A finishing agent for fabric dyeing-water repellent one-bath treatment and its application

Abstract

The present invention discloses a fabric dyeing-water repellent one-bath treatment finishing agent and its application, and belongs to the field of environmentally friendly polymer technology. The present invention is based on the compound use of a specific cationic disperse dye and a cationic fluorine-free water repellent agent to prepare a fabric dyeing-water repellent one-bath treatment finishing agent; the finishing agent can be used in one bath, avoiding the conventional polyester fabric dyeing and water repellent finishing usually using a 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, which can shorten the production process, save water sources, improve production efficiency, and reduce production costs. The fabric prepared by the dyeing-water repellent one-bath treatment finishing agent of the present invention has good water repellency, hydrostatic pressure resistance, softness, wear resistance, moisture permeability, and anti-pilling; the full color spectrum can be achieved without changing the concentration of the water repellent; the finished fabric is equivalent to 50 times of home washing, and the contact angle is still higher than 130°, with good water washing resistance.

Description

Technical Field

[0001] The invention relates to a finishing agent for fabric dyeing-water repellent one-bath treatment and application thereof, belonging to the technical field of environmentally friendly polymers. Background Art

[0002] Polyester fabrics are favored by consumers for their high breaking strength, high modulus, durability, wrinkle resistance, no ironing, no deformation, and no fear of mold and insects. They are the most popular synthetic fibers. Since the main chain of polyester macromolecules is a repeating unit of ethylene terephthalate, the linear coplanarity of the molecules is good, the concave and convex parts on adjacent macromolecules are easy to embed each other, the structure is compact, and there is a lack of hydrophilic groups and active groups in the structure, resulting in low fiber swelling and low reactivity in water. Therefore, polyester needs to be colored with disperse dyes with a molecular structure close to it and a smaller molecular weight. Disperse dyes themselves are insoluble in water and rely on surfactants for dispersion. Since cationic surfactants are not as good as anionic surfactants in dispersibility and are expensive, anionic surfactants are often used commercially to prepare disperse dyes that can be stably dispersed in the water phase.

[0003] Functional fabrics are popular among consumers. For polyester, which is mainly used for external use, the water-repellent function has attracted attention due to its wide range of daily needs. The water-repellent function of fabrics is obtained by finishing with water-repellents. Commonly used water-repellents 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 they are harmful to the environment to a certain extent. Long-term use will cause siliconization of the material surface 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-repellent and anti-fouling effects, but they have great bioaccumulation and toxicity during synthesis and use, which has a negative impact on the ecological environment. Long-chain aliphatic hydrocarbon water-repellents have high water-repellent properties, but long-chain aliphatic hydrocarbon water-repellents are not resistant to washing and have defects such as hot stickiness and cold brittleness, poor flexibility, and solvent resistance when used. Polyurethane is a polymer compound containing carbamate repeating units on the main chain of the molecule, which has the advantages of low temperature resistance, good flexibility, and high bonding strength. The organic combination of polyurethane and long-chain aliphatic hydrocarbons can bring out the advantages of both. Conventional water repellents are prepared by adding emulsifiers. The added emulsifiers will affect the water repellent effect of the water repellent. At the same time, they are soluble in water and cause 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. 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. Therefore, most commercially available water repellents are cationic products.

[0004] Polyester fabric dyeing and water repellent finishing usually adopts the two-bath method, that is, the fabric is first dyed, and then the dyed polyester is treated with a water repellent finishing agent. The process is long and consumes a lot of water, labor and energy. The main reason for adopting the two-bath 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 view of the above problems, in order to shorten the polyester fabric coloring and water-repellent finishing process, reduce water consumption, labor consumption and energy consumption, and broaden the application scope and practical application performance of waterborne polyurethane-acrylate fluorine-free water repellent, the present invention constructs a cationic disperse dye and a fluorine-free water repellent. The present invention adopts polymer polyol, diisocyanate, olamine compound, dihydroxy small molecule containing carbon-carbon double bond and end-capping agent to prepare polyurethane; the polyurethane is used as a dispersing aid to prepare cationic disperse dye and cationic fluorine-free water repellent. The prepared cationic disperse dye and cationic fluorine-free water repellent can be mixed and used in any proportion, and polyester fabric can be treated in one bath to achieve fabric coloring and water-repellent finishing.

[0006] The first object of the present invention is to provide a finishing agent for fabric dyeing-water repellent one-bath treatment, comprising a cationic disperse dye and a cationic fluorine-free water repellent;

[0007] Among them, cationic disperse dyes and cationic fluorine-free water repellents are prepared by the following methods:

[0008] (1) using polymer polyols, diisocyanates, amine compounds, dihydroxy small molecules containing carbon-carbon double bonds as polyurethane monomers and a capping agent to prepare polyurethane;

[0009] (2) adding disperse dye filter cake to a portion of polyurethane, adding a neutralizing agent, and then adding water for self-emulsification to prepare a liquid cationic disperse dye;

[0010] (3) After adding acrylate monomers to the remaining polyurethane, a neutralizing agent is added, and then water is added for self-emulsification, and the temperature is raised under the action of an initiator to prepare a cationic fluorine-free water repellent.

[0011] In one embodiment of the present invention, the mass ratio of the cationic disperse dye to the cationic fluorine-free water repellent is 2:(10-100); further, 2:(20-50) may be selected; specifically, 2:25, 2:30, or 2:40 may be selected.

[0012] 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.

[0013] 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.

[0014] In one embodiment of the present invention, the structure of the alcoholamine compound in step (1) is as follows:

[0015] or

[0016] 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.

[0017] 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.

[0018] In one embodiment of the present invention, the alcoholamine compound in step (1) accounts for 6-10% of the total mass of the polyurethane monomer.

[0019] 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:

[0020] or HO-R 10 -C=CR 11 -OH

[0021] Among them, R8, R9, R 10 , R 11 Selected from chain alkyl groups having any number of carbon atoms, phenyl groups, cycloalkyl groups, acyl groups, ester groups, carbonyl groups, and ether groups.

[0022] In one embodiment of the present invention, the acyl structural formula is as follows:

[0023]

[0024] Wherein m and n are respectively and independently natural numbers ranging from 1 to 10.

[0025] In one embodiment of the present invention, the ester group structural formula is as follows:

[0026]

[0027] Wherein a and b are independently natural numbers from 1 to 10.

[0028] In one embodiment of the present invention, the carbonyl structural formula is as follows:

[0029]

[0030] Wherein c and d are respectively and independently natural numbers from 1 to 10.

[0031] In one embodiment of the present invention, the ether group structural formula is as follows:

[0032]

[0033] Wherein, e and f are respectively and independently natural numbers from 1 to 10.

[0034] 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)- 2-(3-isocyanatomethyl)-3,5,5-trimethylcyclohexylcarbamoyloxy)acrylate, ethyl 2-(3-isocyanatomethyl)-3,5,5-trimethylcyclohexylcarbamoyloxy)acrylate, 3-hexene-2,5-diol, trans-3-hexene-2,5-diol, 1,4-dihydroxy-2-butene, 2,5-dihydroxyhex-3-enal, 2,3-dimethyl-2-butene-1,4-diol, 2-pentene-1,4-diol, 4-methyl-2-ene-1,4-diol.

[0035] In one embodiment of the present invention, the dihydroxy small molecule chain extender containing carbon-carbon double bonds in step (1) accounts for 1 to 10% of the total mass of the polyurethane monomer.

[0036] 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.

[0037] In one embodiment of the present invention, the end-capping agent in (1) comprises any one of the following or a mixture of several thereof: butanone oxime, butyrimidine oxime, acetone oxime, formaldehyde oxime, bromophenol oxime, cyclohexanone oxime, n-heptanaldoxime, dimethylglyoxime, tetramethylcyclobutanedione monoxime.

[0038] 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.

[0039] In one embodiment of the present invention, the mass ratio of the disperse dye filter cake to the polyurethane used in step (2) is (3-0.01):1; further (3-1):1, and the degree of neutralization is 80%-120%.

[0040] In one embodiment of the present invention, the disperse dye filter cake in the self-emulsification in step (2) accounts for 1% to 40% of the total mass of the liquid after the self-emulsification, and more preferably 10% to 30% of the total mass of the liquid after the self-emulsification.

[0041] In one embodiment of the present invention, the mass ratio of the acrylate monomer to the polyurethane used in step (3) is (0.5-2):1; more preferably (0.5-1):1.

[0042] In one embodiment of the present invention, the initiator in step (3) includes one or more of azobisisobutyronitrile, azobisisoheptylnitrile, azobisisobutyramidine hydrochloride, potassium persulfate, ammonium persulfate, and dibenzoyl peroxide.

[0043] In one embodiment of the present invention, the amount of the initiator used in step (3) is 0.1-1% of the total mass of the acrylate monomers.

[0044] In one embodiment of the present invention, in the self-emulsification in step (3), the total mass of the cationic water repellent monomer substrate used accounts for 15% to 40% of the mass of the liquid.

[0045] In one embodiment of the present invention, the neutralizing agent in steps (2) and (3) includes one or more of glacial acetic acid, hydrochloric acid, lactic acid, and dimethylmercaptopropionic acid.

[0046] In one embodiment of the present invention, the degree of neutralization in steps (2) and (3) is 80% to 120%.

[0047] In one embodiment of the present invention, the preparation method of polyurethane in step (1) specifically comprises:

[0048] The polymer polyol, olamine (accounting for 6-10% of the total mass of the monomers used in the polyurethane prepolymer), and a dihydroxy small molecule chain extender containing a carbon-carbon double bond (accounting for 1-10% of the total mass of the monomers) are vacuum dried at 80-90° C. to remove water for 3-4 hours; diisocyanate is slowly added dropwise to a mixture of the polymer polyol, olamine (accounting for 0.01-50% 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) at a temperature of 75-85° C. under nitrogen protection, with the ratio of isocyanate to hydroxyl being 1.1-1.6; the reaction is determined by the di-n-butylamine method. When the -NCO value in the system reaches the theoretical value (theoretical residual amount of isocyanate is ≤32%), the temperature is lowered to 45-55° C., and the remaining alcohol amine dissolved in acetone is added to react for 1-3 hours (theoretical residual amount of isocyanate is ≤12-16%); a small molecule chain extender containing a carbon-carbon double bond is added to react for 1.5-3 hours (theoretical residual amount of isocyanate is ≤8%); the temperature is raised to 70-75° C., a blocking agent (with a molar ratio of 1.1-1.5 to unreacted isocyanate) is added to block the reaction until the -NCO content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate is ≤0.5%), thereby obtaining a polyurethane.

[0049] In one embodiment of the present invention, the preparation method of the cationic disperse dye in step (2) specifically comprises:

[0050] The prepared polyurethane is taken, and an acetone solution of a disperse dye filter cake is added at 50° C. (the mass ratio of the disperse dye filter cake to the used polyurethane is (3-1):1), and after being uniformly stirred, a neutralizer (neutralization degree is 80%-120%) is added at 30-40° C., and the reaction pH (pH=5-6) is adjusted, and the reaction is carried out for 0.5-1 hour; deionized water is slowly added under mechanical stirring (800-2000 r / min) for self-emulsification (the disperse dye filter cake accounts for 10%-30% of the total mass of the liquid), and the acetone is removed under reduced pressure to obtain a cationic disperse dye.

[0051] In one embodiment of the present invention, the method for preparing the cationic fluorine-free water repellent in step (3) specifically comprises:

[0052] The prepared polyurethane is taken, a neutralizer (neutralization degree is 80% to 120%) is added at 30 to 40° C., the reaction pH (pH=5 to 6) is adjusted, and the reaction is carried out for 0.5 to 1 hour; an acrylate monomer (the mass ratio of the acrylate monomer to the polyurethane used is (0.5 to 1):1) is added, and the mixture is stirred evenly; deionized water is slowly added for self-emulsification (the total mass of the monomer substrate used accounts for 15% to 40% of the mass of the liquid) under stirring by a high-speed disperser (5000 to 8000 r / min), acetone is removed under reduced pressure, the mixture is heated to 70 to 80° C., an initiator (accounting for 50 to 70% of the total mass of the initiator, and the total initiator accounts for 0.1 to 1% of the total mass of the acrylate monomer) is added, the mixture is heated for reaction for 2 to 3 hours, the remaining initiator is added, the mixture is heated for reaction for 1 to 2 hours, the temperature is lowered and the material is discharged, and a cationic polyurethane-acrylate fluorine-free water repellent is obtained.

[0053] The second object of the present invention is to provide a polyester fabric dyeing-water repellent one-bath treatment method, the method is to disperse the above-mentioned fabric dyeing-water repellent one-bath treatment finishing agent in water to obtain a corresponding finishing liquid, and then treat the fabric and bake it.

[0054] The third object of the present invention is to provide a colored hydrophobic fabric, which is prepared by the one-bath treatment method.

[0055] The present invention has the following beneficial effects:

[0056] 1. The polyurethane prepared in the present invention is used to prepare cationic disperse dyes and cationic fluorine-free water repellents, which can be used for fabric dyeing and water repellent one-bath treatment, and can give the fabric good water repellency while maintaining good dyeing performance.

[0057] 2. The preparation of cationic disperse dyes by the present invention avoids the problem that traditional anionic disperse dyes cannot be used with textile water repellents in one bath. The mixed use of cationic disperse dyes and the prepared cationic fluorine-free water repellent avoids the problems of long process flow and high energy consumption caused by the conventional polyester fabric dyeing and water repellent finishing usually using a two-bath method (first dyeing the fabric, then treating the dyed polyester with a water repellent finishing agent). The one-bath method for polyester fabric dyeing and water repellent finishing can shorten the production process, save water, improve production efficiency, and reduce production costs.

[0058] 3. The present invention prepares cationic disperse dyes and cationic fluorine-free water repellents for mixed use. While keeping the amount of water repellent unchanged, the amount of cationic disperse dyes can be changed to achieve a change in fabric color depth; mixing cationic disperse dyes can achieve a change in fabric color. Color matching can be performed as needed in actual production.

[0059] 4. The present invention uses oxime organic compounds to block the isocyanate groups of polyurethane at the ends of the polyurethane, which can undergo a deblocking reaction at a certain temperature, so that the isocyanate groups exposed at the outer ends react with the active hydrogen groups on the fabric, and the water repellent and the fabric are cross-linked through chemical bonds, thereby solving the problem of poor water washing fastness of long carbon chain water repellents.

[0060] 5. The cationic fluorine-free water repellent prepared by the present invention avoids the environmental pollution and bioaccumulation toxicity problems caused by the use of fluorine-containing water repellents. The fabric after finishing has excellent washing resistance and can still maintain a high water repellency after multiple washings. DETAILED DESCRIPTION

[0061] 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.

[0062] The detection method involved in the present invention is:

[0063] 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".

[0064] 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.

[0065] 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.

[0066] Embodiment 1:

[0067] Prepare cationic disperse dyes and cationic fluorine-free water repellents and finish fabrics according to the following steps:

[0068] Preparation of polyurethane:

[0069] Polyether diol (molecular weight 600), tert-butyl diethanolamine (accounting for 8% of the mass of polyurethane monomer), dihydroxy small molecule chain extender pentaerythritol diacrylate containing carbon-carbon double bonds (accounting for 3% of the total mass of polyurethane monomer) were vacuum dried at 85°C to remove water for 4 hours. According to the molar ratio of isocyanate to hydroxyl group of 1.1, polyester diol and olamine (accounting for 20% of the total mass of olamine) were added with dibutyltin dilaurate (accounting for 0.2% of the total mass of monomers involved in the reaction) and isophorone diisocyanate was slowly added dropwise at 75°C under nitrogen protection. The -NCO value in the reaction system was determined by the di-n-butylamine method. When the theoretical value (theoretical residual amount of isocyanate ≤32%) was reached, the next step was carried out; the temperature was lowered to 45°C, and the remaining tert-butyl diethanolamine dissolved in acetone (acetone and olamine mass ≤32%) was added. The ratio is 2:1), and the -NCO content in the reaction system is measured to reach the theoretical value (theoretical residual amount of isocyanate ≤12%); a small molecule chain extender containing a carbon-carbon double bond is added at a temperature of 65°C, and the next step is carried out after the -NCO% content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate ≤8%); the temperature is then raised to 70°C, and a blocking agent butanone oxime is added to block the extended polyurethane until the -NCO content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate ≤0.5%), and the polyurethane blocking is completed to obtain the polyurethane.

[0070] Preparation of cationic disperse dyes:

[0071] Take 100g of the polyurethane prepared above, add the acetone solution of the disperse dye filter cake at 50°C (the mass ratio of the disperse red filter cake 153 to the polyurethane used is 3:1, and the mass ratio of the disperse dye filter cake to the acetone used is 10:1), stir evenly, add glacial acetic acid neutralizer (neutralization degree is 100%) at 30-40°C, adjust the reaction pH (pH=5), and react for 0.5 hours; under mechanical stirring (800r / min), slowly add deionized water for self-emulsification (the disperse dye filter cake accounts for 10% of the total mass of the liquid after self-emulsification), and remove acetone under reduced pressure to obtain a cationic disperse dye.

[0072] Preparation of cationic fluorine-free water repellent:

[0073] Take 100g of the above polyurethane, add glacial acetic acid neutralizer (neutralization degree is 100%) at 30-40°C, adjust the reaction pH (pH=5), and react for 0.5 hour; add acrylate monomer (the mass ratio of acrylate monomer to polyurethane used is 0.5:1), stir evenly, slowly add deionized water for self-emulsification (the total mass of the monomer substrate used accounts for 15% of the liquid mass) under stirring of a high-speed disperser (5000r / min), remove acetone under reduced pressure, heat to 70°C, add ammonium persulfate initiator (accounting for 50% of the total mass of the initiator, and the total initiator accounts for 0.1% of the total mass of the acrylate monomer), keep warm for 2 hours, add the remaining initiator, react for 1 hour, cool and discharge, and obtain a cationic polyurethane-acrylate fluorine-free water repellent.

[0074] Preparation of finishing agent for fabric dyeing-water repellent one-bath treatment:

[0075] According to the mass ratio of cationic disperse dye to cationic fluorine-free water repellent of 2:25, the above cationic disperse dye and cationic fluorine-free water repellent are taken and mixed evenly to obtain a finishing agent for fabric dyeing-water repellent one-bath treatment.

[0076] Dyeing - Water-repellent one-bath treatment of polyester fabric:

[0077] Take the above fabric dyeing-water repellent one-bath treatment finishing agent and disperse it in water (wherein the cationic disperse dye accounts for 2% of the polyester fabric mass, and the cationic fluorine-free water repellent is dispersed in water at 50g / L), and prepare the finishing solution at a bath ratio of 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 2min. The relevant parameters of the treated fabric are shown in Table 1.

[0078] Embodiment 2:

[0079] Prepare cationic disperse dyes and cationic fluorine-free water repellents and finish fabrics according to the following steps:

[0080] Preparation of polyurethane:

[0081] Polyester diol (molecular weight 200), N-ethyldiethanolamine (accounting for 6% of the total weight of the monomers used for the polyurethane prepolymer), and dihydroxy small molecule chain extender 6-heptene-2,4-diol containing carbon-carbon double bonds (accounting for 10% of the total weight of the monomers) were vacuum dried at 90°C to remove water for 3 hours; according to the molar ratio of isocyanate to hydroxyl group of 1.2, polyester diol and olamine (accounting for 50% of the total weight of the olamine), dibutyltin dilaurate (accounting for 0.2% of the total weight of the monomers involved in the reaction) were added, and isophorone diisocyanate was slowly added dropwise at a temperature of 80°C under nitrogen protection, and the -NCO value in the reaction system was determined by the di-n-butylamine method. When the theoretical value (isocyanate) was reached, the -NCO value was 0.0447 W / v. After the theoretical residual amount of cyanate is ≤32%), the temperature is lowered to 55°C, and the residual N-ethyldiethanolamine dissolved in acetone is added (the mass ratio of acetone to alcoholamine is 2:1), and the -NCO content in the reaction system is measured to reach the theoretical value (the theoretical residual amount of isocyanate is ≤16%); a small molecule chain extender containing a carbon-carbon double bond is added at a temperature of 65°C, and the next step is carried out after the -NCO% content in the reaction system reaches the theoretical value (the theoretical residual amount of isocyanate is ≤8%); the temperature is then raised to 75°C, and a blocking agent dimethylglyoxime is added to block the extended polyurethane until the -NCO content in the reaction system reaches the theoretical value (the theoretical residual amount of isocyanate is ≤0.5%) to obtain a polyurethane.

[0082] Preparation of cationic disperse dyes:

[0083] The corresponding part of Example 1 is the same as that of Example 1, that is, 100g of the polyurethane prepared above is taken, and the acetone dissolution of the disperse dye filter cake is added at 50°C (the mass ratio of the disperse red filter cake 153 to the polyurethane used is 3:1, and the mass ratio of the disperse dye filter cake to the acetone used is 10:1), and after stirring evenly, glacial acetic acid neutralizer (neutralization degree is 100%) is added at 30-40°C, the reaction pH (pH=5) is adjusted, and the reaction is carried out for 0.5 hour; deionized water is slowly added under mechanical stirring (800r / min) for self-emulsification (the disperse dye filter cake accounts for 10% of the liquid mass), and the acetone is removed under reduced pressure to obtain a cationic disperse dye.

[0084] Preparation of cationic fluorine-free water repellent:

[0085] The corresponding part of Example 1, that is, take 100g of the above-mentioned polyurethane, add glacial acetic acid neutralizer (neutralization degree is 100%) at 30-40°C, adjust the reaction pH (pH=5), and react for 0.5 hour; add acrylate monomer (the mass ratio of acrylate monomer to the polyurethane used is 0.5:1), stir evenly, slowly add deionized water for self-emulsification (the total mass of the monomer substrate used accounts for 15% of the liquid mass) under stirring in a high-speed disperser (5000r / min), remove acetone under reduced pressure, heat to 70°C, add ammonium persulfate initiator (accounting for 50% of the total mass of the initiator, and the total initiator accounts for 0.1% of the total mass of the acrylate monomer), keep the reaction for 2 hours, add the remaining initiator, react for 1 hour, cool and discharge, and obtain a cationic polyurethane-acrylate fluorine-free water repellent.

[0086] Preparation of finishing agent for fabric dyeing-water repellent one-bath treatment:

[0087] According to the mass ratio of cationic disperse dye to cationic fluorine-free water repellent of 2:25, the above cationic disperse dye and cationic fluorine-free water repellent are taken and mixed evenly to obtain a finishing agent for fabric dyeing-water repellent one-bath treatment.

[0088] Dyeing - Water-repellent one-bath treatment of polyester fabric:

[0089] Same as Example 1: Take the above fabric dyeing-water repellent one-bath treatment finishing agent and disperse it in water (wherein the cationic disperse dye accounts for 2% of the polyester fabric mass, and the cationic fluorine-free water repellent is dispersed in water at 50g / L), and prepare the finishing solution at a bath ratio of 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 2min. The relevant parameters of the treated fabric are shown in Table 2.

[0090] Embodiment 3:

[0091] Preparation of polyurethane:

[0092] Polyether diol (molecular weight 1000), N-butyl diethanolamine (accounting for 10% of the total weight of the monomers used in the polyurethane prepolymer), and dihydroxy small molecule chain extender 3-hexene-2,5-diol containing carbon-carbon double bonds (accounting for 5% of the total weight of the monomers) were vacuum dried at 80°C to remove water for 3 hours; according to the molar ratio of isocyanate to hydroxyl group of 1.6, polyether diol and olamine (accounting for 10% of the total weight of the olamine), dibutyltin dilaurate (accounting for 0.2% of the total weight of the monomers involved in the reaction) were added slowly under nitrogen protection at a temperature of 80°C, and the -NCO value in the reaction system was determined by the di-n-butylamine method. When the theoretical value (theoretical residual amount of isocyanate) was reached, the reaction mixture was stirred for 2 hours. After adding 3-allyloxy-1,2-propylene glycol (5% of the total monomer mass) at 60°C, the next step is carried out after the -NCO% content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate is ≤8%); the temperature is then raised to 70°C, and the end-capping agent dimethylglyoxime is added to cap the chain-extended polyurethane, until the -NCO content in the reaction system reaches the theoretical value (theoretical residual amount of isocyanate is ≤0.5%) to obtain the polyurethane.

[0093] Preparation of cationic disperse dyes:

[0094] The corresponding part of Example 1 is the same as that of Example 1, that is, 100g of the polyurethane prepared above is taken, and the acetone dissolution of the disperse dye filter cake is added at 50°C (the mass ratio of the disperse red filter cake 153 to the polyurethane used is 3:1, and the mass ratio of the disperse dye filter cake to the acetone used is 10:1), and after stirring evenly, glacial acetic acid neutralizer (neutralization degree is 100%) is added at 30-40°C, the reaction pH (pH=5) is adjusted, and the reaction is carried out for 0.5 hour; deionized water is slowly added under mechanical stirring (800r / min) for self-emulsification (the disperse dye filter cake accounts for 10% of the liquid mass), and the acetone is removed under reduced pressure to obtain a cationic disperse dye.

[0095] Preparation of cationic fluorine-free water repellent:

[0096] The corresponding part of Example 1, that is, take 100g of the polyurethane prepared above, add glacial acetic acid neutralizer (neutralization degree is 100%) at 30-40°C, adjust the reaction pH (pH=5), and react for 0.5 hour; add acrylate monomer (the mass ratio of acrylate monomer to the polyurethane used is 0.5:1), stir evenly, slowly add deionized water for self-emulsification (the total mass of the monomer substrate used accounts for 15% of the liquid mass) under stirring in a high-speed disperser (5000r / min), remove acetone under reduced pressure, heat to 70°C, add ammonium persulfate initiator (accounting for 50% of the total mass of the initiator, and the total initiator accounts for 0.1% of the total mass of the acrylate monomer), keep the reaction for 2 hours, add the remaining initiator, react for 1 hour, cool and discharge, and obtain a cationic polyurethane-acrylate fluorine-free water repellent.

[0097] Preparation of finishing agent for fabric dyeing-water repellent one-bath treatment:

[0098] According to the mass ratio of cationic disperse dye to cationic fluorine-free water repellent of 2:25, the above cationic disperse dye and cationic fluorine-free water repellent are taken and mixed evenly to obtain a finishing agent for fabric dyeing-water repellent one-bath treatment.

[0099] Dyeing - Water-repellent one-bath treatment of polyester fabric:

[0100] Same as Example 1: Take the above fabric dyeing-water repellent one-bath treatment finishing agent and disperse it in water (wherein the cationic disperse dye accounts for 2% of the polyester fabric mass, and the cationic fluorine-free water repellent is dispersed in water at 50g / L), and prepare the finishing solution at a bath ratio of 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 2min. The relevant parameters of the treated fabric are shown in Table 2.

[0101] Embodiment 4:

[0102] Preparation of polyurethane:

[0103] Same as the corresponding part of Example 1.

[0104] Preparation of cationic disperse dyes:

[0105] The corresponding part of Example 1 is the same as that of Example 1, that is, 100g of the polyurethane prepared above is taken, and the acetone dissolution of the disperse dye filter cake is added at 50°C (the mass ratio of the disperse red filter cake 153 to the polyurethane used is 3:1, and the mass ratio of the disperse dye filter cake to the acetone used is 10:1), and after stirring evenly, a lactic acid neutralizer (neutralization degree is 100%) is added at 30-40°C, the reaction pH (pH=5-6) 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 disperse dye filter cake accounts for 10% of the liquid mass), and the acetone is removed under reduced pressure to obtain a cationic disperse dye.

[0106] Preparation of cationic fluorine-free water repellent:

[0107] Take 100g of the polyurethane prepared above, add lactic acid neutralizer (neutralization degree is 120%) at 30-40°C, adjust the reaction pH (pH=5-6), and react for 0.5 hour; add a mixture of acrylate monomers (octadecyl acrylate: methyl methacrylate: butyl acrylate=2:1:1, molar ratio) (the mass ratio of acrylate monomer to the polyurethane used is 1:1), slowly add deionized water for self-emulsification (the total mass of the monomer substrate used accounts for 40% of the liquid mass) under stirring of a high-speed disperser (8000r / min), remove acetone under reduced pressure, heat to 75°C, add initiator (accounting for 70% of the total mass of the initiator, and the total initiator accounts for 0.5% of the total mass of the acrylate monomer), keep warm for reaction for 3 hours, add the remaining initiator, react for 2 hours, cool and discharge, and obtain a cationic polyurethane-acrylate fluorine-free water repellent.

[0108] Preparation of finishing agent for fabric dyeing-water repellent one-bath treatment:

[0109] According to the mass ratio of cationic disperse dye to cationic fluorine-free water repellent of 2:30, the above cationic disperse dye and cationic fluorine-free water repellent are taken and mixed evenly to obtain a finishing agent for fabric dyeing-water repellent one-bath treatment.

[0110] Dyeing - Water-repellent one-bath treatment of polyester fabric:

[0111] Take the above fabric dyeing-water repellent one-bath treatment finishing agent and disperse it in water (wherein the cationic disperse dye accounts for 2% of the weight of the polyester fabric, and the cationic fluorine-free water repellent is dispersed in water at 60g / L), and prepare the finishing solution with a bath ratio of 1:50. After adding the fabric, heat it from room temperature to 130℃ at a rate of 2℃ / min, keep it warm for 45min, then cool it to 80℃ at a rate of 4℃ / min, rinse it thoroughly, dry it at 105℃ for 5min, and bake it at 150℃ for 5min. The relevant parameters of the treated fabric are shown in Table 2.

[0112] Embodiment 5:

[0113] Preparation of polyurethane:

[0114] In the corresponding part of Example 1, polyurethane is prepared by using polymer polyol, diisocyanate, olamine compound, dihydroxy small molecule containing carbon-carbon double bond and end-capping agent.

[0115] Preparation of cationic disperse dyes:

[0116] The corresponding part of Example 1 is the same as that of Example 1, that is, 100g of the polyurethane prepared above is taken, and the acetone dissolution of the disperse dye filter cake is added at 50°C (the mass ratio of the disperse red filter cake 153 to the polyurethane used is 3:1, and the mass ratio of the disperse dye filter cake to the acetone used is 10:1), and after stirring evenly, hydrochloric acid neutralizer (neutralization degree is 100%) is added at 30-40°C, the reaction pH (pH=6) is adjusted, and the reaction is carried out for 0.5 hour; deionized water is slowly added under mechanical stirring (800r / min) for self-emulsification (the disperse dye filter cake accounts for 10% of the liquid mass), and the acetone is removed under reduced pressure to obtain a cationic disperse dye.

[0117] Preparation of cationic fluorine-free water repellent:

[0118] Take 100g of the polyurethane prepared above, add hydrochloric acid neutralizer (neutralization degree is 80%) at 30-40°C, adjust the reaction pH (pH=6), and react for 0.5 hour; add a mixture of acrylate monomers (hexadecyl acrylate: methyl acrylate: hexyl acrylate=3:2:1, molar ratio) (the mass ratio of acrylate monomer to the polyurethane used is 0.8:1), slowly add deionized water for self-emulsification (the total mass of the monomer substrate used accounts for 40% of the liquid mass) under stirring of a high-speed disperser (6000r / min), remove acetone under reduced pressure, heat to 75°C, add initiator (accounting for 60% of the total mass of the initiator, and the total initiator accounts for 0.1% of the total mass of the acrylate monomer), keep warm for reaction for 1 hour, add the remaining initiator, react for 3 hours, cool and discharge, and obtain a cationic polyurethane-acrylate fluorine-free water repellent.

[0119] Preparation of finishing agent for fabric dyeing-water repellent one-bath treatment:

[0120] According to the mass ratio of cationic disperse dye to cationic fluorine-free water repellent of 2:40, the cationic disperse dye and the cationic fluorine-free water repellent are taken and mixed evenly to obtain a finishing agent for fabric dyeing-water repellent one-bath treatment.

[0121] Dyeing - Water-repellent one-bath treatment of polyester fabric:

[0122] Take the above fabric dyeing-water repellent one-bath treatment finishing agent and disperse it in water (wherein the cationic disperse dye accounts for 2% of the weight of the polyester fabric, and the cationic fluorine-free water repellent is dispersed in water at 80g / L), and prepare the finishing solution with a bath ratio of 1:20. After adding the fabric, heat it from room temperature to 130℃ at a rate of 2℃ / min, keep it warm for 30min, then cool it to 80℃ at a rate of 4℃ / min, rinse it thoroughly, dry it at 105℃ for 5min, and bake it at 140℃ for 10min. The relevant parameters of the treated fabric are shown in Table 2.

[0123] Embodiment 6-7:

[0124] Preparation of polyurethane:

[0125] In the corresponding part of Example 1, polyurethane is prepared by using polymer polyol, diisocyanate, olamine compound, dihydroxy small molecule containing carbon-carbon double bond and end-capping agent.

[0126] Preparation of cationic disperse dyes:

[0127] Only the amount of disperse dye was changed, and the other parts were the same as those in Example 1. The mass ratios of disperse red filter cake 153 and the polyurethane used were 2:1 (Example 6) and 1:1 (Example 7), respectively.

[0128] Preparation of cationic fluorine-free water repellent:

[0129] The same as the corresponding part of Example 1, that is, 100g of the polyurethane prepared above was taken, and glacial acetic acid neutralizer (neutralization degree was 100%) was added at 30-40°C, the reaction pH (pH = 5) was adjusted, and the reaction was reacted for 0.5 hours; acrylate monomer (the mass ratio of acrylate monomer to polyurethane used was 0.5: 1), stirred evenly, and deionized water was slowly added under stirring (5000r / min) in a high-speed disperser for self-emulsification (the total mass of the monomer substrate used accounted for 15% of the liquid mass), acetone was removed under reduced pressure, and the temperature was raised to 70°C, and ammonium persulfate initiator (accounting for 50% of the total mass of the initiator, and the total initiator accounted for 0.1% of the total mass of the acrylate monomer) was added, and the remaining initiator was added after the reaction was kept warm for 2 hours, and the reaction was continued for 1 hour, and the temperature was lowered to obtain a cationic polyurethane-acrylate fluorine-free water repellent.

[0130] Fabrics finished with cationic disperse dyes and cationic fluorine-free water repellents:

[0131] Same as Example 1: Cationic disperse dyes and cationic fluorine-free water repellent were used to finish polyester fabrics. The relevant parameters of the treated fabrics are shown in Table 2.

[0132] Embodiment 8-9:

[0133] Preparation of polyurethane:

[0134] In the corresponding part of Example 1, polyurethane is prepared by using polymer polyol, diisocyanate, olamine compound, dihydroxy small molecule containing carbon-carbon double bond and end-capping agent.

[0135] Preparation of cationic disperse dyes:

[0136] 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 8) and disperse blue filter cake 183:1 (Example 9)

[0137] Preparation of cationic fluorine-free water repellent:

[0138] The same as the corresponding part of Example 1, that is, 100g of the polyurethane prepared above was taken, and glacial acetic acid neutralizer (neutralization degree was 100%) was added at 30-40°C, the reaction pH (pH = 5) was adjusted, and the reaction was reacted for 0.5 hours; acrylate monomer (the mass ratio of acrylate monomer to polyurethane used was 0.5: 1), stirred evenly, and deionized water was slowly added under stirring (5000r / min) in a high-speed disperser for self-emulsification (the total mass of the monomer substrate used accounted for 15% of the liquid mass), acetone was removed under reduced pressure, and the temperature was raised to 70°C, and ammonium persulfate initiator (accounting for 50% of the total mass of the initiator, and the total initiator accounted for 0.1% of the total mass of the acrylate monomer) was added, and the remaining initiator was added after the reaction was kept warm for 2 hours, and the reaction was continued for 1 hour, and the temperature was lowered to obtain a cationic polyurethane-acrylate fluorine-free water repellent.

[0139] Fabrics finished with cationic disperse dyes and cationic fluorine-free water repellents:

[0140] Same as Example 1: Cationic disperse dyes and cationic fluorine-free water repellent were used to finish polyester fabrics. The relevant parameters of the treated fabrics are shown in Table 2.

[0141] Embodiment 10-13:

[0142] Preparation of polyurethane: same as the corresponding part of Example 1.

[0143] Preparation of cationic disperse dyes: same as the corresponding part of Example 1.

[0144] Preparation of cationic fluorine-free water repellent: same as the corresponding part of Example 1.

[0145] Fabrics finished with cationic disperse dyes and cationic fluorine-free water repellents:

[0146] According to the following formula, the cationic disperse dyes prepared in Examples 1, 8 and 9 (2% by weight of the fabric) and 60 g / L of a cationic fluorine-free water repellent were used to finish polyester fabrics (corresponding to Examples 10-13, respectively), with a bath ratio of 1:50 to prepare a finishing solution.

[0147]

[0148] 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 2 minutes. The relevant parameters of the treated fabric are shown in Table 3.

[0149] Comparative Example 1:

[0150] Finishing fabric: Only the cationic fluorine-free water repellent prepared in Example 1 was used without adding dye, and polyester fabric was treated according to the fabric finishing method of Example 1. The relevant parameters of the treated fabric are shown in Table 1.

[0151] Comparative Example 2:

[0152] Finishing fabric: Only the cationic disperse dye prepared in Example 1 was used without adding a water repellent, and polyester fabric was treated according to the fabric finishing method of Example 1. The relevant parameters of the treated fabric are shown in Table 1.

[0153] Comparative Example 3:

[0154] Conventional polyester fabric is dyed first and then water-repellent finished:

[0155] The dye liquor was prepared with commercial disperse red 153 dye 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, the dye liquor was dried at 105°C for 5 minutes and baked at 160°C for 2 minutes.

[0156] Comparative Example 4:

[0157] Conventional disperse dyes and water repellent one-bath process for treating polyester fabrics:

[0158] Prepare a finishing solution of commercial disperse red 153 dye and the water repellent prepared in Example 1, wherein the amount of commercial disperse red 153 dye is the amount of dye in Example 1, the water repellent is 50g / L, and the finishing solution bath ratio is 1:50. After adding the fabric, the temperature is raised from room temperature to 130°C at a rate of 2°C / min, kept warm for 60min, and then cooled to 80°C at a rate of 4°C / min. After fully rinsing, dry at 105°C for 5min and bake at 160°C for 2min. The relevant parameters of the treated fabric are shown in Table 1.

[0159] Comparative Example 5:

[0160] Preparation of polyurethane: same as the corresponding part of Example 1.

[0161] Preparation of cationic disperse dye: Only the amount of disperse dye was changed, and the other parts were the same as those in Example 1. The mass ratio of disperse red filter cake 153 to the polyurethane used was 4:1.

[0162] Preparation of cationic fluorine-free water repellent: same as the corresponding part of Example 1.

[0163] Finishing fabric: Same as the corresponding part of Example 1, the relevant parameters of the treated fabric are shown in Table 1.

[0164] Table 1 Relevant parameters of treated fabrics

[0165]

[0166]

[0167] 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.

[0168] Comparing Example 1 and Control Example 1 in Table 1, after the cationic disperse dye and the cationic fluorine-free water repellent designed by the present invention are used to finish the polyester fabric, the fabric has excellent water repellency, hydrostatic pressure resistance, softness, abrasion resistance, moisture permeability, and anti-pilling properties, and also has excellent dyeing performance. After the fabric is finished without adding dye during the preparation process (Control Example 1), although it also has various excellent properties, it does not have color (Integ value is 0.23, indicating that the fabric is basically white).

[0169] Comparing Example 1 and Control Example 2, the fabric can be colored by using only the prepared cationic disperse dye, but does not have water repellency.

[0170] Comparative Example 1, Reference Example 3, Reference Example 4, the cationic release type disperse dye and cationic release type fluorine-free water repellent designed by the present invention complete the one-bath processing of dyeing and water repellency (Example 1), and can achieve the same dyeing effect and excellent fabric performance such as water repellency as the traditional dyeing first and then water repellency (separate bath and separate steps) process (Reference Example 3). The one-bath treatment of polyester fabric dyeing and water repellency finishing achieved by this method shortens the production process, saves the source of water, improves production efficiency, and reduces production costs. The product designed by the present invention can avoid the long process flow of conventional polyester fabric dyeing and water repellency finishing, large energy consumption, and the problem of needing to prepare and use the water repellent and dyeing at the same time.

[0171] Comparing Example 1 and Control Example 5, the present invention uses cationic polyurethane to disperse disperse dye filter cake, and the amount of disperse dye filter cake needs to be controlled. If the amount of dye filter cake is too large, the polyurethane cannot form an effective coating for the dye, the disperse dye precipitates during the preparation process, and a stable product cannot be obtained, making it difficult to complete the dyeing and water-repellent finishing of the fabric.

[0172] 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 water repellent prepared by the present invention.

[0173] Repeatability of the hydrophobic effect of the product: 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°. It can be seen from the contact angle data that the hydrophobic effect of the treated fabric is repeatable.

[0174] Table 2 Relevant parameters of treated fabrics

[0175]

[0176]

[0177] 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.

[0178] Product hydrophobic effect: Compared with Examples 1-7 in Table 2, the cationic disperse dyes and cationic fluorine-free water repellents designed by the present invention have good water repellency, hydrostatic pressure resistance, softness, abrasion resistance, moisture permeability, and anti-pilling properties. The color Integ values ​​of Examples 1-4 are similar (with the same dye content); the color Integ value of Example 1 is greater than the color Integ value of Examples 6-7, indicating that the amount of dye is controlled during the preparation process, and fabrics with different dyeing depths can be obtained under the same fabric finishing conditions.

[0179] Product washing fastness: From the fabric water resistance test results, it can be seen that after the fabrics finished in Examples 1-7 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 washing fastness after being finished with a cationic polyurethane-acrylate water repellent coated with disperse dyes.

[0180] Table 3 Relevant parameters of treated fabrics

[0181]

[0182] 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.

[0183] Product hydrophobic effect: Comparing Example 1 and Examples 8-13 in Table 3, the cationic polyurethane-acrylate water repellents coated with disperse dyes 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 23.95, the color Integ value of Example 8 (dispersed yellow filter cake 211) is 18.23, and the color Integ value of Example 9 (dispersed blue filter cake 183:1) is 8.65, indicating that changing the type of disperse dyes in the preparation process of the water repellent can obtain dyed fabrics of different colors. Examples 10-13 show that mixed use of prepared cationic disperse dyes of different colors can obtain dyed fabrics with a color matching effect.

[0184] Product washing fastness: From the test results of fabric water resistance, it can be seen that after the fabrics finished in Examples 8-13 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°, which shows that the fabrics have high washing fastness after being finished with the water repellent prepared by the present invention by changing the type of dye and the mixed use of the water repellent product during the preparation process.

[0185] Comparative Example 5

[0186] Configure different dye systems:

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] 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.

[0192] Dye system 6 (the present invention) uses the cationic disperse dye prepared in Example 1 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.

[0193] Table 4 Dispersion properties of dye system

[0194]

[0195] 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 dye (dye system 5) and the cationic disperse dye prepared by the present invention (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 disperse dye 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 finishing agent for fabric dyeing-water repellent one-bath treatment, characterized in that: Comprising a cationic disperse dye and a cationic fluorine-free water repellent, wherein the mass ratio of the cationic disperse dye to the cationic fluorine-free water repellent is 2:10-2:100; Among them, cationic disperse dyes and cationic fluorine-free water repellents are prepared by the following methods: (1) Polyurethane is prepared by using polymer polyol, diisocyanate, amine compound, dihydroxy small molecule chain extender containing carbon-carbon double bond as polyurethane monomer and end-capping agent; (2) Add disperse dye filter cake to part of the polyurethane, add neutralizing agent, and then add water for self-emulsification to prepare liquid cationic disperse dye; (3) After adding acrylate monomers to the remaining polyurethane, a neutralizing agent is added, and then water is added for self-emulsification, and the temperature is raised to prepare a cationic fluorine-free water repellent under the action of an initiator; The end-capping agent in step (1) includes any one of butanone oxime, butyrimidine oxime, acetone oxime, formaldehyde oxime, bromophenol oxime, cyclohexanone oxime, n-heptanaldoxime, dimethylglyoxime, and tetramethylcyclobutanedione monoxime, or a mixture of several thereof; The preparation method of the cationic disperse dye in step (2) specifically comprises: taking the polyurethane prepared in step (1), adding the acetone solution of the disperse dye filter cake at 50° C., stirring evenly, adding a neutralizing agent at 30-40° C. to make the neutralization degree 80-120%, adjusting the pH of the reaction to 5-6, and reacting for 0.5-1h; slowly adding deionized water for self-emulsification under mechanical stirring at a speed of 800-2000 r / min, and removing acetone under reduced pressure to obtain a cationic disperse dye; wherein the mass ratio of the disperse dye filter cake to the polyurethane is 3:1-1:1, and the neutralizing agent comprises one or more of glacial acetic acid, hydrochloric acid, lactic acid, and dimethylmercaptopropionic acid; The preparation method of the cationic fluorine-free water repellent described in step (3) specifically comprises: taking the polyurethane prepared in step (1), adding a neutralizing agent at 30-40° C. to make the neutralization degree 80-120%, adjusting the pH of the reaction to 5-6, and reacting for 0.5-1h; adding an acrylate monomer, stirring evenly, slowly adding deionized water for self-emulsification under stirring in a high-speed disperser, removing acetone under reduced pressure, heating to 70-80° C., adding an initiator accounting for 50-70% of the total mass of the initiator, keeping the temperature for reaction for 2-3h, and then adding the remaining Initiator, keep the reaction warm for 1-2h, cool and discharge to obtain a cationic polyurethane-acrylate fluorine-free water repellent; wherein the speed of the high-speed disperser during stirring is 5000-8000r / min, the total initiator accounts for 0.1-1% of the total mass of the acrylate monomer, the neutralizer includes one or more of glacial acetic acid, hydrochloric acid, lactic acid, and dimethylmercaptopropionic acid, and the initiator includes one or more of azobisisobutyronitrile, azobisisoheptanenitrile, azobisisobutyramidine hydrochloride, potassium persulfate, ammonium persulfate, and dibenzoyl peroxide.

2. The finishing agent according to claim 1, characterized in that The structure of the alcoholamine compound in step (1) is as follows: ,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 finishing agent according to claim 1, characterized in that The structure of the dihydroxy small molecule chain extender containing a carbon-carbon double bond in step (1) is as follows: ,or Wherein, R8, R9, R10, and R11 are selected from chain alkyl groups, phenyl groups, cycloalkyl groups, acyl groups, ester groups, carbonyl groups, and ether groups having any number of carbon atoms.

4. The finishing agent according to claim 1, characterized in that In step (2), after the self-emulsification, the disperse dye filter cake accounts for 1 to 40% of the total mass of the liquid after the self-emulsification.

5. The finishing agent according to claim 1, characterized in that In step (3), the mass ratio of the acrylic ester monomer to the polyurethane used is 0.5:1 to 2:

1.

6. The finishing agent according to claim 1, characterized in that In step (3), after the self-emulsification, the total mass of the cationic water repellent monomer substrate accounts for 15 to 40% of the mass of the liquid.

7. A polyester fabric dyeing-water repellent one-bath treatment method, characterized in that: The method comprises firstly immersing the fabric in an aqueous solution containing the finishing agent according to any one of claims 1 to 6, and then baking.

8. A colored hydrophobic fabric prepared by the treatment method according to claim 7.

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