Color fixing agent for polyester and preparation method of color fixing agent

Abstract

The invention belongs to the technical field of textile printing and dyeing, and discloses a color fixing agent for polyester and a preparation method thereof. Polyethyleneimine, glycidyl methacrylate, a cationic monomer and 1-allylimidazole are used as main raw materials, a novel cationic polymer is constructed through amido epoxy ring opening and free radical copolymerization, the cationic polymer has a medium molecular weight, and a molecular chain is rich in acting force anchor points, so that the cationic polymer can be used for preparing a polymer with high molecular weight. Strong electrostatic adsorption, hydrogen bonds, Van der Waals force and the like can be generated with polyester groups, carboxyl groups and dye molecules on the fibers at the same time, so that the affinity adsorption of the dye to the fibers is ensured. Moreover, the color fixing agent molecules with medium chain length can realize rapid permeation in the fiber, and can wrap the dye molecules sufficiently, so that the color fixing effect is improved.

Description

Technical Field

[0001] This invention belongs to the field of textile printing and dyeing technology, specifically relating to a color-fixing agent for polyester and its preparation method. Background Technology

[0002] Polyester fiber possesses excellent tensile strength and chemical resistance, and is widely used in clothing, automotive, and civil engineering industries. However, due to its dense structure, strong hydrophobicity, and lack of chemically active groups, dyeing polyester under aqueous conditions is quite difficult. Therefore, the industry generally uses disperse dyes with low molecular weight and high solubility to dye polyester. However, because there is a lack of strong chemical bonds between the fiber and dye molecules, dye sublimation often occurs during high-temperature finishing of the dyed fabric, resulting in patchy or streaky color changes and decreased color fastness, causing significant production problems. Although this problem can be repaired using methods such as re-reduction washing, it is often costly. Therefore, to prevent the sublimation and migration of disperse dyes and improve color fastness, it is necessary to fix the dyed polyester fabric surface.

[0003] However, due to the inertness of polyester fiber's structure and its tightly packed molecular arrangement, it is difficult for fixing agent molecules to penetrate into the fiber's interior, making color fixing of polyester difficult and a long-standing technical challenge. In existing technologies, most fixing agents are primarily suitable for polyester-cotton blends. For example, Chinese invention patent CN109183468A discloses a fixing agent for black dyeing of polyester-cotton fabrics, whose raw material components, by weight, include: 10-20 parts polyoxyethylene diamine, 5-15 parts epichlorohydrin, 8-10 parts triethanolamine, 2-10 parts ammonium persulfate, 3-6 parts 1,5-dihydroxynaphthalene, 3-5 parts phenolic resin, 0.3-1 part concentrated sulfuric acid, 2-4 parts glacial acetic acid, 2-5 parts 25% ammonia, 3-6 parts ethylene glycol monobutyl ether, and 260-300 parts deionized water. Chinese invention patent CN115726203A discloses a high-fastness fixing agent for polyester-cotton blends. Its raw material components, by weight, include: 30-70 parts of quaternary ammonium salt cationic monomer, 8-15 parts of unsaturated amines such as acrylamide, 2-6 parts of epichlorohydrin, 1-5 parts of small molecule acid cationic chain extender, 8-15 parts of polyol, 1-4 parts of persulfate initiator, and 10-25 parts of soft water. Chinese invention patent CN114753171A discloses a cationic hydrophilic polyester fixing agent. Its raw material components, by weight, include: 40-50 parts of epichlorohydrin, 35-45 parts of small molecule amine, 3-10 parts of quaternary ammonium salt cationic monomer, 0.1-1 part of initiator, an appropriate amount of chelating agent, and 5-10 parts of deionized water. The aforementioned color-fixing agents each have their own advantages in terms of fastness to polyester and polyester-cotton fabrics, but without exception, they all use epichlorohydrin as a raw material. While epichlorohydrin plays a crucial role in the preparation of various color-fixing agents as an excellent crosslinking monomer, it is also a toxic and hazardous substance that can paralyze the central nervous system and poses a carcinogenic risk, harming human health. Therefore, color-fixing agents using epichlorohydrin as a raw material do not meet environmental protection requirements and are not conducive to industrial production.

[0004] Therefore, there is an urgent need to develop a new fixing agent for polyester using environmentally friendly and safe raw materials to improve the fixing effect and better meet the growing market demand. Summary of the Invention

[0005] This invention aims to solve at least one of the technical problems existing in the prior art. To this end, this invention proposes a fixing agent for polyester and its preparation method. This invention abandons the unhealthy and environmentally friendly epichlorohydrin, using non-toxic and harmless raw materials. During the fixing process, the fixing agent molecules can quickly penetrate into the interior of the polyester fiber, forming a strong interaction between the dye and the fiber, enhancing the fixing effect and improving the sublimation fastness and wash fastness of the dye.

[0006] To solve the above-mentioned technical problems, a first aspect of the present invention provides a color-fixing agent, the raw material components of which include a cationic polymer and an auxiliary agent, wherein the chemical structural formula of the cationic polymer is shown in formula (1) or formula (2):

[0007] Equation (1)

[0008] Equation (2) Wherein: R1 and R2 are independently selected from C1-18 alkyl groups, and m, n, x, and y are all integers between 2 and 25.

[0009] Specifically, most polyester fibers have a high degree of structural regularity and are densely packed, which strongly hinders the diffusion of dye molecules in the fiber. Furthermore, the narrow fiber gaps also hinder the penetration of fixing agent molecules with larger molecular weights and longer molecular chains. Based on this, the present invention constructs a cationic polymer with a chemical structure as shown in formula (1) or formula (2). This cationic polymer has a medium molecular weight and its molecular chains are rich in force anchoring points, allowing it to simultaneously generate strong electrostatic adsorption, hydrogen bonding, and van der Waals forces with polyester groups, carboxyl groups (negatively charged), and dye molecules (negatively polar) on the fiber, thereby ensuring the affinity adsorption of the dye onto the fiber (see [link to relevant documentation]). Figure 1 Moreover, medium-chain-length fixing agent molecules can both rapidly penetrate the fiber and encapsulate the dye molecules, which helps to improve the color-fixing effect.

[0010] In some embodiments of the present invention, R1 and R2 are independently selected from CH3 and C, respectively. 12 H 25 C 16 H 33 Or C 18 H 37 .

[0011] In some embodiments of the present invention, m is an integer between 10 and 12, and n is an integer between 10 and 20.

[0012] In some embodiments of the present invention, x is an integer between 3 and 5, and y is an integer between 10 and 15.

[0013] In some embodiments of the present invention, the preparation process of the cationic polymer includes the following steps: (1) After neutralizing polyethyleneimine with an acidifying agent, glycidyl methacrylate is added under an inert atmosphere to carry out a ring-opening reaction. After the reaction is completed, the reaction product is obtained. (2) Add a cationic monomer, 1-allylimidazolium and an initiator to the reaction product and carry out a copolymerization reaction to obtain the cationic polymer.

[0014] In some embodiments of the present invention, the cationic monomer is selected from at least one of trimethylallyl ammonium chloride, dodecyl dimethylallyl ammonium chloride, hexadecyl dimethylallyl ammonium chloride, and octadecyl dimethylallyl ammonium chloride.

[0015] In some embodiments of the present invention, the polyethyleneimine is selected from linear polyethyleneimine or branched polyethyleneimine, wherein the weight-average molecular weight of the linear polyethyleneimine is 500-800, and the weight-average molecular weight of the branched polyethyleneimine is 1500-2000. That is, low molecular weight linear polyethyleneimine or low molecular weight branched polyethyleneimine is used.

[0016] When linear polyethyleneimine is used as the raw material, the chemical structure of the cationic polymer is shown in formula (1); when linear branched polyethyleneimine is used as the raw material, the chemical structure of the cationic polymer is shown in formula (2).

[0017] Specifically, the present invention first uses polyethyleneimine and glycidyl methacrylate (GMA) as starting materials to carry out an amino epoxy ring-opening reaction; then the reaction product is subjected to a free radical copolymerization reaction with a cationic monomer and 1-allyl imidazole under the action of an initiator to obtain the cationic polymer.

[0018] Taking linear polyethyleneimine as an example and trimethylallyl ammonium chloride as the cationic monomer, the synthetic route of the cationic polymer is as follows: (1) Ring-opening reaction:

[0019]

[0020] (2) Copolymerization reaction:

[0021] In some embodiments of the present invention, the acidifying agent is selected from at least one of glacial acetic acid, dilute hydrochloric acid, and ammonium chloride.

[0022] In some embodiments of the present invention, the initiator is selected from at least one of sodium persulfate, ammonium persulfate, potassium persulfate, and azobisisobutyronitrile.

[0023] In some embodiments of the present invention, the amount of the initiator is 0.01-2.0% of the total mass of polyethyleneimine, GMA, cationic monomer and 1-allylimidazol; preferably 0.1-0.5%.

[0024] In some embodiments of the present invention, the inert atmosphere is a nitrogen atmosphere, an argon atmosphere, or a helium atmosphere.

[0025] In some embodiments of the present invention, the molar ratio of polyethyleneimine to glycidyl methacrylate is (1-2):1.

[0026] In some embodiments of the present invention, the molar ratio of the cationic monomer, 1-allyl imidazole and the reaction product is (1-10):1:(0.1-1).

[0027] In some embodiments of the present invention, the temperature of the ring-opening reaction is 20-100°C; preferably 40-60°C.

[0028] In some embodiments of the present invention, the ring-opening reaction takes 0.5-6 hours; preferably 2.5-4 hours. The reaction is considered complete when the characteristic peak of the epoxy group disappears completely as monitored by infrared spectroscopy.

[0029] In some embodiments of the present invention, the temperature of the copolymerization reaction is 40-120°C; preferably 75-90°C.

[0030] In some embodiments of the present invention, the copolymerization reaction takes 0.5-10 hours; preferably 3-4 hours.

[0031] In some embodiments of the present invention, the additive is selected from at least one of cationic reinforcing agents, fatty alcohol polyoxyethylene ethers, dispersants, and soft water.

[0032] In some embodiments of the present invention, the mass ratio of the cationic polymer to the auxiliaries is 1:(1-4).

[0033] In some embodiments of the present invention, the raw material components of the color-fixing agent include, by weight: 25-45 parts of cationic polymer, 2-5 parts of cationic reinforcing agent, 1-3 parts of fatty alcohol polyoxyethylene ether (JFC), 0.5-2 parts of dispersant, and 50-75 parts of soft water.

[0034] In some embodiments of the present invention, the cationic enhancer may be a commonly used cationic enhancer in the art, such as Lupasol PN50.

[0035] In some embodiments of the present invention, the dispersant may be a commonly used dispersant in the art, such as SokalanHP 22.

[0036] A second aspect of the present invention provides a method for preparing the above-mentioned fixing agent, comprising the following steps: The raw material components for preparing the curing agent are mixed to obtain the color-fixing agent.

[0037] A third aspect of the present invention provides the application of the above-mentioned fixing agent in the fixing of polyester fibers.

[0038] In some embodiments of the present invention, the polyester is selected from polyester fabrics or polyester-cotton fabrics with high polyester content.

[0039] Compared with the prior art, the above-described technical solution of the present invention has at least the following technical effects or advantages: (1) This invention uses polyethyleneimine, glycidyl methacrylate, cationic monomers and 1-allyl imidazole as main raw materials, and constructs cationic polymers with chemical structures such as formula (1) or formula (2) through ring-opening of amino epoxy and free radical copolymerization. The cationic polymer has a medium molecular weight and is rich in force anchors on the molecular chain, which can generate strong electrostatic adsorption, hydrogen bonding and van der Waals forces with polyester groups, carboxyl groups and dye molecules on the fiber at the same time, thereby ensuring the affinity adsorption of dye to fiber. Moreover, the medium chain length of the fixing agent molecule can not only achieve rapid penetration into the fiber, but also encapsulate the dye molecules, which is beneficial to improving the fixing effect.

[0040] (2) The color-fixing agent of the present invention does not involve any toxic or harmful substances in the synthesis process, and is green and environmentally friendly; and the color-fixing agent has excellent color fastness, which can effectively reduce the cost of wastewater treatment after dyeing, and is conducive to energy conservation and consumption reduction. Attached Figure Description

[0041] Figure 1 This is a schematic diagram of the fixing force of the fixing agent of the present invention; Figure 2 The infrared spectrum of the cationic polymer prepared in Example 1 of this invention; Figure 3 The results are from a water fastness test on a 15 g / L concentration of color-fixing agent. Figure 4 The results are from a water fastness test of a 40 g / L fixing agent. Detailed Implementation

[0042] The present invention will now be described in detail with reference to embodiments to facilitate understanding of the invention by those skilled in the art. It is particularly important to note that the embodiments are merely illustrative of the invention and should not be construed as limiting the scope of protection of the invention. Non-essential improvements and adjustments made to the invention by those skilled in the art based on the above description should still fall within the scope of protection of the invention. Furthermore, all raw materials mentioned below, unless otherwise specified, are commercially available products; all process steps or preparation methods not mentioned in detail are process steps or preparation methods known to those skilled in the art.

[0043] Example 1 A color-fixing agent, the raw material components of which, by weight, include: 38 parts of cationic polymer, 3 parts of cationic reinforcing agent Lupasol PN50, 3 parts of fatty alcohol polyoxyethylene ether JFC, 1 part of dispersant Sokalan HP 22, and 55 parts of soft water.

[0044] The chemical structural formula of the cationic polymer is shown in formula (3):

[0045] Equation (3) Where m is an integer between 10 and 12, and n is an integer between 10 and 20.

[0046] The preparation method of the above-mentioned fixing agent includes the following steps: (1) Add 265g of low molecular weight linear polyethyleneimine PL-60 (average molecular weight Mw≈600) to a 500mL four-necked flask equipped with a mechanical stirrer and condenser, and start stirring. Add a small amount of glacial acetic acid to adjust the pH of the system to 3-4. After heating to 45℃ under nitrogen protection, start adding 57g of glycidyl methacrylate dropwise, which will be completed in 30min. Then maintain the reaction temperature at 45-50℃ and stir continuously for 3 hours at a stirring speed of 300rpm. Take a sample every 30min during the reaction for infrared spectroscopy analysis until the spectrum reaches 910-920cm. -1 The reaction is considered complete when the characteristic peaks of the epoxy groups completely disappear, yielding a bright yellow transparent liquid A.

[0047] (2) In a 1000 mL four-necked flask, 217 g of trimethylallyl ammonium chloride solution (50 wt%), 22 g of 1-allyl imidazole, and 66 g of liquid A were added sequentially, maintaining the theoretical molar ratio of the raw materials at 4:1:0.4. At 70 °C, under nitrogen protection, 1.0 mL of saturated ammonium persulfate solution was added dropwise, and the addition was completed in 15 min. Then, the reaction was carried out at 80-85 °C for 2 hours with a stirring speed of 200 rpm. After the reaction was completed, a slightly viscous, deep yellow transparent liquid B was obtained, which is the cationic polymer of this embodiment. Its dynamic viscosity (25 °C, S3, 100 rpm, where S3 represents rotor No. 3) was tested to be 882 cp.

[0048] (3) At room temperature, add deep yellow transparent liquid B, Lupasol PN50, JFC, Sokalan HP 20 and soft water to the mixing tank, stir at 500 rpm for 30 minutes and then let stand for 1 hour. Filter out the material and collect the light yellow transparent solution, which is the color fixing agent of this embodiment, with a pH value of 5.6.

[0049] Figure 2The image shows the infrared spectrum of the cationic polymer obtained in Example 1. Figure 2 As can be seen from this, 3163cm -1 The broad peak at 2968 cm⁻¹ is attributed to the stretching vibration of OH in the branched structure. -1 These absorption peaks belong to the stretching vibrations of CH in -CH3 and -CH2-. After the ring-opening condensation of polyethyleneimine with GMA, the -C=NH group undergoes a redshift due to the conjugation effect of adjacent imine groups, reaching 2100-2200 cm⁻¹. -1 There is a distinct absorption peak between them. 1649cm -1 1553cm -1 1400cm -1 1292cm -1 These absorptions are attributed to the symmetrical absorption of the carbonyl group of methacrylate, the asymmetric angle-changing absorption of the quaternary ammonium salt cation, the bending vibration of -C=N in the imidazole group, and the stretching vibration of -CN. The branched structure contains numerous positively charged imine groups, and its characteristic peak extends from 1800 cm⁻¹. -1 The peaks are present in the fingerprint region, but due to the large number and complexity of peaks, they often overlap with the absorption peaks of other groups.

[0050] Example 2 A color-fixing agent, the raw material components of which, by weight, include: 38 parts of cationic polymer, 3 parts of cationic reinforcing agent Lupasol PN50, 3 parts of fatty alcohol polyoxyethylene ether JFC, 1 part of dispersant Sokalan HP 22, and 55 parts of soft water.

[0051] The chemical structural formula of the cationic polymer is shown in formula (4):

[0052] Equation (4) Where m is an integer between 10 and 12, and n is an integer between 10 and 20.

[0053] The preparation method of the above-mentioned fixing agent includes the following steps: (1) Add 265g of low molecular weight linear polyethyleneimine PL-60 (average molecular weight Mw≈600) to a 500mL four-necked flask equipped with a mechanical stirrer and condenser, and start stirring. Add a small amount of glacial acetic acid to adjust the pH of the system to 3-4. After heating to 45℃ under nitrogen protection, start adding 57g of glycidyl methacrylate dropwise, which will be completed in 30min. Then maintain the reaction temperature at 45-50℃ and stir continuously for 3 hours at a stirring speed of 300rpm. Take a sample every 30min during the reaction for infrared spectroscopy analysis until the spectrum reaches 910-920cm. -1 The reaction is considered complete when the characteristic peaks of the epoxy groups completely disappear, yielding a bright yellow transparent liquid A.

[0054] (2) In a 1000 mL four-necked flask, 217 g of dodecyl dimethyl allyl ammonium chloride solution (50 wt%), 22 g of 1-allyl imidazole, and 66 g of liquid A were added sequentially, maintaining the theoretical molar ratio of the raw materials at 4:1:0.4. At 70 °C, under nitrogen protection, 1.0 mL of saturated sodium sulfate solution was added dropwise, which was completed in 15 min. Then, the reaction was carried out at 80-85 °C for 2 hours with a stirring speed of 200 rpm. After the reaction was completed, a slightly viscous yellow transparent liquid B was obtained, which is the cationic polymer of this embodiment. Its dynamic viscosity (25 °C, S3, 100 rpm, S3 represents rotor No. 3) was tested to be 799 cp.

[0055] (3) At room temperature, add yellow transparent liquid B, Lupasol PN50, JFC, Sokalan HP 20 and soft water to the mixing tank, stir at 500 rpm for 30 minutes and then let stand for 1 hour. Filter out the material and collect the light yellow transparent solution, which is the color fixing agent of this embodiment, with a pH value of 6.0.

[0056] Example 3 A color-fixing agent, the raw material components of which, by weight, include: 38 parts of cationic polymer, 3 parts of cationic reinforcing agent Lupasol PN50, 3 parts of fatty alcohol polyoxyethylene ether JFC, 1 part of dispersant Sokalan HP 22, and 55 parts of soft water.

[0057] The chemical structural formula of the cationic polymer is shown in formula (5):

[0058] Equation (5) Where: x is an integer between 3 and 5, and y is an integer between 10 and 15.

[0059] The preparation method of the above-mentioned fixing agent includes the following steps: (1) Add 265g of low molecular weight branched polyethyleneimine PB-10 (average molecular weight Mw≈1800) to a 500mL four-necked flask equipped with a mechanical stirrer and condenser, and start stirring. Add a small amount of glacial acetic acid to adjust the pH of the system to 3-4. After heating to 45℃ under nitrogen protection, start adding 57g of glycidyl methacrylate dropwise, which will be completed in 30min. Then maintain the reaction temperature at 45-50℃ and stir continuously for 3 hours at a stirring speed of 300rpm. Take a sample every 30min during the reaction for infrared spectroscopy analysis until the spectrum reaches 910-920cm. -1 The reaction is considered complete when the characteristic peaks of the epoxy groups completely disappear, yielding a bright yellow transparent liquid A.

[0060] (2) In a 1000 mL four-necked flask, 217 g of trimethylallyl ammonium chloride solution (50 wt%), 22 g of 1-allyl imidazole, and 66 g of liquid A were added sequentially, maintaining the theoretical molar ratio of the raw materials at 4:1:0.4. At 70 °C, under nitrogen protection, 1.0 mL of saturated ammonium persulfate solution was added dropwise, and the addition was completed in 15 min. Then, the reaction was carried out at 80-85 °C for 2 hours with a stirring speed of 200 rpm. After the reaction was completed, a slightly viscous, light brown transparent liquid B was obtained, which is the cationic polymer of this embodiment. Its dynamic viscosity (25 °C, S4, 100 rpm, where S4 represents rotor No. 4) was tested to be 1047 cp.

[0061] (3) At room temperature, add yellow transparent liquid B, Lupasol PN50, JFC, Sokalan HP 20 and soft water to the mixing tank, stir at 500 rpm for 30 minutes and then let stand for 1 hour. Filter out the material and collect the light yellow transparent solution, which is the color fixing agent of this embodiment, with a pH value of 5.1.

[0062] Example 4 A color-fixing agent, the raw material components of which, by weight, include: 38 parts of cationic polymer, 3 parts of cationic reinforcing agent Lupasol PN50, 3 parts of fatty alcohol polyoxyethylene ether JFC, 1 part of dispersant Sokalan HP 22, and 55 parts of soft water.

[0063] The chemical structural formula of the cationic polymer is shown in formula (6):

[0064] Equation (6) Where: x is an integer between 3 and 5, and y is an integer between 10 and 15.

[0065] The preparation method of the above-mentioned fixing agent includes the following steps: (1) Add 265g of low molecular weight branched polyethyleneimine PB-10 (average molecular weight Mw≈1800) to a 500mL four-necked flask equipped with a mechanical stirrer and condenser, and start stirring. Add a small amount of glacial acetic acid to adjust the pH of the system to 3-4. After heating to 45℃ under nitrogen protection, start adding 57g of glycidyl methacrylate dropwise, which will be completed in 30min. Then maintain the reaction temperature at 45-50℃ and stir continuously for 3 hours at a stirring speed of 300rpm. Take a sample every 30min during the reaction for infrared spectroscopy analysis until the spectrum reaches 910-920cm. -1 The reaction is considered complete when the characteristic peaks of the epoxy groups completely disappear, yielding a bright yellow transparent liquid A.

[0066] (2) In a 1000 mL four-necked flask, 217 g of dodecyl dimethyl allyl ammonium chloride solution (50 wt%), 22 g of 1-allyl imidazole, and 66 g of liquid A were added sequentially, maintaining the theoretical molar ratio of the raw materials at 4:1:0.4. At 65 °C, under nitrogen protection, 1.0 mL of saturated AIBN solution was added dropwise, completing the addition in 15 min. Then, the reaction was carried out at 80-85 °C for 2 hours with a stirring speed of 200 rpm. After the reaction was complete, a slightly viscous, brownish-yellow transparent liquid B was obtained, which is the cationic polymer of this embodiment. Its dynamic viscosity (25 °C, S4, 100 rpm, where S4 represents rotor No. 4) was tested to be 1232 cp.

[0067] (3) At room temperature, add brownish-yellow transparent liquid B, Lupasol PN50, JFC, Sokalan HP 20 and soft water to the mixing tank, stir at 500 rpm for 30 minutes and then let stand for 1 hour. Filter out the material and collect the light yellow transparent solution, which is the color fixing agent of this embodiment, with a pH value of 5.1.

[0068] Comparative Example 1 The only difference between Comparative Example 1 and Example 1 is that the fixing agent of Comparative Example 1 uses an equal amount of ethylenediamine to replace the linear polyethyleneimine in Example 1 during the preparation process, and the pH value of the resulting fixing agent is 5.0.

[0069] Comparative Example 2 The only difference between Comparative Example 2 and Example 1 is that the fixing agent in Comparative Example 2 uses an equal amount of triethylamine to replace the linear polyethyleneimine in Example 1 during the preparation process, and the pH value of the resulting fixing agent is 5.2.

[0070] Comparative Example 3 The only difference between Comparative Example 3 and Example 1 is that the fixing agent in Comparative Example 3 uses an equal amount of high molecular weight polyethyleneimine MD-12 (average molecular weight M) during the preparation process. w =20000-30000) Replaces the low molecular weight polyethyleneimine in Example 1. In the experiment, it was found that the solution B prepared in step (2) of Comparative Example 3 was a dark yellow semi-transparent turbid liquid, which became clear and transparent after adding a small amount of water. However, in the preparation process of step (3), a small amount of beige insoluble matter was produced at the bottom of the pot. After centrifugation, a yellow slightly viscous transparent liquid was obtained by filtration with a pH value of 5.9.

[0071] Comparative Example 4 The only difference between Comparative Example 4 and Example 1 is that the fixing agent in Comparative Example 4 did not contain a cationic polymer. Its raw material components, by weight, included: 20 parts of cationic reinforcing agent Lupasol PN50, 20 parts of fatty alcohol polyoxyethylene ether JFC, 6 parts of dispersant Sokalan HP 22, and 54 parts of soft water. The fixing agent solution obtained in Comparative Example 4 was a light yellow transparent solution, and the pH was adjusted to 5.5 with glacial acetic acid.

[0072] Performance testing 1. Estimation of molecular weight of cationic polymers In 2014, engineers at Shin Etsu Chemicals in Japan conducted extensive research and testing on silicone oils of different molecular weights, summarized the relationship between dynamic viscosity and viscosity-average molecular weight, and proposed the following empirical formula (AJFormula): (1); in: This represents the kinematic viscosity of the polymer at 25°C, expressed in mm. 2 / s; This represents the viscosity-average molecular weight of the polymer. α is an exponent, ranging from 0.50 to 0.55.

[0073] Subsequently, this formula was proven to be equally applicable to many other polymer systems, including polyethers, polyamides, polyacrylates, and polyacrylonitrile. Therefore, this invention uses this empirical formula to estimate the molecular weight of cationic polymers.

[0074] Taking Example 1 as an example, the main active ingredient in the deep yellow transparent liquid B is a cationic polymer, with a content of approximately 70%. Rotary evaporation removes most of the water, and the resulting viscous solution has a kinematic viscosity of 945 cp. Since the kinematic viscosity of water at 25°C is <1 cp, the kinematic viscosity of this deep yellow transparent liquid B is very close to that of 100% cationic polymer. Under normal conditions, the relationship between kinematic viscosity μ and kinematic viscosity ν is: (2); Where: ρ is the density of the polymer solution, in g / cm³. 3 With μ=945cp and ρ=1.28g / cm³, 3 Substituting into formulas (1) and (2), the viscosity-average molecular weight range was calculated to be 9200-23000. Because polyester fibers have a very tight molecular arrangement and small intermolecular gaps, it is difficult for fixing agents with larger molecular weights and longer molecular chains to penetrate and fix the color. However, if the fixing agent has a very small molecular weight, although it can easily penetrate into the fiber, it is easily washed away due to insufficient interaction with the fiber, resulting in poor wash fastness. Therefore, based on the results of subsequent application experiments, this estimation result is reasonable and in line with the expectations of this invention.

[0075] 2. Colorfastness The dyeing process for polyester fabrics is as follows: First, soak the polyester fabric in 1.5 g / L TF-1151 cleaning solution for 20 minutes. After removal, rinse with 40℃ warm water for 10 minutes, dehydrate, and pre-dry at 80℃. Take 300 g of dry polyester fabric and put it into a high-temperature and high-pressure dyeing machine. Add 6 g of dispersing leveling agent TF-1011 and adjust the pH to 4.0-5.5 with glacial acetic acid. Set the liquor ratio to 1:15. After running for 20 minutes, inject the disperse dye mixture (dye ratio: Disperse Ruby SE-GFL 1.5% owf, Disperse Yellow Brown S-2RFL 1.5% owf, Disperse Blue HGL 5% owf). Increase the temperature to 75℃ at 2℃ / min and hold for 15 minutes. Then, increase the temperature to 130℃ at a rate of 1.5℃ / min and hold for 60 minutes under high pressure. After dyeing, decrease the temperature to 80℃ at a gradient of 2℃ / min and drain the solution.

[0076] Impregnation and color-fixing process: The color-fixing agents prepared in Examples 1-4 and Comparative Examples 1-4 were formulated into sample working solutions of two concentrations: 15 g / L and 40 g / L, respectively. The samples were impregnated and rubbed twice, with a liquid retention rate of 80%. The samples were baked at 160°C for 3 minutes on a setting machine, then rinsed with soft water at 50°C for 1 minute. Finally, the samples were treated with 1 g / L of antistatic finishing agent TF-481A, dehydrated, and then dried and set with hot air at 100°C.

[0077] The test method for the water immersion fastness of the color-fixed polyester fabric is as follows: First, dissolve 2g of Tide laundry detergent in 100mL of deionized water. Then, take 2g of the cut color-fixed fabric sample, immerse it in the soap solution, and place it in a shaking color testing machine. Shake and vibrate it in an 85℃ water bath for 5 minutes. After cooling, remove the fabric and observe the color of the residual liquid. According to GB / T 3920-2008 Textiles - Tests for Color Fastness to Rubbing, the dry and wet rubbing fastness grades of the color-fixed polyester fabric are assessed using GB / T 251-2008 Textiles - Tests for Color Fastness to Rubbing - Gray Scale for Staining. The results are as follows. Figure 3-4 As shown in Table 1, grades 1-5 represent the fastness rating, with grade 5 being the best and grade 1 being the worst.

[0078] Figure 3 and Figure 4 The results are shown in the water fastness test results for two concentrations of fixing agent, 15 g / L and 40 g / L, respectively. The lighter the color, the better the fastness. The blank group is the sample that has not been fixed.

[0079] Table 1: Comparison of rubbing fastness of polyester fabrics after color fixing

[0080] Figure 3-4Table 1 shows the blister fastness and rubbing fastness of the fabric samples after color fixation treatment. The results show that the polyester fabrics treated with the color fixation agents prepared in Examples 1-4 have good color fastness and rubbing fastness.

[0081] Depend on Figure 3-4 It can be seen that when the color-fixing agent reaches a high concentration of 40g / L or above, the residual color of the fabric sample after soaking in water is very light, proving that the treated fabric sample has very little color loss and excellent fastness.

[0082] As shown in Table 1, the color-fixing agents of Examples 1-4, when used in the same amount, all achieved a dry and wet rubbing fastness of grade 4 or higher, demonstrating excellent color-fixing and rubbing fastness. In contrast, Comparative Examples 1-2, due to the use of small-molecule polyamines instead of polyethyleneimine, significantly reduced the anchor points of the cationic polymers, weakening the adsorption force between the color-fixing agent molecules and the fibers and dyes, resulting in a lower color-fixing effect. In Comparative Example 3, when high-molecular-weight polyethyleneimine was used as a raw material, the low reactivity of the terminal amine groups restricted its ring-opening with the epoxy groups, and the high-molecular-weight branched chains affected the penetration of the color-fixing agent molecules onto the fiber surface and subsequent color-fixing, resulting in water fastness and rubbing fastness that were 1-2 grades lower than those of the Examples. In Comparative Example 4, when only the compound components from the Examples were used for color-fixing, although multiple components contained polyethyleneimine derivatives that could generate certain interactions with the fibers or dyes, the lack of a cationic polymer backbone structure capable of strong adsorption resulted in generally poor water wash and water immersion performance after color-fixing, indicating a poor overall effect.

[0083] For those skilled in the art, several simple deductions or substitutions can be made without departing from the inventive concept, without requiring creative effort. Therefore, any simple improvements made to this invention by those skilled in the art based on the disclosure of this invention should be within the scope of protection of this invention. The above embodiments are preferred embodiments of this invention, and all processes similar to this invention and equivalent changes should fall within the scope of protection of this invention.

Claims

1. A color-fixing agent, characterized in that, Its raw material components include cationic polymers and additives, and the chemical structural formula of the cationic polymer is shown in formula (1) or formula (2): Equation (1) Equation (2) Wherein: R1 and R2 are independently selected from C1-18 alkyl groups, and m, n, x, and y are all integers between 2 and 25.

2. The fixing agent according to claim 1, characterized in that, R1 and R2 are independently selected from CH3 and C, respectively. 12 H 25 C 16 H 33 Or C 18 H 37 .

3. The color-fixing agent according to claim 1, characterized in that, The preparation process of the cationic polymer includes the following steps: (1) After neutralizing polyethyleneimine with an acidifying agent, glycidyl methacrylate is added under an inert atmosphere to carry out a ring-opening reaction. After the reaction is completed, the reaction product is obtained. (2) Add a cationic monomer, 1-allylimidazolium and an initiator to the reaction product and carry out a copolymerization reaction to obtain the cationic polymer.

4. The fixing agent according to claim 3, characterized in that, The polyethyleneimine is selected from linear polyethyleneimine or branched polyethyleneimine, wherein the weight-average molecular weight of the linear polyethyleneimine is 500-800, and the weight-average molecular weight of the branched polyethyleneimine is 1500-2000. And / or, the cationic monomer is selected from at least one of trimethylallyl ammonium chloride, dodecyl dimethylallyl ammonium chloride, hexadecyl dimethylallyl ammonium chloride, and octadecyl dimethylallyl ammonium chloride.

5. The fixing agent according to claim 3, characterized in that, The molar ratio of polyethyleneimine to glycidyl methacrylate is (1-2):1; And / or, the molar ratio of the cationic monomer, 1-allylimidazolium and the reaction product is (1-10):1:(0.1-1).

6. The fixing agent according to claim 3, characterized in that, The ring-opening reaction is carried out at a temperature of 20-100℃, and the copolymerization reaction is carried out at a temperature of 40-120℃.

7. The fixing agent according to claim 1, characterized in that, The additive is selected from at least one of cationic reinforcing agents, fatty alcohol polyoxyethylene ethers, dispersants, and soft water, and the mass ratio of the cationic polymer to the additive is 1:(1-4).

8. The fixing agent according to claim 7, characterized in that, Its raw material components, by weight, include: 25-45 parts cationic polymer, 2-5 parts cationic reinforcing agent, 1-3 parts fatty alcohol polyoxyethylene ether, 0.5-2 parts dispersant, and 50-75 parts soft water.

9. A method for preparing a color-fixing agent as described in any one of claims 1-8, characterized in that, Includes the following steps: The raw material components for preparing the curing agent are mixed to obtain the color-fixing agent.

10. The application of the fixing agent according to any one of claims 1-8 in the fixing of polyester fibers.

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