Preparation and application of a polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product

Abstract

The invention discloses the preparation and application of a polyurethane acrylate fluorine-free water repellent disperse dye integrated product, and belongs to the field of environmentally friendly polymer technology. The polyester fabric prepared by the integrated product has good water repellency, hydrostatic pressure resistance, softness, wear resistance, moisture permeability, and anti-pilling. The product can be used for full-color color matching, and the contact angle of the finished fabric is still higher than 130 ° after 50 times equivalent to home washing, and has good water washing resistance. The prepared integrated product can realize polyester fabric dyeing, water repellent finishing one-bath processing, avoiding the conventional polyester fabric dyeing and water repellent finishing usually using two-bath method (first dyeing the fabric, and then treating the dyed polyester with a water repellent finishing agent) The process flow is long and the energy consumption is large. Polyester fabric dyeing, water repellent finishing one-bath method can shorten the production process, save water, improve production efficiency, and reduce production costs.

Description

Technical Field

[0001] The invention relates to the preparation and application of a polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product, belonging to the technical field of environmentally friendly polymers. Background Art

[0002] The development of waterproof and water-repellent materials can be traced back to ancient times. In the early days, people used oil and wax substances to achieve such effects. With the continuous development of the textile industry, the technology of water repellents has also been continuously improved. Modern hydrophobic fabrics are widely used due to their excellent water repellency, anti-fouling, self-cleaning and other properties. The commonly used water repellents today are mainly silicone water repellents, fluorine-containing water repellents, and aliphatic hydrocarbon water repellents. Silicone water repellents have excellent water repellency and can effectively prevent the penetration of water, grease and pollutants, but silicone water repellents have certain damage to the environment, and long-term use will cause the surface of the material to silicify and increase pilling. Fluorine-containing water repellents can form a solid protective layer on the surface of the fabric to give the fabric excellent water repellency and anti-fouling effects. However, during the synthesis and use process, fluorine-containing water repellents have great bioaccumulation and toxicity, which have a negative impact on the ecological environment. Long-chain aliphatic hydrocarbon water repellents have high water repellency, but long-chain aliphatic hydrocarbon water repellents are easy to contact acidic and alkaline substances and lose their water repellency. When used, they have defects such as hot stickiness and cold brittleness, poor flexibility, and solvent resistance. Polyurethane is a polymer compound containing repeating carbamate units in the main chain of the molecule, which has the advantages of low temperature resistance, good flexibility, high bonding strength, etc. The organic combination of polyurethane and long-chain aliphatic hydrocarbons can bring out the advantages of both.

[0003] The external emulsifier used in conventional water repellents will affect the water repellent effect of the water repellent, and it is soluble in water, causing harm to the environment. Self-emulsification is to introduce hydrophilic segments into the molecular structure of the water repellent to achieve the emulsification of the water repellent macromolecules, which can effectively avoid product defects caused by the addition of emulsifiers. Conventional textiles are negatively charged in water. Due to the charge repulsion, anionic water repellents cannot be closely adsorbed to the fabric, and the water repellent effect is not ideal. At present, most water-based polyurethanes are anionic polyurethanes, and there are few reports on cationic water-based polyurethane-acrylate water repellents.

[0004] Polyester fabric dyeing and water repellent finishing usually adopts the two-bath method, that is, the fabric is first dyed and then treated with a water repellent finishing agent. The process is long and energy consumption is high. The main reason for adopting the two-step method is that the disperse dyes used in polyester dyeing use anionic and non-ionic dispersing agents, while the water repellent used in textiles is a cationic product, and the two cannot be used in one bath. Summary of the invention

[0005] In order to solve the above problems and broaden the application scope of waterborne polyurethane-acrylate water repellents, the present invention constructs a cationic waterborne polyurethane-acrylate fluorine-free water repellent disperse dye integrated product. The present invention prepares an integrated product of polyurethane acrylate polymer encapsulating disperse dye by emulsifying a mixture of disperse dye and acrylate monomer through the prepared polyurethane prepolymer, polymerizing the acrylate monomer and the polyurethane structure under the action of an initiator.

[0006] The first object of the present invention is to provide a method for preparing a polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product, the method comprising:

[0007] (1) using polymer polyol, diisocyanate, amine compound, dihydroxy small molecule chain extender containing carbon-carbon double bond as polyurethane monomer, and end-capping agent to prepare polyurethane system;

[0008] (2) adding disperse dye filter cake and acrylate monomer to the obtained polyurethane system, mixing and then adding a neutralizing agent;

[0009] (3) adding water for self-emulsification to obtain a cationic waterborne polyurethane emulsion encapsulating disperse dyes and acrylate monomers;

[0010] (4) adding an initiator, mixing and reacting, and obtaining a polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product.

[0011] In one embodiment of the present invention, the polymer polyol in step (1) comprises any one or more of polyether diol and polyester diol having a molecular weight of 200 to 1000.

[0012] In one embodiment of the present invention, the diisocyanate in step (1) includes any one or more of isophorone diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, lysine diisocyanate, 1,6-hexamethylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthalene diisocyanate, dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

[0013] In one embodiment of the present invention, the structure of the alcoholamine compound in step (1) is as follows:

[0014] or

[0015] Where R 1 , R 2 , R 4 , R 5 R are independently substituted or unsubstituted alkyl, phenyl, or cycloalkyl; 3 , R 6 , R7 Each of them is independently hydrogen, substituted or unsubstituted alkyl, phenyl or cycloalkyl.

[0016] In one embodiment of the present invention, the alcoholamine compound in step (1) includes one or more of diethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-propyldiethanolamine, tert-butyldiethanolamine, N-butyldiethanolamine, N-benzyldiethanolamine; N-phenyldiethanolamine, N,N-bis(2-hydroxypropyl)aniline, 3-dimethylamino-1,2-propylene glycol, 3-(diethylamino)-1,2-propylene glycol, 1,4-bis(2-hydroxyethyl)piperazine, etc.

[0017] In one embodiment of the present invention, the olamine compound in step (1) accounts for 6-8% of the total mass of the polyurethane monomer (the total mass of polymer polyol+diisocyanate+olamine compound+dihydroxy small molecule chain extender containing carbon-carbon double bonds).

[0018] In one embodiment of the present invention, the structure of the dihydroxy small molecule chain extender containing a carbon-carbon double bond in step (1) is as follows:

[0019]

[0020] Among them, R 8 is selected from chain alkyl, phenyl, cycloalkyl, acyl, ester, carbonyl, and ether groups having any number of carbon atoms; R 9 Selected from C2-C18 chain alkyl, phenyl, and cycloalkyl.

[0021] In one embodiment of the present invention, the dihydroxy small molecule chain extender containing a carbon-carbon double bond in step (1) comprises a mixture of any one or more of the following: 7-octene-1,2-diol, pentaerythritol diacrylate, 6-heptene-2,4-diol, 3-allyloxy-1,2-propanediol, trimethylolpropane monoallyl ether, 2,2-bishydroxymethylbutyric acid-3-hydroxy-2-(2-methacryloyloxy)-propyl ester, and 2-(3-isocyanatomethyl)-3,5,5-trimethylcyclohexylcarbamoyloxy)ethyl acrylate.

[0022] In one embodiment of the present invention, the dihydroxy small molecule chain extender containing carbon-carbon double bonds in step (1) accounts for 3-6% of the total mass of the polyurethane monomer.

[0023] In one embodiment of the present invention, in step (1), the molar ratio of isocyanate (diisocyanate monomer) to hydroxyl (total of polymer polyol, olamine and dihydroxy chain extender containing carbon-carbon double bonds) is 1.1 to 1.6.

[0024] In one embodiment of the present invention, the end-capping agent in step (1) comprises any one or a mixture of the following: hydroxyethyl acrylate, hydroxyethyl methacrylate, butanone oxime, butyrimidine oxime, acetone oxime, formaldehyde oxime, bromophenol oxime, cyclohexanone oxime, n-heptanal oxime, dimethylglyoxime, and tetramethylcyclobutanedione monoxime.

[0025] In one embodiment of the present invention, the molar ratio of the blocking agent to the unreacted isocyanate in step (1) is between 1.2 and 1.5.

[0026] In one embodiment of the present invention, the acrylic acid ester monomer in step (2) comprises any one or more of the following: methyl acrylate, butyl acrylate, hexyl acrylate, octyl acrylate, decyl acrylate, dodecyl acrylate, tetradecyl acrylate, hexadecyl acrylate, octadecyl acrylate, methyl methacrylate, butyl methacrylate, hexyl methacrylate, octyl methacrylate, decyl methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate.

[0027] In one embodiment of the present invention, the mass ratio of the acrylate monomer to the polyurethane monomer in step (2) is (0.5-1):1.

[0028] In one embodiment of the present invention, the disperse dye in step (2) includes any one or more of the following: azo disperse dyes, anthraquinone disperse dyes, and heterocyclic disperse dyes.

[0029] In one embodiment of the present invention, the amount of disperse dye used in step (2) accounts for 0.01 to 15% of the total mass of the acrylate monomers, and more preferably 2 to 8%.

[0030] In one embodiment of the present invention, the neutralizing agent in step (2) includes one or more of glacial acetic acid, hydrochloric acid, lactic acid, and dimethylmercaptopropionic acid.

[0031] In one embodiment of the present invention, the degree of neutralization in step (2) is 80% to 120%.

[0032] In one embodiment of the present invention, the total mass of all monomer substrates in the self-emulsification process in step (3) accounts for 15% to 40% of the mass of the liquid.

[0033] In one embodiment of the present invention, the initiator in step (4) includes one or more of azobisisobutyronitrile, azobisisoheptylnitrile, azobisisobutyramidine hydrochloride, potassium persulfate, ammonium persulfate, and dibenzoyl peroxide.

[0034] In one embodiment of the present invention, the amount of the initiator used in step (4) accounts for 0.1 to 1% of the total mass of the acrylic ester monomers.

[0035] In one embodiment of the present invention, the step (1) specifically comprises:

[0036] The polymer polyol, olamine (accounting for 6-10% of the total mass of the monomers used in the polyurethane prepolymer), and the dihydroxy small molecule chain extender containing carbon-carbon double bonds (accounting for 3-6% of the total mass of the monomers) are vacuum dried at 80-90°C to remove water for 3-4 hours; according to the ratio of isocyanate to hydroxyl group of 1.1-1.6, the polymer polyol, olamine (accounting for 10-50% of the total mass of the olamine), and dibutyltin dilaurate (accounting for 0.2% of the total mass of the monomers involved in the reaction) are slowly added dropwise at a temperature of 75-85°C under nitrogen protection; the -NCO value in the reaction system is determined by the di-n-butylamine method, When the theoretical value (theoretical residual amount of isocyanate is ≤32%) is reached, the temperature is lowered to 45-55° C., and the residual alcohol amine dissolved in acetone is added, and the reaction is carried out for 1-3 hours (theoretical residual amount of isocyanate is ≤12-16%); the temperature is raised to 60-65° C., a small molecule chain extender containing a carbon-carbon double bond is added, and the reaction is carried out for 1.5-3 hours (theoretical residual amount of isocyanate is ≤8%); a blocking agent (with a molar ratio of 1.2 to 1.5 to unreacted isocyanate) is added, and blocking is carried out at 70-75° C. until the -NCO content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate is ≤0.5%), thereby obtaining polyurethane.

[0037] In one embodiment of the present invention, the step (2) specifically comprises:

[0038] Add a mixture of disperse dye and acrylate monomer (the amount of disperse dye accounts for 2-8% of the total mass of acrylate monomer, and the mass ratio of acrylate monomer to polyurethane monomer is (0.5-1):1); cool to 30-40° C., add a neutralizer (neutralization degree is 80%-120%), adjust the reaction pH (pH=6-7), and react for 0.5-1 hour.

[0039] In one embodiment of the present invention, the step (3) specifically comprises:

[0040] After the reaction in step (2) is completed, deionized water is slowly added under mechanical stirring (800-2000 r / min) for self-emulsification (the total mass of the monomer substrate accounts for 15-40% of the total mass of the liquid) to obtain a cationic waterborne polyurethane blend emulsion coated with disperse dyes and acrylate monomers.

[0041] In one embodiment of the present invention, the step (4) specifically comprises:

[0042] After the cationic water-based polyurethane blend emulsion of the coated disperse dye and acrylate monomer obtained in step (3) is heated to 70-80° C., an initiator (accounting for 0.1-1% of the total mass of the acrylate monomer) is added, and the mixture is kept warm for 2-4 hours. After the acetone is removed under reduced pressure, a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product is obtained.

[0043] The second object of the present invention is to provide a polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product based on the above method.

[0044] The third object of the present invention is to provide a method for dyeing and hydrophobicizing polyester fabrics, wherein the fabrics are first immersed in an aqueous solution of the integrated product prepared by the above method, and then rolled and baked.

[0045] The fourth object of the present invention is to provide a colored hydrophobic fabric, which comprises the above-mentioned polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product, or is prepared by the above-mentioned dyeing and hydrophobic treatment method.

[0046] The present invention has the following beneficial effects:

[0047] 1. The present invention prepares a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product by wrapping a disperse dye and an acrylate monomer mixture with the prepared polyurethane, and then uses the active double bonds on the polyurethane chain to undergo free radical polymerization with the acrylate monomer, and applies it to the dyeing and water-repellent finishing of polyester fabrics.

[0048] 2. The polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product prepared by the present invention can realize the one-bath process of polyester fabric dyeing and water repellent finishing, avoiding the problem of long process flow and high energy consumption of conventional polyester fabric dyeing and water repellent finishing (first dyeing the fabric, then treating the dyed polyester with a water repellent finishing agent). The one-bath process of polyester fabric dyeing and water repellent finishing can shorten the production process, save water, improve production efficiency and reduce production costs.

[0049] 3. The polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product prepared by the present invention has self-emulsification, thereby avoiding the harm to the environment caused by the emulsifier dissolved in water due to the addition of an external emulsifier.

[0050] 4. The present invention adds dyes during the process of synthesizing the polyurethane-acrylate water repellent. During the dyeing and finishing process, the dyes are dyed onto the fibers and the water repellent forms a uniform coating on the surface of the fabric, thereby improving the consistency and stability of the product and solving the problem that the color of conventional polyester is easily changed after being dyed and then subjected to water repellent finishing.

[0051] 5. The present invention uses dye and water repellent together, which improves the fastness and durability of dyeing compared with the traditional water repellent post-dyeing treatment. After 50 times of home washing, the fabric contact angle is still higher than 130°, which has good water-resistant performance.

[0052] 6. The polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product prepared by the present invention can be used for full-color color matching. Since only the type of dye is changed during the product preparation process, the amount of dye in dyeing can be changed by changing the single amount of red, yellow and blue products while keeping the total amount of the integrated product in the fabric dyeing and finishing process unchanged. The color change law conforms to the change law of the CIE1976L*a*b* color system, and the color can be adjusted and matched as needed in actual production.

[0053] 7. The polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product prepared by the present invention has complementary structural advantages of polyurethane and acrylate, and the physical and mechanical properties, water resistance and thermodynamic properties of the finished fabric are improved; it avoids the environmental pollution and bioaccumulation toxicity problems caused by the traditional use of fluorine-containing water repellents. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 This is the static water contact angle diagram of the fabric treated in Example 1. DETAILED DESCRIPTION

[0055] The present invention is further described below in conjunction with specific examples. The examples are only used to explain the present invention and are not used to limit the scope of the present invention.

[0056] Detection method:

[0057] 1. Disperse dye diffusion: Accurately weigh 0.5g of dye sample, place in a 200mL beaker, add 5mL of 30℃ deionized water to make the dye slurry, and then add deionized water to make the total volume 100mL. Maintain the solution temperature at about 30℃ and stir for 5min. Spread 110mm medium-speed filter paper on a dry glass sheet, use a pipette to absorb 0.2ml of liquid disperse dye from each sample while stirring, make the pipette perpendicular to the middle of the filter paper, and keep the pipette droplet about 10mm away from the filter paper surface, drip the dye drop by drop, wait for the dye to penetrate completely, and then drip the next drop, so that the dye drips on the same position of the filter paper, and after drying naturally, compare and rate according to the filter paper penetration circle on the "Dye Diffusion Performance Rating Card".

[0058] 2. Low temperature dispersibility of disperse dyes: weigh 2.0g dye and 5mL 45℃ deionized water in a 250mL beaker, then dilute with deionized water to a total volume of 200mL, stir for 1min, and then adjust the pH value to 4.5-5.0 with 100g / L acetic acid solution. Then place the beaker in a super constant temperature water bath, heat to 70℃, keep warm and stir for 5min, and set aside. Connect and install the Buchner funnel, suction filter bottle (2500mL), buffer bottle (2500mL), and solubility dispersion insoluble tester. After adjusting the vacuum degree to 0.075MPa, place the funnel and stainless steel ring in 75℃ deionized water so that the funnel and stainless steel ring can be heated by hot water, and evacuate the water after 30s. The smooth side of the two filter papers faces up, and the 110mm fast filter paper is placed under the medium-speed filter paper. After the funnel is placed, it is pressed with a stainless steel aperture. Pour the 70℃ liquid disperse dye suspension into the funnel and start the vacuum pump and the timer of the test machine. When the filter paper turns from wet to dry, record the filtration time and close the vacuum valve, remove the filter paper, and wait for the medium-speed filter paper to dry. Compare the filter paper residue with the "Five-level Residue Card" for rating.

[0059] 3. High-temperature dispersibility of disperse dyes: Weigh 2.0g of dye and 5mL of 45℃ deionized water in a 250mL beaker, then dilute with deionized water to a total volume of 200mL, stir for 1min, and then adjust the pH value to 4.5-5.0 with 100g / L acetic acid solution. Place the dye solution in an infrared sample dyeing machine, heat it to 130℃ at 3℃ / min, then keep it warm for 30min, cool it to 90℃ at 4℃ / min, and prepare it for filtration. Connect and install the Buchner funnel, suction filter bottle (2500mL), buffer bottle (2500mL), and solubility dispersion insoluble matter tester. After adjusting the vacuum degree to 0.075MPa, place the funnel and stainless steel ring in 95℃ deionized water so that both the funnel and the stainless steel ring can be heated by hot water. The smooth sides of the two filter papers face up, and the 110mm fast filter paper is stacked under the medium-speed filter paper. After the funnel is placed, it is pressed with a stainless steel aperture. Pour the 85°C liquid disperse dye suspension in the reactor into the funnel and start the vacuum pump and the timer of the testing machine. When the filter paper turns from wet to dry, record the filtration time and close the vacuum valve, remove the filter paper, and wait for the medium-speed filter paper to dry. Compare the filter paper residue with the "Five-level Residue Card" for rating.

[0060] Embodiment 1:

[0061] Prepare the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product and finish the fabric according to the following steps:

[0062] Preparation of polyurethane-acrylate fluorine-free water repellent disperse dye integrated products:

[0063] Polyether diol (molecular weight 1000), diethanolamine (accounting for 6% of the total mass of polyurethane monomers), and dihydroxy small molecule chain extender 7-octene-1,2-diol containing carbon-carbon double bonds (accounting for 3% of the total mass of polyurethane monomers) were vacuum dried at 80°C for 3 to 4 hours to remove water.

[0064] According to the ratio of isocyanate to hydroxyl group of 1.1, polyether diol, olamine (accounting for 10% of the total olamine mass), dibutyltin dilaurate (accounting for 0.2% of the total monomer mass participating in the reaction) are slowly added dropwise at a temperature of 75°C under nitrogen protection; the -NCO value in the reaction system is determined by the di-n-butylamine method. When the theoretical value (theoretical residual amount of isocyanate ≤32%) is reached, the temperature is lowered to 45°C, and the remaining olamine dissolved in acetone (the mass ratio of acetone to olamine is 2:1), react for 1 hour (theoretical residual amount of isocyanate ≤12-16%); add 7-octene-1,2-diol, a small molecule chain extender containing carbon-carbon double bonds, and react for 1.5 hours (theoretical residual amount of isocyanate ≤8%) at a temperature of 60°C; add butanone oxime, a blocking agent (with a molar ratio of 1.2 to unreacted isocyanate), and block at 70°C until the -NCO content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate ≤0.5%) to obtain polyurethane;

[0065] A mixture of disperse dye (disperse red filter cake 153) and acrylate monomer (octadecyl acrylate) was added to 100g of the polyurethane prepared above (the amount of disperse dye accounted for 8% of the total mass of acrylate monomers, and the mass ratio of acrylate monomers to polyurethane monomers was 1:1); the temperature was lowered to 30-40°C, and glacial acetic acid (neutralization degree was 100%) was added as a neutralizer to adjust the reaction pH (pH=6-7), and the reaction was carried out for 0.5 hour; deionized water was slowly added under mechanical stirring (800r / min) for self-emulsification (the total mass of polyurethane monomer, acrylate monomer and disperse dye accounted for 20% of the total mass of the emulsion) to obtain a cationic waterborne polyurethane blended emulsion coated with disperse dye and acrylate monomer; after heating to 70°C, azobisisobutyramidine hydrochloride (accounting for 0.1% of the total mass of acrylate monomers) was added as an initiator, and the reaction was kept warm for 2 hours. After removing acetone under reduced pressure, a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product was obtained.

[0066] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0067] The above product was dispersed in water at 50g / L, and the bath ratio was 1:50 to prepare the finishing solution. After adding the fabric, the temperature was raised from room temperature to 130℃ at a rate of 2℃ / min, kept warm for 60min, and then cooled to 80℃ at a rate of 4℃ / min. After fully rinsing, it was dried at 105℃ for 5min and baked at 160℃ for 3min. The relevant parameters of the treated fabric are shown in Table 1.

[0068] Embodiment 2:

[0069] Prepare the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product and finish the fabric according to the following steps:

[0070] Preparation of polyurethane-acrylate fluorine-free water repellent disperse dye integrated products:

[0071] Polyester diol (molecular weight 200), N-ethyldiethanolamine (accounting for 10% of the total weight of the monomers used in the polyurethane prepolymer), and a dihydroxy small molecule chain extender containing a carbon-carbon double bond, 2,2-bishydroxymethylbutyric acid-3-hydroxy-2-(2-methacryloyloxy)-propyl ester (accounting for 6% of the total weight of the monomers) were vacuum dried at 90°C to remove water for 3 hours; polyester diol, olamine (accounting for 50% of the total olamine weight), and dibutyltin dilaurate (accounting for 0.2% of the total weight of the monomers involved in the reaction) were slowly added dropwise at a temperature of 85°C under nitrogen protection; di-n-butylamine was used to prepare the reaction mixture; The -NCO value in the reaction system is determined by the method. When the theoretical value (theoretical residual amount of isocyanate ≤32%) is reached, the temperature is lowered to 55°C, and the remaining alcohol amine dissolved in acetone is added (the mass ratio of acetone to alcohol amine is 2:1), and the reaction is carried out for 3 hours (theoretical residual amount of isocyanate ≤12-16%); the temperature is raised to 65°C, and a small molecule chain extender containing a carbon-carbon double bond is added, and the reaction is carried out for 3 hours (theoretical residual amount of isocyanate ≤8%); a blocking agent butyrimidine oxime (with a molar ratio of 1.5 to unreacted isocyanate) is added, and the end-capping is carried out at 75°C until the -NCO content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate ≤0.5%), and polyurethane is obtained;

[0072] The subsequent steps are the same as those in Example 1, i.e., a mixture of disperse dye (disperse red filter cake 153) and acrylate monomer (octadecyl acrylate) is added to the polyurethane (the amount of disperse dye accounts for 8% of the total mass of acrylate monomers, and the mass ratio of acrylate monomers to polyurethane monomers is 1:1); the temperature is lowered to 30-40°C, glacial acetic acid (neutralization degree is 100%) is added as a neutralizer, the reaction pH (pH=6-7) is adjusted, and the reaction is carried out for 0.5 hours; deionized water is slowly added under mechanical stirring (800r / min) for self-emulsification (the total mass of the monomer substrate accounts for 20% of the total mass of the liquid) to obtain a cationic aqueous polyurethane blend emulsion coated with disperse dye and acrylate monomer; after heating to 70°C, azobisisobutyramidine hydrochloride (accounting for 0.1% of the total mass of acrylate monomers) is added as an initiator, the reaction is kept warm for 2 hours, and after removing acetone under reduced pressure, a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product is obtained.

[0073] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0074] Same as Example 1: Polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product was used to treat polyester fabric. The relevant parameters of the treated fabric are shown in Table 2.

[0075] Embodiment 3:

[0076] Prepare the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product and finish the fabric according to the following steps:

[0077] Preparation of polyurethane-acrylate fluorine-free water repellent disperse dye integrated products:

[0078] Polyether diol (molecular weight 600), tert-butyl diethanolamine (accounting for 8% of the total mass of monomers used in polyurethane prepolymer), and dihydroxy small molecule chain extender 3-allyloxy-1,2-propylene glycol containing carbon-carbon double bonds (accounting for 5% of the total mass of monomers) were vacuum dried at 90°C for 3 hours; polyether diol, olamine (accounting for 30% of the total mass of olamines), and dibutyltin dilaurate (accounting for 0.2% of the total mass of monomers involved in the reaction) were slowly added dropwise at a temperature of 85°C under nitrogen protection according to the ratio of isocyanate to hydroxyl of 1.4; the -NCO value in the reaction system was determined by the di-n-butylamine method. , when the theoretical value is reached (theoretical residual amount of isocyanate is ≤32%), the temperature is lowered to 50°C, and the remaining alcohol amine dissolved in acetone is added (the mass ratio of acetone to alcohol amine is 2:1), and the reaction is carried out for 2 hours (theoretical residual amount of isocyanate is ≤12-16%); the temperature is raised to 65°C, and a small molecule chain extender containing a carbon-carbon double bond is added, and the reaction is carried out for 2 hours (theoretical residual amount of isocyanate is ≤8%); a blocking agent hydroxyethyl methacrylate (with a molar ratio of 1.3 to unreacted isocyanate) is added, and the end-capping is carried out at 75°C until the -NCO content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate is ≤0.5%), and a polyurethane is obtained;

[0079] The subsequent steps are the same as those in Example 1, i.e., a mixture of disperse dye (disperse red filter cake 153) and acrylate monomer (octadecyl acrylate) is added to the polyurethane (the amount of disperse dye accounts for 8% of the total mass of acrylate monomers, and the mass ratio of acrylate monomers to polyurethane monomers is 1:1); the temperature is lowered to 30-40°C, glacial acetic acid (neutralization degree is 100%) is added as a neutralizer, the reaction pH (pH=6-7) is adjusted, and the reaction is carried out for 0.5 hours; deionized water is slowly added under mechanical stirring (800r / min) for self-emulsification (the total mass of the monomer substrate accounts for 20% of the total mass of the liquid) to obtain a cationic aqueous polyurethane blend emulsion coated with disperse dye and acrylate monomer; after heating to 70°C, azobisisobutyramidine hydrochloride (accounting for 0.1% of the total mass of acrylate monomers) is added as an initiator, the reaction is kept warm for 2 hours, and after removing acetone under reduced pressure, a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product is obtained.

[0080] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0081] Same as Example 1: Polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product was used to treat polyester fabric. The relevant parameters of the treated fabric are shown in Table 2.

[0082] Embodiment 4:

[0083] Prepare the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product and finish the fabric according to the following steps:

[0084] Preparation of polyurethane-acrylate fluorine-free water repellent disperse dye integrated products:

[0085] The preparation of polyurethane is the same as in Example 1;

[0086] A mixture of disperse dye (disperse red filter cake 153) and acrylate monomer (octadecyl acrylate: methyl methacrylate: butyl acrylate = 2:1:1, molar ratio) is added to polyurethane (the amount of disperse dye accounts for 8% of the total mass of acrylate monomers, and the mass ratio of acrylate monomers to polyurethane monomers is 0.5:1); the temperature is lowered to 30-40°C, glacial acetic acid (neutralization degree is 120%) as a neutralizer is added, the reaction pH (pH = 6-7) is adjusted, and the reaction is carried out for 1 hour; deionized water is slowly added under mechanical stirring (2000r / min) for self-emulsification (the total mass of the monomer substrate accounts for 40% of the total mass of the liquid) to obtain a cationic waterborne polyurethane blend emulsion encapsulating disperse dye and acrylate monomer; after heating to 80°C, potassium persulfate (accounting for 1% of the total mass of the acrylate monomers) as an initiator is added, the reaction is kept warm for 4 hours, and after reducing the pressure to remove acetone, a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product is obtained.

[0087] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0088] The above products were used to prepare finishing liquid at 100g / L and bath ratio of 1:20. After adding the fabric, the temperature was raised from room temperature to 130℃ at a rate of 2℃ / min, kept warm for 30min, and then cooled to 80℃ at a rate of 4℃ / min. After fully rinsing, the fabric was dried at 105℃ for 5min and baked at 140℃ for 10min. The relevant parameters of the treated fabric are shown in Table 2.

[0089] Embodiment 5:

[0090] Prepare the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product and finish the fabric according to the following steps:

[0091] Preparation of polyurethane-acrylate fluorine-free water repellent disperse dye integrated products:

[0092] The preparation of polyurethane is the same as in Example 1;

[0093] A mixture of disperse dye (disperse red filter cake 153) and acrylate monomer (hexadecyl acrylate:methyl acrylate:hexyl acrylate=3:2:1, molar ratio) is added to polyurethane (the amount of disperse dye accounts for 8% of the total mass of acrylate monomers, and the mass ratio of acrylate monomers to polyurethane monomers is 0.8:1); the temperature is lowered to 30-40°C, glacial acetic acid (neutralization degree is 80%) is added as a neutralizer, the reaction pH (pH=6-7) is adjusted, and the reaction is carried out for 1 hour; deionized water is slowly added under mechanical stirring (2000r / min) for self-emulsification (the total mass of the monomer substrate accounts for 40% of the total mass of the liquid) to obtain a cationic waterborne polyurethane blend emulsion encapsulating disperse dye and acrylate monomer; after heating to 80°C, potassium persulfate (accounting for 0.5% of the total mass of the acrylate monomers) as an initiator is added, the reaction is kept warm for 3 hours, and after reducing the pressure to remove acetone, a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product is obtained.

[0094] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0095] The above product was used to prepare the finishing solution at 80g / L and the bath ratio was 1:50. After adding the fabric, the temperature was raised from room temperature to 130℃ at a rate of 2℃ / min, kept warm for 45min, and then cooled to 80℃ at a rate of 4℃ / min. After fully rinsing, it was dried at 105℃ for 5min and baked at 170℃ for 2min. The relevant parameters of the treated fabric are shown in Table 2.

[0096] Embodiment 6-8:

[0097] Prepare the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product and finish the fabric according to the following steps:

[0098] Preparation of polyurethane-acrylate fluorine-free water repellent disperse dye integrated products:

[0099] Only the amount of disperse dye was changed, and the rest was the same as in Example 1: the amount of disperse dye to the total mass of acrylate monomer was replaced to 2% (Example 6), 4% (Example 7), and 6% (Example 8), respectively.

[0100] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0101] Same as Example 1: Polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product was used to treat polyester fabric. The relevant parameters of the treated fabric are shown in Table 2.

[0102] Embodiment 9-10:

[0103] Prepare the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product and finish the fabric according to the following steps:

[0104] Preparation of polyurethane-acrylate fluorine-free water repellent disperse dye integrated products:

[0105] Only the type of dye was changed, and the rest was the same as in Example 1. The dyes were disperse yellow filter cake 211 (Example 9) and disperse blue filter cake 183:1 (Example 10).

[0106] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0107] Same as Example 1: Polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product was used to treat polyester fabric. The relevant parameters of the treated fabric are shown in Table 3.

[0108] Embodiment 11-14:

[0109] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0110] According to the following formula, the integrated products prepared in Example 1, Example 9 and Example 10 were used to treat polyester fabric (corresponding to Examples 11-14, respectively), and the finishing liquid was prepared with a bath ratio of 1:50.

[0111]

[0112]

[0113] After adding the fabric, the temperature was raised from room temperature to 130°C at a rate of 2°C / min, kept at that temperature for 60 minutes, and then cooled to 80°C at a rate of 4°C / min. After being fully rinsed, the fabric was dried at 105°C for 5 minutes and baked at 160°C for 3 minutes. The relevant parameters of the treated fabric are shown in Table 3.

[0114] Comparative Example 1:

[0115] Without adding dye, the other steps were the same as in Example 1 to prepare a water repellent.

[0116] The polyester fabric was treated according to Example 1. The relevant parameters of the treated fabric are shown in Table 1.

[0117] Comparative Example 2:

[0118] Polyurethane was prepared in the same manner as in Example 1, and disperse dye (disperse red filter cake 153) was added to the polyurethane (the amount of disperse dye accounted for 8% of the total mass of the acrylate monomer in Example 1); the temperature was lowered to 30-40° C., glacial acetic acid (neutralization degree was 100%) was added as a neutralizer, the reaction pH was adjusted to pH=6-7, and the reaction was allowed to react for 0.5 hour; deionized water was slowly added under mechanical stirring (800 r / min) for self-emulsification (the total mass of the monomer substrate accounted for 20% of the total mass of the liquid) to obtain a cationic aqueous polyurethane emulsion coated with disperse dye.

[0119] The polyester fabric was treated according to Example 1. The relevant parameters of the treated fabric are shown in Table 1.

[0120] Comparative Example 3:

[0121] Conventional polyester fabric is dyed first and then water-repellent finishing process:

[0122] The dye liquor was prepared with 2% of commercial disperse red 153 dye to the fabric weight at a bath ratio of 1:50. After adding the fabric, the temperature was raised from room temperature to 130°C at a rate of 2°C / min, kept at that temperature for 60 minutes, and then cooled to 80°C at a rate of 4°C / min. After being fully rinsed, it was dried at 105°C for 5 minutes and baked at 160°C for 3 minutes.

[0123] The water repellent prepared in Control Example 1 was used to prepare a finishing solution at 50 g / L and a bath ratio of 1:50. The fabric was immersed in the finishing solution and then squeezed out at a squeeze rate of 130%, pre-baked at 105°C for 2 minutes, and then baked at 160°C for 3 minutes. The relevant parameters of the treated fabric are shown in Table 1.

[0124] Comparative Example 4:

[0125] Conventional disperse dyes and water repellent one-bath process for treating polyester fabrics:

[0126] Prepare a finishing solution of commercial disperse red 153 dye and the water repellent prepared in control example 1, wherein the amount of commercial disperse red 153 dye used is the amount of dye used in control example 3, the water repellent is 50g / L, and the finishing solution bath ratio is 1:50. After adding the fabric, heat it from room temperature to 130℃ at a rate of 2℃ / min, keep it warm for 60min, then cool it to 80℃ at a rate of 4℃ / min, rinse it thoroughly, dry it at 105℃ for 5min, and bake it at 160℃ for 3min. The relevant parameters of the treated fabric are shown in Table 1.

[0127] Comparative Example 5:

[0128] Prepare the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product and finish the fabric according to the following steps:

[0129] Preparation of polyurethane-acrylate fluorine-free water repellent disperse dye integrated products:

[0130] Only the amount of disperse dye was changed, and the rest was the same as in Example 1: the amount of disperse dye accounted for 20% of the total mass of the acrylate monomer.

[0131] Polyurethane-acrylate fluorine-free water repellent disperse dye integrated product for treating polyester fabrics:

[0132] Same as Example 1: Polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product was used to treat polyester fabric. The relevant parameters of the treated fabric are shown in Table 1.

[0133] Table 1 Relevant parameters of treated fabrics

[0134]

[0135] Note: The washability test is carried out according to the 2A test standard in AATCC Test Method 61-2010 "Color Fastness to Washing". One AATCC 2A soap wash is equivalent to five washes in an ordinary household washing machine. A contact angle of 0 means that water droplets penetrate into the fabric, and - means that the fabric cannot be treated, so there is no data for this item.

[0136] Comparing Example 1 and Control Example 1 in Table 1, after the fabric is finished with the polyurethane-acrylate fluorine-free water repellent disperse dye integrated product designed by the present invention, the fabric has good water repellency, hydrostatic pressure resistance, softness, abrasion resistance, moisture permeability, and pilling resistance, and is also dyed. After the fabric is finished with the product (Control Example 1) in which no dye is added during the preparation process, the fabric has water repellency, hydrostatic pressure resistance, softness, abrasion resistance, moisture permeability, and pilling resistance, but has no color (Integ value is 0.23, indicating that the fabric is basically white).

[0137] Comparing Example 1 and Control Example 2, only the dye filter cake was added without the acrylate monomer during the preparation of the integrated product, and the product could only color the fabric but could not impart water-repellent properties to the fabric.

[0138] Comparing Example 1 and Comparative Example 3, the polyurethane-acrylate fluorine-free water repellent disperse dye integrated product designed by the present invention completes the one-bath processing of dyeing and water repelling, and can achieve the same dyeing effect and water repellency, hydrostatic pressure resistance, softness, wear resistance, moisture permeability, and anti-pilling property as the traditional dyeing first and then water repelling (separate bath and separate steps) process. The one-bath method for dyeing and water repellent finishing of polyester fabric can shorten the production process, save water, improve production efficiency, and reduce production costs. The product designed by the present invention can avoid the problems of long process flow and high energy consumption of conventional polyester fabric dyeing and water repellent finishing.

[0139] Comparing Example 1 and Control Example 4, the polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product designed by the present invention can complete dyeing and water repellent one-bath processing, while commercial disperse dyes (anionic) cannot be used with water repellents (cationic) in one bath (Control Example 4). The one-bath process of the two will cause the precipitation of disperse dyes and water repellent polymers, and the dyeing and water repellent finishing of the fabric cannot be completed.

[0140] Comparing Example 1 and Control Example 5, the polyurethane-acrylate fluorine-free water repellent disperse dye integrated product designed by the present invention needs to control the amount of disperse dye. If the amount of dye is too large, the polyurethane cannot form an effective coating for the dye, the disperse dye precipitates during the preparation process, and the integrated product cannot be obtained, making it difficult to complete the dyeing and water-repellent finishing of the fabric.

[0141] Product washing fastness: From the test results of fabric water resistance, it can be seen that after the fabric finished in Example 1 is washed with water equivalent to 50 times in a household washing machine, the static water contact angle (hydrophobicity) is higher than 130°, which shows that the fabric has high water fastness after being finished with the integrated product prepared by the present invention.

[0142] Repeatability of product hydrophobic effect: The fabric treated according to Example 1 was treated in batches 10 times, and the static water contact angle of the treated fabric each time was in the range of 150±2°. From the contact angle data, it can be seen that the hydrophobic effect of the treated fabric is highly repeatable. Figure 1 .

[0143] Table 2 Relevant parameters of treated fabrics

[0144]

[0145] Note: The washing test is carried out according to the 2A test standard in AATCC Test Method 61-2010 "Color Fastness to Washing". One soap wash according to the AATCC 2A standard is equivalent to five washes in an ordinary household washing machine.

[0146] Product hydrophobic effect: Compared with Examples 1-8 in Table 2, the polyurethane-acrylate fluorine-free water repellent disperse dye integrated products designed by the present invention all have good water repellency, hydrostatic pressure resistance, softness, wear resistance, moisture permeability, and anti-pilling properties. The color Integ values ​​of Examples 1-5 are similar (with the same dye content) and are greater than the color Integ values ​​of Examples 6-8, indicating that fabrics with different dyeing depths can be obtained by controlling the dye content during the preparation of the integrated product.

[0147] Product washing fastness: From the test results of fabric water resistance, it can be seen that after the fabrics finished in Examples 1-8 were washed with water equivalent to 50 times in a household washing machine, the static water contact angle (hydrophobicity) was higher than 130°, which shows that the fabrics have high water fastness after being finished with the integrated product prepared by the present invention.

[0148] Table 3 Relevant parameters of treated fabrics

[0149]

[0150] Note: The washing test is carried out according to the 2A test standard in AATCC Test Method 61-2010 "Color Fastness to Washing". One soap wash according to the AATCC 2A standard is equivalent to five washes in an ordinary household washing machine.

[0151] Product hydrophobic effect: Comparing Example 1 and Examples 9-14 in Table 3, the polyurethane-acrylate fluorine-free water repellent disperse dye integrated products designed by the present invention all have good water repellency, hydrostatic pressure resistance, softness, wear resistance, moisture permeability, and anti-pilling properties. The color Integ value of Example 1 (dispersed red filter cake 153) is 23.93, the color Integ value of Example 9 (dispersed yellow filter cake 211) is 17.92, and the color Integ value of Example 10 (dispersed blue filter cake 183:1) is 8.23, indicating that by changing the type of disperse dyes in the preparation process of the integrated product, dyed fabrics of different colors can be obtained. Examples 11-14 show that when integrated products containing different color dyes are mixed and used, dyed fabrics with a color matching effect can be obtained.

[0152] Product washing fastness: From the test results of fabric water resistance, it can be seen that after the fabrics finished in Examples 9-14 and Example 1 were washed with water equivalent to 50 times in a household washing machine, the static water contact angle (hydrophobicity) was higher than 130°, and the fabrics had high hydrophobicity. This shows that after the fabrics were finished by changing the dye types and mixing the integrated products prepared by the present invention during the preparation process, the fabrics had high washing fastness.

[0153] Comparative Example 6

[0154] Configure different dye systems:

[0155] Dye system 1: Disperse red filter cake 153 The diffusibility, low-temperature dispersibility and high-temperature dispersibility of the dye were tested according to the test methods for disperse dye diffusibility, disperse dye low-temperature dispersibility and disperse dye high-temperature dispersibility. The results are shown in Table 4.

[0156] Dye system 2: Disperse red filter cake 153 and perchlorate were mixed in a mass ratio of 1:1, ground in a ball mill (the mass ratio of dye to zirconium beads was 1:10, and the solid content of dye was 50%) for 8 hours, dried and ground into powder. The obtained powder product was tested for the diffusibility, low-temperature dispersibility and high-temperature dispersibility of the dye according to the test methods for disperse dye diffusibility, disperse dye low-temperature dispersibility and disperse dye high-temperature dispersibility. The results are shown in Table 4.

[0157] Dye system 3: Disperse red filter cake 153 and octadecyl trimethyl ammonium chloride were mixed in a mass ratio of 1:1, ground in a ball mill (the mass ratio of dye to zirconium beads was 1:10, and the solid content of dye was 50%) for 8 hours, dried and ground into powder. The obtained powder product was tested for the diffusibility, low-temperature dispersibility and high-temperature dispersibility of the dye according to the test methods for disperse dye diffusibility, disperse dye low-temperature dispersibility and disperse dye high-temperature dispersibility. The results are shown in Table 4.

[0158] Dye system 4: Disperse red filter cake 153 was mixed with octadecyl trimethyl ammonium chloride and perchlorate in a mass ratio of 1:0.5:0.5, ground in a ball mill (the mass ratio of dye to zirconium beads was 1:10, and the solid content of dye was 50%) for 8 hours, and ground into powder after drying. The obtained powder product was tested for the diffusibility, low-temperature dispersibility and high-temperature dispersibility of the dye according to the test methods for disperse dye diffusibility, disperse dye low-temperature dispersibility and disperse dye high-temperature dispersibility, and the results are shown in Table 4.

[0159] Dye system 5: Commercial disperse red 153 dye (anionic type) was used to test the diffusivity, low-temperature dispersibility and high-temperature dispersibility of the dye according to the test methods for disperse dye diffusivity, disperse dye low-temperature dispersibility and disperse dye high-temperature dispersibility. The results are shown in Table 4.

[0160] Dye system 6 (Example 1): The polyurethane-acrylate fluorine-free water repellent disperse dye integrated product prepared in Example 1 was used to test the diffusivity, low-temperature dispersibility and high-temperature dispersibility of the dye according to the test methods for disperse dye diffusivity, disperse dye low-temperature dispersibility and disperse dye high-temperature dispersibility. The results are shown in Table 4.

[0161] Table 4 Dispersion properties of dye system

[0162]

[0163]

[0164] The diffusion of disperse dye system is divided into 5 levels. The larger the number, the better the diffusion performance of the dye, which is conducive to fabric dyeing. The filtration time of low-temperature dispersibility and high-temperature dispersibility of dye is divided into 5 levels, namely A (0-24s), B (25-49s), C (50-74s), D (75-120s), and E (greater than 120s). The longer the filtration time, the larger the dye particles, which is not conducive to dyeing. The residue level of low-temperature dispersibility and high-temperature dispersibility of dye is divided into 1 (worst), 2 (poor), 3 (medium), 4 (good), and 5 (excellent). The more residues, the lower the level. The residues indicate that the dye particles are too large, which is not conducive to dyeing. From the diffusibility, low-temperature dispersibility and high-temperature dispersibility levels of the dye system in Table 4, it can be seen that the disperse dye filter cake (dye system 1) without any surfactant has the worst diffusibility, low-temperature dispersibility and high-temperature dispersibility, and the dye is suspended in water, and fabric dyeing cannot be performed; the disperse dye prepared by using nonionic surfactant (dye system 2), cationic surfactant (dye system 3), and nonionic and cationic surfactant compound (dye system 4) as dispersants respectively, its diffusibility, low-temperature dispersibility and high-temperature dispersibility are all poor, and the dye particles are too large to complete fabric dyeing; commercial dyes (dye system 5) and integrated products (dye system 6) have excellent diffusibility, low-temperature dispersibility and high-temperature dispersibility, and can be used for polyester dyeing. Comparison of dye systems 1-5 shows that the disperse dye filter cake needs to be dispersed by anionic dispersants to obtain good diffusibility, low-temperature dispersibility and high-temperature dispersibility. Comparison of dye systems 5-6 shows that the integrated product prepared by the present invention is cationic but has excellent diffusibility, low-temperature dispersibility and high-temperature dispersibility as anionic commercial disperse dyes.

Claims

1. A method for preparing a polyurethane-acrylate fluorine-free water repellent disperse dye integrated product, characterized in that: The preparation method comprises: (1) A polyurethane system is prepared by using polymer polyols, diisocyanates, amine compounds, dihydroxy small molecule chain extenders containing carbon-carbon double bonds as polyurethane monomers, and end-capping agents; (2) adding disperse dye filter cake and acrylate monomer to the obtained polyurethane system, mixing well and then adding a neutralizing agent; (3) adding water for self-emulsification to obtain a cationic waterborne polyurethane emulsion encapsulating disperse dyes and acrylate monomers; (4) adding an initiator, mixing and reacting, and obtaining a polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product; The step (1) specifically includes: The polymer polyol, 6-10% of the total mass of the amine compounds, and 3-6% of the total mass of the monomer containing a carbon-carbon double bond dihydroxy small molecule chain extender are vacuum dried at 80-90°C for 3-4 hours to remove water; according to the ratio of isocyanate to hydroxyl group of 1.1-1.6, the polymer polyol, 10-50% of the total mass of the amine compounds, and 0.2% of the total mass of the monomers participating in the reaction are slowly added with diisocyanate at a temperature of 75-85°C under nitrogen protection; the -NCO value in the reaction system is determined by the di-n-butylamine method, and when After the theoretical residual amount of isocyanate reaches ≤32%, the temperature is lowered to 45-55°C, and the residual alcohol amine compound dissolved in acetone is added, and the reaction is carried out for 1-3 hours, and the theoretical residual amount of isocyanate is ≤12-16%; the temperature is raised to 60-65°C, a small molecule chain extender containing a carbon-carbon double bond is added, and the reaction is carried out for 1.5-3 hours, and the theoretical residual amount of isocyanate is ≤8%; a blocking agent with a molar ratio of 1.2-1.5 to the unreacted isocyanate is added, and the end-capping is carried out at 70-75°C until the -NCO content in the reaction system reaches the theoretical value of the theoretical residual amount of isocyanate ≤0.5%, and a polyurethane system is obtained; In the step (2), the disperse dye accounts for 0.01-15% of the total mass of the acrylate monomer, and the mass ratio of the acrylate monomer to the polyurethane monomer is (0.5-1):

1.

2. The method according to claim 1, characterized in that The alcoholamine compound in step (1) is ,or Wherein R1, R2, R4, and R5 are independently substituted or unsubstituted alkyl, phenyl, or cycloalkyl; R3, R6, and R7 are independently hydrogen, substituted or unsubstituted alkyl, phenyl, or cycloalkyl.

3. The method according to claim 1, characterized in that The structure of the dihydroxy small molecule containing a carbon-carbon double bond in step (1) is as follows: Wherein, R8 is selected from chain alkyl, phenyl, cycloalkyl, acyl, ester, carbonyl and ether groups having any number of carbon atoms; R9 is selected from chain alkyl, phenyl and cycloalkyl groups having C2 to C18 carbon atoms.

4. The method according to claim 1, characterized in that: In the step (1), the end-capping agent is one of hydroxyethyl acrylate, hydroxyethyl methacrylate, butanone oxime, acetone oxime, cyclohexanone oxime, methyl ethyl ketone oxime, n-heptanal oxime, dimethylglyoxime, and tetramethylcyclobutanedione monoxime, or a mixture of several of them.

5. A polyurethane-acrylate type fluorine-free water repellent disperse dye integrated product prepared by the method according to any one of claims 1 to 4.

6. A method for dyeing and water-repellent treatment of fabrics, characterized in that: The method comprises firstly immersing the fabric in an aqueous solution containing the product according to claim 5, and then pad-baking.

7. A colored hydrophobic fabric, characterized in that: The fabric comprises the polyurethane-acrylate fluorine-free water repellent disperse dye integrated product of claim 5, or is prepared by the fabric dyeing and water repellent treatment method of claim 6.

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