A polyester-spandex blended fabric sublimation fastness improver and a preparation method thereof

Abstract

The present application relates to the field of textile functional finishing agent, in particular to a polyester spandex blended fabric sublimation fastness improver and a preparation method thereof, comprising the following components by mass fraction: modified polyester-polyether block copolymer 40-60%; nano titanium dioxide and zinc oxide composite carrier 10-20%; crosslinking agent 5-10%; silicone oil emulsion 3-8%; pH regulator 1-3%. The present application forms a dense and high-temperature-resistant protective film on the fiber surface through the synergistic effect of modified polyester-polyether block copolymer and nano composite carrier, which can inhibit the thermal motion of dye molecules.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of textile functional finishing agents, in particular to a polyester-spandex blended fabric sublimation fastness improver and a preparation method thereof. BACKGROUND

[0002] Polyester is one of the widely used materials in textiles, which is made from polyterephthalic acid or dimethyl terephthalate and ethylene glycol as raw materials through esterification or ester exchange and polycondensation. Polyester fiber has many excellent properties, such as good heat resistance, high strength, etc. The close arrangement between polyester macromolecules, strong hydrophobicity and high crystallinity make it difficult for dyes to penetrate the inside of the fiber. Polyester is mainly dyed with disperse dyes, and the dye is prone to sublimation during high-temperature setting, which leads to insufficient fastness, so a fixing agent is needed to improve it. The fixing agent belongs to a kind of chemical reagents that improve the combination of textiles and dyes.

[0003] With people's increasing demand for the quality of textiles, the industry has more comprehensive requirements for the fixing of dyed textiles. In terms of environmental protection, traditional fixing agents may contain harmful substances such as formaldehyde, which threatens the safety of humans or the environment. At the same time, it also has poor biodegradability, which puts pressure on the environment for a long time. In terms of fabric performance, some fixing agents can make the fabric feel hard and the color light change. In terms of fixing effect, the fastness of some fixing agents to colors such as red and blue needs to be improved.

[0004] Based on the above background, developing a sublimation fastness improver with environmental protection, high efficiency and fabric compatibility has become a technical problem to be solved in the field of finishing of polyester-spandex blended fabric after dyeing. SUMMARY

[0005] In order to solve the problems in the background art, the present application provides an environmentally friendly, efficient, and non-affecting fabric elasticity and hand feeling polyester-spandex blended fabric sublimation fastness improver and its preparation method. Through molecular structure design and compounding technology, it can inhibit the sublimation of dyes at high temperature, improve the water soaking fastness, washing fastness and rubbing fastness of polyester-spandex blended fabric.

[0006] The technical scheme adopted by the present application to solve its technical problems is to provide a polyester-spandex blended fabric sublimation fastness improver, which comprises the following components by mass fraction:

[0007] Modified polyester-polyether block copolymer 40-60%;

[0008] Nanometer titanium dioxide and zinc oxide composite carrier 10-20%;

[0009] Crosslinking agent 5-10%;

[0010] Silicone oil emulsion 3-8%;

[0011] pH adjuster 1-3%.

[0012] Further, the modified polyester-polyether block copolymer has a structure of R-A m -B n -H;

[0013] wherein A is a polyether structure, m is 20-500, B is a polyester structure, n is 10-300, and R is a carboxyl or hydroxyl containing active group.

[0014] Further, the polyester structure comprises -CH2-CH2-O-; and the polyether structure comprises -O-CO-C6H4-CO-O-CH2-CH2- or -O-CO-CH=CH-CO-O-CH2-CH2-.

[0015] Further, the modified polyester-polyether block copolymer is obtained by condensation of a polyester prepolymer and a polyether diol.

[0016] Further, the polyester prepolymer is obtained by copolymerization of terephthalic acid, ethylene glycol and maleic anhydride; the polyether diol comprises polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol or polybutylene glycol; and the mixing ratio of the polyester prepolymer to the polyether diol is 4:1 to 5:1.

[0017] Further, the crosslinking agent comprises an epoxy crosslinking agent; and the pH adjuster comprises a combination of sodium dihydrogen phosphate and disodium hydrogen phosphate; and the molar ratio of sodium dihydrogen phosphate to disodium hydrogen phosphate is 1:0.8 to 1:1.2.

[0018] Further, the crosslinking agent comprises crosslinking agent EH. Crosslinking agent EH is a polyamine polyol low molecular condensate with multiple functional groups, which can bind with the hydrophilic groups in the dye and the -OH groups in cellulose to form a protective film, thereby improving the dyeing fastness of disperse dyes, and is a commonly used auxiliary chemical in the market.

[0019] Further, the composite carrier has a particle size of 20-50nm, and the mass ratio of titanium dioxide to zinc oxide is 1:1-2.

[0020] A preparation method of a polyester-spandex blended fabric sublimation fastness improver, comprising the following steps:

[0021] S1, preparing a modified polyester-polyether block copolymer: mixing a polyester prepolymer and a polyether diol, and performing condensation reaction under inert gas protection;

[0022] S2, preparing a nano-composite carrier: dispersing nano-titanium dioxide and zinc oxide in ethanol, adding a crosslinking agent after ultrasonic treatment, and performing reflux reaction to form a surface coating structure;

[0023] S3, compounding: mixing the modified polyester-polyether block copolymer of step S1, the nanocomposite carrier of step S2 and a pH regulator and performing shear emulsification treatment, and adjusting the pH to neutral.

[0024] Further, in S1, the temperature of the polycondensation reaction is 70-80 DEG C; the reaction time is 4-6 hours; and the inert gas is nitrogen.

[0025] Further, in S2, the mass ratio of the nanometer titanium dioxide to zinc oxide is 1:1-2; the ultrasonic treatment time is 20-40 minutes; the temperature of the reflux reaction is 55-65 DEG C, and the reaction time is 1.5-2.5 hours.

[0026] Further, in S3, the temperature of the shear emulsification is 40-60 DEG C; the shear rotation speed is 1000-3000 rpm; and the emulsification time is 30-60 minutes.

[0027] The beneficial effects of the present application are:

[0028] (1) The present application forms a dense and high-temperature-resistant protective film on the surface of the fiber through the synergistic effect of the modified polyester-polyether block copolymer and the nanocomposite carrier, which can inhibit the thermal motion of dye molecules.

[0029] (2) The present application does not contain environmental pollutants such as formaldehyde and alkyl phenol polyoxyethylene ether.

[0030] (3) The present application uses citric acid ester plasticizers and degradable crosslinking agents, and the overall biodegradation rate of the composition is more than 80%, which can reduce the environmental load.

[0031] (4) The present application can be applied to the existing dyeing or printing process without additional equipment or process. BRIEF DESCRIPTION OF DRAWINGS

[0032] Figure 1 The schematic diagram after the soaping fastness test of Example 1 is shown;

[0033] Figure 2 The schematic diagram after the soaping fastness test of the comparative example is shown. DETAILED DESCRIPTION

[0034] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the drawings in the embodiments of the present application. It can be understood that the specific embodiments described herein are only used to explain the present application, and not to limit the present application. In addition, it should be noted that only the parts related to the present application are shown in the drawings for convenience of description, and not all the structures.

[0035] Example 1: Preparation of polyester-spandex blended fabric sublimation fastness improver A.

[0036] S1, preparation of modified polyester-polyether block copolymer: polyester prepolymer and polytetramethylene ether glycol are mixed in a mixing ratio of 4:1, and the total mass accounts for 40% of the total mass of the final lifting agent. Under the protection of nitrogen, condensation reaction is carried out at 70°C, and the reaction time is 4 hours to obtain modified polyester-polyether block copolymer emulsion.

[0037] S2, preparation of nanocomposite carrier: nanometer titanium dioxide and zinc oxide are dispersed in ethanol in a mass ratio of 1:1, and the total mass accounts for 10% of the total mass of the final lifting agent. Ultrasonic treatment for 20 minutes, add crosslinking agent, mass accounts for 5% of the total mass of the lifting agent, reflux reaction at 55°C for 1.5 hours to form a surface coating structure.

[0038] S3, compounding: the modified polyester-polyether block copolymer emulsion of step 1, the nanocomposite carrier of step 2 and the pH regulator are mixed, the mass of the pH regulator accounts for 2% of the total mass of the lifting agent, and the mass of the silicone oil emulsion accounts for 3% of the total mass of the lifting agent. Shear emulsification treatment is carried out at 40°C with a rotation speed of 1000 rpm, the emulsification time is 30 minutes, the pH is adjusted to neutral, and the polyester spandex blended fabric sublimation fastness enhancer is obtained.

[0039] Example 2: Preparation of polyester spandex blended fabric sublimation fastness enhancer B.

[0040] S1, preparation of modified polyester-polyether block copolymer: polyester prepolymer and polypropylene glycol are mixed in a mixing ratio of 4.5:1, and the total mass accounts for 50% of the total mass of the final lifting agent. Under the protection of nitrogen, condensation reaction is carried out at 75°C, and the reaction time is 5 hours to obtain modified polyester-polyether block copolymer emulsion.

[0041] S2, preparation of nanocomposite carrier: nanometer titanium dioxide and zinc oxide are dispersed in ethanol in a mass ratio of 1:1.5, and the total mass accounts for 15% of the total mass of the final lifting agent. Ultrasonic treatment for 30 minutes, add crosslinking agent, mass accounts for 7% of the total mass of the lifting agent, reflux reaction at 60°C for 2 hours to form a surface coating structure.

[0042] S3, compounding: the modified polyester-polyether block copolymer emulsion of step 1, the nanocomposite carrier of step 2 and the pH regulator are mixed, the mass of the pH regulator accounts for 3% of the total mass of the lifting agent, and the mass of the silicone oil emulsion accounts for 5% of the total mass of the lifting agent. Shear emulsification treatment is carried out at 50°C with a rotation speed of 2000 rpm, the emulsification time is 45 minutes, the pH is adjusted to neutral, and the polyester spandex blended fabric sublimation fastness enhancer is obtained.

[0043] Example 3: Preparation of polyester spandex blended fabric sublimation fastness enhancer C.

[0044] S1, preparation of modified polyester-polyether block copolymer: polyester prepolymer and polyethylene glycol are mixed in a mixing ratio of 5:1, and the total mass accounts for 60% of the total mass of the final enhancer. Under the protection of nitrogen, condensation reaction is carried out at 80℃ for 6 hours to obtain modified polyester-polyether block copolymer emulsion.

[0045] S2, preparation of nano-composite carrier: nano-titanium dioxide and zinc oxide are dispersed in ethanol in a mass ratio of 1:2, and the total mass accounts for 20% of the total mass of the final enhancer. Ultrasonic treatment for 40 minutes, add crosslinking agent, the mass accounts for 10% of the total mass of the enhancer, reflux reaction at 65℃ for 2.5 hours to form a surface coating structure.

[0046] S3, compounding: the modified polyester-polyether block copolymer emulsion of step 1, the nano-composite carrier of step 2 and the pH regulator are mixed, the mass of the pH regulator accounts for 1% of the total mass of the enhancer, and the mass of the silicone oil emulsion accounts for 8% of the total mass of the enhancer. Shear emulsification treatment is carried out at 60℃ with a rotation speed of 3000 rpm, the emulsification time is 60 minutes, the pH is adjusted to neutral, and the polyester spandex blended fabric sublimation fastness enhancer is obtained.

[0047] Example 4: Preparation of polyester spandex blended fabric sublimation fastness enhancer D.

[0048] S1, preparation of modified polyester-polyether block copolymer: polyester prepolymer and polybutylene glycol are mixed in a mixing ratio of 4.2:1, and the total mass accounts for 45% of the total mass of the final enhancer. Under the protection of nitrogen, condensation reaction is carried out at 72℃ for 4.5 hours to obtain modified polyester-polyether block copolymer emulsion.

[0049] S2, preparation of nano-composite carrier: nano-titanium dioxide and zinc oxide are dispersed in ethanol in a mass ratio of 1:1.2, and the total mass accounts for 12% of the total mass of the final enhancer. Ultrasonic treatment for 25 minutes, add crosslinking agent, the mass accounts for 6% of the total mass of the enhancer, reflux reaction at 58℃ for 1.8 hours to form a surface coating structure.

[0050] S3, compounding: the modified polyester-polyether block copolymer emulsion of step 1, the nano-composite carrier of step 2 and the pH regulator are mixed, the mass of the pH regulator accounts for 2.5% of the total mass of the enhancer, and the mass of the silicone oil emulsion accounts for 4% of the total mass of the enhancer. Shear emulsification treatment is carried out at 45℃ with a rotation speed of 1500 rpm, the emulsification time is 35 minutes, the pH is adjusted to neutral, and the polyester spandex blended fabric sublimation fastness enhancer is obtained.

[0051] Example 5: Preparation of polyester spandex blended fabric sublimation fastness enhancer E.

[0052] S1, preparation of modified polyester-polyether block copolymer: mix polyester prepolymer and polytetramethylene ether glycol at a mixing ratio of 4.8:1, and the total mass accounts for 55% of the total mass of the final lifting agent. Under the protection of nitrogen, the condensation reaction is carried out at 78℃ for 5.5 hours to obtain a modified polyester-polyether block copolymer emulsion.

[0053] S2, preparation of nanocomposite carrier: disperse nanometer titanium dioxide and zinc oxide in ethanol at a mass ratio of 1:1.8, and the total mass accounts for 18% of the total mass of the final lifting agent. Ultrasonic treatment for 35 minutes, add crosslinking agent, which accounts for 8% of the total mass of the lifting agent, and reflux at 62℃ for 2.2 hours to form a surface coating structure.

[0054] S3, compounding: mix the modified polyester-polyether block copolymer emulsion of step 1, the nanocomposite carrier of step 2, and the pH regulator, which accounts for 2% of the total mass of the lifting agent, and the silicone oil emulsion, which accounts for 6% of the total mass of the lifting agent. Shear emulsification treatment is carried out at 55℃ and 2500 rpm for 50 minutes, the pH is adjusted to neutral, and a polyester spandex blended fabric sublimation fastness enhancer is obtained.

[0055] Example 6: Performance test of polyester spandex blended fabric sublimation fastness enhancer.

[0056] Fabric: Select polyester spandex blended fabric, red and white interlaced samples; the size of the fabric sample is XX mm x XX mm, and the thickness is XX mm.

[0057] Instrument: P-AO small padder; F&P AD-12 normal temperature small sample machine; Y571(L) friction fastness tester; sublimation fastness tester; constant temperature oven; ultraviolet visible spectrophotometer.

[0058] Reagent: The polyester spandex blended fabric sublimation fastness enhancer prepared in examples 1-5 of the present application; the dosage is 10-40 g / L.

[0059] Comparative example: The fabric sample is not treated with polyester spandex blended fabric sublimation fastness enhancer.

[0060] Treatment process: padding method.

[0061] Pour the prepared sublimation fastness enhancer into the padder, immerse the fabric sample in the prepared sublimation fastness enhancer, and ensure sufficient wetting, the immersion time is 30 seconds; pass the fabric sample smoothly through the padder roller for rolling. Control the pick-up rate: adjust the padder pressure to control the pick-up rate at 70%. Pick-up rate=(fabric weight after padding-dry fabric weight before padding) / dry fabric weight before padding*100%)

[0062] Drying: The wet fabric sample after padding is immediately moved into a drying oven at 100-120℃, and dried until the fabric sample is completely dry. This step is mainly to remove water to avoid water stains or migration during high-temperature baking.

[0063] High-temperature setting: The dried fabric sample is moved into a constant-temperature oven preheated to 170-200℃, and set at the specified temperature for 1-3 minutes.

[0064] Cooling and testing: After setting, the fabric sample is immediately removed and hung to cool at room temperature. After cooling, sublimation fastness testing is performed according to relevant standards to evaluate the color fixation effect.

[0065] Reagent concentration: 30g / L; padding rate: 80%; one dip and one pad, pressure 0.3MPa; drying: 100℃x3min; setting: 170-200℃x2min. One dip and one pad, setting at 170-200℃ for 2min.

[0066] Test method:

[0067] Soaping fastness: According to GB / T3921-2008 "Textile color fastness test method for color fastness to washing", the soaping fastness of the fabric is determined by the absorbance of the soaping residue. The bath ratio is 1:20, and the color of the multi-fiber fabric is observed after drying after the soaping of the dyed fabric with 4g / L of synthetic detergent and 2g / L of soda ash at 60℃ for 30min. The rating standard is 1-5 levels.

[0068] Water soaking fastness: The bath ratio is 1:20, and the color of the multi-fiber fabric is observed after soaking the dyed fabric with 4g / L of synthetic detergent at 100℃ for 10min. The rating standard is 1-5 levels.

[0069] Rubbing fastness: According to GB / 29865-2013 "Textile color fastness test for color fastness to rubbing", the rubbing fastness of the fabric is determined by the degree of staining of the gray sample card after dry and wet rubbing.

[0070] The test for sublimation color fastness is performed according to the relevant provisions of GB / T8427-2008 "Textile color fastness test for color fastness to heat and pressure".

[0071] Table 1 shows the results of color fastness testing of the fabric samples using the sublimation fastness improver for polyester / spandex blended fabric according to Examples 1-5 and the fabric samples of the comparative examples.

[0072]

[0073] As Figure 1 and Figure 2As shown, the soaping fastness and water immersion fastness of Example 1 are better than those of the comparative examples. As shown in Table 1, according to the test data of the examples and the comparative examples (as shown in the following table), the sublimation fastness improver for polyester-spandex blended fabric of the present application significantly improves various fastness indexes: the soaping fastness of the comparative examples is only 2-3 levels, the water immersion fastness is 2 levels, the dry / wet rubbing fastness is 2-3 levels / 1-2 levels, and the sublimation fastness is 2 levels; the various indexes of the fabric samples of Examples 1-5 are all improved to 4 levels or more, among which Examples 3 and 5 perform best: the soaping fastness is 5 levels, the water immersion fastness is 5 levels, the dry rubbing fastness is 4-5 levels, the wet rubbing fastness is 4 levels, and the sublimation fastness is 5 levels.

[0074] The present application forms a high-temperature-resistant protective film on the surface of the fiber by the synergistic effect of the modified polyester-polyether block copolymer and the nano-composite carrier TiO2 / ZnO, thereby inhibiting the sublimation of dyes; and the fastness improver does not contain formaldehyde and alkylphenol polyoxyethylene ether, and the biodegradation rate is more than 80%, which meets the green chemical standard; the addition of silicone emulsion in the fastness improver maintains the elasticity and hand feeling of the fabric, and is suitable for the existing padding process without the need to add new equipment. The present application can solve the problem of insufficient color fastness of polyester-spandex blended fabric caused by the sublimation of dyes during high-temperature setting; can replace traditional formaldehyde-containing fixing agents, and has wide popularization value in the field of high-end functional fabric processing.

[0075] The above describes the present application in detail in combination with examples and comparative examples, but the present application is not limited to the above examples, and various changes can be made within the knowledge of those skilled in the art without departing from the purpose of the present application. The contents not described in detail in the present application can adopt the existing technology.

Claims

1. A polyester spandex blended fabric sublimation fastness improver, characterized in that, Components comprising the following mass fractions: Modified polyester-polyether block copolymer 40-60%; Nano titanium dioxide and zinc oxide composite carrier 10-20%; Crosslinking agent 5-10%; Silicone oil emulsion 3-8%; pH regulator 1-3%; The preparation method of the modified polyester-polyether block copolymer is as follows: polyesters pre-polymer and polyether glycol are mixed, and condensation polymerization is carried out under inert gas protection to obtain the modified polyester-polyether block copolymer. The polyester pre-polymer is copolymerized from terephthalic acid, ethylene glycol and maleic anhydride. The polyether glycol includes polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol or polybutylene glycol. The mixing ratio of the polyester pre-polymer to the polyether glycol is 4:1 to 5:

1.

2. The polyester spandex blended fabric sublimation fastness improver according to claim 1, characterized in that: The structure of the modified polyester-polyether block copolymer is R-A m -B n -H; Wherein, A is a polyether structure, m is 20-500, B is a polyester structure, n is 10-300, and R is an active group containing carboxyl or hydroxyl.

3. The polyester spandex blended fabric sublimation fastness improver according to claim 1, characterized in that: The crosslinking agent includes an epoxy crosslinking agent; The pH regulator includes a combination of sodium dihydrogen phosphate and disodium hydrogen phosphate, wherein the molar ratio of sodium dihydrogen phosphate to disodium hydrogen phosphate is 1:0.8 to 1:1.

2.

4. The polyester spandex blended fabric sublimation fastness improver according to claim 1, characterized in that, The composite carrier has a particle size of 20-50 nm, and the mass ratio of titanium dioxide to zinc oxide is 1:1-2.

5. A method for preparing the polyester spandex blended fabric sublimation fastness improver according to any one of claims 1-4, characterized in that, The method comprises the following steps: S1, preparing a modified polyester-polyether block copolymer: mixing polyester pre-polymer and polyether glycol, and carrying out condensation polymerization under inert gas protection to obtain the modified polyester-polyether block copolymer; S2, preparing a nano composite carrier: dispersing nano titanium dioxide and zinc oxide in ethanol, and then adding a crosslinking agent for reflux reaction after ultrasonic treatment to form a surface coating structure; S3, compounding: mixing the modified polyester-polyether block copolymer of step S1, the nano composite carrier of step S2 and the pH regulator, and carrying out shear emulsification treatment to adjust the pH to neutral.

6. The preparation method of the polyester spandex blended fabric sublimation fastness improver according to claim 5, characterized in that: In S1, the condensation polymerization temperature is 70-80°C; the reaction time is 4-6 hours; and the inert gas is nitrogen; In S2, the mass ratio of nano titanium dioxide to zinc oxide is 1:1-2; the ultrasonic treatment time is 20-40 minutes; the reflux reaction temperature is 55-65°C, and the reaction time is 1.5-2.5 hours.

7. The preparation method of the polyester spandex blended fabric sublimation fastness improver according to claim 5, characterized in that: In S3, the shear emulsification temperature is 40-60°C; the shear rotation speed is 1000-3000 rpm; and the emulsification time is 30-60 minutes.

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