Multifunctional finishing agent, preparation method and application thereof

Abstract

The application discloses a multifunctional finishing agent, a preparation method and application thereof, relates to the field of functional textile materials and wool fabric finishing technology, and raw materials include silicone modified waterborne polyurethane emulsion and wax emulsion based on multiple dynamic reversible action, and the silicone modified waterborne polyurethane emulsion and the wax emulsion can play the roles of self-repairing and anti-pilling of the wool fabric. The self-repairing system with multiple reversible crosslinking structures is constructed, namely, a trinity of hydrogen bond-disulfide bond-ion bond cooperatively forms a closed loop of adsorption-repairing-reinforcing, so that the thin film formed on the surface of the fabric has the wound self-repairing performance under low temperature conditions, the durability of the fabric is given, and the wearability of the fabric is prolonged.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of functional textile materials and wool fabric finishing technology, and particularly relates to a multifunctional finishing agent, a preparation method and application. BACKGROUND

[0002] Wool fabric, as a high-grade textile material, has a wide range of applications in many fields such as clothing and home decoration. However, in the daily wearing and using process, wool fabric inevitably suffers from various rubbing actions. When the scale structure of wool fiber is rubbed, the end of the fiber is easily pulled out of the surface of the fabric to form fluff. These fluffs will further entangle together under the action of continuous friction and gradually form a ball. The pilling phenomenon makes the surface of the fabric rough and uneven, reduces its aesthetic and grade, and further affects the acceptance and satisfaction of consumers to wool products.

[0003] For wool fabric anti-pilling finishing, many research results have been reported in the existing chemical finishing technology, but these finishing agents still have many shortcomings in practical production application. For example, the invention patent CN102995419B discloses a kind of wool anti-pilling finishing agent, which is prepared from hexamethylene diisocyanate, polyoxypropylene glycol, diethylene glycol, dimethylol butyric acid and ethylenediamine. But the finishing film formed on the surface of wool fiber by this finishing agent may be too hard or thick, which greatly reduces the softness of the fabric, making the originally soft and comfortable wool fabric become stiff, affecting the wearing experience. At the same time, this finishing agent has a sticky phenomenon, which will stick to the roller during application, and is not friendly to the machine, resulting in low production efficiency. At the same time, some scholars refer to the synthesis method of similar waterborne polyurethane resin emulsion to prepare wool finishing agent, for example, the invention patent CN117127409A discloses a preparation method of multifunctional water-repellent antibacterial durable organic silicon polyurethane fabric treatment agent, which is prepared from isocyanate, polysiloxane, polyether, antibacterial agent and self-healing agent modified organic silicon waterborne polyurethane fabric coating material. Although the introduction of organic silicon and self-healing agent in this finishing agent makes the hand feeling of the finished fabric not affected, and also has self-repairing property, but the self-repairing effect is relatively not strong enough. And this method does not have hydrophilic monomer when preparing prepolymer, and the viscosity is large, so more organic solvents need to be added to adjust the viscosity. This method uses acetone or tetrahydrofuran as viscosity regulator, even if it is removed by rotary evaporation, there will still be residues, and the use of toxic reagents such as acetone or tetrahydrofuran is also limited in textile production. In addition, the prepared emulsion is unstable and stratifies after a long time.

[0004] Therefore, there is an urgent need in the market to develop an efficient, environmentally friendly, durable and multifunctional anti-pilling finishing agent with excellent performance and less impact on the hand feeling, air permeability and moisture absorption of wool fabric. SUMMARY

[0005] The purpose of the present application is to overcome the shortcomings of the prior art and provide a multifunctional finishing agent, a preparation method and an application.

[0006] The purpose of the present application is achieved by the following technical solutions:

[0007] The first aspect of the present application provides a multifunctional finishing agent, comprising the following raw materials in parts by weight: 50-100 parts of modified silicone waterborne polyurethane emulsion based on multiple dynamic reversible action, and 2.5-5 parts of wax emulsion.

[0008] The present application obtains a multifunctional finishing agent by compounding modified polyurethane emulsion and wax emulsion, which has good self-repairing and wool anti-pilling performance. After applying it to the fabric, the two emulsions jointly act to form a low surface energy on the surface of the fabric, reduce the friction coefficient, and the finished fabric is not sticky, and the stiffness, hand feeling and air permeability of the finished wool fabric are not affected; and it is stable in production and application, and continuously runs without sticking to the roller during machine processing.

[0009] The raw materials of the present application include modified silicone waterborne polyurethane emulsion based on multiple dynamic reversible action. Here, "modification" refers to modification of silicone and further modification based thereon to prepare waterborne polyurethane with multiple dynamic reversible crosslinking structure, which forms a "hydrogen bond-disulfide bond-ionic bond" three-in-one synergistic self-healing system of non-covalent hydrogen bond crosslinking, dynamic reversible covalent bond disulfide bond and ionic cluster containing sulfonate side chain. When used for preparing fabric finishing agent, it can form a film on the surface of the fabric and realize the "wound" self-repairing effect at low temperature, and has better self-repairing performance on the fabric. When the fabric film is damaged in a low temperature environment, the hydrogen bond first quickly adsorbs the fracture interface, the disulfide bond is broken and recombined to realize structure splicing, and the ionic bond is simultaneously tightened to maintain the original density of the repaired film, thereby realizing self-repairing and strengthening durability.

[0010] Meanwhile, the ionic bond formed between the non-covalent hydrogen bond and the sulfonate side chain constitutes a "supporting network", providing a stable reaction environment for the dynamic recombination of the dynamic reversible covalent bond disulfide bond, avoiding the disordered diffusion of molecular chains during the repair process; the breakage and recombination of the disulfide bond further compensate for the defects of insufficient strength of hydrogen bond alone and poor reversibility of ionic bond alone; and the ionic bond enhances the intermolecular force to improve the persistence of the synergistic action of hydrogen bond and disulfide bond.

[0011] Preferably, the wax emulsion is one of the OE series, and the solid content is 20%-30%.

[0012] Preferably, the solid content of the modified silicone waterborne polyurethane emulsion based on multiple dynamic reversible action is 30%, and the particle size is 100-150 nm. The modified silicone waterborne polyurethane emulsion of the present application can be better compounded with the wax emulsion under the solid content and particle size.

[0013] Preferably, the raw materials for preparing the modified silicone waterborne polyurethane emulsion based on multiple dynamic reversible action include: polyisocyanate, polyester polyol, dimethylol propionic acid (DMPA), hydroxypropyl dimethicone, catalyst, compound containing dynamic reversible disulfide bond, polyhydroxy alcohol amine, sulfamate, sodium bisulfite (NaHSO3), sodium sulfite (Na2SO3), triethylamine (TEA), viscosity regulator, deionized water.

[0014] The hydroxypropyl dimethicone silicone modification introduced in the application not only improves the crosslinking of the polymer to achieve good film forming effect, but on the other hand, it also synergistically improves the softness of the fabric and reduces the surface energy with other ingredients, so that the final finishing agent not only has excellent anti-pilling performance, but also maintains the smooth and soft hand feeling.

[0015] Further, the modified silicone waterborne polyurethane of the application also forms a hyperbranched structure, so that the polymer has low viscosity, easy control, less chain entanglement, high solubility, and the introduction of hydrophilic monomer DMPA makes the self-emulsifying effect of the whole polyurethane good, the prepared emulsion is stable in state, does not separate after centrifugation, has excellent dispersibility, further optimizes the compatibility with other additives, and the highly branched topological structure provides a three-dimensional support skeleton for the self-repairing system, further strengthening the stability and repair efficiency of the self-healing system.

[0016] Secondly, the application uses Na2SO3 and NaHSO3 to cap the isocyanate groups, maintains the activity of the isocyanate groups, and can stabilize the polyurethane emulsion, better maintain and establish the self-repairing system. The blocked isocyanate groups are de-blocked by heat during the finishing process and react with the active groups on the surface of the fabric fibers, and the polymer is firmly combined with the wool fibers through covalent bonds, has a strong adhesion to the fabric and does not lose the self-repairing performance. And the de-blocking temperature of the isocyanate capped by Na2SO3 and NaHSO3 is relatively low, which not only makes the finishing process low in energy consumption, green and low in carbon, but also protects the mechanical properties of the wool fibers from being affected during the finishing process.

[0017] Preferably, the polyisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenyl methane diisocyanate.

[0018] Preferably, the polyester polyol is one or two of polyethylene adipate glycol, polycarbonate glycol, polycaprolactone glycol, polyethylene adipate glycol, polyethylene adipate glycol diethylene glycol, with a number average molecular weight Mn of one of 1000, 1500, 2000, the Mn within the range makes the viscosity of the prepolymer suitable, ensures that the subsequent emulsification can be carried out smoothly, and ensures that the synthesis reaction has controllability and repeatability, ensures the stability of product quality, and can accurately control the mechanical properties of the waterborne polyurethane material.

[0019] Preferably, the molecular weight of the hydroxypropyl dimethicone is 2000.

[0020] Preferably, the catalyst is an organic bismuth catalyst. An environmentally friendly organic bismuth catalyst Coscat® 83 AC83 is selected, which does not cause environmental pollution.

[0021] Preferably, the compound containing a dynamic reversible disulfide bond is one of bis(2-hydroxyethyl) disulfide, 4,4'-dihydroxydiphenyl disulfide, and 2,2'-diaminodiphenyl disulfide.

[0022] Preferably, the polyhydroxy alcohol amine is one of ethylene glycol amine, triethanolamine, N-methyl diisopropanolamine, and N-ethyldiethanolamine.

[0023] Preferably, the aminosulfonate is one of ethylenediamine sodium ethanesulfonate, ethylenediamine sodium (propyl) sulfonate, N-(2-aminoethyl)-aminobutane sodium sulfonate, N-(2-aminoethyl)-2-aminobutane sodium sulfonate, and 2-(diethanolamine) sodium ethanesulfonate.

[0024] Preferably, the viscosity regulator is diethylene glycol ethyl ether acetate (DCAC). Using DCAC as a viscosity regulator is non-toxic and harmless, and meets the requirements of environmentally friendly production.

[0025] The second aspect of the present application also provides a preparation method of a multifunctional finishing agent, comprising the following steps:

[0026] S1. Preparing a prepolymer: under nitrogen protection, dehydrating a polyisocyanate for 3 h, then adding a polyester polyol, dimethylolpropionic acid, and hydroxypropyl dimethicone after cooling to 50-60℃, adding a catalyst at 50-60℃, after the system temperature tends to be stable, heating to 70-90℃, and keeping the temperature for 1-4 h, and adding a viscosity regulator to adjust the viscosity during the reaction, to obtain a prepolymer.

[0027] S2. Chain extension reaction: reducing the temperature of the prepolymer system to 50-60℃, and adding a compound containing a dynamic reversible disulfide bond thereto, and carrying out chain extension reaction for 2-3 h.

[0028] S3. Branching reaction: keep the temperature at 50-60 DEG C, add polyhydric alcohol amine to carry out branching reaction, and react for 1-2 h to obtain the modified organic silicon waterborne polyurethane.

[0029] S4. Emulsification and capping: reduce the temperature of the reaction system to 0-5 DEG C, add sodium bisulfite and sodium sulfite, and after reacting for 40-60 min, add triethylamine to neutralize the reaction for 20-40 min, set the end point pH to 6-7, add deionized water under stirring at a rotation speed of 1000-1500 rpm for 30 min, then add the amino sulfonate solution drop by drop under the shearing action at 2000-2500 rpm, and stir for 30 min to obtain a translucent modified organic silicon waterborne polyurethane emulsion.

[0030] S5. Emulsion compounding: under room temperature conditions, add the wax emulsion into the modified organic silicon waterborne polyurethane emulsion based on multiple dynamic reversible action, and homogenize for 20-30 min under a rotation speed of 1000-1500 rpm to obtain the multifunctional finishing agent.

[0031] The specific reaction process is as follows:

[0032]

[0033] In this embodiment, ethylenediamine sodium ethanesulfonate is used to introduce ionic bonds, and ethylene glycol amine is used to carry out branching reaction. The structure of R4 is as follows: In this structure, bis (2-hydroxyethyl) disulfide is used to introduce disulfide bonds. The structure of R3 is as follows:

[0034] The structure of R is one of the structures of polyisocyanate OCN-R-NCO; the structure of R1 is one of the structures of polyol HO-R1-OH; and the structure of R2 is as follows: , wherein n is about 22.

[0035] The preparation process of the application comprises pre-polymerization and modification, which can better play the cooperation of raw materials. In the pre-polymerization stage, the soft and hard segments form a stable intermediate with low molecular weight, laying a uniform "skeleton" for the subsequent reaction, avoiding the problems of explosive polymerization or insufficient reaction when the raw materials are directly reacted. In the modification stage, the functional groups disulfide bond and hyperbranched structure are introduced, the performance of the final product is precisely controlled, the synergistic effect between different raw materials is further amplified, and the preparation process is easy to operate and efficient, which is suitable for industrial production.

[0036] Secondly, the waterborne polyurethane adopts the method of first end capping and then modifying, specifically, first adding an end capping agent to end cap, adding alkali to neutralize, adding deionized water to emulsify to form a stable emulsion, which is equivalent to "wearing a protective film" for the polyurethane particles, so that the particles are uniformly suspended in water; when the sulfonate is added subsequently, it can be precisely and uniformly grafted on the polyurethane molecular chain, avoiding local aggregation of the sulfonate, and ensuring that the modification reaction can be carried out synchronously on the particles. This method of first end capping and then emulsifying and modifying can make the sulfonate uniformly distributed in the polyurethane, and there will be no situation of local performance being too strong or too weak, and the final product emulsion has better stability and is less likely to separate, precipitate, and is more convenient to store and use.

[0037] Preferably, dimethylol propionic acid accounts for 6%-7% of the mass of the prepolymer, hydroxypropyl polydimethylsiloxane accounts for 8%-10% of the mass of the prepolymer, the mass ratio of the compound containing a dynamic reversible disulfide bond to the polyester polyol is 2:1-1:2, the polyhydroxy alcohol amine accounts for 5%-8% of the mass of the prepolymer, the catalyst accounts for 0.05% of the mass of the prepolymer, and the viscosity regulator accounts for 5% of the mass of the prepolymer.

[0038] Preferably, the R (n-NCO / n-OH) value of the modified silicone waterborne polyurethane in S3 is 1.4-1.6, and in this range, the prepolymer has a suitable molecular weight and viscosity, ensuring that the subsequent modification and emulsification process is feasible and can provide the necessary reaction sites to balance and optimize the performance of the final product.

[0039] Preferably, the blocking rate of the modified silicone waterborne polyurethane emulsion in S4 is 25%-50%, and the grafting rate of the side chain amino sulfonate is 50%-100%.

[0040] The third aspect of the present application also provides an application of the multifunctional finishing agent, characterized in that the multifunctional finishing agent is used for self-repairing and anti-pilling finishing of wool fabric.

[0041] The present application has the following advantages:

[0042] 1. The multifunctional finishing agent of the present application includes a self-repairing hyperbranched silicone modified waterborne polyurethane based on multiple dynamic reversible actions, which can achieve self-repairing and anti-pilling effects on wool fabric. The main method is to construct a self-healing system with multiple reversible crosslinking structures, i.e. a "hydrogen bond-disulfide bond-ion bond" trinity cooperatively forming a closed loop of "adsorption-repairing-reinforcement", so as to realize the "wound" self-repairing performance of the film formed on the fabric surface under low temperature conditions, and to give the fabric strong durability and extend the wearability of the fabric.

[0043] 2. The finishing agent prepared by the present application has good self-repairing and anti-pilling properties of wool, and through good compounding of modified silicone waterborne polyurethane emulsion and wax emulsion, the finishing agent forms low surface energy on the surface of the fabric, reduces the friction coefficient, and the finished fabric is not sticky. The stiffness, hand feeling and air permeability of the wool fabric after finishing are not affected, and the state is stable in production and application, the machine runs continuously without sticking to the roller, which is beneficial to industrial production.

[0044] 3. The modified polyurethane of the present application also includes silicone modification, which improves the crosslinking property of the polymer and has good film forming effect. It can also synergistically improve the softness of the fabric and reduce its surface energy with the self-repairing system of "hydrogen bond-disulfide bond-ion bond", so that the finally prepared finishing agent not only has excellent anti-pilling property, but also maintains smooth and soft hand feeling.

[0045] 4. The modified silicone waterborne polyurethane emulsion prepared by the present application has hyperbranched structure, which makes the polymer have low viscosity, easy to control, less chain entanglement, high solubility. In addition, the introduction of hydrophilic monomers makes the self-emulsifying effect of the system good, the prepared emulsion is stable in state, does not separate after centrifugation, has excellent dispersibility, good compatibility with other additives, and the highly branched topological structure provides a three-dimensional support skeleton for the self-repairing system, further strengthening the stability and repair efficiency of the self-repairing system.

[0046] 5. The present application uses Na2SO3 and NaHSO3 to cap and protect the active isocyanate group, so that the prepared emulsion has excellent stability. The deblocking temperature of isocyanate capped by Na2SO3 and NaHSO3 is low, which not only makes the energy consumption low and green and low carbon in the finishing process, but also protects the mechanical properties of wool fibers in the finishing process.

[0047] 6. The composition of the finishing agent of the present application does not contain harmful substances restricted for use internationally, such as formaldehyde and heavy metals. For example, the present application uses water as a solvent and uses DCAC as a viscosity regulator, which is non-toxic and harmless. The use of organic bismuth catalyst for catalysis is environmentally friendly, and the amount of additives in the whole system can be almost ignored. It is better than most existing technologies, meets the requirements of environmental protection and energy saving in textile production, does not pollute the environment in the production, use and disposal processes, and is conducive to sustainable development. It is an environmentally friendly textile printing and dyeing auxiliary with good market prospect. DETAILED DESCRIPTION

[0048] The technical solutions of the present application will be described below in conjunction with the embodiments. Obviously, the described embodiments are only a part of the embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor belong to the scope of protection of the present application.

[0049] The present application provides a technical solution comprising preparing a modified silicone waterborne polyurethane emulsion and using it to prepare a multifunctional finishing agent:

[0050] S1. Preparation of a prepolymer: under nitrogen protection, the polyisocyanate is dehydrated for 3 h, cooled to 50-60°C, then the polyester polyol, dimethylol propanoic acid, hydroxypropyl polydimethylsiloxane are added, the catalyst is added at 50-60°C, after the system temperature tends to be stable, the temperature is raised to 70-90°C, and the reaction is kept for 1-4 h, and the viscosity adjusting agent is added to adjust the viscosity during the reaction, to obtain the prepolymer.

[0051] S2. Chain extension reaction: the temperature of the prepolymer system is reduced to 50-60°C, and a compound containing a dynamic reversible disulfide bond is added, and the chain extension reaction is carried out for 2-3 h.

[0052] S3. Branching reaction: the temperature is kept at 50-60°C, and a polyhydroxy alcohol amine is added to carry out the branching reaction, and the reaction is carried out for 1-2 h, to obtain the modified silicone waterborne polyurethane.

[0053] S4. Emulsification and capping: the temperature of the reaction system is reduced to 0-5°C, sodium bisulfite and sodium sulfite are added, and the reaction is carried out for 40-60 min, then triethylamine is added to neutralize the reaction for 20-40 min, the end point pH is set to 6-7, deionized water is added under stirring at a rotation speed of 1000-1500 rpm for 30 min, then an aminosulfonate solution is added dropwise under the action of high-speed shearing at 2000-2500 rpm, and stirring is carried out for 30 min, to obtain a translucent modified silicone waterborne polyurethane emulsion.

[0054] S5. Emulsion compounding: the wax emulsion is added to the purified modified silicone waterborne polyurethane emulsion, and homogenization is carried out at a rotation speed of 1000-1500 rpm for 20-30 min, to obtain the multifunctional finishing agent.

[0055] Example 1

[0056] R is set to 1.4, the hydroxypropyl polydimethylsiloxane accounts for 8% of the mass of the prepolymer, the DMPA accounts for 6% of the mass of the prepolymer, the mass ratio of bis(2-hydroxyethyl) disulfide to polycarbonate diol is 0.5, the ethylene glycol amine accounts for 5% of the mass of the prepolymer, the organobismuth catalyst (Coscat® 83 AC83) accounts for 0.05% of the mass of the prepolymer, the DCAC accounts for 5% of the mass of the prepolymer, the capping rate is 25%, the grafting rate of the side chain aminosulfonate is 50%, and the solid content of the modified silicone waterborne polyurethane emulsion is 30%.

[0057] The preparation process comprises the following specific steps:

[0058] S1: Under nitrogen protection, isophorone diisocyanate is dehydrated for 3 h, cooled to 50°C, and polycarbonate diol, DMPA, hydroxypropyl polydimethylsiloxane, and Coscat® 83 AC83 are added at 50°C. When the system temperature tends to be stable, the temperature is raised to 70°C, and the reaction is kept for 4 h. During the reaction, DCAC is added to adjust the viscosity of the prepolymer. The temperature is reduced to 50°C, and chain extender bis(2-hydroxyethyl) disulfide is added to the prepolymer for chain extension reaction for 2 h. The temperature is kept at 50°C, and ethylene glycol amine is added for branching reaction for 1 h. The system temperature is reduced to 0°C, and Na2SO3 and NaHSO3 are added for capping reaction for 40 min. TEA is added for neutralization reaction for 30 min, and the end point pH is 6-7. Deionized water is added under stirring at a rotation speed of 1500 rpm for emulsification for 30 min, and then sodium ethylenediamine sulfonate is added dropwise under high-speed shearing at 2500 rpm for 30 min, to obtain a semi-transparent modified silicone waterborne polyurethane emulsion.

[0059] S2: 50 parts of the modified silicone waterborne polyurethane emulsion of step S1 is mixed with 2.5 parts of polyethylene wax emulsion OE-6516 at room temperature, and homogenized at 1000 rpm for 30 min to obtain a multifunctional finishing agent.

[0060] Example 2

[0061] R is set to 1.4, the mass fraction of hydroxypropyl polydimethylsiloxane in the prepolymer is 8%, the mass fraction of DMPA in the prepolymer is 6%, the mass ratio of bis(2-hydroxyethyl) disulfide to polycaprolactone diol is 1, the mass fraction of triethanolamine in the prepolymer is 6%, the mass fraction of bismuth organic catalyst (Coscat® 83 AC83) in the prepolymer is 0.05%, the mass fraction of DCAC in the prepolymer is 5%, the capping rate is 50%, the grafting rate of side chain amino sulfonate is 50%, and the solid content of the modified silicone waterborne polyurethane emulsion is 30%.

[0062] The preparation process includes the following specific steps:

[0063] S1: Under nitrogen protection, toluene diisocyanate is dehydrated for 3 h, and the temperature is lowered to 50°C. Polycarbonate diol, DMPA, hydroxypropyl polydimethylsiloxane, Coscat® 83 AC83 are added at 50°C. When the system temperature tends to be stable, the temperature is raised to 70°C, and the reaction is kept for 4 h. DCAC is added to adjust the viscosity of the prepolymer during the reaction. The temperature is lowered to 50°C, and the chain extender bis(2-hydroxyethyl) disulfide is added to the prepolymer. The chain extension reaction is carried out for 2 h. The temperature is kept at 50-60°C, and triethanolamine is added for branching reaction, which is carried out for 1 h. The system temperature is lowered to 0°C, and Na2SO3 and NaHSO3 are added for end capping reaction, which is carried out for 60 min. TEA is added for neutralization reaction, which is carried out for 30 min, and the final pH is 6-7. Deionized water is added under stirring at a rotation speed of 1500 rpm for 30 min, and then sodium ethylenediamine sulfonate is added dropwise under high-speed shearing at 2500 rpm. The stirring is carried out for 30 min to obtain a semi-transparent modified silicone waterborne polyurethane emulsion.

[0064] S2: 100 parts of the modified silicone waterborne polyurethane emulsion of step S1 is mixed with 2.5 parts of polyethylene wax emulsion OE-6201 at room temperature, and homogenized at 1000 rpm for 30 min to obtain a multifunctional finishing agent.

[0065] Example 3

[0066] R is set to 1.5, the mass fraction of hydroxypropyl polydimethylsiloxane in the prepolymer is 9%, the mass fraction of DMPA in the prepolymer is 7%, the mass ratio of bis(2-hydroxyethyl) disulfide to polycaprolactone diol is 1, the mass fraction of N-methyl diisopropylolamine in the prepolymer is 7%, the mass fraction of bismuth organic catalyst (Coscat® 83 AC83) in the prepolymer is 0.05%, the mass fraction of DCAC in the prepolymer is 5%, the blocking rate is 50%, the grafting rate of side chain amino sulfonate is 100%, and the solid content of the modified silicone waterborne polyurethane emulsion is 30%.

[0067] The preparation process includes the following specific steps:

[0068] S1: Under nitrogen protection, isophorone diisocyanate is dehydrated for 3 h, cooled to 60°C, and then poly (ε-caprolactone) diol, DMPA, hydroxypropyl polydimethylsiloxane, and Coscat® 83 AC83 are added at 50°C. After the system temperature tends to be stable, the temperature is increased to 70°C, and the reaction is maintained for 4 h. During the reaction, DCAC is added to adjust the viscosity of the prepolymer. The temperature is then reduced to 50°C, and a chain extender, bis (2-hydroxyethyl) disulfide, is added to the prepolymer for chain extension reaction for 2 h. The temperature is maintained at 50-60°C, N-methyl diisopropyl ethanolamine is added for branching reaction, and the reaction is maintained for 1 h. The system temperature is reduced to 0°C, Na2SO3 and NaHSO3 are added for end capping reaction for 60 min, TEA is added for neutralization reaction for 30 min, the final pH is 6-7, deionized water is added under stirring at a rotation speed of 1500 rpm for emulsification for 30 min, and then N- (2-aminoethyl) -2-aminobutane sulfonic acid sodium is added dropwise under high-speed shearing at 2500 rpm for 30 min to obtain a semi-transparent modified silicone waterborne polyurethane emulsion.

[0069] S2: 50 parts of the modified silicone waterborne polyurethane emulsion from step S1 and 2.5 parts of polyethylene wax emulsion OE-6112 are mixed at room temperature, and homogenized at 1000 rpm for 30 min to obtain a multifunctional finishing agent.

[0070] Example 4

[0071] R is set to 1.5, the mass fraction of hydroxypropyl polydimethylsiloxane in the prepolymer is 10%, the mass fraction of DMPA in the prepolymer is 7%, the mass ratio of bis (2-hydroxyethyl) disulfide to poly (ε-caprolactone) diol is 1.5, the mass fraction of N-ethyldiethanolamine in the prepolymer is 8%, the mass fraction of bismuth organic catalyst (Coscat® 83 AC83) in the prepolymer is 0.05%, the mass fraction of DCAC in the prepolymer is 5%, the blocking rate is 50%, the grafting rate of side chain amino sulfonate is 100%, and the solid content of the modified silicone waterborne polyurethane emulsion is 30%.

[0072] The preparation process includes the following specific steps:

[0073] S1: Under nitrogen protection, isophorone diisocyanate is dehydrated for 3 h, and the temperature is lowered to 60°C. Polycaprolactone diol, DMPA, hydroxypropyl polydimethylsiloxane, and Coscat® 83 AC83 are added at 50°C. When the system temperature tends to be stable, the temperature is raised to 70°C, and the reaction is kept for 4 h. DCAC is added to the prepolymer to adjust the viscosity during the reaction. The temperature is lowered to 50°C, and the chain extender bis(2-hydroxyethyl) disulfide is added to the prepolymer. The chain extension reaction is carried out for 2 h. The temperature is kept at 50-60°C, N-ethyldiethanolamine is added for branching reaction, and the reaction is carried out for 1 h. The system temperature is lowered to 0°C, Na2SO3 and NaHSO3 are added, and the end-capping reaction is carried out for 60 min. TEA is added for neutralization reaction for 30 min, and the final pH is 6-7. Deionized water is added under stirring at a rotation speed of 1500 rpm for 30 min, and then 2-(diethanolamino) ethanesulfonic acid sodium is added dropwise under high-speed shearing at 2500 rpm. The stirring is carried out for 30 min to obtain a translucent modified silicone waterborne polyurethane emulsion.

[0074] S2: At room temperature, 100 parts of the modified polyurethane emulsion obtained in step S1 is mixed with 5 parts of a wax emulsion polyethylene wax emulsion OE-6112B under homogenization at 1000 rpm for 30 min to obtain a multifunctional finishing agent.

[0075] Comparative Example 1

[0076] The main difference between this comparative example 1 and Example 1 is that no bis(2-hydroxyethyl) disulfide, ethylene glycol amine, and ethylenediamine ethanesulfonic acid sodium are added in step S1, and no wax emulsion is added in step 2.

[0077] Comparative Example 2

[0078] The main difference between this comparative example 2 and Example 1 is that no bis(2-hydroxyethyl) disulfide is added in step S1.

[0079] Comparative Example 3

[0080] The main difference between this comparative example 3 and Example 1 is that no ethylenediamine ethanesulfonic acid sodium is introduced in step S1.

[0081] Comparative Example 4

[0082] The main difference between this comparative example 4 and Example 1 is that no ethylene glycol amine is added in step 1.

[0083] Performance Test

[0084] The multifunctional finishing agent prepared in the examples is subjected to performance test, and the specific test results are shown in the following table.

[0085] Table 1 Performance test results of examples

[0086]

[0087] The multifunctional finishing agent prepared in the comparative example was subjected to performance test, and the specific test results are shown in the following table:

[0088] Table 2 Performance test results of the comparative example

[0089]

[0090] The prepared finishing agent was prepared into a finishing solution of 20 g / L, and the fabric was finished. The finished fabric and the unfinishing fabric were subjected to performance test.

[0091] The anti-pilling performance of the fabric before and after finishing was tested according to the method of GB / T 4802.3-2008 “Textiles-Determination of the pilling behavior of textiles-Part 3: Pilling box method”; the durability of the fabric before and after finishing was tested with reference to the method of GB / T 8629-2017 “Textiles-Home washing and drying procedures for use in testing”; the stiffness of the fabric before and after finishing was tested according to the method of ZB W04003-87 “Textile Stiffness Test Method Inclined Cantilever Method”; the hand feeling was evaluated by hand touch method, and the hand feeling of the unfinishing fabric was defined as 1 point, the hand feeling evaluation was up to 5 points, at least 6 professional persons were subjectively evaluated and scored, and the average value was taken, the larger the value, the better the hand feeling. The breaking strength of the fabric before and after finishing was tested according to GB / T 3923.1-2013 “Textiles-Determination of the tensile properties of fabrics-Part 1: Breaking force and elongation at break”; the air permeability of the fabric before and after finishing was tested according to GB / T 5453-1997 “Textiles-Determination of the air permeability of fabrics”, and the test index was air permeability, and the average value of 10 times of test results was taken. The performance test results of the fabric before and after finishing are shown in Table 3.

[0092] Table 3 Comparison of various performances of the wool fabric before and after finishing

[0093]

[0094] As can be seen from Table 3, the anti-pilling grade of the wool fabric after finishing with the multifunctional finishing agent prepared in Examples 1-4 is 4 or above, and the anti-pilling grade after 30 times of cycle washing can still be maintained at 4 or above, reflecting good self-repairing performance of the fabric. At the same time, the breaking strength, stiffness, air permeability and hand feeling of the fabric are not much different from those before finishing, indicating that the finishing agent has little effect on the excellent performance of the wool itself, that is, the finishing agent can give the wool fabric good anti-pilling performance, self-repairing (durability) and well retain the excellent performance of the wool itself.

[0095] And from the comparative example can be seen, the comparative example 1 does not add bis (2-hydroxyethyl) disulfide, ethylene glycol amine, ethylenediamine ethyl sulfonate sodium in step S1, does not add wax emulsion in step S2, the anti-pilling performance is poor, and the anti-pilling level after 30 times of cyclic washing reflects that it has no self-repairing effect, and the prepared sample is sticky and sticky roll; Comparative example 2 and comparative example 3 only introduce one of bis (2-hydroxyethyl) disulfide and ethylenediamine ethyl sulfonate sodium, that is, only one disulfide bond and ionic bond exists, the anti-pilling and self-repairing effect is about 1 level weaker than when both are present; Comparative example 4 shows that when no branching unit is introduced, the prepared finishing frame will appear delamination, instability, relatively poor dispersion effect, and relatively poor performance and hand feeling.

[0096] In summary, the environmentally friendly self-repairing wool anti-pilling multifunctional finishing agent prepared by the application has excellent anti-pilling effect, durability, and does not affect the stiffness, air permeability and hand feeling, and has high market application value.

[0097] The above description is only the preferred embodiment of the present application, and it should be understood that the present application is not limited to the form disclosed herein, and should not be considered as excluding other embodiments, but can be used in various other combinations, modifications and environments, and can be modified within the scope of the concept described herein, by the above teaching or related art or knowledge. The modification and change made by the person skilled in the art without departing from the spirit and scope of the present application shall be within the protection scope of the claims of the present application.

Claims

1. A multifunctional finishing agent, characterized by, The raw materials include the following: 50-100 parts of a modified silicone waterborne polyurethane emulsion based on multiple dynamic reversible action, and 2.5-5 parts of a wax emulsion, by weight; The raw materials for preparing the modified silicone waterborne polyurethane emulsion based on multiple dynamic reversible action include: a polyisocyanate, a polyester polyol, dimethylol propionic acid, a hydroxypropyl dimethyl silicone, a catalyst, a compound containing a dynamic reversible disulfide bond, a polyhydroxy alcohol amine, an aminosulfonate, sodium bisulfite, sodium sulfite, triethylamine, a viscosity regulator, and deionized water; the modified silicone waterborne polyurethane emulsion prepared has a multiple dynamic reversible crosslinking structure: non-covalent bond hydrogen bond crosslinking in the soft and hard segments, dynamic reversible covalent bond disulfide bond, and ionic clusters containing sulfonate side chains.

2. The multi-functional finishing agent according to claim 1, characterized in that, The wax emulsion is one of the OE series, and has a solid content of 20%-30%.

3. The multi-functional finishing agent according to claim 1, characterized in that, The modified silicone waterborne polyurethane emulsion based on multiple dynamic reversible action has a solid content of 30% and a particle size of 100-150 nm.

4. The multi-functional finishing agent according to claim 1, characterized in that, The polyisocyanate is one of isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, and diphenyl methane diisocyanate.

5. The multi-functional finishing agent according to claim 1, characterized in that, The polyester polyol is one or two of polyethylene adipate glycol, polycarbonate diol, polycaprolactone diol, polyethylene adipate glycol, and polyethylene adipate glycol diethylene glycol, and has a number average molecular weight Mn of one of 1000, 1500, and 2000.

6. The multi-functional finishing agent according to claim 1, characterized by, The hydroxypropyl dimethyl silicone has a molecular weight of 2000.

7. The multi-functional finishing agent according to claim 1, characterized by, The catalyst is an organic bismuth catalyst.

8. The multi-functional finishing agent according to claim 1, characterized by, The compound containing a dynamic reversible disulfide bond is one of bis(2-hydroxyethyl) disulfide, 4,4'-dihydroxydiphenyl disulfide, and 2,2'-diaminodiphenyl disulfide.

9. The multi-functional finishing agent according to claim 1, characterized by, The polyhydroxy alcohol amine is one of ethylene glycol amine, triethanolamine, N-methyl diisopropanolamine, and N-ethyl diethanolamine.

10. The multi-functional finishing agent according to claim 1, characterized by, The aminosulfonate is one of ethylenediamine sodium ethyl sulfonate, ethylenediamine sodium (propyl) sulfonate, N-(2-aminoethyl)-aminobutane sodium sulfonate, N-(2-aminoethyl)-2-aminobutane sodium sulfonate, and 2-(diethanolamine) sodium ethyl sulfonate.

11. The multi-functional finishing agent according to claim 1, characterized in that, The viscosity regulator is diethylene glycol ethyl ether acetate.

12. A method for preparing the multifunctional finishing agent according to any one of claims 1, 4 to 11, characterized by, The method comprises the following steps: S1. Preparing a prepolymer: under nitrogen protection, dehydrate the polyisocyanate for 3 h, cool to 50-60℃, and then add the polyester polyol, dimethylol propionic acid, and hydroxypropyl dimethyl silicone; add the catalyst at 50-60℃; when the system temperature tends to be stable, increase the temperature to 70-90℃, and keep the temperature for 1-4 h; during the reaction, add the viscosity regulator to adjust the viscosity, and obtain the prepolymer; S2. Chain extension reaction: reduce the temperature of the prepolymer system to 50-60℃, and then add the compound containing a dynamic reversible disulfide bond, and keep the temperature for 2-3 h; S3. Branching reaction: keep the temperature at 50-60℃, add the polyhydroxy alcohol amine to generate a branching reaction, and keep the temperature for 1-2 h, and obtain the modified silicone waterborne polyurethane. S4. Emulsification capping: the temperature of the reaction system is reduced to 0-5℃, sodium bisulfite and sodium sulfite are added, and after 40-60 min of reaction, triethylamine is added to neutralize the reaction for 20-40 min, the end point pH is set to 6-7, deionized water is added under stirring at a speed of 1000-1500 rpm for 30 min, then an aminosulfonate solution is added dropwise under stirring at a speed of 2000-2500 rpm for 30 min, to obtain the modified silicone waterborne polyurethane emulsion based on multiple dynamic reversibility; S5. Emulsion compounding: under room temperature conditions, the wax emulsion is added to the modified silicone waterborne polyurethane emulsion based on multiple dynamic reversibility, and homogenized at a speed of 1000-1500 rpm for 20-30 min, to obtain the multifunctional finishing agent.

13. The method for preparing a multifunctional finishing agent according to claim 12, characterized in that, The dimethylol propionic acid accounts for 6%-7% of the mass of the prepolymer, the hydroxypropyl polydimethylsiloxane accounts for 8%-10% of the mass of the prepolymer, the mass ratio of the compound containing dynamic reversible disulfide bond to the polyester polyol is 2:1-1:2, the polyhydroxy alcohol amine accounts for 5%-8% of the mass of the prepolymer, the catalyst accounts for 0.05% of the mass of the prepolymer, and the viscosity regulator accounts for 5% of the mass of the prepolymer.

14. The method for preparing a multifunctional finishing agent according to claim 12, characterized in that, The R(n-NCO / n-OH) value of the modified silicone waterborne polyurethane in S3 is 1.4-1.

6.

15. The method for preparing a multifunctional finishing agent according to claim 12, characterized in that, The capping rate of the modified silicone waterborne polyurethane emulsion based on multiple dynamic reversibility in S4 is 25%-50%, and the grafting rate of the side chain aminosulfonate is 50%-100%.

16. Use of a multifunctional finishing agent according to any one of claims 1 to 11, characterized in that The multifunctional finishing agent is used for self-repairing and anti-pilling finishing of wool fabric.

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