strength and elastic recovery ability, and is currently the most widely used fiber material among synthetic fibers. Polyurethane-coated polyester fabric is widely used in curtains, outdoor leisure or emergency rescue tents and other material fields, and these application scenarios have high requirements for the flame retardant properties of polyester tent cover materials.

[0003] The coating method is to physically blend the flame retardant with the coating agent or copolymerize the flame retardant group with the monomer to obtain a reactive flame retardant coating agent, and then rely on the physical entanglement of the polymer chain and the fiber in the coating agent or the intermolecular hydrogen bond to bond the flame retardant to the fabric. Its characteristics are high flame retardant utilization rate, low processing cost, and can effectively improve the flame retardant properties of the coated fabric, and has been widely promoted and applied.

[0004] However, existing flame-retardant polyurethane coated polyester fabrics have the disadvantages of low flame retardant efficiency, high dosage, and poor environmental protection.

[0005] Reference 1 (Chen Huifen, Zheng Jinhuan. Application and mechanism of action of flame-retardant coating finishing agent containing hydrotalcite [J]. Journal of Textile Research, 2014, 35(11): 107-111, 117) Compounded hydrotalcite with waterborne polyurethane (PU) to prepare a flame-retardant functional coating finishing agent for flame-retardant coating of polyester fabric; however, hydrotalcite is an inorganic flame retardant with low flame retardant efficiency. It has a good flame retardant effect only when the content of hydrotalcite in the coating PU reaches 9%.

[0006] Chinese invention patent CN200610085269.X discloses the preparation of a vapor-permeable, flame-retardant, oil-proof, waterproof, acid-proof and near-infrared-proof polyester tarpaulin. The polyester fabric is firstly flame-retarded by using a 9- to 15% bromine antimony flame retardant, and then the polyester fabric is coated with a flame-retardant PU to develop a flame-retardant polyester tarpaulin. The halogen flame retardant system has a high flame retardant efficiency, but the harmful gases generated during the combustion process are destructive to the human body and the environment, and the process flow is complicated.

[0007] Reference 2 (Yang Chuanchuan, Gu Hao, Fang Juanjuan, Xie Kongliang, Hou Aiqin. Production of flame-retardant polyester low-elastic yarn tent fabric for emergency rescue [J]. Printing and Dyeing, 2019, 45(8): 35-39) selected halogen flame retardants and other phosphorus nitrogen series flame retardants mixed with solvent-based PU to coat polyester fabrics. Halogen flame retardants are highly efficient but are gradually banned due to poor environmental performance; the selected phosphorus nitrogen flame retardant RF-603A also has a low flame retardant efficiency. When the addition amount in PU reaches 50%, the coated polyester fabric has a good flame retardant effect. However, excessive addition of flame retardants in PU can easily lead to difficulties in PU curing and affect the film-forming properties of the coating.

[0008] Phytic acid is also known as inositol hexaphosphate, and is often found in beans, grains and oilseeds in the form of phytate. It is the main storage form of phosphorus in plants and is also known as a "green" molecule. Phytic acid has good biocompatibility, is non-toxic and environmentally friendly, and has good renewability. The phosphorus content in its molecule is as high as 28wt%, and it is rich in 6 highly active phosphate groups, which have strong chelating ability with cationic compounds or metal ions.

[0009] Reference 3 (Xiao Wencheng. Flame retardant finishing of polyester fabrics based on phytic acid [D]. Suzhou University, 2019.) The flame retardant properties of polyester fabrics were improved by using phytic acid through the rolling baking method, but the water washing resistance of the flame retardant polyester fabric was poor.

[0010] Phytic acid easily migrates in PU coatings, resulting in poor water wash resistance of phytic acid-coated polyester fabrics. It is a difficult problem to develop flame-retardant PU using a phytic acid-based system and to apply durable functional coatings to polyester fabrics, and there are currently no relevant reports.

[0011] Therefore, it is of great significance to study a flame retardant and antibacterial polyurethane coating agent and a method and application thereof to solve the problems in the prior art that flame retardants are prone to migration and the fabrics have poor water resistance when applied to the fabrics. Summary of the invention

[0012] The purpose of the present invention is to solve the above-mentioned problems and provide a flame retardant and antibacterial polyurethane coating agent and a method and application thereof.

[0013] In order to achieve the above object, the technical solution adopted by the present invention is as follows:

[0014] A flame retardant and antibacterial polyurethane coating agent comprises a waterborne polyurethane component, a phytic acid guanidine salt phosphorus / nitrogen type flame retardant component and a blocked polyisocyanate crosslinking agent component. The phytic acid guanidine salt phosphorus / nitrogen type flame retardant is a salt formed by phytic acid and polyhexamethylene biguanide through ionic bonding, and the ionic bond is specifically a bond formed between anionic phosphate groups in phytic acid molecules and cationic imino groups in polyhexamethylene biguanide.

[0015] As the preferred technical solution:

[0016] In the flame retardant and antibacterial polyurethane coating agent as described above, the content of the phytic acid guanidine salt phosphorus / nitrogen type flame retardant is 1 to 4 wt %.

[0017] In the flame retardant and antibacterial polyurethane coating agent as described above, the solubility of the phytic acid guanidine salt phosphorus / nitrogen type flame retardant in water with a temperature of 25° C. and a volume of 100 mL is less than or equal to 0.01 g.

[0018] In the flame retardant and antibacterial polyurethane coating agent as described above, the average particle size of the phytic acid guanidine salt phosphorus / nitrogen type flame retardant is 80-120 μm.

[0019] The flame retardant and antibacterial polyurethane coating agent as described above further comprises 2-4 wt % of an anti-ultraviolet absorber or an anti-aging agent.

[0020] The present invention also provides a method for preparing a flame retardant and antibacterial polyurethane coating agent as described in any one of the above items, wherein the components are mixed and stirred evenly according to a ratio to obtain the flame retardant and antibacterial polyurethane coating agent, wherein the preparation process of the phytic acid guanidine salt phosphorus / nitrogen type flame retardant is as follows: phytic acid and polyhexamethylene biguanide are mixed and dissolved in a solvent (preferably the solvent is deionized water, because deionized water has low economic cost, is harmless to the environment, and is suitable for the preparation of flame retardants; other reagents compatible with phytic acid and polyhexamethylene biguanide can also replace deionized water, but have high cost and also need to be recovered), then the pH of the solution is adjusted to 8-9 with an alkali, and the solution is dried (80°C, 6h) and ball-milled after continuous stirring until precipitation is generated, to obtain the phytic acid guanidine salt phosphorus / nitrogen type flame retardant; when the pH of the solution is 8-9, phytic acid and polyhexamethylene biguanide can be combined to produce a polymer precipitate well, and too high or too low pH is not conducive to the ionization of polyhexamethylene biguanide and phytic acid, and is not conducive to the combination of the two to produce a polymer precipitate.

[0021] As the preferred technical solution:

[0022] According to the method described above, the degree of polymerization of polyhexamethylene biguanide is 11-15.

[0023] In the method described above, the mass ratio of phytic acid to polyhexamethylene biguanide is 1:2-4. Too high or too low a ratio of the two will lead to a decrease in the yield of the product.

[0024] The present invention also provides an application of a flame retardant antibacterial polyurethane coating agent as described above, wherein the flame retardant antibacterial polyurethane coating agent is coated on a single surface of a polyester fabric and then pre-baked and baked to obtain a flame retardant antibacterial polyester coating awning material.

[0025] As the preferred technical solution:

[0026] In the application as described above, the polyester fabric is a polyester fabric that has been waterproofed and calendered; wherein, the waterproof grade of the polyester fabric after waterproofing is grade 4; if the waterproof grade is too low, the waterproof effect cannot be achieved, and the water-based polyurethane will penetrate into the back of the fabric (i.e., the surface not coated with the coating agent); if the waterproof grade is too high, the water-based polyurethane is not easily applied to the fabric surface.

[0027] For the application described above, the pre-baking temperature is 100-120°C, and the pre-baking time is 2-4 minutes; the baking temperature is 160-180°C, and the baking time is 2-4 minutes. The baking process ensures that the polyurethane can form a good film on the surface of the polyester fabric; the coating amount of the flame retardant and antibacterial polyurethane coating agent on the surface of the polyester fabric is 50-100g / m 2 .

[0028] For the above application, the damaged length of the flame-retardant and antibacterial polyester coated awning material is not higher than 14.5cm, and the limiting oxygen index is not lower than 28.2%. The test standard is GB8624-2012 "Classification of Combustion Performance of Building Materials and Products Textiles"; after 45 times of washing, the change rate of the damaged length does not exceed 12.47%, and the change rate of the limiting oxygen index does not exceed 12.36%. The washing adopts the D / Max-IIIC type washing fastness tester. According to AATCC61-2013 "Color Fastness to Washing", the specific process is: put the fabric into the soap solution with a concentration of 3 .7g / L, in a steel cup with a bath ratio of 1:50, at 40℃, oscillate and wash for 45min, then take out and wash with cold water, which is one accelerated water wash (equivalent to five ordinary water washes), and the "45 washes" mentioned above refer to nine accelerated water washes; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.1-0.8mm and 0.1-0.8mm respectively, and the test standard is GB / T20944.1-2007 "Evaluation of Antibacterial Properties of Textiles Part 1_Agar Plate Diffusion Method", which are all between 0 and 1mm, indicating that the fabric has a good antibacterial effect.

[0029] The principle of the present invention is as follows:

[0030] (1) Figure 2As shown in the figure, the phytic acid molecule contains 6 anionic phosphate groups, which form ionic bonds with the cationic imino groups of polyhexamethylene biguanide. The ionic bonds are relatively stable and not easily ionized in deionized water, thereby preparing phytic acid guanidine salt phosphorus / nitrogen type flame retardant; the pH value of waterborne polyurethane is about 7.5, while the pH value of the combination of phytic acid and polyhexamethylene biguanide is 8-9. The prepared phytic acid guanidine salt polyelectrolyte phosphorus / nitrogen flame retardant has little effect on the pH value of polyurethane when added to polyurethane. Therefore, the phytic acid guanidine salt phosphorus / nitrogen type flame retardant will not cause waterborne polyurethane In addition, the prepared phytic acid guanidine salt phosphorus / nitrogen flame retardant is insoluble in water and has high hydrolysis stability. At room temperature, the functional groups between the phytic acid guanidine salt phosphorus / nitrogen flame retardant and the waterborne polyurethane will not undergo chemical reactions. At the same time, both are alkaline substances and will not undergo acid-base neutralization reactions. Therefore, the phytic acid guanidine salt phosphorus / nitrogen flame retardant has good dispersion performance in the polyurethane coating network structure and is not easy to migrate. Compared with phytic acid with good water solubility, the fabric obtained by applying the phytic acid guanidine salt phosphorus / nitrogen flame retardant has good water washing resistance.

[0031] (2) Phytic acid molecules contain a high phosphorus content, so they have certain flame retardant properties, but they cannot meet the requirements of high-efficiency and durable coated polyester fabrics. The present invention uses polyhexamethylene biguanide and phytic acid to form a phosphorus / nitrogen flame retardant system. During the combustion process, the phosphorus-containing flame retardant groups of phytic acid can release phosphoric acid and polyphosphoric acid, catalyzing the polyurethane coated polyester fabric to charcoal, thereby improving the flame retardant effect; the nitrogen-containing flame retardant groups of polyhexamethylene biguanide will release a large amount of non-flammable gas during the combustion process, thereby playing the role of diluting combustible gases and oxygen, and the generated non-flammable gas can cause the carbon layer to expand. The expanded carbon layer has a high heat insulation effect, isolating heat and combustible gases from the exchange with the underlying matrix, thereby further improving the flame retardant efficiency. Therefore, the prepared phytic acid guanidine salt phosphorus / nitrogen type flame retardant can improve the flame retardant properties of coated polyester fabrics through the expansion flame retardant mechanism;

[0032] (3) Polyhexamethylene biguanide is an environmentally friendly antibacterial agent. Its positively charged hydrophilic groups can adsorb negatively charged bacteria and viruses, enter the cell membrane, inhibit the synthesis of liposomes in the membrane, cause bacterial apoptosis, and achieve the best bactericidal effect.

[0033] Beneficial Effects

[0034] (1) In the flame-retardant and antibacterial polyurethane coating agent of the present invention, the phytic acid guanidine salt phosphorus / nitrogen type flame retardant can improve the flame retardant properties of the coated fabric through the expansion flame retardant mechanism, has high flame retardant efficiency, and uses a small amount;

[0035] (2) The preparation method of the flame retardant and antibacterial polyurethane coating agent of the present invention is simple, quick and convenient;

[0036] (3)) When the flame-retardant and antibacterial polyurethane coating agent of the present invention is applied to fabrics, it has good water resistance and antibacterial properties, and the phytic acid guanidine salt phosphorus / nitrogen type flame retardant is not easy to migrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 Schematic diagram of vertical combustion of polyester fabric before and after using flame retardant antibacterial polyurethane coating agent; the left picture is polyester fabric without using flame retardant antibacterial polyurethane coating agent; the right picture is polyester fabric with using flame retardant antibacterial polyurethane coating agent;

[0038] Figure 2 Schematic diagram of preparing phytic acid guanidine salt (i.e. phytic acid guanidine salt phosphorus / nitrogen flame retardant) from phytic acid and polyhexamethylene biguanide;

[0039] Figure 3 This is a graph showing the relationship between the amount of flame retardant and coating added and the flame retardant properties of the fabric. DETAILED DESCRIPTION

[0040] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that after reading the content taught by the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms fall within the scope limited by the appended claims of the application equally.

[0041] Example 1

[0042] A method for preparing a flame retardant and antibacterial polyurethane coating agent, the specific steps are as follows:

[0043] (1) Prepare raw materials:

[0044] Phytic acid: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand number is P816024;

[0045] Polyhexamethylene biguanide: The manufacturer is Wuhan Xinbeimei Biotechnology Co., Ltd., brand number 24568;

[0046] Waterborne polyurethane: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand name is W909580;

[0047] Blocked polyisocyanate crosslinker: manufacturer is Stahl Fine Coatings Co., Ltd., brand number 903;

[0048] (2) Preparation of flame retardant and antibacterial polyurethane coating agent:

[0049] (2.1) dissolving a mixture of phytic acid and polyhexamethylene biguanide in a mass ratio of 1:3 in deionized water, adjusting the pH of the solution to 8.5 with NaOH, and continuously stirring until precipitation occurs. The precipitate is washed, filtered, dried, and ball-milled to obtain a phytic acid guanidine salt phosphorus / nitrogen type flame retardant;

[0050] The yield of the prepared phytic acid guanidine salt phosphorus / nitrogen flame retardant is 59.79%, the average particle size is 100 μm, and the solubility in 100 mL of water at a temperature of 25° C. is 0.008 g;

[0051] (2.2) adding guanidine phytate phosphorus / nitrogen flame retardant and blocked polyisocyanate crosslinking agent into waterborne polyurethane and stirring evenly to obtain flame retardant antibacterial polyurethane coating agent;

[0052] The prepared flame retardant and antibacterial polyurethane coating agent consists of waterborne polyurethane, guanidine phytate phosphorus / nitrogen type flame retardant and blocked polyisocyanate crosslinking agent, wherein the content of guanidine phytate phosphorus / nitrogen type flame retardant is 1wt%, and the content of blocked polyisocyanate crosslinking agent is 5wt%.

[0053] A method for preparing a flame-retardant and antibacterial polyester coating awning material, the specific process is: firstly, a waterproofing agent (manufacturer is Guangdong Demei Fine Chemical Group Co., Ltd., brand Furx-9033) is used to waterproof polyester fabric by a calendering-baking-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then the waterproof polyester fabric is calendered, and finally the flame-retardant and antibacterial polyurethane coating agent prepared in this embodiment is coated at a coating amount of 50 g / m 2 After being coated on one side surface of waterproof polyester fabric, the material is pre-baked and baked to obtain a flame-retardant and antibacterial polyester coating awning material, wherein the pre-baking temperature is 110° C., the pre-baking time is 3 minutes, the baking temperature is 170° C., and the baking time is 3 minutes.

[0054] The damage length of the flame-retardant and antibacterial polyester coated awning material is 14 cm, and the limiting oxygen index is 28.5%; after 45 times of water washing, the change rate of the damage length is 12.47%, and the change rate of the limiting oxygen index is 5.26%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.1 mm and 0.1 mm, respectively.

[0055] Example 2

[0056] A method for preparing a flame retardant and antibacterial polyurethane coating agent is the same as that in Example 1.

[0057] A method for preparing a flame retardant and antibacterial polyester coating canopy material is basically the same as that in Example 1, except that the coating amount of the flame retardant and antibacterial polyurethane coating agent is 100 g / m 2 .

[0058] The damage length of the flame-retardant and antibacterial polyester coated awning material is 13.8 cm, and the limiting oxygen index is 29.2%; after 45 times of water washing, the change rate of the damage length is 8.69%, and the change rate of the limiting oxygen index is 4.11%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.3 mm and 0.2 mm, respectively.

[0059] Example 3

[0060] A method for preparing a flame retardant and antibacterial polyurethane coating agent is basically the same as that in Example 1, except that the content of the phytic acid guanidine salt phosphorus / nitrogen type flame retardant in step (2.2) is 2wt%.

[0061] A method for preparing a flame-retardant and antibacterial polyester coating awning material, the specific process is: firstly, a waterproofing agent (manufacturer is Guangdong Demei Fine Chemical Group Co., Ltd., brand Furx-9033) is used to waterproof polyester fabric by a calendering-baking-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then the waterproof polyester fabric is calendered, and finally the flame-retardant and antibacterial polyurethane coating agent prepared in this embodiment is coated at a coating amount of 50 g / m 2 After being coated on one side surface of waterproof polyester fabric, the material is pre-baked and baked to obtain a flame-retardant and antibacterial polyester coating awning material, wherein the pre-baking temperature is 110° C., the pre-baking time is 3 minutes, the baking temperature is 170° C., and the baking time is 3 minutes.

[0062] The damage length of the flame-retardant and antibacterial polyester coated awning material is 13.6 cm, and the limiting oxygen index is 32.7%; after 45 times of water washing, the change rate of the damage length is 9.33%, and the change rate of the limiting oxygen index is 4.05%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.2 mm and 0.2 mm, respectively.

[0063] Example 4

[0064] A method for preparing a flame retardant and antibacterial polyurethane coating agent is the same as that in Example 3.

[0065] A method for preparing a flame retardant and antibacterial polyester coating canopy material is basically the same as that in Example 3, except that the coating amount of the flame retardant and antibacterial polyurethane coating agent is 100 g / m 2 .

[0066] The damage length of the flame-retardant and antibacterial polyester coated awning material is 12.4 cm, and the limiting oxygen index is 33.9%; after 45 times of water washing, the change rate of the damage length is 4.83%, and the change rate of the limiting oxygen index is 4.72%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.5 mm and 0.3 mm, respectively.

[0067] Comparative Example 1

[0068] A method for preparing a flame retardant polyurethane coating agent, the specific steps are as follows:

[0069] (1) Prepare raw materials:

[0070] Phytic acid: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand number is P816024;

[0071] Sodium phytate: The manufacturer is Suzhou Great Pharmaceutical Technology Co., Ltd., brand number S30224;

[0072] Waterborne polyurethane: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand name is W909580;

[0073] Blocked polyisocyanate crosslinker: manufacturer is Stahl Fine Coatings Co., Ltd., brand number 903;

[0074] (2) Preparation of flame retardant polyurethane coating agent:

[0075] (2.1) Mix phytic acid and sodium phytate in a mass ratio of 5:17 to obtain a flame retardant;

[0076] (2.2) adding a flame retardant and a blocked polyisocyanate crosslinking agent into the waterborne polyurethane and stirring evenly to obtain a flame retardant polyurethane coating agent;

[0077] The prepared flame retardant polyurethane coating agent consists of waterborne polyurethane, flame retardant and blocked polyisocyanate crosslinking agent, wherein the content of the flame retardant is 2wt% and the content of the blocked polyisocyanate crosslinking agent is 5wt%.

[0078] A method for preparing a flame-retardant polyester coated awning material, the specific process is: firstly, a waterproofing agent (manufacturer is Guangdong Demei Fine Chemical Group Co., Ltd., brand Furx-9033) is used to waterproof polyester fabric by a calendering-baking-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then the waterproof polyester fabric is calendered, and finally the flame-retardant polyurethane coating agent prepared in the comparative example is coated at a coating amount of 100g / m 2 After coating on one side surface of waterproof polyester fabric, pre-baking and baking are performed to obtain flame-retardant polyester coated awning material, wherein the pre-baking temperature is 110°C, the pre-baking time is 3 minutes, the baking temperature is 170°C, and the baking time is 3 minutes.

[0079] The damage length of the flame-retardant polyester coated awning material is 12.5 cm, and the limiting oxygen index is 33.2%; after 45 times of water washing, the change rate of the damage length is 13.6%, and the change rate of the limiting oxygen index is 15.1%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0 mm and 0 mm, respectively.

[0080] The washing fastness of the flame-retardant and antibacterial polyester coated awning material of Example 4 and the polyester coated awning material of Comparative Example 1 are shown in Table 1. The flame retardant performance of the flame-retardant and antibacterial polyester coated awning material of Example 4 is reduced after washing. This is because the phytic acid guanidine salt phosphorus / nitrogen type flame retardant on the surface of the coating is dissolved in water under the action of water molecules and the external environment, thereby reducing the flame retardant performance of the fabric. However, when washed the same number of times, the limiting oxygen index of the flame-retardant and antibacterial polyester coated awning material of Example 4 is higher than that of the polyester coated awning material of Comparative Example 1. The flame-retardant and antibacterial polyester coated awning material of Example 4 can still reach Class B1 after washing 45 times, while the flame retardant level of the polyester coated awning material of Comparative Example 1 drops to Class B2 after washing 10 times, indicating that the water-insoluble phytic acid / guanidine salt particles are not easy to migrate in PU and have good durability.

[0081] Table 1

[0082]

[0083] Example 5

[0084] A method for preparing a flame retardant and antibacterial polyurethane coating agent is basically the same as that of Example 3, except that the content of the phytic acid guanidine salt phosphorus / nitrogen type flame retardant in step (2.2) is 4wt%.

[0085] A method for preparing a flame-retardant and antibacterial polyester coating awning material, the specific process is: firstly, a waterproofing agent (manufacturer is Guangdong Demei Fine Chemical Group Co., Ltd., brand Furx-9033) is used to waterproof polyester fabric by a calendering-baking-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then the waterproof polyester fabric is calendered, and finally the flame-retardant and antibacterial polyurethane coating agent prepared in this embodiment is coated at a coating amount of 50 g / m 2 After being coated on one side surface of waterproof polyester fabric, the material is pre-baked and baked to obtain a flame-retardant and antibacterial polyester coating awning material, wherein the pre-baking temperature is 110° C., the pre-baking time is 3 minutes, the baking temperature is 170° C., and the baking time is 3 minutes.

[0086] The damage length of the flame-retardant and antibacterial polyester coated awning material is 12.5 cm, and the limiting oxygen index is 33.0%; after 45 times of water washing, the change rate of the damage length is 12.14%, and the change rate of the limiting oxygen index is 6.45%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.4 mm and 0.3 mm, respectively.

[0087] Example 6

[0088] A method for preparing a flame retardant and antibacterial polyurethane coating agent is the same as that in Example 5.

[0089] A method for preparing a flame retardant and antibacterial polyester coating awning material is basically the same as that in Example 5, except that the coating amount of the flame retardant and antibacterial polyurethane coating agent is 100 g / m 2 .

[0090] The damage length of the flame-retardant and antibacterial polyester coated awning material is 12.2 cm, and the limiting oxygen index is 36.8%; after 45 times of water washing, the change rate of the damage length is 5.73%, and the change rate of the limiting oxygen index is 13.23%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.8 mm and 0.6 mm, respectively.

[0091] like Figure 1 and Figure 3 As shown, from Examples 1 to 6 and the untreated polyester fabric, it can be concluded that with the increase in the amount of guanidine phytate phosphorus / nitrogen type flame retardant, the damaged length of the flame retardant and antibacterial polyester coated awning material gradually decreases, the damaged area is significantly reduced, and the limiting oxygen index gradually increases, indicating that the flame retardant effect is improved; when the amount of guanidine phytate phosphorus / nitrogen type flame retardant is constant, the more weight gain, the more guanidine phytate phosphorus / nitrogen type flame retardant content, and the better the flame retardant effect.

[0092] Example 7

[0093] A method for preparing a flame retardant and antibacterial polyurethane coating agent is basically the same as that of Example 1, except that in step (2.1), the mass ratio of phytic acid to polyhexamethylene biguanide is 1:5.

[0094] A method for preparing a flame-retardant and antibacterial polyester coating awning material, the specific process is: firstly, a waterproofing agent (manufacturer is Guangdong Demei Fine Chemical Group Co., Ltd., brand Furx-9033) is used to waterproof polyester fabric by a calendering-baking-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then the waterproof polyester fabric is calendered, and finally the flame-retardant and antibacterial polyurethane coating agent prepared in this embodiment is coated at a coating amount of 50 g / m 2 After being coated on one side surface of waterproof polyester fabric, the material is pre-baked and baked to obtain a flame-retardant and antibacterial polyester coating awning material, wherein the pre-baking temperature is 110° C., the pre-baking time is 3 minutes, the baking temperature is 170° C., and the baking time is 3 minutes.

[0095] The damage length of the flame-retardant and antibacterial polyester coated awning material is 14.5 cm, and the limiting oxygen index is 28.2%; after 45 times of water washing, the change rate of the damage length is 10.34%, and the change rate of the limiting oxygen index is 4.41%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.8 mm and 0.8 mm, respectively.

[0096] Example 8

[0097] A method for preparing a flame retardant and antibacterial polyurethane coating agent, the specific steps are as follows:

[0098] (1) Prepare raw materials:

[0099] Phytic acid: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand number is P816024;

[0100] Polyhexamethylene biguanide: The manufacturer is Wuhan Xinbeimei Biotechnology Co., Ltd., brand number 24568;

[0101] Waterborne polyurethane: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand name is W909580;

[0102] Blocked polyisocyanate crosslinker: manufacturer is Stahl Fine Coatings Co., Ltd., brand number 903;

[0103] (2) Preparation of flame retardant and antibacterial polyurethane coating agent:

[0104] (2.1) dissolving a mixture of phytic acid and polyhexamethylene biguanide in a mass ratio of 1:2 in deionized water, adjusting the pH of the solution to 8 with NaOH, and continuously stirring until precipitation occurs. The precipitate is washed, filtered, dried, and ball-milled to obtain a phytic acid guanidine salt phosphorus / nitrogen type flame retardant;

[0105] The yield of the prepared phytic acid guanidine salt phosphorus / nitrogen flame retardant is 54.65%, the average particle size is 80 μm, and the solubility in 100 mL of water at a temperature of 25° C. is 0.006 g;

[0106] (2.2) adding guanidine phytate phosphorus / nitrogen flame retardant and blocked polyisocyanate crosslinking agent into waterborne polyurethane and stirring evenly to obtain flame retardant antibacterial polyurethane coating agent;

[0107] The prepared flame retardant and antibacterial polyurethane coating agent consists of waterborne polyurethane, guanidine phytate phosphorus / nitrogen type flame retardant and blocked polyisocyanate crosslinking agent, wherein the content of guanidine phytate phosphorus / nitrogen type flame retardant is 1wt%, and the content of blocked polyisocyanate crosslinking agent is 5wt%.

[0108] A method for preparing a flame-retardant and antibacterial polyester coating awning material, the specific process is: firstly, a waterproofing agent (manufacturer is Guangdong Demei Fine Chemical Group Co., Ltd., brand Furx-9033) is used to waterproof polyester fabric by a calendering-baking-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then the waterproof polyester fabric is calendered, and finally the flame-retardant and antibacterial polyurethane coating agent prepared in this embodiment is coated at a coating amount of 100g / m 2After being coated on one side surface of waterproof polyester fabric, the material is pre-baked and baked to obtain a flame-retardant and antibacterial polyester coated awning material, wherein the pre-baking temperature is 100°C, the pre-baking time is 4 minutes, the baking temperature is 160°C, and the baking time is 4 minutes.

[0109] The damage length of the flame-retardant and antibacterial polyester coated awning material is 13.8 cm, and the limiting oxygen index is 29.2%; after 45 times of water washing, the change rate of the damage length is 8.69%, and the change rate of the limiting oxygen index is 4.11%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.3 mm and 0.2 mm, respectively.

[0110] Example 9

[0111] A method for preparing a flame retardant and antibacterial polyurethane coating agent, the specific steps are as follows:

[0112] (1) Prepare raw materials:

[0113] Phytic acid: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand number is P816024;

[0114] Polyhexamethylene biguanide: The manufacturer is Wuhan Xinbeimei Biotechnology Co., Ltd., brand number 24568;

[0115] Waterborne polyurethane: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand name is W909580;

[0116] Blocked polyisocyanate crosslinker: manufacturer is Stahl Fine Coatings Co., Ltd., brand number 903;

[0117] (2) Preparation of flame retardant and antibacterial polyurethane coating agent:

[0118] (2.1) dissolving a mixture of phytic acid and polyhexamethylene biguanide in a mass ratio of 1:3 in deionized water, adjusting the pH of the solution to 8.5 with NaOH, and continuously stirring until precipitation occurs. The precipitate is washed, filtered, dried, and ball-milled to obtain a phytic acid guanidine salt phosphorus / nitrogen type flame retardant;

[0119] The yield of the prepared phytic acid guanidine salt phosphorus / nitrogen flame retardant is 59.79%, the average particle size is 100 μm, and the solubility in 100 mL of water at a temperature of 25° C. is 0.008 g;

[0120] (2.2) adding guanidine phytate phosphorus / nitrogen flame retardant and blocked polyisocyanate crosslinking agent into waterborne polyurethane and stirring evenly to obtain flame retardant antibacterial polyurethane coating agent;

[0121] The prepared flame retardant and antibacterial polyurethane coating agent consists of waterborne polyurethane, guanidine phytate phosphorus / nitrogen type flame retardant and blocked polyisocyanate crosslinking agent, wherein the content of guanidine phytate phosphorus / nitrogen type flame retardant is 2wt%, and the content of blocked polyisocyanate crosslinking agent is 5wt%.

[0122] A method for preparing a flame-retardant and antibacterial polyester coating awning material, the specific process is: firstly, a waterproofing agent (manufacturer is Guangdong Demei Fine Chemical Group Co., Ltd., brand Furx-9033) is used to waterproof polyester fabric by a calendering-baking-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then the waterproof polyester fabric is calendered, and finally the flame-retardant and antibacterial polyurethane coating agent prepared in this embodiment is coated at a coating amount of 100g / m 2 After being coated on one side surface of waterproof polyester fabric, the material is pre-baked and baked to obtain a flame-retardant and antibacterial polyester coating awning material, wherein the pre-baking temperature is 110° C., the pre-baking time is 3 minutes, the baking temperature is 170° C., and the baking time is 3 minutes.

[0123] The damage length of the flame-retardant and antibacterial polyester coated awning material is 12.4 cm, and the limiting oxygen index is 33.9%; after 45 times of water washing, the change rate of the damage length is 4.83%, and the change rate of the limiting oxygen index is 1.77%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.5 mm and 0.3 mm, respectively.

[0124] Example 10

[0125] A method for preparing a flame retardant and antibacterial polyurethane coating agent, the specific steps are as follows:

[0126] (1) Prepare raw materials:

[0127] Phytic acid: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand number is P816024;

[0128] Polyhexamethylene biguanide: The manufacturer is Wuhan Xinbeimei Biotechnology Co., Ltd., brand number 24568;

[0129] Waterborne polyurethane: manufacturer is Suzhou Grete Pharmaceutical Technology Co., Ltd., brand name is W909580;

[0130] Blocked polyisocyanate crosslinker: manufacturer is Stahl Fine Coatings Co., Ltd., brand number 903;

[0131] (2) Preparation of flame retardant and antibacterial polyurethane coating agent:

[0132] (2.1) dissolving a mixture of phytic acid and polyhexamethylene biguanide in a mass ratio of 1:4 in deionized water, adjusting the pH of the solution to 9 with NaOH, and continuously stirring until precipitation occurs. The precipitate is washed, filtered, dried, and ball-milled to obtain a phytic acid guanidine salt phosphorus / nitrogen type flame retardant;

[0133] The yield of the prepared phytic acid guanidine salt phosphorus / nitrogen flame retardant is 52.65%, the average particle size is 120 μm, and the solubility in 100 mL of water at a temperature of 25° C. is 0.01 g;

[0134] (2.2) adding guanidine phytate phosphorus / nitrogen flame retardant and blocked polyisocyanate crosslinking agent into waterborne polyurethane and stirring evenly to obtain flame retardant antibacterial polyurethane coating agent;

[0135] The prepared flame retardant and antibacterial polyurethane coating agent consists of waterborne polyurethane, guanidine phytate phosphorus / nitrogen type flame retardant and blocked polyisocyanate crosslinking agent, wherein the content of guanidine phytate phosphorus / nitrogen type flame retardant is 4wt%, and the content of blocked polyisocyanate crosslinking agent is 5wt%.

[0136] A method for preparing a flame-retardant and antibacterial polyester coating awning material, the specific process is: firstly, a waterproofing agent (manufacturer is Guangdong Demei Fine Chemical Group Co., Ltd., brand Furx-9033) is used to waterproof polyester fabric by a calendering-baking-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then the waterproof polyester fabric is calendered, and finally the flame-retardant and antibacterial polyurethane coating agent prepared in this embodiment is coated at a coating amount of 100g / m 2 After being coated on one side surface of waterproof polyester fabric, the material is pre-baked and baked to obtain a flame-retardant and antibacterial polyester coating awning material, wherein the pre-baking temperature is 120°C, the pre-baking time is 2 minutes, the baking temperature is 180°C, and the baking time is 2 minutes.

[0137] The damage length of the flame-retardant and antibacterial polyester coated awning material is 12.3 cm, and the limiting oxygen index is 36.4%; after 45 times of water washing, the change rate of the damage length is 5.56%, and the change rate of the limiting oxygen index is 12.36%; the widths of the inhibition zones for Escherichia coli and Staphylococcus aureus are 0.8 mm and 0.6 mm, respectively.

Claims

1. A flame retardant and antibacterial polyurethane coating agent, characterized in that: The invention comprises a waterborne polyurethane component, a phytic acid guanidine salt phosphorus / nitrogen type flame retardant component and a blocked polyisocyanate crosslinking agent component, wherein the phytic acid guanidine salt phosphorus / nitrogen type flame retardant is a salt formed by phytic acid and polyhexamethylene biguanide through ionic bonding; The preparation process of the guanidine phytate phosphorus / nitrogen flame retardant is as follows: after phytic acid and polyhexamethylene biguanide are mixed and dissolved in a solvent, the pH of the solution is adjusted to 8-9, and the solution is continuously stirred until precipitation is generated, and then dried and ball-milled to obtain the guanidine phytate phosphorus / nitrogen flame retardant; The content of phytic acid guanidine salt phosphorus / nitrogen type flame retardant in the flame retardant antibacterial polyurethane coating agent is 1-4wt%; The solubility of the guanidine phytate phosphorus / nitrogen flame retardant in 100 mL of water at a temperature of 25°C is less than or equal to 0.01 g; The average particle size of the guanidine phytate phosphorus / nitrogen flame retardant is 80~120μm.

2. A method for preparing a flame retardant and antibacterial polyurethane coating agent as claimed in claim 1, characterized in that: The components are mixed and stirred evenly according to the proportion to obtain a flame-retardant antibacterial polyurethane coating agent. The preparation process of the phytic acid guanidine salt phosphorus / nitrogen type flame retardant is as follows: after phytic acid and polyhexamethylene biguanide are mixed and dissolved in a solvent, the pH of the solution is adjusted to 8-9, and the solution is continuously stirred until precipitation occurs, and then dried and ball-milled to obtain the phytic acid guanidine salt phosphorus / nitrogen type flame retardant.

3. The method according to claim 2, characterized in that The degree of polymerization of polyhexamethylene biguanide is 11-15; the mass ratio of phytic acid to polyhexamethylene biguanide is 1:2-4.

4. The use of a flame retardant and antibacterial polyurethane coating agent as claimed in claim 1, characterized in that: The flame-retardant and antibacterial polyurethane coating agent is coated on one side of the polyester fabric and then pre-baked and baked to obtain the flame-retardant and antibacterial polyester coating awning material.

5. The use according to claim 4, characterized in that: The polyester fabric is a polyester fabric that has been waterproofed and calendered; wherein the waterproof grade of the polyester fabric after the waterproofing treatment is grade 4.

6. The use according to claim 4, characterized in that: The pre-baking temperature is 100~120℃, and the pre-baking time is 2~4min; the baking temperature is 160~180℃, and the baking time is 2~4min; the coating amount of the flame retardant and antibacterial polyurethane coating agent on the polyester fabric surface is 50~100g / m 2 .

7. The use according to claim 4, characterized in that: The damaged length of the flame-retardant and antibacterial polyester coated awning material is not higher than 14.5cm, and the limiting oxygen index is not lower than 28.2%; after 45 times of water washing, the change rate of the damaged length does not exceed 12.47%, and the change rate of the limiting oxygen index does not exceed 12.36%; the width of the inhibition zone for Escherichia coli and Staphylococcus aureus is 0.1~0.8mm and 0.1~0.8mm respectively.

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