阅读说明：本技术 一种耐久型阻燃抗菌防水整理剂及其制备方法和应用 (Durable flame-retardant antibacterial waterproof finishing agent and preparation method and application thereof ) 是由 王天舒 杨宝敬 林庭丰 金翁佳 于 2020-06-24 设计创作，主要内容包括：本发明公开了一种耐久型阻燃抗菌防水整理剂及其制备方法和应用。本发明的耐久型阻燃抗菌防水整理剂包括包括A组分和B组分,其制备原料,以重量份计,A组分包括18～50份环状磷酸酯阻燃剂、6.0～18份氟系防水剂、0.6～6.0份阻燃交联剂、0.1-1.0份氨基酸、9-30份去离子水,0.05-0.3份非离子表面活性剂,B组分包括0.03～0.2份银系抗菌剂、0.3～2.0份有机抗菌剂、0.01-0.2份润湿分散剂,1.0-6.0份含磷氮阻燃剂,2.5-9.0份去离子水。本发明的产品,应用于涤纶纺织品后,可赋予涤纶织物良好的阻燃性、抗菌性、防水性,并且具有良好的亲和性、环保性、耐久性,在医院、影院、剧院、车船、飞机、宾馆、酒店、学校、养老院、医美中心、康复中心、疾控中心等场所都有着良好的应用前景。(The invention discloses a durable flame-retardant antibacterial waterproof finishing agent, and a preparation method and application thereof. The durable flame-retardant antibacterial waterproof finishing agent comprises a component A and a component B, wherein the preparation raw materials comprise, by weight, 18-50 parts of a cyclic phosphate flame retardant, 6.0-18 parts of a fluorine waterproof agent, 0.6-6.0 parts of a flame-retardant cross-linking agent, 0.1-1.0 part of amino acid, 9-30 parts of deionized water and 0.05-0.3 part of a nonionic surfactant, and the component B comprises 0.03-0.2 part of a silver antibacterial agent, 0.3-2.0 parts of an organic antibacterial agent, 0.01-0.2 part of a wetting dispersant, 1.0-6.0 parts of a phosphorus-nitrogen-containing flame retardant and 2.5-9.0 parts of deionized water. The product of the invention can endow the terylene textile with good flame retardance, antibacterial property and waterproof property, has good affinity, environmental protection and durability after being applied to terylene textiles, and has good application prospect in places such as hospitals, cinemas, theaters, vehicles and boats, airplanes, hotels, schools, nursing homes, medical and beauty centers, rehabilitation centers, disease control centers and the like.)

1. A durable flame-retardant antibacterial waterproof finishing agent is characterized by comprising a component A and a component B, wherein the component A comprises 18-50 parts by weight of cyclic phosphate flame retardant, 6.0-18 parts by weight of fluorine waterproof agent, 0.6-6.0 parts by weight of flame-retardant cross-linking agent, 0.1-1.0 part by weight of amino acid, 9-30 parts by weight of deionized water and 0.05-0.3 part by weight of nonionic surfactant, the component B comprises 0.03-0.2 part by weight of silver antibacterial agent, 0.3-2.0 parts by weight of organic antibacterial agent, 0.01-0.2 part by weight of wetting dispersant, 1.0-6.0 parts by weight of phosphorus-nitrogen flame retardant and 2.5-9.0 parts by weight of deionized water, wherein,

the cyclic phosphate ester flame retardant is a cyclic phosphate ester diester flame retardant;

the fluorine-based waterproofing agent is a six-carbon fluorine-based waterproofing agent;

the flame-retardant cross-linking agent is sulfonic acid type phosphorus-containing closed polyurethane with a plurality of blocked NCO on the molecular chain;

the amino acid is amino acid with the total number of carboxyl and primary amino group not less than 3;

the nonionic surfactant is polyoxyethylene fatty alcohol ether surfactant;

the silver-based antibacterial agent is a nano silver-based antibacterial finishing agent containing a nano silver simple substance;

the quaternary organic antibacterial agent is a quaternary ammonium salt antibacterial agent without organic silicon;

the wetting dispersant is a non-ionic wetting dispersant;

the phosphorus-nitrogen-containing flame retardant is diphenoxy aniline phosphate.

2. The durable flame-retardant antibacterial waterproof finishing agent according to claim 1, characterized in that the flame-retardant crosslinking agent is a methyl ethyl ketoxime-terminated sulfonic acid type phosphorus-containing blocked polyurethane.

3. The durable flame-retardant antibacterial waterproof finishing agent according to claim 1, wherein the hydrophilic chain extender used in the flame-retardant cross-linking agent is one of ethylenediamine ethyl sodium sulfonate, 1, 2-dihydroxy-3-propane sodium sulfonate, ethylenediamine hexanesulfonic acid sodium, N-bis (2-hydroxyethyl) -2-aminopropanesulfonic acid sodium and 2, 4-diaminobenzene sodium sulfonate.

4. The durable flame-retardant antibacterial waterproof finishing agent according to claim 1, wherein the amino acid is one of aspartic acid, glutamic acid, lysine and arginine.

5. The durable flame-retardant antibacterial waterproof finishing agent according to claim 1, wherein the nonionic surfactant is one or more of O-8, O-9, O-10, O-15, O-20 and O-25 in peregal O type.

6. The durable flame-retardant antibacterial waterproof finishing agent according to claim 1, wherein the quaternary ammonium salt antibacterial agent is one or more of fatty alcohol polyoxyethylene methyl dioctyl ammonium chloride, trilaury ammonium chloride, methacryloyloxyethyl-benzyl-dimethyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, hydroxypropyl trimethyl ammonium chloride chitosan, quaternary ammonium salt cationic polymer antibacterial agent, and long-chain alkyl diquaternary ammonium salt.

7. The durable flame-retardant antibacterial waterproof finishing agent according to claim 1, wherein the fluorine-based waterproof agent is one or more of a six-carbon fluorine-based waterproof and oil-proof agent AC-E570 in Kyowa chemical technology, a six-carbon fluorine-based waterproof and oil-proof agent AC-E90A in Kyowa chemical technology, a six-carbon fluorine-based waterproof and oil-proof agent AC-E301 in Kyowa chemical technology, a six-carbon fluorine-based waterproof and oil-proof agent AC-N35A in Kyowa chemical technology, an AG-E5500 in Kyowa chemical technology, and a six-carbon fluorine-based waterproof and oil-proof agent GL-MSE6 in Kyowa chemical technology.

8. The durable flame retardant antibacterial waterproof finish according to any one of claims 1 to 7, characterized in that the flame retardant cross-linking agent is prepared by the steps of:

(1) carrying out polycondensation reaction on diisocyanate, phosphorus-containing polyester polyol or phosphorus-containing polyether polyol, reacting for 0.5-3.0 hours at 60-85 ℃, then adding trimethylolpropane, adding acetone or butanone for dissolution assisting and viscosity reduction, reacting for 0.5-1.0 hours at 60-85 ℃, then adding acetone or butanone for viscosity reduction, cooling, adding sulfonic acid type hydrophilic chain extender, reacting for 0.5-1.5 hours at 30-85 ℃, and controlling the molar ratio of NCO/(OH + NH) in the materials₂) At 1.2-1.8:1, the molar ratio of diisocyanate/trimethylolpropane is between 6: 1-30: 1, the molar ratio of diisocyanate/sulfonic acid type hydrophilic chain extender is 5: 1-30: 1;

(2) blocking the residual NCO in the end group by methyl ethyl ketoxime, and reacting for 0.3-2.0 hours at the temperature of 60-75 ℃ to realize 100 percent blocking of NCO groups;

(3) adding deionized water, emulsifying, and removing acetone or butanone under reduced pressure to obtain the flame-retardant crosslinking agent.

9. A process for the preparation of a durable flame retardant, antimicrobial and water repellent finish according to any of claims 1 to 8 comprising the steps of:

(1) weighing the materials by weight;

(2) adding 0.05-0.3 part of nonionic surfactant into 9-30 parts of deionized water, adding 0.1-1.0 part of amino acid, adding 18-50 parts of cyclic phosphate ester flame retardant, heating to 30-60 ℃, stirring for 0.2-2.0 hours, uniformly dispersing, adding 6.0-18 parts of fluorine waterproofing agent and 0.6-6.0 parts of flame retardant crosslinking agent, stirring for 0.2-2.0 hours, and uniformly dispersing to obtain a component A;

(3) adding 0.01-0.2 part of wetting dispersant into 2.5-9.0 parts of deionized water, uniformly dispersing, adding 0.03-0.2 part of silver antibacterial agent, 0.3-2.0 parts of organic antibacterial agent and 1.0-6.0 parts of phosphorus-nitrogen-containing flame retardant, stirring for 0.2-2.0 hours, and uniformly dispersing to obtain the component B.

10. Use of a durable flame retardant, antimicrobial and water repellent finish according to any of claims 1 to 8, comprising the steps of:

(1) dispersing 10 parts of the component A in 15-70 parts of deionized water, adding 0.01-0.8 part of glacial acetic acid, stirring for 1-10 minutes, and uniformly dispersing;

(2) adding 1.5-7.5 parts of the component B into the uniformly dispersed liquid, stirring for 1-10 minutes, and uniformly dispersing to obtain a durable flame-retardant antibacterial waterproof finishing agent dispersion liquid mixed with A and B;

(3) transferring the durable flame-retardant antibacterial waterproof finishing agent dispersion liquid into a mangle;

(4) and (3) padding polyester fabric into the durable flame-retardant antibacterial waterproof finishing agent dispersion liquid, controlling the padding liquid rate to be 60-100% after padding, pre-drying at 105-plus-120 ℃ for 1.5-3.0 minutes, then baking at 180-plus-195 ℃ for 0.75-3.0 minutes, washing with water at normal temperature, drying and shaping, and obtaining the durable flame-retardant antibacterial waterproof fabric.

Technical Field

The invention relates to the technical field of functional finishing agents, in particular to a durable flame-retardant antibacterial waterproof finishing agent, and a preparation method and application thereof

Background

With the rapid increase in the consumption of decorative textiles in recent years, the fire caused by textiles has increased. The improvement of the flame retardant function of textiles is one of the focuses of the industry. GB/T17591-2006 "flame retardant fabric", GB20286-2006 "requirements and marks for flame retardant products and assemblies in public places" and GB8624-2012 "grades for combustion performance of building materials and products" all put forward harsh flame retardant requirements for the flame retardance of textiles, and especially GB20286-2006 and GB8624-2012 have higher requirements for oxygen index indexes and vertical combustion performance.

On the other hand, the market demand for the antibacterial and waterproof functions of textiles is also increasing. However, in the textile field, flame retardance, antibiosis and water resistance are difficult to balance. The waterproof mechanism of the waterproof agent, particularly the fluorine waterproof agent, usually forms a structure with low surface energy on the surface of the fabric to achieve the hydrophobic effect. The antimicrobial agent has different modes of action according to different systems. In the case of silver-based antibacterial agents, the continuous elution of silver ions plays an important role in exerting antibacterial effects, and in the case of organic quaternary ammonium salt systems, the migration, hydrophilicity, and durability of organic quaternary ammonium cations are also important points to be paid attention. It is also a matter of technical difficulty to realize a good antibacterial and waterproof function for the combination of the above-mentioned (fluorine-based) waterproof product and a silver-based antibacterial agent or an organic quaternary ammonium salt antibacterial agent. In addition, for a flame-retardant system, especially a phosphorus flame-retardant system, a very important mechanism in the flame-retardant process is condensed phase charring, an acid source is heated to generate polyphosphoric acid, and the polyphosphoric acid migrates and is enriched to the surface of a material, so that a flame-retardant carbon layer for heat insulation and oxygen insulation is formed on the surface of the material. In a conventional waterproof flame-retardant one-bath finishing product, a low surface energy structure formed by a waterproof agent (in a broad range, except a simple waterproof finishing agent, a waterproof oil-proof agent and a waterproof oil-proof antifouling finishing agent) causes that the flame-retardant components (especially phosphorus flame-retardant components) in a textile material (especially a polyester textile) are difficult to migrate, spread and concentrate to the surface, especially an acid source playing a key role in coacervation phase resistance finishing is difficult to form a polyphosphoric acid coating layer and a catalytic carbon layer on the surface of the material, so that efficient waterproof flame-retardant is difficult to realize, and the LOI of the conventional product is difficult to reach the standard. In addition, in the processing process, in the process of finishing the flame retardant, the antibacterial agent and the waterproof agent in the prior art in one bath, effective action and resultant force cannot be formed among various components, synergy cannot be realized, on the contrary, mutual antagonism is often realized, the product cannot be durable, and the overall application performance of the final product is influenced.

The invention with the application number of CN201810727206.2 discloses a high-washing-resistance fluorine-containing waterproof processing agent for textile, which comprises the following components in parts by weight: 70-80 parts of component A, 20-30 parts of cross-linking agent and 0-1 part of glacial acetic acid, wherein: the component A comprises, by weight, 30-35 parts of six-carbon fluorine alkyl acrylate, 1-2 parts of a surfactant, 9-10 parts of propanol ether, 0.1-0.5 part of glacial acetic acid and 54-56 parts of deionized water, and the crosslinking agent comprises, by weight, 40-50 parts of polyurethane resin and 50-60 parts of deionized water. The highly washable fluoride waterproof processing agent for textile does not contain octafluorocarbon alkyl acrylate, does not contain PFOS, PFOA and other environmental harmful substances, and meets the requirement of environmental protection; the component A in the high-washable fluorine-containing waterproof processing agent for textiles has an excellent waterproof effect through testing, is bonded on fabric fibers more firmly through the cross-linking agent, provides excellent washability, and can be widely applied to various internal and external textile products.

The invention with the application number of CN201810727210.9 discloses a washable fluoride-free waterproof processing finishing agent, which comprises the following components in parts by weight: 70-80 parts of component A and 20-30 parts of cross-linking agent, wherein: the component A comprises, by weight, 20-26 parts of stearyl alcohol acrylate copolymer, 7-12 parts of surfactant and 67-69 parts of deionized water, and the crosslinking agent comprises, by weight, 40-50 parts of polyurethane resin and 50-60 parts of deionized water. The washable fluoride-free waterproof finishing agent does not contain fluoride alkyl acrylate and does not contain PFOS, PFOA and other environmental harmful substances, wherein the component A has excellent waterproof effect through testing and has a wide application range, the component A is bonded on fabric fibers through the cross-linking agent by firmer bonds, the washability of the washable fluoride-free waterproof finishing agent is greatly improved under the condition that the waterproof effect of the component A is not influenced, and the washable fluoride-free waterproof finishing agent is applied to textile fabrics and can greatly enhance the quality and the protective performance of textile products.

The invention with the application number of CN201610147435.8 discloses a processing method of waterproof, antifouling and antibacterial fabric. After the polyurethane water dispersion finishing agent comprising the nano material with antibacterial property and polyethylene oxide is applied to the fabric, drying treatment is carried out under the vacuum condition with the temperature of 130-170 ℃, and the waterproof, antifouling and antibacterial fabric can be obtained. From the main claim and the partial claims of the invention, the details of the polyurethane containing the oligodimethylsiloxane chain are not mentioned, and the technical principle of the oligodimethylsiloxane chain is not clarified in some examples. Examples 1,2, 4 and 5 do not mention the oligodimethylsiloxane chain, but the invention states that the oligodimethylsiloxane chain segments on the surface of the polyurethane (part of the preferred technical scheme in the invention) are induced to be separated to the surface of the polyurethane by using the low surface energy environment created by the vacuum drying environment, so that the surface of the polymer is mainly occupied by the high molecular chain segments with lower surface energy, thereby achieving the hydrophobization of the surface of the polymer; the lotus effect of the nano material in the finishing agent enhances the hydrophobization effect, and meanwhile, the antibacterial property of the nano material endows the fabric with excellent antibacterial performance.

The invention discloses an antibacterial fabric with application number CN201410838761.4, and relates to a composite antibacterial fabric. The long-acting antibacterial fabric is characterized in that the fabric is woven by hydrophilic yarn with an antibacterial agent and hydrophobic yarn to form a kind of fabric with an inner layer and an outer layer, wherein the inner layer of the fabric has hydrophilicity and hydrophobicity, and the outer layer of the fabric has hydrophobicity.

The invention discloses a fluorine-containing waterproof agent for fabrics with application number CN201210116970.9 and a preparation method thereof, belonging to the field of chemical materials. The invention utilizes ARGETATRP to synthesize self-emulsifying fluorine-containing acrylic acid block copolymer, which can be directly used after being emulsified and diluted. The self-emulsifying fluorine-containing acrylic acid block copolymer prepared by the method has good pH stability, chemical stability, dilution stability and storage stability, and fluorine-containing acrylic acid ester block copolymer has fluorine-containing structural units distributed in a block form on a polymer chain, and fluorine-containing chain segments can be effectively utilized. Compared with random fluorocarbon resin, the fluorine-containing acrylate block copolymer can achieve the same performance, and the usage amount of the fluorine-containing monomer is very low. The finished fabric has good waterproof performance, improves the fluorine efficiency compared with similar products, and reduces the cost.

The invention with application number CN201910137075.7 relates to a preparation method of antibacterial waterproof paper, and belongs to the technical field of antibacterial waterproof paper. According to the invention, a chemical reduction method is adopted to reduce silver nitrate by sodium borohydride, a layer of nano-silver is loaded on the surface of the plant fiber, and then a layer of nano-titanium dioxide is coated on the surface of the plant fiber loaded with the silver, so that the prepared antibacterial waterproof paper has a good antibacterial effect, the nano-silver has strong antibacterial and broad-spectrum antibacterial effects, and because microorganisms including viruses, bacteria and fungi are all composed of organic matters, the titanium dioxide can degrade organic components of the microorganisms under the excitation of light to damage and even kill the bacteria, the fungi and the viruses; according to the invention, castor oil with high functionality and a polyhydroxy value, isophorone diisocyanate, solvent acetone and polymerization inhibitor orthophosphoric acid are used as raw materials to synthesize a polyurethane prepolymer, and asphalt modified polyurethane is utilized, so that the prepared antibacterial waterproof paper has a good waterproof effect, and the asphalt has good cohesiveness, water resistance, corrosion resistance and durability.

The invention of application number CN201811601422.9 discloses a preparation process of washable, antibacterial, three-proofing and flame-retardant fabric, which comprises the following steps in sequence: pretreatment → dyeing bottom → printing → CP flame retardant finishing → antibacterial finishing → three-proofing finishing → preshrinking → inspection → finished product, the antibacterial finishing, three-proofing finishing and flame retardant finishing are not affected by the preparation process. Although the patent claims that the flame-retardant, antibacterial and three-proofing effects can be achieved, the finishing processing steps are very complicated, the flame-retardant finishing, the antibacterial finishing and the three-proofing finishing are respectively carried out, and the flame-retardant finishing adopts a CP flame retardant, contains formaldehyde and is not environment-friendly.

Application number CN 201620395822.9's utility model relates to an antibiotic three proofings surface fabric, including the precoat and weave the base cloth layer that forms by bamboo fibre, the precoat includes waterproof outer layer, weaving inlayer and cold-proof intermediate level, cold-proof intermediate level sets up between waterproof outer layer and weaving inlayer, be provided with the antibiotic body that can the atress give off the antiseptic between weaving inlayer and the base cloth layer, be equipped with the clearance of fixed antibiotic body on the base cloth layer, the cockscomb structure is personally submitted with the contact of antibiotic body to weaving inlayer, the thickness sum that the thickness of weaving inlayer equals waterproof outer layer and cold-proof intermediate level

The invention of application number CN201811229573.6 discloses a preparation method of a multifunctional coating fabric, which comprises the following steps: weaving, scouring and bleaching, dyeing, heat setting, front water repellent finishing, micro-bubble coating finishing and finishing to obtain a finished product. The invention has simple and environment-friendly process and no wastewater discharge, can realize multiple functions of flame retardance, static resistance, crease resistance and water resistance by one-step finishing of a direct coating, and the finished fabric has soft hand feeling, and is resistant to washing because the flame retardant and the antistatic agent are completely coated on the surface of the fabric by the coating.

None of the above patents relate to flame retardant, antimicrobial, waterproof, one-bath finishing, durable bonding and synergistic synergy of polyester textiles. In the prior art, a durable flame-retardant antibacterial waterproof finishing agent which is safe and environment-friendly is lacked in the field of polyester textiles.

Disclosure of Invention

The invention aims to overcome the defects in the prior art and provides a durable flame-retardant antibacterial waterproof finishing agent, and a preparation method and application thereof.

In order to achieve the purpose, the invention adopts the following technical scheme:

a durable flame-retardant antibacterial waterproof finishing agent is characterized by comprising a component A and a component B, wherein the component A comprises 18-50 parts by weight of cyclic phosphate flame retardant, 6.0-18 parts by weight of fluorine waterproof agent, 0.6-6.0 parts by weight of flame-retardant cross-linking agent, 0.1-1.0 part by weight of amino acid, 9-30 parts by weight of deionized water and 0.05-0.3 part by weight of nonionic surfactant, the component B comprises 0.03-0.2 part by weight of silver antibacterial agent, 0.3-2.0 parts by weight of organic antibacterial agent, 0.01-0.2 part by weight of wetting dispersant, 1.0-6.0 parts by weight of phosphorus-nitrogen flame retardant and 2.5-9.0 parts by weight of deionized water, wherein,

the cyclic phosphate ester flame retardant is a cyclic phosphate ester diester flame retardant;

the fluorine-based waterproofing agent is a six-carbon fluorine-based waterproofing agent;

the flame-retardant cross-linking agent is sulfonic acid type phosphorus-containing closed polyurethane with a plurality of blocked NCO on the molecular chain;

the amino acid is amino acid with the total number of carboxyl and primary amino group not less than 3;

the nonionic surfactant is polyoxyethylene fatty alcohol ether surfactant;

the silver-based antibacterial agent is a nano silver-based antibacterial finishing agent containing a nano silver simple substance;

the quaternary organic antibacterial agent is a quaternary ammonium salt antibacterial agent without organic silicon;

the wetting dispersant is a non-ionic wetting dispersant;

the phosphorus-nitrogen-containing flame retardant is diphenoxy aniline phosphate.

Preferably, the flame-retardant cross-linking agent is methyl ethyl ketoxime-terminated sulfonic acid type phosphorus-containing closed polyurethane.

Preferably, the hydrophilic chain extender used in the flame-retardant cross-linking agent is one of ethylenediamine ethyl sodium sulfonate, 1, 2-dihydroxy-3-propane sodium sulfonate, ethylenediamine hexamethylene sodium sulfonate, N-bis (2-hydroxyethyl) -2-aminopropane sodium sulfonate and 2, 4-diaminobenzene sodium sulfonate.

Preferably, the amino acid is one of aspartic acid, glutamic acid, lysine and arginine.

Preferably, the nonionic surfactant is one or more of O-8, O-9, O-10, O-15, O-20 and O-25 in the peregal O type.

Preferably, the quaternary ammonium salt antibacterial agent is one or more of fatty alcohol polyoxyethylene methyl dioctyl ammonium chloride, trilauryl ammonium chloride, methacryloyloxyethyl-benzyl-dimethyl ammonium chloride, tetradecyl dimethyl benzyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, hydroxypropyl trimethyl ammonium chloride chitosan, quaternary ammonium salt cationic polymer antibacterial agent and long-chain alkyl biquaternary ammonium salt.

Preferably, the fluorine-based water-proofing agent is a hexacarbon fluorine-based water-proofing and oil-proofing agent prepared by Kyowa chemical technology

AC-E570, one or more of a six-carbon fluorine water-and-oil-proof agent AC-E90A, an AC-E301, an AC-N35A, an AG-E5500 and a GL-MSE 6.

Preferably, the durable flame-retardant antibacterial waterproof finishing agent is characterized in that the flame-retardant cross-linking agent is prepared by the following steps:

(1) carrying out polycondensation reaction on diisocyanate, phosphorus-containing polyester polyol or phosphorus-containing polyether polyol, reacting for 0.5-3.0 hours at 60-85 ℃, then adding trimethylolpropane, adding acetone or butanone for dissolution assisting and viscosity reduction, reacting for 0.5-1.0 hours at 60-85 ℃, then adding acetone or butanone for viscosity reduction, cooling, adding sulfonic acid type hydrophilic chain extender, reacting for 0.5-1.5 hours at 30-85 ℃ (the reaction speed of aliphatic amino is higher, if the sulfonic acid type hydrophilic chain extender contains aliphatic amino, the reaction temperature is relatively low, if the sulfonic acid type hydrophilic chain extender contains aliphatic amino, the sulfonic acid type hydrophilic chain extender contains aliphatic aminoThe active group of the hydrophilic chain extender is hydroxyl, the reaction temperature is higher if the reactivity of the hydroxyl is lower than that of the amino), and the molar ratio of NCO/(OH + NH) in the materials is controlled through reaction₂) At 1.2-1.8:1, the molar ratio of diisocyanate/trimethylolpropane is between 6: 1-30: 1, the molar ratio of diisocyanate/sulfonic acid type hydrophilic chain extender is 5: 1-30: 1;

(2) blocking the residual NCO in the end group by methyl ethyl ketoxime, and reacting for 0.3-2.0 hours at the temperature of 60-75 ℃ to realize 100 percent blocking of NCO groups;

(3) adding deionized water, emulsifying, and removing acetone or butanone under reduced pressure to obtain the flame-retardant crosslinking agent.

The preparation method of the durable flame-retardant antibacterial waterproof finishing agent is characterized by comprising the following steps of:

(1) weighing the materials by weight;

(2) adding 0.05-0.3 part of nonionic surfactant into 9-30 parts of deionized water, adding 0.1-1.0 part of amino acid, adding 18-50 parts of cyclic phosphate ester flame retardant, heating to 30-60 ℃, stirring for 0.2-2.0 hours, uniformly dispersing, adding 6.0-18 parts of fluorine waterproofing agent and 0.6-6.0 parts of flame retardant crosslinking agent, stirring for 0.2-2.0 hours, and uniformly dispersing to obtain a component A;

(3) adding 0.01-0.2 part of wetting dispersant into 2.5-9.0 parts of deionized water, uniformly dispersing, adding 0.03-0.2 part of silver antibacterial agent, 0.3-2.0 parts of organic antibacterial agent and 1.0-6.0 parts of phosphorus-nitrogen-containing flame retardant, stirring for 0.2-2.0 hours, and uniformly dispersing to obtain the component B.

The application of the durable flame-retardant antibacterial waterproof finishing agent is characterized by comprising the following steps:

(1) dispersing 10 parts of the component A in 15-70 parts of deionized water, adding 0.01-0.8 part of glacial acetic acid, stirring for 1-10 minutes, and uniformly dispersing;

(2) adding 1.5-7.5 parts of the component B into the uniformly dispersed liquid, stirring for 1-10 minutes, and uniformly dispersing to obtain a durable flame-retardant antibacterial waterproof finishing agent dispersion liquid mixed with A and B;

(3) transferring the durable flame-retardant antibacterial waterproof finishing agent dispersion liquid into a mangle;

(4) and (3) padding polyester fabric into the durable flame-retardant antibacterial waterproof finishing agent dispersion liquid, controlling the padding liquid rate to be 60-100% after padding, pre-drying at 105-plus-120 ℃ for 1.5-3.0 minutes, then baking at 180-plus-195 ℃ for 0.75-3.0 minutes, washing with water at normal temperature, drying and shaping, and obtaining the durable flame-retardant antibacterial waterproof fabric.

The durable flame-retardant antibacterial waterproof finishing agent is prepared by adopting an A, B bi-component system, wherein the component A comprises 18-50 parts by weight of cyclic phosphate ester flame retardant, 6.0-18 parts by weight of fluorine waterproof agent, 0.6-6.0 parts by weight of flame-retardant cross-linking agent, 0.1-1.0 part by weight of amino acid, 9-30 parts by weight of deionized water and 0.05-0.3 part by weight of nonionic surfactant, and the component B comprises 0.03-0.2 part by weight of silver antibacterial agent, 0.3-2.0 parts by weight of organic antibacterial agent, 0.01-0.2 part by weight of wetting dispersant, 1.0-6.0 parts by weight of phosphorus-nitrogen-containing flame retardant and 2.5-9.0 parts by weight of deionized water.

In the invention, the dosage of each component is in a proportion range optimized by a large amount of exploratory experiments. The main components are selected from specific materials through fine design and experimental optimization.

The cyclic phosphate ester flame retardant is a cyclic phosphate ester diester flame retardant. FIG. 1 is a schematic diagram of the structure of cyclic phosphates. When n is 0, it is a cyclic phosphoric acid ester diester. The invention adopts the cyclic phosphate diester flame retardant and controls the dosage range to be certain, does not adopt cyclic phosphate monoester, and is an optimized technical scheme obtained by a great amount of experimental exploration. The cyclic phosphate diester flame retardant has the advantages of large molecular weight, high viscosity, high phosphorus content and good flame retardance, has high bonding degree with terylene after entering an amorphous area of the terylene at high temperature, is not easy to migrate out at low temperature, and is beneficial to improving the flame retardance and the durability of products. In the technical scheme of the invention, the flame retardant also comprises waterproof and antibacterial components and other auxiliary agents, and has higher requirements on the flame retardant. The adoption of the cyclic phosphate diester flame retardant is more effective for the flame retardance of the terylene body, and is beneficial to the realization of the comprehensive performance of waterproof, antibacterial and flame retardant.

The fluorine-based waterproof agent is a six-carbon fluorine-based waterproof agent, does not adopt an eight-carbon fluorine-based waterproof agent, does not contain PFOS and PFOA, and has excellent environmental protection performance and waterproof performance.

The flame-retardant cross-linking agent is sulfonic acid type phosphorus-containing closed polyurethane, and the nonionic surfactant is polyoxyethylene fatty alcohol ether surfactant. The amino acid is amino acid with the sum of carboxyl and primary amino group being not less than 3, and the phosphorus-nitrogen-containing flame retardant is diphenoxy aniline phosphate. The nonionic surfactant is polyoxyethylene fatty alcohol ether surfactant, and the wetting dispersant is nonionic wetting dispersant. After the polyoxyethylene fatty alcohol ether surfactant plays a role in dispersion, emulsification and stabilization, under the condition of high-temperature baking, the polyoxyethylene fatty alcohol ether surfactant can also be combined with a flame-retardant cross-linking agent and other macromolecular structures through the reaction of hydroxyl and NCO deblocked by sulfonic acid type phosphorus-containing closed polyurethane. The introduction of the nonionic surfactant in the invention is to further improve the compatibility stability of the sulfonic acid type phosphorus-containing closed polyurethane. The non-ionic wetting dispersant is adopted, not only from the perspective of compatibility stability in the product application process, but also for realizing good wetting dispersion of raw materials such as diphenoxyl aniline phosphate and the like.

In the invention, the sulfonic acid type phosphorus-containing closed polyurethane is adopted instead of the carboxylic acid type phosphorus-containing closed polyurethane, because experiments show that the sulfonic acid type phosphorus-containing closed polyurethane has better compatibility stability in the technical scheme of the invention, and the compatibility stability of the carboxylic acid type phosphorus-containing closed polyurethane is relatively inferior.

The introduction of the sulfonic acid type phosphorus-containing closed polyurethane enables the durable flame-retardant antibacterial waterproof finishing agent to realize bridging connection among multiple functional additives in textile finishing application, for example, after the end-capped NCO of the sulfonic acid type phosphorus-containing closed polyurethane is unsealed, the durable flame-retardant antibacterial waterproof finishing agent can react with amino groups of amino acids, can also react with a six-carbon fluorine waterproofing agent in a crosslinking way, and can also react with a phosphorus-nitrogen flame retardant (diphenoxyaniline phosphate), the amino acids contain three functional groups and can realize reaction or complexation in three directions, the carboxylic acids of the amino acids can realize combination with quaternary ammonium salt (the carboxylic acids of the amino acids and the cations of the quaternary ammonium salt act to replace small-molecule anions, namely the carboxyl groups and the quaternary ammonium groups of the quaternary ammonium salt (A) form ionic bonds, so that an ionic bond body is formed, a macromolecular structure with a huge molecular structure is formed, and, The combination fastness of the waterproof agent and the phosphorus-nitrogen-containing flame retardant is realized, the bonding and the coating of the nano-silver antibacterial finishing agent containing a nano-silver simple substance are realized, the amino acid and the sulfonic acid type phosphorus-containing closed polyurethane are subjected to multiple combination/bonding/connection/complexation/coating of the waterproof agent, the antibacterial agent and the flame retardant in a network space, the durability, the washability and the migration resistance of the product are greatly improved, and the antibacterial, waterproof and flame-retardant multi-position integrated structure is very beneficial to the realization of the flame-retardant, antibacterial and waterproof functions of the product on the surface of the polyester fabric. Especially when the surface has a waterproof component with low surface energy, the phosphorus flame-retardant component in the terylene body/interior is difficult to rapidly migrate and enrich on the surface at the first time, and the diphenoxy aniline phosphate on the surface of the terylene is combined with the fastness of the antibacterial, waterproof and flame-retardant cross-linking agent, so that the diphenoxy aniline phosphate can be directly dehydrated in situ to form carbon, and the phosphorus and the nitrogen cooperate to form a flame-retardant carbon layer which can insulate heat, oxygen and flame. And the cyclic phosphate diester structure in the polyester fiber endows the product with good flame retardant property from the aspect of material body.

The present invention uses silicone-free quaternary ammonium salt antibacterial agents, while discarding silicone quaternary ammonium salts such as DC5700(3- (trimethoxysilyl) propyldimethyloctadecyl quaternary ammonium chloride), not only from an economic cost perspective, but more importantly from a flame retardant and water repellent perspective. The invention does not utilize the mechanism that the silicon-oxygen active group of the organosilicon quaternary ammonium salt is combined with the fabric and a silicon-containing layer is formed on the surface of the fabric, but introduces the assistants such as phosphorus-nitrogen-containing flame retardant, antibacterial agent, amino acid, waterproof agent, flame-retardant cross-linking agent and the like, and realizes the connection of a space network structure through various assistants.

The durable flame-retardant antibacterial waterproof finishing agent has the beneficial effects that through the combination of the component A and the component B, in the finishing of the polyester fabric, the antibacterial, waterproof and flame-retardant one-bath finishing and the continuous durable functionalization of the polyester fabric can be realized through the respective fixation and fastness combination of various auxiliaries on the surface and the inside. The flame retardant containing phosphorus and nitrogen, the antibacterial agent, the amino acid, the waterproof agent and the flame-retardant cross-linking agent are formed on a spatial network layer by pre-baking and baking in the application process, so that good combination/bonding/connection/complexation/coating is realized, the in-situ surface flame-retardant and carbon-forming effect of a macromolecular structure is improved, the surface carbon layer is more compact and complete, and the flame-retardant effect is good due to the internal synergistic effect of the cyclic phosphate diester. Meanwhile, the combination/bonding/connection/complexation/cladding of the spatial network layer formed in the application process of the invention also improves the stability, the washability and the durability of the antibacterial agent, and also improves the waterproofness, the durability and the washability of the waterproof agent. In addition, the amino acid structure adopted by the invention has good affinity with human body, and the introduction of the amino acid also has the effect of improving the product affinity.

The product of the invention can endow the terylene textile with good flame retardance, antibacterial property and waterproof property, has good affinity, environmental protection and durability after being applied to terylene textiles, and has good application prospect in public places or private places such as hospitals, cinemas, theaters, vehicles and boats, airplanes, hotels, schools, nursing homes, medical and beauty centers, rehabilitation centers, disease control centers and the like.

Drawings

FIG. 1 is a schematic diagram of the structure of cyclic phosphates.

Detailed Description

The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples. Other variations and modifications which may occur to those skilled in the art without departing from the spirit and scope of the invention are intended to be included within the scope of the invention.