CN104727150A - Waterproof moisture-penetrable antibacterial anti-ultraviolet waterborne polyurethane material and preparation method thereof - Google Patents

Abstract

The present invention provides a waterproof, moisture-permeable, anti-bacterial and anti-ultraviolet water-based polyurethane material used in the dry coating finishing of cotton and polyester textiles and a preparation method thereof. ～10wt% silver-loaded nano-titanium dioxide, 0.05wt%～1wt% silane coupling agent of resin mass, 5wt%～40wt% absolute ethanol of resin mass, 3wt%～10wt% curing agent of resin mass, 1wt% resin mass ~5wt% thickener and 0.1wt%~1wt% wetting agent by resin mass are mixed. The high-moisture-permeable antibacterial and anti-ultraviolet water-based polyurethane material of the present invention is finished into the fabric, and the obtained coated fabric has not only good waterproof and moisture-permeable functions, but also antibacterial and anti-ultraviolet functions.

Description

A waterproof, moisture-permeable, antibacterial, anti-ultraviolet water-based polyurethane material and preparation method thereof

technical field

The invention relates to a water-based polyurethane emulsion in the technical field of textile chemical industry and a preparation method thereof, in particular to a waterproof, moisture-permeable, antibacterial, anti-ultraviolet water-based polyurethane material and a preparation method thereof.

Background technique

Early polyurethane-coated fabrics generally have good waterproof effect, but poor moisture permeability. When the human body wears this type of clothing during strenuous exercise, a large amount of sweat cannot be discharged in the form of steam, and condensed water droplets will form inside the clothing, making people feel sticky. Wet and uncomfortable. Waterproof and moisture-permeable means that polymer materials do not allow liquids such as water droplets to pass through, but can ensure the free passage of water vapor. Water-based polyurethane has become an important development direction in the field of polyurethane waterproof and moisture-permeable fabric coatings because it uses water instead of organic solvents as the dispersion medium, and is safe, inexpensive, energy-saving, environmentally friendly, and easy to use. Due to the destruction of the ozone layer brought about by the rapid development of today's society, the intensity of ultraviolet rays reaching the ground has increased significantly, causing damage to the human body, and because the human skin provides suitable temperature, nutrients and nutrients for various bacteria and other microorganisms. Moisture makes the reproduction of bacteria on textiles very fast, and fabrics coated with polyurethane have therefore become a breeding ground for microorganisms, causing various skin diseases. With the improvement of people's living standards and the enhancement of health awareness, the development of water-based polyurethane fabric coating agents with waterproof, moisture-permeable, antibacterial, and anti-ultraviolet functions has attracted more and more attention.

Nano-titanium dioxide has strong photocatalysis, antibacterial and ultraviolet shielding functions, and is widely used in sunscreen cosmetics, fabrics, coatings and other fields. The antibacterial property of silver-loaded nano-titanium dioxide refers to the inhibition or killing of common bacteria such as Escherichia coli and Staphylococcus aureus in the environment. The anti-ultraviolet function of silver-loaded nano-titanium dioxide means that nano-titanium dioxide can not only absorb ultraviolet rays, but also reflect and scatter ultraviolet rays, and can also pass through visible light. It is a non-toxic physical shielding ultraviolet protective agent with superior performance.

Patent CN 1931941A discloses a preparation method of water-based polyurethane waterproof, breathable and moisture-permeable antibacterial coating adhesive. This patent uses inorganic silver-loaded antibacterial agents to improve the antibacterial properties of polyurethane films, but the moisture-permeable and water-resistant properties of the polyurethane films still need to be improved. Patent CN 103910969A discloses a waterproof and breathable polyurethane film and its preparation method. Although the polyurethane film prepared by this patent has high moisture permeability, its function is single and cannot provide antibacterial and anti-ultraviolet functions. The waterproof, moisture-permeable, antibacterial, and ultraviolet-resistant water-based polyurethane material synthesized by the invention can not only satisfy the waterproof and moisture-permeable function of the coated fabric, but also provide the antibacterial and anti-ultraviolet function of the coated fabric.

Contents of the invention

Technical problem: The purpose of this invention is to provide a waterproof, moisture-permeable, anti-bacterial, anti-ultraviolet and water-based polyurethane material used in the coating finishing of cotton, polyester textiles, etc. At the same time, it can achieve the composite function of antibacterial and anti-ultraviolet.

Technical solution: A waterproof, moisture-permeable, antibacterial, and UV-resistant water-based polyurethane material of the present invention is realized through the following technical solutions:

The material is composed of waterproof and moisture-permeable water-based polyurethane resin and the following components based on the mass of waterproof and moisture-permeable water-based polyurethane resin:

The average particle size of the silver-loaded nano-titanium dioxide is 20nm-60nm, and the silane coupling agent is γ-(methacryloyloxy)propyltrimethoxysilane or γ-aminopropyltriethoxysilane.

The curing agent is polyether-modified hexamethylene diisocyanate trimer or carboxyl-modified hexamethylene diisocyanate trimer, and the thickener is hydrophobically modified polyacrylate alkali-swellable emulsion or hydrophobic Group modified ethoxypolyurethane water-soluble polymer, wetting agent is polyether modified polydimethylsiloxane copolymer or ethoxypolydimethylsiloxane.

The preparation method of a kind of waterproof and moisture-permeable antibacterial anti-ultraviolet water-based polyurethane material of the present invention is:

a) At room temperature, based on the total mass of the polyurethane prepolymer, the mixed polyether diol compound constituting 50wt% to 80wt% of the mass of the polyurethane prepolymer, 1wt% to 10wt% of dimethylol butyric acid, 0.5wt% %~5wt% of 1,4-butanediol and 10wt%~40wt% of isophorone diisocyanate are added to the reaction kettle at the same time, the temperature is raised to 60~90°C, and the reaction is carried out for 5~9h to obtain the isocyanate group sealed The polyurethane prepolymer at the end; the polyurethane prepolymer is cooled to 20-30°C, and diluted with 20wt%-40wt% butanone of the total mass of the polyurethane prepolymer, the mole of dimethylolbutyric acid added According to the number of neutralizing agent: dimethylol butyric acid molar ratio is 0.9 ~ 1.1: 1, add neutralizing agent for neutralization, and react for 0.5 ~ 1h to obtain neutralized mixed solution; Add 200wt% to 300wt% deionized water based on the total mass of the polyurethane prepolymer, and emulsify for 0.5 to 1 hour; based on the number of moles of isophorone diisocyanate added, the moles of small molecular amine: isophorone diisocyanate The ratio is 0.1-0.3:1, adding small molecule amine, and continuing to stir at high speed for 0.5-1h to obtain a water-based polyurethane emulsion. The emulsion is distilled under reduced pressure at 40-50°C to remove butanone, and the weight percentage of water in the water-based polyurethane is maintained at 70wt% to 75wt%, to obtain waterproof and moisture-permeable water-based polyurethane resin;

b) at room temperature, according to the material composition ratio described in claim 1, and taking the waterproof and moisture-permeable water-based polyurethane resin quality prepared in step a) as the base, adding silver-loaded nano-titanium dioxide in dehydrated alcohol, after stirring and dispersing Perform ultrasonic treatment in an ultrasonic cleaner for 0.5-1h, add a silane coupling agent, and continue ultrasonic dispersion for 0.5-1h to obtain a silane coupling agent-modified silver-loaded nano-titanium dioxide solution; the waterproof and moisture-permeable water-based polyurethane prepared in step a) Add the resin into the silane coupling agent-modified silver-loaded nano-titanium dioxide solution and mix evenly. After stirring for 0.5-1 hour, add curing agent, thickener, and wetting agent, and continue stirring for 0.5-1 hour to obtain waterproof, moisture-permeable, antibacterial, anti-ultraviolet and water-resistant Polyurethane material.

in:

The mixed polyether diol compound described in step a) of the preparation method is formed by mixing polyethylene glycol with a molecular weight of 1000, polyethylene glycol with a molecular weight of 2000 and polytetrahydrofuran diol with a molecular weight of 2000, and the three The molar ratio is 1:1～2:1～2.

In the preparation method, the neutralizing agent described in step a) is one of triethylamine, ammonia water, and triethanolamine, and the described small molecule amine is diethylenetriamine, ethylenediamine, or isophoronediamine. kind of.

Performance test: A waterproof, moisture-permeable, antibacterial, and UV-resistant water-based polyurethane material of the present invention is dry-finished on polyester fabrics, and measured according to "GB/T 12704.1-2009 Textile Fabric Moisture Permeability Test Method Part 1: Moisture Absorption Method" Moisture permeability of coated fabrics; measure the water resistance of coated fabrics according to "GB/T 4744-1997 Determination of Water Resistance of Textile Fabrics and Water Pressure Resistance Test"; measure the anti-ultraviolet properties of fabrics according to "AATCC 183-2000" method (with UPF index is the index); According to "FZ/T01021-1992", the antibacterial performance of the fabric is measured (indicated by the antibacterial rate).

Beneficial effects: the present invention provides a waterproof, moisture-permeable, antibacterial, and anti-ultraviolet water-based polyurethane material and a preparation method thereof. The main technical problems to be solved are:

(1) The waterproof, moisture-permeable, antibacterial, and UV-resistant water-based polyurethane material of the present invention uses polyethylene glycol (molecular weights of 1000 and 20,000) and polytetrahydrofuran diol (molecular weight of 20,000) as soft segments, and preferably uses polyethylene glycol with high ether bond content. Diol is used to improve the moisture permeability of water-based polyurethane, polytetrahydrofuran diol with high crystallinity and high regularity is used to improve the mechanical properties of water-based polyurethane material, and by optimizing the ratio of the three, the water-based polyurethane material has good moisture permeability. At the same time, it has the characteristics of excellent water resistance, mechanical strength and hydrolysis resistance.

(2) Silver-loaded nano-titanium dioxide not only has the functions of nano-titanium dioxide to sterilize and resist viruses under visible light and ultraviolet light, and degrade bacteria and organic matter, but also has strong antibacterial and virus-killing effects of nano-silver under no light source. By adding silver-loaded nano-titanium dioxide to the water-based polyurethane resin, the water-based polyurethane coated fabric not only has good waterproof and moisture-permeable properties, but also can play the good antibacterial and anti-ultraviolet functions of silver-loaded nano-titanium dioxide, ensuring non-toxicity during the antibacterial process , safe to use. By adding silane coupling agent to modify silver-loaded nano-titanium dioxide, the uniform dispersion of silver-loaded nano-titanium dioxide in polyurethane emulsion is improved, and its antibacterial and anti-ultraviolet functions are fully exerted.

Detailed ways

The material is composed of waterproof and moisture-permeable water-based polyurethane resin, silver-loaded nano-titanium dioxide with a mass of 0.5 wt% to 10 wt% of the resin, a silane coupling agent with a mass of 0.05 wt% to 1 wt% of the resin, 5 wt% to 40 wt% of the resin without It is prepared by mixing water ethanol, a curing agent of 3wt% to 10wt% of the resin mass, a thickener of 1wt% to 5wt% of the resin mass, and a wetting agent of 0.1wt% to 1wt% of the resin mass; silver-loaded nano-titanium dioxide The average particle size is 20nm~60nm, the silane coupling agent is γ-(methacryloyloxy)propyltrimethoxysilane or γ-aminopropyltriethoxysilane; the curing agent is polyether modified hexamethylene base diisocyanate trimer or carboxyl modified hexamethylene diisocyanate trimer, the thickener is hydrophobically modified polyacrylate alkali swelling emulsion or hydrophobic group modified ethoxy polyurethane water-soluble polymer, The wetting agent is polyether modified polydimethylsiloxane copolymer or ethoxypolydimethylsiloxane.

The preparation method of the waterproof, moisture-permeable, antibacterial, anti-ultraviolet water-based polyurethane material of the present invention is:

At room temperature, based on the total mass of the polyurethane prepolymer, 50wt% to 80wt% of the mixed polyether diol compound, 1wt% to 10wt% of dimethylol butyric acid, 0.5wt% to 5wt% of the polyurethane prepolymer are mixed % of 1,4-butanediol and 10wt% to 40wt% of isophorone diisocyanate are added to the reaction kettle at the same time, the temperature is raised to 60-90°C, and the reaction is carried out for 5-9 hours to obtain isocyanate group-terminated polyurethane pre- Polymer; the polyurethane prepolymer is cooled to 20-30°C, and diluted with butanone of 20wt%-40wt% of the total mass of the polyurethane prepolymer, in terms of the moles of dimethylolbutyric acid added, According to the neutralizing agent: dimethylol butyric acid molar ratio is 0.9 ~ 1.1: 1, add the neutralizing agent for neutralization, react for 0.5 ~ 1h, and get the neutralized mixed solution, add the neutralized mixed solution to the neutralized mixed solution under high-speed stirring 200wt% to 300wt% deionized water based on the total mass of the polyurethane prepolymer, emulsified for 0.5 to 1h; based on the molar number of isophorone diisocyanate added, the molar ratio of small molecule amine: isophorone diisocyanate is Add small molecule amine at 0.1～0.3:1, continue to stir at high speed for 0.5～1h to obtain water-based polyurethane emulsion, distill the emulsion under reduced pressure at 40-50°C to remove butanone, and keep the weight percentage of water in the water-based polyurethane at 70wt% ~75wt% to obtain waterproof and moisture-permeable water-based polyurethane resin; based on the mass of the waterproof and moisture-permeable water-based polyurethane resin, silver-loaded nano-titanium dioxide of 0.5wt% to 10wt% of the resin quality is added to 5wt% to 40wt% of the resin quality without In water ethanol, after stirring and dispersing, carry out ultrasonic treatment in an ultrasonic cleaner for 0.5-1h, add 0.05wt%-1wt% silane coupling agent of resin mass, continue ultrasonic dispersion for 0.5-1h, and obtain silane coupling agent-modified silver-loaded Nano-titanium dioxide solution; at room temperature, add the above-mentioned waterproof and moisture-permeable water-based polyurethane resin to the silane coupling agent-modified silver-loaded nano-titanium dioxide solution and mix evenly, after stirring for 0.5-1h, add a curing agent with a resin mass of 3wt%-10wt% 1. Thickener with 1wt%-5wt% of resin mass, and wetting agent with 0.1wt%-1wt% resin mass, and continue to stir for 0.5-1h to obtain waterproof, moisture-permeable, antibacterial, anti-ultraviolet, water-based polyurethane material.

The mixed polyether diol compound described in the above preparation method is formed by mixing polyethylene glycol with a molecular weight of 1000, polyethylene glycol with a molecular weight of 2000 and polytetrahydrofuran diol with a molecular weight of 2000. The molar ratio of the three mixed 1:1~2:1~2; the neutralizer is one of triethylamine, ammonia water, and triethanolamine, and the small molecule amine is diethylenetriamine, ethylenediamine, or isophoronediamine One of.

Example 1:

At 25°C, 21.3g of polyethylene glycol with a molecular weight of 1000, 49.63g of polyethylene glycol with a molecular weight of 2000, 61.45g of polytetrahydrofuran diol with a molecular weight of 2000, 6g of dimethylolbutyric acid, and 1.67g of 1, Add 4-butanediol and 60g of isophorone diisocyanate into the reaction kettle at the same time, raise the temperature to 60°C, and react for 9 hours to obtain a polyurethane prepolymer terminated with isocyanate groups; cool down the polyurethane prepolymer to 20°C , and add 40g of butanone to dilute, then add 4.10g of triethylamine to carry out neutralization reaction for 0.5h, and obtain a neutralized mixed solution, add 470g of deionized water to the neutralized mixed solution under high-speed stirring, emulsify for 0.5h, and then add 4.87g of ethylenediamine was subjected to a post-chain extension reaction for 0.5h to obtain a water-based polyurethane emulsion. The emulsion was distilled at 40°C to remove butanone under reduced pressure, and the weight percentage of water in the water-based polyurethane material was kept at 70wt% to obtain a water-based polyurethane emulsion. Wet water-based polyurethane resin; at 25°C, add 0.5g of silver-loaded nano-titanium dioxide with an average particle size of 60nm into 5g of absolute ethanol, stir and disperse, and perform ultrasonic treatment in an ultrasonic cleaner for 0.5h, and add 0.05g of γ-(methyl Acryloyloxy)propyltrimethoxysilane, continue to ultrasonically disperse for 0.5h to obtain a silane coupling agent-modified silver-loaded nano-titanium dioxide solution; at 25°C, add 100g of waterproof and moisture-permeable water-based polyurethane resin Mix well in the silver-loaded nano-titanium dioxide solution, stir for 0.5h, then add 3g of polyether-modified hexamethylene diisocyanate trimer, 1g of hydrophobic group-modified ethoxypolyurethane water-soluble polymer, 0.2g of polyether The modified polydimethylsiloxane copolymer was stirred continuously for 0.5h to obtain a waterproof, moisture-permeable, antibacterial, anti-ultraviolet, and water-based polyurethane material. The moisture permeability of the finished fabric was measured to be 5200g/m ² ·day, the water pressure resistance was 57.9KPa, the UPF index was 60.3, and the antibacterial rate was 80.6%.

Example 2:

At 25°C, 21.2g of polyethylene glycol with a molecular weight of 1000, 49.37g of polyethylene glycol with a molecular weight of 2000, 61.13g of polytetrahydrofuran diol with a molecular weight of 2000, 6g of dimethylolbutyric acid, and 2.32g of 1, Add 4-butanediol and 60g of isophorone diisocyanate into the reaction kettle at the same time, raise the temperature to 70°C, and react for 8 hours to obtain a polyurethane prepolymer terminated with isocyanate groups; cool the polyurethane prepolymer to 25°C , and add 45g methyl ethyl ketone to dilute, then add 1.42g ammonia water to carry out neutralization reaction for 40min, and obtain a neutralized mixed solution, add 500g deionized water to the neutralized mixed solution under high-speed stirring, emulsify for 40min, and then add 13.06g isofor Alone diamine was subjected to a post-chain extension reaction for 40 minutes to obtain a water-based polyurethane emulsion. The emulsion was distilled off under reduced pressure to remove methyl ethyl ketone at 50° C., and the weight percentage of water in the water-based polyurethane material was kept at 71 wt % to obtain a waterproof and moisture-permeable water-based emulsion. Polyurethane resin; at 25°C, add 2g of silver-loaded nano-titanium dioxide with an average particle size of 50nm into 10g of absolute ethanol, stir and disperse, and perform ultrasonic treatment in an ultrasonic cleaner for 40min, add 0.2g of γ-aminopropyltriethoxy Silane, continue to ultrasonically disperse for 40 minutes to obtain a silane coupling agent-modified nano-titanium dioxide solution; at 25°C, add 100 g of waterproof and moisture-permeable water-based polyurethane resin to the silane coupling agent-modified silver-loaded nano-titanium dioxide solution and mix well, and stir for 40 minutes , after adding 4g sulfonate modified hexamethylene diisocyanate trimer, 2g hydrophobic group modified ethoxy polyurethane water-soluble polymer, 0.4g polyether modified polydimethylsiloxane interpolymer, Continue to stir for 40 minutes to obtain a waterproof, moisture-permeable, antibacterial, anti-ultraviolet, and water-based polyurethane material. The moisture permeability of the finished fabric was measured to be 5150g/m ² ·day, the water pressure resistance was 58.7KPa, the UPF index was 64.6, and the antibacterial rate was 83.1%.

Example 3:

At 25°C, 20.9g of polyethylene glycol with a molecular weight of 1000, 48.77g of polyethylene glycol with a molecular weight of 2000, 60.38g of polytetrahydrofuran diol with a molecular weight of 2000, 6g of dimethylolbutyric acid, and 3.91g of 1, Add 4-butanediol and 60g of isophorone diisocyanate into the reaction kettle at the same time, raise the temperature to 80°C, and react for 7 hours to obtain a polyurethane prepolymer terminated with isocyanate groups; cool the polyurethane prepolymer to 30°C , and add 50g butanone to dilute, then add 3.69g triethylamine to carry out neutralization reaction for 35min to obtain a neutralized mixed solution, add 515g deionized water to the neutralized mixed solution under high-speed stirring, emulsify for 35min, then add 6.88g Diethylenetriamine was subjected to a post-chain extension reaction for 35 minutes to obtain a water-based polyurethane emulsion. The emulsion was distilled off under reduced pressure to remove butanone at 48° C., and the weight percentage of water in the water-based polyurethane material was kept at 72 wt % to obtain waterproof and moisture-permeable water. Polyurethane resin. At 25°C, add 4g of silver-loaded nano-titanium dioxide with an average particle size of 40nm into 20g of absolute ethanol, stir and disperse, and perform ultrasonic treatment in an ultrasonic cleaner for 35min, add 0.4g of γ-(methacryloyloxy)propane base trimethoxysilane, and continue to ultrasonically disperse for 35 minutes to obtain a silane coupling agent-modified silver-loaded nano-titanium dioxide solution; at 25°C, add 100g of waterproof and moisture-permeable water-based polyurethane resin Mix in medium, stir for 35min, then add 5g polyether modified hexamethylene diisocyanate trimer, 3g hydrophobically modified polyacrylate salt alkali swelling emulsion, 0.3g ethoxy polydimethylsiloxane, Continue stirring for 35 minutes to obtain a waterproof, moisture-permeable, antibacterial, anti-ultraviolet, and water-based polyurethane material. The moisture permeability of the finished fabric was measured to be 5115g/m ² ·day, the water pressure resistance was 60.2KPa, the UPF index was 67.5, and the antibacterial rate was 87.9%.

Example 4:

At 25°C, 20.8g of polyethylene glycol with a molecular weight of 1000, 48.44g of polyethylene glycol with a molecular weight of 2000, 59.97g of polytetrahydrofuran diol with a molecular weight of 2000, 6g of dimethylolbutyric acid, and 4.85g of 1, Add 4-butanediol and 60g of isophorone diisocyanate into the reaction kettle at the same time, raise the temperature to 90°C, and react for 7 hours to obtain a polyurethane prepolymer terminated with isocyanate groups; cool down the polyurethane prepolymer to 25°C , and added 55g butanone for dilution, then added 6.65g triethanolamine for neutralization reaction for 0.5h to obtain a neutralized mixed solution, added 540g deionized water to the neutralized mixed solution under high-speed stirring, emulsified for 0.5h, and then added 3.65 g of ethylenediamine undergoes a post-chain extension reaction for 0.5h to obtain a water-based polyurethane emulsion. The emulsion is distilled off under reduced pressure to remove methyl ethyl ketone at 45° C., and the weight percentage of water in the water-based polyurethane material is kept at 73wt% to obtain waterproof and moisture-permeable. Waterborne polyurethane resin. At 25°C, add 6g of silver-loaded nano-titanium dioxide with an average particle size of 35nm into 35g of absolute ethanol, stir and disperse, perform ultrasonic treatment in an ultrasonic cleaner for 0.5h, and add 0.6g of γ-aminopropyltriethoxy Silane, continue to ultrasonically disperse for 0.5h to obtain a silane coupling agent-modified silver-loaded nano-titanium dioxide solution; at 25°C, add 100g of waterproof and moisture-permeable water-based polyurethane resin to the silane coupling agent-modified silver-loaded nano-titanium dioxide solution and mix well , stirred for 0.5h, then added 6g sulfonate modified hexamethylene diisocyanate trimer, 4g hydrophobic group modified ethoxy polyurethane water-soluble polymer, 0.5g polyether modified polydimethylsiloxane alkane copolymer, and continue to stir for 0.5h to obtain a waterproof, moisture-permeable, antibacterial, anti-ultraviolet, and water-based polyurethane material. The moisture permeability of the finished fabric was measured to be 5106g/m ² ·day, the water pressure resistance was 63.4KPa, the UPF index was 70.6, and the antibacterial rate was 89.7%.

Example 5:

At 25°C, 20.6g of polyethylene glycol with a molecular weight of 1000, 48.07g of polyethylene glycol with a molecular weight of 2000, 59.51g of polytetrahydrofuran diol with a molecular weight of 2000, 6g of dimethylolbutyric acid, and 5.91g of 1, Add 4-butanediol and 60g of isophorone diisocyanate into the reaction kettle at the same time, raise the temperature to 75°C, and react for 6 hours to obtain a polyurethane prepolymer terminated with isocyanate groups; cool down the polyurethane prepolymer to 20°C , and add 60g butanone to dilute, then add 4.10g triethylamine to carry out neutralization reaction for 1h, and obtain a neutralized mixed solution, add 600g deionized water to the neutralized mixed solution under high-speed stirring, emulsify for 1h, and then add 9.2g Isophorone diamine was subjected to a post-chain extension reaction for 1 h to obtain a water-based polyurethane emulsion. The emulsion was distilled off under reduced pressure to remove butanone at 47° C., and the weight percentage of water in the water-based polyurethane material was kept at 75 wt % to obtain a water-based polyurethane emulsion. Wet waterborne polyurethane resin. At 25°C, add 10 g of silver-loaded nano-titanium dioxide with an average particle size of 30 nm into 40 g of absolute ethanol, stir and disperse, and perform ultrasonic treatment in an ultrasonic cleaner for 1 h, and add 1 g of γ-(methacryloyloxy)propane base trimethoxysilane, and continue to ultrasonically disperse for 1 hour to obtain a silane coupling agent-modified silver-loaded nano-titanium dioxide solution; at 25°C, add 100 g of waterproof and moisture-permeable water-based polyurethane resin Mix well, stir for 1 hour, then add 7g polyether-modified hexamethylene diisocyanate trimer, 5g hydrophobic group-modified ethoxy polyurethane water-soluble polymer, 0.6g polyether-modified polydimethylsiloxane The oxane copolymer was stirred for 1 hour to obtain a waterproof, moisture-permeable, antibacterial, anti-ultraviolet, water-based polyurethane material. The moisture permeability of the finished fabric was measured to be 5003g/m ² ·day, the water pressure resistance was 64.7KPa, the UPF index was 79.3, and the antibacterial rate was 94.6%.

Claims (6)

1. A waterproof and moisture-permeable antibacterial anti-ultraviolet water-based polyurethane material, characterized in that the material is composed of waterproof and moisture-permeable water-based polyurethane resin and the following components based on the quality of the waterproof and moisture-permeable water-based polyurethane resin: 2. A kind of waterproof and moisture-permeable antibacterial anti-ultraviolet water-based polyurethane material according to claim 1, characterized in that the average particle diameter of the described silver-loaded nano-titanium dioxide is 20nm～60nm, and the described silane coupling agent is γ-( Methacryloxy)propyltrimethoxysilane or γ-aminopropyltriethoxysilane. 3. A kind of waterproof, moisture-permeable, antibacterial, anti-ultraviolet water-based polyurethane material according to claim 1, characterized in that said curing agent is polyether modified hexamethylene diisocyanate trimer or carboxyl modified hexamethylene base diisocyanate trimer, the thickener is hydrophobically modified polyacrylate salt alkali swelling emulsion or hydrophobic group modified ethoxy polyurethane water-soluble polymer, the wetting agent is polyether modified polydimethylsiloxane Oxane Copolymer or Ethoxylated Dimethicone. 4. a kind of preparation method of a kind of waterproof and moisture-permeable antibacterial anti-ultraviolet water-based polyurethane material as claimed in claim 1, is characterized in that this preparation method is: a) At room temperature, based on the total mass of the polyurethane prepolymer, the mixed polyether diol compound constituting 50wt% to 80wt% of the mass of the polyurethane prepolymer, 1wt% to 10wt% of dimethylol butyric acid, 0.5wt% %~5wt% of 1,4-butanediol and 10wt%~40wt% of isophorone diisocyanate are added to the reaction kettle at the same time, the temperature is raised to 60~90°C, and the reaction is carried out for 5~9h to obtain the isocyanate group sealed The polyurethane prepolymer at the end; the polyurethane prepolymer is cooled to 20-30°C, and diluted with 20wt%-40wt% butanone of the total mass of the polyurethane prepolymer, the mole of dimethylolbutyric acid added According to the number of neutralizing agent: dimethylol butyric acid molar ratio is 0.9 ~ 1.1: 1, add neutralizing agent for neutralization, and react for 0.5 ~ 1h to obtain neutralized mixed solution; Add 200wt% to 300wt% deionized water based on the total mass of the polyurethane prepolymer, and emulsify for 0.5 to 1 hour; based on the number of moles of isophorone diisocyanate added, the moles of small molecular amine: isophorone diisocyanate The ratio is 0.1-0.3:1, adding small molecule amine, and continuing to stir at high speed for 0.5-1h to obtain a water-based polyurethane emulsion. The emulsion is distilled under reduced pressure at 40-50°C to remove butanone, and the weight percentage of water in the water-based polyurethane is maintained at 70wt% to 75wt%, to obtain waterproof and moisture-permeable water-based polyurethane resin; b) at room temperature, according to the material composition ratio described in claim 1, and taking the waterproof and moisture-permeable water-based polyurethane resin quality prepared in step a) as the base, adding silver-loaded nano-titanium dioxide in dehydrated alcohol, after stirring and dispersing Perform ultrasonic treatment in an ultrasonic cleaner for 0.5-1h, add a silane coupling agent, and continue ultrasonic dispersion for 0.5-1h to obtain a silane coupling agent-modified silver-loaded nano-titanium dioxide solution; the waterproof and moisture-permeable water-based polyurethane prepared in step a) Add the resin into the silane coupling agent-modified silver-loaded nano-titanium dioxide solution and mix evenly. After stirring for 0.5-1 hour, add curing agent, thickener, and wetting agent, and continue stirring for 0.5-1 hour to obtain waterproof, moisture-permeable, antibacterial, anti-ultraviolet and water-resistant Polyurethane material. 5. The preparation method of a kind of waterproof and moisture-permeable antibacterial anti-ultraviolet water-based polyurethane material according to claim 4, it is characterized in that the mixed polyether glycol compound described in step a) in the preparation method is made of polyether glycol compound with molecular weight of 1000 Ethylene glycol, polyethylene glycol with a molecular weight of 2000 and polytetrahydrofuran diol with a molecular weight of 2000 are mixed, and the molar ratio of the three is 1:1-2:1-2. 6. the preparation method of a kind of waterproof and moisture-permeable antibacterial anti-ultraviolet water-based polyurethane material according to claim 4 is characterized in that the neutralizing agent described in step a) in the preparation method is triethylamine, ammoniacal liquor, triethanolamine A kind of, described small molecule amine is a kind of in diethylenetriamine, ethylenediamine or isophoronediamine.