CN115928454A - Flame-retardant antibacterial polyurethane coating agent and method and application thereof - Google Patents
Flame-retardant antibacterial polyurethane coating agent and method and application thereof Download PDFInfo
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Abstract
The invention relates to a flame-retardant antibacterial polyurethane coating agent and a method and application thereof, wherein the flame-retardant antibacterial polyurethane coating agent comprises an aqueous polyurethane component, a phytic acid guanidine salt phosphorus/nitrogen type flame retardant component (salt formed by combining phytic acid and polyhexamethylene biguanide through ionic bonds) and a blocked polyisocyanate cross-linking agent component; the method comprises the following steps: the components are mixed and stirred uniformly according to the proportion, wherein the preparation process of the phytic guanidine salt phosphorus/nitrogen type flame retardant comprises the following steps: mixing and dissolving phytic acid and polyhexamethylene biguanide in a solvent, adjusting the pH value of the solution to 8-9, and continuously stirring until precipitates are generated, wherein the precipitates are the phytic guanidine salt phosphorus/nitrogen type flame retardant; the application is as follows: and (3) coating the flame-retardant antibacterial polyurethane coating agent on the surface of one side of the polyester fabric, and then pre-baking and baking to obtain the flame-retardant antibacterial polyester coating canopy material. The method is simple, the flame-retardant antibacterial polyurethane coating agent has good flame-retardant performance, and the flame-retardant antibacterial polyester coating awning material still has a flame-retardant effect after being washed for 45 times.
Description
Technical Field
The invention belongs to the technical field of textile functional finishing, and particularly relates to a flame-retardant antibacterial polyurethane coating agent, and a method and application thereof.
Background
The terylene fabric has better crease resistance, shape retention, higher strength and elastic recovery capability, and is a fiber material which is most widely applied in the prior synthetic fiber. The polyester fabric with the polyurethane coating is widely applied to the fields of materials such as curtains, outdoor leisure or emergency rescue tents and the like, and the application scenes have higher requirements on the flame retardant property of the polyester tent cover material.
The coating method is to physically blend the flame retardant and the coating agent or copolymerize the flame retardant group and the monomer to obtain a reactive flame retardant coating agent, and then bond and fix the flame retardant on the fabric by means of physical entanglement of macromolecular chains and fibers or intermolecular hydrogen bonds in the coating agent. The flame retardant has the characteristics of high utilization rate of the flame retardant and low processing cost, can effectively improve the flame retardant property of the coated fabric, and is widely popularized and applied.
However, the existing flame-retardant polyurethane coating polyester fabric has the defects of low flame retardant efficiency, high dosage, poor environmental protection property and the like.
Document 1 (Chenhuifen, zhenghuan, hydrotalcite, application of hydrotalcite-containing flame-retardant coating finishing agent and action mechanism [ J ]. Textile science, 2014,35 (11): 107-111, 117) compounds hydrotalcite and waterborne Polyurethane (PU) to prepare flame-retardant functional coating finishing agent for flame-retardant coating of polyester fabric; however, the hydrotalcite is an inorganic flame retardant, so that the flame retardant efficiency is low, and the hydrotalcite in the coating PU has a good flame retardant effect when the content of the hydrotalcite in the coating PU reaches 9%.
The Chinese invention patent CN200610085269.X discloses a preparation method of a breathable flame-retardant oil-proof water-proof acid-proof near-infrared polyester tarpaulin, which comprises the steps of firstly adopting 9-15% of bromine antimony flame retardant to carry out flame-retardant modification on a polyester fabric, then adopting flame-retardant PU to coat the polyester fabric, and developing the flame-retardant polyester tarpaulin; the halogen flame-retardant system has high flame-retardant efficiency, but harmful gases generated in the combustion process have certain damage to human bodies and the environment, and the process flow is complex.
Document 2 (yanchuan, guhao, juan, xielian, waiei, production of dacron low-elastic yarn flame-retardant tent fabric for emergency rescue [ J ] printing and dyeing, 2019,45 (8): 35-39) selects halogen flame retardants and other phosphorus-nitrogen flame retardants to mix with solvent-based PU to coat dacron, wherein the halogen flame retardants have high efficiency but are gradually forbidden due to the problem of poor environmental protection performance; the screened phosphorus-nitrogen flame retardant RF-603A is low in flame retardant efficiency, and the coating polyester fabric has a good flame retardant effect only when the addition amount of the phosphorus-nitrogen flame retardant in PU reaches 50%. However, the PU is difficult to cure due to the excessive addition of the flame retardant, and the film-forming performance of the coating is affected.
Phytic acid, known as phytic acid, is often found in legumes, grains and oilseeds in phytate form and is the major storage form of phosphorus in plants, also known as the "green" molecule. The phytic acid has good biocompatibility, no toxicity, environmental protection and better reproducibility, the content of phosphorus element in the molecule is up to 28wt%, 6 high-activity phosphate groups are enriched, and the phytic acid has stronger chelating ability with cation compounds or metal ions.
Document 3 (xiaozhencheng, flame retardant finishing of polyester fabric based on phytic acid [ D ]. Suzhou university, 2019.) the use of phytic acid by the pad baking method improves the flame retardant performance of polyester fabric, but the water washing resistance of flame retardant polyester fabric is poor.
The phytic acid is easy to migrate in the PU coating, so that the washing resistance of the phytic acid coated polyester fabric is poor, the development of flame-retardant PU by adopting a phytic acid matrix system and the durable functional coating of the polyester fabric are difficult problems, and no relevant report is found at present.
Therefore, the research on the flame-retardant antibacterial polyurethane coating agent, the method and the application thereof is of great significance for solving the problems that the flame retardant is easy to migrate and the fabric has poor water resistance when being applied to the fabric in the prior art.
Disclosure of Invention
The invention aims to solve the existing problems and provides a flame-retardant antibacterial polyurethane coating agent, and a method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a flame-retarding antibacterial polyurethane coating agent contains water-base polyurethane component, phytic guanidine salt phosphorus/nitrogen type flame-retarding agent and end-capped polyisocyanate cross-linking agent, in which the phytic guanidine salt phosphorus/nitrogen type flame-retarding agent is the salt formed by binding phytic acid with polyhexamethylene biguanide through ionic bond, and the ionic bond is the bond formed between anionic phosphate radical in phytic acid molecule and cationic imino group of polyhexamethylene biguanide.
As a preferred technical scheme:
the flame-retardant antibacterial polyurethane coating agent has the content of the phytic guanidine salt phosphorus/nitrogen type flame retardant of 1-4 wt%.
The flame-retardant antibacterial polyurethane coating agent has the solubility of the phytic guanidine salt phosphorus/nitrogen type flame retardant in water with the temperature of 25 ℃ and the volume of 100mL being less than or equal to 0.01g.
The flame-retardant antibacterial polyurethane coating agent has the average particle size of 80-120 mu m of the phytic guanidine salt phosphorus/nitrogen flame retardant.
The flame-retardant antibacterial polyurethane coating agent also comprises 2-4 wt% of an anti-ultraviolet absorbent or an anti-aging agent.
The invention also provides a method for preparing the flame-retardant antibacterial polyurethane coating agent, which is characterized in that the flame-retardant antibacterial polyurethane coating agent is prepared by uniformly mixing and stirring the components according to the proportion, wherein the preparation process of the phytic guanidine salt phosphorus/nitrogen flame retardant comprises the following steps: mixing and dissolving phytic acid and polyhexamethylene biguanide in a solvent (deionized water is preferred as the solvent, because the deionized water is low in economic cost and harmless to the environment, the method is suitable for preparing the flame retardant, other reagents compatible with the phytic acid and the polyhexamethylene biguanide can also replace the deionized water, but the cost is high, and the reagents also need to be recovered), adjusting the pH value of the solution to 8-9 by using alkali, continuously stirring until precipitation is generated, drying (80 ℃,6 hours) and ball-milling to obtain the phytic acid guanidine salt phosphorus/nitrogen type flame retardant; when the pH value of the solution is 8-9, the phytic acid and the polyhexamethylene biguanide are combined with each other to generate polymer precipitate, and the excessive high or low pH value is not beneficial to ionization of the polyhexamethylene biguanide and the phytic acid and is not beneficial to the combination of the polyhexamethylene biguanide and the phytic acid to generate the polymer precipitate.
As a preferable technical scheme:
as described above, the polymerization degree of polyhexamethylene biguanide is 11 to 15.
In the method, the mass ratio of the phytic acid to the polyhexamethylene biguanide is 1-4, and the ratio of the phytic acid to the polyhexamethylene biguanide is too high or too low, which can cause the yield of the product to be reduced.
The invention also provides application of the flame-retardant antibacterial polyurethane coating agent, and the flame-retardant antibacterial polyurethane coating agent is coated on the surface of one side of the polyester fabric and then is pre-baked and baked to prepare the flame-retardant antibacterial polyester coating canopy material.
As a preferred technical scheme:
in the above-mentioned application, the polyester fabric is subjected to waterproof treatment and calendering treatment; wherein, the waterproof grade of the polyester fabric after waterproof treatment is 4 grade; the waterproof grade is too low to achieve the waterproof effect, and the water-based polyurethane can permeate into the back surface (namely the surface which is not coated with the coating agent) of the fabric; the waterproof grade is too high, and the waterborne polyurethane is not easy to be coated on the surface of the fabric.
The application is that the pre-drying temperature is 100-120 ℃, and the pre-drying time is 2-4 min; the baking temperature is 160-180 ℃, the baking time is 2-4 min, and the baking process ensures that polyurethane can form a film on the surface of the polyester fabric well; the coating amount of the flame-retardant antibacterial polyurethane coating agent on the surface of the polyester fabric is 50-100 g/m 2 。
The application is that the damage length of the flame-retardant antibacterial polyester coating awning material is not higher than 14.5cm, the limit oxygen index is not lower than 28.2%, and the test standard is GB8624-2012 'building material and product combustion performance grading textile'; after 45 times of washing, the change rate of the damage length is not more than 12.47 percent, the change rate of the limiting oxygen index is not more than 12.36 percent, a D/Max-IIIC type washing fastness tester is adopted for washing, and according to AATCC 61-2013 'washing fastness', the concrete process is as follows: putting the fabric into a steel cup with soap lotion concentration of 3.7g/L and bath ratio of 1; the widths of inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.1-0.8 mm and 0.1-0.8 mm, the test standard is GB/T20944.1-2007 'evaluation of textile antibacterial performance part 1 _ agar plate diffusion method', which is 0-1 mm, and the inhibition effect of the textile is better.
The principle of the invention is as follows:
(1) As shown in fig. 2, the phytic acid molecule contains 6 anionic phosphate radicals, which are combined with the cationic imino group of polyhexamethylene biguanide to generate ionic bonds, which are relatively stable and are not easy to ionize in deionized water, so as to prepare the phytic guanidine salt phosphorus/nitrogen type flame retardant; the pH value of the waterborne polyurethane is about 7.5, the pH value of the combination of the phytic acid and the polyhexamethylene biguanide is 8-9, and the influence of the prepared phytic guanidine salt polyelectrolyte phosphorus/nitrogen flame retardant on the pH value of the polyurethane is small when the phytic acid guanidine salt polyelectrolyte phosphorus/nitrogen flame retardant is added into the polyurethane, so that the phytic acid guanidine salt phosphorus/nitrogen flame retardant cannot cause coagulation of the waterborne polyurethane; in addition, the prepared phytic guanidine salt phosphorus/nitrogen type flame retardant is insoluble in water and has high hydrolysis stability, functional groups between the phytic guanidine salt phosphorus/nitrogen type flame retardant and waterborne polyurethane do not have chemical reaction at normal temperature, and the phytic guanidine salt phosphorus/nitrogen type flame retardant and the waterborne polyurethane are both alkaline substances and do not have acid-base neutralization reaction, so that the phytic guanidine salt phosphorus/nitrogen type flame retardant has good dispersibility and is not easy to migrate in a network structure of a polyurethane coating, and compared with phytic acid with good water solubility, the fabric obtained by applying the phytic guanidine salt phosphorus/nitrogen type flame retardant has good water washing resistance;
(2) The phytic acid molecules contain higher phosphorus content, so the phytic acid has certain flame retardant property, but the requirements of high-efficiency durable coating polyester fabrics cannot be met, the polyhexamethylene biguanide and the phytic acid are organically compounded to form a phosphorus/nitrogen flame retardant system, and in the combustion process, phosphorus-containing flame retardant groups of the phytic acid can release phosphoric acid and polyphosphoric acid to catalyze the polyurethane coating polyester fabrics to form carbon, so that the flame retardant effect is improved; the polyhexamethylene biguanide nitrogen-containing flame-retardant group can release a large amount of non-flammable gas in the combustion process, so that the effect of diluting the flammable gas and oxygen is achieved, the generated non-flammable gas can enable the carbon layer to expand, the expanded carbon layer has a high heat insulation effect, and the exchange between heat and the flammable gas and a lower substrate is isolated, so that the flame-retardant efficiency is further improved, and therefore, the prepared phytic acid guanidine salt phosphorus/nitrogen type flame retardant can improve the flame-retardant property of the coating polyester fabric through an expansion flame-retardant mechanism;
(3) Polyhexamethylene biguanide is an environment-friendly antibacterial agent, and the positively charged hydrophilic groups of the polyhexamethylene biguanide can adsorb negatively charged bacteria and viruses, enter cell membranes to inhibit synthesis of intramembrane liposomes, cause apoptosis of thalli and achieve the optimal bactericidal effect.
Advantageous effects
(1) In the flame-retardant antibacterial polyurethane coating agent, the phytic guanidine salt phosphorus/nitrogen type flame retardant can improve the flame-retardant property of the coated fabric through an intumescent flame-retardant mechanism, and has high flame-retardant efficiency and small using amount;
(2) The preparation method of the flame-retardant antibacterial polyurethane coating agent is simple, quick and convenient;
(3) When the flame-retardant antibacterial polyurethane coating agent is applied to fabrics, the flame-retardant antibacterial polyurethane coating agent has good water resistance and antibacterial performance, and the phytic guanidine salt phosphorus/nitrogen flame retardant is not easy to migrate.
Drawings
FIG. 1 is a schematic view of vertical burning of a polyester fabric before and after a flame retardant antibacterial polyurethane coating agent is used; wherein, the left picture is the terylene fabric without using the flame-retardant antibacterial polyurethane coating agent; the right picture is the terylene fabric using the flame-retardant antibacterial polyurethane coating agent;
FIG. 2 is a schematic diagram of the preparation of phytic acid guanidine salt (i.e., phytic acid guanidine salt phosphorus/nitrogen type flame retardant) from phytic acid and polyhexamethylene biguanide;
FIG. 3 is a graph of the relationship between the amount of flame retardant and the amount of coating added and the flame retardant properties of the fabric.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of a flame-retardant antibacterial polyurethane coating agent comprises the following specific steps:
(1) Preparing raw materials:
phytic acid: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is P816024;
polyhexamethylene biguanide: the manufacturer is Wuhanxin Beimei biotechnology limited and the brand is 24569;
aqueous polyurethane: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is W909580;
blocked polyisocyanate crosslinker: the manufacturer is Steyr Fine coatings Co., ltd, under the trade name 903;
(2) Preparing a flame-retardant antibacterial polyurethane coating agent:
(2.1) dissolving a mixture of phytic acid and polyhexamethylene biguanide in deionized water according to a mass ratio of 1;
the yield of the obtained phytic guanidine salt phosphorus/nitrogen flame retardant is 59.79 percent, the average grain diameter is 100 mu m, and the solubility in water with the temperature of 25 ℃ and the volume of 100mL is 0.008g;
(2.2) adding the phytic guanidine salt phosphorus/nitrogen type flame retardant and the blocked polyisocyanate crosslinking agent into the waterborne polyurethane, and uniformly stirring to obtain the flame-retardant antibacterial polyurethane coating agent;
the prepared flame-retardant antibacterial polyurethane coating agent consists of waterborne polyurethane, a phytic guanidine salt phosphorus/nitrogen flame retardant and a blocked polyisocyanate crosslinking agent, wherein the content of the phytic guanidine salt phosphorus/nitrogen flame retardant is 1wt%, and the content of the blocked polyisocyanate crosslinking agent is 5wt%.
A preparation method of a flame-retardant antibacterial polyester coating awning material comprises the following specific steps: firstly, waterproof treatment is carried out on polyester fabric by adopting a waterproof agent (the manufacturer is Furx-9033, manufactured by Guangdong Germany and American group of Fine chemical industries, ltd.) through a rolling-drying-baking technology to obtain waterproof polyester fabric with the waterproof grade of 4, then calendering treatment is carried out on the waterproof polyester fabric, and finally the flame-retardant antibacterial polyurethane prepared by the embodiment is subjected to calendering treatmentEster coating agent in coating amount of 50g/m 2 And coating the flame-retardant antibacterial polyester fabric on the surface of one side of the waterproof polyester fabric, and then pre-baking and baking to obtain the flame-retardant antibacterial polyester coating awning material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 3min, the baking temperature is 170 ℃, and the baking time is 3min.
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 14cm, and the limiting oxygen index is 28.5%; after 45 times of washing, the damage length change rate is 12.47 percent, and the limit oxygen index change rate is 5.26 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.1mm and 0.1mm.
Example 2
A preparation method of a flame-retardant antibacterial polyurethane coating agent, which is the same as the example 1.
A preparation method of a flame-retardant antibacterial polyester coating awning material is basically the same as that in example 1, except that the coating amount of the flame-retardant antibacterial polyurethane coating agent is 100g/m 2 。
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 13.8cm, and the limiting oxygen index is 29.2%; after 45 times of washing, the damage length change rate is 8.69 percent, and the limiting oxygen index change rate is 4.11 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.3mm and 0.2mm.
Example 3
A preparation method of a flame-retardant antibacterial polyurethane coating agent, which is basically the same as the example 1, except that the content of the phytic guanidine salt phosphorus/nitrogen type flame retardant in the step (2.2) is 2wt%.
A preparation method of a flame-retardant antibacterial polyester coating awning material comprises the following specific steps: firstly, waterproof treatment is carried out on polyester fabric by adopting a waterproof agent (the manufacturer is Furx-9033, manufactured by Guangdong Germany fine chemical group Co., ltd.) through a rolling-drying-baking technology to obtain waterproof polyester fabric with the waterproof grade of 4, then calendering treatment is carried out on the waterproof polyester fabric, and finally the flame-retardant antibacterial polyurethane coating agent prepared by the embodiment is applied according to the coating amount of 50g/m 2 Coating the flame-retardant antibacterial polyester coating on the surface of one side of the waterproof polyester fabric, and then pre-baking and baking to obtain the flame-retardant antibacterial polyester coatingThe canopy material is prepared by pre-baking at 110 deg.C for 3min at 170 deg.C for 3min.
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 13.6cm, and the limiting oxygen index is 32.7%; after 45 times of washing, the damage length change rate is 9.33 percent, and the limit oxygen index change rate is 4.05 percent; the widths of inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.2mm and 0.2mm.
Example 4
A preparation method of a flame-retardant antibacterial polyurethane coating agent, which is the same as the example 3.
A preparation method of a flame-retardant antibacterial polyester coating awning material is basically the same as that in example 3, but the difference is that the coating amount of the flame-retardant antibacterial polyurethane coating agent is 100g/m 2 。
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 12.4cm, and the limiting oxygen index is 33.9%; after washing for 45 times, the damage length change rate is 4.83 percent, and the limiting oxygen index change rate is 4.72 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.5mm and 0.3mm.
Comparative example 1
A preparation method of a flame-retardant polyurethane coating agent comprises the following specific steps:
(1) Preparing raw materials:
phytic acid: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is P816024;
sodium phytate: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is S30224;
aqueous polyurethane: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is W909580;
blocked polyisocyanate crosslinker: the manufacturer is Steyr Fine coatings Co., ltd, under the trade name 903;
(2) Preparing a flame-retardant polyurethane coating agent:
(2.1) mixing phytic acid and sodium phytate in a mass ratio of 5;
(2.2) adding the flame retardant and the blocked polyisocyanate crosslinking agent into the waterborne polyurethane, and uniformly stirring to obtain the flame-retardant polyurethane coating agent;
the prepared flame-retardant polyurethane coating agent consists of waterborne polyurethane, a flame retardant and a blocked polyisocyanate crosslinking agent, wherein the content of the flame retardant is 2wt%, and the content of the blocked polyisocyanate crosslinking agent is 5wt%.
A preparation method of a flame-retardant polyester coating canopy material comprises the following specific steps: firstly, adopting a waterproof agent (manufactured by Guangdong German and American group of Fine chemical industries, ltd., brand number of Furx-9033) to perform waterproof treatment on a polyester fabric by a rolling-drying-baking technology to obtain a waterproof polyester fabric with a waterproof grade of 4, then performing calendering treatment on the waterproof polyester fabric, and finally performing 100g/m coating amount on the flame-retardant polyurethane coating agent prepared by the comparative example 2 And coating the flame-retardant polyester fabric on the surface of one side of the waterproof polyester fabric, and then pre-baking and baking to obtain the flame-retardant polyester coating awning material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 3min, the baking temperature is 170 ℃, and the baking time is 3min.
The damage length of the prepared flame-retardant polyester coating awning material is 12.5cm, and the limiting oxygen index is 33.2%; after 45 times of washing, the damage length change rate is 13.6 percent, and the limit oxygen index change rate is 15.1 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0mm and 0mm.
The washing fastness of the flame-retardant antibacterial polyester coating canopy material of the example 4 and the polyester coating canopy material of the comparative example 1 is shown in table 1, the flame retardant performance of the flame-retardant antibacterial polyester coating canopy material of the example 4 after washing is reduced, because under the action of water molecules and external environment, the phytic guanidine salt phosphorus/nitrogen type flame retardant on the coating surface is dissolved in water, so the flame retardant performance of the fabric is reduced, but when the washing times are the same, the limit oxygen index of the flame-retardant antibacterial polyester coating canopy material of the example 4 is higher than that of the polyester coating canopy material of the comparative example 1, the flame-retardant antibacterial polyester coating canopy material of the example 4 can still reach the B1 level after washing for 45 times, and the flame-retardant level of the polyester coating canopy material of the comparative example 1 after washing for 10 times is reduced to the B level 2 Grade, indicating that the water-insoluble particulate phytic acid/guanidine salt is not easy to migrate in PUGood durability.
TABLE 1
Example 5
A preparation method of a flame-retardant antibacterial polyurethane coating agent, which is basically the same as the example 3, except that the content of the phytic guanidine salt phosphorus/nitrogen type flame retardant in the step (2.2) is 4wt%.
A preparation method of a flame-retardant antibacterial polyester coating awning material comprises the following specific steps: firstly, waterproof treatment is carried out on polyester fabric by adopting a waterproof agent (the manufacturer is Furx-9033, manufactured by Guangdong Germany fine chemical group Co., ltd.) through a rolling-drying-baking technology to obtain waterproof polyester fabric with the waterproof grade of 4, then calendering treatment is carried out on the waterproof polyester fabric, and finally the flame-retardant antibacterial polyurethane coating agent prepared by the embodiment is applied according to the coating amount of 50g/m 2 And coating the flame-retardant antibacterial polyester fabric on the surface of one side of the waterproof polyester fabric, and then pre-baking and baking to obtain the flame-retardant antibacterial polyester coating awning material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 3min, the baking temperature is 170 ℃, and the baking time is 3min.
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 12.5cm, and the limiting oxygen index is 33.0 percent; after 45 times of washing, the damage length change rate is 12.14 percent, and the limiting oxygen index change rate is 6.45 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.4mm and 0.3mm.
Example 6
A preparation method of a flame-retardant antibacterial polyurethane coating agent, which is the same as the example 5.
A preparation method of a flame-retardant antibacterial polyester coating awning material is basically the same as that in example 5, except that the coating amount of the flame-retardant antibacterial polyurethane coating agent is 100g/m 2 。
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 12.2cm, and the limiting oxygen index is 36.8%; after 45 times of washing, the damage length change rate is 5.73 percent, and the limiting oxygen index change rate is 13.23 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.8mm and 0.6mm.
As shown in fig. 1 and 3, it can be concluded from examples 1 to 6 and the untreated polyester fabric that the damaged length of the fire-retardant antibacterial polyester coating awning material is gradually reduced, the damaged area is obviously reduced, the limiting oxygen index is gradually increased with the increase of the usage amount of the phytic guanidine salt phosphorus/nitrogen type fire retardant, indicating that the fire-retardant effect is increased; when the dosage of the phytic guanidine salt phosphorus/nitrogen type flame retardant is fixed, the weight is increased more, the content of the phytic guanidine salt phosphorus/nitrogen type flame retardant is also increased, and the flame retardant effect is better.
Example 7
A preparation method of a flame-retardant antibacterial polyurethane coating agent, which is basically the same as the example 1, except that the mass ratio of phytic acid to polyhexamethylene biguanide in the step (2.1) is 1.
A preparation method of a flame-retardant antibacterial polyester coating awning material comprises the following specific steps: firstly, waterproof treatment is carried out on polyester fabric by adopting a waterproof agent (the manufacturer is Furx-9033, manufactured by Guangdong Germany fine chemical group Co., ltd.) through a rolling-drying-baking technology to obtain waterproof polyester fabric with the waterproof grade of 4, then calendering treatment is carried out on the waterproof polyester fabric, and finally the flame-retardant antibacterial polyurethane coating agent prepared by the embodiment is applied according to the coating amount of 50g/m 2 And coating the flame-retardant antibacterial polyester fabric on the surface of one side of the waterproof polyester fabric, and then pre-baking and baking to obtain the flame-retardant antibacterial polyester coating awning material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 3min, the baking temperature is 170 ℃, and the baking time is 3min.
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 14.5cm, and the limiting oxygen index is 28.2%; after 45 times of washing, the damage length change rate is 10.34 percent, and the limiting oxygen index change rate is 4.41 percent; the widths of inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.8mm and 0.8mm.
Example 8
A preparation method of a flame-retardant antibacterial polyurethane coating agent comprises the following specific steps:
(1) Preparing raw materials:
phytic acid: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is P816024;
polyhexamethylene biguanide: the manufacturer is Wuhanxin Bei Mei Biotechnology Limited company, and the brand is 24569;
aqueous polyurethane: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is W909580;
blocked polyisocyanate crosslinker: the manufacturer is Steyr Fine coatings Co., ltd, under the trade name 903;
(2) Preparing a flame-retardant antibacterial polyurethane coating agent:
(2.1) dissolving a mixture of phytic acid and polyhexamethylene biguanide in deionized water according to a mass ratio of 1;
the yield of the phytic guanidine salt phosphorus/nitrogen flame retardant is 54.65%, the average particle size is 80 mu m, and the solubility in water with the temperature of 25 ℃ and the volume of 100mL is 0.006g;
(2.2) adding the phytic guanidine salt phosphorus/nitrogen type flame retardant and the blocked polyisocyanate crosslinking agent into the waterborne polyurethane, and uniformly stirring to obtain the flame-retardant antibacterial polyurethane coating agent;
the prepared flame-retardant antibacterial polyurethane coating agent consists of waterborne polyurethane, a phytic guanidine salt phosphorus/nitrogen flame retardant and a blocked polyisocyanate crosslinking agent, wherein the content of the phytic guanidine salt phosphorus/nitrogen flame retardant is 1wt%, and the content of the blocked polyisocyanate crosslinking agent is 5wt%.
A preparation method of a flame-retardant antibacterial polyester coating awning material comprises the following specific steps: firstly, waterproof treatment is carried out on polyester fabric by adopting a waterproof agent (the manufacturer is Furx-9033, manufactured by Guangdong Germany fine chemical group Co., ltd.) through a rolling-drying-baking technology to obtain waterproof polyester fabric with the waterproof grade of 4, then calendering treatment is carried out on the waterproof polyester fabric, and finally the flame-retardant antibacterial polyurethane coating agent prepared by the embodiment is coated according to the coating amount of 100g/m 2 Coating the water-proof polyester fabric on one side surface of the polyester fabric, and then pre-baking and baking to obtain the water-proof polyester fabricThe antibacterial polyester coating tent cover material is fired, wherein the pre-drying temperature is 100 ℃, the pre-drying time is 4min, the baking temperature is 160 ℃, and the baking time is 4min.
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 13.8cm, and the limiting oxygen index is 29.2%; after washing for 45 times, the damage length change rate is 8.69 percent, and the limiting oxygen index change rate is 4.11 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.3mm and 0.2mm.
Example 9
A preparation method of a flame-retardant antibacterial polyurethane coating agent comprises the following specific steps:
(1) Preparing raw materials:
phytic acid: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is P816024;
polyhexamethylene biguanide: the manufacturer is Wuhanxin Beimei biotechnology limited and the brand is 24569;
aqueous polyurethane: the manufacturer is Suzhou Grey pharmaceutical technology Co., ltd, and the brand is W909580;
blocked polyisocyanate crosslinker: the manufacturer is Steyr Fine coatings, inc. under the designation 903;
(2) Preparing a flame-retardant antibacterial polyurethane coating agent:
(2.1) dissolving a mixture of phytic acid and polyhexamethylene biguanide in deionized water according to a mass ratio of 1;
the yield of the prepared phytic guanidine salt phosphorus/nitrogen type flame retardant is 59.79%, the average grain diameter is 100 mu m, and the solubility in water with the temperature of 25 ℃ and the volume of 100mL is 0.008g;
(2.2) adding the phytic guanidine salt phosphorus/nitrogen type flame retardant and the blocked polyisocyanate crosslinking agent into the waterborne polyurethane, and uniformly stirring to obtain the flame-retardant antibacterial polyurethane coating agent;
the prepared flame-retardant antibacterial polyurethane coating agent consists of waterborne polyurethane, a phytic guanidine salt phosphorus/nitrogen flame retardant and a blocked polyisocyanate crosslinking agent, wherein the content of the phytic guanidine salt phosphorus/nitrogen flame retardant is 2wt%, and the content of the blocked polyisocyanate crosslinking agent is 5wt%.
A preparation method of a flame-retardant antibacterial polyester coating awning material comprises the following specific steps: firstly, waterproof treatment is carried out on polyester fabric by adopting a waterproof agent (the manufacturer is Furx-9033, manufactured by Guangdong Germany fine chemical group Co., ltd.) through a rolling-drying-baking technology to obtain waterproof polyester fabric with the waterproof grade of 4, then calendering treatment is carried out on the waterproof polyester fabric, and finally the flame-retardant antibacterial polyurethane coating agent prepared by the embodiment is coated according to the coating amount of 100g/m 2 And coating the flame-retardant antibacterial polyester fabric on the surface of one side of the waterproof polyester fabric, and then pre-baking and baking to obtain the flame-retardant antibacterial polyester coating awning material, wherein the pre-baking temperature is 110 ℃, the pre-baking time is 3min, the baking temperature is 170 ℃, and the baking time is 3min.
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 12.4cm, and the limiting oxygen index is 33.9%; after 45 times of washing, the damage length change rate is 4.83 percent, and the limit oxygen index change rate is 1.77 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.5mm and 0.3mm.
Example 10
A preparation method of a flame-retardant antibacterial polyurethane coating agent comprises the following specific steps:
(1) Preparing raw materials:
phytic acid: the manufacturer is Suzhou Grey pharmaceutical technology, inc., and the brand is P816024;
polyhexamethylene biguanide: the manufacturer is Wuhanxin Beimei biotechnology limited and the brand is 24569;
aqueous polyurethane: the manufacturer is Suzhou Grey pharmaceutical technology Co., ltd, and the brand is W909580;
blocked polyisocyanate crosslinker: the manufacturer is Steyr Fine coatings Co., ltd, under the trade name 903;
(2) Preparing a flame-retardant antibacterial polyurethane coating agent:
(2.1) dissolving a mixture of phytic acid and polyhexamethylene biguanide in deionized water according to a mass ratio of 1;
the yield of the obtained phytic guanidine salt phosphorus/nitrogen type flame retardant is 52.65%, the average particle size is 120 mu m, and the solubility in water with the temperature of 25 ℃ and the volume of 100mL is 0.01g;
(2.2) adding the phytic guanidine salt phosphorus/nitrogen type flame retardant and the blocked polyisocyanate crosslinking agent into the waterborne polyurethane, and uniformly stirring to obtain the flame-retardant antibacterial polyurethane coating agent;
the prepared flame-retardant antibacterial polyurethane coating agent consists of waterborne polyurethane, a phytic guanidine salt phosphorus/nitrogen flame retardant and a blocked polyisocyanate crosslinking agent, wherein the content of the phytic guanidine salt phosphorus/nitrogen flame retardant is 4wt%, and the content of the blocked polyisocyanate crosslinking agent is 5wt%.
A preparation method of a flame-retardant antibacterial polyester coating canopy material comprises the following specific steps: firstly, waterproof treatment is carried out on polyester fabric by adopting a waterproof agent (the manufacturer is Furx-9033, manufactured by Guangdong Germany fine chemical group Co., ltd.) through a rolling-drying-baking technology to obtain waterproof polyester fabric with the waterproof grade of 4, then calendering treatment is carried out on the waterproof polyester fabric, and finally the flame-retardant antibacterial polyurethane coating agent prepared by the embodiment is coated according to the coating amount of 100g/m 2 And coating the flame-retardant antibacterial polyester fabric on the surface of one side of the waterproof polyester fabric, and then pre-baking and baking to obtain the flame-retardant antibacterial polyester coating awning material, wherein the pre-baking temperature is 120 ℃, the pre-baking time is 2min, the baking temperature is 180 ℃, and the baking time is 2min.
The damage length of the prepared flame-retardant antibacterial polyester coating awning material is 12.3cm, and the limiting oxygen index is 36.4%; after 45 times of washing, the damage length change rate is 5.56 percent, and the limit oxygen index change rate is 12.36 percent; the widths of inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.8mm and 0.6mm.
Claims (10)
1. The flame-retardant antibacterial polyurethane coating agent is characterized by comprising a water-based polyurethane component, a phytic guanidine salt phosphorus/nitrogen type flame retardant component and a blocked polyisocyanate crosslinking agent component, wherein the phytic guanidine salt phosphorus/nitrogen type flame retardant is salt formed by combining phytic acid and polyhexamethylene biguanide through ionic bonds.
2. The flame retardant antibacterial polyurethane coating agent according to claim 1, wherein the content of the phytic guanidine salt phosphorus/nitrogen type flame retardant is 1 to 4wt%.
3. The flame retardant antibacterial polyurethane coating agent according to claim 1, wherein the solubility of the phytic guanidine salt phosphorus/nitrogen type flame retardant in water having a temperature of 25 ℃ and a volume of 100mL is 0.01g or less.
4. The flame-retardant antibacterial polyurethane coating agent according to claim 1, wherein the average particle diameter of the phytic guanidine salt phosphorus/nitrogen type flame retardant is 80 to 120 μm.
5. The method for preparing the flame-retardant antibacterial polyurethane coating agent according to any one of claims 1 to 4, characterized in that the flame-retardant antibacterial polyurethane coating agent is obtained by uniformly mixing and stirring the components according to the mixture ratio, wherein the preparation process of the phytic guanidine salt phosphorus/nitrogen type flame retardant comprises the following steps: mixing and dissolving phytic acid and polyhexamethylene biguanide in a solvent, adjusting the pH value of the solution to 8-9, continuously stirring until precipitates are generated, drying and ball-milling to obtain the phytic acid guanidine salt phosphorus/nitrogen type flame retardant.
6. The method of claim 5, wherein the degree of polymerization of polyhexamethylene biguanide is from 11 to 15; the mass ratio of the phytic acid to the polyhexamethylene biguanide is 1.
7. The use of the flame retardant antibacterial polyurethane coating agent according to any one of claims 1 to 4, characterized in that the flame retardant antibacterial polyurethane coating agent is coated on the surface of one side of the polyester fabric and then pre-baked and baked to obtain the flame retardant antibacterial polyester coating canopy material.
8. The use according to claim 7, wherein the polyester fabric is a polyester fabric subjected to water repellent treatment and calendering treatment; wherein, the waterproof grade of the polyester fabric after waterproof treatment is 4 grade.
9. The use according to claim 7, wherein the pre-drying temperature is 100-120 ℃ and the pre-drying time is 2-4 min; the baking temperature is 160-180 ℃, and the baking time is 2-4 min; the coating amount of the flame-retardant antibacterial polyurethane coating agent on the surface of the polyester fabric is 50-100 g/m 2 。
10. The use as claimed in claim 7, wherein the damaged length of the fire-retardant antibacterial polyester coating canopy material is not higher than 14.5cm, and the limiting oxygen index is not lower than 28.2%; after 45 times of washing, the damage length change rate is not more than 12.47 percent, and the limit oxygen index change rate is not more than 12.36 percent; the widths of the inhibition zones for escherichia coli and staphylococcus aureus are respectively 0.1-0.8 mm and 0.1-0.8 mm.
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